Preparation of quartz glass bodies with dew point monitoring in the melting oven
11492282 · 2022-11-08
Assignee
Inventors
- Nigel Robert Whippey (Seligenstadt, DE)
- Boris Gromann (Aschaffenburg, DE)
- Matthias Söhn (Darmstadt, DE)
Cpc classification
Y02P40/57
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C03B17/04
CHEMISTRY; METALLURGY
C03B20/00
CHEMISTRY; METALLURGY
C03B19/066
CHEMISTRY; METALLURGY
C03C1/022
CHEMISTRY; METALLURGY
C03B37/01211
CHEMISTRY; METALLURGY
C03C3/06
CHEMISTRY; METALLURGY
International classification
C03B19/06
CHEMISTRY; METALLURGY
C03C3/06
CHEMISTRY; METALLURGY
C03B17/04
CHEMISTRY; METALLURGY
C03B37/012
CHEMISTRY; METALLURGY
Abstract
One aspect relates to a process for the preparation of a quartz glass body. The process includes providing silicon dioxide particles, making a glass melt out of the silicon dioxide particles in an oven and making a quartz glass body out of at least part of the glass melt. The oven has a gas outlet through which gas is removed from the oven, wherein the dew point of the gas on exiting the oven through the gas outlet is less than 0° C. One aspect further relates to a quartz glass body which is obtainable by this process. One aspect further relates to a light guide, an illuminant and a formed body, which are each obtainable by further processing of the quartz glass body.
Claims
1. A process for the preparation of a quartz glass body comprising: providing silicon dioxide particles, wherein the silicon dioxide particles have a residual moisture; making a glass melt out of the silicon dioxide particles in an oven, wherein the oven has a gas outlet through which gas is removed from the oven; wherein making the glass melt out of the silicon dioxide particles further comprises: providing the silicon dioxide particles in the oven; operating the oven, wherein a gas flow is passed through the oven at a gas replacement rate; and varying the residual moisture of the silicon dioxide particles and varying the gas replacement rate of the gas flow in order to control a dew point of the gas at the outlet of the oven such that the dew point of the gas on exiting the oven through the gas outlet is less than 0° C.; and making a quartz glass body out of at least part of the glass melt.
2. The process according to claim 1, wherein the dew point is less than −10° C.
3. The process according to claim 1, wherein the dew point of the gas before entering the oven is at least 50° C. lower than the dew point on exiting the oven through the gas outlet.
4. The process according to claim 1, wherein the silicon dioxide particles are warmed in a melting crucible made of a material comprising one or more metals selected from molybdenum, tungsten, rhenium, iridium, osmium.
5. The process according to claim 1, wherein the quartz glass body comprises a total amount of less than 1000 ppb of one or more metals selected from molybdenum, tungsten, rhenium, iridium, osmium, the total amount being based on the total weight of the quartz glass body.
6. The process according to claim 1, wherein the dew point is determined in a measuring cell, wherein the measuring cell is separated by a membrane from the gas stream passing through the gas outlet.
7. The process according to claim 1, wherein a dew point mirror hygrometer is used for determining moisture.
8. The process according to claim 1, wherein melting energy is transmitted to the silicon dioxide particles via a solid surface of the oven.
9. The process according to claim 1, wherein hydrogen, helium, nitrogen or a combination of two or more thereof is present in a gas space of the oven.
10. The process according to claim 1, wherein the silicon dioxide particles are present as silicon dioxide granulate and wherein a provision of the silicon dioxide granulate comprises: providing a silicon dioxide powder; wherein the silicon dioxide powder comprises the following: a BET surface area in a range from 20 to 60 m.sup.2/g; and a bulk density in a range from 0.01 to 0.3 g/cm.sup.3; processing the silicon dioxide powder to obtain a silicon dioxide granulate, wherein the silicon dioxide granulate has a greater particle diameter than the silicon dioxide powder.
11. The process according to claim 10, wherein the silicon dioxide powder comprises at least one of the following: a carbon content of less than 50 ppm; a chlorine content of less than 200 ppm; an aluminium content of less than 200 ppb; a total content of metals different from aluminium of less than 5 ppm; at least 70 wt.-% of the silicon dioxide powder have a primary particle size in a range from 10 to 100 nm; a tamped density in a range from 0.001 to 0.3 g/cm.sup.3; a residual moisture content of less than 5 wt.-%; a particle size distribution D.sub.10 in a range from 1 to 7 μm; a particle size distribution D.sub.50 in a range from 6 to 15 μm; and a particle size distribution D.sub.90 in a range from 10 to 40 μm; wherein the wt. %, ppm and ppb are each based on the total weight of the silicon dioxide powder.
12. The process according to claim 10, wherein the silicon dioxide powder can be prepared from a compound selected from the group consisting of siloxanes, silicon alkoxides and silicon halides.
13. The process according to claim 1, wherein the silicon dioxide particles are present as silicon dioxide granulate and wherein the silicon dioxide granulate comprises at least one of the following: a BET surface area in a range from 5 to 50 m.sup.2/g; a mean particle size in a range from 50 to 500 μm; a bulk density in a range from 0.5 to 1.2 g/cm.sup.3; a carbon content of less than 50 ppm; an aluminium content of less than 200 ppb; a tamped density in a range from 0.7 to 1.3 g/cm.sup.3; a pore volume in a range from 0.1 to 2.5 mL/g; an angle of repose in a range from 23 to 26°, a particle size distribution D.sub.10 in a range from 50 to 150 μm; a particle size distribution D.sub.50 in a range from 150 to 300 μm; and a particle size distribution D.sub.90 in a range from 250 to 620 μm, wherein the ppm and ppb are each based on the total weight of the silicon dioxide granulate.
14. The process according to claim 1, comprising the following: making a hollow body with at least one opening out of the quartz glass body.
15. A process for the preparation of a light guide comprising preparing a quartz glass body by the process of claim 1, wherein the quartz glass body is first processed to obtain a hollow body with at least one opening; introducing one or multiple core rods into the hollow body through the at least one opening to obtain a precursor; and drawing the precursor in a warm temperature range from 1700 to 2500° C. to obtain a light guide with one or multiple cores and a jacket M1.
16. A process for the preparation of an illuminant comprising preparing a quartz glass body by the process of claim 1, wherein the quartz glass body is first processed to obtain a hollow body; fitting the hollow body with electrodes; and filling the hollow body with a gas.
17. A process for the preparation of a formed body comprising preparing a quartz glass body by the process of claim 1, and forming the quartz glass body to obtain the formed body comprising one or more of a group comprising hollow bodies, round bottomed flasks, standing flasks, fixtures, caps for hollow bodies, open articles, bowls, wafer carrier, crucibles, sheets, windows, cuvettes, tubes, hollow cylinders, reaction tubes, section tubes, cuboid chambers, rods, bars, blocks, tubes closed off at one or both ends, domes, bells, flanges, lenses, prisms, parts welded to each other, curved parts, convex surfaces, concave surfaces, and curved rods.
18. The process according to claim 1, further comprising at least one of: increasing the dew point of the gas on exiting the oven by increasing the residual moisture of the silicon dioxide particles; decreasing the dew point of the gas on exiting the oven by decreasing the residual moisture of the silicon dioxide particles; decreasing the dew point of the gas on exiting the oven by increasing the gas replacement rate of the gas flow; and increasing the dew point of the gas on exiting the oven by decreasing the gas replacement rate of the gas flow.
19. The process according to claim 1, wherein the residual moisture of the silicon dioxide particles varies from 0.001 to 5 wt. %, and the gas replacement rate of the gas flow varies from 200 to 3,000 L/h.
Description
FIGURES
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DESCRIPTION OF THE FIGURES
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(19) Preferably, moulds are used for the melting which can be introduced into and removed from an oven. Such moulds are often made of graphite. They provide a negative form for the caste item. The silicon dioxide granulate is filled into the mould and is first melted in the mould in step 103. Subsequently, the quartz glass body is formed in the same mould by cooling the melt. It is then freed from the mould and processed further, for example in an optional step 104. This procedure is discontinuous. The forming of the melt is preferably performed at reduced pressure, in particular in a vacuum. Further, it is possible during step 103 to charge the oven intermittently with a reducing, hydrogen containing atmosphere.
(20) In another procedure, hanging or standing crucibles are preferably employed. The melting is preferably performed in a reducing, hydrogen containing atmosphere. In a third step 103, a quartz glass body is formed. The formation of the quartz glass body is preferably performed by removing at least a part of the glass melt from the crucible and cooling. The removal is preferably performed through a nozzle at the lower end of the crucible. In this case, the form of the quartz glass body can be determined by the design of the nozzle. In this way, for example, solid bodies can be obtained. Hollow bodies are obtained for example if the nozzle additionally has a mandrel. This example of a process for the preparation of quartz glass bodies, and in particular step 103, is preferably performed continuously. In an optional step 104, a hollow body can be formed from a solid quartz glass body.
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(51) Test Methods
(52) a. Fictive Temperature The fictive temperature is measured by Raman spectroscopy using the Raman scattering intensity at about 606 cm.sup.−1. The procedure and analysis described in the contribution of Pfleiderer et. al.; “The UV-induced 210 nm absorption band in fused Silica with different thermal history and stoichiometry”; Journal of Non-Crystalline Solids, volume 159 (1993), pages 145-153.
(53) b. OH Content The OH content of the glass is measured by infrared spectroscopy. The method of D. M. Dodd & D. M. Fraser “Optical Determinations of OH in Fused Silica” (J.A.P. 37, 3991 (1966)) is employed. Instead of the device named therein, an FTIR-spectrometer (Fourier transform infrared spectrometer, current System 2000 of Perkin Elmer) is employed. The analysis of the spectra can in principle be performed on either the absorption band at ca. 3670 cm.sup.−1 or on the absorption band at ca. 7200 cm.sup.−1. The selection of the band is made on the basis that the transmission loss through OH absorption is between 10 and 90%.
(54) c. Oxygen Deficiency Centers (ODCs) For the quantitative detection, the ODC(I) absorption is measured at 165 nm by means of a transmission measurement at a probe with thickness between 1-2 mm using a vacuum UV spectrometer, model VUVAS 2000, of McPherson, Inc. (USA). Then:
N=α/σ with N=defect concentration [1/cm.sup.3] α=optical absorption [1/cm, base e] of the ODC(I) band σ=effective cross section [cm.sup.2] wherein the effective cross section is set to σ=7.5.Math.10.sup.−17 cm.sup.2 (from L. Skuja, “Color Centers and Their Transformations in Glassy SiO.sub.2”, Lectures of the summer school “Photosensitivity in optical Waveguides and glasses”, Jul. 13-18 1998, Vitznau, Switzerland).
(55) d. Elemental Analysis d-1) Solid samples are crushed. Then, ca. 20 g of the sample is cleaned by introducing it into a HF-resistant vessel fully, covering it with HF and thermally treating at 100° C. for an hour. After cooling, the acid is discarded and the sample cleaned several times with high purity water. Then, the vessel and the sample are dried in the drying cabinet. Next, ca. 2 g of the solid sample (crushed material cleaned as above; dusts etc. without pre-treatment) is weighed into an HF resistant extraction vessel and dissolved in 15 ml HF (50 wt.-%). The extraction vessel is closed and thermally treated at 100° C. until the sample is completely dissolved. Then, the extraction vessel is opened and further thermally treated at 100° C., until the solution is completely evaporated. Meanwhile, the extraction vessel is filled 3× with 15 ml of high purity water. 1 ml HNO.sub.3 is introduced into the extraction vessel, in order to dissolve separated impurities and filled up to 15 ml with high purity water. The sample solution is then ready. d-2) ICP-MS/ICP-OES measurement Whether OES or MS is employed depends on the expected elemental concentrations. Typically, measurements of MS are 1 ppb, and for OES they are 10 ppb (in each case based on the weighed sample). The measurement of the elemental concentration with the measuring device is performed according to the stipulations of the device manufacturer (ICP-MS: Agilent 7500ce; ICP-OES: Perkin Elmer 7300 DV) and using certified reference liquids for calibration. The elemental concentrations in the solution (15 ml) measured by the device are then converted based on the original weight of the probe (2 g). Note: It is to be kept in mind that the acid, the vessels, the water and the devices must be sufficiently pure in order to measure the elemental concentrations in question. This is checked by extracting a blank sample without quartz glass. The following elements are measured in this way: Li, Na, Mg, K, Ca, Fe, Ni, Cr, Hf, Zr, Ti, (Ta), V, Nb, W, Mo, Al. d-3) The measurement of samples present as a liquid is carried out as described above, wherein the sample preparation according to step d-1) is skipped. 15 ml of the liquid sample are introduced into the extraction flask. No conversion based on the original sample weight is made.
(56) e. Determination of Density of a Liquid For measuring the density of a liquid, a precisely defined volume of the liquid is weighed into a measuring device which is inert to the liquid and its constituents, wherein the empty weight and the filled weight of the vessel are measured. The density is given as the difference between the two weight measurements divided by the volume of the liquid introduced.
(57) f. Fluoride Determination 15 g of a quartz glass sample is crushed and cleaned by treating in nitric acid at 70° C. The sample is then washed several times with high purity water and then dried. 2 g of the sample is weighed into a nickel crucible and covered with 10 g Na.sub.2CO.sub.3 and 0.5 g ZnO. The crucible is closed with a Ni-lid and roasted at 1000° C. for an hour. The nickel crucible is then filled with water and boiled up until the melt cake has dissolved entirely. The solution is transferred to a 200 ml measuring flask and filled up to 200 ml with high purity water. After sedimentation of undissolved constituents, 30 ml are taken and transferred to a 100 ml measuring flask, 0.75 ml of glacial acetic acid and 60 ml TISAB are added and filled up with high purity water. The sample solution is transferred to a 150 ml glass beaker. The measurement of the fluoride content in the sample solution is performed by means of an ion sensitive (fluoride) electrode, suitable for the expected concentration range, and display device as stipulated by the manufacturer, here a fluoride ion selective electrode and reference electrode F-500 with R503/D connected to a pMX 3000/pH/ION from Wissenschaftlich-Technische Werkstatten GmbH. With the fluoride concentration in the solution, the dilution factor and the sample weight, the fluoride concentration in the quartz glass is calculated.
(58) g. Determination of Chlorine (>=50 ppm) 15 g of a quartz glass sample is crushed and cleaned by treating with nitric acid at ca. 70° C. Subsequently, the sample is rinsed several times with high purity water and then dried. 2 g of the sample are then filled into a PTFE-insert for a pressure container, dissolved with 15 ml NaOH (c=10 mol/l), closed with a PTFE lid and placed in the pressure container. It is closed and thermally treated at ca. 155° C. for 24 hours. After cooling, the PTFE insert is removed and the solution is transferred entirely to a 100 ml measuring flask. There, 10 ml HNO.sub.3 (65 wt.-%) and 15 ml acetate buffer and added, allowed to cool and filled to 100 ml with high purity water. The sample solution is transferred to a 150 ml glass beaker. The sample solution has a pH value in the range between 5 and 7. The measurement of the chloride content in the sample solution is performed by means of an ion sensitive (Chloride) electrode which is suitable for the expected concentration range, and a display device as stipulated by the manufacturer, here an electrode of type C1-500 and a reference electrode of type R-503/D attached to a pMX 3000/pH/ION from Wissenschaftlich-Technische Werkstatten GmbH.
(59) h. Chlorine Content (<50 ppm) Chlorine content <50 ppm up to 0.1 ppm in quartz glass is measured by neutron activation analysis (NAA). For this, 3 bores, each of 3 mm diameter and 1 cm long are taken from the quartz glass body under investigation. These are given to a research institute for analysis, in this case to the institute for nuclear chemistry of the Johannes-Gutenberg University in Mainz, Germany. In order to exclude contamination of the sample with chlorine, a thorough cleaning of the sample in an HF bath on location directly before the measurement was arranged. Each bore is measured several times. The results and the bores are then sent back by the research institute.
(60) i. Optical Properties The transmission of quartz glass samples is measured with the commercial grating- or FTIR-spectrometer from Perkin Elmer (Lambda 900 [190-3000 nm] or System 2000 [1000-5000 nm]). The selection is determined by the required measuring range. For measuring the absolute transmission, the sample bodies are polished on parallel planes (surface roughness RMS <0.5 nm) and the surface is cleared off all residues by ultrasound treatment. The sample thickness is 1 cm. In the case of an expected strong transmission loss due to impurities, dopants etc., a thicker or thinner sample can be selected in order to stay within the measuring range of the device. A sample thickness (measuring length) is selected at which only slight artefacts are produced on account of the passage of the radiation through the sample and at the same time a sufficiently detectable effect is measured. The measurement of the opacity, the sample is placed in front of an integrating sphere. The opacity is calculated using the measured transmission value T according to the formula: O=1/T=I.sub.0/I.
(61) j. Refractive Index and Distribution of Refractive Index in a Tube or Rod The distribution of refractive index of tubes/rods can be characterised by means of a York Technology Ltd. Preform Profiler P102 or P104. For this, the rod is placed lying in the measuring chamber the chamber is closed tight. The measuring chamber is then filled with an immersion oil which has a refractive index at the test wavelength of 633 nm, which is very similar to that of the outermost glass layer at 633 nm. The laser beam then goes through the measuring chamber. Behind the measuring chamber (in the direction of the of the radiation) is mounted a detector which measures the angle of deviation (of the radiation entering the measuring chamber compared to the radiation exiting the measuring chamber). Under the assumption of radial symmetry of the distribution of refractive index of the rod, the diametral distribution of refractive index can be reconstructed by means of an inverse Abel transformation. These calculations are performed by the software of the device manufacturer York. The refractive index of a sample is measured with the York Technology Ltd. Preform Profiler P104 analogue to the above description. In the case of isotropic samples, measurement of distribution of refractive index gives only one value, the refractive index.
(62) k. Carbon Content The quantitative measurement of the surface carbon content of silicon dioxide granulate and silicon dioxide powder is performed with a carbon analyser RC612 from Leco Corporation, USA, by the complete oxidation of all surface carbon contamination (apart from SiC) with oxygen to obtain carbon dioxide. For this, 4.0 g of a sample are weighed and introduced into the carbon analyser in a quartz glass boat. The sample is bathed in pure oxygen and heated for 180 seconds to 900° C. The CO.sub.2 which forms is measured by the infrared detector of the carbon analyser. Under these measuring conditions, the detection limit lies at <1 ppm (weight-ppm) carbon. A quartz glass boat which is suitable for this analysis using the above named carbon analyser is obtainable as a consumable for the LECO analyser with LECO number 781-335 on the laboratory supplies market, in the present case from Deslis Laborhandel, Flurstraße 21, D-40235 Dusseldorf (Germany), Deslis-No. LQ-130XL. Such a boat has width/length/height dimensions of ca. 25 mm/60 mm/15 mm. The quartz glass boat is filled up to half its height with sample material. For silicon dioxide powder, a sample weight of 1.0 g sample material can be reached. The lower detection limit is then <1 weight ppm carbon. In the same boat, a sample weight of 4 g of a silicon dioxide granulate is reached for the same filling height (mean particle size in the range from 100 to 500 μm). The lower detection limit is then about 0.1 weight ppm carbon. The lower detection limit is reached when the measurement surface integral of the sample is not greater than three times the measurement surface integral of an empty sample (empty sample=the above process but with an empty quartz glass boat).
(63) l. Curl Parameter The curl parameter (also called: “Fibre Curl”) is measured according to DIN EN 60793-1-34:2007-01 (German version of the standard IEC 60793-1-34:2006). The measurement is made according to the method described in Annex A in the sections A.2.1, A.3.2 and A.4.1 (“extrema technique”).
(64) m. Attenuation The attenuation is measured according to DIN EN 60793-1-40:2001 (German version of the standard IEC 60793-1-40:2001). The measurement is made according to the method described in the annex (“cut-back method”) at a wavelength of λ=1550 nm.
(65) n. Viscosity of the Slurry The slurry is set to a concentration of 30 weight-% solids content with demineralised water (Direct-Q 3UV, Millipore, Water quality: 18.2 MΩcm). The viscosity is then measured with a MCR102 from Anton-Paar. For this, the viscosity is measured at 5 rpm. The measurement is made at a temperature of 23° C. and an air pressure of 1013 hPa.
(66) o. Thixotropy The concentration of the slurry is set to a concentration of 30 weight-% of solids with demineralised water (Direct-Q 3UV, Millipore, water quality: 18.2 MΩ cm). The thixotropy is then measured with an MCR102 from Anton-Paar with a cone and plate arrangement. The viscosity is measured at 5 rpm and at 50 rpm. The quotient of the first and the second value gives the thixotropic index. The measurement is made at a temperature of 23° C.
(67) p. Zeta Potential of the Slurry For zeta potential measurements, a zeta potential cell (Flow Cell, Beckman Coulter) is employed. The sample is dissolved in demineralised water (Direct-Q 3UV, Millipore, water quality: 18.2 MΩcm) to obtain a 20 mL solution with a concentration of 1 g/L. The pH is set to 7 through addition of HNO.sub.3 solutions with concentrations of 0.1 mol/L and 1 mol/L and an NaOH solution with a concentration of 0.1 mol/L. The measurement is made at a temperature of 23° C.
(68) q. Isoelectric Point of the Slurry The isoelectric point, a zeta potential measurement cell (Flow Cell, Beckman Coulter) and an auto titrator (DelsaNano AT, Beckman Coulter) is employed. The sample is dissolved in demineralised water (Direct-Q 3UV, Millipore, water quality: 18.2 MΩcm) to obtain a 20 mL solution with a concentration of 1 g/L. The pH is varied by adding HNO.sub.3 solutions with concentrations of 0.1 mol/L and 1 mol/L and an NaOH solution with a concentration of 0.1 mol/L. The isoelectric point is the pH value at which the zeta potential is equal to 0. The measurement is made at a temperature of 23° C.
(69) r. pH value of the slurry The pH value of the slurry is measured using a WTW 3210 from Wissenschaftlich-Technische-Werkstatten GmbH. The pH 3210 Set 3 from WTW is employed as electrode. The measurement is made at a temperature of 23° C.
(70) s. Solids Content A weighed portion m.sub.1 of a sample is heated for 4 hours to 500° C. reweighed after cooling (m.sub.2). The solids content w is given as m.sub.2/m.sub.1*100 [Wt. %].
(71) t. Bulk Density The hulk density is measured according to the standard DIN ISO 697:1984-01 with an SMG 697 from Powtec. The bulk material (silicon dioxide powder or granulate) does not clump.
(72) u. Tamped Density (Granulate) The tamped density is measured according to the standard DIN ISO 787:1995-10.
(73) v. Measurement of the Pore Size Distribution The pore size distribution is measured according to DIN 66133 (with a surface tension of 480 mN/m and a contact angle of 140°). For the measurement of pore sizes smaller than 3.7 nm, the Pascal 400 from Porotec is used. For the measurement of pore sizes from 3.7 nm to 100 μm, the Pascal 140 from Porotec is used. The sample is subjected to a pressure treatment prior to the measurement. For this a manual hydraulic press is used (Order-No. 15011 from Specac Ltd., River House, 97 Cray Avenue, Orpington, Kent BR5 4HE, U.K.). 250 mg of sample material is weighed into a pellet die with 13 mm inner diameter from Specac Ltd. and loaded with 1 t, as per the display. This load is maintained for 5 s and readjusted if necessary. The load on the sample is then released and the sample is dried for 4 h at 105±2° C. in a recirculating air drying cabinet. The sample is weighed into the penetrometer of type 10 with an accuracy of 0.001 g and in order to give a good reproducibility of the measurement it is selected such that the stem volume used, i.e. the percentage of potentially used Hg volume for filling the penetrometer is in the range between 20% to 40% of the total Hg volume. The penetrometer is then slowly evacuated to 50 μm Hg and left at this pressure for 5 min. The following parameters are provided directly by the software of the measuring device: total pore volume, total pore surface area (assuming cylindrical pores), average pore radius, modal pore radius (most frequently occurring pore radius), peak n. 2 pore radius (μm).
(74) w. Primary Particle Size The primary particle size is measured using a scanning electron microscope (SEM) model Zeiss Ultra 55. The sample is suspended in demineralised water (Direct-Q 3UV, Millipore, water quality: 18.2 MΩcm), to obtain an extremely dilute suspension. The suspension is treated for 1 min with the ultrasound probe (UW 2070, Bandelin electronic, 70 W, 20 kHz) and then applied to a carbon adhesive pad.
(75) x. Mean Particle Size in Suspension The mean particle size in suspension is measured using a Mastersizer 2000, available from Malvern Instruments Ltd., UK, according to the user manual, using the laser deflection method. The sample is suspended in demineralised water (Direct-Q 3UV, Millipore, water quality: 18.2 MΩcm) to obtain a 20 mL suspension with a concentration of 1 g/L. The suspension is treated with the ultrasound probe (UW 2070, Bandelin electronic, 70 W, 20 kHz) for 1 min.
(76) y. Particle Size and Core Size of the Solid The particle size and core size of the solid are measured using a Camsizer XT, available from Retsch Technology GmbH, Deutschland according to the user manual. The software gives the D10, D50 and D90 values for a sample.
(77) z. BET Measurement For the measurement of the specific surface area, the static volumetric BET method according to DIN ISO 9277:2010 is used. For the BET measurement, a “NOVA 3000” or a “Quadrasorb” (available from Quantachrome), which operate according to the SMART method (“Sorption Method with Adaptive dosing Rate”), is used. The micropore analysis is performed using the t-plot process (p/p0=0.1-0.3) and the mesopore analysis is performed using the MBET process (p/p0=0.0-0.3). As reference material, the standards alumina SARM-13 and SARM-214, available from Quantachrome are used. The tare weight of the measuring cell (clean and dry) is weighed. The type of measuring cell is selected such that the sample material which is introduced and the filler rod fill the measuring cell as much as possible and the dead space is reduced to a minimum. The sample material is introduced into the measuring cell. The amount of sample material is selected so that the expected value of the measurement value corresponds to 10-20 m.sup.2/g. The measuring cells are fixed in the baking positions of the BET measuring device (without filler rod) and evacuated to <200 mbar. The speed of the evacuation is set so that no material leaks from the measuring cell. Baking is performed in this state at 200° C. for 1 h. After cooling, the measuring cell filled with the sample is weighed (raw value). The tare weight is then subtracted from the raw value of the weight=net weight=weight of the sample. The filling rod is then introduced into the measuring cell this is again fixed at the measuring location of the BET measuring device. Prior to the start of the measurement, the sample identifications and the sample weights are entered into the software. The measurement is started. The saturation pressure of nitrogen gas (N2 4.0) is measured. The measuring cell is evacuated and cooled down to 77 K using a nitrogen bath. The dead space is measured using helium gas (He 4.6). The measuring cell is evacuated again. A multi-point analysis with at least 5 measuring points is performed. N2 4.0 is used as absorptive. The specific surface area is given in m.sup.2/g.
(78) za. Viscosity of Glass Bodies The viscosity of the glass is measured using the beam bending viscosimeter of type 401—from TA Instruments with the manufacturer's software WinTA (current version 9.0) in Windows 10 according to the DIN ISO 7884-4:1998-02 standard. The support width between the supports is 45 mm. Sample rods with rectangular cross section are cut from regions of homogeneous material (top and bottom sides of the sample have a finish of at least 1000 grain). The sample surfaces after processing have a grain size=9 μm & RA=0.15 μm. The sample rods have the following dimensions: length=50 mm, width=5 mm & height=3 mm (ordered: length, width, height, as in the standards document). Three samples are measured and the mean is calculated. The sample temperature is measured using a thermocouple tight against the sample surface. The following parameters are used: heating rate=25 K up to a maximum of 1500° C., loading weight=100 g, maximum bending=3000 μm (deviation from the standards document).
(79) zb. Dew Point Measurement The dew point is measured using a dew point mirror hygrometer called “Optidew” of the company Michell Instmments GmbH, D-61381 Friedrichsdorf. The measuring cell of the dew point mirror hygrometer is arranged at a distance of 100 cm from the gas outlet of the oven. For this, the measuring device with the measuring cell is connected in gas communication to the gas outlet of the oven via a T-piece and a hose (Swagelok PFA, Outer diameter: 6 mm). The over pressure at the measuring cell is 10±2 mbar. The through flow of the gas through the measuring cell is 1-2 standard litre/min. The measuring cell is in a room with a temperature of 25° C., 30% relative air humidity and a mean pressure of 1013 hPa.
(80) zc. Residual Moisture (Water Content) The measurement of the residual moisture of a sample of silicon dioxide granulate is performed using a Moisture Analyzer HX204 from Mettler Toledo. The device functions using the principle of thermogravimetry. The HX204 is equipped with a halogen light source as heating element. The drying temperature is 220° C. The starting weight of the sample is 10 g±10%. The “Standard” measuring method is selected. The drying is carried out until the weight change reaches not more than 1 mg/140 s. The residual moisture is given as the difference between the initial weight of the sample and the final weight of the sample, divided by the initial weight of the sample. The measurement of residual moisture of silicon dioxide powder is performed according to DIN EN ISO 787-2:1995 (2 h, 105° C.).
Examples
(81) The example is further illustrated in the following through examples. The invention is not limited by the examples.
(82) A. 1. Preparation of Silicon Dioxide Powder (OMCTS Route) An aerosol formed by atomising a siloxane with air (A) is introduced under pressure into a flame which is formed by igniting a mixture of oxygen enriched air (B) and hydrogen. Furthermore, a gas flow (C) surrounding the flame is introduced and the process mixture is then cooled with process gas. The product is separated off at a filter. The process parameters are given in Table 1 and the specifications of the resulting product are given in Table 2. Experimental data for this example are indicated with A1-x.
(83) 2. Modification 1: Increased Carbon Content A process was carried out as described in A.1., but the burning of the siloxane was performed in such a way that an amount of carbon was also formed. Experimental data for this example are indicated with A2-x.
(84) TABLE-US-00002 TABLE 1 Example A1-1 A2-1 A2-2 Aerosol formation Siloxane OMCTS* OMCTS* OMCTS* Feed rate kg/h 10 10 10 (kmol/h) (0.0337) (0.0337) (0.0337) Feed rate of air (A) Nm.sup.3/h 14 10 12 Pressure barO 1.2 1.2 1.2 Burner feed Oxygen enriched air (B) Nm.sup.3/h 69 65 68 O.sub.2-content Vol. % 32 30 32 total O.sub.2 feed rate Nm.sup.3/h 25.3 21.6 24.3 kmol/h 1.130 0.964 1.083 Hydrogen feed rate Nm.sup.3/h 27 27 12 kmol/h 1.205 1.205 0.536 Feed — — Carbon compound Material methane Amount Nm.sup.3/h 5.5 Air flow (C) Nm.sup.3/h 60 60 60 Stoichiometric ratio V 2.099 1.789 2.011 X 0.938 0.80 2.023 Y 0.991 0.845 0.835 V = molar ratio of employed O.sub.2/O.sub.2 required for completed oxidation of the siloxane; X = molar ratio O.sub.2/H.sub.2; Y = (molar ratio of employed O.sub.2/O.sub.2 required for stoichiometric conversion OMCTS + fuel gas); barO = over pressure; *OMCTS = Octamethylcyclotetrasiloxane.
(85) TABLE-US-00003 TABLE 2 Example A1-1 A2-1 A2-2 BET m.sup.2/g 30 33 34 Bulk density g/ml 0.114 +− 0.011 0.105 +− 0.011 0.103 +− 0.011 tamped density g/ml 0.192 +− 0.015 0.178 +− 0.015 0.175 +− 0.015 Primary particle size nm 94 82 78 particle size distribution D10 μm 3.978 ± 0.380 5.137 ± 0.520 4.973 ± 0.455 particle size distribution D50 μm 9.383 ± 0.686 9.561 ± 0.690 9.423 ± 0.662 particle size distribution D90 μm 25.622 ± 1.387 17.362 ± 0.921 18.722 ± 1.218 C content ppm 34 ± 4 73 ± 6 80 ± 6 Cl content ppm <60 <60 <60 Al content ppb 20 20 20 Total content of metals other than Al ppb <700 <700 <700 residual moisture content wt.-% 0.02-1.0 0.02-1.0 0.02-1.0 pH value in water 4% (IEP) — 4.8 4.6 4.5 Viscosity at 5 rpm, aqueous mPas 753 1262 1380 suspension 30 Wt-%, 23° C. Alkali earth metal content ppb 538 487 472
(86) B. 1. Preparation of Silicon Dioxide Powder (Silicon Source: SiCl.sub.4) A portion of silicon tetrachloride (SiCl.sub.4) is evaporated at a temperature T and introduced with a pressure P into a flame of a burner which is formed by igniting a mixture of oxygen enriched air and hydrogen. The mean normalised gas flow to the outlet is held constant. The process mixture is then cooled with process gas. The product was separated off at a filter. The process parameters are given in Table 3 and the specifications of the resulting products are given in Table 4. They are indicated with B1-x.
(87) 2. Modification 1: Increased Carbon Content A process was carried out as described in B.1., but the burning of the silicon tetrachloride was performed such that an amount of carbon was also formed. Experimental data for this example are indicated with B2-x.
(88) TABLE-US-00004 TABLE 3 Example B1-1 B2-1 Aerosol formation Silicon tetrachloride feed kg/h 50 50 (kmol) (0.294) (0.294) Temperature T ° C. 90 90 Pressure p barO 1.2 1.2 Burner feed Oxygen enriched air, Nm.sup.3/h 145 115 O.sub.2 content therein Vol. % 45 30 Feed — Carbon compound Material methane Amount Nm.sup.3/h 2.0 Hydrogen feed Nm.sup.3/h 115 60 kmol/h 5.13 2.678 Stoichiometric ratios X 0.567 0.575 Y 0.946 0.85 X = as molar ratio O.sub.2/H.sub.2; Y = molar ratio of employed O.sub.2/O.sub.2 required for stoichiometric reaction with SiCl4 + H2 + CH4); barO = Over pressure.
(89) TABLE-US-00005 TABLE 4 Example B1-1 B2-1 BET m.sup.2/g 49 47 Bulk density g/ml 0.07 ± 0.01 0.06 ± 0.01 tamped density g/ml 0.11 ± 0.01 0.10 ± 0.01 Primary particle size nm 48 43 particle size distribution D10 μm 5.0 ± 0.5 4.5 ± 0.5 particle size distribution D50 μm 9.3 ± 0.6 8.7 ± 0.6 particle size distribution D90 μm 16.4 ± 0.5 15.8 ± 0.7 C content ppm <4 76 Cl content ppm 280 330 Al content ppb 20 20 Total of the concentrations of Ca, Co, Cr, ppb <1300 <1300 Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr residual moisture content wt.-% 0.02-1.0 0.02-1.0 pH value in water 4% (IEP) pH 3.8 3.8 Viscosity at 5 rpm, aqueous suspension mPas 5653 6012 30 Wt-%, 23° C. Alkali earth metal content ppb 550 342
(90) C. Steam Treatment A particle flow of silicon dioxide powder is introduced via the top of a standing column. Steam at a temperature (A) and air are fed via the bottom of the column. The column is maintained at a temperature (B) at the top of the column and at a second temperature (C) at the bottom of the column by an internally situated heater. After leaving the column (holding time (D)) the silicon dioxide powder has in particular the properties shown in Table 6. The process parameters are given in Table 5.
(91) TABLE-US-00006 TABLE 5 Example C-1 C-2 Educt: Product of B1-1 B2-1 Educt feed kg/h 100 100 Steam feed kg/h 5 5 Steam temperature (A) ° C. 120 120 Air feed Nm.sup.3/h 4.5 4.5 Column height m 2 2 Inner diameter mm 600 600 T (B) ° C. 260 260 T (C) ° C. 425 425 Holding time (D) silicon dioxide s 10 10 powder
(92) TABLE-US-00007 TABLE 6 Example C-1 C-2 pH value in water 4% (IEP) — 4.6 4.6 Cl content ppm <60 <60 C content ppm <4 36 Viscosity at 5 rpm, aqueous mPas 1523 1478 suspension 30 Wt-%, 23° C. The silicon dioxide powders obtained in the examples C-1 and C-2 each have a low chlorine content as well as a moderate pH value in suspension. The carbon content of example C-2 is higher as for C-1.
(93) D. Treatment with a Neutralising Agent A particle flow of silicon dioxide powder is introduced via the top of a standing column. A neutralising agent and air are fed via the bottom of the column. The column is maintained at a temperature (B) at the top of the column and at a second temperature (C) at the bottom of the column by an internally situated heater. After leaving the column (holding time (D)) the silicon dioxide powder has in particular the properties shown in Table 8. The process parameters are given in Table 7.
(94) TABLE-US-00008 TABLE 7 Example D-1 Educt: Product from B1-1 Educt feed kg/h 100 Neutralising agent Ammonia Neutralising agent feed kg/h 1.5 Neutralising agent Obtainable from Air Liquide: specifications Ammonia N38, purity ≥ 99.98 Vol. % Air feed Nm.sup.3/h 4.5 Column height m 2 inner diameter mm 600 T (B) ° C. 200 T (C) ° C. 250 Holding time (D) of silicon di- s 10 oxide powder
(95) TABLE-US-00009 TABLE 8 Example D-1 pH value in water 4% (IEP) — 4.8 Cl content ppm 210 C content Ppm <4 Viscosity at 5 rpm, aqueous suspension mPas 821 30 Wt-%, 23° C.
(96) E. 1. Preparation of Silicon Dioxide Granulate from Silicon Dioxide Powder
(97) A silicon dioxide powder is dispersed in fully desalinated water. For this, an intensive mixer of type R from the Gustav Eirich machine factory is used. The resulting suspension is pumped with a membrane pump and thereby pressurised and converted into droplets by a nozzle. These are dried in a spray tower and collect on the floor of the tower. The process parameters are given in Table 9 and the properties of the obtained granulate in Table 10. Experimental data for this example are indicated with E1-x.
(98) 2. Modification 1: Increased Carbon Content The process is analogous to that described in E.1. Additionally, carbon powder is dispersed into the suspension. Experimental data for these examples are indicated with E2-x.
(99) 3. Modification 2: Addition of Silicon The process is analogous to that described in E.1. Additionally, a silicon component is dispersed into the suspension. Experimental data for these examples are identified with E3-1.
(100) TABLE-US-00010 TABLE 9 Example E1-1 E1-2 E1-3 E1-4 E1-5 E2-1 E3-1 E3-2 Educt = Product from A1-1 A2-1 B1-1 C-1 C-2 A1-1 A1-1 A2-1 Amount of educt Kg 10 10 10 10 10 10 10 10 Carbon powder — — — — — — — Material C** Max. Particle size 75 μm Amount 1 g Silicon component — — — — — — — Material silicon powder*** Grain size (d50) 8 μm Amount 1000 ppm Carbon content 0.5 ppm Total of the 5 ppm concentrations of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr Water Rating* FD FD FD FD FD FD FD FD Liter 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 Dispersion Solids content Wt. % 65 65 65 65 65 65 65 65 Nozzle Diameter mm 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Temperature ° C. 25 25 25 25 25 25 25 25 Pressure Bar 16 16 16 16 16 16 16 16 Installation height m 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Spray tower Height m 18.20 18.20 18.20 18.20 18.20 18.20 18.20 18.20 Timer diameter m 6.30 6.30 6.30 6.30 6.30 6.30 6.30 6.30 T (introduced gas) ° C. 380 380 380 380 380 380 380 380 T (exhaust) ° C. 110 110 110 110 110 110 110 110 Air flow m.sup.3/h 6500 6500 6500 6500 6500 6500 6500 6500 Example E8-5 E8-6 E8-7 E8-8 Educt = product from A1-1 A1-1 A1-1 A1-1 Amount of educt kg 10 10 10 10 Carbon powder — — — — Material Max. particle size Amount Silicon Component — — — — Material Grain size (d50) Amount Carbon content Water Rating* VE VE VE VE Liter 5.4 5.4 5.4 5.4 Dispersion Solids content Wt. % 65 65 65 65 Nozzle Diameter Mm 2.2 2.2 2.2 2.2 Temperatur ° C. 25 25 25 25 Pressure Bar 16 16 16 16 Installation height M 6.5 6.5 6.5 6.5 Spray tower Height M 18.2 18.2 18.2 18.2 Inner diameter M 6.3 6.3 6.3 6.3 T (Introduced gas) ° C. 380 380 380 380 T (Exhaust) ° C. 110 110 110 110 Air flow m.sup.3/h 6500 6500 6500 6500 Installation height = distance between nozzle and lowest point of the spray tower interior in the direction of gravity. *FD = fully desalinated, conductance ≤0.1 μS; **C 006011: Graphite powder, max. particle size: 75 μm, high purity (available from Goodfellow GmbH, Bad Nauheim (Germany); ***available from Wacker Chemie AG (Munich, Germany).
(101) TABLE-US-00011 TABLE 10 Example E1-1 E1-2 E1-3 E1-4 E1-5 E2-1 E3-1 E3-2 BET m.sup.2/g 30 33 49 49 47 28 31 35 Bulk density g/ml 0.8 ± 0.1 0.8 ± 0.1 0.8 ± 0.1 0.8 ± 0.1 0.8 ± 0.1 0.8 ± 0.1 0.8 ± 0.1 0.8 ± 0.1 tamped density g/ml 0.9 ± 0.1 0.9 ± 0.1 0.9 ± 0.1 0.9 ± 0.1 0.9 ± 0.1 0.9 ± 0.1 0.9 ± 0.1 0.9 ± 0.1 mean particle size μm 255 255 255 255 255 255 255 255 particle size μm 110 110 110 110 110 110 110 110 distribution D10 particle size μm 222 222 222 222 222 222 222 222 distribution D50 particle size μm 390 390 390 390 390 390 390 390 distribution D90 SPHT3 Dim- 0.64-0.98 0.64-0.98 0.64-0.98 0.64-0.98 0.64-0.98 0.64-0.98 0.64-0.98 0.64-0.98 less Aspect ratio W/L Dim- 0.64-0.94 0.64-0.94 0.64-0.94 0.64-0.94 0.64-0.94 0.64-0.94 0.64-0.94 0.64-0.94 (width to length) less C content ppm <4 39 <4 <4 32 100 <4 39 Cl content ppm <60 <60 280 <60 <60 <60 <60 <60 Al content ppb 20 20 20 20 20 20 20 20 Total of the ppb <700 <700 <1300 <1300 <1300 <700 <700 <700 concentrations of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr residual moisture wt.-% <3 <3 <3 <3 <3 <3 <3 <3 content Alkaline earth metal ppb 538 487 550 550 342 538 538 487 content pore volume ml/g 0.33 0.33 0.45 0.45 0.45 0.33 0.33 0.33 angle of repose ° 26 26 26 26 26 26 26 26 Example E8-5 E8-6 E8-7 E8-8 BET m.sup.2/g 28 26 28 27 Bulk density g/ml 0.8 ± 0.1 0.8 ± 0.1 0.8 ± 0.1 0.8 ± 0.1 Tamped density g/ml 0.9 ± 0.1 0.9 ± 0.1 0.9 ± 0.1 0.9 ± 0.1 mean particle size μm 255 255 255 255 Particle size μm 110 110 110 110 distribution D10 Particle size μm 222 222 222 222 distribution D50 Particle size μm 390 390 390 390 distribution D90 SPHT3 Dim. 0.64-0.98 0.64-0.98 0.64-0.98 0.64-0.98 Less Aspect ratio W/L Dim. 0.64-0.94 0.64-0.94 0.64-0.94 0.64-0.94 (Width to length) Less C content ppm 100 100 100 100 Cl content ppm <60 <60 <60 <60 Al content ppb 20 20 20 20 Total of the ppb <700 <700 <700 <700 concentrations of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr Residual moisture Wt.-% <3 <3 <3 <3 Alkali earth metal ppb 512 516 506 486 content Pore volume ml/g 0.33 0.33 0.33 0.33 Angle of repose ° 26 26 26 26
(102) The granulates are all open pored, have a uniform and spherical shape (all by microscopic investigation). They tend not to stick together or cement.
(103) F. Cleaning of Silicon Dioxide Granulate Silicon dioxide granulate is first optionally treated with oxygen or nitrogen (see Table 11) at a temperature T1. Subsequently, the silicon dioxide granulate is treated with a co-flow of a chlorine containing component, wherein the temperature is raised to a temperature T2. The process parameters are given in Table 11 and the properties of the obtained treated granulate in Table 12.
(104) TABLE-US-00012 TABLE 11 Example F1-1 F1-2 F1-3 F1-4 F1-5 F2-1 F3-1 F3-2 F8-5 F8-6 F8-7 F8-8 Educt = Product from E1-1 E1-2 E1-3 E1-4 E1-5 E2-1 E3-1 E3-2 E8-5 E8-6 E8-7 E8-8 Rotary kiln length cm 200 200 200 200 200 200 200 200 200 200 Inner diameter cm 10 10 10 10 10 10 10 10 10 10 Throughput kg/h 2 2 2 2 2 2 2 2 2 2 Rotational speed rpm 2 2 2 2 2 2 2 2 2 2 T1 ° C. 1100 NA 1100 1100 1100 NA 1100 1100 1100 1100 1100 1100 Atmosphere O2 pure NA O2 pure O2 pure O2 pure NA N2 N2 N2 N2 N2 N2 Reactant O2 NA O2 O2 O2 NA None None None None None None Feed 300 1/h NA 300 1/h 300 1/h 300 1/h NA residual moisture wt.-% <1 <3 <1 <1 <1 <3 <1 <1 <1 <1 <1 <1 content T2 ° C. 1100 1100 1100 1100 1100 1100 NA NA NA NA NA NA Co-flow Component 1: HCl l/h 50 50 50 50 50 50 NA NA NA NA NA NA Component 2: Cl2 l/h 0 15 0 0 0 15 NA NA NA NA NA NA Component 3: N2 l/h 50 35 50 50 50 35 NA NA NA NA NA NA Total co-flow l/h 100 100 100 100 100 100 NA NA NA NA NA NA .sup.1) For the rotary kiln, the throughput is selected as the control variable. That means that during operation the mass flow exiting from the rotary kiln is weighed and then the rotational speed and/or the inclination of the rotary kiln is adapted accordingly. For example, an increase in the throughput can be achieved by a) increasing the rotational speed, or b) increasing the inclination of the rotary kiln away from horizontal, or a combination of a) and b).
(105) TABLE-US-00013 TABLE 12 Example F1-1 F1-2 F1-3 F1-4 F1-5 F2-1 F3-1 F3-2 F8-5 F8-6 F8-7 F8-8 BET m.sup.2/g 25 27 43 45 40 23 25 26 24 24 25 26 C content ppm <4 <4 <4 <4 <4 <4 <4 <4 <4 <4 <4 <4 Cl content ppm 100- 100- 300- 100- 100- 100- <60 <60 <60 <60 <60 <60 200 200 400 200 200 200 Al content ppb 20 20 20 20 20 20 20 20 20 20 20 20 pore volume mm.sup.3/g 650 650 650 650 650 650 650 650 650 650 650 650 Total of the ppb <200 <200 <200 <200 <200 <200 <700 <700 <700 <700 <700 <700 concentrations of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr Alkaline earth ppb 115 55 95 115 40 35 136 33 118 124 136 33 metal content tamped density g/cm.sup.3 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.95 ± 0.05 0.05 0.05 0.05 0.05 0.05 0.05 00.5 0.05 0.05 0.05 0.05 In the case of F1-2, F2-1 and F3-2, the granulates after the cleaning step show a significantly reduced carbon content (like low carbon granulate, e.g. F1-1). In particular, F1-2, F1-5, F2-1 and F3-2 show a significantly reduced content of alkaline earth metals. SiC formation was not observed.
(106) G. Treatment of Silicon Dioxide Granulate by Warming Silicon dioxide granulate is subjected to a temperature treatment in a pre chamber in the form of a rotary kiln which is positioned upstream of the melting oven and which is connected in flow connection to the melting oven via a further intermediate chamber. The rotary kiln is characterised by a temperature profile which increases in the flow direction. A further treated silicon dioxide granulate was obtained. In example G-4-2 no treatment by warming was performed during mixing in the rotary kiln. The process parameters are given in Table 13 and the properties of the obtained treated granulate in Table 14.
(107) TABLE-US-00014 TABLE 13 Example G1-1 G1-2 G1-3 G1-4 G1-5 G2-1 G3-1 Educt = Product F1-1 F1-2 F1-3 F1-4 F1-5 F2-1 F3-1 from Silicon components Material — — — — — — — Amount Rotary kiln Length cm 200 200 200 200 200 200 200 Inner diameter cm 10 10 10 10 10 10 10 Throughput kg/h 8 5 5 5 5 5 5 Rotation speed rpm 30 30 30 30 30 30 30 T1 (Rotary kiln ° C. RT RT RT RT RT RT RT inlet) T2 (Rotary kiln ° C. 500 500 500 500 500 500 500 outlet) Atmosphere Gas, flow direction air, free O.sub.2, in O.sub.2, in O.sub.2, in O.sub.2, in O.sub.2, in O.sub.2, in convection contraflow contraflow contraflow contraflow contraflow contraflow Total Nm.sup.3/h 0.6 0.6 0.6 0.6 0.6 0.6 throughput of gas flow Example G3-2 G4-1 G4-2 G8-5 G8-6 G8-7 G8-8 Educt = Product F3-2 F1-1 F1-1 F8-5 F8-6 F8-7 F8-8 from Silicon components Material — Silicon Silicon — — — — powder*** powder*** Amount 0.01% 0.1% Rotary kiln Length cm Inner diameter cm 200 200 NA 200 200 200 200 Throughput kg/h 10 10 10 10 10 10 Rotation speed rpm 5 5 10 10 10 10 T1 (Rotary kiln ° C. 30 30 8 8 8 8 inlet) RT RT 30 30 30 30 T2 (Rotary kiln ° C. outlet) 500 500 RT RT RT RT Atmosphere Gas, flow direction O.sub.2, in O.sub.2, in Air, free Air, free Air, free Air, free Total Nm.sup.3/h contraflow contraflow convection convection convection convection throughput of 0.6 0.6 0.6 0.6 0.6 0.6 gas flow ***Grain size D.sub.50 = 8 μm; carbon content ≤5 ppm; Total foreign metals ≤5 ppm 0.5 ppm; available from Wacker Chemie AG (Munich, Germany). .sup.1) For the rotary kiln, the throughput is selected as the control variable. That means that during operation the mass flow exiting from the rotary kiln is weighed and then the rotational speed and/or the inclination of the rotary kiln is adapted accordingly. For example, an increase in the throughput can be achieved by a) increasing the rotational speed, or b) increasing the inclination of the rotary kiln away from horizontal, or a combination of a) and b).
(108) TABLE-US-00015 TABLE 14 Example G1-1 G1-2 G1-3 G1-4 G1-5 G2-1 G3-1 G3-2 G4-1 G4-2 G8-5 G8-6 G8-7 G8-8 BET m.sup.2/g 22 23 38 42 37 22 22 21 22 24 23 22 24 22 Water content ppm 500 100 100 100 100 100 500 100 500 <10000 300 500 700 1000 C content ppm <4 <4 <4 <4 <4 <4 <4 <4 <4 <4 <4 <4 <4 <4 Cl content ppm 100- 100- 300- 100- 100- 100- <60 <60 100- 100- <60 <60 <60 <60 200 200 400 200 200 200 200 200 Al content ppb 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Total of the concentrations ppb ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr Alkaline earth metal content ppb 115 55 95 115 40 35 136 33 115 115 116 119 115 31 angle of repose ° 26 26 26 26 26 26 26 26 26 26 26 26 26 26 Due to this treatment, G3-1 and G3-2 exhibit a significantly reduce alkaline earth metal content in comparison to before (F3-1 & F3-2 respectively).
(109) H. Melting of Granulate to Obtain Quartz Glass Silicon dioxide granulate according to line 2 of Table 15 is employed for preparing a quartz glass tube in a vertical crucible drawing process. The structure of the standing oven, for example H5-1 comprising a standing melting crucible is shown schematically in
(110) TABLE-US-00016 TABLE 15 Example H1-1 H1-2 H1-3 H1-4 H1-5 H3-1 H3-2 H4-1 H4-2 Educt = Product from G1-1 G1-2 G1-3 G1-4 G1-5 G3-1 G3-2 G4-1 G4-2 Melting crucible Type Hanging Hanging Hanging Hanging Hanging Hanging Hanging Hanging Hanging metal metal metal metal metal metal metal metal metal sheet sheet sheet sheet sheet sheet sheet sheet sheet crucible crucible cmcible crucible crucible crucible crucible cmcible cmcible Type of metal cm tungsten tungsten tungsten tungsten tungsten tungsten tungsten tungsten tungsten length cm 200 150 150 150 150 200 150 200 200 Inner diameter 40 25 25 25 25 40 25 40 40 Throughput kg/h 30 20 20 20 20 30 20 30 30 T1 (Gas compartment of ° C. 300 300 300 300 300 300 300 300 300 the melting crucible) T2 (glass melt) ° C. 2100 2100 2100 2100 2100 2100 2100 2100 2100 T3 (nozzle) ° C. 1900 1900 1900 1900 1900 1900 1900 1900 1900 Atmosphere/Flushing gas He Vol.-% 50 50 50 50 50 50 50 50 50 Concentration H.sub.2 Vol.-% 50 50 50 50 50 50 50 50 50 Concentration Total gas flow throughput Nm.sup.3/h 4 4 4 4 4 2 4 2 2 O.sub.2 ppm ≤100 ≤100 ≤100 ≤100 ≤100 ≤100 ≤100 ≤100 ≤100
(111) TABLE-US-00017 TABLE 16 Example H1-1 H1-2 H1-3 H1-4 H1-5 C content ppm <4 <4 <4 <4 <4 Cl content ppm 100-200 100-200 300-400 100-200 100-200 Al content ppb 20 20 20 20 20 Total of the ppb <400 <400 <400 <400 <400 concentrations of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr OH content ppm 400 400 400 400 400 Alkaline earth ppb 115 55 95 115 40 metal content ODC content l/cm.sup.3 4*10.sup.15 2*10.sup.16 4*10.sup.15 4*10.sup.15 4*10.sup.15 pore volume mL/g 0.1 0.1 0.1 0.1 0.1 Outer cm 19.7 3.0 19.7 19.7 19.7 diameter tubular thread/quartz glass body Viscosity @1250° C. Lg(η/ 11.69 ± 0.13 11.69 ± 0.13 11.69 ± 0.13 11.69 ± 0.13 11.69 ± 0.13 @1300° C. dPas) 11.26 ± 0.1 11.26 ± 0.1 11.26 ± 0.1 11.26 ± 0.1 11.26 ± 0.1 @1350° C. 10.69 ± 0.07 10.69 ± 0.07 10.69 ± 0.07 10.69 ± 0.07 10.69 ± 0.07 Example H3-1 H3-2 H4-1 H4-2 C content ppm <4 <4 <4 <4 Cl content ppm <60 <60 100-200 100-200 Al content ppb 20 20 20 20 Total of the ppb <400 <400 <400 <400 concentrations of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr OH content ppm 80 400 80 80 Alkaline earth metal ppb 136 33 115 115 content ODC content l/cm.sup.3 5*10.sup.18 2*10.sup.16 5*10.sup.18 8*10.sup.18 pore volume mL/g 0.1 0.1 0.1 0.1 Outer diameter cm 19.7 3.0 19.7 19.7 tubular thread/quartz glass body Viscosity @1250° C. Lg(η/dPas) 12.16 ± 0.2 11.69 ± 0.13 12.16 ± 0.2 12.16 ± 0.2 @1300° C. 11.49 ± 0.15 11.26 ± 0.1 11.49 ± 0.15 11.49 ± 0.15 @1350° C. 10.88 ± 0.1 10.69 ± 0.07 10.88 ± 0.1 10.88 ± 0.1 “± ”—value are the standard deviation.
(112) TABLE-US-00018 TABLE 17 Example H5-1 H6-1 H7-1 H8-1 H8-2 H8-3 Educt = Product from G1-1 G1-1 G1-1 G1-1 G1-1 G1-1 Melting crucible Type Standing Hanging Hanging Hanging Hanging Hanging sinter sinter metal plate metal plate metal plate metal plate Type of metal crucible crucible crucible crucible crucible crucible tungsten tungsten tungsten tungsten tungsten tungsten Additional fittings — — Gas dew point dew point dew point and fixtures distributor measurement measurement measurement ring Length cm 250 250 200 200 200 200 Inner diameter cm 40 36 40 40 40 40 Throughput kg/h 40 35 30 30 30 30 T1 (Gas compartment ° C. 300 400 300 300 300 300 of melting crucible) T2 (glass melt) ° C. 2100 2150 2100 2100 2100 2100 T3 (Nozzle) ° C. 1900 1900 1900 1900 1900 1900 Atmosphere He Vol.-% 30 50 50 50 50 50 Concentration H.sub.2 Vol.-% 70 50 50 50 50 50 Concentration Total gas flow Nm.sup.3/h 4 4 8 8 4 3 throughput O.sub.2 ppm <100 <100 ≤10 ≤100 ≤100 ≤100 Example H8-4 H8-5 H8-6 H8-7 H8-8 Educt = Product from G1-1 G8-5 G8-6 G8-7 G8-8 Melting crucible Type Hanging Hanging Hanging Hanging Hanging metal plate metal plate metal plate metal plate metal plate Type of metal crucible crucible crucible crucible crucible tungsten tungsten tungsten tungsten tungsten Additional fittings and fixtures dew point dew point dew point dew point dew point measurement measurement measurement measurement measurement Length cm 200 200 200 200 200 Timer diameter cm 40 40 40 40 40 Throughput kg/h 30 30 30 30 30 T1 (Gas compartment of ° C. 300 300 300 300 300 melting crucible) T2 (glass melt) ° C. 2100 2100 2100 2100 2100 T3 (Nozzle) ° C. 1900 1900 1900 1900 1900 Atmosphere He Concentration Vol.-% 50 50 50 30 50 H.sub.2 Concentration Vol.-% 50 50 50 70 50 Total gas flow throughput Nm.sup.3/h 2 4 4 4 4 O.sub.2 ppm ≤100 ≤100 ≤100 ≤100 ≤100
(113) TABLE-US-00019 TABLE 18 Example H5-1 H6-1 H7-1 H8-1 H8-2 H8-3 C content ppm <4 <4 <4 <4 <4 <4 Cl content ppm 100-200 100-200 100-200 100-200 100-200 100-200 Al content ppb 20 20 20 20 20 20 Total of the ppb <400 <400 <400 <400 <400 <400 concentrations of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr OH content ppm 400 400 400 250 400 500 Alkaline earth ppb 115 115 115 115 115 115 metal content ODC content 1/cm.sup.3 <4*10.sup.15 <4*10.sup.15 <4*10.sup.15 <4*10.sup.15 <4*10.sup.15 <4*10.sup.15 Content of W, ppb <300 ppb <300 ppb <100 ppb <50 ppb <100 ppb <5 ppm Mo, Re, Ir, Os Outer diameter cm 26.0 19.7 19.7 19.7 19.7 19.7 of tubular thread/quartz glass body Viscosity @1250° C. lg(η/ 11.69 ± 0.13 11.69 ± 0.13 11.69 ± 0.13 12.06 ± 0.15 11.69 ± 0.13 11.69 ± 0.13 @1300° C. dPas) 11.26 ± 0.1 11.26 ± 0.1 11.26 ± 0.1 11.38 ± 0.1 11.26 ± 0.1 11.26 ± 0.1 @1350° C. 10.69 ± 0.07 10.69 ± 0.07 10.69 ± 0.07 10.75 ± 0.08 10.69 ± 0.07 10.69 ± 0.07 Example H8-4 H8-5 H8-6 H8-7 H8-8 C content ppm <4 <4 <4 <4 <4 Cl content ppm 100-200 <60 <60 <60 <60 Al content ppb 20 20 20 20 20 Total of the ppb <400 <400 <400 <400 <400 concentrations of Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr OH content ppm 800 400 350 450 500 Alkaline earth metal ppb 115 116 119 115 31 content ODC content 1/cm.sup.3 <4*10.sup.15 <4*10.sup.15 <4*10.sup.15 <4*10.sup.15 <4*10.sup.15 Content of W, Mo, ppb 100 ppm 94 ppb 25 ppb 1 ppm 1.5 ppm Re, Ir, Os Outer diameter of cm 19.7 19.7 19.7 19.7 19.7 tubular thread/quartz glass body Viscosity @1250° C. lg(η/dPas) 11.63 ± 0.13 11.69 ± 0.13 11.69 ± 0.13 11.69 ± 0.13 11.69 ± 0.13 @1300° C. 11.22 ± 0.1 11.26 ± 0.1 11.26 ± 0.1 11.2g ± 0.1 11.26 ± 0.1 @1350° C. 10.65 ± 0.07 10.69 ± 0.07 10.69 ± 0.07 10.69 ± 0.07 10.69 ± 0.07
(114) TABLE-US-00020 TABLE 19 Example H-7-1 H8-1 H8-2 H8-3 H8-4 Distributor ring cm 2 — — — — (Gas inlet in the melting crucible), Height above the glass melt Location of gas In the In the In the In the In the outlet lid of lid of lid of lid lid the the the of the of the melting melting melting melting melting crucible crucible crucible crucible crucible Dew point of the gas flow Before introduction −90 −90 −90 −90 −90 into melting crucible After removal from −10 −30 −10 0 +10 melting crucible
(115) I. Post Processing of a Quartz Glass Body A quartz glass body obtained in example H1-1 and which has already been drawn (1000 kg, Surface area=110 m.sup.2; Diameter=1.65 cm, Total length 2120 m) is cut into pieces with a length of 200 cm by scoring and striking. The end surfaces were post worked by sawing to obtain a flat end surface. The obtained batch of quartz glass bodies (I-1) was cleaned by dipping in an HF bath (V=2 m.sup.3) for 30 minutes and then rinsed with fully desalinated water (to obtain quartz glass body (I-1′)).
(116) J. “Used Acid” (HF Bath after Use) The liquid in the dipping bath in example I (V=2 m.sup.3) is tested directly after the treatment of the quartz glass body (I-1′) and without further treatment. The liquid employed for the above described treatment is characterised before and after the treatment by the properties given in Table 20.
(117) TABLE-US-00021 TABLE 20 After treatment of a quartz glass body Before treatment of mass m = 1000 kg of a quartz glass and surface area of Element Unit body 110 m.sup.2 Al ppm 0.04 0.8 Refractory metal (W, ppm 0 0.15 Mo, . . . ) Further metals according ppm 0.15 1 to entire list * in total, of which Ca ppm 0.01 0.3 Mg ppm 0.04 0.09 Na ppm 0.04 0.1 Cr ppm 0.01 0.01 Ni ppm 0.001 0.01 Fe ppm 0.01 0.05 Zr ppm 0.01 0.05 Ti ppm 0.01 0.05 HF wt.-% 40 35 Content of Si—F com- wt.-% 4 6 pounds Density g/cm.sup.3 1.14 1.123