Sputtered titanium oxynitride films

DESCRIPTION

The present invention relates in general to the technique of deposition by means of cathodic evaporation, films containing a metal, on non-metallic substrates, and more particularly, to the technique of depositing by magnetic evaporation, transparent films of several layers of dielectric metal on glass.

United States Document A 3,990,784, by Gelber, describes a coated glass system, for use in Architecture, comprising a transparent substrate and a multi-layer coating composed of a first and second metal layers with a layer of a dielectric between the two, in which the first and second metal layers have a thickness ratio such that the transmission of the coating can be changed irrespective of its reflection properties by varying the thickness of the metallic layers but maintaining their relationship constant. The dielectric has a thickness such that the reflection of the coating is not of an intense color.

US Document 4,022,947, by Grubb et al., Describes a transparent panel capable of transmitting a desired fraction of visible radiation while reflecting a large fraction of the incident solar radiation, and a method for preparing said panel, by cathode evaporation of an alloy of iron, nickel and chromium to obtain a transparent metal film, and by reactive cathode evaporation of the same or of a similar alloy in the presence of oxygen to form an oxide film. In a preferred arrangement, the metal film extends between the substrate and the metal oxide film. In another preferred arrangement, the metalic oxide film extends between the substrate and the metalic film.

United States Document A 4,534,841, by Hartig et al., Describes the formation of a glassy surface for the control of solar energy, produced by first applying an oxide layer having an optic thickness of 20 to 280 nanometers on a transparent substrate by cathodic evaporation, and secondly a layer of chromium nitride having a geomometric thickness of 10 to 40 nanometers. A third optic layer of a dielectric material can be applied to the second layer. The oxide layer is selected from tin, titanium and aluminum oxides.

The US Document 4,535,000, of Gordon, describes the deposition of a thin film of a metalic nitride, for example titanium nitride, on a glass substrate, mixing a methanol halide with a reducing gas, such as ammonia, at a temperature of 250 to 320 C, and reacting the gases on the heated glass surface at a temperature of 400 to 700 C ', to form the film on the glass.

US Document A 4,546,050, of Amberger et al., Describes a glass laminate with a multilayer coating, selected from the group consisting of copper, stainless steel, titanium dioxide; copper, titanium, titanium dioxide; and copper, titanium, titanium nitride.

Glass products with metal films and / or metal oxides, for use in Architecture, are growing in importance because the energy requirements for heating and cooling are becoming increasingly expensive. Coated glass products, for use in Architecture, generally belong to two categories, coated products for solar energy control and coated products with high transmittance / low emissivity.

Products for solar energy control are generally glass substrates, often colored, coated with a colored film of low transmittance to visible radiation, which reduces the transmittance of solar energy through the windows inside the buildings, reducing Roasted air conditioning costs. These products are more effective in hot climates and are more frequently seen in commercial buildings. In areas where heating costs are of great importance, and especially in residential constructions, coatings of high transmittance / low emissivity are desirable in order to allow a high transmittance of visible light to the interior and at the same time reflect infrared radiation to retain The heat inside the building. High transmittance / low emissivity coatings are topically multi-layered films in which a metal that reflects infrared radiation, such as silver, gold or copper, is interposed between anti-reflective layers of metalic oxides, such as bismuth, indium and / or tin oxides . Solar energy control films, on the other hand, are topically single-layer films of one or more metals or metal oxides such as cobalt, iron, chromium, nickel, copper, etc.

Chemical methods by way of smoke to produce metallic films for solar energy control are well known from the United States Documents at 3,846,152, 4,091,172, 3,723,158 and

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3,457,138. Pyrolytic methods for producing metal Oxide films for solar energy control are well known from US Documents A 3,660,051, 3,658,568, 3,978,272 and 4,100,330.

Technologies of cathode evaporation to produce multi-layer coatings of high transmittance / low emissivity are described in US Documents 4,462,884 and 4,508,789. Cathodic evaporation techniques for producing films for solar energy control are described in US Documents A 4,512,863 and 4,594,137.

JP-A-57.2875 (Patent Abstract of Japan, volume 6, number 63, of April 22, 1982, page 42C99) describes a vacuum deposition of * 1 classes of elements, selected from B, C, N and O, and Ti, to form colored protective coatings of TiN, TiO Ti (NxOy) -Ti (CxNy) and Ti (CxNyOz) on wrist watch cases.

In Metals Handbook, 1982, volume 5, chapter "Sputtering", pages 412 to 415, the coating of substrates by cathode evaporation is described. Reactive cathodic evaporation using a gas to introduce one or mine of the coating components is mentioned. The cathodic evaporation of a Ti anticatode, in an atmosphere of Ar + N2, causes hard, wear-resistant, TiN coatings for tools. The ability to control the coating compositions makes cathodic evaporation useful in the electroin industry in applications such as amorphous optic films for integrated optical systems, transparent conductive electrodes, etc.

It is an object of the invention to provide a method of coating transparent nonmetallic substrates with a dielectric film in order to use the coated article as structural elements.

This object is achieved by a method of manufacturing a coated article by placing a substrate in a coating chamber, making the vacuum in said chamber and providing a reactive atmosphere containing nitrogen and depositing a coating on the surface of said substrate by cathodic evaporation of a titanium catode located in front of the surface of said substrate, characterized by providing in said chamber an atmoisphere containing oxygen additions and depositing a transparent coating of titanium oxynitride on said surface of a transparent nonmetallic substrate.

This object is also achieved by using the coated article, prepared according to claims 1 to 6, 9 and 15, as a structural element to reflect solar energy; by using the coated article, prepared according to claims 1 to 9 and 15, and having a reduced total light reflectance, as a structural element for the reflectance of solar energy; and by using the coated article, prepared according to claims 1 to 3 and 10 to 15, as a colored product for Architecture.

The present invention provides a new and superior dielectric film for use in Architecture in a wide variety of multi-layer coatings on glass. The present invention involves the cathodic evaporation of a titanium catode in an atmoisphere containing oxygen and nitrogen in order to deposit a coating composed of titanium oxynitride. The titanium oxynitride film of the present invention can be deposited in combination with a film reflecting infrared radiation, such as silver, to form a multilayer film of low emissivity. The titanium oxynitride film of the present invention can also be deposited in combination with a film of a metal alloy, such as stainless steel or Inconel, to form various colored coatings in several layers, with relatively saturated colors. The titanium oxynitride film of the present invention can also be deposited in combination with both a film reflecting infrared radiation, such as silver, and with a metal film that reduces the light reflectance, especially with a film of such a metal alloy like Inconel, to produce a multilayer coating that has a relatively saturated color and low emissivity.

Figure 1 indicates the transmittance at 550 nanometers (nm) of a film of titanium oxynitride deposited on glass, as a function of the thickness of the film measured as a number of passes of the cathode, at various percentages of oxygen in nitrogen.

Figure 2 indicates the deposition rate of titanium oxynitride, in Angstroms (10^-10 m) by passage of the cathode, depending on the percentage of oxygen in the atmosphere of the coating chamber.

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Figure 3 indicates the absorption of a titanium oxynitride film of an approximate thickness of 600 Angtroms (6x10^-8 m), depending on the percentage of oxygen in the atmosphere of the coating chamber.

Figure 4 indicates the transmittance at 550 nanometers of a titanium oxynitride film deposited on an Inconel film, depending on the thickness of the film at various levels of potential of the cathode.

A transparent non-metallic substrate, preferably glass, is coated by cathodic evaporation, preferably by cathode evaporation with magnetron, providing a product composed of titanium oxynitride with desirable durability and aesthetic properties.

In a conventional process of cathode evaporation with magnetron, a substrate is placed inside a coating chamber in front of a coatode having an anticatoate of the material to be evaporated. Preferred substrates according to the present invention include glass, ceraomic or plastic material that are not adversely affected by the operating conditions of the coating process.

The cathode can be of conventional design, preferably of elongated rectangular design, connected to a source of electrical potential, and preferably used in combination with a magnetic field that intensifies the process of cathodic evaporation. At least one surface of the anticaotope is composed of titanium that evaporates in a reactive atmosphere to form a film of titanium oxynitride. Preferably, the anode is a set designed and symmetrically located, as indicated in US Document A 4,478,702, by Gillery et al.

The titanium oxynitride of the present invention is deposited by cathode evaporation of a titanium coatode in an atmosphere containing oxygen and nitrogen. Preferably, the composition of the atmosphere varies from 10 to 50 percent oxygen and 90 to 50 percent nitrogen. An atmosphere that contains 10 to 25 percent oxygen and the rest of nitrogen is especially preferred.

The figures indicate that the properties of titanium oxynitride change gradually and continuously when the gas composition changes. In contrast, titanium evaporated cathodetically into an oxygen / argon atmosphere that exhibits an abrupt change from metal oxide. The figures further indicate that it is possible to choose the deposition conditions so that a titanium oxynitride film with the desired transmission and absorption properties can be evaporated cathodetically at a desired rate.

Certain desired coatings colors can be produced, for application in Architecture, by combining a colorless dielectric material with colored, inner and outer metallic layers, or by combining colored metalic oxides with a reflective metal. According to the present invention, the desired colors of the coating can be obtained by combining titanium oxynitride with a metal highly reflective of infrared radiation, such as silver, to produce intense colors with a high degree of saturation as well as low emissivity. If the luminous reflectance of said coating is higher than desired, it can be reduced, without sacrificing color purity or emissivity, with an optional neutral metal coating, such as nickel and iron alloys, especially Inconel and stainless steel .

The present invention provides the possibility of manufacturing a series of colored coatings with a mony of layers and materials. The coating system of the present invention has a relatively low reflection, a high color saturation and a monolotic durability.

It is known that a series of colors can be obtained with a first and second surrounding metal layers, a layer of a transparent dielectric material; the color can be modified by varying the thickness of the dielectric layer. However, no previously tested dielectric has had the required properties of rapid cathodic evaporation, high refractive index and good durability. The titanium oxynitride of the present invention has the above properties, as well as the ability, in combination with a suitable metabolic film, to produce intensely colored coatings, for use in Architecture. For example, titanium oxynitride, in combination with a nickel alloy, can be used to obtain a range of attractive colors with excellent durability.

Using circular diagrams of reflection and calculations with computers, it has been determined that, in a combination of two layers of a metal and a dielectric, there is an optimum thickness of both layers that gives the combination of maximum reflection and maximum color saturation. The higher the refractive index

016 397 of the dielectric, the transmission of the coating with the optimum thickness is smaller and the color saturation is greater. Metals with low n and high k, being nk the real and complex parts of the Index of complex refraction, which define the propagation of an electromagnetic radiation in the middle, tend to give the lowest transmission and the greatest saturation.

If the thickness of the metal is increased to try to lower the transmission, the reflectance is increased and results in a dyeable coloration. By depositing a very thin metal layer before the deposition of the dielectric layer, it can decrease the reflectance and give a more saturated color. If the thickness of the primary metal layer is increased, in combination with the deposition of a very thin metal layer, a very colored, low transmittance and low reflectance coating can be obtained. If two primary metal layers are used, a dielectric with a low refractive index, in combination with a low and high metal, the most attractive appearance is obtained. The calculi indicate that, at 20 percent of light transmission, adequate saturation can be obtained using a metal in combination with a dielectric with a refractive index of 2.3. For a lower light transmission, a metal-dielectric-metal system is preferred.

With the titanium oxynitride of the present invention, many metal or metal alloy films can be used to provide a multi-layer coating with good properties. Preferred films include metals such as titanium, and metal alloys such as nickel alloys and iron alloys. A nickel alloy is preferred because it has very good chemical resistance, neutral color and is easy to deposit.

A clean glass substrate is placed in a coating chamber, in which the vacuum is made, preferably less than 1.33x10^-2Pa (10^-4 torr), and more preferably less than 2.66x10^-3Pa (2x10^-5torr). A selected atmosphere of reactive gases, preferably oxygen and nitrogen, is introduced into the chamber at a pressure between 6.65x10^-2 y10Pa (5x10^-4 y10^-2 torr). A coatode having a titanium anticatoate surface is put into operation on the surface of the substrate to be coated. The metal of the anti-cathode evaporates, reacting with the chamber's atmosphere and placing a layer of titanium oxynitride coating on the surface of the glass.

After the initial layer of titanium oxynitride has been deposited, the vacuum is made in the coating chamber, and an inert atmosphere, as pure argon, is introduced at a pressure between 6.65x10^-2and 10 Pa (5x10^-4 y10^-2 torr). A coatode having an anti-cathode surface of a metal or a metal alloy is put into operation on the surface coated with titanium oxynitride. The anticóatodo evaporates depositing a metallic layer on the surface of the glass covered by the titanium oxynitride. A preferred metal is titanium. Preferred metal alloys include Inconel, a nickel alloy, and stainless steel, an iron alloy, preferably evaporated at a pressure of 0.533 to 0.7998 Pa (4 to 6 millitorr) in a pure argoon atmosphere.

In some preferred embodiments of the present invention, a metal film is deposited below, as well as above, the titanium oxynitride film. As in the case of a two-layer film, the dominant wavelength of the color reflected by the uncoated surface depends almost exclusively on the thickness of the titanium oxynitride layer. The thickness of the upper metal layer is modified until the transmission has approximately the required value; The thickness of the lower metal layer is then modified until the desired reflection of the uncoated side of the article is achieved. A final modification of the thickness of the upper metabolic film may be necessary to obtain the final optimal transmission. Within the range of interest thicknesses, modifying the thickness of the upper metal film, the transmission decreases and the reflection of the uncoated side of the coated article increases. By increasing the thickness of the background metal film, the transmission and reflectance of the uncoated side decrease.

In a preferred embodiment of the present invention, a multilayer film is deposited by cathodic evaporation to form a coating of high transmittance and low emissivity. In addition to the titanium anticatode, at least one other anticoat surface contains a metal to evaporate to form a reflective metal layer of infrared radiation. A multilayer coating, which has a reflective infrared radiation reflecting metal layer in combination with a titanium anti-reflective layer, is produced as follows.

A clean glass substrate is placed in a coating chamber, in which the vacuum is made, preferably less than 10^-2 Pa (10^-4 torr), and more preferably less than 2.66x10^-3 Pa (2x10^-5 torr). A selected atmosphere of reactive gases, preferably nitrogen and oxygen, is introduced into the chamber at a pressure between 6.65x10^-2 y10^-3 Pa (5x10^-4 y10^-5 torr). A coatode that

016 397 has a titanium anticóatodo surface is put into operation on the surface of the substrate to be coated, preferably at a power level of 5 to 10 kilowatts. The metal of the anti-cathode evaporates, reacting with the chamber's atmosphere and placing a layer of titanium oxynitride coating on the surface of the glass.

After the initial layer of titanium oxynitride has been deposited, the vacuum is made in the coating chamber, and an inert atmosphere, such as pure argoon, is introduced at a pressure between 6.65x10^-2 and 10 Pa (5x10^-4 y10^-2 torr). A coatode having an anticóatodo surface of metallic silver is put into operation on the surface coated with titanium oxynitride. The metal of the anti-cathode evaporates and a conductive, uniform, highly reflective, metallic layer of infrared radiation is deposited on the surface of the glass coated with titanium oxynitride. A second layer of titanium oxynitride is deposited on the silver layer under essentially the same conditions used to deposit the first layer of titanium oxynitride.

The present invention can be better understood by the descriptions of the specific examples that follow.

Example I

A titanium anticóatodo, of dimensions 12.7 x 43.2 centimeters, is subjected to 10 kilowatts in a vacuum chamber containing an atmosphere of 23 percent oxygen and 77 percent nitrogen at a pressure of 0.583 Pa (4 militorr). The cathode remains stationary while a glass substrate passes at an approximate speed of 3 meters per minute under the surface of the evaporating anticóatodo. Four passes deposit a film composed of titanium oxynitride on the glass surface, with a luminous transmittance of 75.7 percent.

Example II

A glass substrate is coated with a first layer composed of titanium oxynitride, as in Example I. The surface coated with titanium oxynitride is then coated with a uniform layer of silver by evaporation of a silver anticatode subjected to 0.27 kilowatts in an armoson atmosphere at a pressure of 5.32x10^-1 Pa (4 millitorr), with a final light transmittance of 68 percent. To protect the silver from oxidation, a very thin protective layer of titanium is deposited through a pass of the titanium cathode subjected to 0.03 kilowatts in an argoon atmosphere at 5.32x10^-1 Pa (4 millitorr), with a final light transmittance of 67.5 percent.

Example III

A glass substrate is coated with titanium and silver oxynitride, as in the previous examples. After depositing the thin titanium protective layer, a second layer of titanium oxynitride is deposited, with a final light transmittance of 82.1 percent, thus producing a coated article of high transmittance and low emissivity.

Example IV

A titanium anticóatodo, of approximate dimensions 12.7 x 43.2 centimeters, is subjected to 10 kilowatts at 645 volts in a vacuum chamber containing an atmosphere composed of 23 percent oxygen and 77 percent nitrogen at a pressure of 5.32x10^-1 Pa (4 millitorr). A glass substrate passes once in front of the cathode at an approximate speed of 2.74 meters per minute and is coated with titanium oxynitride. The vacuum is made in the chamber and an atmosphere of pure argon is introduced at a pressure of 5.32x10^-1 Pa (4 millitorr). A silver cathode is subjected to 441 volts at 2.5 amps to deposit a film of silver by evaporation on the surface coated with titanium oxynitride, in one pass at a speed of approximately 3.05 meters per minute. To protect the silver from oxidation, a very thin layer of a nickel alloy is deposited on it. An Inconel 625 anticathode, composed of 18.6 percent chromium, 3 percent iron, 4 percent niobium, 9 percent molybdenum and the rest of nickel, is subjected to 1 amp at 352 volts. The nickel alloy evaporates in the atmosphere of pure argon at 4 millimeters while the substrate passes at an approximate speed of 3.05 meters per minute. The coated article has a light transmittance of 21.3 percent and a reflectance on the uncoated side of 54.6 percent. The uncoated surface color coordinates are x = 0.3516 and y = 0.3805. The color observed is pale yellow.

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Example V

A titanium oxynitride film, in combination with a silver film, produces a sufficiently reflective film with a color sufficiently saturated to have the appearance of a gold film. A titanium cathode subjected to 10 kilowatts at 640 volts is evaporated as in Example IV, except that the atmosphere at 5.32x10^-1 Pa (4 millitorr) contains less oxygen. A pass at an approximate speed of 3.05 meters per minute, with a slightly oxygen deficient atmoisphere, produces a titanium oxynitride film that is somewhat more absorbent than the oxynitride film of Example IV. A silver catode subjected to 441 volts at 2.4 amps is evaporated, in a pure argon atmosphere at 0.532 Pa (4 millitorr), depositing a silver film on the surface coated with titanium oxynitride, in one pass at a speed Approximately 3.05 meters per minute. To protect the silver from oxidation, a very thin film of a nickel alloy, as in Example IV, is deposited by evaporation in an argoin atmosphere at 5.32x10^-1 Pa (4 millitorr), by means of a pass at a speed of 3.05 meters per minute, by evaporation of an Inconel 625 anticode subjected to 356 volts at an ampere. The coated article has approximately the same light transmittance as the article in Example IV, but the reflectance of the uncoated surface is 40.2 percent and the color coordinates are x = 0.3833 and y = 0.4093. The color observed is gold, a more saturated color than that of Example IV. This film withstands thermal tests without turbidity. Example VI

A coating of several layers of titanium oxynitride and a nickel alloy is deposited on a glass substrate under the following conditions. A clean glass substrate is kept in a vacuum chamber in an atmosphere of 15 percent oxygen and 85 percent nitrogen at a pressure of 7.98x10^-1 Pa (6 millitorr). With a titanium catode subjected to 6.7 kilowatts and with an approximate linear speed of 3 meters per minute, eight passes are needed to produce a titanium oxynitride coating with a thickness that is initially blue in color. The surface of the glass coated with titanium oxynitride is then passed under a nickel alloy anti-cathode, in an atmosphere of pure argon. The nickel alloy of this Example is Inconel 625, composed of 18.6 percent chromium, 3 percent iron, 4 percent niobium, 9 percent molybdenum and the rest of nickel. A layer of nickel alloy with a thickness sufficient to reduce the transmittance to 22 percent is deposited by evaporation. The chromaticity coordinates of this coating are x = 0.3198 and y = 0.2863, measured on the surface of the uncoated glass. The color observed is violet pink and the luminous reflectance is 5.65 percent on the surface of the uncoated glass.

Example VII

Using the titanium-Inconel oxynitride layer system as in Example VI, a coating with an approximate luminous transmittance of 20 percent and an attractive blue color is produced under the conditions given in Table I. The coating color control Two layer is simple. The thickness of the titanium oxynitride controls the color tone. If it is too green, the layer is too thick. If it is too red, the layer is too thin. The thickness of the titanium oxynitride also affects the transmission (or reflectance), since blue-reddish coatings generally have a transmission greater than the blue-green ones. However, once the color tone has been set, the transmission (or reflectance) can be regulated by changing the thickness of the Inconel layer. As expected, an increase in thickness decreases the transmittance and increases the reflectance. This change has an insignificant effect on the dominant wavelength of the color tone. Table II presents the effects of the changes in the thickness of the layers, expressed as percentages of the thickness of the layers produced by the conditions of Table I, on the color of five two-layer coatings of this Example.

(Table I passes next page)

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Table I

Typical deposition conditions for a two-layer blue coating with a transmittance of 20 percent

<td>Condition</td><td>First layer</td><td>Second layer</td>

<td>Film composition</td><td>Titanium oxynitride</td><td>Nickel alloy</td>

<td>Anticathode Metal</td><td>Titanium</td><td>Inconel 625</td>

<td>Gaseous mixture (% by volume)</td><td>81 nitrogen 19 oxygen</td><td>100 argon</td>

<td>Pressure, Pa (militorr)</td><td>5.32x10^-1 (4)</td><td>5.32x10^-1 (4)</td>

<td>Power, kilowatts</td><td> 10</td><td> 1,53</td>

<td>Volts</td><td> 637</td><td> 424</td>

<td>Anticode size, cm</td><td>12.7 x 43.2</td><td>12.7x43.2</td>

<td>Pass speed, m / min</td><td> 3</td><td> 3</td>

<td>Final transmission (% at 500 nm)</td><td> 71,6</td><td> 19,4</td>

Table II

Variation of color coordinates when modifying the thickness of the layers - 2-layer coating

<td rowspan="2">Shows</td><td rowspan="2">Relative thickness of the Oxinitride / Metal layers</td><td colspan="3">Reflectance of uncovered surface</td><td rowspan="2">Transmittance bright %</td><td rowspan="2">Color</td>

<td>Y</td><td>x</td><td>Y</td>

<td> 2-1001</td><td> 100/100</td><td> 11,5</td><td> 0,2284</td><td> 0,2453</td><td> 19,4</td><td>blue</td>

<td> 2-1002</td><td> 120/100</td><td> 11,12</td><td> 0,2280</td><td> 0,2442</td><td> 18,3</td><td>blue</td>

<td> 2-1003</td><td> 83/100</td><td> 17,08</td><td> 0,2459</td><td> 0,2834</td><td> 21,3</td><td>greenish blue</td>

<td> 2-1005</td><td> 100/83</td><td> 9,93</td><td> 0,2266</td><td> 0,2430</td><td> 23,2</td><td>blue</td>

<td> 2-1006</td><td> 100/120</td><td> 14,13</td><td> 0,2345</td><td> 0,2559</td><td> 16,1</td><td>blue</td>

Example VIII

A glass is coated by cathodic evaporation, as in the previous examples, with a first layer of Inconel 625, with a light transmittance of 60 percent. A film of titanium oxynitride is deposited on the nickel alloy, as in the previous examples. A second film of the nickel alloy is deposited, with a final light transmittance of 22 percent. The chromaticity coordinates of the coating are x = 0.2644 and y = 0.2340, on the surface of the glass. The color observed is violet and the luminous reflectance is 8.9 percent on the surface of the uncoated glass. Example IX

A series of three-layer coatings is prepared, changing the thickness of the individual layers of titanium oxynitride and Inconel. The results of these examples are presented in Table IV, in which the thicknesses are expressed as percentages of the thicknesses obtained using the conditions set out in Table III.

(Table III passes next page)

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Table III

Typical deposition conditions of a 3-layer blue coating with a transmittance of 12 percent

<td>Condition</td><td>First layer</td><td>Second layer</td><td>Third layer</td>

<td>Anticode Metal</td><td>Inconel 625</td><td>Titanium</td><td>Inconel 625</td>

<td>Gaseous mixture (% by volume)</td><td>100 argon</td><td>81 nitrogen / 19 oxygen</td><td>100 argon</td>

<td>Pressure, Pa (militorr)</td><td>1.33x10^-1 (4)</td><td>1.33x10^-1 (4)</td><td>1.33x10^-1 (4)</td>

<td>Power, kilowatts</td><td> 0,04</td><td> 10</td><td> 2,11</td>

<td>Volts</td><td> 285</td><td> 637</td><td> 432</td>

<td>Anticode size, cm</td><td>12.7x43.2</td><td>12.7 x 43.2</td><td>12.7x43.2</td>

<td>Pass speed, m / min</td><td> 3</td><td> 3</td><td> 3</td>

<td>Final transmission (% at 500 nm)</td><td> 72,8</td><td> 62,9</td><td> 12,3</td>

Table IV

Variation of color coordinates when modifying the thickness of the layers - 3-layer coating

<td rowspan="2">Shows</td><td colspan="3">Relative coating thickness</td><td colspan="3">Reflectance of uncoated surface</td><td></td>

<td>Metal lower</td><td>Oxynitride</td><td>Metal higher</td><td>^Y</td><td>x</td><td>Y</td><td>Color</td>

<td> 2-933</td><td> 100</td><td> 100</td><td> 133</td><td> 17,48</td><td> 0,2427</td><td> 0,2527</td><td>blue</td>

<td> 2-928</td><td> 100</td><td> 100</td><td> 117</td><td> 15,69</td><td> 0,2306</td><td> 0,2661</td><td>greenish blue</td>

<td> 2-923</td><td> 100</td><td> 100</td><td> 100</td><td> 14,44</td><td> 0,2237</td><td> 0,2664</td><td>blue</td>

<td> 2-929</td><td> 100</td><td> 100</td><td> 83</td><td> 11,43</td><td> 0,2234</td><td> 0,2357</td><td>blue</td>

<td> 2-934</td><td> 100</td><td> 100</td><td> 67</td><td> 9,00</td><td> 0,2206</td><td> 0,2248</td><td>blue</td>

<td> 2-926</td><td> 100</td><td> 117</td><td> 100</td><td> 22,16</td><td> 0,2472</td><td> 0,2853</td><td>greenish blue</td>

<td> 2-923</td><td> 100</td><td> 100</td><td> 100</td><td> 14,44</td><td> 0,2237</td><td> 0,2444</td><td>blue</td>

<td> 2-927</td><td> 100</td><td> 83</td><td> 100</td><td> 7,46</td><td> 0,2710</td><td> 0,2436</td><td>Violet</td>

<td> 2-943</td><td> 0</td><td> 100</td><td> 100</td><td> 13,75</td><td> 0,2367</td><td> 0,2492</td><td>blue</td>

<td> 2-944</td><td> 50</td><td> 100</td><td> 100</td><td> 11,97</td><td> 0,2386</td><td> 0,2422</td><td>blue</td>

<td> 2-945</td><td> 100</td><td> 100</td><td> 100</td><td> 11,36</td><td> 0,2252</td><td> 0,2302</td><td>blue</td>

<td> 2-946</td><td> 150</td><td> 100</td><td> 100</td><td> 8,92</td><td> 0,2143</td><td> 0,2084</td><td>blue</td>

<td> 2-946</td><td> 200</td><td> 100</td><td> 100</td><td> 8,49</td><td> 0,2048</td><td> 0,2013</td><td>blue</td>

Example X

A film of titanium oxynitride is deposited on a glass surface, as in Example VI. A stainless steel film is deposited on the titanium oxynitride. The chromaticity coordinates of this coating are x = 0.2466 and y = 0.2680, on the glass surface. The color observed is blue-green and the light reflectance is 18.5 percent, on the surface of the uncoated glass. Example XI

A film of titanium oxynitride is deposited, in 8 passes, on a glass surface, as in the previous examples. A titanium metal film is deposited by cathodic evaporation of a titanium catode in an argon atmosphere. The chromaticity coordinates of the coating are x = 0.3317 and y = 0.3037, on the surface of the glass. The color observed is violet-pink and the reflectance

016 397 light is 5.17 percent, on the surface of the uncoated glass.

Example XII

A film of titanium oxynitride is deposited, in 9 passes, on a glass surface, as in Example XI. A titanium metalic film is deposited by evaporation of a titanium coatode in an argoon atmosphere. The chromaticity coordinates of the coating are x = 0.2402 and y = 0.2265, on the surface of the glass. The color observed is blue-violet and the luminous reflectance is 5.32 percent, on the surface of the uncoated glass.

The above examples are offered to illustrate the advantages of the present invention. The coatings in Tables II and III are not attacked in 24 hours by 20 percent hydrochloric acid, cold, or by 30 percent nitric acid, cold. In a test at 135 ° C for five hours, there is a small change in the transmittance and in the reflected color. This could be a consequence of a growth of the protective oxide on the surface of Inconel, a process that would be self-limited.

In the Cleveland condensate moisture test at 66 ° C, no change in coatings was observed in four months. The coatings are not affected by scraping with a scraping pencil, or by the cyclic test with bristle brushes, used to evaluate the coatings of internal monolithic varnishes. However, rubbing with dry or humid pumice stone shows that the coating is not as hard as the coatings composed of titanium oxynitride.

The combination of layers of titanium oxynitride / metal alloy can produce unattractive products. However, the titanium / metal metal / oxynitride system can produce a range of colors by reflection and more extensive transmittance than if only two materials were used. Titanium oxynitride is transparent, chemically resistant, has a high refractory index and is as fast to deposit as tin and zinc oxides, which have inferior properties. The concentration of oxygen in nitrogen is not critical to the process as can be understood unless the deposition rate is accelerated to its maximum absolute value. This mitigates the complication that only machine monitors are reliable in the transmission mode that cannot distinguish a decrease in transmission due to an increase in film thickness from a decrease in transmission due to an increase in absorption. . Therefore, color control in a two-layer coating should not be difficult. Color control is somewhat more complicated in a three-layer coating, which, for example, if it is too reflective, can be decreased by thinning the upper metal layer or by thickening the lower metal layer.

The above examples are offered to illustrate the present invention. Various conditions of cathodic evaporation can be used, the ratio of oxygen and nitrogen can be modified, and the titanium oxynitride film of the present invention can be used with various thicknesses and configurations with other metal films to provide a wide range of colors by reflection. The scope of the present invention is defined by the following claims.

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