Process for the production of photocatalytic coatings on substrates

The invention is illustrated by, but not limited to, the following drawings.

54453

Figure 1 is a graph of the photocatalytic effect of the coated glass produced by the method according to the invention as a function of the thickness of the titanium oxide layer.

FIG. 2 illustrates an apparatus for the computer-associated chemical vapor deposition of coatings according to the invention.

In Figure 1, the coated glasses were produced using a computer-linked CVD method as described in the Examples below. The open encircled areas (1) relate to deposited titanium oxide layers using titanium tetrachloride as the titanium precursor, and crosses (2) to the deposited titanium oxide layers using titanium tetraethoxide as the titanium precursor.

The layers of the coating can be applied to the glass substrate in a computer-connected manner by chemical vapor deposition during the glass manufacturing process. Figure 2 illustrates an apparatus generally indicated by 10, useful for the computer-connected production of the coated glass article of the present invention, which apparatus comprises a floating portion 11, a glass annealing furnace 12, and a cooling section (13). The supernatant 11 does not leak together so as to provide an enclosed zone in which a non-oxidizing atmosphere is maintained to prevent oxidation of the tin bath 15.

54453 and a base (14) comprising a molten tin bath (15), a ceiling (16), side walls (not shown) and end walls (17) forming an environment. During operation of the apparatus 10, the molten glass 19 is poured onto a furnace bottom 20, and flows therefrom under a measuring wall 21, and then flows downward onto the surface of the tin bath 15, where a floating glass forming the strip (37), which is removed by the lift-off rollers (22) and transported through the glass annealing furnace (12), and then through the cooling section (13).

The floating section 11 is introduced into the zone 18 by introducing a suitable gas into the zone 18 through the pipes 23 operably connected to a partition pipe 24, for example nitrogen and a gas containing 2% hydrogen by volume. a non-oxidizing atmosphere is maintained. Non-oxidizing gas to compensate for losses of gas from the pipes 23 into the zone 18 (a portion of the non-oxidizing atmosphere flows below the end walls 17 leaving the zone 18), and to maintain a slight positive pressure above the ambient pressure is injected at a rate sufficient to. The tin bath 15 and the enclosed zone 18 are heated by a bright heat directed downwardly from the heaters 25. The heating zone 18 is generally maintained at a temperature of 1330 ° F to 1400 ° F (721 ° C to 760 ° C). Glass Annealing

54453 The atmosphere in the furnace 12 is typically air, and the cooling section 13 is not covered. Ambient air is blown by the propellers 26 on the glass.

The apparatus 10 also comprises coaters 27, 28, 29 and 30 which are positioned in series within the floating region 11 above the floating glass strip 37. The respective coaters are supplied with precursor gaseous mixtures of separate layers for coating, which in turn direct the precursor gaseous mixtures to the hot surface of the floating glass strip 37. The temperature of the floating glass strip 37 is at the highest level in the position of the coater 27 closest to the furnace bottom 27 and at the lowest level in the position of the coater 30 closest to the glass annealing furnace 12.

The invention is further illustrated by the following Examples, wherein the coatings are applied by a layered flow chemical vapor deposit in a floating bath on a moving strip of floating glass during the method of glass production. In the Examples, two ply coatings were applied to the glass strip.

All gas volumes are measured at standard temperature and pressure unless otherwise stated.

The thickness values ​​transferred to the layers are highly diffusive scanning electron microscopy and the reflection and transmission waveband of the coated glass 21.

54453 using the corresponding optical shaping. The thicknesses of the coatings were measured with an uncertainty of about 5%. The transmission and reflection characteristics of the coated glasses were determined using a Hitachi U-4000 spectrophotometer. For the transmission and / or reflection color of the glasses, the a, b and L * values ​​indicated herein refer to the colors of the CIE Lab. Visible reflection and visible transmission of coated glasses were determined using the standard CIE 2 ° observer in accordance with the D65 illuminator and ISO 9050 standard (Parry Moon air mass 2). The misting of the coated glasses was measured using a WYK - Gardner Haze Observer + Haze meter.

The photocatalytic effect of the coated glasses was determined by the rate of reduction of the area of ​​the infrared peaks corresponding to the CH stresses of a stearic acid film on the coated surface of the glass under UVA light illumination. Stearic acid, 7 to 8 cm square, on samples of glasses, for 1 minute at 2000 rpm on the coated surface of glass in methanol a solution of stearic acid (8.8 χ 10³ mol dm^-3) It is formed by rotating 20 μΐ. The infrared waveband was measured in conduction, and the CH stresses of the stearic acid film (about 2700 to 3000 cm)^-1) the corresponding peak height was measured and the corresponding peak area was determined from an adjustment curve of the peak area versus the peak height. The coated side of the glass is 351 nm 22.

54453 with a wavelength of approximately 32 W / m on the surface of the coated glass.² UVA-351 (obtained from P-Panel Company, Cleveland, Ohio, USA). The rate of reduction in photocatalytic effect or the area of ​​IR peaks in this specification (cm)^-1 minute^-1 (in units of)) or the time taken for UV exposure to reduce the peak height (absorption) of a peak within the wavelength down to 10% of its initial value._SG0 (in units of minutes).

The angle of contact of the coated glasses with the static water was determined by measuring the diameter of a droplet of water (1 to 5 μΐ) placed on the surface of the coated glass after illumination of the coated glass using UVA 351 lamp for about 2 hours (or otherwise determined).

Examples 1-15

300 A strip of 1 mm thick lime-cream floating glass moving at a speed of m / h was coated with a two-ply coating while the strip was running over the floating bath in a position where the glass temperature was in the range of from 650 ° C to about 670 ° C. The floating bath atmosphere contained a flowing gaseous mixture of nitrogen and 9% hydrogen at a bath pressure of approximately 0.15 mbar.

54453 nitrogen (8 mixture, gas

Layer 1 (the first layer to be deposited on glass) was a layer of silicon oxide. Cat 1, monosilane (SiH₄Oxygen (120 ml / min), British patent specification 1 507 966 (particularly in FIG. 2 and on page 3) with a passage for circulating ethylene (360 ml / min) and liter / min) of a gaseous mixture over the glass surface of approximately 0.15 m. 73 to page 4, line 75), allowing the glass to contact in the direction of movement of the glass and flow parallel to the surface of the glass. The extraction was approximately 0.9 to 1.2 mbar. The glass strip is coated at a point where its temperature is approximately 670 ° C, approximately 10 cm. The thickness of the silica layer was about 20 to 25 m.

Layer 2 (the second layer to be deposited) was a layer of titanium dioxide. Cat 2, titanium tetrachloride in flowing nitrogen carrier gas, the separate gas streams containing ethyl acetate in the flowing nitrogen carrier gas and a volume flow of 8 l / min (flow rate measured at 20 psi) into nitrogen and then the gaseous mixture (about 250 ° C). through the lines maintained in Fig. 1) to a coating apparatus consisting of an oil-cooled dual flow coater. Nitrogen carrier and bulky

54453 the pressure of the nitrogen gases was approximately 20 pounds per square inch (9,080 g). The gaseous mixture contacted the glass surface both upstream and downstream along the glass strip and flowed in parallel. The passageway for the circulation of the gaseous mixture was about 0.15 m downstream and 0.15 m upstream with the extraction of 0.15 mbar. Titanium tetrachloride and ethyl acetate were charged into separate streams of flowing nitrogen carrier gas by passing nitrogen through fountains containing either titanium tetrachloride or ethyl acetate. Flow rates of nitrogen carrier gas Table 1^v(flow rates measured at 20 psi). The titanium tetrachloride fountain was maintained at a temperature of 69 ° C, and the ethyl acetate fountain was maintained at a temperature of 42 ° C. Estimated flow rates of charged titanium tetrachloride and superimposed ethyl acetate are also described in Table 1 for each of Examples 1 to 15.

The characteristics of the two-ply coatings were measured. Values ​​for the thickness of layer 2 (titanium oxide layer), and values ​​for visible reflection measured on the coated side, L * and fogging for coated glasses are described in Table 2 for Examples 1 to 15. The misting of each coated glass was below 0.2%.

54453

The photocatalytic effect of the coated glasses and the angle of contact with the static water were determined. For examples 1 to 15, the initial peak height and initial peak area of ​​the IR peaks corresponding to the stearic acid CH stresses, photocatalytic effect, static water contact angle and t%₉o Table 3. The thickness of the titanium oxide layer surprisingly had little effect on the photocatalytic effect.

Examples 16-19

Examples 16 to 19 have a bath pressure of about 0.11 mbar, extraction for depositing the silica substrate (ply 1) is about 0.7 mbar, maintaining the titanium tetrachloride fountain at a temperature of about 100 ° C; 45 ° C and transport lines are maintained at a temperature of approximately 220 ° C. Examples 1 to 15 were carried out under the same conditions.

The flow rates of the nitrogen carrier gas, and the estimated flow rates of the charged titanium tetrachloride and the charged ethyl acetate are described in Table 1 for each of Examples 16 to 19.

The values ​​for the thickness of layer 2 (titanium oxide layer), and the values ​​for visible reflection measured on the coated side, L * and coated

54453 fogging of glasses is described in Table 2 for each of Examples 16 to 19.

For each of Examples 16 to 19, the initial peak height and initial peak area of ​​the IR peaks corresponding to 5 stearic acid CH stresses, photocatalytic effect, static water contact angle and t% go

It is described in Table 3, (

The photocatalytic effect of Examples 16 to 19 was not substantially greater than that of Examples 1 to 15 in contrast to the thicker (and therefore more reflective) titanium oxide coatings.

54453

TABLE 1

<td>i &amp; tnek</td><td colspan="2">Flow Rates of Nitrogen Carrying Instrument to Sprinklers measured at 20 psi)</td><td rowspan="2">TIC1 &lt;Flow rate (1 min)</td><td rowspan="2">Style: Acetate Flow rate (1 / minute)</td>

<td>İ4-</td><td>TIC1 * Fountain</td><td>Style: Acetate the Siakivea</td>

<td>- - '· - I</td><td> 016</td><td> 1</td><td> 0.032</td><td> 0.46</td>

<td> 2</td><td> 0.12</td><td> 0.3</td><td> 0.024</td><td> 0.14</td>

<td> 3</td><td> 0.12</td><td> 0.45</td><td> 0.024</td><td> 0.21</td>

<td> 4</td><td> 0.08</td><td> 0.2</td><td> 0.016</td><td> 0.09</td>

<td> 5</td><td> 0.12</td><td> 0.15</td><td> 0.024</td><td> 0.07</td>

<td> 6</td><td> 0.12</td><td> 0.75</td><td> 0.024</td><td> 0.35</td>

<td> 7</td><td> 0.08</td><td> 0.3</td><td> 0.016</td><td> 0.14</td>

<td> 8</td><td> 0.08</td><td> 0.5</td><td> 0.016</td><td> 0.23</td>

<td> 9</td><td> 0.04</td><td> 0.1</td><td> 0.008</td><td> 0.05</td>

<td> 10</td><td> 0.04</td><td> 0.15</td><td> 0.008</td><td> 0.07</td>

<td> 11</td><td> 0.04</td><td> 0.25</td><td> 0.008</td><td> 0.12</td>

<td> 12</td><td> 0.16</td><td> 0.1</td><td> 0.032</td><td> 0.05</td>

<td> 13</td><td> 0.08</td><td> 0.1</td><td> 0.016</td><td> 0.05</td>

<td> 14</td><td> 0.16</td><td> 0.4</td><td> 0.032</td><td> 0.19</td>

<td> 15</td><td> 0.16</td><td> 0.2</td><td> 0.032</td><td> 0.09</td>

<td> 16</td><td> 0.1</td><td> 0.5</td><td> 0.088</td><td> 0.27</td>

<td> 17</td><td> 0.08</td><td> 0.4</td><td> 0.070</td><td> 0.22</td>

<td> 18</td><td> 0.06</td><td> 0.3</td><td> 0.053</td><td> 0.16</td>

<td> 19</td><td> 0.04</td><td> 0.2</td><td> 0.035</td><td> 0.11</td>

54453

TABLE 2

<td>Sample</td><td>Thickness of titanium oxide layer (nm)</td><td>Visible reflection of coated glass (%&gt;</td><td>L * value of coated glass (%)</td><td>Haze man ma (%)</td>

<td> 1</td><td> 15</td><td> 14.1</td><td> 44</td><td> 0.12</td>

<td> 2</td><td> 14.3</td><td> 13.9</td><td> 44</td><td> 0.07</td>

<td> 3</td><td> 14.2</td><td> 13.2</td><td> 43</td><td> 0.12</td>

<td> 4</td><td> 11.3</td><td> 11.4</td><td> 40</td><td> 0.08</td>

<td> 5</td><td> 12.1</td><td> 12.1</td><td> 41</td><td> 0.08</td>

<td> 6</td><td> 11.0</td><td>a</td><td>a</td><td> 0.07</td>

<td> 7</td><td> 8</td><td>a</td><td>a</td><td> 0.11</td>

<td> 8</td><td> 7.2</td><td> 9.7</td><td> 37</td><td> 0.04</td>

<td> 9</td><td> - 6.1</td><td> 9.1</td><td> 36</td><td> 0.05</td>

<td> 10</td><td> 5.6</td><td> 9</td><td> 36</td><td> 0.07</td>

<td> 11</td><td> 4.6</td><td> 8.7</td><td> 35</td><td> 0.06</td>

<td> 12</td><td> 15.6</td><td> 15.4</td><td> 46</td><td> 0.1</td>

<td> 13</td><td> 16.0</td><td>a</td><td>a</td><td> 0.13</td>

<td> 14</td><td> 17.5</td><td> 16.2</td><td> 47</td><td> 0.14</td>

<td> 15</td><td> 20.3</td><td> 19.5</td><td> 51</td><td> 0.1</td>

<td> 16</td><td>a</td><td> 28.4</td><td> 47.8</td><td> 0.3</td>

<td> 17</td><td>ca68</td><td> 29.1</td><td> 58.4</td><td> 0.37</td>

<td> 18</td><td>ca32</td><td> 25.9</td><td> 55.6</td><td> 0.24</td>

<td> 19</td><td>CA27</td><td> 20.5</td><td> 50.2</td><td> 0.2</td>

a not measured

54453

TABLE 3

<td rowspan="2">subject</td><td colspan="2">IR Peaks corresponding to CH stresses of stearic acid film (2700-3000 cm¹)</td><td rowspan="2">Photocatalytic Effect (x IO)²cm ^ min¹)</td><td rowspan="2">Static by S Contact angle c&gt;</td><td rowspan="2">t 90% (Min)</td>

<td>Start Peak Height (optional)</td><td>Start Summit from Area (cm)¹)</td>

<td> 1</td><td> 0.030</td><td> 1.04</td><td> 9.4</td><td> 17 ± 5</td><td> 10</td>

<td> 2</td><td> 0.0331</td><td> 1.15</td><td> 10.4</td><td> 15 ± 1</td><td> 10</td>

<td> 3</td><td> 0.0311</td><td> 1.08</td><td> 12.2</td><td> 13 ± 2</td><td> 8</td>

<td> 4</td><td> 0.0324</td><td> 1.13</td><td> 6.8</td><td> 14 ± 1</td><td> 15</td>

<td> 5</td><td> 0.0287</td><td> 1.00</td><td> 8.2</td><td> 16 ± 3</td><td> 11</td>

<td> 6</td><td> 0.028</td><td> 0.98</td><td> 8.8</td><td> 15 ± 1</td><td> 10</td>

<td> 7</td><td> 0.0343</td><td> 1.20</td><td> 10.8</td><td> 15 ± 1</td><td> 10</td>

<td> 8</td><td> 0.0289</td><td> 1.03</td><td> 6.6</td><td> 16 ± 1</td><td> 14</td>

<td> 9</td><td> 0.0289</td><td> 1.01</td><td> 6.5</td><td> 14 ± 2</td><td> 14</td>

<td> 10</td><td> 0.0278</td><td> 0.97</td><td> 6.2</td><td> 18 ± 2</td><td> 14</td>

<td> 11</td><td> 0.0344</td><td> 1.20</td><td> 5.4</td><td> 18 ± 1</td><td> 20</td>

<td> 12</td><td> 0.0291</td><td> 1.02</td><td> 10.2</td><td> 12 ± 1</td><td> 9</td>

<td> 13</td><td> 0.0289</td><td> 1.01</td><td> 9.1</td><td> 14 ± 2</td><td> 10</td>

<td> 14</td><td> 0.0269</td><td> 0.94</td><td> 9.4</td><td> 15 ± 2</td><td> 9</td>

<td> 15</td><td> 0.0331</td><td> 1.15</td><td> 8.7</td><td> 15 ± 2</td><td> 12</td>

<td> 16</td><td> 0.0227</td><td> 0.79</td><td> 17.8</td><td> 12</td><td> 4</td>

<td> 17</td><td> 0.026</td><td> 0.91</td><td> 10.2</td><td> 12</td><td> 8</td>

<td> 18</td><td> 0.0225</td><td> 0.79</td><td> 10.1</td><td> 13</td><td> 7</td>

<td> 19</td><td> 0.0258</td><td> 0.90</td><td> 10.1</td><td> 16</td><td> 8</td>

Examples 20-27

Examples 20 to 27, except that the carrier gas of layer 2 was deposited from a gaseous mixture containing titanium tetraethoxide loaded into the nitrogen carrier gas by passing it through a fountain containing titanium tetraethoxide maintained at a temperature of I70 ° C. under the same conditions. Nitrogen for one of the examples 20 to 27

54453 flow rates of carrier gas (measured at 20 psi) and titanium tetraethoxide are described in Table 4. The flow rate of bulky nitrogen was 8.5 l / min (measured at 20 psi).

The characteristics of the two-ply coatings were measured. Values ​​for the thickness of layer 2 (titanium oxide layer), and values ​​for visible reflection measured on the coated side are described in Table 5 for Examples 20 to 27. The misting of each coated glass was below 0.7%.

The photocatalytic effect of the coated glasses and the angle of contact with the static water were determined. For each of Examples 20 to 27, the initial peak height and initial peak area of ​​the IR peaks corresponding to stearic acid CH stresses, photocatalytic effect, static water contact angle and t% go are described in Table 6.

Examples 28 and 29

Examples 28 and 29 were conducted under the same conditions as in Examples 20 to 27 except that the titanium tetraethoxide fountain was maintained at a temperature of 168 ° C and the bath pressure was 0.11 mbar. The data for Examples 28 to 29, equivalent to the data for Examples 20 to 27, are described in Tables 4, 5 and 6.

54453

TABLE 4

<td>Sample</td><td>Flow rates of Nitrogen Carrier Gas to Titanium tetraethoxide fountain (measured at 1 / minute, 20 psi)</td><td>Titanium ethoxide flow rate (1 / minute)</td>

<td> 20</td><td> 0.25</td><td> 0.014</td>

<td> 21</td><td> 0.15</td><td> 0.008</td>

<td> 22</td><td> 0.2</td><td> 0.011</td>

<td> 23</td><td> 0.25</td><td> 0.014</td>

<td> 24</td><td> 0.3</td><td> 0.017</td>

<td> 25</td><td> 0.35</td><td> 0.019</td>

<td> 26</td><td> 0.2</td><td> 0.011</td>

<td> 27</td><td> 0.1</td><td> 0.006</td>

<td> 28</td><td> 0.6</td><td> 0.030</td>

<td> 29</td><td> 0.4</td><td> 0.020</td>

TABLE 5

<td>Sample</td><td>Thickness of titanium oxide layer ()m)</td><td>Visible reflection of coated glass (%)</td><td>Haze (%)</td>

<td> 20</td><td> 13</td><td>to</td><td> 0.4</td>

<td> 21</td><td> 13</td><td>to</td><td> 0.29</td>

<td> 22</td><td> 16</td><td> 15.7</td><td> 0.29</td>

<td> 23</td><td> 18</td><td>to</td><td> 0.28</td>

<td> 24</td><td> 24</td><td>to</td><td>a</td>

<td> 25</td><td> 26</td><td>to</td><td> 0.61</td>

<td> 26</td><td> 9.9</td><td> 10.9</td><td> 0.19</td>

<td> 27</td><td> 4.7</td><td> 8.8</td><td> 0.29</td>

<td> 28</td><td> 38.3</td><td> 35.2</td><td> 0.29</td>

<td> 29</td><td> 31.9</td><td> 28.4</td><td> 0.22</td>

a Not measured

54453

TABLE 6

<td rowspan="2">Sample</td><td colspan="2">IR Peaks corresponding to CH stresses of stearic acid film (2700-3000 tan¹)</td><td rowspan="2">Photocatalytic Effect (x 10 “²suck^_1minute^_1)</td><td rowspan="2">Static by S Contact angle ( "&gt;</td><td rowspan="2">t% 90 (in k&gt;</td>

<td>Starting Peak height (optional units)</td><td>Starting Peak Area (cm)¹)</td>

<td> 20</td><td> 0.027</td><td> 0.953</td><td> 5.7</td><td> 19±5</td><td> 15</td>

<td> 21</td><td> 0.031</td><td> 1.095</td><td> 5.7</td><td>a</td><td> 17</td>

<td> 22</td><td> 0.024</td><td> 0.838</td><td> 3.6</td><td> 15 ±2</td><td> 21</td>

<td> 23</td><td> 0.030</td><td> 1.029</td><td> 7.1</td><td> 11±3</td><td> 13</td>

<td> 24</td><td> 0.029</td><td> 1.015</td><td> 7</td><td> 17±3</td><td> 13</td>

<td> 25</td><td> 0.031</td><td> 1.071</td><td> 7.4</td><td> 13±4</td><td> 13</td>

<td> 26</td><td> 0.031</td><td> 1.085</td><td> 4.4</td><td> 21±3</td><td> 22</td>

<td> 27</td><td> 0.029</td><td> 0.998</td><td> 3.2</td><td> 16±5</td><td> 28</td>

<td> 28</td><td> 0.021</td><td> 0.733</td><td> 3.6</td><td> 13</td><td> 18</td>

<td> 29</td><td> 0.024</td><td> 0.848</td><td> 3.3</td><td> 14</td><td> 23</td>

a Not measured

Examples 30-42

In Examples 30 to 42, two-ply coatings were applied to a floating glass strip with computer-connected CVD in the floating bath during the floating glass production method, from one side of the full width of about 132 inches (3.35m) to the other side. The device used to deposit is illustrated in Figure 2. The floating bath atmosphere contained nitrogen and 2% hydrogen by volume. The bath pressure was 0.15 mbar.

The two-ply coating is made of a silicon oxide layer previously deposited on the floating glass strip and titanium oxide deposited on the silicon oxide layer.

54453 floor. The precursor chemical treatment of the gaseous mixtures used to deposit the coating was the same as that used in Examples 1 to 15. The temperature for laying the plies was varied using different coats (27,28,29 or 30) (referring to Figure 2). The coater (27) located near the furnace base is the warmest and the coater (30) located closest to the glass annealing furnace is the coldest. Two coaters (Examples (28) and (29) in Examples 30 to 33) and (27) and (28) were used to deposit the silicon oxide coating in Examples 30 to 33 and 42. The benefit of using two coaters to deposit silicon oxide solids is that longer production flow times are possible.

For examples 30 to 41, the gaseous mixture used to deposit the silicon oxide solid consisted of the following gases at the following flow rates: helium (2501 / min), nitrogen (2851 / min), monosilane (2.51 / min), ethylene (151 / min) minute) and oxygen (101 / minute). For Example 42, the same gases and flow rates were used except for monosilane (2.31 / min), ethylene (13.81 / min) and oxygen (9.21 / min). In Examples 30 to 42, when two coaters were used to deposit the silicon oxide solid, the above flow rates were used for each coater.

54453

In Examples 30 to 42, the temperature of the floating glass strip under the coater corresponding to each of the coats (ie 27 to 30) was as shown in Table 7. The temperatures in Table 7 were ± 50 ° F ( ± 28 [deg.] C. The pressure for each coater was approximately 2 mbar.

TABLE 7

<td>coater</td><td>Approximate Heat Degree of Glass Strip</td>

<td> 27</td><td>1330 ° F (721 ° C)</td>

<td> 28</td><td>1275 ° F (690 ° C)</td>

<td> 29</td><td>1250 ° F (677 ° C)</td>

<td> 30</td><td>1150 ° F (621 ° C)</td>

Titanium tetrachloride (TiCl₄and ethyl acetate were charged into separate nitrogen / helium carrier gas streams. TiCl₄ A thin layer evaporator was used to evaporate. Liquid TiCl₄is held in a pressurized container (head pressure of about 5 psi). This was used to transfer the liquid to a metering pump and Coriolis force flow metering system. The measured flow of the precursor was then fed into a thin-layer evaporator at a temperature of 110 ° F (43 ° C). TiCl₄After that, the TiCU carrier gas (helium) into

54453 and transferred to the mixing point down the lines maintained at 250 ° F (121 ° C). Ethyl acetate was transferred in a similar manner. Liquid ethyl acetate was maintained in a pressurized vessel (head pressure of about 5 psi). Liquid TiCl₄pressurized container (head pressure of about 5 psi). This was used to transfer the liquid to a metering pump and Coriolis force flow metering system. The measured flow of the precursor was then fed into a thin layer evaporator at a temperature of 268 ° F (131 ° C). The evaporated ethyl acetate was then charged into the carrier gas (helium / nitrogen mixture) and transported down the lines at approximately 250 ° F (121 ° C) to the mixing point.

The TiCl 4 and ethyl acetate gas streams are combined to form the gaseous mixture used to deposit the titanium oxide solid. This mixing point was located just before the coater.

The line velocity of the floating glass strip, the temperature of depositing the silicon oxide, and the temperature of depositing the titanium oxide oxide layers, the flow rates of the He / N2 volume carrier gas, and the flow rate of TIC4 and ethyl acetate are shown in Table 8 for Examples 30 to 42. are also described.

54453

The coated floating glass strip was cooled and cut, and the optical properties and photocatalytic effect of the samples were determined. Table 9 describes the misting of the samples, their optical characteristics in transmission and reflection (visible transmission / reflection percentage and color co-ordinates using the LAB system). The coated glasses were subjected to abrasion testing in accordance with BS EN 1096 and a 300 mm x 300 mm sample was secured to the vertical test bed at all four corners, ensuring that the sample would not move at all. An unused felt pad cut according to the dimensions stated in the standard (BS EN 1096 Part 2 (1999)) was then mounted on the test tab and the tab lowered towards the glass surface. A loading pressure of 4N on the test tab was then adjusted and the test started. The nail was allowed to process up and down, from one side of the sample to the other, for 500 impact pulses at a rate of 60 impact pulses / minute ± 6 impact pulses / minute. Upon completion of this wear, the sample was removed and examined optically and for photocatalytic effect. If the abrasion test results in an amount of not more than ± 5% in conduction when measured at 550 nm and the coated substrate remains photocatalytically effective, the sample is deemed to have passed the test, which results in static illumination with UV light for 2 hours after the test. means that the angle of contact with water is reduced to less than 15 °.

54453

The glasses were also subjected to a humidity cycle test in which the coating was subjected to a temperature cycle of 35 ° C to 75 ° C and again 35 ° C within 4 hours, as well as 100% relative humidity.

Coated glass as produced and without UV illumination (approx. 32 W / m² The UVA 351 lamp in FIG. The contact angles of the abraded samples were determined after 2 hours of illumination.

Samples deposited at higher temperatures of 1330-1250 ° F (721 ° C to 677 ° C) were photocatalytically effective even after 1000 European standard abrasion impact pulses and after 200 moisture cycles. The photocatalytic effects of coated glasses as they are produced and at t% go after 300, 500 and / or 1000 impact strokes for the European standard wear test are described in Table 11. In Table 11, the term Effective means that coated glasses are photocatalytically effective, but t% go is not determined.

54453

TABLE e

<td rowspan="5">rl 41 2nd 41 -r « S I • H TO*</td><td rowspan="2">8 4 ' rl a 3 she is . 4 rl 2nd a rl H • rl * 3 ©</td><td>S the^H 8 t »0 4 · M</td><td>m © »M</td><td>tn \she is</td><td>-most Vue »H</td><td>tn © »- &lt;</td><td> © «*&lt;</td><td>Ό W «4</td><td> ©</td><td>D</td><td>{ 'Φ</td><td>r-</td><td>D V</td><td>ro</td><td>rf vi D</td>

<td>J -J-'CJ ⁰P °</td><td>m \she is</td><td>m von</td><td>tn ©</td><td>tn ©</td><td> ©</td><td> ©</td><td> ©</td><td>«n vi</td><td>Ώ vi</td><td>v&gt; vi</td><td>of vî</td><td>V ·</td><td>&lt;R&gt; o</td>

<td rowspan="2">833 * S ® 8 H ° rl 5 ? a 4 H</td><td>one to* 2nd</td><td>8 tn</td><td></td><td>8 m</td><td>she is she is tn</td><td> © 8</td><td>8 tn</td><td>8 tn</td><td>she is 8</td><td>8 tn</td><td>8 tn</td><td>SHE IS © tn</td><td>she is she is tn</td><td>she is she is tn</td>

<td>3 S</td><td>8 tn</td><td> §</td><td>8 tn</td><td>SHE IS she is tn</td><td>8 tn</td><td>S tn</td><td>SHE IS she is tn</td><td>8 -most</td><td>she is © tn</td><td>SHE IS © tn</td><td>8 tn</td><td>8 tn</td><td>8 tn</td>

<td>rl L&gt; «^H M M 8 8 £ 3</td><td></td><td>• 4 D ©</td><td>D ©</td><td>«M D ©</td><td>D ©</td><td>D ©</td><td>· - &lt;d ©</td><td>3 Ό</td><td>Γ ©</td><td>r ~ 55</td><td>© r</td><td>t ©</td><td> 8 ©</td><td>rd ©</td>

<td colspan="2">r | ¥ iii * 38 3 · · 3-A «Rl H</td><td></td><td>r ~ © she is SHE IS\ ©</td><td>t · © r ~ &lt;* 8 ©</td><td>t * t © SHE IS SHE IS\ ©</td><td>Γ \SHE IS SHE IS SHE IS\ ©</td><td> 8 ©</td><td>she is «a ©</td><td>SHE IS σ \ ©</td><td> 8 ©</td><td> © &lt;25 ©</td><td> 8 ©</td><td>she is she is" ©</td><td>• rt D D</td><td>© © &lt;* ^ 4 D</td>

<td>1H 41 M 23 «4</td><td></td><td></td><td>Cher he is M</td><td>She SHE IS</td><td>she is • H</td><td>SHE IS\ SHE IS</td><td>Cher © RRT</td><td>SHE IS\ ©</td><td>© © rh</td><td>Cher&gt; ©</td><td>σ \ she is</td><td>Cher she is • rt</td><td>SHE IS\ he is r-i</td><td>v&gt; ©</td><td rowspan="2">ci w «t D tf</td>

<td>4 «' -SHE IS</td><td></td><td></td><td>she is tn</td><td>tn</td><td>D tn</td><td>tn tn</td><td>tn</td><td>«n -most</td><td>© tn</td><td> £</td><td>oo tn</td><td>SHE IS\ tn</td><td> 8</td><td>»H</td>

54453

<td colspan="2">Η Μ S&amp;</td><td>W4 1-4 ό</td><td> 0.30 1</td><td>0.12 I</td><td> 0.15 1</td><td> 0.12 |</td><td>1-4 he is</td><td>• 't - &lt;ö</td><td>00 she is she is</td><td>I 0.07</td><td>she is «4 he is</td><td> 1 0.08 1</td><td>spouse</td><td> 0.14 1</td>

<td rowspan="4">one 4 * • Η &gt; Η</td><td>χ&gt;</td><td> 3.6 1</td><td>xt o</td><td>\D &lt;* IR</td><td> 2.9</td><td> 2.7</td><td> 2.6</td><td>v » ci</td><td> 2.3</td><td> 1.7</td><td> 00</td><td> 1.8</td><td>ee</td><td> 3.1</td>

<td>to</td><td>Weed *</td><td> —4 •</td><td>— · 1</td><td> »·&lt; • 1</td><td> *4 1</td><td>»4 • 1-4 t</td><td>1-4 t</td><td> «</td><td> 1·^ •</td><td>«4 to</td><td> —4</td><td> 0»</td><td>I</td>

<td>1 * τ</td><td> 93.6 1</td><td> 93.7 1</td><td>î 93.6</td><td> 94.1</td><td> 93.8</td><td>S</td><td> 94.2</td><td>SHE IS\</td><td>oo s</td><td> 94.8</td><td> 94.7</td><td>ee</td><td> 93.8</td>

<td>g Η</td><td>ΓΟ οο</td><td> 84,5 1</td><td>! 84.3 I</td><td>85.5 I</td><td>1 84.8 I</td><td> 85.4 |</td><td> 85.8</td><td> 86.1</td><td>r4 oo</td><td> 87.2</td><td> 86.9 1</td><td>hand</td><td>I 84.8</td>

<td rowspan="4">Η » « s Η Η Μ 4 Η 4 Β I β 0 β 44</td><td>Χ&gt;</td><td> -10.3 1</td><td>he is one</td><td>î -10.5</td><td> -9.8 1</td><td>t; oo one</td><td> -8.8</td><td>D OO one</td><td>SHE IS\ c ^ one</td><td>SHE IS v £&gt; I</td><td>«n \SHE IS •</td><td>Ό \SHE IS &gt;</td><td>ee</td><td>SHE IS\ o •</td>

<td>α</td><td> 0.3 1</td><td> 0.3 1</td><td> 1 0.3 1</td><td> 0.3 1</td><td>«M SHE IS</td><td>I 0.1</td><td> 0.1</td><td>SHE IS</td><td>o i</td><td>0Ό</td><td>0Ό</td><td>CO</td><td>she is</td>

<td>* • J</td><td>«η $</td><td> 45.1</td><td>- « vi -T</td><td> 44.0</td><td> ! 43.7</td><td>i 43.9</td><td> 42.6</td><td>CJ ci 'Ί'</td><td> 41.0</td><td> 40.4 !</td><td> 40.6</td><td>ee</td><td> 44.3</td>

<td>Ο £ S-/ 06</td><td> 14.2 1</td><td> [ 14.6</td><td>&gt; or -t</td><td>oo o »«</td><td> 13.6 1</td><td> 13.8</td><td> 12.9</td><td>Ό ci</td><td> 11.9</td><td> 2 *4</td><td>VOA • * 4</td><td>ee</td><td> 1—4</td>

<td>β = ο</td><td></td><td>130_J</td><td>r « cn</td><td> 132</td><td>133_ of</td><td> 134 1</td><td>v&gt; she is"</td><td>Ό Be</td><td>I 37</td><td> 138</td><td> 1 39</td><td> 140 !</td><td>w * 4</td><td></td>

Μ rt +&gt;

»Rt ο ·

Η ^:Ο (8

54453

TABLE 10

<td rowspan="2">Sample</td><td colspan="5">Static After Number of Wear Impact Strokes Water Contact Angle (°)</td>

<td> 0</td><td>0 (130 minutes after OV illumination)</td><td> 300</td><td> 500</td><td> 1000</td>

<td> 30</td><td> 2.3</td><td> 3.3</td><td>Unsuccessful</td><td></td><td></td>

<td> 31</td><td> 2.0</td><td> 3.2</td><td>Unsuccessful</td><td></td><td></td>

<td> 32</td><td>a</td><td>to</td><td>Unsuccessful</td><td></td><td></td>

<td> 33</td><td> 2.0</td><td> 3.2</td><td>Unsuccessful</td><td></td><td></td>

<td> 34</td><td>a</td><td>to</td><td>Unsuccessful</td><td></td><td></td>

<td> 35</td><td> 2.0</td><td> 3.2</td><td>Unsuccessful</td><td></td><td></td>

<td> 36</td><td> 2.1</td><td> 3.4</td><td>Unsuccessful</td><td></td><td></td>

<td> 37</td><td> 2.2</td><td> 3.3</td><td></td><td> &lt;15</td><td></td>

<td> 38</td><td> 2.0</td><td> 3.1</td><td></td><td> &lt;15</td><td></td>

<td> 39</td><td> 1.9</td><td> 3.1</td><td></td><td> &lt;15</td><td></td>

<td> 40</td><td> 2.2</td><td> 3.2</td><td></td><td> &lt;15</td><td></td>

<td> 41</td><td> 7.8</td><td> 7.8</td><td></td><td></td><td> 10.1</td>

<td> 42</td><td>4.7 K</td><td> 4.7 - 5.3</td><td></td><td></td><td> 5.6 - 9.8</td>

a not measured

TABLE 11

<td rowspan="2">Sample</td><td colspan="4">Number of Wear Impact Strokes Then t »₉₀ (minute)</td><td rowspan="2">200 After Humidity Cycle t_t90 (minute)</td>

<td> 0</td><td> 300</td><td> 500</td><td> 1000</td>

<td> 30</td><td> 7.5</td><td>Unsuccessful</td><td></td><td></td><td>Unsuccessful</td>

<td> 31</td><td> 18.5</td><td>Unsuccessful</td><td></td><td></td><td>Unsuccessful</td>

<td> 32</td><td> 8.5</td><td>Unsuccessful</td><td></td><td></td><td>Unsuccessful</td>

<td> 33</td><td> 8</td><td>Unsuccessful</td><td></td><td></td><td>Unsuccessful</td>

<td> 34</td><td> 21</td><td>Unsuccessful</td><td></td><td></td><td>Unsuccessful</td>

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

<td> 36</td><td> 8.5</td><td>Unsuccessful</td><td></td><td></td><td>Unsuccessful</td>

<td> 37</td><td> 15.5</td><td></td><td>Ca.2160</td><td></td><td>Effective</td>

<td> 38</td><td> 18.5</td><td></td><td>Ca.2160</td><td></td><td>Effective</td>

<td> 39</td><td> 17</td><td></td><td>Ca.2160</td><td></td><td>Effective</td>

<td> 40</td><td> 18.5</td><td></td><td>Ca. 2160</td><td></td><td>Effective</td>

<td> 41</td><td>a</td><td></td><td></td><td>ca.2160</td><td>Effective</td>

<td> 42</td><td> 45</td><td></td><td></td><td> 2800</td><td>Effective</td>

a Not measured

54453