Patent Application
20220371943
This application claims priority to European Patent Application No. 211753561.1 filed on May 21, 2021, which is incorporated in its entirety herein by reference.
The present invention relates to a glass having high UV transmittance and high solarization resistance.
Short-wavelength ultraviolet (UVC) light is used to kill or inactivate microorganisms by destroying nucleic acids and disrupting their DNA, leaving them unable to perform vital cellular functions. This is used in a variety of applications, such as purification of food, air, and/or water. A wavelength of 260 nm is particularly relevant in this respect as nucleic acids such as DNA have an absorption maximum at this wavelength. For example, the A260/A280 ratio is often used to indicate the purity of a DNA sample. “A260” refers to the absorption at a wavelength of 260 nm and “A280” refers to the absorption at a wavelength of 280 nm. A high A260/A280 ratio indicates a high purity of the DNA sample. The reason is that DNA strongly absorbs at 260 nm whereas protein contaminations mainly absorb at 280 nm. Thus, a high A260/A280 ratio means that the sample contains a high amount of DNA and a low amount of protein.
There are two main demands on glasses used in such lamps. First, the glasses should have a high UV transmittance, in particular in the UVC region. Second, the glasses should have a high solarization resistance so that their performance does not decrease too quickly upon use. Thus, a high solarization resistance increases the lifetime of the UV lamps. Consequently, there is a need for glasses combining both a high UV transmittance and a high solarization resistance.
Moreover, in view of the climate change, reducing consumption of fossil energy is more and more desired throughout different industries. In particular, the energy consumption during production of glasses is high. In order to improve the climate footprint of glass production, electrical energy can be used. Electrical energy may, for example, be produced from renewable energy sources such as wind energy or solar energy.
Using electrical energy, an electric current may be passed through the bath of molten glass between electrodes immersed in the molten glass. However, the choice of materials of the electrodes may be critical, in particular when glasses having high UV transmittance and high solarization resistance are concerned.
What is needed in the art is a way to allow a reduction of fossil energy consumption during production of glasses having high UV transmittance and high solarization resistance as well as such glass with particularly high quality.
In some exemplary embodiments provided according to the present invention, a glass includes SiO2 in an amount of at least 60.0 wt.-% and an amount of WO3 from 0.1 ppm to 60.0 ppm. Tungsten is present in such oxidation states that a transmittance of the glass at a wavelength of 260 nm is at least 75.0%.
In some exemplary embodiments provided according to the invention, a lamp for emitting ultraviolet light includes a glass including SiO2 in an amount of at least 60.0 wt.-% and an amount of WO3 from 0.1 ppm to 60.0 ppm. Tungsten is present in such oxidation states that a transmittance of the glass at a wavelength of 260 nm is at least 75.0%.
The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate embodiments of the invention and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
For obtaining glass articles having high UV transmittance and high solarization resistance, so far technologies associated with high consumption of fossil energy had to be used.
However, the present invention provides a glass having high UV transmittance and high solarization resistance that can be obtained with reduced consumption of fossil energy without substantially compromising UV transmittance and solarization resistance. Exemplary embodiments provided according to the invention are based on the finding that tungsten electrodes can be used during production and that a certain amount of tungsten emanating from the electrodes into the melt can be tolerated if reducing melting conditions are applied.
In some embodiments, the invention relates to a glass comprising SiO2 in an amount of at least 60.0 wt.-%, wherein the amount of WO3 is from 0.1 ppm to 60.0 ppm, and wherein tungsten is present in such oxidation states that the transmittance at a wavelength of 260 nm is at least 75.0% (at a reference thickness of 1.0 mm).
The present disclosure refers to tungsten present in the glasses as “WO3”. However, that is not supposed to mean that tungsten is present in the glass predominantly as tungsten (VI). Rather, the term “WO3” simply follows the common way of referring to tungsten in the glass and refers to the total amount of tungsten irrespective of the oxidation state. Exemplary embodiments provided according to the present invention are based on reducing melting conditions. Thus, in some embodiments provided according to the invention the amount of tungsten (VI) in the glasses is rather low. In the glasses provided according to the invention, tungsten is present in such oxidation states that the transmittance at a wavelength of 260 nm is at least 75.0% (at a reference thickness of 1.0 mm).
Some exemplary embodiments provided according to the invention relate to a glass comprising the following components in the indicated amounts (in wt.-%):
0-20.0
0-15.0
In some embodiments, the partial pressure of oxygen (pO2) in the glass melt at a temperature of 1500° C. is 0.5 bar or less when the glass melt is produced from the glass by inductively heating to a temperature of 1500° C. in a platinum crucible under argon atmosphere. The pO2 at 1500° C. may, for example, be at most 0.4 bar, at most 0.3 bar, or at most 0.2 bar. In some embodiments, the pO2 may, for example, be at least 0.01 bar, at least 0.02 bar, at least 0.05 bar, or at least 0.1 bar. The pO2 may, for example, be from 0.01 bar to 0.5 bar, from 0.02 bar to 0.4 bar, from 0.05 bar to 0.3 bar, or from 0.1 bar to 0.2 bar. A comparably low pO2 is advantageous as is associated with lower oxidation states of tungsten. However, the pO2 should not be too low in order to avoid occurrence of metallic tungsten.
The pO2 of the glass melt may, for example, be determined based on the voltage between a reference electrode and a measuring electrode both of which are positioned in the glass melt. The pO2 can be calculated from the voltage between the electrodes by using the Nernst equation. A platinum plate can be used as measuring electrode. The reference electrode may comprise a platinum wire positioned inside a ZrO2 ceramic tube that is closed at the tip, wherein the platinum wire is in electrically conducting contact with the wall of the ZrO2 tube. The ZrO2 ceramic may be yttrium-stabilized, calcium-stabilized, or magnesium-stabilized (see, for example, EP 1 101 740 A1, par. [0012], [0013]). For the measurement of the pO2 of the glass melt, pure oxygen is flowing around the platinum wire so that there is a constant pO2 of 1.0 bar at the platinum wire inside the reference electrode. The ZrO2 is an oxygen conductor and forms a bridge between the platinum inside the reference electrode and the glass melt, and thus indirectly also with the platinum measuring electrode inside the glass melt. Oxygen ions migrate. The concentration cell “platinum (pO2=constant=1.0 bar)/ZrO2/glass melt/platinum (pO2 of the glass melt)” generates a voltage. The voltage between the reference electrode and the measuring electrode is proportional to the pO2 in the glass melt and can thus be converted to determine the pO2 in the glass melt based on the Nernst equation.
The glass may comprise the following components in the indicated amounts (in wt.-%):
The glass may comprise the following components in the indicated amounts (in wt.-%):
In some embodiments, the glass has a transmittance at a wavelength of 260 nm of at least 75.0%, for example at least 76.0%, at least 77.0%, at least 78.0%, at least 79.0%, or at least 80.0%. Transmittance values in the present disclosure refer to a reference thickness of 1.0 mm of the glass if not indicated otherwise. That does not mean that the glass necessarily have a thickness of 1.0 mm. Rather, the reference thickness simply indicates what the transmittance would be if the glass had a thickness of 1.0 mm. The transmittance at a reference thickness may be determined by measuring the transmittance of a sample having a thickness of 1.0 mm. Alternatively, the transmittance at a thickness of 1.0 mm may also be determined by measuring the transmittance at another sample thickness, for example at a sample thickness of 0.7 mm, and then extrapolating what the transmittance would be at a thickness of 1.0 mm. Generally speaking, the extrapolation of a transmittance T1 at a thickness d1 to a transmittance T2 at a thickness d2 can be done using the following formula:
T2=((T1/P){circumflex over ( )}(d2/d1))*P, wherein P is a wavelength-dependent reflection coefficient (P=P(λ)) given in the unit “%”. P can be determined via the Sellmeier n coefficient.
In some embodiments, the transmittance at a wavelength of 260 nm may be at most 99.0%, at most 97.5%, at most 95.0%, at most 92.5%, at most 90.0% or at most 87.5% (at a reference thickness of 1.0 mm). The transmittance at a wavelength of 260 nm may, for example, be in a range of from 75.0% to 99.0%, from 76.0% to 97.5%, from 77.0% to 95.0%, from 78.0% to 92.5%, from 79.0% to 90.0% or from 80.0% to 87.5%.
The glasses provided according to the invention are characterized by a particularly high solarization resistance. The solarization resistance can be determined by irradiating the glass with a HOK 4 lamp for 144 hours and comparing the transmittance (at a reference thickness of 1.0 mm) at a wavelength of 260 nm before and after irradiation. The term “HOK 4 lamp” refers to the high pressure mercury-vapor lamp HOK 4/120 of Phillips. The emission spectrum of the HOK4 lamp is shown in
The lower the difference between the transmittance before and after irradiation is, the higher is the solarization resistance. For example, there may be two glasses, each having a transmittance (at a reference thickness of 1.0 mm) of 80% at a wavelength of 260 nm (before irradiation). After irradiation with the HOK 4 lamp for 144 hours, the transmittance may be 75% for the first glass and 70% for the second glass. Thus, the difference between transmittance (at a reference thickness of 1.0 mm) at a wavelength of 260 nm prior to irradiation with the HOK 4 lamp and transmittance (at a reference thickness of 1.0 mm) at a wavelength of 260 nm after irradiation with the HOK 4 lamp for 144 hours is 5% for the first glass and 10% for the second glass. Hence, the solarization resistance of the first glass is higher as compared to the second glass because the difference between the transmittance before and after irradiation is lower for the first glass as compared to the second glass. A high solarization resistance is associated with low solarization and vice versa. A high solarization correlates with a high induced extinction Extind.
The induced extinction Extind can be determined based on the transmittance before and after irradiation with the HOK 4 lamp for 144 hours and the thickness of the glass sample using the following formula:
Extind is the induced extinction, Tafter is the transmittance after irradiation with the HOK 4 lamp for 144 hours, Tbefore is the transmittance before irradiation with the HOK 4 lamp for 144 hours, d is the sample thickness, and ln is the natural logarithm. If not indicated otherwise, the sample thickness d is given in cm so that the induced extinction is given in 1/cm. If not indicated otherwise, the transmittance before and after irradiation with the HOK 4 lamp are given for a wavelength of 260 nm. Thus, the induced extinction as described in the present disclosure refers to the induced extinction at a wavelength of 260 nm if not indicated otherwise.
In some embodiments, the induced extinction at a wavelength of 260 nm is at most 3.5/cm, at most 3.2/cm, at most 3.0/cm, at most 2.9/cm, at most 2.8/cm, at most 2.7/cm, at most 2.6/cm, at most 2.5/cm, at most 2.4/cm, at most 2.3/cm, at most 2.2/cm, at most 2.1/cm, at most 2.0/cm, at most 1.9/cm, at most 1.8/cm, at most 1.7/cm, at most 1.6/cm, at most 1.5/cm, at most 1.4/cm, or at most 1.3/cm. The induced extinction at a wavelength of 260 nm may, for example, be at least 0.01/cm, at least 0.02/cm, at least 0.05/cm, at least 0.1/cm, at least 0.2/cm, at least 0.3/cm, at least 0.4/cm, at least 0.5/cm, at least 0.55/cm, at least 0.6/cm, at least 0.65/cm, at least 0.7/cm, at least 0.75/cm, at least 0.8/cm, at least 0.85/cm, at least 0.9/cm, at least 0.95/cm, at least 1.0/cm, at least 1.05/cm, or at least 1.1/cm. The induced extinction at a wavelength of 260 nm may, for example, be from 0.01/cm to 3.5/cm, from 0.02/cm to 3.2/cm, from 0.05/cm to 3.0/cm, from 0.1/cm to 2.0/cm, from 0.2/cm to 2.8/cm, from 0.3/cm to 2.7/cm, from 0.4/cm to 2.6/cm, from 0.5/cm to 2.5/cm, from 0.55/cm to 2.4/cm, from 0.6/cm to 2.3/cm, from 0.65/cm to 2.2/cm, from 0.7/cm to 2.1/cm, from 0.75/cm to 2.0/cm, from 0.8/cm to 1.9/cm, from 0.85/cm to 1.8/cm, from 0.9/cm to 1.7/cm, from 0.95/cm to 1.6/cm, from 1.0/cm to 1.5/cm, from 1.05/cm to 1.4/cm, or from 1.1/cm to 1.3/cm.
In some embodiments, the glass provided according to the invention is characterized by a high UV transmittance and a low induced extinction. This combination is associated with a high transmittance (at a reference thickness of 1.0 mm) at a wavelength of 260 nm after irradiation with the HOK 4 lamp for 144 hours. The transmittance (at a reference thickness of 1.0 mm) at a wavelength of 260 nm after irradiation with the HOK 4 lamp for 144 hours may, for example, be at least 59.0%, at least 60.0%, at least 61.0%, at least 62.0%, at least 63.0%, at least 64.0%, at least 65.0%, at least 66.0%, at least 67.0%, at least 68.0%, at least 69.0%, at least 70.0%, at least 71.0%, at least 72.0%, at least 73.0%, or at least 74.0%.
The transmittance (at a reference thickness of 1.0 mm) at a wavelength of 260 nm after irradiation with the HOK 4 lamp for 144 hours may, for example, be at most 95.0%, at most 92.5%, at most 90.0%, at most 88.0%, at most 86.0%, at most 85.0%, at most 84.0%, at most 83.0%, at most 82.0%, at most 81.0%, at most 80.0%, at most 79.0%, at most 78.0%, at most 77.0%, at most 76.0%, or at most 75.0%. The transmittance at a wavelength of 260 nm may, for example, be in a range of from 59.0% to 95.0%, from 60.0% to 92.5%, from 61.0% to 90.0%, from 62.0% to 88.0%, from 63.0% to 86.0%, from 64.0% to 85.0%, from 65.0% to 84.0%, from 66.0% to 83.0%, from 67.0% to 82.0% from 68.0% to 81.0%, from 69.0% to 80.0%, from 70.0% to 79.0%, from 71.0% to 78.0%, from 72.0% to 77.0%, from 73.0% to 76.0%, or from 74.0% to 75.0%.
Tungsten (W) electrodes are subject to corrosion and removal of electrode material during use. Tungsten emanating from the electrodes can then also be found in the molten glass material. This leads to contaminations of the final glass articles produced from the molten glass. Such contaminations are in turn associated with compromised properties of the resulting glasses, in particular with reduced UV transmittance and/or reduced solarization resistance. The present invention includes the finding that tungsten electrodes can be used during production and that a certain amount of tungsten emanating from the electrodes into the melt can be tolerated if reducing melting conditions are applied.
The glass provided according to the invention comprises WO3 in an amount of from 0.1 ppm to 60.0 ppm. The amount of WO3 may, for example, be at least 0.2 ppm, at least 0.4 ppm, at least 0.5 ppm, at least 1.0 ppm, at least 2.0 ppm, at least 3.0 ppm, or at least 5.0 ppm. The amount of WO3 may, for example, be at most 50.0 ppm, at most 40.0 ppm, at most 30.0 ppm, at most 25.0 ppm, at most 20.0 ppm, at most 15.0 ppm, or at most 10.0 ppm. The amount of WO3 may, for example, be from 0.2 ppm to 50.0 ppm, from 0.4 ppm to 40.0 ppm, from 0.5 ppm to 30.0 ppm, from 1.0 ppm to 25.0 ppm, from 2.0 ppm to 20.0 ppm, from 3.0 ppm to 15.0 ppm, or from 5.0 ppm to 10.0 ppm.
The glass provided according to the invention may comprise SiO2 in an amount of from 60.0 to 80.0 wt.-%, such as from 60.0 to 75.0 wt.-% or from 62.5 to 75.0 wt.-%. The amount of SiO2 is at least 60.0%, for example at least 62.5%. The amount of SiO2 may, for example, be at most 80.0 wt.-% or at most 75.0 wt.-%.
The glass provided according to the invention may comprise B2O3 in an amount of from 0.5 to 30.0 wt.-%, such as from 0.5 to 25.0 wt.-%, from 0.5 to 20.0 wt.-%, from 0.5 to 20.0 wt.-%, from 0.5 to 15.0 wt.-%, from 0.5 to 10.0 wt.-%, from 0.5 to 5.0 wt.-% or from 1.0 to 4.0 wt.-%. The amount of B2O3 may, for example, be at least 0.5 wt.-% or at least 1.0 wt.-%. The amount of B2O3 may, for example, be at most 30.0 wt.-%, at most 25.0 wt.-%, at most 20.0 wt.-%, at most 15.0 wt.-%, at most 10.0 wt.-%, at most 5.0 wt.-% or at most 4.0 wt.-%.
The glass provided according to the invention may comprise Al2O3 in an amount of from 0.5 to 10.0 wt.-%, such as from 0.5 to 7.5 wt.-%, from 0.5 to 5.0 wt.-% or from 1.0 wt.-% to 4.5 wt.-%. The amount of Al2O3 may, for example, be at least 0.5 wt.-% or at least 1.0 wt.-%. The amount of Al2O3 may, for example, be at most 10.0 wt.-%, at most 7.5 wt.-%, at most 5.0 wt.-% or at most 4.5 wt.-%.
The glass provided according to the invention may comprise Na2O in an amount of from 2.0 to 20.0 wt.-%, from 2.25 to 19.0 wt.-%, or from 2.5 to 18.0 wt.-%, from 5.0 wt.-% to 17.5 wt.-%, from 6.0 wt.-% to 15.0 wt.-%, or from 7.0 to 10.0 wt.-%. The amount of Na2O may, for example, be at least 2.0 wt.-%, at least 2.25 wt.-%, at least 2.5 wt.-%, at least 5.0 wt.-%, at least 6.0 wt.-% or at least 7.0 wt.-%. The amount of Na2O may, for example, be at most 20.0 wt.-%, at most 19.0 wt.-%, at most 18.0 wt.-%, at most 17.5 wt.-%, at most 15.0 wt.-% or at most 10.0 wt.-%.
The glass provided according to the invention may comprise K2O in an amount of from 0 to 20.0 wt.-% for example from 1.0 to 18.0 wt.-%, from 2.0 to 16.0 wt.-%, from 5.0 to 14.0 wt.-% or from 8.0 to 12.0 wt.-%. The amount of K2O may, for example, be at least 1.0 wt.-%, at least 2.0 wt.-%, at least 5.0 wt.-% or at least 8.0 wt.-%. The amount of K2O may, for example, be at most 20.0 wt.-%, at most 18.0 wt.-%, at most 16.0 wt.-%, at most 14.0 wt.-% or at most 12.0 wt.-%. In some embodiments, the amount of K2O is at most 1.0 wt.-%, at most 0.5 wt.-%, at most 0.2 wt.-% or at most 0.1 wt.-%.
The glass provided according to the invention may comprise Li2O. The amount of Li2O may, for example, be in an amount of from 0 to 5.0 wt.-%, for example from 0.1 to 2.0 wt.-% or from 0.5 to 1.5 wt.-%. The amount of Li2O may, for example, be at least 0.1 wt.-%, at least 0.2 wt.-% or at least 0.5 wt.-%. The amount of Li2O may, for example, be at most 5.0 wt.-%, at most 2.0 wt.-% or at most 1.5 wt.-%. In some embodiments, the amount of Li2O is at most 1.0 wt.-%, at most 0.5 wt.-%, at most 0.2 wt.-% or at most 0.1 wt.-%.
In some embodiments, the sum of the amounts of Li2O, Na2O and K2O is in a range of from 4.0 wt.-% to 30.0 wt.-% or from 5.0 to 30.0 wt.-%, for example from 7.5 wt.-% to 27.5 wt.-%, from 10.0 wt.-% to 25.0 wt.-%, from 12.5 wt.-% to 22.5 wt.-% or from 15.0 wt.-% to 20.0 wt.-%. The sum of the amounts of Li2O, Na2O and K2O may, for example, be at least 4.0 wt.-%, at least 5.0 wt.-%, at least 7.5 wt.-%, at least 10.0 wt.-%, at least 12.5 wt.-% or at least 15.0 wt.-%. The sum of the amounts of Li2O, Na2O and K2O may, for example, be at most 30.0 wt.-%, at most 27.5 wt.-%, at most 25.0 wt.-%, at most 22.5 wt.-% or at most 20.0 wt.-%.
In some embodiments, the sum of the amounts of Na2O and K2O is in a range of from 3.5 wt.-% to 30.0 wt.-% or from 5.0 to 30.0 wt.-%, for example from 7.5 wt.-% to 27.5 wt.-%, from 10.0 wt.-% to 25.0 wt.-%, from 12.5 wt.-% to 22.5 wt.-% or from 15.0 wt.-% to 20.0 wt.-%. The sum of the amounts of Na2O and K2O may, for example, be at least 3.5 wt.-%, at least 5.0 wt.-%, at least 7.5 wt.-%, at least 10.0 wt.-%, at least 12.5 wt.-% or at least 15.0 wt.-%. The sum of the amounts of Na2O and K2O may, for example, be at most 30.0 wt.-%, at most 27.5 wt.-%, at most 25.0 wt.-%, at most 22.5 wt.-% or at most 20.0 wt.-%.
The base glass composition provided according to the invention may comprise BaO in an amount of from 0 to 15.0 wt.-%, such as from 2.5 to 12.5 wt.-%, from 4.5 to 10.0 wt.-% or from 5.0 to 8.0 wt.-%. The amount of BaO may, for example, be at least 2.5 wt.-%, at least 4.5 wt.-% or at least 5.0 wt.-%. The amount of BaO may, for example, be at most 15.0 wt.-%, at most 12.5 wt.-%, at most 10.0 wt.-% or at most 8.0 wt.-%. In some embodiments, the amount of BaO is at most 1.0 wt.-%, at most 0.5 wt.-%, at most 0.2 wt.-% or at most 0.1 wt.-%.
The base glass composition may consist of SiO2, B2O3, Al2O3, Na2O, K2O and BaO to an extent of at least 95.0 wt.-%, for example at least 97.0 wt.-% or at least 99.0 wt.-%.
In some embodiments, the amount of Fe2O3 is less than 100 ppm, less than 50 ppm, less than 20 ppm, less than 15 ppm, or less than 10 ppm.
In some embodiments, the amount of TiO2 is less than 100 ppm, less than 50 ppm, less than 20 ppm, less than 15 ppm, or less than 10 ppm.
In some embodiments, the amount of NiO is less than 100 ppm, less than 50 ppm, less than 20 ppm, less than 15 ppm, or less than 10 ppm.
In some embodiments, the amount of Cr2O3 is less than 100 ppm, less than 50 ppm, less than 20 ppm, less than 15 ppm, less than 10 ppm, or less than 5 ppm.
In some embodiments, the amount of at least one, at least two, or at least three of Fe2O3, TiO2, NiO and Cr2O3 is less than 100 ppm, less than 50 ppm, less than 20 ppm, less than 15 ppm, or less than 10 ppm.
In some embodiments, the amount of Fe2O3, TiO2, NiO and Cr2O3 is less than 100 ppm, less than 50 ppm, less than 20 ppm, less than 15 ppm, or less than 10 ppm.
The term “ppm” as used herein refers to ppm on a weight basis if not indicated otherwise. For example, 1000 ppm correspond to 0.1 wt.-%.
In some embodiments, the amount of ZrO2 is less than 1.0 wt.-%, less than 0.5 wt.-%, less than 0.2 wt.-% or less than 0.1 wt.-%.
The glass provided according to the invention may comprise Cl in an amount of more than 100 ppm, more than 200 ppm or more than 500 ppm, for example at least 0.1 wt.-%. In some embodiments, the amount of Cl is at most 1.5 wt.-%, at most 1.2 wt.-%, at most 1.0 wt.-% or at most 0.8 wt.-%. The amount of Cl may, for example, be from 100 ppm to 1.5 wt.-%, from 200 ppm to 1.2 wt.-%, from 500 ppm to 1.0 wt.-% or from 0.1 wt.-% to 0.8 wt.-%.
In some embodiments, the glass has a composition that makes it particularly resistant against the influence of WO3 on UV transmittance and/or solarization. The glass may have a good UV transmittance and a good solarization resistance even though certain amounts of WO3 are present in the glass. A certain amount of WO3 can be accepted in the glasses provided according to the invention, in particular due to the reducing melting conditions applied.
In some embodiments, the influence of WO3 on transmittance at a wavelength of 260 nm is very low or even negligible. The glass composition is such that tungsten induced extinction is low. Therefore, higher amounts of WO3 then expected may be acceptable in the glasses provided according to the present invention.
The tungsten induced extinction WExtind can be determined based on the transmittance before and after irradiation with the HOK 4 lamp for 144 hours, the thickness of the glass sample, and the amount of WO3 using the following formula:
WExtind is the tungsten induced extinction, Tafter is the transmittance after irradiation with the HOK 4 lamp for 144 hours, Tbefore is the transmittance before irradiation with the HOK 4 lamp for 144 hours, d is the sample thickness, ln is the natural logarithm, and W is the amount of WO3 in ppm. If not indicated otherwise, the sample thickness d is given in cm so that the tungsten induced extinction is given in 1/(cm*ppm). If not indicated otherwise, the transmittance before and after irradiation with the HOK 4 lamp is given for a wavelength of 260 nm. Thus, the tungsten induced extinction as described in the present disclosure refers to the tungsten induced extinction at a wavelength of 260 nm if not indicated otherwise.
In some embodiments, the tungsten induced extinction at a wavelength of 260 nm is at most 0.20/(cm*ppm), at most 0.15/(cm*ppm), at most 0.14/(cm*ppm), at most 0.13/(cm*ppm), at most 0.12/(cm*ppm), at most 0.11/(cm*ppm), or at most 0.10/(cm*ppm) at a reference amount of WO3 of 20 ppm. The tungsten induced extinction at a wavelength of 260 nm may, for example, be at least 0.01/(cm*ppm), at least 0.02/(cm*ppm), at least 0.03/(cm*ppm), at least 0.04/(cm*ppm), at least 0.05/(cm*ppm), at least 0.06/(cm*ppm), or at least 0.07/(cm*ppm) at a reference amount of WO3 of 20 ppm. The tungsten induced extinction at a wavelength of 260 nm may, for example, be from 0.01/(cm*ppm) to 0.20/(cm*ppm), from 0.02/(cm*ppm) to 0.15/(cm*ppm), from 0.03/(cm*ppm) to 0.14/(cm*ppm), from 0.04/(cm*ppm) to 0.13/(cm*ppm), from 0.05/(cm*ppm) to 0.12/(cm*ppm), from 0.06/(cm*ppm) to 0.11/(cm*ppm), or from 0.07/(cm*ppm) to 0.10/(cm*ppm) at a reference amount of WO3 of 20 ppm.
The invention also relates to a method of producing a glass provided according to the invention, the method comprising the following steps:
a) Melting glass raw materials, the melting step comprising the use of tungsten electrodes,
b) Optionally refining the melt,
c) Cooling the melt.
The method is characterized by reducing melting conditions such that tungsten is present in such oxidation states that the transmittance at a wavelength of 260 nm is at least 75.0% (at a reference thickness of 1.0 mm). Such conditions result in the compromising influence of tungsten on UV transmittance and solarization resistance to be drastically reduced so that a certain amount of tungsten emanating from the electrodes into the melt can be tolerated without substantially compromising UV transmittance and solarization resistance. The reducing character of the melt is also influenced by the temperature. The method may comprise temperatures of 1440° C. or more, for example 1500° C. or more. The viscosity at a given temperature is dependent on the glass composition. The method provided according to the invention may involve viscosities of 2.5 dPas or less.
However, the conditions should not be too reducing in order to avoid metallic tungsten.
Providing reducing melting conditions may comprise adding one or more reducing agents, for example one or more carbohydrate, in particular one or more sugar, for example sucrose, to the glass raw materials, for example in an amount of from 0.1 to 1.0 wt.-%, for example from 0.2 to 0.6 wt.-%. Glass raw materials comprising nitrates may be avoided. In some embodiments, the amount of nitrates is at most 200 ppm, at most 100 ppm, at most 50 ppm, at most 20 ppm, at most 10 ppm, at most 5 ppm, at most 2 ppm, or at most 1 ppm.
The optional refining step may comprise using Cl as refining agent. Cl is an exemplary refining agent as it has a reducing character as well. Oxidizing refining agents may be avoided. In some embodiments, the amount of oxidizing refining agents is at most 200 ppm, at most 100 ppm, at most 50 ppm, at most 20 ppm, at most 10 ppm, at most 5 ppm, at most 2 ppm, or at most 1 ppm.
The invention also relates to the use of glass provided according to the invention for or as UVC detectors, envelope in germicidal lamps, UV-LED (in particular UVC-LED), UV-transmitting lamps, protective tubing for UV-lamps, UV-transmitting material for UV oxidation reactors, UV flame detectors, UV photoelectric cells, sun reactors, spectral analysis device, photomultiplier, and for windows (in particular EPROM windows), cover plate for solar cells (e.g. in space), UV-transmitting cuvette (e.g. for photoluminescence measurements with UV excitation), UV-CCL (cold cathode lamps) and/or xenon flash lamps.
In some embodiments, the invention relates to the use of the glass provided according to the invention in diagnostics, in particular for or as microfluidic component, e.g. for photoluminescence-based diagnostics. The glass may be used for or as the bottom plate or the cover plate of a microfluidic component. The high UV-transmittance is advantageous for the signal-to-noise ratio of the diagnostic method.
In some embodiments, the invention relates to the use of the glass provided according to the invention for lamps emitting UV light, in particular UV lamps with or without protective tubing.
In some embodiments, the invention relates to the use of a glass provided according to the invention in UVC detectors or as envelope in germicidal lamps.
The invention also relates to a UVC detector or a germicidal lamp comprising the glass provided according to the invention.
Alkali-containing silicate glasses provided in accordance with the glass composition as described in the present disclosure have been tested with respect to UV transmittance and solarization resistance. The composition of the glasses merely differed with respect to the amount of WO3. The amount of WO3 was less than 3 ppm in Example 1, and about 21 ppm in Example 2. All examples were obtained under reducing melting conditions by adding sucrose to the glass raw materials in an amount of 0.4 wt.-%. Samples having a thickness of about 0.7 mm have been tested for transmittance in the wavelength range of from 200 nm to 400 nm before and after irradiation with the HOK 4 lamp. The results are shown in
In particular, regarding the particularly relevant wavelength of 260 nm, the results obtained are summarized in the following table.
The results show that an increasing amount of WO3 results in an increased induced extinction.
Alkali-containing silicate glasses provided in accordance with the glass composition as described in the present disclosure comprising WO3 in an amount of about 20 to 25 ppm have been tested with respect to UV transmittance and solarization resistance. The glasses of Examples 4 and 5 whose compositions were basically identical (23 ppm WO3 in Example 4 and 19 ppm WO3 in Example 5) mainly differed with respect to the melting conditions applied. Example 4 was obtained under reducing melting conditions by adding sucrose to the glass raw materials. In contrast, Example 5 was obtained under oxidizing melting conditions (1 wt.-% nitrate). Samples having a thickness of about 1.0 mm have been tested for transmittance at a wavelength of 260 nm before and after irradiation with the HOK 4 lamp. The results obtained are summarized in the following table.
The transmittance at a wavelength of 260 nm was higher in Example 4 obtained under reducing melting conditions as compared to Example 5 obtained under oxidizing melting conditions both before and after irradiation with the HOK 4 lamp.
While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21175356.1 | May 2021 | EP | regional |
