Heat treatable, durable, ir-reflecting sputter-coated glass and method of making same

BACKGROUND OF THE INVENTION The present invention relates to dust-coated glasses which are heat-treated and strong, whose luminous sensitivity can be varied over a wide range to be useful in the artistic, automotive and residential construction.

BACKGROUND OF THE INVENTION

The popularity of metal and metal oxide coating on glass in the construction and automotive industries is well known. As is well described in patents and other literature, such glasses, by manipulating the coating system, generally achieve a fully acceptable degree of reflection, transmittance, radiation, chemical resistance and strength, as well as the required color. See, for example, U.S. Pat. 3 935,351, 4,413,877, 4,462,883, 3,826,728, 3,681,042, 3,798,146, and 4,594,137, to name just a few.

It is also well known that while there are several acceptable uses for such coatings, one of the most effective and therefore acceptable is the well known technique known as magnetically reinforced spray coating. Such a method is described in U.S. Pat. 4,166,018, recognized as a fundamental teaching subject (see also Munz et al., Performance and Sputtering Criteria of Modern Architectural Glass Coatings, SPIE Vol.325, Optical Thin Films, 1982, pp. 65-73).

Although many effective layer systems are known, the use of some older spray coating system is known to yield mechanical strength properties lower than those achieved by another known method known as pyrolysis technology. In addition, as a counterfactual, dust-coated systems often achieve better infrared reflectance than typical pyrolytic coatings. In addition, sputtered glasses are generally recognized as having higher optical and thermal performance than pyrolysis formed coatings and with improved coating uniformity, good radiation and better sunlight performance. It is clear that if a spray coating method could be invented for a specific coating system in which the mechanical strength properties of the spray coating system could exceed or match those obtained by pyrolysis technology, this would at the same time provide significant further benefits of the spray coating technology. technical level tier.

U.S. Pat. No. 5,229,194 to Improved Heat Treated Dust Coated Glass Systems, which discloses certain unique layer systems that have reached this important further stage in the art. These systems are a known state of the art for the subject matter of the invention as of the date of the commercial review, more than one year after the filing date of our application. This is discussed further below.

First, although it has to be started in recent years, the popularity of coated glass has led to many attempts to obtain a coated glass product which can be coated before heat treatment and can subsequently be heat treated without coating or damaging changes to the glass itself (ie replacement glass). product). One reason for this, for example, is that it can be extremely difficult to achieve even coverage on an already curved piece of glass. It is well known that if a flat glass surface can be coated and then curved, a much easier way can be used to obtain an even coating than when the glass is pre-curved. From this point of view, this is true for artistic and residential glass, but especially for automotive glass, such as convex windscreens, which in recent years have been popularizing a more aerodynamically efficient design to achieve fuel economy.

In the past, certain methods have been discovered for producing coated heat-treated glass products, which can be heat-treated, folded or known as thermal curing during and after production. Generally speaking, many of these pre-coated products suffer from untreated heat at the higher temperatures necessary to achieve economical bending, hardening, and / or thermal curing (i.e., 1150 ° F - 1450 ° F (621.1-787.8 ° C)). In short, such techniques often suffer from the need to raise the temperature to about 1100 ° F (593.3 ° C) or less to achieve heat treatment without damaging the coating or substrate.

Here is the latter situation; it is precisely the absence of any significant deleterious effect to cover or underlie what is meant by the term heat-treated herein. Although in some situations several characteristics may change during heat treatment, heat treatment as used herein means that the desired core properties of the coating system and the product as a whole must be achieved despite the fact that the coated glass has undergone one or more heat treatments, discussed above (ie bending, hardening and / or thermal curing). Mostly for artistic purposes contemplated by the present invention, optimized heat treatment means that the glass and its layered coating do not substantially change their visual (optical) appearance between the preheated product and the final product after heat treatment. In most applications for automotive applications, modifications to better adapt to heat treatment may be tolerated and even desirable while optimized heat treatment means that the change occurs evenly over the substrate and is independent of the parameters used to perform the heat treatment.

In this regard, U.S. Pat. No. 5,188,887 discloses certain prior art coatings systems that can be successfully heat treated at higher, more elevated temperatures than those described above to achieve the desired result regardless of temperature effects, bending or thermal curing. Simply put, these prior art coating compositions find their uniqueness in a layer system that acts as a metal layer, a high-nickel alloy which, when properly formulated, is known as Haynes 214, usually containing 75.45% Ni, 4.00% Fe, 16.00% Cr, 0.04% C, 4.50% Al, and 0.01% Y (percent by weight). Using an alloy with a high content of nickel such as Haynes 214 and coating it with stoichiometric tin oxide (SnCb) or with one or other layers (such as undercoating of the same stoichiometric tin oxide and / or middle aluminum layer between the upper SnC> 2 layer and high-alloy nickel alloy), it has been found that heat treatment of glassware at elevated temperatures of approximately 1150 ° F to 1450 ° F (621.1 to 787.8 ° C) for about 2 to 30 minutes, can be achieved without significant change in color, mechanical strength, radiation, reflection or transmission. As a result, these compositions have an important improvement over prior heat treatment systems such as those disclosed in the following patents: 4,790,922; 4,816,034; 4,826,525; 4,715,879 and 4,857,094.

In addition to the prior disclosure in the aforementioned patents, the Leybold windscreen of the TCC-2000 system is also known. This system employs four or five layers of metal or metal oxides to produce sputtered glass which, after being slightly heat-treated at temperatures above 1100 ° F (593.3 ° C), can be used as pre-coated glass to form convex or straightening when manufacturing windshields for cars, provided that the fast tempo limits are placed in the heat treatment. The layering from the glass substrate to the outside is usually as follows: first layer of tin oxide, second layer of nickel / chromium alloy (usually about 80/20), third layer of silver, fourth layer of nickel / chromium alloy and fifth layer of tin oxide. In addition, with relatively low upper temperatures and time limits for heat treatment, the final coatings are relatively soft and reveal such unacceptably low chemical resistance characteristics that they can only be realistically applied to the interior surfaces of laminated windscreens.

In the aforementioned patent no. Specifically, 4,715,879 states that a layer system cannot be obtained therein unless a protective layer of metal oxide (i.e., tin oxide) is formed such that the oxide has an oxygen deficiency (i.e., non-stoichiometric). This of course requires careful balancing in the production process. Heat treatment in this regard is also disclosed in U.S. Pat.

826 525. In addition, this patent specifically states that the aluminum layer must be adapted to achieve heat treatment.

U.S. Pat. No. 5,229,194 discloses important advances in the spraying of heat-treated coatings, even compared to such descriptions in U.S. Pat. 5,188,887. In the present invention, it has been found that unique results in the heat treatment of dust-coated glasses have been achieved especially when used as bicycles for private use when the metallic nickel or alloy high metal nickel layer is surrounded by lower and upper individual oxide or nickel nitride layers or alloys and subsequent supernatant of oxides such as SnCh, ZnO, TiCE, or oxide alloys used there. Silicon is also mentioned as useful for the first topcoat of metallic nickel-plated coatings.

Such layered systems, in their acceptable forms, have proven to be heat-treated and wear-resistant. In addition, although the systems were initially found to be chemically resistant when introduced into mass production, some systems were found not to pass a fairly stringent chemical resistance test for 5% HCl (discussed below). In addition, their infrared and ultraviolet reflectance characteristics were found to be excellent over a wide range of applications. Moreover, their visible light transmittance values ​​were suitably low for private glazing but turned out to be too low to be really useful as window or panel glass for artistic or residential applications where a high visible light transmittance is required. Thus, when products requiring a dusting coating to completely fill the needs of artistic or residential covered glass under glass sheets for private windows, the coating had to be completed so that a new layer system could be formed. If such completion could be eliminated, significant progress would be achieved.

Our Co-Owned Property Application No. 07 / 876,350, filed April 30, 1992, entitled Good Performance, Resilient, Low E Glass, and Its Manufacturing Method, Revealing Some Unique Dust-Coated Layer Systems With Unique Applicability to Artistic and Residential Construction Applications as they achieve more than good chemical and mechanical resistance but also sunlight control properties. These systems are worthy of consideration as low E glasses (coatings) because they have a semi-spherical radiation (Eh) generally less than about 0.16 and their normal radiant power (E)_n) typically less than about 0.12. Measured in another way, their sheet resistance was approximately less than about 10.50 ohms / area. In addition, with normal glass thinnings (e.g., 2-6 mm), the visible light transmission was approximately 78% or more (compared to less than about 22-23% in certain suitable embodiments of the above-mentioned heat treatment private window coatings systems). .

The present invention in the aforementioned prepared application no. 07/876 350, now U.S. Pat. No. 5,344,718, has achieved its unique low E, high visible light transmission values, combined with good chemical and wear resistance application of a layer system which typically has (from the outside of the glass) a coating of Si.₃N4, first layer of nickel or nickel alloy, layer of silver, another layer of nickel or nickel alloy and outer layer of Si₃N4. The system of layers of glass with some proper implementation consists essentially of:

Si₃N4 / Ni: Cr / AG / Ni: Cr / Ag / Ni: Cr / Si₃N4

These seven layers of the system allowed for some higher strength and scratch resistance characteristics than the five-layer system described above. In addition, in each system, a suitable Ni: Cr layer contained nichrome, i.e. 80/20 by weight Ni / Cr, in which Cr nitride is the predominant chromium, whereas the Ni: Cr layer is formed in a nitrogen-containing atmosphere.

Unfortunately, these resistant low-E, high visible light transmittance glass coatings have proven that they cannot be heat treated. It is now proven that this is not true because the silver layer or layers are oxidized, but because the metallic silver layer or layers become discontinuous during heat treatment due to non-wetting; in this case, the Ni: Cr surrounding layers are insufficient to maintain the continuity of the silver layer or layers during heat treatment. Therefore, these otherwise useful layer systems cannot be used where the laminated glass will then be heat treated, tempered and cured. Unfortunately, silver layers were necessary to use to obtain the specified low E layers.

In this respect, it must be remembered that this is not suitable for the automotive windshield industry, where heat-treated dust-coated film systems have found their applicability. Some uses for artistic applications and in residential construction also require coated glass to be tempered, flexed or thermally cured. Moreover, the aforementioned Invention no. 07/876 350, now U.S. Pat. 5 344,718, low E glazing systems could not easily be adapted to achieve low visibility transmission values ​​to render them useful for private windows, even if they are not heat treated. For these reasons, these low E glass systems have not overcome the aforementioned production problem of completing the system to meet customer demand for more extensive sunlight control in spray-coated glass products.

In combination with the problem described above, there was a problem created by sputter coating the chamber with the need to create a layer or layers of S13N4 in the aforementioned application no. 07/876 In 350 layers system. To obtain such a layer, a Si shield (usually alloyed with aluminum) was used as a cathode. The sealed coating is then electrically exposed under N2 to produce S13N4 by reaction. Unfortunately, S13N4 is not a conductor (since a small amount of aluminum nitride is derived from the Al dopant, which also coats the anode during sputter coating). Coating performance deteriorates and completion time can be extended.

In our application no. No. 08/102 585, filed simultaneously herein and entitled "Dust Cover and Application", discloses a unique solution to this problem. Generally speaking, the solution is to create a cathodic latch that contains the required amount of conductive metal dispersed in Si so that its nitride (or metal if not obtained during the sputter coating operation) is formed in sufficient amount on the anode to maintain conductivity for a longer period of time. avoiding multiple closures. The full description of this application is incorporated herein by reference.

Until now, if a specialist in the field wanted to continue to reap the known benefits of wear and corrosion resistance using S13N4 layers, but also wanted to avoid costly downtime, while having to achieve heat treatment while still having the flexibility to change the control characteristics of sunlight over a fairly wide range. range, to prevent further production closures (according to the needs of various buyers), that specialist faced an insoluble problem. In this regard, a clear choice of any conductive metal as a dispersant (i.e., an alloying impurity) in the Si pad would not solve the problem, although overcoming the anode coating problem could completely disrupt the heat treatment of this metal and / or the desired resistance level and / or sunlight control. color) characteristics to be achieved.

This is because, apparently, there is a need for a spray-coated layer system that achieves the benefits of spray-coating while overcoming the problems and disadvantages described above in this field. The object of the present invention is to fulfill the needs of this field, as well as other objects, which will become apparent to one of ordinary skill in the art upon the following description.

THE SUBSTANCE OF THE INVENTION

Generally speaking, the present invention fully accomplishes the foregoing uses in the art by providing a glass article comprising a glass substrate having a sputter-coated layer system consisting of a glass substrate externally of (a) a substantially metallic layer consisting of nickel or nickel alloy. and which is substantially free of nitride; and (b) an upper layer of silicon nitride (S13N4); and wherein the layers are of sufficient thickness such that, when the glass substrate is about 1.5 to 13 mm thin and has the aforementioned layer system thereon, the laminated glass article is heat-treated and has a viscosity transmission of about 1 to 80% and capacity (E_n) about 0.10 - 0.60. In certain suitable embodiments, layer (a) is substantially free of nitride and the glass product, both before and after heat treatment, is strong and chemically resistant. Certain other suitable layers of the system of the present invention do not have a silver layer.

The present invention further fulfills the above-described needs in this field by providing a method of heat treating a coated glass article which typically comprises:

(a) application by sputtering on a glass substrate layer system situated away from the glass substrate, consisting essentially of a metal layer comprising nickel or nickel alloy; and a topcoat layer of silicon nitride; and

b) thereafter heat treating said coated glass substrate selected from the group consisting of bending, hardening, thermal curing, and combinations thereof; and

(c) the stage at which, after such heat treatment, the product so obtained has a normal radiant power (E_n) of about 0.10 to 0.60 and visibility transmission of about 1 to 80%.

A system of certain suitable layers of the present invention further comprises a lower layer of Si₃N₄, and each of Si₃N₄The layers contain a small amount of conductive metal alloying impurity or conductive metal nitride, where the use of this metal as a dispersant (alloying impurity) in the Si cathode shutter sputtering apparatus overcomes the above problem of downtime for anode impermeable Si₃N₄. Alloying impurities, conductive metals, of course, are selected so that they do not, at worst, adversely affect the control of sunlight or other physically desirable characteristics of the finished product. In certain suitable systems, this alloying impurity metal is selected from titanium, zirconium, hafnium, and mixtures thereof.

As stated earlier, the layer systems are better formed by spraying each layer with the required thinness on the glass substrate. Although the thinness of the glass can be widely varied, typically the glass article will be of a volatile glass type and will have a thinness of about 1.5 to 13.0 mm (i.e. about 0.060 0.50) and usually about 2 to 6 mm. The glass can be colored or black and white or decorated with patterns. Such glass may be of the only hardness type. According to certain suitable forms of the invention and determined by application to a glass substrate having a conventional thickness of about 4.0 mm, the resulting glass article after heat treatment will have the following properties:

<td>Feature</td><td>Boundaries</td>

<td>Visibility transfer:</td><td>about 1% - 80%</td>

<td>Visibility reflection (from the glass side):</td><td>about 4% 55%</td>

<td>Visibility reflection (film side):</td><td>about 4% - 65%</td>

<td>Visible color (glass side):</td><td>silver, pewter, blue, gray</td>

<td>Radiation power (normal, ie_n):</td><td>about 0.10 -0.60</td>

<td>Leaf resistance (R_s):</td><td>about 2 - 250 ohms / area</td>

<td>Transmission of sunlight:</td><td>about 1% to 80%</td>

The table above shows how the flexible systems of the present invention meet a wide range of solar control needs.

Transmission and reflection is shown as a 2 ° observable light source C.

More suitable for most applications normal radiant power (E_n) ranges from about 0.15 to about 0.35. More suitable for many applications, the sheet has a resistance range of about 15 to 35 ohms / area.

Preferred forms of the present invention thus obtained product and its layer system exhibit excellent chemical resistance and robustness (i.e. resistance to abrasion or scratching) both before and after heat treatment. The "chemical resistance" is determined by welding a sample of 2 x 5 (50x125 mm) on the product at 500 cm³ 5% HCl for one hour (about 220 ° F (104.4 ° C)). The product is considered to have passed this test if it has a micro crack size of less than about 0.003 (0.075 mm) in diameter after one hour of welding. "Strength" is measured by two tests, the first conventional Taber abrasion test using a 4 x 4 (100 x 100 mm) sample and a single 500 g charge connected to each of the two CS 10F abrasive wheels rotating at 300 rpm. Strength can also be determined using the Pacific Scientists Wear Tester (1 (25mm) nylon brush cycles through coating for 500 cycles of 150g, covering a 6 χ 17 (150x425mm sample)). If both tests show no significant, noticeable rupture when viewed with the naked eye in daylight, the test shall be considered passed and the product considered strong.

The transmission properties of the preferred forms of the present invention are, as above, measured by a conventional light source C, 2 ° observation test using a 4 mm glass base. To be "heat treated" in the sense of the present invention means that the transmission (visibility and sunlight) must not be replaced by more than about 20% and preferably less than 10%. Ideally, changes are less than about 2%. Further, to be "heat treatable" in the sense of the present invention means that the sheet resistance (R_s) shall not be increased by more than 10% during heat treatment. It is preferable that it does not increase at all, and preferably that it slightly decreases during such heat treatment.

In further explaining the above properties, the terms "radiant power" and "transmission coefficient" are well understood in the art and are used herein in their well-known sense. Thus, for example, the term "transmittance", as used herein, refers to the transmission of sunlight, consisting of visible light transmission, infrared transmission and ultraviolet transmission. The total transmission of sunlight is typically characterized as an estimated average of all other values. For the purpose of these transmissions, the transmission of visibility as described herein is characterized by the state of the art C2 ° light source monitoring technique at 380 720 nm, infra-red 800 to 2100 nm; for ultraviolet - 300 - 400 nm; and total sunlight is 300 - 2100 nm. In addition, the characteristic infrared area (ie 2 500 40,000 nm) which is discussed below.

Visibility transmission can be measured using known, conventional means. For example, using a spectrophotometer such as the Beckman 5240 (Beckman Sci. Inst. Corp.), a transmission spectral curve is obtained for each wavelength. The visibility transfer is then calculated using ASTM E308, "Object Color Evaluation Method Using the CIE System" (Annual Book of ASTM Standards, Vol. 14.02). If necessary, smaller wavelength points may be used as indicated. Another way to measure visibility transfer is to use a spectrometer, a commercially available one manufactured by the Pacific Science Cooperative. This unit directly measures and transmits visibility.

"Radiation power" (E) is a measure or characteristic of light and absorption and reflection at a given wavelength. This is usually expressed by the formula:

E = 1 - ReflectionSpičvcic

For artistic purposes, the irradiance values ​​become completely important in the so-called "mid-range" of the infrared spectrum, sometimes called the "further-range", that is, about 2,500-40,000 nm. The term "irradiance" as used herein is thus used to refer to the irradiance values ​​measured within these infrared bands as defined in the ASTM Standard 1991 for Measuring Infrared Energy to determine the irradiance, as provided by the General Council of Glass Manufacturers and entitled Continue Method for Measuring and Calculating Emittance of Architectural Fiat Glass Products Using Radiometric Measurements. This standard and its provisions are incorporated herein by reference. For the purpose of this standard, the irradiance is divided into two parts, the hemispheric irradiance (Eh) and the normal irradiance (E_n).

Actual collection of data for the measurement of such radiation values ​​is common and can be performed using, for example, a Beckman Model 4260 spectrometer with a VW instrument (Beckman Scientific Inst. Corp.). This spectrometer measures reflectance relative to wavelength and then calculates the irradiance using the aforementioned ASTM Standard 1991, incorporated herein by reference.

Another term used here is "sheet resistance". Sheet resistance (R_s) is a term well known in the art and used herein in its well-known meaning. In simple terms, this term refers to the resistivity of a layer system on a glass substrate to ohms to any area of ​​electrical current passing through a layer system. Sheet resistance is an indication of how the layer reflects infrared energy, and is thus often used in conjunction with radiation as a measure of this characteristic, so important to many artistic and automotive glasses. The "sheet resistance" is properly measured using a 4-point test ohmmeter, such as the non-essential 4-point resistance test by magnetron Instruments Corp.. nozzle, model M-800, made by Signatone Corp. of Santa Clara, California.

This invention will now be described with reference to certain embodiments which are discussed and illustrated below in the following drawings, in which:

DRAWINGS IN THE DRAWINGS:

S13N4 = a layer consisting of at least about 90% silicon nitride;

Ni = metal layer;

M = nickel-containing metal layer substantially free of nitride of this metal;

M / O = a layer having a very low degree of oxidation of the nickel-containing metal layer, the layer remaining essentially free of metal nitrides;

MO_X = the layer is a stoichiometrically oxidized metal; glass = glass base (also “G” Fig.7);

Wi = first detergent;

W₂ = second detergent;

T = tunnel;

C = conveyor;

F = separator chamber wall;

FIG. 1-6 are partial cross-sectional views showing:

FIG. 1A illustrates a two-layer system according to the present invention;

FIG. 1B illustrates FIG. 1A layer system with silicon nitride undercoating; FIG. 2A illustrates another two-layer system according to the present invention;

FIG. 2B illustrates FIG. 2A layer system with silicon nitride undercoating; FIG. 3A illustrates a four-layer system according to the present invention;

FIG. 3B illustrates FIG. 3A layer system with silicon nitride undercoating;

FIG. 4A illustrates a five-layer system according to the present invention;

FIG. 4B illustrates FIG. 4A a five-layer system in which the metal "M" is partially oxidized;

FIG. 5A illustrates another two-layer system according to the present invention;

FIG. 5B illustrates FIG. 5A two layer system with silicon nitride undercoating;

FIG. 6 illustrates a nine-layer system according to the present invention;

FIG. 7 is a schematic illustration of a conventional air-cooled five-chamber spray coating useful in the manufacture of coated glass articles in accordance with the present invention.

DETAILED DESCRIPTION OF SOME EMBODIMENTS

The layer systems contemplated by the present invention and illustrated (e.g., Figs. 1A - 6) are heat treated to the meaning of the term as described above. In addition, as confirmed above in their more appropriate forms, heat treatment can actually improve the product by increasing its IR reflectance (e.g._s reduction).

It was found that in order to achieve this heat treatment capability, each layer should have a finite thickness, which is generally substantially continuous.

The thickness of a given layer or the entire system can, since each layer is substantially continuous, be varied over a wide range depending on the material used for the layer, the heat treatment used, the number of layers in the system and the desired properties of the final product. However, generally speaking, the following thickness ranges have been found to yield the best results for the most discussed applications:

Thickness (A)

<td>S13N4 (top cover)</td><td> 10 - 750</td>

<td>M (nickel or nickel alloy)</td><td> 50 - 300</td>

<td>MO_X</td><td> 50 -100</td>

<td>M / O</td><td> 50 - 500</td>

<td>Ni / Si₃N₄</td><td> 50 - 300</td>

<td>S13N4 (intermediate coating)</td><td> 500 - 1200</td>

<td>S13N4 (bottom cover)</td><td> 10 - 750</td>

An important aspect of the present invention is the use of silicon nitride (S13N4) as a system layer or layers. In this regard, materials containing various forms of silicon nitride have previously been known in use as coating systems for coatings which can provide resistance to abrasion and corrosion. See, for example, U.S. Pat. 4,769,291; 5,062,937; 4,954,232; 4,948,482 and 4,680,742. The present invention takes advantage of these useful properties of a layer or layers of S13N4. However, it has been further uniquely and wholly unexpectedly found that when such a layer or layers of S13N4 are used in combination with another selected metal or metals, these layer systems achieve higher desirable properties than heat treatment. What's more, it is also unexpectedly found that whether due to synergism or other unknown mechanism, S13N4 is used with such a selected metal layer or layers to complement these layer systems, significant improvement in chemical resistance is known from prior art, known and highly appreciated. high-Ni layer systems from U.S. Pat. 5,229,194.

In the practice of the present invention, the metal used (as M, M / O and / or MO_X), in combination with S13N4, could be selected from a relatively limited group of alternatives to achieve the desired results of heat treatment, strength and chemical resistance, while achieving the desired color and desired control properties of sunlight. Although such a group is no longer limited to high levels of nickel alloy, as disclosed, for example, in U.S. Pat. 5 188,887 and 5,229,194, however, the metal must be either nickel or a nickel-containing alloy containing at least about 10% nickel by weight, since pure nickel is difficult to dust. Nickel alloy is suitable, and in this regard such alloys often contain sufficient chromium to render the system non-magnetic and thus more suitable for dusting.

In this respect, the unexpected feature of the present invention is that the previously considered important disadvantage of using a high nickel (or pure nickel) alloy to achieve heat treatment capability is no longer present when used in combination with the S13N4 layer or layers. Although at least one nickel-containing layer is still important to use, it does not need to be an alloy with a high nickel content. Nevertheless, it is a requirement of the present invention that while any small or insignificant amount of oxidation may be tolerated in the nickel-containing layer or layers, the nickel-containing layer or layers must be substantially nitride-free in order to be sufficiently chemically resistant. In this regard, although nitrides do not, in most cases, significantly impede the attainment of heat treatment in most cases, the formation of such nitride has been found to reduce the chemical resistance as measured by the 5% HCl boiling test mentioned above.

As claimed above, the nickel-containing layer or layers may be substantially pure nickel, but much better is a simple Ni / Cr alloy. One identified useful example of this group of alloys is many stainless steels containing as little nickel as possible, eg about 10% nickel (eg SS316 containing 10% Ni and 90% other metals, mainly Fe and Cr). Of course, high nickel / chromium alloys remain useful in the present invention. These include Ni / Cr 80/20 by weight and Haynes 214 alloy with a nominal weight composition consisting essentially of:

The element

Ni

Fe

Cr

C

Al

Y

Approximate weight%

75,45

4,00

16,00

0,04

4,50

0,01

Other examples of Ni / Cr alloys used in the practice of the present invention include Inconel and nichrome. Generally speaking, the metal layer or layers used in combination with the S13N4 layer or layers as discussed in the present invention will have at least about 10 weight percent nickel and at least one of these layers must be substantially unoxidized (or contain only a negligible amount of oxidation) and it would be better to be nitride free to increase chemical resistance.

Referring now to the drawings, Figures 1A and 1B illustrate one particular type of heat treatable layer system discussed herein. In these two figures, the nickel containing the metal "M", which is virtually unaffected by oxidation or virtually free of nitride, is formed by a sputter coating (e.g., from 50 to 300

A). In Fig. 1A, this metallized layer is typically coated with a S13N4 sputter coating (e.g., 10 to 750 A thick). In Figure 1B, the S13N4 undercoat was initially dust-coated on a glass substrate (e.g., 10 to 750 A thick).

The layer system in Figure 2A is similar to that in Figure 1A and the layer system in Figure 2B is similar to that in Figure 1B except that the "M / O" designation indicates that an acceptable heat treatment layer system can be achieved despite the low degree of oxidation in the metal layer. . Although accurate quantification is not possible, in some cases about 15% oxygen sputtering of gas may be tolerated while the desired result of the present invention is still achieved. The layer thickness here is the same as that of Figures 1A and 1B, respectively.

Figures 3A and 3B show a family of layer systems according to the present invention. Here, and only with the upper S13N4 coating (Figure 3A), and additionally with the lower one also from the S13N4 coating (Figure 3B), the stoichiometric metal oxide layers MO_X surrounded by a substantially metallic layer of M / O. The layers are spray-coated to a thickness consistent with the above landmarks.

Figures 4A and 4B illustrate another family of layer systems contemplated by the present invention. Here, two layers of metal “M” or slightly oxidized metal “M / O” are separated and surrounded by layers of S13N4. The layers are also spray-coated to a thickness corresponding to the above landmarks.

Figure 6 is a mixed hybrid of the families of Figures 3A, 3B and 4A, 4B, with two M / O metal layers each surrounded by layers of stoichiometric oxide MO_X, which are alternately surrounded by three layers of S13N4. The layers are also spray-coated with thicknesses that match the above landmarks.

Figures 5A and 5B further illustrate another family of layer systems according to the present invention. Here, the metal layer is coated (single, Figure 5A) or has a lower coating of S13N4 (Figure 5B) as in other families. However, in this embodiment, substantially pure nickel is mixed with S13N4 as a separate metal layer. This middle Ni / Si₃In some circumstances, the N4 layer uniquely serves to achieve desirable sunlight control characteristics while still being very strong, heat-treated and resistant to abrasion. In preferred embodiments, the percentage by weight of Ni is about 80-90%, the remainder being S13N4.

The layer systems of the present invention may be formed by any conventional dusting technique using, for example, a conventional dusting agent such as

Airco-Temescal multi-zone dust collector of known design. However, one suitable method of forming coatings according to the present invention is to utilize unique techniques and shutters as disclosed in our prepared application no. No. 08 / 102,585, entitled "Dust Cover and Application", filed on or after this date. The full description of this prepared application is hereby incorporated by reference. Generally speaking, and as disclosed in this ready-made application, the unique sputtering coating used to fabricate S13N4 layers is used to overcome the problem of anode non-conductive coating (e.g., S13N4). This is achieved by evenly mixing the shutter Si with another element, in small amounts, which will convert the base layer formed (and thus the layer formed on the anode) to conductive, thereby reducing the downtime for anode refurbishing common in the prior art.

In the practice of the subject, where heat treatment capability, sunlight control, strength, and abrasion resistance are desirable properties of the layered system, care must be taken to select a conductive element to be mixed with the Si shutter so as not to defeat their purpose in the core formed S13N4. properties. Thus, in the practice of the present invention, it is appropriate for many of the systems discussed that the use of a conductive member will be limited to small amounts, typically less than about 10% and preferably less than about 5%. In addition, such elements generally need to be highly resistant to oxidation. Metals such as gold, platinum and nickel can be used. However, metals such as titanium, zirconium, chromium, hafnium and their alloys are preferred for most of the applications discussed herein. These elements are preferred because they usually form nitrides which are electrically conductive, both optically and mechanically, and do not interfere (and are compatible) with the parent material S13N4. They form nitrides to some degree, but the amount of such nitrides can be reduced. Because some of the silicide is formed from these metals, it is believed that it is an intermediate that is rapidly degraded to their respective nitrides and is in any case compatible and does not interfere optically or mechanically with S13N4, there are cases where this may remain.

Particularly suitable for use here is a Si screen with about 5% titanium impurity. The final layer or layers formed (e.g. S13N4, shown in Figures 1-6) were found to contain about 95% S13N4, the remainder being titanium nitride. It has been found that low levels of titanium nitride do not materially interfere with the optical, mechanical, chemical, color or heat treatment properties as defined in the practice of the present invention. In addition, similarly, zirconium, chromium or hafnium nitride may also be tolerated to achieve production efficiencies in approximately the same amounts.

The present invention will now be described with reference to some examples:

EXAMPLES

These coat systems are coated with a clean glass substrate using Si or flaps (with 5% aluminum impurity) and standard spray application as described. The strength and chemical resistance tests were used as described above. The heat treatment utilized a sample exemplary tempering process at a temperature of 1265 ° F (685 ° C) for 5 minutes. Examples of heat treatment are either 3 x 3 (75 x 75 mm) or 4 x 4 (100 x 100 mm).

EXAMPLE 1 (Technique Example)

A prior art exemplary layer system such as that described in U.S. Pat. 5,229,194 spheres, was formed by sputter deposition. The resulting layer system from the outside of the glass was -SnO2 / MO_x/ M / O / MO_x/ SnO₂, where M = Haynes 214 alloy. The product showed excellent heat treatment and Rs_s equal to 79 ohms / area. But he did not pass the chemical resistance test (ie boiling 5% HCl at 220 ° F (48.9 ° C) for one hour) before heat treatment for 5 min and 12 min after heat treatment. The Taber abrasion test passed with a 7.6% change in transmission before heat treatment at 300 revolutions, but only 1.2% change in transmission after heat treatment at 300 revolutions. This proved the perfectly acceptable mechanical strength properties. Despite its partially low chemical resistance, as determined by the weld test, this coating system proves to be a state of the art heat-treatable coating suitable for many applications that require or are not interested in significantly reduced visibility transfer and low chemical resistance. An example of such use is "private" windows in cars. In this respect, the typical visibility transfer at this state of the art is about 23%.

EXAMPLES 2 - 24

A number of layered films have now been made for comparison purposes using standard spraying techniques and thicknesses according to the above instructions. The results are as follows:

Fig. Layer system no.

SnO2 / 214OX / 214-0 / 214OX / SnO2 / Si₃N4

SnO₂/ 214OX / 214-0 / 214OX / Si₃N₄

SnO2 / 214OX / 214-0 / 214OX / Si₃N4 / SnO₂

Si₃N₄/ 214OX / 214-0 / 214OX / Si₃N₄

Si₃N₄/ 214 / Si₃N₄

Si₃N₄/ 214-N / Si₃N₄

Si₃N₄/ 214-N / Si₃N₄

Si₃N₄/ 214-N / Si₃N₄

SbN ^ M / SisbU

Π δ ^ Ν ^ ΚΟΧ ^ Ν-Ο ^ ΜΟΧ / Ξΐ ^ **

Si₃N₄/ 214 / Si₃N₄/ 214 / Si₃N₄

Si₃N₄/ 214 / Si₃N₄/ 214 / Si₃N₄

Si₃N₄/ 214OX / 214-0 / 214OX / Si₃N₄/ 214OX / 214-0 / 214OX / Si₃N₄

Si₃N₄/ 214OX / 214-0 / 214OX / Si₃N₄/ 214OX / 214-0 / 214OX / Si₃N₄

Si₃N₄/ 214-0 / Si₃N₄ *** Si₃N₄/ Ni / Si₃N₄

Si ^ / Ni / SbN ^ i / SbKt

Si₃N₄/ Ni / Si₃N₄/ Ni / Si₃N₄

SisNVSSG ^ / SbNi

Si₃N₄/ SS-316 / SnO₂

Si₃N₄/ (80/20) / Si₃N₄ **** Si₃N₄/ (80/20) -0 / Si₃N₄

Si₃N₄/ (80/20) -0 / Si₃N₄* P = passed test * PP = test passed before and after heat treatment 5 * F = failed test

Heat treatment

F

P

P

P

P

P

P

P

P

P

P

P

P

P

P

F

P

P

P

Acid boiling

F

P

PP

P

P

F

F

F

P

PP

PP

P

P

P

P

P

P ** this layer system was tested and passed Taber test both before and after heat treatment *** this layer system exhibited low radiation properties (E_n = 17) **** 80/20 is an alloy of 80 wt% Ni and 20 wt% Cr

Samples 22 through 24 from the table above (shown here as 2A, B, C) were prepared in this manner on an ILS - 1600 Airco coating made by spraying with 5/32 clean glass. The following conditions were used:

<td rowspan="2">Gam. lines no.</td><td rowspan="2">Layer film</td><td rowspan="2">Basic pressure, IG</td><td colspan="2">Gas 1: Can</td><td>Gas 2: b</td><td>2 (O₂)</td>

<td>Traffic, (cm³)</td><td>Monom. impr.</td><td>Traffic (cm³)</td><td>Monom. impr.</td>

<td> 1</td><td>S13N4</td><td>4, lx10 '⁶</td><td> 25</td><td>5.5x1ο ·⁴</td><td> 25</td><td>8.8x10 '⁴</td>

<td>2A</td><td> 80/20</td><td>2.0x10 '⁶</td><td> 40</td><td>6.9x1ο ·⁴</td><td></td><td></td>

<td>2B</td><td> 80/20-0</td><td>1.5x10 '⁶</td><td> 40</td><td>7.1x1ο ·⁴</td><td>3 (O₂)</td><td>7.5x1ο ·⁴</td>

<td>2C</td><td> 80/20-0</td><td>2.0x10 '⁶</td><td> 40</td><td>7.1x1ο ·⁴</td><td>6 (O₂)</td><td>7.8x1ο ·⁴</td>

<td> 3</td><td>S13N4</td><td>2.5x10 '⁶</td><td> 25</td><td>5.8-10 '⁴</td><td> 25</td><td>9, Οχ ΙΟ '⁴</td>

<td rowspan="2">Gam. lines no.</td><td rowspan="2">Layered nio film</td><td rowspan="2">Vedanč. gears speed, %</td><td colspan="4">Cathode parameters</td><td rowspan="2">Kato- do tension</td><td rowspan="2">Wholesale nimo pressure, ROI 1</td>

<td>Galin- rubber level, %</td><td>Voltage load block</td><td>Galin- rubber, kW</td><td>N.current, Amp.</td>

<td> 1</td><td>S13N4</td><td>35x16</td><td> 7,0</td><td> 420</td><td> 2,9</td><td> 7,0</td><td> 424</td><td>5.5x 10 '⁴</td>

<td>2A</td><td> 80/20</td><td>35x2</td><td> 8,5</td><td> 473</td><td> 4,0</td><td> 8,7</td><td> 477</td><td>5.0x ΙΟ⁴</td>

<td>2B</td><td> 80/20-0</td><td>35x2</td><td> 8,5</td><td> 486</td><td> 4,2</td><td> 8,7</td><td> 490</td><td>5.3x 10 '⁴</td>

<td>2C</td><td> 80/20-0</td><td>35x2</td><td> 8,5</td><td> 501</td><td> 4,2</td><td> 8,7</td><td> 503</td><td>5.0x 10 '⁴</td>

<td> 3</td><td>S13N4</td><td>35x8</td><td> 7,0</td><td> 424</td><td> 2,9</td><td> 7,0</td><td> 426</td><td>5.7x 10 '⁴</td>

24-0 of Example E_n (at 10 microns) before heat treatment were 0.34 and Rs_s was 58.1. After heat treatment R_s was 28.0 and E_n was 0.23. The values ​​of the light source C 2 ° before and after heat treatment were as follows:

Before heat treatment:

TY 19.42 x 0.2873 y 0.2967 a -1.24 b -6.77

RGY 16.11 x 0.3259 y 0.3255 a -1.87 b -3.53

RFY 34.48 x 0.3459 y 0.3556 a -0.96 b +15.11

After heat treatment:

TY 26.28 x 0.2869 y 0.2986 a -2.17 b -7.04

RGY 12.61 x 0.3209 y 0.3173 a +2.58 b +1.19

RFY 28.36 x 0.3558 y 0.3641 a -0.41 b +17.54

All these products were found to be heat-treated, strong and chemically resistant.

Example 17 from the table above was formed in a similar manner using 5/32 clean glass with minor changes in the operating conditions as below to form three examples a, b, c. The Ni layer was sealed using 10% O2 and heated for 10 minutes, then the sputtering was stopped. All samples were heat treated, chemically resistant and strong. The terms of the operation were as follows:

<td rowspan="2">Gam. lines no.</td><td rowspan="2">Layer film</td><td rowspan="2">Basic pressure, IG</td><td colspan="2">Gas 1: Can</td><td colspan="2">Gas 2: N2</td>

<td>Traffic (cm³)</td><td>Monom. impr.</td><td>Traffic (cm³)</td><td>Monom. impr.</td>

<td> 1</td><td>S13N4</td><td>7.8x10 '⁶</td><td> 25</td><td>4.8x1ο ·⁴</td><td> 25</td><td>7.1x1ο ·⁴</td>

<td>2a</td><td>Ni</td><td>6.0x10 '⁶</td><td> 80</td><td>1.6-10 '³</td><td></td><td></td>

<td>2b</td><td>Ni</td><td>8.4x10 '⁶</td><td> 80</td><td>l, 6x10 '³</td><td></td><td></td>

<td>2c</td><td>Ni</td><td>2.2x10 '⁶</td><td> 80</td><td>1.6-10 '³</td><td></td><td></td>

<td> 3</td><td>S13N4</td><td>8.4x10 '⁶</td><td> 25</td><td>5.4x10⁴</td><td> 25</td><td>8.2 - 10 '⁴</td>

<td rowspan="2">Gam. lines no.</td><td rowspan="2">Layer nio film</td><td rowspan="2">I'll bet. gear speed, %</td><td colspan="4">Cathode parameters</td><td rowspan="2">Cathodes. tension</td><td rowspan="2">Wholesale nimo pressure IG1</td>

<td>Galin- rubber level, %</td><td>Voltage loads block</td><td>Galin- rubber, kW</td><td>N. sr. Amp.</td>

<td> 1</td><td>S13N4</td><td>35x16</td><td> 7,0</td><td> 422</td><td> 2,9</td><td> 7,0</td><td> 425</td><td>4.5x ΙΟ⁴</td>

<td>2a</td><td>Ni</td><td>35x1</td><td> 8,5</td><td> 562</td><td> 5,3</td><td> 9,5</td><td> 564</td><td>8.8x 10 ·⁴</td>

<td>2b</td><td>Ni</td><td>35x2</td><td> 6,0</td><td> 543</td><td> 3,8</td><td> 7,0</td><td> 545</td><td>8.9x SO⁴</td>

<td>2c</td><td>Ni</td><td>35x2</td><td> 7,0</td><td> 547</td><td> 4,1</td><td> 7,5</td><td> 550</td><td>7.5x 10 '⁴</td>

<td> 3</td><td>S13N4</td><td>35x8</td><td> 7,0</td><td> 429</td><td> 2,9</td><td> 7,0</td><td> 428</td><td>4.3x 10 '⁴</td>

For Sample 17 sample C, light source C 2 ° observation values ​​were measured before and after heat treatment and recorded as follows:

Before heat treatment:

TY 23.48 x 0.2847 y 0.2948 a -1.56 b -7.97

RGY 12.74 x 0.33369 y 0.333444 a -2.27 b +6.02

RFY 31.94 x 0.3418 y 0.3499 a -0.47 b + 12.77

After heat treatment:

TY 22.44 x 0.2835 y 0.2932 a -1.41 b -8.37

RGY 14.45 x 0.3370 y 0.33367 a + 1.78 b + 6.72

RFY 32.41 x 0.33390 y 0.3461 a -0.17 b + 11.48

Sheet resistance R_s before heat treatment was 23.5 and after heat treatment 5 was 17.0. Normal radiated power (E_n) was 0.24 before heat treatment and 0.17 after heat treatment. Example 17 was suitable for heat treatment, strong and chemically resistant.

Now, with reference to Example 11 in the upper table, a specimen of 8x8 (200x200mm) 5/32 thick clean glass was formed by sputtering under the following conditions:

<td rowspan="2">Gas 3: O2 1</td><td>Monom. impr.</td><td></td><td> || _t.0I * Z'9</td><td>T 0 r-4 X co</td><td>II „.οιχε'9</td><td></td>

<td>Cost, (cm³)_</td><td></td><td> 40</td><td>m</td><td> 40</td><td></td>

<td rowspan="2">Gas 2: N2</td><td>Monom. impr.</td><td>0 r-1 X O 00</td><td></td><td></td><td></td><td>Tf 0 1— ( X O 00</td>

<td>Cost, (cm³)_</td><td> 25</td><td></td><td></td><td></td><td>m CN</td>

<td rowspan="2">Gas 1: Can</td><td>Monom. impr.</td><td>i b 1-1 X C;</td><td>• 't b X r-4</td><td>T 0 T-1 X Etc. O</td><td>sr b T-4 X 'Φ</td><td>b r-4 X</td>

<td>Cost, (cm³)_</td><td> 25</td><td> 0</td><td> 40</td><td> 10</td><td> 25</td>

<td colspan="2">Basic pressure, ROI 1</td><td>• C b «—4 X 03 cn</td><td>• C b r-4 X cn r-4</td><td>0 • —1 X co CN</td><td>• C b r-4 X 'φ</td><td>G b H X CM cn</td>

<td colspan="2">Layer film</td><td>z cn c / 5</td><td>214ΟΧ</td><td> 214-0</td><td>At 214ΟΧ</td><td>z 00</td>

<td colspan="2">Production lines no.</td><td>r-4</td><td>CM</td><td>cn</td><td>M-</td><td>tn</td>

<td colspan="2">Dusting pressure, IG1</td><td>T o rH X cn K?</td><td>T o T "4 X co cri</td><td>T O τ-1 X σγ cri</td><td>O Γ “4 X cn</td><td></td>

<td colspan="2">Cathode tension</td><td> 430</td><td> 335</td><td> 429</td><td> 335</td><td></td>

<td rowspan="4">Cathode parameters</td><td>N. current, Amp.</td><td>o r- ''</td><td>o 1%</td><td>T-4 cri</td><td>o o '</td><td>o r- "</td>

<td>Power, kW</td><td> 3,0</td><td>of</td><td>σγ cn</td><td> 2,3</td><td> 3,0</td>

<td>Voltage load block</td><td> 429</td><td> 333</td><td> 427</td><td> 332</td><td> 430</td>

<td>Galing. level,%</td><td>o S '</td><td>o r- ''</td><td> 8,5 |</td><td>o</td><td> 7,0</td>

<td colspan="2">Vedanč. gears speed, %</td><td>35x16</td><td>35x2</td><td>35χ2</td><td>35x2</td><td>35x8</td>

<td colspan="2">Layer film</td><td>z m c73</td><td>214ΟΧ</td><td> 214-0</td><td>214ΟΧ</td><td>z c / 5</td>

<td colspan="2">Production lines no.</td><td>r-4</td><td>CN</td><td>(Ω</td><td></td><td>tn</td>

The sheet resistance before heat treatment was 82.6 and after heat treatment was 46.1. Normal radiated power (E_n) before heat treatment was 0.48 and after heat treatment was 0.33. Before and after 2 ° observation with light source C, the data were as follows:

Before heat treatment:

TY 26.04 x 0.2869 y 0.2958 a -1.17 b -7.76

RGY 12.29 x 0.33319 y 0.3327 a + 1.40 b + 5.15

RFY 29.27 x 0.3436 y 0.3527 a -0.74 b + 13.30

After heat treatment:

TY 28.34 x 0.2895 y 0.2988 a -1.34 b -6.88

RGY 11.54 x 0.3321 y 0.33341 a +1.09 b +5.32

RFY 26.69 x 0.33395 y 0.3472 a -0.31 b +11.09

The Taber test before heat treatment showed a change of 7.6%. The change after heat treatment was only 1.2%. The manufactured product was heat treated, strong and chemically resistant.

Examples 12 and 13 from the above table were formed in a similar manner and exhibited superior heat treatment characteristics and extreme chemical resistance. Sample 12 was dark and Sample 13 was not dark. The processing conditions were as follows:

12 and 13 for both examples

<td rowspan="2">Gam. lines no.</td><td rowspan="2">Layer film</td><td rowspan="2">Basic pressure, IG</td><td colspan="2">Gas 1: Can</td><td colspan="2">Gas 2: N2</td>

<td>Costs, (cm³)</td><td>Monom. impr.</td><td>Costs, (cm³)</td><td>Monom. impr.</td>

<td> 1</td><td>S13N4</td><td>3.4x10^-6</td><td> 25</td><td>4.7x1ο ·⁴</td><td> 25</td><td>8.0x10^-4</td>

<td> 2</td><td> 214</td><td>l, 6x10^-6</td><td> 40</td><td>6.0χ10^-4</td><td></td><td></td>

<td> 3</td><td>S13N4</td><td>l, 3x10^-6</td><td> 25</td><td>4.6x10^-4</td><td> 25</td><td>8.0x10⁴</td>

<td> 4</td><td> 214</td><td>Ι, ΙχΙΟ^-6</td><td> 40</td><td>6.3x10 '⁴</td><td></td><td></td>

<td> 5</td><td>S13N4</td><td>9.8x10^-7</td><td> 25</td><td>5.0x10 '⁴</td><td> 25</td><td>8.2x10^-4</td>

Examples 12 and 13 are shown as A and B respectively

<td rowspan="2">Gam. line s no.</td><td rowspan="2">Layered nio film</td><td rowspan="2">I'll bet. gear speed, %</td><td colspan="4">Cathode parameters</td><td rowspan="2">Kato- do tension</td><td rowspan="2">Dulkin mo pressure, IG1</td>

<td>Galin- rubber level, %</td><td>Voltage load block</td><td>Galin- rubber, kW</td><td>N. sr., Amp.</td>

<td> 1</td><td>S13N4</td><td>35x16</td><td> 7,0</td><td> 430</td><td> 3,0</td><td> 7,1</td><td> 432</td><td>4.8x1ο ·⁴</td>

<td>2A</td><td> 214</td><td>35x2</td><td> 5,0</td><td> 396</td><td> 2,6</td><td> 6,4</td><td> 401</td><td>3.9x10^-4 -4,0</td>

<td>2B</td><td> 214</td><td>35x2</td><td> 4,3</td><td> 376</td><td> 1,8</td><td> 4,6</td><td> 379</td><td>4.1x1ο^-4</td>

<td> 3</td><td>S13N4</td><td>35x8</td><td> 7,0</td><td> 431</td><td> 3,0</td><td> 7,0</td><td> 434</td><td>4.6x10⁴</td>

<td>4A</td><td> 214</td><td>35x2</td><td> 5,0</td><td> 398</td><td> 2,6</td><td> 6,4</td><td> 397</td><td>3.9x1ο^-4 -4,0</td>

<td>4B</td><td> 214</td><td>35x2</td><td> 4,3</td><td> 376</td><td> 1,8</td><td> 4,6</td><td> 379</td><td>4.1x1ο^-4</td>

<td> 5</td><td>S13N4</td><td>35x8</td><td> 7,0</td><td> 431</td><td> 3,0</td><td> 7,0</td><td> 433</td><td>4.8-10⁴</td>

Example 25

Coated glass product is useful for artistic or automotive applications on dust-coated coats using typical 5/32 ground glass and Haynes 214 as metal “M”. Fig. 1B shows the resulting layer system, wherein the S13N4 undercoat is about 550 A thick, the Haynes 214 coat is about 100 A thick, and the upper S13N4 coating is about 275 A thick. A conventional Airco (Solar Products) -Temescal multi-zone articulator was used as shown in Fig.7. The various parts of this unit are described in more detail in Example 26 below. The conditions of the operation were as follows:

<td>Coating zone</td><td>Cathode #</td><td>Material</td><td>Volts</td><td>Amps</td><td>P (kW)</td>

<td rowspan="6"> 1</td><td> 1</td><td>Si</td><td> 417</td><td> 60,7</td><td> 25,3</td>

<td> 2</td><td>Si</td><td> 428</td><td> 97,7</td><td> 41,8 .</td>

<td> 3</td><td>Si</td><td> 412</td><td> 97,0</td><td> 40,0</td>

<td> 4</td><td>Si</td><td> 419</td><td> 69,8</td><td> 29,2</td>

<td> 5</td><td>Si</td><td> 409</td><td> 90,0</td><td> 36,8</td>

<td> 6</td><td>Si</td><td> 448</td><td> 92,9</td><td> 41,6</td>

<td rowspan="6"> 2</td><td> 7</td><td>Si</td><td> 415</td><td> 70,7</td><td> 29,3</td>

<td> 8</td><td>Si</td><td> 417</td><td> 42,5</td><td> 17,7</td>

<td> 9</td><td>Si</td><td> 431 '</td><td> 86,3</td><td> 37,2</td>

<td> 10</td><td>Si</td><td> 416</td><td> 81,6</td><td> 33,9</td>

<td> 11</td><td>Si</td><td> 420</td><td> 86,3</td><td> 36,2</td>

<td> 12</td><td>Si</td><td> 430</td><td> 90,4</td><td> 38,8</td>

<td rowspan="3"> 3</td><td> 31</td><td> 214</td><td> 469</td><td> 36,9</td><td> 17,3</td>

<td> 32</td><td> 214</td><td> 462</td><td> 36,7</td><td> 17,0</td>

<td> 33</td><td> 214</td><td> 463</td><td> 36,1</td><td> 16,7</td>

<td> 4</td><td> 19</td><td> 214</td><td> 426</td><td> 18,9</td><td> 8,1</td>

<td rowspan="6"> 5</td><td> 25</td><td>Si</td><td> 402</td><td> 30,9</td><td> 12,4</td>

<td> 26</td><td>Si</td><td> 433</td><td> 66,1</td><td> 28,6</td>

<td> 27</td><td>Si</td><td> 410</td><td> 75,1</td><td> 30,8</td>

<td> 28</td><td>Si</td><td> 418</td><td> 49,9</td><td> 20,9</td>

<td> 29</td><td>Si</td><td> 452</td><td> 70,8</td><td> 32,0</td>

<td> 30</td><td>Si</td><td> 424</td><td> 71,3</td><td> 30,2</td>

ZONE 1

Gas

Gas Ratio Gas Cost Throttling Cost Ratio

Pressure

Argon and Nitrogen 80% N₂; 20% Ar 1448 N₂, 365 Ar 10%

ABCDE

29 0 29 21 (%)

2.0x10 '³ Torres (~ 0.27 Pa)

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

<td>Gas Gas ratio</td><td>Argon and nitrogen 80% N₂; 20% Ar</td>

<td>Gas costs Throttling</td><td>1856 N₂, 433 Ar 9%</td>

<td>Cost ratio</td><td>ABCDE 24 26 0 26 24 (%)</td>

<td>Pressure</td><td>2, lx10 '³ Torres (~ 0.28 Pa)</td>

<td> 5</td><td>ZONE 3 and 4</td>

<td>Gas</td><td>Argon (100%)</td>

<td>Gas costs Throttling</td><td>1821 cm³) With 17%</td>

<td>Cost ratio</td><td>ABCDE 20 20 20 20 20 (%)</td>

<td>Pressure</td><td>2.0 - 2, lx10 '³ Torres (~ 0.27-0.28 Pa) ZONE 5</td>

<td>Gas Gas ratio</td><td>Argon and nitrogen 80% N₂; 20% Ar</td>

<td>Gas costs Throttling</td><td>1421 N₂, 312 Ar 14%</td>

<td>Cost ratio</td><td>ABCDE 19 31 0 31 19 (%)</td>

<td>Pressure</td><td>2.2x10 '³ Torres (~ 0.29 Pa)</td>

The final product has been tested and has the following results:

I. (a) Visibility transmission (light source C 2 ° observation):

23% before heat treatment 22% after heat treatment (b):

before heat treatment on glass side: «15-16% on film side:« 22-24% after heat treatment on glass side: «14-15% on film side:« 17-18% (c) radiant power (E)_n):

0.50 after heat treatment 0.55 (d) sheet resistance (ohms / area):

before heat treatment 60.0 after heat treatment 73.5

II. Strength (mechanical) (tested by Taber test only) 8-9% after heat treatment 5-6%

III. The chemical resistance (weld test) before heat treatment has passed after heat treatment has passed

Example 26

Uses the conventional Airco (Solar Products) Temescal 10 multi-zone artistic dusting system of known design. This coating device is schematically illustrated in FIG. 7. Coverage zones 1, 2, 4 and 5 are provided with three cathodes, each with two swing valves. Covering area # 3 employs three cathodes, each with one flat shutter. Thus, the number of shields is 1 to 27 (eg: coating area # 1, cathode section # 1, shield “1”). The glass substrate G, shown here as a flat sheet of glass (e.g., the flat portion may still be bent and / or hardened) is transported in rolls through a sputtering apparatus in which the zones are separated in a known manner by walls (F) having a bottom adjustable tunnel ( T). Input washer (Wj) and outlet washer (W₂) fitted in the usual way.

Using this device, a layer system is formed in Fig. 1, wherein the metal "M" is essentially a metal alloy of nickel and chromium (80/20% by weight Ni: Cr). All 12 latches in coating zones # 1 and # 2 are of the same metal (eg: silicon with 5% Al) to form a layer of silicon nitride. In this case 80% N in zone 1 and zone 2₂ and 20% argon atmosphere thanks to adjustable pressure to approx

2-3x10 '³ Torres. As glass G moves forward through zones # 1 and # 2 at the above pressure, silicon nitride is deposited on the glass as layer "A" approximately 500 A thick.

As the glass (G) moves forward to the coating zone # 3, the cathodes 7, 8 and 9 deposit a layer of pure metallic nickel-chromium alloy (80-20) in argon gas at a pressure of l-2x10 '.³ Torres. The thickness achieved is approximately 150A.

The glass (G) then moves through coating area # 4, where the pressure is adjusted to about 2-3x10 '³ Thanks to the 80% N2 and 20% Ar atmospheres of the Torres. Cathodes 10.11 and 12 (six metal silicon valves) are used to obtain the silicon nitride layer. The glass then moves through coating area # 5 where the pressure is also adjusted to approximately 23x10 '³ Thanks to the 80% N2 and 20% Ar atmospheres of the Torres. To further obtain the silicon nitride, all six latches are used in this coating area. All silicon flaps are 95% by weight Si and 5% Al. The total thickness of the top layer of S13N4 formed in zones 4 and 5 is approximately 300 A. This forms a heat treatable coating system.

The process conditions are as follows:

<td>Zone</td><td>Kato- das</td><td>Close landa</td><td>kW</td><td>Kato- do tension</td><td>Amp.</td><td>Me- joy</td><td>Pressure</td><td>Material, N₂% / With%</td>

<td rowspan="6"> 1</td><td> 1</td><td> 1</td><td> 32,1</td><td> 416</td><td> 70,9</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 1</td><td> 2</td><td> 19,8</td><td> 401</td><td> 42,9</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 2</td><td> 3</td><td> 27,6</td><td> 402</td><td> 60,0</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 2</td><td> 4</td><td> 26,9</td><td> 400</td><td> 60,8</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 3</td><td> (5)</td><td>X</td><td>X</td><td>X</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 3</td><td> (6)</td><td>X</td><td>X</td><td>X</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td rowspan="6"> 2</td><td> 4</td><td> 1</td><td> 26,5</td><td> 396</td><td> 60,8</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 4</td><td> 2</td><td> 34,8</td><td> 407</td><td> 74,8</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 5</td><td> 3</td><td> 36,0</td><td> 449</td><td> 76,8</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 5</td><td> 4</td><td> 39,6</td><td> 412</td><td> 88,5</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 6</td><td> 5</td><td> 44,6</td><td> 421</td><td> 97,8</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 6</td><td> 6</td><td> 46,7</td><td> 449</td><td> 93,7</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td rowspan="3"> 3</td><td> 7</td><td> 1</td><td> 11,1</td><td> 436</td><td> 25,5</td><td>80Ni 20Cr</td><td>1.5x10 '³Torres</td><td>100% argon</td>

<td> 8</td><td> 2</td><td> 11,1</td><td> 456</td><td> 25,4</td><td>80Ni 20Cr</td><td>1.5-10 '³Torres</td><td>100% argon</td>

<td> 9</td><td> 3</td><td> 10,9</td><td> 442</td><td> 24,8</td><td>80Ni 20Cr</td><td>1.5-10 '³^Torr9 _ί</td><td>100% argon</td>

<td rowspan="6"> 4</td><td> 10</td><td> 1</td><td> 18,4</td><td> 410</td><td> 41,0</td><td>Si</td><td>2.1χ10 '³Torres</td><td> 80/20</td>

<td> 10</td><td> 2</td><td> 18,2</td><td> 410</td><td> 40,0</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 11</td><td> 3</td><td> 17,2</td><td> 409</td><td> 39,5</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 11</td><td> 4</td><td> 17,8</td><td> 411</td><td> 39,6</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 12</td><td> 5</td><td> 18,1</td><td> 407</td><td> 39,5 _</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 12</td><td> 6</td><td> 18,4</td><td> 403</td><td> 40,4</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td rowspan="6"> 5</td><td> 13</td><td> 1</td><td> 20,7</td><td> 38,7</td><td> 46,6</td><td>Si</td><td>2.2x10 '³Torres</td><td> 80/20</td>

<td> 13</td><td> 2</td><td> 20,9</td><td> 406</td><td> 45,3</td><td>Si</td><td>2.2x10 '³Torres</td><td> 80/20</td>

<td> 14</td><td> 3</td><td> 19,5</td><td> 396</td><td> 44,6</td><td>Si</td><td>2.2x10 '³Torres</td><td> 80/20</td>

<td> 14</td><td> 4</td><td> 19,7</td><td> 394</td><td> 45,2</td><td>Si</td><td>2.2x10 '³Torres</td><td> 80/20</td>

<td> 15</td><td> 5</td><td> 19,8</td><td> 414</td><td> 45,3</td><td>Si</td><td>2.2x10 '³Torres</td><td> 80/20</td>

<td> 15</td><td> 6</td><td> 22,5</td><td> 447</td><td> 45,4</td><td>Si</td><td>2.2x10 '³Torres</td><td> 80/20</td>

Production line speed: 200 / min 5 Glass thickness and type: 3.9 mm, green color

The final optical characteristics are as follows:

When covered, light cools. "C", 2 ° observ.

TY 22.65 RGY 16.02 a * -4.53 a * -2.51

RFY 22.43 a * +1.21 b * -8.82 b * -0.45 b * +27.12

Sheet resistance = 65.3 ohms / area Normal radiant power = 0.50

After heat treatment ^, the light source cooled. "C", 2 ° observ.

<td>TY 23.04</td><td>RGY 15.37</td><td colspan="2">RFY 23.46</td>

<td>a * -4.07</td><td>a * -3.52</td><td>a *</td><td> +0,04</td>

<td>b * -7.13</td><td>b * +1.15</td><td>b *</td><td> +22,15</td>

<td>Sheet resistance</td><td>= 47.3 ohms / area</td><td></td><td></td>

<td colspan="2">Normal radiated power = 0.45</td><td></td><td></td>

<td>AT +0.39</td><td>ARG -0.65</td><td>ARF</td><td> +1,03</td>

<td>AE 1.87</td><td>AE 1.09</td><td>AE</td><td> 5,90</td>

ALpac resistance = -18.0 ohms / area

ANnormal radiant power = -0.05

The test

Chemical resistance:

Coated - Physical properties unchanged after boiling at 230 ° F (110 ° C) for one hour in 5% HCl

After heating - Physical properties unchanged after boiling at 230 ° F (110 ° C) for one hour in 5% HCl

Taber abrasion test: AT (transmission) 300 cycles and 500 gram load Coated - AT = 8.1%

After heating - AT = 6.3% * (heat treatment at 665 ° C was periodically repeated with a 16 minute period)

Example 27

This example is formed by a device as described in Example 26 above. The same cathodes, shutter gas ratio, pressure, and process conditions are maintained in coating zones # 1 and # 2 as in Example 26 to provide an overcoat of S13N4 (and some aluminum nitride from impurities) of the same thickness as in Example 26. But process the conditions changes were made in coverage areas # 3, # 4 and # 5.

The gas mixture in coating zone # 3 was changed from 100% argon to a mixture of 95% argon and 5% oxygen at the same pressure and the shutter power was increased in coating zone # 3 to obtain a metal layer on glass (G) of a similar thickness. The formed layer system as in Figs. 2B, where M is the same Ni / Cr alloy as used in Example 26, but only partially oxidized here. The glass passes over coating areas # 4 and # 5, where, as before, a layer of silicon nitride, now partially oxidized (M / O), is formed on the metal top. This S13N4 topcoat is retained somewhat thinner than that of Example 26 due to its much greater resemblance to the preferred optical characteristics of Example 26. The advantage of the coating system of this example over that of Example 26 is that the sheet strength (and normal radiant power) of the articles after heat treatment is certainly achieved and is present in typical coatings with a "low E" range. In this way, this coating system has the ability to reflect more infrared light than the coating system in Example 26. The chemical resistance is only slightly reduced compared to Example 26, but the mechanical strength is improved compared to the already good strength of Example 26.

The process conditions are as follows:

<td>Zone</td><td>Kato- das</td><td>Close landa</td><td>kW</td><td>Kato- do tension</td><td>Amp.</td><td>Me- joy</td><td>Pressure</td><td>Material, N₂% / With%</td>

<td rowspan="6"> 1</td><td> 1</td><td> 1</td><td> 32,4</td><td> 424</td><td> 70,9</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 1</td><td> 2</td><td> 20,1</td><td> 413</td><td> 43,0</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 2</td><td> 3</td><td> 27,7</td><td> 409</td><td> 60,4</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 2</td><td> 4</td><td> 27,2</td><td> 405</td><td> 59,7</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 3</td><td> 5</td><td>X</td><td>X</td><td>X</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 3</td><td> 6</td><td>X</td><td>X</td><td>X</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td rowspan="6"> 2</td><td> 4</td><td> 1</td><td> 27,2</td><td> 408</td><td> 60,0</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 4</td><td> 2</td><td> 35,5</td><td> 422</td><td> 75,4</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 5</td><td> 3</td><td> 31,8</td><td> 457</td><td> 67,7</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 5</td><td> 4</td><td> 40,0</td><td> 422</td><td> 88,7</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 6</td><td> 5</td><td> 45,5</td><td> 433</td><td> 97,8</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 6</td><td> 6</td><td> 43,4</td><td> 457</td><td> 86,6</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td rowspan="3"> 3</td><td> 7</td><td> 1</td><td> 18,6</td><td> 451</td><td> 39,9</td><td>80 Ni 20 Cr</td><td>1.5x10 '³Torres</td><td>95 oxygen 5 Ar</td>

<td> 8</td><td> 2</td><td> 19,1</td><td> 481</td><td> 39,8</td><td>80 Ni 20 Cr</td><td>1.5x10 '³Torres</td><td>95 oxygen 5 Ar</td>

<td> 9</td><td> 3</td><td> 18,7</td><td> 468</td><td> 39,1</td><td>80 Ni 20 Cr</td><td>1.5x10 '³Torres</td><td>95 oxygen 5 Ar</td>

<td rowspan="6"> 4</td><td> 10</td><td> 1</td><td> 12,3</td><td> 409</td><td> 27,7</td><td>Si</td><td>2.0x10 '³Torres</td><td>80/20 I</td>

<td> 10</td><td> 2</td><td> 12,1</td><td> 409</td><td> 26,6</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 11</td><td> 3</td><td> 11,3</td><td> 408</td><td> 26,1</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 11</td><td> 4</td><td> 11,8</td><td> 410</td><td> 26,1</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 12</td><td> 5</td><td> 12,0</td><td> 412</td><td> 26,4</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td> 12</td><td> 6</td><td> 12,3</td><td> 404</td><td> 27,2</td><td>Si</td><td>2.0x10 '³Torres</td><td> 80/20</td>

<td rowspan="6"> 5</td><td> 13</td><td> 1</td><td> 12,1</td><td> 385</td><td> 27,6</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 13</td><td> 2</td><td> 12,4</td><td> 401</td><td> 26,7 '</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 14</td><td> 3</td><td> 11,3</td><td> 390</td><td> 26,3</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 14</td><td> 4</td><td> 11,5</td><td> 392</td><td> 26,6</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 15</td><td> 5</td><td> 11,5</td><td> 410</td><td> 26,8</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

<td> 15</td><td> 6</td><td> 13,2</td><td> 442</td><td> 26,8</td><td>Si</td><td>2, lx10 '³Torres</td><td> 80/20</td>

Optical results achieved were as follows: "C", observe

<td>TY 18.70</td><td>RGY 12.76</td><td>RFY 25.12</td>

<td>a * -5.06</td><td>a * -0.43</td><td>a * +0.40</td>

<td>b * -1.04</td><td>b * -4.27</td><td>b * + 24.56</td>

<td>Sheet resistance</td><td>= 104.5 ohms / area</td><td></td>

Normal radiant power = 0.55

After heat treatment *, light source, “C”, 2 ° observ.

<td>TY</td><td> 23,59</td><td>RGY</td><td> 10,77</td><td>RFY 21.61</td>

<td>a *</td><td> -5,46</td><td>a *</td><td> -0,36</td><td>a * +0.54</td>

<td>b *</td><td> -3,47</td><td>b *</td><td> -4,84</td><td>b * + 26.77</td>

Sheet resistance = 15.2 ohms / area Normal radiant power = 0.183

<td>ΔΤ +4.89</td><td>ARG -1.99 ARF -3.51</td>

<td>ΔΕ 6.03</td><td>AE 3.45 AE 4.74</td>

<td>ALpact resistance =</td><td>- -89.3 ohms / area</td>

ANnormal radiant power = -0.37

The test

<td>Chemical resistance: Coated -</td><td>slight change in physical properties after boiling at 230 ° F (110 ° C) in 5% HCl acid</td>

<td>After heating -</td><td>one hour slight change in physical properties after boiling at 230 ° F (110 ° C) in 5% HCl acid one hour</td>

Taber abrasion test: AT (transmission) 300 cycles and 500 grams load

<td>Coated -</td><td>AT = 3.1%</td>

<td>After heating -</td><td>AT = 1.8%</td>

When the above description is given, many other features, modifications, and improvements will be apparent to one skilled in the art. Therefore, such other features, modifications, and improvements are considered to be part of the present invention, the scope of which is defined by the following definition: