Coatings on glass

Field of application of the invention

The invention relates to a method for producing a coating on a glass surface, in which an underlayer is applied to the glass surface, via which further layers can be applied. They are preferably used in the manufacture of float glass.

Characteristic of the known prior art

GB-PS 2031756B discloses thin, transparent, infrared-reflecting semiconductor coatings which are suitable for improving the insulation properties of windows and which, electrically conductive, can serve as resistance heating, for example for removing ice or condensation on windows. According to this patent, the use of such coatings is restricted by being iridescent in color, especially with reflected light. These iridescent effects are widely regarded as aesthetically unsatisfactory, and the problem is compounded by the change in iridescent color that occurs with small changes in coating thickness. From GB-PS 2031756B it is known, in order to overcome the iridescence problem, to apply a corresponding underlayer preventing the iridescence under the half-liter coating, the preferred form of the underlayer being its layer with a rofraction indox in the range from 1.7 to 1.8 and a thickness in the range from 64 nm to ^ri0nm is used. According to GB-PS 2 031756 B the underlayer can be produced by jointly depositing a mixture of components, which is calculated in such a way that it achieves the required refractive index, for example a mixture of 84 ± 3% silicon nitride and the rest silicon dioxide, designated as silicon nitride.

Such silicon oxynitride films can be obtained by chemical vapor deposition from a silicon supplier, for example SiH₄, (CH₃I.₂SiH₂, (C₂H₆I.₂SiH ^ (CHj)₄Si, SiCI₄, SiBr₄; an oxygen supplier, for example O₂, H₂O, N₂O and a nitrogen supplier, for example N₂H₄, NH₃, HNj, CH₃NHNH₂ (CH₃I.₂NNH₂, or an oxygen and nitrogen supplier NO, NH₂OH, N₂H₄ H₂O, on hot glass at a temperature of 500 to 600⁰C are formed. Although it is necessary to have an appropriate iridescence-reducing underlayer, the compositions thereof disclosed in GB 2031756B have become commercially important. This can be explained by the difficulties that have arisen in particular as a result of the long deposition times required to produce an underlayer of sufficient quality and strength using the known methods.

GB-PS 2163146 A discloses a method for producing barrier coatings on a glass surface to prevent the migration of alkali metal ions into an overlying layer which is sensitive to alkali metal ions, for example indium tin oxide. This involves a process for the production of transparent barrier layers with good light transmission and excellent barrier properties by pyrolysis of the silane on a hot glass surface of over 600⁰C in the presence of a gaseous electron donor compound, the presence of the electron donor compound being found as a result of the inclusion of oxygen from the glass in the coating, through which a transparent barrier layer of up to 50nm thick is formed on the glass surface. The electron donor compounds which can be used in the process of GB-PS 2163146 A are compounds which, either in bonds or as lonely electron pairs, contain electrons which can be released into the electron structure of suitable acceptor molecules. It has been found that the use of an electron donor compound to incorporate oxygen from the glass using silicon from the silane results in the formation of a transparent barrier layer on the glass. Although the mechanism is not clear, it is believed that the electron donor compound is adsorbed on the glass surface. It is preferred to use an oxygen-free electron donor compound, for example ethylene, or compounds generally considered reducing, although they contain some oxygen, such as carbon monoxide and alcohols.

Because the transparent barrier layers are made in the absence of free oxygen and compounds which are generally considered to be oxygens, the barrier layer can be applied to a ribbon of float glass as it is formed over a molten metal bath on which it is formed without the risk of oxidation of the molten metal.

However, while the use of acid-free electrode donor compounds reduces the risk of oxidation of the silicon before it reaches the glass surface and of the molten metal bath from which the glass ribbon is carried by the gas involved in the reaction, the glass has an insufficient ability to absorb oxygen for the formation of thicker, anti-iridescent sub-layers as described in GB-PS 2031756B. While thicker layers can be made using oxygen-containing electron donor compounds, for example carbon dioxide, it has been found that the use of a combination of silane and carbon dioxide either results in thin coatings with low durability, or a white cloudy precipitate occurs in attempts to increase the thickness of the coatings.

When trying to make barrier layers of very high transparency, for example with a light transmission of not less than 2% below that of the base glass, using a combination of silane and ethylene in accordance with GB-PS 2163146A, the barrier properties of the coatings result have insufficient consistency for some applications.

Aim of the invention

The aim of the invention is to develop a method for producing a coating on a glass surface so that it can be used inexpensively in an industrial float glass system and the utility properties of the glass products produced thereby have been increased .

State the nature of the invention

The invention has for its object to provide a method for producing a coating on a glass surface, in which an underlayer is applied to the glass surface, over which further layers can be applied, in which the underlayer reduces the iridescence and as a barrier against migration of alkali metal ions from the glass is effective, with a high degree of transparency.

It has now been found that this object can be achieved by directing a gaseous mixture of a silane, an ethylenically unsaturated hydrocarbon and carbon dioxide onto a hot glass surface in order to deposit a precipitate containing silicon and oxygen on the glass surface.

In accordance with the invention, the object is achieved in that the hot glass surface at a temperature of 600 to 76O⁰C is passed a gaseous mixture consisting of a silane, an unsaturated hydrocarbon compound and carbon dioxide, whereby a transparent layer containing silicon and oxygen is deposited on the glass surface. The lower layer produced by the method according to the invention acts as a barrier against the migration of alkali metal ions from the glass. It can push an overlying Sunic.it, which is sensitive to the migration of alkali metal ions from the glass and which is applied directly or indirectly to the underlayer. Proceeding from this, the solution according to the invention is further characterized in that it is possible to apply a layer which is sensitive to the migration of alkali metal ions from the glass over the lower layer.

In order to produce an infrared radiation reflecting and / or electrically conductive coating of reduced iridescence, it is advantageous to apply an infrared radiation reflecting and / or electrically conductive layer over the underlayer. This results in a further embodiment of the invention in that infrared radiation is reflective and / or

electrically conductive layer is deposited over the lower layer. This top layer can consist of a semiconductor metal oxide, for example a tin-doped indium oxide or doped tin oxide, especially a fluorine-doped tin oxide.

It is particularly advantageous that both the bottom layer and the top layer can be applied to float glass during its manufacture. In this case, the top layer can be a fluorine-doped tin oxide layer, applied by pyrolytic decomposition from a solid or from a liquid or else from a vaporous source, for example gaseous tin chloride in the presence of water vapor and hydrogen fluoride. The decomposition can take place when the float glass enters the cooling tunnel.

If the coating is to be used as an infrared reflecting coating, the infrared reflecting layer will usually have a thickness in the range from 200ηm to 500nm. Thicker layers, for example up to 10OOnm, can also be used, but they are generally not necessary because of the properties of Untorschic.it that reduce iridescence. If it is intended to conduct an electrical current through the coating, for example in the case of a resistance heater or a liquid crystal display, the thickness of the coating depends on the required electrical conductivity, but will usually be in the range from 100 nm to 100 nm.

The silane is preferably monosilane (SiH₄), although if desired also other substituted or unsubstituted silanes in gaseous form, for example dimethylsilane (CH₃I.₂SiH₂ and Disilan Si₂H₆, can be used.

The unsaturated hydrocarbon can be an ethylenically unsaturated hydrocarbon compound, an acetylenically unsaturated compound (e.g. acetylene) or an aromatic compound (e.g. toluene), although in general it is most advisable to use an ambient unsaturated hydrocarbon. The unsaturated hydrocarbon is preferably an olefin, especially an olefin having two to four carbon atoms. Ethylene is particularly preferred.

The proportions of the gas components that are present in the gaseous mixture and the flow rate of the gaseous mixture over the hot glass can be adjusted so that the bottom layer of the desired thickness and with the desired properties, ie with the corresponding refractive index, is obtained.

The carbon dioxide acts as an oxygen supplier, so that although only a small amount of oxygen is available from the glass surface, transparent layers with a thickness of up to 80 nm can easily be obtained.

In addition, by appropriately regulating the relative properties of the glass components present, an underlayer with a refractive index in the range from 1.7 to 1.8 can be obtained. According to a preferred embodiment of the invention, the proportions of the glass components which are present in the gaseous mixture for the application of the underlayer are regulated in such a way that in connection with the flow rate of the gaseous mixture over the hot glass, the application of an underlayer with a thickness in the range from 60 to 80 nm and a refractive index in the range from 1.6 to 1.8.

According to another embodiment of the invention, the proportions of the gas components that are present in the gaseous mixture for the application of the underlayer and the flow rate of the gaseous mixture over the hot glass regulate the application of an underlayer with a thickness and refractive index such that the the undercoated glass has a light transmission within 2% of the light transmission of the uncoated glass, the underlayer simultaneously being an effective barrier against the wall of alkali metal ions from the glass. The light transmission of the coated glass is preferably within 1% of the light transmission of the base glass. The term “effective barrier” is understood to mean that according to the test according to the method described here, the lower layer prevents the passage of no more than 100 and preferably no more than 60 micrograms of sodium, expressed as Na₂O per square decimeter of glass allowed.

In general, the higher the ratio of unsaturated hydrocarbon to silane, the thinner the coatings and the lower the refractive index of the coating. It is generally preferred to operate at a ratio of unsaturated hydrocarbon to silane that is in the range of 2: 1 to 5: 1 parts by volume, although ratios outside this range, for example 1: 1 to 8: 1 or higher , are applicable. It is believed that the unsaturated hydrocarbon is adsorbed on the glass surface, so in general the following applies: the more the unsaturated hydrocarbon is adsorbed on the glass, the lower the ratio of unsaturated hydrocarbons to silane required for a given action. The ratio of carbon dioxide to silane is preferably in the range from 2: 1 to 8: 1 by volume, although ratios outside this range, for example 1: 1 to 20: 1 (or even higher), can also be used . The higher ratios are generally only used when working at very low silane concentrations.

The gaseous mixture used will generally contain an inert carrier gas, for example nitrogen, in an amount of, for example, 10 to 90 parts by volume in% of the gaseous mixture.

Increasing the overall flow rate of the gaseous mixture of a given composition results in an underlayer with increased thickness. It was also found that the lower layer had a higher refractive index.

The glass preferably has a temperature in the range from 630 to 720 ° C. during the production of the coating.

The process according to the invention facilitates the continuous production of lower layers which reduce iridescence and of lower layers which serve as a barrier against the migration of alkali metal ions and which have a very high degree of transparency for visible light. Since the reactants used do not have a strong oxidizing effect, the process can moreover be applied to a float glass tape as it lies on the shaping molten metal bath without there being an undue risk of oxidation of the molten metal.

Export bolsplele

The invention is explained on the basis of several exemplary embodiments. These form favorable forms of concrete implementation, but the invention is not restricted to these. In the examples, all percentages are given in percentages by volume, unless stated otherwise. The gas flow rates were at 69kPa (10psi) and about 20⁰C measured. The refractive index and the thickness values ​​given for the underlayer were below

Application of thin film theory calculated from the wavelength and the value of the maximum reflection of the lower layer. The light transmission of the coated glass was expressed as dT; dT is the difference between the percentage of light transmission of the glass coated with the underlayer and the percentage of light transmission of the non-coated glass.

The effectiveness of the sublayers as barrier layers against the migration of alkali metal ions was determined using the following procedure. Two samples of the coated glass, each 10 cm ', were cut and clamped together with a round silicone rubber ring with an inner diameter of 8.6 cm, so that a cylindrical cell was formed, the walls of which were defined by the coated surface of the glass and the inner surface of the silicone rubber ring . The cell was filled with deionized water through a hole in the rubber ring, the hole was closed and the closed cell was immersed in a water bath at 96 ° C. for 48 hours. The solution was then removed and examined for sodium by flame emission spectroscopy. The sodium content was determined and as Miki ogremm Na₃O expressed per square decimeter of the glass exposed to the water in the cell.

example 1

A band of 6mm float glass, which was moved at a cooling tunnel speed of 322 m / h, was covered with an underlayer by directing a gaseous mixture onto the top surface of the glass as it was moved over the molten metal bath Place where the glass temperature is about 645⁰C was. Do:. gaseous mixture consisted of 11% monosilane, 23% ethylene, 23% carbon dioxide and 44% nitrogen as the carrier gas. The gaseous mixture was forced to flow parallel to the glass surface in the direction of the glass movement under laminar flow conditions, the path of the gaseous mixture over the glass surface being approximately 0.2 m. The flow rate of 'Jes gaseous mixture was 22 liters per minute per meter of coated glass.

A clear, essentially haze-free underlayer was formed on the glass surface with a thickness of 76.1 nm and a refractive index of 1.77.

Examples 2 and 3

The procedure of Example 1 was repeated with an increased flow rate of ethylene and carbon dioxide. This resulted in a slight reduction in both the thickness and the refractive index Jer formed. The process conditions and results obtained are listed in Table 1 with the corresponding information from Example 1 for comparison.

Examples 4 to 8

The procedure of Example 1 was repeated using different gas mixtures and changing the ratio of ethylene to carbon dioxide while maintaining both the ratio of monosilane to ethylene plus carbon dioxide and the overall gas flow rate. The procedural conditions and the results obtained are listed in Table 2.

The use of a high ethylene: silane ratio, as in Examples 4 and 5, leads to a very thin underlayer (less than 55 nm). Reducing the ratio of ethylsilane and increasing the ratio of carbon dioxide: silane initially increases the thickness of the underlayer (Examples β and T), but the thickness of the underlayer decreases when the ratio of carbon dioxide: Sflan to 8: 1 increases.

Examples 9 to 13

The procedure of Example 1 was repeated using a gaseous mixture containing 10% monosilane, 25% ethylene, 25% carbon dioxide and 40% nitrogen at different total flow rates. The results are shown in Table 3 (Examples 9 to 11). It has been found that both the thickness and the refractive index of the underlayer increase with increasing total flow rate.

The procedure of Example 9 was repeated with the same flow rates of silane, ethylene and carbon dioxide at increased nitrogen rates. The flow velocities used and the characteristics of the underlayers produced are listed in Table 3 (Examples 9, 13 and 14). The thickness of the sublayers has been found to decrease as the refractive index increases as nitrogen velocity increases.

Examples 14 to 19

In these examples, which were carried out in a manner similar to Example 1, underlayers were produced on 6 mm float glass under the conditions listed in TaLeIIe 4, and the refractive indices and thicknesses given in the table were found. Then, tin oxiride layers doped with fluorine were applied to the float glass tape over the underlayer by chemical vapor deposition from a gaseous mixture of tin chloride, water and hydrogen fluoride, specifically when it entered the cooling tunnel. The thickness of the tin oxide layers was measured, and the color coordinates of the light reflected from the coated side of the glass (CI.E.IIIuminant C) were measured and, in Examples 14 to 17, with the color coordinates of the reflected light from similar fluorine-doped tin oxide coatings without that Lower class.

; r ι »» r<i>'II</i>

compared. (The use of color coordinates to define the colors is described in "The Measurement of Appearances" by RS Hunter, published in 1975 by John Wiley &amp; Sons). The results obtained are shown in Table 5. Darb js can be seen that the sublayers show the Suppress reflection colors of the tin oxide layers.

Examples 20 to 23

The procedure of Example 1 was repeated using a gaseous mixture containing 10% silane, 20% ethylene, 30Vo carbon dioxide and 40% nitrogen, and glass being drawn over at a rate of 50 liters per minute per meter over a belt of 2.1 mm flowed float glass that pich moved at a cooling tunnel speed of 1130 meters per hour. The gaseous mixture was passed over the glass where the glass temperature was about 645 ° C. The glass was found to be coated with a layer that had a high degree of transparency; the coated glass had a light transmission which was only 1.1% lower than that of the non-coated glass. The effectiveness of the layer as a barrier against the migration of alkali was 90 micrograms Na₂O square decimeter of glass measured. The process was repeated using different gas compositions with a thickness of the float glass of 6 mm and 4 mm. The glass transition temperature at the coating point, the cooling tunnel speed of the strip, the gas composition and the flow speed together with the properties of the coated product are shown in Table 6. The comparison of Examples 21 and 22 shows that the increase in glass temperature and silane concentration and the reduction in the ratios of ethylene and carbon dioxide to silane were more than compensatory for the reduction in gas flow (from 55 to 24 liters / minute / meter) so that the coating formed in Example 22 was approximately twice as thick as the coating of Example 21. A good barrier effect was seen in all examples, with the underlayer of Example 22 giving the highest light transmission relative to the light transmission of the uncoated glass.

Examples 24 to 30

These examples illustrate the use of butene as an unsaturated hydrocarbon with silane and carbon dioxide to make color-suppressing sub-layers and barrier layers in the context of the invention. The examples were carried out using the method described in Example 1, but only a narrow glass strip was coated at the end of the float glass strip. The float glass was 6 mm thick, moved at a cooling tunnel speed of 360 meters / hour and was coated at a point where the glass temperature was 685 ° C. The conditions, the gas composition and the flow rates used, as well as the properties of the sublayers produced are listed in Table 7.

Satisfactory color suppression layers were made with a thickness in the range of 60nm to 80nm and a refractive index in the range of 1.6 to 1.8 in Examples 25 to 27, the results of Example 24 being just outside these ranges. Examples 28 to 30, which were carried out at lower flow rates, gave thinner coatings with excellent barrier properties, the coated glass having a light transmittance close to that of the uncoated glass. When comparing Examples 24 to 30 with the previous examples, it should be noted that higher overall gas velocities are subsequently required in order to produce coatings of similar thickness. This is believed, at least in part, to be so in the process of Examples 24-30, which was carried out on a narrower glass strip, because of the significant gas loss on the sides of the coated strip.

Examples 31 to 36

Solid samples of 3mm float glass (10 χ 10cm) were coated in the laboratory by heating the glass in a quartz tube at a temperature of about 650 ° C and passing a coating gas over the hot glass surface, the gas consisting of a mixture of silane, carbon dioxide and unsaturated Hydrocarbon and nitrogen existed. The gas compositions used and the treatment times are listed in Table 8 together with the measurement results of the light transmission and the barrier properties of the coated products. Good barrier effects were achieved with each of the hydrocarbon gases used, with a high degree of transparency (within 1% deviation from the transparency of the uncoated glass).

Examples 37 to 40

The procedure of Example 1 was repeated using a gaseous mixture of silane, ethylene and carbon dioxide in nitrogen to coat 2mm float glass which was moving at a cooling tunnel speed of 1100 meters / hour. The light transmittance of the glass was measured and compared with the license transmittance of the uncoated glass to determine the difference dT. The barrier effect of the glass was determined as described above. The

The thickness of the coatings was too small for the optical measurement described above, so the measurement was carried out using an argon ion etching technique.

The coating conditions and results are shown in Table 9.

Examples 37-40 illustrate the production of barrier layers so that the coated glass had a light transmission within 1.5% of the light transmission of the uncoated glass (dT). The final comparative examples show that in the absence of carbon dioxide, the light transmission is significantly lower (dT = 2.3%), although the underlayer is actually thicker than the underlayer produced in Examples 37 and 39. A comparison of Examples 37 and 38 shows that increasing the ratio of dopants (ethylene and carbon dioxide) to silane reduced the thickness of the underlayer while improving the light transmittance but reducing the sputtering effect. A slight reduction in the ratio of dopants to silane (Comparative Examples 37 and 39) reduced the light transmission, while the thickness and barrier effect remained the same. The reduction in ethylene and a substantial increase in carbon dioxide (Example 40) reduced the thickness and increased the permeability to Li, but led to a substantial reduction in the barrier effect.

The preceding examples show that by regulating the gas component proportions used in the gaseous mixture of the process according to the invention and the flow rate of the gaseous mixture over the hot glass surface, sublayers of the desired thickness and refractive index can be produced. The method according to the invention is thus not only useful for the production of color-suppressing underlayers as described in the characteristic of the known prior art GB-PS 2031756B, but also for the production of other color-suppressing underlayers which are also known from the prior art , as well as for sub-layers with a high degree of transparency, which is useful for their blocking properties.

<table><tgroup cols="23"><tbody><row><entry>Table 1</entry><entry>Glass ribbon</entry><entry>Glass</entry><entry>Gns composition (%)</entry><entry>C.₂H₄</entry><entry>CO₂</entry><entry>N₂</entry><entry>Gas composition (%)</entry><entry>C.₂H₄</entry><entry>CO₂</entry><entry>N₂</entry><entry>Gas composition (%)</entry><entry>C.₂H₄</entry><entry>CO₂</entry><entry>N₂</entry><entry>Gas composition (%)</entry><entry>C.₂H₄</entry><entry>CO₂</entry><entry>N₂</entry><entry>Gas flow</entry><entry>Lower class</entry><entry>thickness</entry><entry>72,4</entry></row><row><entry>example</entry><entry>speed.</entry><entry>temperature</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>(Liters / min /</entry><entry></entry><entry>(nm)</entry><entry>78,9</entry></row><row><entry></entry><entry>!. Cooling tunnel</entry><entry></entry><entry>SiH₄</entry><entry>23</entry><entry>23</entry><entry>44</entry><entry>SiH₄</entry><entry>53</entry><entry>13</entry><entry>27</entry><entry>SiH₄</entry><entry>25</entry><entry>26</entry><entry>40</entry><entry>SiH₄</entry><entry>22</entry><entry>22</entry><entry>47</entry><entry>Meters width)</entry><entry>Refract.</entry><entry>76,1</entry><entry>65,8</entry></row><row><entry></entry><entry>(m / h)</entry><entry></entry><entry></entry><entry>28</entry><entry>28</entry><entry>37</entry><entry></entry><entry>44</entry><entry>22</entry><entry>27</entry><entry></entry><entry>25</entry><entry>25</entry><entry>40</entry><entry></entry><entry>24</entry><entry>24</entry><entry>45</entry><entry></entry><entry>indax</entry><entry>73,7</entry><entry></entry></row><row><entry></entry><entry>322</entry><entry>645 ° C</entry><entry>11</entry><entry>29</entry><entry>29</entry><entry>33</entry><entry>7</entry><entry>33</entry><entry>33</entry><entry>27</entry><entry>10</entry><entry>25</entry><entry>25</entry><entry>40</entry><entry>9</entry><entry>24</entry><entry>24</entry><entry>45</entry><entry>22</entry><entry>1,77</entry><entry>73,6</entry><entry></entry></row><row><entry>1</entry><entry>322</entry><entry>645⁰C.</entry><entry>9</entry><entry></entry><entry></entry><entry></entry><entry>7</entry><entry>22</entry><entry>44</entry><entry>27</entry><entry>10</entry><entry>22</entry><entry>22</entry><entry>48</entry><entry>8</entry><entry>29</entry><entry>29</entry><entry>34</entry><entry>26,25</entry><entry>1,70</entry><entry></entry><entry></entry></row><row><entry>2</entry><entry>322</entry><entry>645 ⁰C.</entry><entry>8</entry><entry></entry><entry></entry><entry>7</entry><entry>13</entry><entry>53</entry><entry>27</entry><entry>10</entry><entry>19</entry><entry>19</entry><entry>54</entry><entry>8</entry><entry>31</entry><entry>31</entry><entry>29</entry><entry>29</entry><entry>1,63</entry><entry></entry><entry>thickness</entry></row><row><entry>3</entry><entry></entry><entry></entry><entry></entry><entry>7</entry><entry></entry><entry></entry><entry></entry><entry>9</entry><entry></entry><entry></entry><entry></entry><entry>9</entry><entry>25</entry><entry>25</entry><entry>40</entry><entry></entry><entry></entry><entry></entry><entry>(nm)</entry></row><row><entry>Table 2</entry><entry>Glass ribbon</entry><entry>Glass</entry><entry></entry><entry>7</entry><entry></entry><entry></entry><entry>8</entry><entry></entry><entry></entry><entry>9</entry><entry></entry><entry></entry><entry></entry><entry>Gas flow</entry><entry>Lower class</entry><entry>thickness</entry><entry>76,0</entry></row><row><entry>example</entry><entry>quickly.</entry><entry>temperature</entry><entry></entry><entry></entry><entry>10</entry><entry></entry><entry></entry><entry></entry><entry>(Liters / min /</entry><entry></entry><entry>(nm)</entry><entry>81,9</entry></row><row><entry></entry><entry>!. Cooling tunnel</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>Meters width)</entry><entry>Refract.</entry><entry></entry><entry>82,6</entry></row><row><entry></entry><entry>(m / h)</entry><entry></entry><entry></entry><entry></entry><entry>index</entry><entry>optical measurement</entry><entry>71,8</entry></row><row><entry></entry><entry>296</entry><entry>63O⁰C.</entry><entry>45 )</entry><entry>too thin for</entry><entry>1,64</entry><entry>66,8</entry></row><row><entry>4</entry><entry>296</entry><entry>63O⁰C.</entry><entry>45 )</entry><entry></entry><entry>1,68</entry><entry></entry></row><row><entry>5</entry><entry>296</entry><entry>63O⁰C.</entry><entry>45</entry><entry></entry><entry>1,83</entry><entry></entry></row><row><entry>6</entry><entry>296</entry><entry>630⁰C.</entry><entry>45</entry><entry></entry><entry></entry><entry></entry></row><row><entry>7</entry><entry>296</entry><entry>63O⁰C.</entry><entry>45</entry><entry>Lower class</entry><entry>thickness</entry></row><row><entry>8</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>(nm)</entry></row><row><entry>Table 3</entry><entry>Glass ribbon</entry><entry>Glass</entry><entry>Glass flow</entry><entry>Refract.</entry><entry>70,3</entry></row><row><entry>example</entry><entry>quickly.</entry><entry>temperature</entry><entry>(Liters / min</entry><entry>index</entry><entry>68,0</entry></row><row><entry></entry><entry>i. Cooling tunnel</entry><entry></entry><entry>Meters width)</entry><entry>1,63</entry><entry>68,0</entry></row><row><entry></entry><entry>(m'h)</entry><entry></entry><entry></entry><entry>1,69</entry><entry>75,0</entry></row><row><entry></entry><entry>331</entry><entry>64O⁰C.</entry><entry>20</entry><entry>1,74</entry><entry>67,7</entry></row><row><entry>9</entry><entry>331</entry><entry>64O⁰C.</entry><entry>24</entry><entry>1,69</entry><entry>64,0</entry></row><row><entry>10</entry><entry>331</entry><entry>64O⁰C.</entry><entry>30</entry><entry>1,74</entry><entry></entry></row><row><entry>11</entry><entry>331</entry><entry>64O⁰C.</entry><entry>23</entry><entry></entry></row><row><entry>12</entry><entry>331</entry><entry>64O⁰C.</entry><entry>26</entry><entry>Lower class</entry></row><row><entry>13</entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry>Table 4</entry><entry>Glass ribbon</entry><entry>Glass</entry><entry>Gas flow</entry><entry>Refreshes.</entry></row><row><entry>example</entry><entry>fast.</entry><entry>temperature</entry><entry>(Liters / min</entry><entry>index</entry></row><row><entry></entry><entry>i. Cooling tunnel</entry><entry></entry><entry>Meters width)</entry><entry>1,69</entry></row><row><entry></entry><entry>(m / h)</entry><entry></entry><entry></entry><entry>1,71</entry></row><row><entry></entry><entry>360</entry><entry>65O⁰C.</entry><entry>18.5</entry><entry>1,/1</entry></row><row><entry>14</entry><entry>360</entry><entry>650⁰C.</entry><entry>21</entry><entry>1,65</entry></row><row><entry>15</entry><entry>360</entry><entry>65O⁰C.</entry><entry>21</entry><entry>1,77</entry></row><row><entry>16</entry><entry>360</entry><entry>65O⁰C.</entry><entry>2i</entry><entry>1,77</entry></row><row><entry>17</entry><entry>360</entry><entry>650 ° C</entry><entry>38</entry><entry></entry></row><row><entry>18</entry><entry>360</entry><entry>650 "C</entry><entry>16</entry></row><row><entry>19</entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry></row><row><entry></entry></row><row><entry></entry></row></tbody></tgroup></table>

Table B

example

Tin oxide thickness (nm)

Color values ​​a

(coords) b

Color values ​​(co-ords) without an underlayer

<table><tgroup cols="20"><tbody><row><entry>14</entry><entry>350</entry><entry>mono-</entry><entry>Glass GIa 3-</entry><entry>+2,2</entry><entry>+0,6</entry><entry>C.₂H₄</entry><entry>CO₂</entry><entry>C.₃H₈</entry><entry>I.</entry><entry>CO₂</entry><entry>N₂</entry><entry>-16</entry><entry>+ 10</entry><entry>(Liters / min</entry><entry>index</entry><entry>%</entry><entry>thickness</entry><entry>2,8</entry><entry>mg</entry></row><row><entry>15</entry><entry>300</entry><entry>silane</entry><entry>temperature</entry><entry>-1,5</entry><entry>+2,3</entry><entry></entry><entry></entry><entry></entry><entry>I.</entry><entry></entry><entry></entry><entry>+ 10</entry><entry>-21</entry><entry>N₂ Meters width) Refr.</entry><entry>1,6</entry><entry>(nm)</entry><entry>&lt;0,2</entry><entry>N / A₂O/</entry></row><row><entry>16</entry><entry>320</entry><entry>%</entry><entry>rature (mm)</entry><entry>-0,1</entry><entry>+4,6</entry><entry>36</entry><entry>36</entry><entry>34,4</entry><entry>1</entry><entry>34,4</entry><entry>2G</entry><entry>-9</entry><entry>-9</entry><entry></entry><entry>1,65</entry><entry>34,6 0,3</entry><entry>&lt;0,1</entry><entry>dm²</entry></row><row><entry>17</entry><entry>250</entry><entry>2,5</entry><entry></entry><entry>+2,7</entry><entry>+ 1,2</entry><entry>21</entry><entry>21</entry><entry>35,3</entry><entry></entry><entry>35,3</entry><entry>23,5</entry><entry>+5</entry><entry>+ 11</entry><entry>22 55</entry><entry>1,6</entry><entry>68,0 &gt; 2</entry><entry>0,6</entry><entry></entry></row><row><entry>18</entry><entry>350</entry><entry>2,7</entry><entry>650⁰C 6</entry><entry>-0,8</entry><entry>+2,2</entry><entry>28</entry><entry>28</entry><entry>37,5</entry><entry></entry><entry>37,5</entry><entry>20</entry><entry></entry><entry></entry><entry>50 24</entry><entry></entry><entry>60 2</entry><entry>0,4</entry><entry>26</entry></row><row><entry>19</entry><entry>350</entry><entry>0,9</entry><entry>670⁰C 6</entry><entry>+0,3</entry><entry>+ 1, ö</entry><entry></entry><entry></entry><entry>35,3</entry><entry>33.3</entry><entry>23,5</entry><entry></entry><entry></entry><entry>33 27</entry><entry>Lower class</entry><entry></entry><entry>0,2</entry><entry>30</entry></row><row><entry>Tobellee</entry><entry></entry><entry>0,9</entry><entry>69O⁰C 4</entry><entry></entry><entry></entry><entry></entry><entry>Glass-gas assembly; «Etching (%)</entry><entry>35,3</entry><entry>35,3</entry><entry>23,5</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>dT mg</entry><entry></entry><entry>13</entry></row><row><entry>example</entry><entry>Glass ribbon</entry><entry>1,6</entry><entry></entry><entry></entry><entry>Gas composition gas flow</entry><entry>tempe</entry><entry>35,3</entry><entry>35,3</entry><entry>23,5</entry><entry>Lower layer dT</entry><entry>Gas flow</entry><entry>Refract. thickness</entry><entry>% N / A₂C.</entry><entry></entry><entry></entry></row><row><entry></entry><entry>quickly.</entry><entry>1,6</entry><entry></entry><entry>(%)</entry><entry>ratur SiH₄</entry><entry>37,5</entry><entry>37,5</entry><entry>20</entry><entry>(Liters / min</entry><entry>index (nm)</entry><entry>ϊ dm²</entry><entry></entry><entry></entry></row><row><entry></entry><entry>!. Cooling tunnel</entry><entry></entry><entry></entry><entry>SiH₄</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>Meters width)</entry><entry>1,82 59,2</entry><entry></entry><entry></entry><entry>D /</entry></row><row><entry></entry><entry>(m / h)</entry><entry></entry><entry></entry><entry></entry><entry>685⁰C 6.2</entry><entry></entry><entry>CO₂</entry><entry></entry><entry></entry><entry>1,76 60,0</entry><entry>7,6</entry><entry></entry><entry></entry></row><row><entry>21</entry><entry>300</entry><entry></entry><entry></entry><entry>6</entry><entry>685 ° C &amp;, 9</entry><entry></entry><entry></entry><entry></entry><entry>75</entry><entry>1,73 63,6</entry><entry>5,4</entry><entry></entry><entry></entry></row><row><entry>22</entry><entry>380</entry><entry></entry><entry></entry><entry>8</entry><entry>685⁰C 5.0</entry><entry></entry><entry>%</entry><entry></entry><entry>75</entry><entry>1.74 64,5</entry><entry>4,4</entry><entry></entry><entry></entry></row><row><entry>23</entry><entry>550</entry><entry></entry><entry></entry><entry>11</entry><entry>68S⁰C 5.9</entry><entry>3.3% acetylene</entry><entry>8,5</entry><entry></entry><entry>80</entry><entry></entry><entry>5,5</entry><entry></entry></row><row><entry>Table 7</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>685 "C 5.9</entry><entry>3.9% acetylene</entry><entry>4,4</entry><entry></entry><entry>68</entry><entry></entry><entry>&lt;0,1 14</entry><entry></entry></row><row><entry>example</entry><entry>Glass ribbon</entry><entry></entry><entry></entry><entry></entry><entry>685⁰C 5.9</entry><entry>2.9% toluene '</entry><entry>31,6</entry><entry></entry><entry>34</entry><entry></entry><entry>0,8 14</entry><entry></entry></row><row><entry></entry><entry>quickly.</entry><entry></entry><entry>685 ° C 5.0</entry><entry>2.9% toluene '</entry><entry>31,6</entry><entry></entry><entry>51</entry><entry></entry><entry>0,1 28</entry><entry></entry></row><row><entry></entry><entry>i. Cooling tunnel</entry><entry></entry><entry></entry><entry>6.6% heptene</entry><entry>26,2</entry><entry></entry><entry>40</entry><entry>Coating</entry><entry></entry><entry></entry></row><row><entry></entry><entry>(m / h)</entry><entry></entry><entry>unsaturated.</entry><entry>2.6% octene</entry><entry>29,3</entry><entry></entry><entry></entry><entry>time</entry><entry>dT</entry><entry></entry></row><row><entry>24</entry><entry>360</entry><entry></entry><entry>Charcoal</entry><entry></entry><entry>N₂</entry><entry>(sec.)</entry><entry></entry><entry></entry></row><row><entry>25</entry><entry>360</entry><entry></entry><entry>hydrogen</entry><entry></entry><entry>35</entry><entry>%</entry><entry>mg</entry></row><row><entry>26</entry><entry>360</entry><entry></entry><entry>%</entry><entry>15</entry><entry>N / A₂O/</entry></row><row><entry>27</entry><entry>360</entry><entry>85,2</entry><entry>15</entry><entry>dm²</entry></row><row><entry>28</entry><entry>360</entry><entry>89,0</entry><entry>20</entry><entry>18</entry></row><row><entry>29</entry><entry>360</entry><entry>64,6</entry><entry>35</entry><entry>13</entry></row><row><entry>30</entry><entry>360</entry><entry>64,6</entry><entry>20</entry><entry>13</entry></row><row><entry>Table 8</entry><entry></entry><entry>65,6</entry><entry>13</entry></row><row><entry>example</entry><entry>66,5</entry><entry>13</entry></row><row><entry></entry><entry>13</entry></row><row><entry></entry></row><row><entry>31</entry></row><row><entry>32</entry></row><row><entry>33</entry></row><row><entry>34</entry></row><row><entry>35</entry></row><row><entry>36</entry></row></tbody></tgroup></table>

¹ The gas was obtained by bubbling nitrogen through the liquid unsaturated hydrocarbon, and the amount of unsaturated hydrocarbon present in the gaseous mixture is calculated from the then known vapor pressure of the liquid with an assumed through-flow effectiveness of 50%, that is, that of the liquid Hydrocarbon bubbling nitrogen saturated 60% with the hydrocarbon vapor.

<table><tgroup cols="11"><tbody><row><entry>Table 9</entry><entry>Glass ribbon</entry><entry>Glass</entry><entry>Gas composition (%)</entry><entry>C.₂H₄</entry><entry>CO₂</entry><entry>N₂</entry><entry>Gas flow</entry><entry>Under</entry><entry>dT</entry><entry>mg Na₂O/</entry></row><row><entry>example</entry><entry>quickly.</entry><entry>tempe</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>Liters / min</entry><entry>layer</entry><entry>%</entry><entry>dm²</entry></row><row><entry></entry><entry>!. Cooling tunnel</entry><entry>maturity</entry><entry>SiH₄</entry><entry>25,7</entry><entry>25,7</entry><entry>39,0</entry><entry>Meters wide</entry><entry>thickness</entry><entry></entry><entry></entry></row><row><entry></entry><entry>(m / h)</entry><entry></entry><entry></entry><entry>28,7</entry><entry>28,7</entry><entry>34,0</entry><entry></entry><entry>(nm)</entry><entry></entry><entry></entry></row><row><entry></entry><entry>1100</entry><entry>655⁰C.</entry><entry>ίΐ.7</entry><entry>22,0</entry><entry>22,0</entry><entry>'5,0</entry><entry>62</entry><entry>17</entry><entry>0,9</entry><entry>&lt;20</entry></row><row><entry>37</entry><entry>1100</entry><entry>655 ° C</entry><entry>8,6</entry><entry>2,0</entry><entry>80,0</entry><entry>14,0</entry><entry>70</entry><entry>11</entry><entry>0,25</entry><entry>62</entry></row><row><entry>38</entry><entry>1100</entry><entry>655⁰C.</entry><entry>11,1</entry><entry></entry><entry></entry><entry></entry><entry>54</entry><entry>17</entry><entry>1,5</entry><entry>&lt;20</entry></row><row><entry>39</entry><entry>1100</entry><entry>655 ⁰C.</entry><entry>4,0</entry><entry>42,0</entry><entry>0</entry><entry>46,0</entry><entry>102</entry><entry>7</entry><entry>0,2</entry><entry>200</entry></row><row><entry>40</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry>Ver</entry><entry>1100</entry><entry>655 ° C</entry><entry>11,8</entry><entry>52</entry><entry>14</entry><entry>2,3</entry><entry>&lt;20</entry></row><row><entry>equal</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry></row><row><entry></entry></row><row><entry></entry></row></tbody></tgroup></table>