Method of making multilayer glass and multilayer glass obtained thereby

The subject of the invention is laminated glass and its production methods, especially glass with a cathodic sputtering coating, having high visible transmission and excellent reflection characteristics of infrared radiation, useful as architectural glass.

In the case of flat architectural glass, such as made in the flow process, two of many known techniques for producing coatings that regulate solar radiation on these glasses are the pyrolytic method and the magnetic sputtering method. The disadvantages hitherto existing in the cathodic sputtering process have been that the coatings can often be easily abraded (i.e. are unstable) and the polymer sealant used in the production of multi-pane architectural windows often attacks the coating. This in turn destroys the seal between the panes, which allows harmful condensate to accumulate between them. On the other hand, sputtered coatings have the ability to achieve low emissivity values ​​and the property of high visible radiation transmission, compared to most pyrolytic coatings, which is important in some architectural glasses.

The terms emissivity and permeability are known and used herein in accordance with known meaning. Transmittance here means solar transmittance, which is visible light transmittance, infrared energy transmittance and ultraviolet light transmittance. The transmittance of all solar energy is defined as the weighted average of these other quantities. Visible radiation transmittance is determined by standard C illuminant technique at 380-720 nm, infrared radiation is 800-2100 nm, ultraviolet radiation is 300-400 nm and total salt radiation is 300-210 nm. To achieve such emissivity a special range of infrared radiation (i.e. 2500-40000 nm) is used.

Visible radiation transmission can be measured using known conventional techniques. For example, using a spectrophotometer, a spectral transmittance curve is obtained for each wavelength. Visible radiation transmission is then calculated using ASTM E-308. The method of calculating the colors of objects using the CIE system (ASTM btandards year, volume 14.2), where fewer wavelength points can be used than recommended. Another technique for measuring visible radiation transmission is to use a spectrometer to measure visible radiation transmission directly.

Emissivity (E) is a measure or characteristic of both absorption and reflection of light at given wavelengths, given by the formula:

E - = 1 - coating reflection coefficient

For architectural applications, emissivity values ​​are important in the so-called middle range, sometimes also referred to as the far range of the infrared spectrum, i.e. for a wavelength of about 2500-40000 nm. The term emissivity is used here to discuss emissivity values ​​measured in this infrared range, as detailed in the 1991 ASTM Standard. dk for measuring energy and sub-energy and in calculating the emissivity calculation, proposed by Primary GIsss Maehfaśturere 'Comcil and entitled Method for controlling the measurement and calculation of architectural emissions of flat glass products using radiometric measurements. In this standard, the emissivity is divided into two components, hemispherical emissivity (Eh) and normal emissivity (E_n).

175 403

It is known to obtain data for measuring such emissivity values, for example using a spectrophotometer that measures reflection as a function of wavelength, and emissivity is calculated using the 1991 ASTM standard.

The term sheet resistance (Rs) used in the description is a known term and refers to the resistance in ohms for any square of a layered system on a glass substrate with electric current flowing through the layered system. The sheet resistance determines to what extent the layer reflects infrared radiation and is used together with emissivity as a dimension of this property. It is measured using a 4-point control ohmmeter, such as, for example, a 4-point resistivity tester with a magnetron head.

For many architectural applications, it is desirable that the emissivity and Rs values ​​are as small as possible so that the glass window reflects significant amounts of infrared radiation incident on the glass. Generally speaking, glasses with a low E (i.e. low emissivity) are considered to have glasses with a hemispherical emissivity Eh of less than about 0.16 and normal emissivity E_n less than about 0.12. Preferably, Eh is about 0.13 or less and En is about 0.10 or less. At the same time, the sheet resistance Rs is preferably less than about 10.5 ohms / square. These glasses let in, according to commercial requirements, about 76% of visible radiation or more, using the C illuminant technique to measure the transmittance of glass about 2 mm - 6 mm thick. The visible transmission is more preferably about 78% or more for glasses with a thickness between about 2 mm - 6 mm, and most preferably about 80% or more.

The technique of producing architectural glass by magnetron sputtering of multiple layers of metal and / or metal oxides or nitrides on sheets of glass obtained by the flow process is well known using a large number of different combinations of metals (e.g. Ag, Au and the like), oxides and nitrides. Here, electrodes are used, either flat or tubular, or a combination thereof, and preferably a magnetron sputtering device described in U.S. Patent Nos. 4,356,073 and 4,422,916.

It is known to use said cathodic sputtering device for the production of architectural glasses having a layered system, successively from glass (e.g., standard glass obtained in the flow process) outside as follows:

Si3N4 / Ni: Cr / Ag / Ni: Cr / Si3N4 where the Ni: Cr alloy is 80/20 by weight Ni / Cr (i.e. nichrome) and two nichrome layers are 7 A thick, the Ag layer is 70 A thick (it can be up to 100 A thick) ), and Si3N4 layers are thicker (e.g. 320 A bottom layer and about 450 A top layer). The silver layer has a rather semi-continuous structure due to the fact that it is thin.

Although this known coating achieves good durability (the coating is scratch-resistant, wear-resistant and chemically stable) compared to pyrolytic coatings, its other properties worsen the reflection of infrared radiation and visible transmission characteristics. For example, for glass about 3 mm thick, the visible transmission (illuminant C) is usually only about 76%, Eh is 0.20-0.22 and Eh is 0.14-0.17. Both these emissivity values ​​are rather large. The sheet resistance Rs has a relatively large value of 15.8 ohms / square (a more preferred value is around 10.5 or less). So, although durability has been significantly improved, and although these coatings have also proved suitable for ordinary sealants (thus overcoming this problem in a known multi-pane window), the quality of solar radiation regulation was worse than optimal for many modern architectural purposes.

Other coatings containing silver and / or Ni: Cr are also known as layers for regulating the reflection of infrared radiation and other radiation, for example, filters or other coatings disclosed in US Patent Nos. 3,682,528 and 4,799,745. Also known are layered dielectric metal systems manufactured on

175 403 example according to U.S. Patent Nos. 4,179 181,3 698 946, 3 987 273, 3 901 997 and 3 889 026.

The efficiency of known methods is, however, insufficient, which is caused by the assumption that silver was isolated from N gas₂ during sputtering. At sputtering, it was believed that N₂ adversely affects silver during this operation.

The coatings obtained were also not stable. The terms durability or durability as used herein means mechanical and chemical resistance to deterioration in the quality of the glass, close to or equal to that obtained in the pyrolytic process.

According to the invention, layered glass coated with a cathodic sputtering layer has a glass substrate, having a layer system on the outside of the glass, consisting of a 40 nm to 42.5 nm thick Si ^ Ni layer and a 54 nm to 57.5 nm thick Si3N top layer , comprising between them at least two layers of nickel or nickel alloy and at least one layer of silver.

The layering is stable and the visible transmission is preferably at least 78%.

Transmittance is preferably greater than 80%.

Normal emissivity En is 0.10 or less and hemispheric emissivity Eh is 0.13 or less.

The normal emissivity En is preferably 0.09-0.10 and the hemispherical emissivity Eh is preferably 0.12-0.13.

Sheet resistance is 10.5 ohms / square or less.

The sheet resistance is preferably 9-10 ohms / square.

The nickel and nickel alloy layers are less than about 7 A thick, and the silver layers are more than 90 A thick.

The silver layer is 90-105 A.

The first layer of Si3N4 is at least 400 A thick and the second layer of Si3N4 is at least 540 A thick.

The layer system consists essentially of five layers.

Layer system consisting essentially of glass outside, a first layer of Si3N4, a second layer of nickel or nickel alloy, a third layer of silver, a fourth layer of nickel or nickel alloy and a fifth layer of Si3N4.

In another embodiment of the invention, the layer system essentially consists of glass from the outside, a first layer of Si3N4, a second layer of nickel or nickel alloy, a third layer of silver, a fourth layer of nickel or nickel alloy, a fifth layer of silver, a sixth layer of nickel or nickel alloy and the seventh layer of Si3N4.

Each of the silver layers is 50 A thick and each of the nichrome layers is less than 7 A.

At least one of the layers of nickel or nickel alloy is a nickel chromium alloy and the major part of chromium is its nitride.

All of the nickel or nickel alloy layers are a nickel chromium alloy in which the major part of chromium is its nitride.

The nickel chromium alloy contains approximately 80% nickel and 20% chromium by weight.

The transmittance is at least 80% or more, the normal emissivity En is 0.10 or less and the emissivity hemispherical Eh is 0.13 or less.

The glass has a sheet resistance of 10.5 ohms / square or less.

The thickness of any dichromic layer is less than 7 A and the total thickness of silver is 90-105 A.

The glass has only one silver layer, 95 A.

The glass has two layers of silver separated by a nichrome layer, each of the silver layers is 50 A thick

In preferred embodiments of the invention, the layered system consists of the above five layers and no other. The layered system may be extended by other known coatings which do not disturb or degrade the basic properties of the coatings according to the invention. These additional layers improve the essential properties of the coatings. One of that kind

175 The 403 layer system is, for example, a seven layer system, created by splitting a silver layer into two silver layers by a nickel-based layer (e.g., nickel-chromium), so that the outer layer of glass now consists of:

SI3 \ VNI: Cr / Ag / Ni: Cr / Ag / Ni: Cr / Si3N4

This seven-layer system usually has a slightly greater durability and scratch resistance compared to the five-layer system described above, as well as an even higher infrared reflection coefficient.

The next layers may simultaneously have any top coatings to increase scratch resistance or bottom coatings for increased adhesion and the like. However, the most preferred systems are five- and seven-layer systems.

In order to achieve the desired optimal emissivity and permeability characteristics, the layer thicknesses are very important due to the required final results. It is important to use silver with an increased thickness beyond the previously recommended 70 A, about 20% -30% more to ensure that silver is a single layer, a substantially continuous silver layer and in all cases to ensure proper infrared reflection properties. Thus, in this invention, instead of using the previously recommended 7 warstwy A silver layer, a total silver thickness of about 90-105 A and preferably 95-105 A is used.

For a five-layer system according to the invention, for example having a single Ag layer, its preferred thickness is 95 A. In those embodiments where the silver layer is divided into two layers by a nickel-based layer, the total thickness of both layers should be 90-105 A and preferably each should be 50 A. Therefore, it should be noted that the 50 A silver layers become somewhat discontinuous. Despite this condition, which is a problem in known systems, no adverse features are observed in carrying out the invention.

The nickel-based layers used are preferably Ni: Cr (80/20) nichrome used in known systems. However, instead of using the 10 A (or greater) thickness recommended so far, Ni: Cr layers usually have a thickness less than 7 A (e.g., 6 A or less, or reduced by about 15-20%).

In a similar manner to the use of the entire silver layer or layers, each of the Si3N4 layers of the invention is thicker than layers of known systems. In preferred embodiments, the increase in silver thickness is of the same order of magnitude as the increase in silver thickness, e.g., about 20% or greater. Thus, in preferred embodiments, instead of using the bottom layer and the top layer of Si3N4, each with a thickness of 320 A and 450 A, respectively (the bottom layer is slightly thinner than the top layer), according to the invention, the thickness of the bottom layer of Si3N4 at least 400 A and thickness is preferred top layer at least 540 A. The bottom layer 400 A - 425 A and the top layer 540 A - 575 A are most preferred. The purpose of these Si3N4 layers is mainly anti-reflection, color control, chemical resistance, scratch resistance and wear resistance.

Multi-layer windows are popular in architectural applications. The layered systems according to the invention are suitable for ordinary sealants used in making these windows and therefore overcome this problem to the same extent as the known layered system.

According to the invention, the method of producing laminated glass in the form of a thin, durable layer system for regulating solar radiation on a glass substrate is that the layers are cathodically sputtered onto the glass substrate in the following order: in the nitrogen-containing atmosphere, the lower layer of SbN4, then in the nitrogen-containing atmosphere, the first nickel-chromium alloy layer, then in the same atmosphere as in the previous stage at least one silver layer, then in the same atmosphere as in the previous two stages a second layer of nickel-chromium alloy, and an upper layer of Si3N4 in a nitrogen-containing atmosphere.

The layers are cathodically sputtered in a plurality of zones isolated from each other, with the Si3N4 layers cathodically sputtered in at least two separate zones, in an atmosphere of essentially 100% N2. Ni: Cr and silver nitride layers are cathodically sputtered in the same zone i

175 403 in an atmosphere consisting essentially of a mixture containing about 75% Ar and 100% -25% N by volume₂.

A mixture of Ar and N is used₂ about 50% by volume of each gas.

Tubular electrodes consisting essentially of silicon are used for the production of the S13N4 layer by sputtering and flat electrodes for the production of Ni: Cr nitride and silver layers of nichrome and silver, respectively.

A permeability greater than 80% is obtained.

Normal emissivity En 0.10 or less and hemispherical emissivity Eh 0.13 or less are obtained.

A sheet resistance of 10.5 ohms / square or less is obtained.

The steps for creating the first and second layers of nickel-chromium alloy are carried out until a layer with a thickness of 7 A is achieved, and the stage of forming a silver layer is carried out until a layer or layers with a total thickness of 90-150 A.

Layers of five layers produced in subsequent stages are most commonly used.

In another embodiment, a layer system of seven layers is used, and the steps of forming the first and second nickel chromium alloy layers and the silver layer or layers are conducted in such a way as to form at least two silver layers with an intermediate layer of nickel and chromium nitride between them .

The Si layers are sputtered preferably in an atmosphere containing a mixture of argon and N₂.

According to the invention, for some preferred layer systems, not only is it unnecessary to isolate silver from N 2 during sputtering, but it is preferable to introduce sputtering of both silver and base nickel together in such an environment. There is no significant loss of performance for Ag. If the nickel-based layer contains chromium and this chromium is converted to nitride during sputtering, the permeability is improved. In preferred embodiments of the invention, the Ni-based alloy is a Ni: Cr and Cr alloy during sputtering is converted (at least in part) to chromium nitride in the same sputtering zone along with silver. This significantly increases the visible transmission in the final product. In addition, by producing this nitride in the same zone where silver sputtering occurs, the cost is reduced and productivity is increased.

Improved efficiency and reduced costs, compared with the known method, are determined as follows: In the known method, Si sputtering is difficult and slow, because the power must be increased, because the atmosphere used is 100% N₂. Assuming that silver does not need to be sputtered in an N2-containing environment and when converting Cr to nitride, Ni: Cr electrodes would have to be introduced into separate zones, which is a hindrance. Sputtering in the same N2-containing zones as well as Si is a variation, but this slows down the process due to the reduction in the number of Si electrodes available for use. According to the invention, it is both beneficial to form chromium nitride and the presence of N2 does not adversely affect silver during sputtering, thus eliminating the need for inefficient and costly methods, since Ni: Cr electrodes can now be installed in the same zone as the silver electrode and sputtering can now be carried out in an Ar / N2 atmosphere, as opposed to a pure argon atmosphere, which was previously considered necessary. Therefore, preferred embodiments of the invention utilize a 50/50 volume A / N2 atmosphere, although a wide range between 0% -75% Ar and 100% -25% N2 is acceptable.

Sputtering of Si according to known methods takes place in a 100% N2 environment. However, under certain conditions (e.g. small unit, small production), argon can be added to N2 during sputtering in the process of the invention to improve the sputtering rate of Si while still creating an acceptable amount of Si3N4.

Sputtering of the coating on electrodes made of Ni: Cr / Ag / Ni: Cr occurs in the same area, using an atmosphere containing enough N2 to produce nitride from Cr. In some embodiments, the cathodic sputtering of the bottom layer and top layer is performed under a 100% N2 atmosphere, while in other argon can

175 403 can be used in amounts of around 3% -50% by volume together with N2 to increase efficiency.

The invention makes it possible to use a highly efficient cathodic sputtering process to obtain, for example, architectural glass, which not only has durability equal to pyrolytic coatings, but which also achieves excellent quality and the ability to regulate permeable solar radiation.

An advantage of the invention is to provide a sputtered layered system whose durability is equal to the durability of pyrolytic coatings, which also achieves optimal solar radiation control characteristics and is simpler than the pyrolytic method.

The subject of the invention is shown in the embodiments of the drawing, in which fig. 1 schematically shows a known device which is used to carry out the method according to the invention, fig. 2 - known arrangement of layers in a partial side view in cross section, fig. 3 - first embodiment Layer Layer of the Invention in Partial Side View in Section, Figure 4 - Second Embodiment of Layer Layer of the Invention in Partial Side View in Section.

Figure 1 shows a known magnetron sputtering device. According to the invention, five zones 1, 2, 3, 4, 5 are preferably used. In zones 1, 2,4 and 5 silicon electrodes t are used, and the sputtering is carried out in an atmosphere of 100% N2. Zone 3 usually uses flat P electrodes and is used to produce three intermediate layers, i.e. Ni: Cr / Ag / Ni: Cr. The layers are successively applied to the glass G as it rises in the direction of arrow A. Zone 1 contains six tubular ii-6 electrodes made of silicon (Si) (e.g. Si doped with 3-5% Al by weight to allow conduction). Zone 2 contains six further tubular electrodes ¢ 7-12 of the same material. Similarly, zones 4 and 5 each contain six further € 19-24 and t25-30 tubular electrodes of the same material.

The central zone 3 is preferably formed of either three flat P1-3 electrodes (31.16 and 33) to produce a five-layer system, such as shown in Figure 3, or five or six tubular or flat type electrodes to form a seven-layer system, such as shown in Fig. 4. Such a triple planar electrode system can also be used to make the known layered system of Fig. 2. The electrode system for the seven-layer system of Fig. 4 in zone 3 it is possible to choose by a specialist. Assuming that the availability of the positions of six electrodes in zones 1-2 and 4-5 is typical for this device, using a small thickness of the three required layers based on nickel (e.g. nichrome), electrodes 31 and 33 (i.e. P1 and P3) are used as nickel-based electrodes and instead of electrode 16 (i.e. P2) the sequence of electrodes between objects P1 and P3 is used, where 113 is silver, here based on nickel, and either <15 or ti6 are silver.

During operation, zones 1-5 are separated by appropriate C-apertures, establishing a controlled atmosphere in each zone. Until now it was believed that when using silver as an electrode in the sputtering operation, it is important to maintain its zone, i.e. zone 3, as devoid of N2. In the known method of Fig. 2, 100% Ar is defined as the preferred atmosphere. It was also thought that Si sputtering should be 100% N2.

Figure 2 shows a known system of layers produced by a known method. The glass substrate G is preferably a glass sheet with a thickness of about 2 mm - 6 mm, made, for example, by flowing from a conventional soda-lime-quartz set. In zones 1-2, a first bottom layer 111 consisting essentially of was formed

100% N2. Zone 3 was then used, using an atmosphere of essentially 100% argon, to first produce a relatively thick (e.g., 7 A or more) layer 113 of 80/20 nichrome, followed by a relatively thin (e.g., 70 A), rather discontinuous silver layer 115, the discontinuity of which is represented by gaps 117. In the same zone 3 another, relatively thin (e.g., 7 A or more) layer 80 and 80/20 nichrome 119 was then applied to silver. Then, in zones 4-5, an upper layer 121 of S13N4 with a thickness slightly greater than the thickness of the upper layer 111 (e.g. 450 A) was formed.

Figure 3 shows two embodiments of the invention that can be implemented using the device of Figure 1. There are five layers formed on the substrate G of flowing

175 403 glass (2 mm - 6 mm thick). First layer 211 is with SisNa and is produced in zones

1-2 using essentially 100% N2 atmosphere. Optimally under certain conditions (for example, when the dimensions are smaller), for example, some argon may be introduced into zone 2 to increase Si sputtering. Layers 213 (213 '), 215 and 219 (219') are then produced in zone 3.

In one embodiment of the invention, the atmosphere used in zone 3 contains substantially 100% argon and the object P1 / 31 / is preferably 80/20 nichrome, although it may be nickel or other nickel-based alloy. In order to obtain improved solar radiation control characteristics, and thus overcome the problems associated with the product of Fig. 2, layer 213, which is essentially a purely metallic layer, has a thickness of less than 7 A. This is done by reducing the power by about 20% or more for the object P / 31 / compared to the one used in the manufacture of the product of Fig. 2. Then the silver layer 215 produced from the P / 16 / electrode is preferably thickened (e.g. to 90-105 A), compared to layer 115, and forms a layer 215 substantially continuous. This is achieved by increasing the power for the P2 object by about 20% -33% or more, compared to the power used for layer 115.

Next, layer 219 is made of substantially pure 80/20 (or other nickel-based) nichrome in the same way as layer 213, and with the same thickness. Then follows in zones 4 and 5 of the upper layer 221 with SisNa in a similar manner as for the lower layer 211. Layer 221 is usually slightly thicker than layer 211 (for example, 540 A compared to 400 A for layer 211). Although sometimes the thickness of the upper and lower layers of S13N4 (e.g. 211 and 221 or 311 and 321 described below) according to the invention may be the same as in a known article (e.g. 111 and 121), in preferred embodiments each is thickened. This is achieved by increasing the power of the sputtering apparatus in zones 1-2 and 4-5 by approximately 20% or more. The final layer system has approximately the same durability as the layer system of the product of Fig. 2, with slightly lower scratch resistance, but much higher emissivity, permeability and strength of the product sheet, while the permeabilities approach 80%, and the emissivity and Rs values ​​are much lower.

In another, particularly preferred embodiment of Fig. 3, a unique method using the device of Fig. 1 is used and even better solar radiation control properties are achieved. This method includes the same basic steps as in the first embodiment, except that N2 gas with argon in zone 3 and a nickel chromium alloy is used as one or preferably both of the electrodes P1 / 31 / and P31331 so that the chromium metal is deposited as its nitride in the layer (s) Ni: Cr, i.e. as one or both layers 213 'and / or 219'. The argon to N2 ratio varies as needed, and the volume ratio of 0% -75% Ar to 100% -25% N2 and preferably 50% -50% Ar to N2 give improved characteristics (e.g., better throughput and R_s), even when compared with the first embodiment of the invention. Preferably, the thicknesses are the same as in the first embodiment.

The layer system of Fig. 4 is produced by applying nickel-based layers as essentially purely metallic layers, using an argon medium containing N2 and a nickel chromium alloy as one or more electrodes, whereby improved results are obtained by producing chromium nitride in one or more layers of Ni: Cr. In this embodiment, the single silver layer 215 of Fig. 3 is divided into two layers of silver, with a nickel-based layer between them. The embodiment of Fig. 4 is implemented using the correct number of electrodes (not shown) in zone 3, by forming in zones 1-2 of the lower layer 311 with Si3N4 and in zones 4-5 of the upper layer 321 with Si3N4. It is preferred to use the same thickness of layers 311 and 321 as layers 211 and 221.

Figure 4 differs from Figure 3 mainly in that in zone 3, a metallic layer 313 based on nickel (i.e., preferably 80/20 nichrome) is first produced or its substitution with nitride 313 'with a thickness less than 7 A. Then a first layer is produced 315A from silver with a thickness of 50 A, followed by another metallic layer 314 based on nickel or its substitution with 314 'nitride less than 7 A. Thickness then a second layer is produced

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315B of silver with a thickness of about 50 A, followed by another metallic layer 319 based on nickel or its substitution with 319 'nitride less than 7 A. The total thickness of the combined silver layers is preferably 90-105 A. The system ends with an upper layer 321 with S13N4.

When, in the embodiment of Fig. 4, each of the layers 315A, B of silver is only 50 A thick, discontinuities represented by gaps 317 appear, as do the gaps 117 of Fig. 2. Such discontinuities do not occur in the embodiment of fig. 4.

The seven-layer system of Fig. 4 is more durable than in the two embodiments of Fig. 3, and although it has lower permeability than in these embodiments, slightly higher than the minimum level of 76%, its emissivity and Rs values ​​are better than in the embodiments of Figure 3 by separating the silver into two layers in combination with the use of an intermediate layer based on Ni, e.g. Ni: Cr. An intermediate Ni-based layer is an important functional layer that helps achieve greater durability, especially when it is in the form of a Ni: Cr alloy, e.g. 80/20 nichrome, where chromium has been transformed into its nitride.

A typical, standard layering arrangement shown, for example, in Fig. 2 and two examples of embodiments of the system, shown for example in Fig. 3, were produced using the device of Fig. 1. The first embodiment of the invention is discussed as type A, and the second, when the nitride is produced in both layers 213 'and 219'; is referred to as type B. The electrodes used were tubular aluminum doped electrodes for 1u2 and 119.30. The electrodes Pi / 31 / and P3 / 33 / were 80% Ni and 20% Cr by weight. The electrode P2 / 16 / was made of silver. The glass used was ordinary soda-lime-quartz glass, produced in the flow process and having a thickness of 3 mm. The line speed used was 876 cm / min. The pressure in zones 1-2 and 4-5 was 2.5x10'3 T. In these zones, 100% N2 atmosphere was used. In zone 3 there was a pressure of 2.0x10 3 T. For the known system and type A according to the invention, a 100% argon atmosphere was used. For type B, 50% Ar / 50% N2 atmosphere was used. The power supply for each electrode was as follows:

Table 1

<td colspan="4">Types A and B, zones 1-2 and 4-5</td>

<td>Electrode No.</td><td>Volts / V /</td><td>Ampery / A /</td><td>Power / kW /</td>

<td> 1</td><td> 470</td><td> 124</td><td> 58, 0</td>

<td> 2</td><td> 481</td><td> 115</td><td> 55, 5</td>

<td> 3</td><td> 431</td><td> 21</td><td> 8, 9</td>

<td> 4</td><td> 446</td><td> 123</td><td> 55, 0</td>

<td> 5</td><td> 446</td><td> 124</td><td> 55, 5</td>

<td> 6</td><td> 449</td><td> 124</td><td> 55, 5</td>

<td> 7</td><td> 440</td><td> 123</td><td> 54,1</td>

<td> 8</td><td> 449</td><td> 130</td><td> 58,2</td>

<td> 9</td><td> 429</td><td> 123</td><td> 52,7</td>

<td> 10</td><td> 420</td><td> 123</td><td> 51,5</td>

<td> 11</td><td> 479</td><td> 30</td><td> 14,3</td>

<td> 12</td><td> 450</td><td> 112</td><td> 50, 4</td>

175 403 cont. table 1

<td></td><td>Types A and B</td><td>and, zones 1-2 and</td><td> 4-5</td>

<td>Electrode No.</td><td>Volts / V /</td><td>Ampery / A /</td><td>Power / kW /</td>

<td> 19</td><td> 425</td><td> 136</td><td> 57,5</td>

<td> 20</td><td> 444</td><td> 135</td><td> 60, 0</td>

<td> 21</td><td> 453</td><td> 129</td><td> 50, 6</td>

<td> 22</td><td> 426</td><td> 130</td><td> 55, 0</td>

<td> 23</td><td> 415</td><td> 104</td><td> 43, 1</td>

<td> 24</td><td> 441</td><td> 135</td><td> 59, 5</td>

<td> 25</td><td> 458</td><td> 35</td><td> 16, 1</td>

<td> 26</td><td> 477</td><td> 138</td><td> 65, 6</td>

<td> 27</td><td> 455</td><td> 133</td><td> 60,5</td>

<td> 28</td><td> 478</td><td> 137</td><td> 58, 6</td>

<td> 29</td><td> 447</td><td> 86</td><td> 38,2</td>

<td> 30</td><td> 429</td><td> 86</td><td> 36, 8</td>

Table 2

<td colspan="4">Type Al, zone 3</td>

<td>Electrode No.</td><td>Volts / V /</td><td>Ampery / A /</td><td>Power / kW /</td>

<td> 31</td><td> 390</td><td> 2, 6</td><td> 1,0</td>

<td> 16</td><td> 447</td><td> 22, 8</td><td> 10, 2</td>

<td> 33</td><td> 392</td><td> 2, 6</td><td> 1,0</td>

175 403

Table 3

<td colspan="4">Type B, zone 3</td>

<td>Electrode No.</td><td>Volts / V /</td><td>Ampery / A / *</td><td>Power / kW / *</td>

<td> 31</td><td> 403</td><td> 5, 0</td><td> 2,0</td>

<td> 16</td><td> 446</td><td> 32</td><td> 14,2</td>

<td> 33</td><td> 400</td><td> 5,1</td><td> 2,0</td>

* Power, amps and volts must be greater for a certain layer thickness when nitride is produced.

Table 4

<td colspan="3">Standard layering /, zones 1-5</td>

<td>Electrode No.</td><td>Ampery / A /</td><td>Power / kW /</td>

<td> 1</td><td> 80</td><td></td>

<td> 2</td><td> 80</td><td></td>

<td> 3</td><td> 80</td><td></td>

<td>4 Zone 1</td><td> 80</td><td></td>

<td> 5</td><td> 80</td><td></td>

<td> 6</td><td> 80</td><td></td>

<td> 7</td><td> 80</td><td></td>

<td> 8</td><td> 80</td><td></td>

<td>9 Zone 2</td><td> 80</td><td></td>

<td> 10</td><td> 80</td><td></td>

<td> 11</td><td> 80</td><td></td>

<td> 12</td><td> 80</td><td></td>

175 403 cont. table 4

<td colspan="3">Standard layering, zones 1-5</td>

<td>Electrode No.</td><td>Ampery / A /</td><td>Power / kW /</td>

<td> 31</td><td> 3, 8</td><td> 1,5</td>

<td>16 Zone 3</td><td> 18,4</td><td> 8,1</td>

<td> 33</td><td> 3,8</td><td> 1,5</td>

<td> 19</td><td> 135</td><td></td>

<td> 20</td><td> 105</td><td></td>

<td> 21</td><td> 125</td><td></td>

<td>22 Zone 4</td><td> 125</td><td></td>

<td> 23</td><td> 105</td><td></td>

<td> 24</td><td> 25</td><td></td>

<td> 25</td><td> 125</td><td></td>

<td> 26</td><td> 120</td><td></td>

<td>27 Zone 5</td><td> 50</td><td></td>

<td> 28</td><td> 110</td><td></td>

<td> 29</td><td> 110</td><td></td>

<td> 30</td><td> 80</td><td></td>

175 403

Table 5

<td colspan="5">Comparative results</td>

<td>System</td><td>layers</td><td>Radiation transmittance visible</td><td>Reflection / Rg / from the side glasses</td><td>Reflection / R_f/ from the side shell</td>

<td>Type A</td><td>Y /% /</td><td> 78, 75</td><td> 8,42</td><td> 4,08</td>

<td>Ośw.C</td><td>X</td><td> 0,3097</td><td> 0,2610</td><td> 0,2449</td>

<td>2 ° EIA.</td><td>s</td><td> 0,3192</td><td> 0,2722</td><td> 0,2427</td>

<td></td><td>and*</td><td> -1, 69</td><td> -1, 64</td><td> + 1,64</td>

<td></td><td>b *</td><td> + 1, 03</td><td> -11,57</td><td> -14,68</td>

<td>Type B</td><td>Y</td><td> 79, 57</td><td> 7, 56</td><td> 3,75</td>

<td>Ośw.C</td><td>X</td><td> 0,3089</td><td> 0, 2641</td><td> 0,2559</td>

<td>2 ° obs</td><td>Y</td><td> 0,3190</td><td> 0,2709</td><td> 0,2441</td>

<td></td><td>and*</td><td> -1, 98</td><td> -0,40</td><td> + 3, 77</td>

<td></td><td>b *</td><td> + 0, 84</td><td> -11,19</td><td> -13,45</td>

<td colspan="2">conventional layering Y</td><td> 76, 45</td><td> 8,26</td><td> 5, 09</td>

<td>Ośw.C</td><td>X</td><td> 0,3078</td><td> 0, 2626</td><td> 0,2723</td>

<td>2 ° obs.</td><td>Y</td><td> 0,3163</td><td> 0,2801</td><td> 0,2857</td>

<td></td><td>and*</td><td> -1,19</td><td> -3, 25</td><td> -1,76</td>

<td></td><td>b *</td><td> -0, 30</td><td> -9, 88</td><td> -6, 95</td>

175 403

Table 6

<td colspan="4">Comparative results</td>

<td>Layer system</td><td>en</td><td>E_h</td><td>R_s/ Ohms / square /</td>

<td>Type A</td><td> 0, 10</td><td> 0,13</td><td> 10, 0</td>

<td>Type</td><td> 0,10</td><td> 0,13</td><td> 9,4</td>

<td>Standard Layer Layer</td><td> 0,16</td><td> 0,20</td><td> 15, 8</td>

As two other examples of the invention to demonstrate the effect of layer thicknesses, particularly Ni-based layers, on the transmission and reflection of infrared radiation, two type B glasses were made using essentially identical conditions in zones 1 and 2 and in zones 4 and 5, the lower and the upper S13N4 layer were produced under 100% N2 atmosphere. The electrodes in zones 1, 2.4 and 5 were Si electrodes with an admixture of aluminum Al, while the electrodes P1 / 31 / and P3 / 33 / were from nichrome 80/20, and the electrode P2 / 16 / was silver. The only difference was that in Zone 3 different power levels were used, as shown in the following table. The glass was made in the flow process as a 3 mm thick soda-lime-quartz glass.

Table 7

<td colspan="8">Zone 3, atmosphere Ar / N2 = 50/50</td>

<td colspan="5">Electrode / kW /</td><td colspan="3">Permeability /Ośw.C/</td>

<td>Pi / 31</td><td>P 2/16 /</td><td>P3 / 33</td><td>rs</td><td>Eh</td><td>Y%</td><td>and*</td><td>b *</td>

<td></td><td></td><td></td><td>Glass</td><td>No. 1</td><td></td><td></td><td></td>

<td> 1,5</td><td> 15, 0</td><td> 1,5</td><td> 8,3</td><td> 0,11</td><td> 80, 97</td><td> -1, 88</td><td> + 1, 13</td>

<td></td><td></td><td></td><td>Glass</td><td>No. 2</td><td></td><td></td><td></td>

<td> 2,0</td><td> 14,0</td><td> 2,0</td><td> 9,1</td><td> 0,12</td><td> 80, 02</td><td> -1,71</td><td> + 0,70</td>

175 403

By slightly increasing the thickness of two layers of Ni: Cr nitrides and by slightly reducing the thickness of the silver layer, infrared reflection and transmittance values ​​are reduced. Both of these glasses are beneficial when used in multi-pane architectural windows.

The following examples of type A glass were manufactured using different power levels in different zones, and the glass was standard glass from Table 7 above and was 3 mm thick.

Table 8

<td rowspan="2">Glass No.</td><td rowspan="2">Electrode No.</td><td rowspan="2">Ampera</td><td rowspan="2">kW</td><td rowspan="2">rs</td><td rowspan="2">Eh</td><td colspan="3">Transmittance (Culver)</td>

<td>Y%</td><td>and*</td><td>b *</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>

<td> 1</td><td> 1-12,19-30</td><td> 85</td><td></td><td> 9,6</td><td> 0,13</td><td> 77,11</td><td> -2,28</td><td> -1,53</td>

<td></td><td> 4</td><td> 35</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 31</td><td> 2,9</td><td> 1,1</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 16</td><td></td><td> 10,2</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 33</td><td> 2,9</td><td> 1,1</td><td></td><td></td><td></td><td></td><td></td>

<td> 2</td><td> 1-3,5-12</td><td> 85</td><td></td><td> 10,3</td><td> 0,14</td><td> 78,02</td><td> -2,38</td><td> -1,56</td>

<td></td><td> 19-30</td><td> 85</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 4</td><td> 35</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 31</td><td> 2,6</td><td> 1,0</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 16</td><td></td><td> 10,2</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 33</td><td> 2,6</td><td> 1,0</td><td></td><td></td><td></td><td></td><td></td>

<td> 3</td><td>H</td><td></td><td></td><td> 10,0</td><td> 0,13</td><td> 77,84</td><td> -2,45</td><td> -1,66</td>

<td></td><td> 16</td><td></td><td> 10,4</td><td></td><td></td><td></td><td></td><td></td>

<td> 4</td><td></td><td></td><td></td><td> 9,8</td><td> 0,13</td><td> 79,41</td><td> -2,13</td><td> -0,30</td>

<td></td><td> 19-30</td><td> 105</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 5</td><td> 1-3,5-12</td><td> 90</td><td></td><td> 9,8</td><td> 0,13</td><td> 79,20</td><td> -2,10</td><td> -0,40</td>

<td></td><td> 19-30</td><td> 90</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 4</td><td> 40</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 6</td><td></td><td></td><td>II</td><td> 9,8</td><td> 0,13</td><td> 79,48</td><td> -1,95</td><td> +0,17</td>

<td></td><td> 19-30</td><td> 115</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 7</td><td> 1-3,5-12</td><td> 95</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 19-30</td><td> 115</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 4</td><td> 40</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 31,16,33</td><td></td><td></td><td> 9,7</td><td> 0,12</td><td> 79,61</td><td> -1,89</td><td> +0,05</td>

<td> 8</td><td></td><td></td><td>H</td><td> 9,7</td><td> 0,13</td><td> 79,78</td><td> -1,81</td><td> +0,31</td>

<td></td><td> 19-30</td><td> 120</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 4</td><td> 40</td><td></td><td></td><td></td><td></td><td></td><td></td>

175 403 cd table 8

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>

<td></td><td> 31,16,33</td><td></td><td>II</td><td> 9,8</td><td> 0,13</td><td> 79,95</td><td> -1,80</td><td> +0,15</td>

<td> 10</td><td> 1-3,5-10,12</td><td> 105</td><td></td><td> 9,8</td><td> 0,13</td><td> 79,48</td><td> -1,68</td><td> +0,66</td>

<td></td><td> 19-30</td><td> 125</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 4</td><td> 95</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 11</td><td> 30</td><td></td><td></td><td></td><td></td><td></td><td></td>

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

<td> 11</td><td></td><td>H</td><td>II</td><td> 9,7</td><td> 0,12</td><td> 79,66</td><td> -1,74</td><td> +0,62</td>

<td> 12</td><td> 1-:2,5-10,12</td><td> 107</td><td></td><td> 10,1</td><td> 0,13</td><td> 79,76</td><td> -1,61</td><td> +0,68</td>

<td></td><td> 3,4</td><td> 47</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 11</td><td> 32</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 19-30</td><td> 125</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 31,33</td><td></td><td> 1,0</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 16</td><td> 10,2</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 13*</td><td></td><td></td><td>II</td><td> 9,9</td><td> 0,13</td><td> 79,60</td><td> -1,62</td><td> +0,64</td>

* This glass is particularly suitable for use on laminated windows.

175 403

<img file="PL175403B1_D0001.tif" />

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