Untitled record

The present invention relates to a process for the preparation of photocatalytically active coated substrates and, more particularly, to a process for the preparation of photocatalytically active coated glass; the invention also relates to glass thus coated.

It is known to apply thin coatings of varying properties on one or more layers to substrates, including glass substrates. One of the properties in question is photocatalytic activity, which is produced by the light generation of a hole-electron pair in a semiconductor when illuminated with light of a specific frequency. The pair of hole electrons can form in sunlight and react in moist air to form hydroxy and peroxy radicals on the surface of the semiconductor. The radicals oxidize organic dirt on the surface. This property is used in self-cleaning substrates, especially in self-cleaning windows for windows.

Titanium dioxide can be an effective photocatalyst and can be applied to substrates to form transparent coatings having photocatalytic self-cleaning properties. Titanium oxide photocatalytic coatings are described in European Patent Application EP 0 901 991 A2, PCT Publication Nos. WO 97/07069, WO / 10186 and WO 98/41480, and in the 187th Electrochemical Society Meeting (187).^th Electrochemical Society Meeting) (Reno, Nevada, United States) 735 (page 1102) and New Scientist (August 26, 19, 1995). PCT Publication No. WO 98/06675 describes a vapor phase chemical deposition process by applying a titanium dioxide coating to a hot flat glass at a high application rate using a gaseous mixture of titanium chloride and an oxygen source organic compound to form the titanium oxide coating.

It is believed that a relatively thick titanium dioxide coating should be applied in order to achieve good photocatalytic activity. For example, PCT Publication No. WO 98/41480 states that a photocatalytically active self-cleaning coating should be thick enough to provide an acceptable level of activity and preferably such a coating should have a thickness of at least about 200 Angstroms, preferably at least about 500 Angstroms. the titanium oxide produced according to the embodiments have measured thicknesses in the range of 400 angstroms to 2100 angstroms each.

However, the problem with relatively thick titanium oxide coatings is a very visible light reflection and thus a relatively low visible light transmission. This problem is recognized by a New Scientist magazine article on coated windshields, where it is recommended that the dashboard be coated with black velvet or some other material that does not reflect light on the coated windshield to reduce the effect of high glare.

EP 0 901 991 A2, cited above, deals with a photocatalytic glass pane with a special crystalline titanium oxide coating characterized by the presence of specific peaks in an X-ray diffraction pattern. The specification describes a range of coating thicknesses (in each embodiment, all thicknesses are in the range of 20 nm to 135 nm; the thinner coating is less photocatalytically active than the thicker coating). The specification also describes a range of application temperatures from 300 ° C to 750 ° C, but prefers a temperature range of 400 ° C to 600 ° C and, in all embodiments of the invention, a titanium dioxide layer within this preferred range. or below.

Applicants of the present invention have found that by applying a titanium oxide coating at higher temperatures, particularly above 800 ° C, they are able to provide a coating with increased photocatalytic activity for a given thickness, and thus enable the same photocatalytic performance with a thinner coating. Such thinner coatings preferably have a tendency to produce less visible light reflectance and, as an obvious consequence of their higher application temperatures, have improved durability, particularly for rubbing and temperature fluctuations in a humid atmosphere.

Accordingly, the present invention provides a process for producing a photocatalytically active coated substrate comprising applying a titanium oxide coating to a substrate surface by contacting the substrate surface with a liquid mixture comprising a titanium source and an oxygen source wherein said substrate has a temperature of at least 600 ° C. substrate coated surface 5.10 '³ cm '¹minute'¹has a photocatalytic activity of greater than 35% and a measured reflectance of 35% or less on the coated side.

The carrier is preferably in the temperature range of 625 ° C to 720 ° C, more preferably the carrier is in the temperature range of 645 ° C to 720 ° C.

Preferably, the liquid mixture contains titanium chloride as the source of titanium and an ester other than methyl ester. Thus, in a preferred embodiment, the present invention provides a process for preparing a photocatalytically active coated substrate comprising applying a titanium oxide coating thinner than 40 nm to a substrate by contacting a surface of a substrate other than a titanium chloride and a methyl ester. ester containing liquid mixture.

The process is carried out by contacting the surface of the carrier with the liquid mixture when the carrier is in the temperature range of 600 ° C to 750 ° C.

The ester is preferably an alkyl ester having a β-hydrogen alkyl group (the alkyl group of an alkyl ester is a group derived from alcohol in the synthesis of an ester and the β-hydrogen atom is a hydrogen atom bonded to a β carbon or in an ester relative to the oxygen of the ether bond ). The ester is preferably a carboxylate ester.

Suitable esters may be alkyl esters having from 2 to 10 carbon atoms, but the ester is preferably an alkyl ester having from 2 to 4 alkyl groups.

The ester is preferably a compound of the formula: RC (O) -OC (X) (X ') - C (Y) (Y') - R ', wherein R and R' are hydrogen or alkyl,

X, X ', Y and Y' represent a monovalent substituent, preferably alkyl or hydrogen, wherein at least one of Y and Y 'must be hydrogen.

Suitable esters that may be used in the process of the invention include, for example:

ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, n-propyl formate, n-propyl acetate, n-propyl propionate, n-propyl butyrate, isopropyl formate, n-butyl formate, n-butyl acetate and t-butyl acetate.

The ester preferably contains an ethyl ester, more preferably the ester comprises ethyl formate, ethyl acetate or ethyl propionate. Most preferably, the ester contains ethyl acetate.

The liquid may be in liquid form, primarily dispersed as a fine spray (a process often referred to as spray application), but the liquid mixture is preferably a gaseous mixture. For the application process using a gaseous mixture as a precursor

<img file="HU0203433A2_D0001.tif" />

are often referred to as chemical vapor deposition (CVD). The preferred form of CVD is laminar flow CVD, although turbulent flow CVD may also be used.

The process may be carried out on substrates of various sizes, including sheet substrates, in particular on glass slit sheets, or may preferably be carried out continuously in the float glass manufacturing process on a continuous strip of glass. Thus, preferably, the process is carried out continuously in the float glass process and the support is a glass tape. If the process is carried out continuously, it is preferably carried out on the glass tape while it is in the float bath.

The advantage of continuous application of the process is that the continuously applied coatings tend to be durable and have particularly good abrasion resistance and chemical resistance.

A continuous application process as well as other application processes can advantageously be carried out at substantially atmospheric pressure.

In a particularly preferred embodiment, the present invention provides a process for producing a sustained photocatalytically active coated glass comprising applying a photocatalytically active titanium oxide layer to a substrate of a glass by contacting the substrate surface with a liquid mixture containing a titanium source. the temperature is in the range of 645 ° C to 720 ° C, preferably in the range of 670 ° C to 720 ° C.

As mentioned above, Applicants of the present invention have realized that by applying titanium oxide at high temperatures, coatings having a relatively high photocatalytic activity can be formed, and since reduced thickness coatings tend to exhibit less reflection, the invention has high photocatalytic activity and low or low provides a new product with an advantageous combination of light reflection.

Thus, in another aspect of the invention, there is provided a photocatalytically active coated substrate having a substrate having a photocatalytically active titanium oxide coating on one surface, wherein the substrate is characterized in that the coated surface of the substrate. Photocatalytic activity greater than 5.10 '³.cm '¹.minute'¹and further characterized in that the coated substrate has a visible reflection of 35% or less when measured on the coated side.

The high photocatalytic activity is advantageous because the amount of impurities (including dirt) on the coated surface of the photocatalytically active coated substrate is reduced more rapidly than those with relatively low photocatalytic activity. The relatively rapid removal of surface contaminants also allows this to occur at low levels of UV light intensity.

The photocatalytic activity for the purposes of this specification is determined by measuring the rate of decrease of the integrated absorbance of the infrared absorption peaks of the thin film of stearic acid formed on the coated substrate at about 32 W / m.² with UV light from an intensity UVA lamp, irradiated on the surface of the coated substrate and at a wavelength of 351 nm. The stearic acid on the coated substrate can be formed by spin casting a solution of stearic acid in methanol, as described below.

The photocatalytic activity of the coated surface of the support is preferably greater than 1.10 '²cm '¹minute'¹, more preferably greater than 3.10 '²cm¹ minute'¹.

Low visible reflection is advantageous because it is less distracting than high reflection, and in particular for glass substrates, low visible reflection corresponds to the high visible light transmission that is often required when using glass in architecture and especially in vehicles.

• ·

The visible reflectance of the coated substrate on the coated side is preferably 20% or less, more preferably 17% or less, and most preferably 15% or less.

In most embodiments of the invention, the substrate is substantially transparent, and in a preferred embodiment, the substrate comprises a glass substrate. The glass substrate is usually soda lime glass substrate.

When the substrate is a soda lime glass substrate or other substrate containing alkali metal ions, the coated substrate preferably has an alkali metal ion blocking undercoat between the substrate surface and the photocatalytically active titanium oxide coating. This reduces the tendency of alkali metal ions to migrate from the support to the photocatalytically active titanium oxide sheath; this is advantageous because it is a well-known tendency that alkali metal ions poison the coating of a semiconductor oxide, thereby reducing activity.

The alkali metal ion blocking lower layer may comprise a metal oxide, but preferably the alkali metal ion blocking layer is a silicon oxide layer. The silicon oxide may be silica but need not necessarily have a stoichiometric ratio and may also contain impurities such as carbon (this is also referred to as silicon oxide carbide and is described as described in GB 2,199,848B). or nitrogen (hence also referred to as silicon oxide nitride).

It is preferred that the alkali metal ion-blocking undercoat is so thin that it has no significant effect on the optical properties of the coating, in particular, does not reduce the transparency of the transparent coated substrate or cause interference colors during reflection or transmission. The appropriate thickness range depends on the properties of the material used to form the alkali metal ion-blocking layer (in particular the refractive index ······· · · · · · · · · · · · · · · · · · · · · ·

...........

but generally the alkali metal ion-blocking lower layer has a thickness of less than 60 nm, and preferably less than 40 nm. If present, the alkali metal ion-blocking undercoat should always be thick enough to block the migration of alkali metal ions from the glass into the titanium oxide coating.

One advantage of the present invention is that the photocatalytically active titanium oxide coating is thin (contributing to low visible reflection of the coated support), but the coated support still has excellent photocatalytic activity. The thickness of the titanium oxide coating is preferably 30 nm or less, the thickness of the titanium oxide coating is more preferably 20 nm or less, and most preferably the thickness of the titanium oxide coating is in the range of 2 nm to about 20 nm.

The invention is also advantageous because the application of thin titanium oxide coatings requires less precursor and the layers can be applied in a relatively short time. A thin titanium oxide coating is less likely to produce interference colors when reflected or transmitted. However, it is particularly advantageous that the light reflectance of a thin titanium oxide coating is low, which is particularly important when the coated substrate is coated glass. Generally, the required visible light transmission of the coated glass determines the thickness of the titanium oxide coating.

The static water contact angle of the coated surface of the substrate is preferably 20 ° or less. Freshly made or cleaned glass has a hydrophilic surface (a static water contact angle of less than 40 ° indicates a hydrophilic surface), but organic contaminants quickly adhere to the surface, increasing the interface angle. A particular advantage of the coated substrates (and particularly coated glasses) of the present invention is that even when the coated surface is contaminated, irradiation of the coated surface with UV light of the appropriate wavelength reduces the fitting fabric. reducing or destroying these pollutants. A further advantage is that the water is spread over the surface with a low contact angle, reducing the discomfort of the water droplets on the surface (for example, in the case of rain) and allowing any dirt and other debris to be swept away by the photocatalytic activity of the surface. The static water contact angle is the angle that the meniscus of a water droplet closes on a glass surface and can be determined in a known manner by measuring the diameter of a water droplet of known volume on a glass surface and can be calculated using an iterative session.

The opacity of the coated substrate is preferably 1% or less, which is advantageous as it allows visual purity through a transparent coated substrate.

In preferred embodiments, the coated surface of the substrate is resistant to abrasion so that the coated surface remains photocatalytically active after being subjected to 300 strokes according to the European standard abrasion test. Preferably, the coated surface remains photocatalytically active even after being subjected to 500 strokes according to the European standard rubbing test, and even more preferably, the coated surface remains photocatalytically active after 1000 strokes according to the European standard rubbing test.

This is advantageous because the self-cleaning coated substrates of the present invention are often used on coated surfaces that are exposed to the exterior (for example, coated glass with the glass surface of the glass as the external surface of a window) where the coating is in an attackable position.

The European Standard Rubbing Test refers to the rubbing test described in BS EN 1096 Part 2 (1999), which involves moving a felt pad back and forth at a set speed and pressure on the sample surface.

In the present specification, a photocatalytic activity is considered to be retained in a coated support when, after being subjected to the European rubbing test, UV bright irradiation (e.g., a wavelength of 351 nm) reduces the static water interface angle below 15 °. In general, less than 48 hours of irradiation is required at about 32 W / m to achieve this angle of fit after rubbing the coated substrate.² at the surface of the coated substrate.

The turbidity of the coated substrate is preferably 2% or less after exposure to the European standard rubbing test.

The sustained coated carriers of the present invention may also be resistant to moisture fluctuations (which also means the effect of rain erosion). Thus, in preferred embodiments of the invention, the coated surface of the substrate is resistant to moisture fluctuations, so that the coated surface remains photocatalytically active after being subjected to 200 cycles of the humidity fluctuation test. As used herein, the humidity fluctuation assay refers to an assay wherein the coating is subjected to a temperature cycle of 35 ° C, 75 ° C, 35 ° C for 4 hours at a relative humidity of approximately 100%. The coated substrate remains photocatalytically active as determined by UV light irradiation below the static water contact angle below 15 °.

In a further preferred embodiment, the invention provides a durable photocatalytically active coated glass comprising a glass substrate coated on one surface, said coating comprising an alkali metal ion-blocking undercoat and a photocatalytically active titanium oxide layer, wherein the coated surface of the substrate is rubbing so that the coated surface remains photocatalytically active even after being subjected to 300 strokes in the European standard rubbing test. In this embodiment, the coated glass preferably has a reflectance of visible light of 35% or less as measured on the coated side, and the photocatalytically active titanium oxide layer is preferably 30 nm or less in thickness. This coating is durable for rubbing, which is surprising because it was previously believed that only a relatively thick coating could have good durability.

In yet another embodiment, the invention provides a coated glass comprising a glass support with a photocatalytically active titanium oxide coating on one surface; this coated glass is characterized by its photocatalytic activity greater than 4.10 '²cm '¹ minute'¹, preferably larger than 6.10 '²cm *¹minute'¹, and more preferably greater than 8.10 ' ²cm '¹minute'¹, furthermore, the coated glass has a visible light reflectance of less than 20% when measured on the coated side.

The coated substrates of the present invention may be used in a variety of applications, for example as a polish on glass, including a multiple polish unit consisting of a first polish board of a coated substrate disposed in opposite relationship to a second polish, or the coated glass having a first glass layer and further comprising a polymeric intermediate layer (e.g., polyvinyl butyral) and a second glass layer.

In addition to being used for self-cleaning substrates (especially self-cleaning windows for windows), the coated substrates of the invention may also be useful in reducing the concentration of atmospheric contaminants. For example, irradiation of coated glasses with UV wavelengths (including UV wavelengths in the sun) can also disrupt atmospheric contaminants such as nitrogen oxide, ozone and organic impurities adsorbed on the coated surface of the glass. This use is particularly advantageous in open built-up areas (such as city streets) where the concentration of organic pollutants can be relatively high (especially in intense sunlight) and where the available glass surface is also relatively large. Alternatively, the coated glass (where the coated surface is on the inside) can be used to reduce the concentration of atmospheric contamination within buildings, particularly within office buildings where the concentration of atmospheric contamination is relatively high.

The invention is illustrated but not limited by the following figures.

Figure 1 is a graph showing the photocatalytic activity of the coated glass produced by the process of the invention as a function of the thickness of the titanium oxide layer.

Figure 2 shows an apparatus for producing a continuous chemical layer in a vapor phase (CVD) of coatings of the invention.

In Figure 1, the coated glasses are produced using the continuous CVD process as described in the Examples below. The open circles 1 refer to the titanium oxide layers using titanium tetrachloride as the titanium precursor and the crosses 2 to the titanium oxide layers using the titanium precursor titanium tetrachloride.

The coating layers can be applied continuously to the glass substrate to produce the chemical layer in the vapor phase during the glass making process. Figure 2 illustrates an apparatus that is assigned a total of 10 numbers; this is suitable for continuous production of the coated glass article according to the invention. It has a floating portion 11, a glass softener 12 and a cooling portion 13. Floating portions 11 or bottom 14 comprising a molten tin bath 15, a lid 16, side walls (not shown) and end walls 17 which together form a seal to form a closed zone 18 where a non-oxidizing atmosphere maintained to prevent oxidation of the tin bath 15. During operation of the apparatus 10, the molten glass 19 is poured into a basin 20 and flows from it under a dispensing wall 21 and then down onto the surface of the tin bath 15 to form a floating glass strip 37 which is supported by the lifting rollers 22. they are removed and passed through the glass softener 12 and then through the cooling portion 13.

Floating 11 is maintained in a partially non-oxidizing atmosphere by introducing a suitable gas comprising, for example, nitrogen and 2% by volume of hydrogen into zone 18 via conduit 23 operatively connected to a distribution conduit 24. The non-oxidizing gas is introduced into the zone 18 from the conduit 23 at a rate sufficient to compensate for the gas losses (a portion of the non-oxidizing atmosphere leaves the zone 18 exiting below the end walls 17) and maintains a slightly positive pressure. above normal pressure. The tin bath 15 and the closed zone 18 are heated with radiant heat directed downwards from the heating elements 25. The heating zone 18 is generally maintained at a temperature between 721 ° C and 760 ° C (1330 ° F and 1400 ° F). The atmosphere in the glass softener 12 is generally air and the cooling portion 13 is not closed. Normal air was blown onto the glass with the fans 26.

The apparatus 10 includes the coaters 27, 28, 29 and 30, arranged in series in the floating zone 11 above the floating glass strip 37. The precursor gas mixture is supplied to each layer of the coating in a suitable layer applicator, which in turn directs the precursor gas mixture onto the hot surface of the floating glass strip. The temperature of the floating glass strip 37 is highest at the location of the layer applicator 27, closest to the pool 20, and lowest at the location of the layer applicator 30, closest to the glass softener 12.

The invention is further illustrated by the following examples in which the coating is applied to a moving strip of glass floating in a floating bath by vapor phase laminar flow continuous chemical preparation. glass manufacturing process. In the exemplary embodiments, two layers of coating are applied to the glass tape.

All gas volumes are measured at standard temperature and pressure unless otherwise indicated. The thickness values ​​quoted for the layers are determined using a high-resolution scanning electromicroscope and optical modeling of the reflection and light transmission spectra of the coated glass. The thickness of the coatings is measured with an uncertainty of about 5%. The light transmission and reflection properties of the coated glasses are measured using a Hitachi U-4000 spectrophotometer. The values ​​of a, b and L * for the light transmission and / or reflection colors of the glasses refer to the colors of the CIE Feet. The apparent reflection and transmission of visible light of the coated glasses is determined using the D65 illuminator and the standard CIE 2 ° observer according to ISO 9050 (Parry Moon Air Mass 2). The opacity of the coated glasses is measured with a WYK-Gardner Hazeguard + opacity meter.

The photocatalytic activity of the coated glasses is determined from the rate of decrease of the area of ​​the infrared peaks of the stearic acid film on the coated surface of the glass during irradiation with UVA light. The stearic acid film is formed on samples of glass 7-8 cm² size 20 μΙ methanolic stearic acid solution (8,8.10 '³ mól.dm '³) by rotating casting on the coated surface of the glass at 2000 rpm for 1 minute. The infrared spectrum was measured at transmission and the CH elongations of the stearic acid film (about 2700-3000 cm¹) are measured and the corresponding peak areas are determined from a peak area calibration curve. The coated side of the glass is irradiated with a UVA-351 lamp (purchased from Q-Panel Co., Cleveland, Ohio, United States of America) with a peak wavelength of 351 nm and an intensity of about 32 at the coated glass surface. W / cm². In this specification, photocatalytic activity or IR peaks (cm ')¹ minute'¹ units), or tg₀% (in units of minutes, which is the duration of UV exposure which reduces the peak height (absorption) of a peak to 10% of its original value in the wavelength range.

The static water contact angle of the coated glass was determined by measuring the diameter of a water droplet on the surface of the coated glass (in the range of 1 μΙ to 5 μΙ) after irradiation of the coated glass using a UVA 351 lamp for approximately 2 hours (or otherwise).

1-15. examples

A 1 mm thick strip of floating soda lime glass, advancing at a glass softening speed of 300 m / h, is coated with a double layer when the strip passes above the floating bath at a position where the glass temperature is in the range of about 650 ° C to about 670 ° C. it is. The floating bath atmosphere contains a liquid gas mixture of nitrogen and 9% hydrogen at a bath pressure of about 15 Pa.

Layer 1 (i.e., the first layer to be applied to the glass) is a silicon oxide layer. Layer 1 is applied by forming a monosilane (SiH₄; 60 mL / min), oxygen (120 mL / min), ethylene (360 mL / min), and nitrogen (8 L / min) to contact and flow in parallel with the glass surface in the direction of glass movement using a coating device that British Patent No. 1,507,966 (with particular reference to Figure 2 and the corresponding description on page 3, line 73 to page 4, line 75), wherein the gas mixture has a propagation path of about 0.15 over the glass surface. m. The extraction is about 9 to 12 Pa. The glass tape is coated over a width of about 10 cm at a point where it has a temperature of about 670 ° C. The silica layer has a thickness of about 20-25 nm.

Layer 2 (i.e., the second layer to be applied) is a layer of titanium dioxide. Layer 2 is applied by combining different gas streams containing titanium tetrachloride in flowing nitrogen carrier gas, ethyl acetate in flowing nitrogen carrier gas and a main nitrogen flow at 8 L / min (flow rate -1.4.10⁵ Measured at Pa) in a gas mixture, and then the gas mixture (through a line maintained at about 250 ° C) is fed to a coating apparatus consisting of an oil-cooled two-channel bed applicator. The pressure of the nitrogen carrier and the main nitrogen gas is about 1.4.10⁵ Pa. The gas mixture contacts the glass surface and flows parallel to and upward along the glass strip. The gas mixture has a propagation path upward of about 0.15 m and downward of about 0.15 m with a pull of about 15 Pa. Various streams of nitrogen carrier gas flowing through titanium tetrachloride and ethyl acetate are captured by bubblers containing either titanium tetrachloride or ethyl acetate. The flow rates of nitrogen carrier gases are shown in Figure 1. It is shown in the table (flow rate - 1.4.10⁵ Measured at Pa). The titanium tetrachloride bubbler was maintained at 69 ° C and the ethyl acetate bubbler was maintained at 42 ° C. Estimated flow rates of entrained titanium tetrachloride and entrained ethyl acetate are also shown in Table 1 on pages 1-15. examples for each.

Measure the Properties of the Double Layer Coating The thickness values ​​of Layer 2 (the titanium oxide layer), the L * values ​​of the visible reflection on the coated side, and the opacity of the coated glasses are shown in Table 2 for Examples 1-15. The opacity of each coated glass is below 0.2%.

• · ··

The photocatalytic activity of the coated glasses and the angle of attachment of the static backbone were determined. The initial peak height and initial peak area of ​​the IR peaks corresponding to the CH elongations of stearic acid, the photocatalytic activity, the static water interface and the tg₀% from Figure 1-15. Examples 3 to 4 are shown in Table 3. Surprisingly, titanium oxide thickness has little effect on photocatalytic activity.

16-19. examples

16-19. Examples 1 to 15 are carried out under the same conditions as in Examples 1-15. with the exception that the bath pressure is about 11 Pa, the extraction is applied at about 7 Pa to apply the silica lower layer (Layer 1), the titanium tetrachloride bubbler at about 100 ° C, and the ethyl acetate bubbler at about 45 ° C. And maintained at about 220 ° C by service lines.

The flow rates of nitrogen carrier gas and the estimated flow rates of entrained titanium tetrachloride and entrained ethyl acetate are shown in Figures 16-19. Examples 1 to 4 are shown in Table 1.

The estimated thickness of the layer 2 (titanium oxide layer) and the L * values ​​of the visible reflection on the coated side, as well as the opacity of the coated glasses are shown in Figs. 16-19. For examples, see Table 2.

Starting peak height and initial peak area of ​​IR peaks of stearic acid at CH stretches, photocatalytic activity, t₉o% and the static water fit angle as shown in Figs. 16-19. Example 3 is shown in Table 3.

16-19. The photocatalytic activity of Examples 1 to 4 is essentially no greater than that of Examples 1 to 15. examples, although the titanium oxide coating is thinner (and thus more reflective).

• · · · • ·

First SPREADSHEET

<td rowspan="2">Example</td><td colspan="2">Nitrogen carrier gas flow rate for bubbling (liter / min, 1.4.10⁵ Measured at Pa)</td><td rowspan="2">TiCU flow rate (liter / min)</td><td rowspan="2">Ethyl acetate flow rate (liter / min)</td>

<td>TiCU buboré- koltató</td><td>Ethyl acetate bu- borékoltató</td>

<td> 1</td><td> 0,16</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>

Second SPREADSHEET

<td>Example</td><td>Thickness of the titanium oxide layer (Nm)</td><td>The coated glass visible reflection (%)</td><td>L * value of coated glass (%)</td><td>opacity (%)</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>the</td><td>the</td><td> 0,07</td>

<td> 7</td><td> 8</td><td>the</td><td>the</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>Ϊ0</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>the</td><td>the</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>the</td><td> 28,4</td><td> 47,8</td><td> 0,3</td>

<td> 17</td><td>approx. 68</td><td> 29,1</td><td> 58,4</td><td> 0,37</td>

<td> 18</td><td>approx. 32</td><td> 25,9</td><td> 55,6</td><td> 0,24</td>

<td> 19</td><td>approx. 27</td><td> 20,5</td><td> 50,2</td><td> 0,2</td>

a We did not measure • ·

Third SPREADSHEET

<td rowspan="2">Example</td><td colspan="2">The stearic acid film is CH elongated IR peaks (2700-3000 cm '¹)</td><td rowspan="2">Fotokata- lithic activity (x10 '²cm '¹ minute'¹)</td><td rowspan="2">Static water fit angle (°)</td><td rowspan="2">tso% (minutes)</td>

<td>initial peak height (arbitrary unit)</td><td>initial peak area (Cm¹)</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>

• · ·

20-27. examples

20-27. Examples 1 to 15 are carried out under the same conditions as in Examples 1-15. with the difference that layer 2 is applied from a gas mixture containing titanium tetraethoxide entrained in a nitrogen carrier gas through a bubbler containing titanium tetraethoxide held at 170 ° C. The nitrogen carrier gas (1.4.10⁵ Pa) and titanium tetraethoxide flow rates are shown in Table 4, Table 20-27. examples for each. The main nitrogen flow rate was 8.5 l / min (1.4.10)⁵ Bucket measured).

The properties of the bilayer coatings are measured. The thickness values ​​of the layer 2 (titanium oxide layer) and the values ​​of the visible reflection on the coated side, as well as the opacity of the coated glasses are shown in Figs. Examples 5 to 9 are shown in Table 5.

The photocatalytic activity of the coated glasses and the contact angle of the static water were determined. Starting peak height and initial peak area of ​​IR peaks of stearic acid at CH stretches, photocatalytic activity, t₉o% and the static water fit angle as shown in Figures 20-27. for each of these examples, see Table 6.

Examples 28 and 29

Examples 28 and 29 were carried out under the same conditions as in Examples 20-27. with the difference that the titanium tetraethoxide bubbler was maintained at 168 ° C and the bath pressure was 11 Pa. Examples 20-27 are equivalent to those of Examples 20-27. Example 4, as shown in Tables 4, 5, and 6.

4th SPREADSHEET

<td>Example</td><td>Nitrogen carrier gas flow rates a titanium tetraethoxide buboré- extinguisher (liter / min 1,4.10⁵ Measured at Pa)</td><td>Titanium ethoxide flow rate (liter / min)</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>

5th SPREADSHEET

<td>Example</td><td>Titanium oxide layer thickness (nm)</td><td>Visible Reflection of Coated Glass (%)</td><td>Blur (%)</td>

<td> 20</td><td> 13</td><td>the</td><td> 0,4</td>

<td> 21</td><td> 13</td><td>the</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>the</td><td> 0,28</td>

<td> 24</td><td> 24</td><td>the</td><td>the</td>

<td> 25</td><td> 26</td><td>the</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>

<td>a We did not measure</td><td colspan="3"></td>

• · ·

6th SPREADSHEET

<td rowspan="2">Example</td><td colspan="2">The stearic acid film is CH elongated IR peaks (2700-3000 cm '¹)</td><td rowspan="2">Photocatalytic activity (x10 '²cm '¹ minute'¹)</td><td rowspan="2">Static water fit angle (°)</td><td rowspan="2">act * (minutes)</td>

<td>initial peak height (arbitrary unit)</td><td>initial 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>the</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 We did not measure • · · «

<img file="HU0203433A2_D0002.tif" />

30-42. examples

30-42. In Examples 1 to 4, a double layer coating is applied to a continuous CVD float glass strip over a width of about 3.35 m in the float bath during the float glass production process. The apparatus used to apply the coating is shown in Figure 2. The atmosphere of the bath contains nitrogen and 2% by volume hydrogen. The pressure of the bath is 15 Pa.

The two-layer coating consists of a layer of silicon oxide first applied to a float glass strip and a titanium oxide layer applied to a layer of silicon oxide. The gas mixture precursor chemistry used to apply the coating is the same as that described in Figures 1-15. examples. The application temperature of the layers varies with the application of layers 27, 28, 29 or 30 (with reference to Figures 2). The layer applicator 27 closest to the pool is the hottest and the layer applicator 30 closest to the glass softener is the coldest. 30-33. Examples 2 and 2 use two coaters (28 and 29 in Examples 30-33 and 27 and 28 in Example 42) to apply the silicon oxide coating. The advantage of using two coaters to apply a layer of silicon oxide is that longer production run times are possible.

The gas mixture used to apply the silica layer is shown in Figs. Examples 1 to 4 consist of the following gases at the following flow rates: helium (250 L / min), nitrogen (285 L / min), monosilane (2.5 L / min), ethylene (15 L / min) and oxygen (10 L / min) ). The same gases and flow rates were used for Example 42 except that monosilane was used at 2.3 l / min, ethylene at 13.8 l / min and oxygen at 9.2 l / min. Where two coaters are used to apply the silicon oxide layer, steps 30-42. In the examples, the flow rate above is used for each layer applicator.

• · ·

30-42. In the examples, the application temperature (i.e., the float glass film temperatures below any of the coaters corresponding to any of the 27-30 barrel barrels) is shown in Table 7. The temperatures in Table 7 are ± 28 ° C (50 ° F). The extraction for each layer applicator is about 200 Pa.

7th SPREADSHEET

<td>coating</td><td>Approximate temperature of glass tape</td>

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

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

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

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

Titanium tetrachloride (TiCl₄) and ethyl acetate were spun separately under nitrogen / helium carrier gas streams. TiCI₄ a thin film evaporator is used to vaporize. Liquid TiCI₄is kept in a pressurized container (head pressure about 3.5.10⁴ Pa). This is used to supply fluid to a metering pump and Coriolis force flow measurement system. The feed stream of the precursor is then fed into a thin film evaporator at 43 ° C. TiCI₄it is then rolled in a carrier gas (helium) and supplied to the mixing point in downstream lines maintained at 121 ° C. Ethyl acetate is obtained in a similar manner. The liquid ethyl acetate was kept in a pressurized container (head pressure about 3.5.10⁴ Pa). This is used to supply fluid to a metering pump and to the Coriolis force flow measurement system. The feed stream of precursor is then fed into a thin film evaporator at 131 ° C. The evaporated ethyl acetate is then triturated with the carrier gas (helium / nitrogen mixture) and served at the mixing point downstream which is maintained at about 121 ° C.

TiCI₄ and combining ethyl acetate gas streams to form a gas mixture which is used to apply the titanium oxide layer. This mixing point is just in front of the layer applicator.

Line velocity of float glass strip, application temperature of silicon oxide, application temperature of titanium oxide layers, He / N₂ main carrier gas flow rate, TiCI₄ and ethyl acetate flow rates as shown in Figs. For examples, see Table 8.

The coated float glass strip was cooled and cut and the optical properties and photocatalytic activity of the samples were determined. Table 9 describes the turbidity, optical properties of the samples in penetration and reflection (visible percentage penetration / reflection and color alignments using the Feet system). Coated glass is subjected to abrasion tests according to BS EN 1096, in which a sample of size 300 nm x 300 mm is firmly fixed at the four corners of the test bench to ensure that no movement of the sample is possible. An unused felt washer, cut to size fixed in the standard [BS EN 1096, part 2 (1999)], is then placed on the test plate and the plate is released onto the glass surfaces. Adjust the test pressure on the test plate to 4 N and start the test. The plate is swirled back and forth along the sample at 500 strokes at 600 strokes per minute +6 strokes per minute. After rubbing is complete, the sample is removed and optically inspected and analyzed for photocatalytic activity. The sample is considered to have passed the assay properly if the rubbing results in a change in penetration of not more than ± 5% when measured at 550 nm and the coated support remains photocatalytically active, which is

<img file="HU0203433A2_D0003.tif" />

below, 2 hours UV irradiation reduces the static water fit angle below 15 °.

The vials are also subjected to a humidity fluctuation assay in which the coating is subjected to temperature cycles (35 ° C to 75 ° C to 35 ° C) for 4 hours at approximately 100% relative humidity.

Coated glasses have a static water contact angle as prepared and after 130 minutes of UV irradiation (UVA 351 lamp approximately 32 W / m²) and after 300, 500 and / or 1000 strokes according to the European Friction Test, are given in Table 10. The angle of fit of the rubbed samples was determined after 2 hours of irradiation.

Samples deposited at higher temperatures, i.e., between 677 ° C and 721 ° C, are still photocatalytically active even after 1000 European standard rubbing strokes or 200 moisture cycles. The photocatalytic activity of the coated glass t₉% at time of manufacture and after 300, 500 and / or 1000 strokes according to the European Standard Rubbing Test or after 200 humidity test cycles are given in Table 11. The term "active" in Table 11 means that the coated glasses are photocatalytically active, but₉₀% was not determined.

8th SPREADSHEET

<td rowspan="5">Titanium oxide layer</td><td rowspan="2">Flow rate of precursors</td><td>Ethyl acetate cm³/minute</td><td> 16,3</td><td> 16,3</td><td> 16,3</td><td> 16,3</td><td>co</td><td>CO V</td><td>co T "</td><td> 14,7</td><td> 14,7</td><td>Γ-</td><td>Γ — _ Ν ' T "</td><td> 10,7</td><td> 25,4</td>

<td>I the</td><td> 6,3</td><td>co co '</td><td> 6,3</td><td>co co</td><td>co</td><td>CD</td><td>co</td><td>m tendon</td><td>m tendon</td><td> 5,5</td><td> 5,5</td><td></td><td>m co</td>

<td rowspan="2">Flow rate of carrier gas</td><td>I 1 z</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td>

<td>He liter / min</td><td> 300</td><td> 300</td><td> 300</td><td rowspan="2">T CN CD</td><td> 300</td><td> 300</td><td></td><td> 300</td><td> 300</td><td>οοε</td><td> 300</td><td> 300</td><td>οοε</td>

<td>Application temperature / ° C</td><td></td><td> 621</td><td>t CN CO</td><td>t CN CO</td><td>T · CN CO</td><td> 621</td><td>V CN CO</td><td> 677</td><td> 677</td><td> 677</td><td> 677</td><td> 069</td><td> 677</td>

<td colspan="2">Silica coating application temperature / ° C</td><td></td><td> 690 &amp; 677</td><td> 690 &amp; 677</td><td> 690 &amp; 677</td><td> 690 &amp; 677</td><td> 069</td><td> 069</td><td> 069</td><td> 069</td><td> 069</td><td> 069</td><td> 069</td><td> 721</td><td> 721 &amp; 690</td>

<td>Line speed (m / min)</td><td></td><td></td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td> 10,9</td><td>m co</td><td>CN</td>

<td>Example</td><td></td><td></td><td>She co</td><td>rO</td><td>CN CO</td><td>co co</td><td>Ν ' CO</td><td>ID co</td><td>co co</td><td>Γ- ΟΟ</td><td>co co</td><td>CO co</td><td>She Ν '</td><td></td><td>CN Ν '</td>

9th SPREADSHEET

<td colspan="2">Turbidity (%)</td><td>She'</td><td> 0,30</td><td> 0,12</td><td> 0,15</td><td> 0,12</td><td>T " Ο *</td><td> 0,14</td><td>S She</td><td> 0,07</td><td>She She'</td><td> 0,08</td><td> (0</td><td> 0,14</td>

<td rowspan="4">Penetration</td><td>GOOD</td><td> 3,6</td><td> 3,4</td><td> 3,6</td><td> 2,9</td><td> 2,7</td><td> 2,6</td><td> 2.5</td><td> 2,3</td><td></td><td>co</td><td>oo_</td><td> (0</td><td> 3,1</td>

<td> (0</td><td>CM 1</td><td>Ύ- τ- ι</td><td>τ- ι</td><td> -1,1</td><td> 1</td><td> -1,1</td><td> 1</td><td> 1</td><td>T " 1</td><td>V 1</td><td>V VJ-</td><td> (0</td><td>τ- ι</td>

<td>« -J</td><td> 93,6</td><td> 93,7</td><td> 93,6</td><td> 5'</td><td> 93,8</td><td></td><td> 94,2</td><td> 94,4</td><td> 94,8</td><td> 94,8</td><td> 94,7</td><td> (0</td><td> 93,8</td>

<td> £ 1-</td><td> 84,3</td><td> 84,5</td><td> 84,3</td><td> 85,5</td><td> 84,8</td><td> 85,4</td><td> 00 £</td><td> 86,1</td><td> 87,1</td><td> 87,2</td><td> 86,9</td><td>C0</td><td> 84,8</td>

<td rowspan="4">Film side reflection</td><td>n</td><td> -10,3</td><td> -10,4</td><td> -10,5</td><td> -9,8</td><td> 1»</td><td> 00</td><td>cs</td><td> -7,9</td><td> 0) 9'</td><td> 9'</td><td>CD «?</td><td> (0</td><td>σ&gt; σ&gt;</td>

<td> (0</td><td> 0,3</td><td> 0,3</td><td> 0,3</td><td> 0,3</td><td>V cf</td><td>5 ' She</td><td>V " cf</td><td> 0,1</td><td>She</td><td> 0,0</td><td> 0,0</td><td> (0</td><td>5 ' ο "</td>

<td>* _J</td><td> 44,5</td><td> 45,1</td><td> 45,1</td><td> 44,0</td><td> 43,7</td><td> 43,9</td><td> 42,6</td><td> 42,2</td><td> 41,0</td><td> 40,4</td><td> 40,6</td><td>CO</td><td> 44,3</td>

<td>R (%)</td><td>CM_ 'T T ~</td><td> 14,6</td><td> 14,6</td><td> 13,8</td><td> 13,6</td><td> 13,8</td><td> 12,9</td><td> 12,6</td><td> 11,9</td><td> 11,5</td><td> 11,6</td><td>co</td><td>ό ·</td>

<td colspan="2">Example</td><td> 30</td><td>CO</td><td> 32</td><td> 33</td><td>³⁴</td><td> 35</td><td> 36</td><td> 37</td><td> 38</td><td> 39</td><td> 40</td><td></td><td> 42</td>

ο c

* &lt;D

E

E ω

H (0 ··· ···

10th SPREADSHEET

<td rowspan="2">Example</td><td colspan="5">Static water fit angle (°) for rubbing! after a given number of strokes</td>

<td> 0</td><td>0 (130 minutes UV irradiation after)</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>the</td><td>the</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>the</td><td>the</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> 4,7-5,3</td><td> 4,7-5,3</td><td></td><td></td><td> 5,6-9,8</td>

a We did not measure • ·· · · * · · · ·

11th SPREADSHEET

<td rowspan="2">Example</td><td colspan="4">tgo% (min) rub after a given number of strokes</td><td rowspan="2">t0o% (min) 200 Moisture! cycle after</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>some 2160</td><td></td><td>active</td>

<td> 38</td><td> 18,5</td><td></td><td>some 2160</td><td></td><td>active</td>

<td> 39</td><td> 17</td><td></td><td>some 2160</td><td></td><td>active</td>

<td> 40</td><td> 18,5</td><td></td><td>some 2160</td><td></td><td>active</td>

<td> 41</td><td>the</td><td></td><td></td><td>some 2160</td><td>active</td>

<td> 42</td><td> 45</td><td></td><td></td><td> 2800</td><td>active</td>

a We did not measure