Patent Grant
11339076
This Utility Patent Application claims the benefit of the filing date of European Application No. 15201145.8, filed Dec. 18, 2015, and International Application No. PCT/EP2016/081462, filed Dec. 16, 2016, both of which are herein incorporated by reference.
The invention relates to a process for the preparation of a quartz glass body comprising the process steps i.) Providing a silicon dioxide granulate I prepared from a pyrogenically produced silicon dioxide powder, ii.) Treating the silicon dioxide granulate I with a reactant at a temperature in a range from 1000 to 1300° C., iii) Making a glass melt out of the silicon dioxide granulate and iv.) Making a quartz glass body out of at least a part of the glass melt. Furthermore, the invention relates to a quartz glass body obtainable by this process. Furthermore, the invention relates to a light guide, an illuminant and a formed body, each of which is obtainable by further processing of the quartz glass body. The invention additionally relates to a process for the preparation of a silicon dioxide granulate II.
Quartz glass, quartz glass products and products which contain quartz glass are known. Likewise, various processes for the preparation of quartz glass and quartz glass bodies are already known. Nonetheless, considerable efforts are still being made to identify preparation processes by which quartz glass of even higher purity, i.e. absence of impurities, can be prepared. In many areas of application of quartz glass and its processed products, high demands are made, for example in terms of homogeneity and purity. This is the case, inter alia, for quartz glass which is processed into light guides or illuminants. Here, impurities can cause absorptions. That is disadvantageous, since it leads to colour changes and attenuation of the emitted light. A further example of an application of high purity quartz glass is production steps in the fabrication of semiconductors. Here, every impurity of the glass body can potentially lead to defects in the semiconductor and thus to rejects in the fabrication. The varieties of high purity, often synthetic quartz glass which are employed in these processes are laborious to prepare. These are valuable.
Furthermore, there is a market requirement for the above mentioned high purity synthetic quartz glass and products derived therefrom at low price. Therefore, it is an aspiration to be able to offer high purity quartz glass at a lower price than before. In this connection, both more cost-efficient preparation processes as well as cheaper sources of raw materials are sought.
Known processes for the preparation of quartz glass bodies comprise melting silicon dioxide and making quartz glass bodies out of the melt. Irregularities in a glass body, for example through inclusion of gases in the form of bubbles, can lead to a failure of the glass body under load, in particular at high temperatures, or can preclude its use for a particular purpose. Impurities in the raw materials for the quartz glass can lead to cracks, bubbles, streaks and discolorations in the quartz glass. When employed in processes for the preparation and processing of semi-conductors, impurities in the glass body can also be released and transferred to the treated semi-conductor components. This is the case, for example, in etching processes and leads to rejects in the semi-conductor billets. A common problem associated with known preparation processes is therefore an inadequate quality of quartz glass bodies.
A further aspect relates to raw materials efficiency. It appears advantageous to input quartz glass and raw materials, which accumulate elsewhere as side products, into a preferably industrial process for quartz glass products, rather than employ these side products as filler, e.g. in construction or to dispose of them as rubbish at a cost. These side products am often separated off as fine dust in filters. The fine dust brings further problems, in particular in relation to health, work safety and handling.
An object of the present invention is to at least partially overcome one or more of the disadvantages present in the state of the art.
It is a further object of the invention to provide light guides, illuminants and components with a long lifetime. The term components in particular is to be understood to include devices which can be employed in reactors for chemical and/or physical treatment steps.
It is a further object of the invention to provide light guides, illuminants and glass components which are free of bubbles or have a low content of bubbles.
It is a further object of the invention to provide light guides and glass components which have a high transparency.
It is a further object of the invention to provide light guides, illuminants and components which have a low opacity.
It is a further object of the invention to provide light guides with a low attenuation.
It is a further object of the invention to provide light guides, illuminants and components which have a high contour accuracy. In particular, it is an object of the invention to provide light guides, illuminants and components which do not deform at high temperatures. In particular, it is an object of the invention to provide light guides, illuminants and components which are form stable, even when formed with large size.
It is a further object of the invention to provide light guides, illuminants and components which are tear-proof and break-proof.
It is a further object of the invention to provide light guides, illuminants and components which are efficient to prepare.
It is a further object of the invention to provide light guides, illuminants and components which are cost-efficient to prepare.
It is a further object of the invention to provide light guides, illuminants and components, the preparation of which does not require long further processing steps, for example tempering.
It is a further object of the invention to provide light guides, illuminants and components which have a high thermal shock resistance. It is in particular an object of the invention to provide light guides, illuminants and components which with large thermal fluctuations exhibit only little thermal expansion.
It is a further object of the invention to provide light guides, illuminants and components with a high hardness.
It is a further object of the invention to provide light guides, illuminants and components which have a high purity and low contamination with foreign atoms. The term foreign atoms is employed to mean constituents which are not purposefully introduced.
It is a further object of the invention to provide light guides, illuminants and components which contain a low content of dopant materials.
It is a further object of the invention to provide light guides, illuminants and components which have a high homogeneity. A homogeneity of a property or of a material is a measure of the uniformity of the distribution of this property or material in a sample.
It is in particular an object of the invention to provide light guides, illuminants and components which have a high material homogeneity. The material homogeneity is a measure of the uniformity of the distribution of the elements and compounds, in particularly of OH, chlorine, metals, in particular aluminium, alkaline earth metals, refractory metals and dopant materials, contained in the light guide, illuminant or semi-conductor device.
It is a further object of the invention to provide a quartz glass body which is suitable for use in light guides, illuminants and quartz glass components and solves at least partly at least one, preferably several, of the above mentioned objects.
It is a further object of the invention to provide a quartz glass body which has a linear form. In particular, it is an object to provide a quartz glass body which has a high bending radius. In particular, it is a further object to provide a quartz glass body which has a high fibre curl.
It is a further object to provide a quartz glass body in which the migration of cations is as low as possible.
It is a further object to provide a quartz glass body which has a high homogeneity over the entire length of the quartz glass body.
In particular, it is a further object of the invention to provide a quartz glass body which has a high homogeneity of refractive index over the entire length of the quartz glass body.
In particular, it is a further object of the invention to provide a quartz glass body which has a high homogeneity of viscosity over the entire length of the quartz glass body.
In particular, it is a further object of the invention to provide a quartz glass body which has a high material homogeneity over the entire length of the quartz glass body.
In particular, it is a further object of the invention to provide a quartz glass body which has a high optical homogeneity over the entire length of the quartz glass body.
It is a further object to provide a quartz glass body that has no or a very low content of carbon impurities.
In particular, it is an object of the invention to provide quartz glass bodies which contain no silicon carbide particles.
It is a further object to provide a quartz glass body which has a low OH content.
It is a further object to provide a quartz glass body which has a low alkaline earth metal content.
It is a further object to provide a quartz glass body which has no or a very low content of crystallisation nuclei.
It is a further object to provide a quartz glass body which has properties that are as unchanged as possible under thermal load. It is in particular a further object of the invention to provide a quartz glass body which does not crystallise under thermal load.
It is a further object to provide a process in which the granulate preparation can be performed in a time- and cost-effective manner in the presence of mains water.
It is a further object of the invention to provide a silicon dioxide granulate with a good handlability.
It is a further object of the invention to provide a silicon dioxide granulate which has a low content of fine dust.
It is a further object to provide a silicon dioxide granulate which can be easily stored, transported and conveyed.
It is a further object of the invention to provide a silicon dioxide granulate which can form bubble free quartz glass bodies. It is a further object of the invention to provide a silicon dioxide granulate which as a bulk material comprises as small a gas volume as possible.
It is a further object of the invention to provide an open-pored silicon dioxide granulate.
It is a further object of the invention to provide a process by which quartz glass bodies can be prepared by which at least part of the above described objects is at least partly solved.
It is a further object of the invention to provide a process by which quartz glass bodies can be more simply prepared. It is a further object of the invention to provide a process by which quartz glass bodies can be prepared continuously. It is a further object of the invention to provide a process by which quartz glass bodies can be prepared by a continuous melting and forming process.
It is a further object of the invention to provide a process by which quartz glass bodies can be formed with a high speed.
It is a further object of the invention to provide a process by which quartz glass bodies can be prepared with a low reject rate.
It is a further object of the invention to provide a process by which assemblable quartz glass bodies can be prepared. It is a further object of the invention to provide an automated process by which quartz glass bodies can be prepared. It is a further object of the invention to provide a process for the preparation of quartz glass bodies in which a silicon dioxide granulate can be processed in a melting oven without the requirement for it to be subjected beforehand to a deliberate compacting step, e.g. by a temperature treatment of more than 1000° C.
It is in particular an object of the invention to provide a process for the preparation of quartz glass bodies in which a silicon dioxide granulate with a BET of 20 m2/g or more can be introduced into a melting oven, melted and processed to obtain a quartz glass body.
It is a further object to provide a process in which the granulate preparation can be performed in a time- and cost-effective manner using mains water in the slurrying of the silicon dioxide powder.
A further object is to improve the processability of quartz glass bodies further.
A further object is to improve the assemblability of quartz glass bodies further.
A contribution to at least partially fulfilling at least one of the aforementioned objects is made by the independent claims. The dependent claims provide preferred embodiments which contribute to at least partially fulfilling at least one of the objects.
General
In the present description disclosed ranges also include the boundary values. A disclosure of the form “in the range from X to Y” in relation to a parameter A therefore means that A can take the values X, Y and values in between X and Y. Ranges bounded on one side of the form “up to Y” for a parameter A mean correspondingly the value Y and those less than Y.
A first aspect of the present invention is a process for the preparation of a quartz glass body comprising the process steps:
Step i.)
According to the invention, the provision of the silicon dioxide granulate I comprises the following process steps:
A powder means particles of a dry solid material with a primary particle size in the range from 1 to less than 100 nm.
The silicon dioxide granulate can be obtained by granulating silicon dioxide powder. A silicon dioxide granulate commonly has a BET surface area of 3 m2/g or more and a density of less than 1.5 g/cm3. Granulating means transforming powder particles into granules. During granulation, clusters of multiple silicon dioxide powder particles, i.e. larger agglomerates, form which am referred to as “silicon dioxide granules”. These am often also called “silicon dioxide granulate particles” or “granulate particles”. Collectively, the granules form a granulate, e.g. the silicon dioxide granules form a “silicon dioxide granulate”. The silicon dioxide granulate has a larger particle diameter than the silicon dioxide powder.
The granulation procedure, for transforming a powder into a granulate, will be described in more detail later.
Silicon dioxide grain in the present context means silicon dioxide particles which are obtainable by reduction in size of a silicon dioxide body, in particular of a quartz glass body. A silicon dioxide grain commonly has a density of more than 1.2 g/cm3, for example in a range from 1.2 to 2.2 g/cm3, and particularly preferably of about 2.2 g/cm3. Furthermore, the BET surface area of a silicon dioxide grain is preferably generally less than 1 m2/g, determined according to DIN ISO 9277:2014-01.
In principle, all silicon dioxide particles which are considered to be suitable by the skilled man can be selected. Preferred are silicon dioxide granulate and silicon dioxide grain.
Particle diameter or particle size mean the diameter of a particle, given as the “area equivalent circular diameter xAi” according to the formula
wherein Ai stands for the surface area of the observed particle by means of image analysis. Suitable methods for the measurement are for example ISO 13322-1:2014 or ISO 13322-2:2009. Comparative disclosures such as “greater particle diameter” always means that the values being compared am measured with the same method.
Silicon Dioxide Powder
In the context of the present invention, synthetic silicon dioxide powder, namely pyrogenically produced silicon dioxide powder, is used.
The silicon dioxide powder can be any silicon dioxide powder which has at least two particles. As preparation process, any process which the skilled man considers to be prevalent in the art and suitable can be used.
According to a preferred embodiment of the present invention, the silicon dioxide powder is produced as side product in the preparation of quartz glass, in particular in the preparation of so called “soot bodies”. Silicon dioxide from such a source is often also called “soot dust”.
A preferred source for the silicon dioxide powder are silicon dioxide particles which are obtained from the synthetic preparation of soot bodies by application of flame hydrolysis burners. In the preparation of a soot body, a rotating carrier tube with a cylinder jacket surface is moved back and forth along a row of burners. Flame hydrolysis burners can be fed with oxygen and hydrogen as burner gases as well as the raw materials for making silicon dioxide primary particles. The silicon dioxide primary particles preferably have a primary particle size of up to 100 mu. The silicon dioxide primary particles produced by flame hydrolysis aggregate or agglomerate to form silicon dioxide particles with particle sizes in of about 9 μm (DIN ISO 13320:2009-1). In the silicon dioxide particles, the silicon dioxide primary particles are identifiable by their form by scanning electron microscopy and the primary particle size can be measured. A portion of the silicon dioxide particles are deposited on the cylinder jacket surface of the carrier tube which is rotating about its longitudinal axis. In this way, the soot body is built up layer by layer. Another portion of the silicon dioxide particles are not deposited on the cylinder jacket surface of the carrier tube, rather they accumulate as dust, e.g. in a filter system. This other portion of silicon dioxide particles make up the silicon dioxide powder, often also called “soot dust”. In general, the portion of the silicon dioxide particles which are deposited on the carrier tube is greater than the portion of silicon dioxide particles which accumulate as soot dust in the context of soot body preparation, based on the total weight of the silicon dioxide particles.
These days, soot dust is generally disposed of as waste in an onerous and costly manner, or used as filler material without adding value, e.g. in road construction, as additive in the dyes industry, as a raw material for the tiling industry and for the preparation of hexafluorosilicic acid, which is employed for restoration of construction foundations. In the case of the present invention, it is a suitable raw material and can be processed to obtain a high-quality product.
Silicon dioxide prepared by flame hydrolysis is normally called pyrogenic silicon dioxide. Pyrogenic silicon dioxide is normally available in the form of amorphous silicon dioxide primary particles or silicon dioxide particles.
According to a preferred embodiment, the silicon dioxide powder can be prepared by flame hydrolysis out of a gas mixture. In this case, silicon dioxide particles are also created in the flame hydrolysis and are taken away before agglomerates or aggregates form. Here, the silicon dioxide powder, previously referred to as soot dust, is the main product.
Suitable raw materials for creating the silicon dioxide powder are preferably siloxanes, silicon alkoxides and inorganic silicon compounds. Siloxanes means linear and cyclic polyalkylsiloxanes. Preferably, polyalkylsiloxanes have the general formula
SipOpR2p,
Particularly preferred are siloxanes selected from the group consisting of hexamethyldisiloxane, hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) or a combination of two or more thereof. If the siloxane comprises D3, D4 and D5, then D4 is preferably the main component. The main component is preferably present in an amount of at least 70 wt.-%, preferably of at least 80 wt.-%, for example of at least 90 wt.-% or of at least 94 wt.-%, particularly preferably of at least 98 wt.-%, in each case based on the total amount of the silicon dioxide powder. Preferred silicon alkoxides am tetramethoxysilane and methyltrimethoxysilane. Preferred inorganic silicon compounds as raw material for silicon dioxide powder are silicon halides, silicates, silicon carbide and silicon nitride. Particularly preferred inorganic silicon compounds as raw material for silicon dioxide powder are silicon tetrachloride and trichlorosilane.
According to a preferred embodiment, the silicon dioxide powder can be prepared from a compound selected from the group consisting of siloxanes, silicon alkoxides and silicon halides.
Preferably, the silicon dioxide powder can be prepared from a compound selected from the group consisting of hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetramethoxysilane, methyltrimethoxysilane, silicon tetrachloride and trichlorosilane or a combination of two or more thereof, for example out of silicon tetrachloride and octamethylcyclotetrasiloxane, particularly preferably out of octamethylcyclotetrasiloxane.
For making silicon dioxide out of silicon tetrachloride by flame hydrolysis, various parameters are significant. A preferred composition of a suitable gas mixture comprises an oxygen content in the flame hydrolysis in a range from 25 to 40 vol.-%. The content of hydrogen can be in a range from 45 to 60 vol.-%. The content of silicon tetrachloride is preferably 5 to 30 vol.-%, all of the afore mentioned vol.-% being based on the total volume of the gas flow. Further preferred is a combination of the above mentioned volume proportions for oxygen, hydrogen and SiCl4. The flame in the flame hydrolysis preferably has a temperature in a range from 1500 to 2500° C., for example in a range from 1600 to 2400° C., particularly preferably in a range from 1700 to 2300° C. Preferably, the silicon dioxide primary particles created in the flame hydrolysis are taken away as silicon dioxide powder before agglomerates or aggregates form.
According to a preferred embodiment of the first aspect of the invention, the silicon dioxide powder has at least one, for example at least two or at least three or at least four, particularly preferably at least five of the following features:
The silicon dioxide powder contains silicon dioxide. Preferably, the silicon dioxide powder contains a proportion of silicon dioxide of more than 95 wt.-%, for example more than 98 wt.-% or more than 99 wt.-%. or more than 99.9 wt.-%, in each case based on the total weight of the silicon dioxide powder. Particularly preferably, the silicon dioxide powder contains a proportion of silicon dioxide of more than 99.99 wt.-%, based on the total weight of the silicon dioxide powder.
Preferably, the silicon dioxide powder has a metal content of metals different from aluminium of less than 5 ppm, for example of less than 2 ppm, particularly preferably of less than 1 ppm, in each case based on the total weight of the silicon dioxide powder. Often however, the silicon dioxide powder has a content of metals different to aluminium of at least 1 ppb. Such metals are for example sodium, lithium, potassium, magnesium, calcium, strontium, germanium, copper, molybdenum, tungsten, titanium, iron and chromium. These can be present for example in elemental form, as an ion, or as part of a molecule or of an ion or of a complex.
Preferably, the silicon dioxide powder has a total content of further constituents of less than 30 ppm, for example of less than 20 ppm, particularly preferably of less than 15 ppm, the ppm in each case being based on the total weight of the silicon dioxide powder. Often however, the silicon dioxide powder has a content of further constituents of at least 1 ppb. Further constituents means all constituents of the silicon dioxide powder which do not belong to the following group: silicon dioxide, chlorine, aluminium, OH-groups.
In the present context, reference to a constituent, when the constituent is a chemical element, means that it can be present as element or as an ion or in a compound or a salt. For example the term “aluminium” includes in addition to metallic aluminium, also aluminium salts, aluminium oxides and aluminium metal complexes. For example, the term “chlorine” includes, in addition to elemental chlorine, chlorides such as sodium chloride and hydrogen chloride. Often, the further constituents are present in the same aggregate state as the material in which they are contained.
In the present context, in the case where a constituent is a chemical compound or a functional group, reference to the constituent means that the constituent can be present in the form disclosed, as a charged chemical compound or as derivative of the chemical compound. For example, reference to the chemical material ethanol includes, in addition to ethanol, also ethanolate, for example sodium ethanolate. Reference to “OH-group” also includes silanol, water and metal hydroxides. For example, reference to derivate in the context of acetic acid also includes acetic acid ester and acetic acid anhydride.
Preferably, at least 70% of the powder particles of the silicon dioxide powder, based on the number of powder particles, have a primary particle size of less than 100 nm, for example in the range from 10 to 100 nm or from 15 to 100 nm, and particularly preferably in the range from 20 to 100 nm. The primary particle size is measured by dynamic light scattering according to ISO 13320:2009-10.
Preferably at least 75% of the powder particles of the silicon dioxide powder, based on the number of powder particles, have a primary particle size of less than 100 nm, for example in the range from 10 to 100 nm or from 15 to 100 nm, and particularly preferably in the range from 20 to 100 nm.
Preferably, at least 80% of the powder particles of the silicon dioxide powder, based on the number of powder particles, have a primary particle size of less than 100 nm, for example in the range from 10 to 100 nm or from 15 to 100 nm, and particularly preferably in the range from 20 to 100 nm.
Preferably, at least 85% of the powder particles of the silicon dioxide powder, based on the number of powder particles, have a primary particle size of less than 100 nm, for example in the range from 10 to 100 nm or from 15 to 100 nm, and particularly preferably in the range from 20 to 100 nm.
Preferably, at least 90% of the powder particles of the silicon dioxide powder, based on the number of powder particles, have a primary particle size of less than 100 nm, for example in the range from 10 to 100 nm or from 15 to 100 nm, and particularly preferably in the range from 20 to 100 nm.
Preferably, at least 95% of the powder particles of the silicon dioxide powder, based on the number of powder particles, have a primary particle size of less than 100 nm, for example in the range from 10 to 100 nm or from 15 to 100 nm, and particularly preferably in the range from 20 to 100 nm.
Preferably, the silicon dioxide powder has a particle size D10 in the range from 1 to 7 μm, for example in the range from 2 to 6 μm or in the range from 3 to 5 μm, particularly preferably in the range from 3.5 to 4.5 μm. Preferably, the silicon dioxide powder has a particle size D50 in the range from 6 to 15 μm, for example in the range from 7 to 13 μm or in the range from 8 to 11 μm, particularly preferably in the range from 8.5 to 10.5 μm. Preferably, the silicon dioxide powder has a particle size D50 in the range from 10 to 40 μm, for example in the range from 15 to 35 μm, particularly preferably in the range from 20 to 30 μm.
Preferably, the silicon dioxide powder has a specific surface area (BET-surface area) in a range from 20 to 60 m2/g, for example from 25 to 55 m2/g, or from 30 to 50 m2 g, particularly preferably from 20 to 40 m2/g. The BET surface area is determined according to the method of Brunauer, Emmet and Teller (BET) by means of DIN 66132 which is based on gas absorption at the surface to be measured.
Preferably, the silicon dioxide powder has a pH value of less than 7, for example in the range from 3 to 6.5 or from 3.5 to 6 or from 4 to 5.5, particularly preferably in the range from 4.5 to 5. The pH value can be determined by means of a single rod measuring electrode (4% silicon dioxide powder in water).
The silicon dioxide powder preferably has the feature combination a./b./c. or a./b./f. or a./b./g., further preferred the feature combination a./b./c./f. or a./b./c./g. or a./b./f./g., further preferably the feature combination a./b./c./g.
The silicon dioxide powder preferably has the feature combination a./b./c., wherein the BET surface area is in a range from 20 to 40 m2/g, the bulk density is in a range from 0.05 to 0.3 g/mL and the carbon content is less than 40 ppm.
The silicon dioxide powder preferably has the feature combination a./b./f., wherein the BET surface area is in a range from 20 to 40 m2/g, the bulk density is in a range from 0.05 to 0.3 g/mL and the total content of metals which am different to aluminium is in a range from 1 ppb to 1 ppm.
The silicon dioxide powder preferably has the feature combination a./b./g., wherein the BET surface area is in a range from 20 to 40 m2/g, the bulk density is in a range from 0.05 to 0.3 g/mL and at least 70 wt. % of the powder particles have a primary particle size in a range from 20 to less than 100 nm.
The silicon dioxide powder further preferably has the feature combination a./b./c./f., wherein the BET surface area is in a range from 20 to 40 m2/g, the bulk density is in a range from 0.05 to 0.3 g/mL, the carbon content is less than 40 ppm and the total content of metals which are different to aluminium is in a range from 1 ppb to 1 ppm.
The silicon dioxide powder further preferably has the feature combination a./b./g., wherein the BET surface area is in a range from 20 to 40 m2/g, the bulk density is in a range from 0.05 to 0.3 g/mL, the carbon content is less than 40 ppm and at least 70 wt. % of the powder particles have a primary particle size in a range from 20 to less than 100 nm.
The silicon dioxide powder further preferably has the feature combination a./b./f./g., wherein the BET surface area is in a range from 20 to 40 m2/g, the bulk density is in a range from 0.05 to 0.3 g/mL, the total content of metals which are different to aluminium is in a range from 1 ppb to 1 ppm and at least 70 wt. % of the powder particles have a primary particle size in a range from 20 to less than 100 nm.
The silicon dioxide powder has particularly preferably the feature combination a./b./c./f./g., wherein the BET surface area is in a range from 20 to 40 m2/g, the bulk density is in a range from 0.05 to 0.3 g/mL, the carbon content is less than 40 ppm, the total content of metals which are different to aluminium is in a range from 1 ppb to 1 ppm and at least 70 wt. % of the powder particles have a primary particle size in a range from 20 to less than 100 nm.
Step II.
According to the invention, the silicon dioxide powder is processed in step II to obtain a silicon dioxide granulate I. For this purpose, any processes known to the skilled man that lead to an increase in the particle diameter are suitable.
“Silicon dioxide granulate I” means a granulate of silicon dioxide which is obtained by granulation of silicon dioxide powder, which was obtained during the pyrolysis of silicon compounds in a fuel gas flame. Preferred as fuel gas are oxyhydrogen gas, natural gas or methane gas, and particularly preferred is oxyhydrogen gas.
The silicon dioxide granulate has a particle diameter which is greater than the particle diameter of the silicon dioxide powder. Preferably, the particle diameter of the silicon dioxide granulate is in a range from 500 to 50,000 times as great as the particle diameter of the silicon dioxide powder, for example 1,000 to 10,000 times as great, particularly preferably 2,000 to 8,000 times as great.
Preferably, at least 90% of the silicon dioxide granulate provided in step i.) is made up of pyrogenically produced silicon dioxide powder, for example at least 95 wt.-% or at least 98 wt.-%, particularly preferably at least 99 wt.-% or more, in each case based on the total weight of the silicon dioxide granulate.
Preferably, step II. comprises the following steps:
In the context of the present invention, a liquid means a material or a mixture of materials which is liquid at a pressure of 1013 hPa and a temperature of 20° C.
A “slurry” in the context of the present invention means a mixture of at least two materials, wherein the mixture, considered under the prevailing conditions, comprises at least one liquid and at least one solid.
Suitable liquids are all materials and mixtures of materials known to the skilled man and which appear suitable for the present application. Preferably, the liquid is selected from the group consisting of organic liquids and water. Preferably, the solubility of the silicon dioxide powder in the liquid is less than 0.5 g/L, preferably less than 0.25 g/L, particularly preferably less than 0.1 g/L, the g/L each given as g silicon dioxide powder per litre liquid.
Preferred suitable liquids are polar solvents. These can be organic liquids or water. Preferably, the liquid is selected from the group consisting of water, methanol, ethanol, n-propanol, iso-propanol, n-butanol, tert-butanol and mixtures of a more than one thereof. Particularly preferably, the liquid is water. Particularly preferably, the liquid comprises distilled or de-ionized water.
Preferably, the silicon dioxide powder is processed to obtain a slurry. The silicon dioxide powder is virtually insoluble in the liquid at room temperature, but can be introduced into the liquid in high weight proportions to obtain the slurry.
The silicon dioxide powder and the liquid can be mixed in any manner. For example, the silicon dioxide powder can be added to the liquid, or the liquid can be added to the silicon dioxide powder. The mixture can be agitated during the addition or following the addition. Particularly preferably, the mixture is agitated during and following the addition. Examples for the agitation am shaking and stirring, or a combination of both. Preferably, the silicon dioxide powder can be added to the liquid under stirring. Furthermore, preferably, a portion of the silicon dioxide powder can be added to the liquid, wherein the mixture thus obtained is agitated, and the mixture is subsequently mixed with the remaining portion of the silicon dioxide powder. Likewise, a portion of the liquid can be added to the silicon dioxide powder, wherein the mixture thus obtained is agitated, and the mixture subsequently mixed with the remaining portion of the liquid.
By mixing the silicon dioxide powder and the liquid, a slurry is obtained. Preferably, the slurry is a suspension in which the silicon dioxide powder is distributed uniformly in the liquid. “Uniform” means that the density and the composition of the slurry at each position does not deviate from the average density and from the average composition by more than 10%, in each case based on the total amount of slurry. A uniform distribution of the silicon dioxide powder in the liquid can prepared, or obtained, or both, by an agitation as mentioned above.
Preferably, the slurry has a weight per litre in the range from 1000 to 2000 g/L, for example in the range from 1200 to 1900 g/L or from 1300 to 1800 g/L, particularly preferably in the range from 1400 to 1700 g/L. The weight per litre is measured by weighing a volume calibrated container.
According to a preferred embodiment, at least one, for example at least two or at least three or at least four, particularly preferably at least five of the following features applies to the slurry:
Preferably, the silicon dioxide particles in a 4 wt.-% aqueous slurry have a particle size D10 in a range from 50 to 250 nm, particularly preferably in the range from 100 to 150 mu. Preferably, the silicon dioxide particles in a 4 wt. % aqueous slurry have a particle size D50 in a range from 100 to 400 nm, particularly preferably in the range from 200 to 250 nm. Preferably, the silicon dioxide particles in a 4 wt.-% aqueous slurry have a particle size D90 in a range from 200 to 600 nm, particularly preferably in a range from 350 to 400 mu. The particle size is measured according to DIN ISO 13320-1.
“Isoelectric point” means the pH value at which the zeta potential takes the value 0. The zeta potential is measured according to ISO 13099-2:2012.
Preferably, the pH value of the slurry is set to a value in the range given above. Preferably, the pH value can be set by adding to the slurry materials such as NaOH or NH3, for example as aqueous solution. During this process, the slurry is often agitated.
Granulation
The silicon dioxide granulate I is obtained from the silicon dioxide powder by granulation. Granulation means the transformation of powder particles into granules. During granulation, larger agglomerates which am referred to as “silicon dioxide granules” am formed by agglomeration of multiple silicon dioxide powder particles. These am often also called “silicon dioxide particles”, “silicon dioxide granulate particles” or “granulate particles”. Collectively, granules make up a granulate, e.g. the silicon dioxide granules make up a “silicon dioxide granulate”.
In the present case, any granulation process which is known to the skilled man and appears to him to be suitable for the granulation of silicon dioxide powder can in principle be selected. Granulation processes can be categorised as agglomeration granulation processes or press granulation processes, and further categorised as wet and dry granulation processes. Known methods are roll granulation in a granulation plate, spray granulation, centrifugal pulverisation, fluidised bed granulation, granulation processes employing a granulation mill, compactification, roll pressing, briquetting, scabbing or extruding.
Spray Drying
According to a preferred embodiment of the first aspect of the invention, a silicon dioxide granulate I is obtained by spray granulation of the slurry. Spray granulation is also known as spray drying.
Spray drying is preferably effected in a spray tower. For spray drying, the slurry is preferably put under pressure at a raised temperature. The pressurised slurry is then depressurised via a nozzle and thus sprayed into the spray tower. Subsequently, droplets form which instantly dry and first form dry minute particles (“nuclei”). The minute particles form, together with a gas flow applied to the particles, a fluidised bed. In this way, they are maintained in a floating state and can thus form a surface for drying further droplets.
The nozzle, through which the slurry is sprayed into the spray tower, preferably forms an inlet into the interior of the spray tower.
The nozzle preferably has a contact surface with the slurry during spraying. “Contact surface” means the region of the nozzle which comes into contact with the slurry during spraying. Often, at least part of the nozzle is formed as a tube through which the slurry is guided during spraying, so that the inner side of the hollow tube comes into contact with the slurry.
The contact surface preferably comprises a glass, a plastic or a combination thereof. Preferably, the contact surface comprises a glass, particularly preferably quartz glass. Preferably, the contact surface comprises a plastic. In principle, all plastics known to the skilled man, which are stable at the process temperatures and do not pass any foreign atoms to the slurry, are suitable. Preferred plastics are polyolefins, for example homo- or co-polymers comprising at least one olefin, particularly preferably homo- or co-polymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more thereof. Preferably, the contact surface is made of a glass, a plastic or a combination thereof, for example selected from the group consisting of quartz glass and polyolefins, particularly preferably selected from the group consisting of quartz glass and homo- or co-polymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more thereof. Preferably, the contact surface comprises no metals, in particular no tungsten, titanium, tantalum, chromium, cobalt, nickel, iron, vanadium, zirconium and manganese.
It is in principle possible for the contact surface and the further parts of the nozzle to be made of the same or from different materials. Preferably, the further parts of the nozzle comprise the same material as the contact surface. It is likewise possible for the further parts of the nozzle to comprise a material different to the contact surface. For example, the contact surface can be coated with a suitable material, for example with a glass or with a plastic.
Preferably, the nozzle is more than 70 wt.-%, based on the total weight of the nozzle, made out of an item selected from the group consisting of glass, plastic or a combination of glass and plastic, for example more than 75 wt.-% or more than 80 wt.-% or more than 85 wt.-% or more than 90 wt.-% or more than 95 wt.-%, particularly preferably more than 99 wt.-%.
Preferably, the nozzle comprises a nozzle plate. The nozzle plate is preferably made of glass, plastic or a combination of glass and plastic. Preferably, the nozzle plate is made of glass, particularly preferably quartz glass. Preferably, the nozzle plate is made of plastic. Preferred plastics are polyolefins, for example homo- or co-polymers comprising at least one olefin, particularly preferably homo- or co-polymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more thereof. Preferably, the nozzle plate comprises no metals, in particular no tungsten, titanium, tantalum, chromium, cobalt, nickel, iron, vanadium, zirconium and manganese.
Preferably, the nozzle comprises a screw twister. The screw twister is preferably made of glass, plastic or a combination of glass and plastic. Preferably, the screw twister is made of glass, particularly preferably quartz glass. Preferably, the screw twister is made of plastic. Preferred plastics are polyolefins, for example homo- or co-polymers comprising at least one olefin, particularly preferably homo- or co-polymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more thereof. Preferably, the screw twister comprises no metals, in particular no tungsten, titanium, tantalum, chromium, cobalt, nickel, iron, vanadium, zirconium and manganese.
Furthermore, the nozzle can comprise further constituents. Preferred further constituents are a nozzle body, particularly preferable is a nozzle body which surrounds the screw twister and the nozzle plate, a cross piece and a baffle. Preferably, the nozzle comprises one or more, particularly preferably all, of the further constituents. The further constituents can independently from each other be made of in principle any material which is known to the skilled man and which is suitable for this purpose, for example of a metal comprising material, of glass or of a plastic. Preferably, the nozzle body is made of glass, particularly preferably quartz glass. Preferably, the further constituents are made of plastic. Preferred plastics are polyolefins, for example homo- or co-polymers comprising at least one olefin, particularly preferably homo- or co-polymers comprising polypropylene, polyethylene, polybutadiene or combinations of two or more thereof. Preferably, the further constituents comprise no metals, in particular no tungsten, titanium, tantalum, chromium, cobalt, nickel, iron, vanadium, zirconium and manganese.
Preferably, the spray tower comprises a gas inlet and a gas outlet. Through the gas inlet, a gas can be introduced into the interior of the spray tower, and through the gas outlet it can be let out. It is also possible to introduce gas into the spray tower via the nozzle. Likewise, gas can be let out via the outlet of the spray tower. Furthermore, gas can preferably be introduced via the nozzle and a gas inlet of the spray tower, and let out via the outlet of the spray tower and a gas outlet of the spray tower.
Preferably, in the interior of the spray tower is present an atmosphere selected from air, an inert gas, at least two inert gases or a combination of air with at least one inert gas, preferably a combination of air with at least two inert gases. Inert gasses are preferably selected from the list consisting of nitrogen, helium, neon, argon, krypton and xenon. For example, in the interior of the spray tower there is present air, nitrogen or Argon, particularly preferably air.
Further preferably, the atmosphere present in the spray tower is part of a gas flow. The gas flow is preferably introduced into the spray tower via a gas inlet and let out via a gas outlet. It is also possible to introduce parts of the gas flow via the nozzle and to let out parts of the gas flow via a solids outlet. The gas flow can take on further constituents in the spray tower. These can come from the slurry during the spray drying and transfer to the gas flow.
Preferably, a dry gas flow is fed to the spray tower. A dry gas flow means a gas or a gas mixture which has a relative humidity at the temperature set in the spray tower below the condensation point. A relative air humidity of 100% corresponds to a water content of 17.5 g/m3 at 20° C. The gas is preferably pre-warmed to a temperature in a range from 150 to 450° C., for example from 200 to 420° C. or from 300 to 400° C., particularly preferably from 350 to 400° C.
The interior of the spray tower is preferably temperature-controllable. Preferably, the temperature in the interior of the spray tower has a value up to 550° C., for example 300 to 500° C., particularly preferably 350 to 450° C.
The gas flow preferably has a temperature at the gas inlet in a range from 150 to 450° C., for example from 200 to 420° C. or from 300 to 400° C., particularly preferably from 350 to 400° C.
The gas flow which is let out at the solids outlet, at the gas outlet or at both locations, preferably has a temperature of less than 170° C., for example from 50 to 150° C., particularly preferably from 100 to 130° C.
Furthermore, the difference between the temperature of the gas flow on introduction and of the gas flow on expulsion is preferably in a range from 100 to 330° C., for example from 150 to 300° C.
The thus obtained silicon dioxide granules are present as an agglomerate of individual particles of silicon dioxide powder. The individual particles of the silicon dioxide powder continue to be recognizable in the agglomerate. The mean particle size of the particles of the silicon dioxide powder is preferably in the range from 10 to 1000 nm, for example in the range from 20 to 500 nm or from 30 to 250 nm or from 35 to 200 nm or from 40 to 150 nm, or particularly preferably in the range from 50 to 100 nm. The mean particle size of these particles is measured according to DIN ISO 13320-1.
The spray drying can be carried out in the presence of auxiliaries. In principle, all materials can be employed as auxiliaries, which are known to the skilled man and which appear suitable for the present application. As auxiliary material for example, so-called binders can be considered. Examples of suitable binding materials are metal oxides such as calcium oxide, metal carbonates such as calcium carbonate and polysaccharides such as cellulose, cellulose ether, starch and starch derivatives.
Particularly preferably, the spray drying is carried out in the context of the present invention without auxiliaries.
Preferably, before, after or before and after the removal of the silicon dioxide granulate from the spray tower a portion thereof is separated off. For separating off, all processes which are known to the skilled man and which appear suitable can be considered. Preferably, the separating off is effected by a screening or a sieving.
Preferably, before removal from the spray tower of the silicon dioxide granulate which have been formed by spray drying, particles with a particle size of less than 50 μm, for example with a particle size of less than 70 μm particularly preferably with a particle size of less than 90 μm are separated off by screening. The screening is effected preferably using a cyclone arrangement, which is preferably arranged in the lower region of the spray tower, particularly preferably above the outlet of the spray tower.
Preferably, after removal of the silicon dioxide granulate from the spray tower, particles with a particle size of greater than 1000 μm, for example with a particle size of greater than 700 μm, particularly preferably with a particle size of greater than 500 μm are separated off by sieving. The sieving of the particles can in principle be effected by all processes known to the skilled man and which are suitable for this purpose. Preferably, the sieving is effected using a vibrating chute.
According to a preferred embodiment, the spray drying of the slurry through a nozzle into a spray tower is characterised by at least one, for example two or three, particularly preferably all of the following features:
Vertical means the direction of the gravitational force vector.
The flight path means the path covered by a droplet of slurry from exiting out of the nozzle in the gas chamber of the spray tower to form a granule up to completion of the action of flying and falling. The action of flying and falling frequently ends by the granule impacting with the floor of the spray tower impacting or the granule impacting with other granules already lying on the floor of the spray tower, whichever occurs first.
The flight time is the period required by a granule to cover the flight path in the spray tower. Preferably, the granules have a helical flight path in the spray tower.
Preferably, at least 60 wt.-% of the spray granulate, based on the total weight of the silicon dioxide granulate created in the spray drying, cover a mean flight path of more than 20 m, for example of more than 30 or of more than 50 or of more than 70 or of more than 100 or of more than 150 or of more than 200 or in a range from 20 to 200 m or from 10 to 150 or from 20 to 100, particularly preferably a range from 30 to 80 m.
Preferably, at least 70 wt.-% of the spray granulate, based on the total weight of the silicon dioxide granulate created in the spray drying, cover a mean flight path of more than 20 m, for example of more than 30 or of more than 50 or of more than 70 or of more than 100 or of more than 150 or of more than 200 or in a range from 20 to 200 m or from 10 to 150 or from 20 to 100, particularly preferably a range from 30 to 80 m.
Preferably, at least 80 wt.-% of the spray granulate, based on the total weight of the silicon dioxide granulate created in the spray drying, cover a mean flight path of more than 20 m, for example of more than 30 or of more than 50 or of more than 70 or of more than 100 or of more than 150 or of more than 200 or in a range from 20 to 200 m or from 10 to 150 or from 20 to 100, particularly preferably a range from 30 to 80 m.
Preferably, at least 90 wt.-% of the spray granulate, based on the total weight of the silicon dioxide granulate created in the spray drying, cover a mean flight path of more than 20 m, for example of more than 30 or of more than 50 or of more than 70 or of more than 100 or of more than 150 or of more than 200 or in a range from 20 to 200 m or from 10 to 150 or from 20 to 100, particularly preferably a range from 30 to 80 m.
Roll Granulation
According to a preferred embodiment of the first aspect of the invention of the invention, a silicon dioxide granulate I is obtained by roll granulation of the slurry.
The roll granulation is carried out by stirring the slurry in the presence of a gas at raised temperature. Preferably, the roll granulation is effected in a stirring vessel fitted with a stirring tool. Preferably, the stirring vessel rotates in the opposite sense to the stirring tool. Preferably, the stirring vessel additionally comprises an inlet through which the silicon dioxide powder can be introduced into the stirring vessel, an outlet through which the silicon dioxide granulate can be removed, a gas inlet and a gas outlet.
For stirring the slurry, preferably a pin-type stirring tool is used. A pin-type stirring tool means a stirring tool fitted with multiple elongate pins having their longitudinal axis coaxial with the rotational axis of the stirring tool. The trajectory of the pins preferably traces coaxial circles around the axis of rotation.
Preferably, the slurry is set to a pH value of less than 7, for example to a pH value in the range from 2 to 6.5, particularly preferably to a pH value in a range from 4 to 6. For setting the pH value, an inorganic acid is preferably used, for example an acid selected from the group consisting of hydrochloric acid, sulphuric acid, nitric acid and phosphoric acid, particularly preferably hydrochloric acid.
Preferably, in the stirring vessel is present an atmosphere selected from air, an inert gas, at least two inert gases or a combination of air with at least one inert gas, preferably at least two inert gases. Inert gases am preferably selected from the list consisting of nitrogen, helium, neon, argon, krypton and xenon. Fore example, air, nitrogen or argon is present in the stirring vessel, particularly preferably air.
Furthermore, preferably, the atmosphere present in the stirring vessel is part of a gas flow. The gas flow is preferably introduced into the stirring vessel via the gas inlet and let out via the gas outlet. The gas flow can take on further constituents in the stirring vessel. These can originate from the slurry in the roll granulation and transfer into the gas flow.
Preferably, a dry gas flow is introduced to the stirring vessel. A dry gas flow means a gas or a gas mixture which has a relative humidity at the temperature set in the stirring vessel under the condensation point. The gas is preferably pre-warmed to a temperature in a range from 50 to 300° C., for example from 80 to 250° C., particularly preferably from 100 to 200° C.
Preferably, per 1 kg of the employed slurry, 10 to 150 m3 gas per hour is introduced into the stirring vessel, for example 20 to 100 m3 gas per hour, particularly preferably 30 to 70 m3 gas per hour.
During the mixing, the slurry is dried by the gas flow to form silicon dioxide granules. The granulate which is formed is removed from the stirring vessel.
Preferably, the removed granulate is dried further. Preferably, the drying is effected continuously, for example in a rotary kiln. Preferred temperatures for the drying are in a range from 80 to 250° C., for example in a range from 100 to 200° C., particularly preferably in a range from 120 to 180° C.
In the context of the present invention, continuous in respect of a process means that it can be operated continuously. That means that the introduction and removal of materials involved in the process can be effected on an ongoing basis whilst the process is being run. It is not necessary to interrupt the process for this.
Continuous as an attribute of an object, e.g. in relation to a “continuous oven”, means that this object is configured in such a way that a process carried out therein, or a process step carried out therein, can be carried out continuously.
The granulate obtained from the roll granulation can be sieved. The sieving occur before or after the drying. Preferably it is sieved before drying. Preferably, granule with a particle size of less than 50 μm, for example with a particle size of less than 80 μm, particularly preferably with a particle size of less than 100 μm, are sieved out. Furthermore, preferably, granules with a particle size of greater than 900 μm, for example with a particle size of greater than 700 μm, particularly preferably with a particle size of greater than 500 μm, sieved out. The sieving out of larger particles can in principle be carried out by any processes known to the skilled man and which are suitable for this purpose. Preferably, the sieving out of larger particles is carried out by means of a vibrating chute.
According to a preferred embodiment, the roll granulation is characterised by at least one, for example two or three, particularly preferably all of the following features:
Preferably, the silicon dioxide granulate I obtained by granulating, preferably by spray- or roll-granulating, is treated before it is processed to obtain quartz glass bodies. This pre-treatment can fulfil various purposes which either facilitate the processing to obtain quartz glass bodies or influence the properties of the resulting quartz glass body. For example, the silicon dioxide granulate I can be compactified, purified, surface-modified or dried.
According to the invention, the silicon dioxide granulate I has a carbon content wC(1) in a range from 1 to 200 ppm, for example in the range from 5 to 100 ppm or from 10 to 50 ppm, particularly preferably in the range from 15 to 35 ppm, in each case based on the total weight of silicon dioxide granulate I. Further preferred ranges for the carbon content wC(1) are from 5 to 200 ppm, 5 to 50 ppm, 5 to 35 ppm or 10 to 35 ppm.
According to the invention, the silicon dioxide granulate I has a content of alkaline earth metal wM(1). The content of alkaline earth metal wM(1) is preferably in a range from 10 ppb to 1000 ppb, for example in a range from 100 ppb to 900 ppb or from 200 ppb to 800 ppb, particularly preferably in a range from 300 ppb to 700 ppb, in each case based on the total weight of silicon dioxide granulate I.
According to a preferred embodiment of the first aspect of the invention, a silicon dioxide I with a carbon content wC(1) can be produced in various ways. In principle, any processes known to the skilled person and which are suitable for producing a specific carbon content may be considered. Preferably, carbon is fed into the process for preparing silicon dioxide I. In this case, carbon can be fed in at any point, for example during the preparation of the pyrogenic silicon dioxide powder, during the preparation of the silicon dioxide granulate I, in particular before, during or after the granulation.
Carbon can be fed into the process in any form that is known to the skilled person and suitable for this purpose. Preferably, carbon is fed in in elemental form or as a compound. Elemental carbon is preferably fed in as a powder, for example as an amorphous powder, particularly preferably as carbon black, further preferably as a powder with a particle size of less than 200 μm, further preferably as a powder with a specific surface area in a range from 50 to 500 m2/g. Particularly preferably, elemental carbon is fed in as carbon black with a specific surface area in a range from 50 to 500 m2/g.
Suitable as carbon compounds are in particular compounds with a decomposition point of less than 600° C., which burn to form carbon black. Examples of these carbon compounds am hydrocarbon gases, in particular natural gas, methane, ethane, propane, butane, ethene and combinations of two or more thereof, siloxanes, in particular hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane decamethylcyclopentasiloxane and combinations of two or more thereof, and silicon alkoxides, in particular tetramethoxysilane and methyltrimethoxysilane.
Preferably, the carbon content wC(1) of the silicon dioxide granulate I can be produced by a deficit of oxygen in the production of the pyrogenic silicon dioxide powder in a flame. Deficit means a substoichiometric use of oxygen in relation to the co-reactants for the preparation of the silicon dioxide, in particular hydrogen and one or more of the above-mentioned carbon compounds. This process is particularly suitable if silicon dioxide powder is prepared from siloxanes or silicon alkoxides.
Preferably, the carbon content wC(1) of the silicon dioxide granulate I can be produced by the addition of carbon to the slurry. Preferably, amorphous carbon powder can be added to the slurry. Preferably, carbon is added to the slurry in a quantity of less than 5000 ppm, for example in a quantity of 1 ppb to 200 ppm, particularly preferably in a quantity of 1 ppb to 20 ppm, in each case based on the total weight of the silicon dioxide powder
Preferably, the carbon content wC(1) of the silicon dioxide granulate I can be produced by the addition of carbon during granulating. In principle, it is possible to add the carbon at any time during granulating. Preferably, carbon is added in the form of a carbon compound or a combination of two or more carbon compounds during granulating, for example hydrocarbon gases, particularly preferably natural gas, methane, ethane, propane, butane, ethene and combinations of two or more thereof.
In the case of spray granulating, the carbon can for example be sprayed through the nozzle into the spray tower together with the slurry. Preferably, the quantity of carbon is in a range from 1 ppb to 200 ppm, based on the total quantity of silicon dioxide that is sprayed into the spray tower together with the carbon. According to a further example, the carbon can be present as a gaseous carbon compound in the gas space of the spray tower into which the slurry is sprayed. Preferably, the carbon compound is present in a quantity of 1 ppb to 500 ppm, based on the volume of the gas space of the spray tower.
In the case of roll granulating, the carbon can be added into the stirring vessel for example after the input of the slurry in solid form, preferably as amorphous carbon powder, or in gaseous form, preferably natural gas, methane, ethane, propane, butane, ethene or a combination of two or more thereof. Preferably, the carbon is added in a quantity of 1 ppb to 500 ppm, based on the total weight of the silicon dioxide in the stirring vessel.
Preferably, the carbon content wC(1) of the silicon dioxide granulate I can be produced by the addition of carbon after the granulating. Preferably, after the granulating, amorphous carbon powder is added to the silicon dioxide granulate I. Preferably, carbon is added in a quantity of less than 5000 ppm, for example in a quantity of 1 ppb to 200 ppm, particularly preferably in a quantity of 1 ppb to 20 ppm, in each case based on the total weight of the silicon dioxide granulate I. Preferably, carbon is added in an oven, for example in a continuous or discontinuous oven, particularly preferably in a rotary kiln. Preferably, the addition of carbon takes place at an oven temperature in a range from 20 to 500° C., particularly preferably at an oven temperature of 50 to 250° C. Preferably, a gas atmosphere is present in the oven, in particular comprising nitrogen, helium, hydrogen or combinations thereof, particularly preferably combinations of nitrogen and hydrogen or of helium and hydrogen. Preferably, the granulate is then thermally treated in a second oven, preferably at a temperature in a range from 1000 to 1300° C.
Preferably, the silicon dioxide granulate I has at least one, for example at least two or at least three or at least four, particularly preferably at least five of the following features:
The OH content, also known as the hydroxy group content, means the content of OH groups in a material, for example in silicon dioxide powder, in silicon dioxide granulate or in a quartz glass body. The content of OH groups is measured spectroscopically in the infrared by comparing the first and third OH bands.
The chlorine content means the content of elemental chlorine or chloride ions in the silicon dioxide granulate, in the silicon dioxide powder or in the quartz glass body.
The aluminium content means the content of elemental aluminium or aluminium ions in the silicon dioxide granulate, in the silicon dioxide powder or in the quartz glass body.
Preferably, the silicon dioxide granulate I has a micropore proportion in a range from 4 to 5 m2/g; for example in a range from 4.1 to 4.9 m2/g; particularly preferably in a range from 4.2 to 4.8 m2/g.
The silicon dioxide granulate I preferably has a specific density in a range from 2.1 to 2.3 g/cm3, particularly preferably in a range from 2.18 to 2.22 g/cm3.
The silicon dioxide granulate I preferably has a mean particle size in a range from 180 to 300 μm, for example in a range from 220 to 280 μm, particularly preferably in a range from 230 to 270 μm.
The silicon dioxide granulate I preferably has a particle size D50 in a range from 150 to 300 μm, for example in a range from 180 to 280 μm, particularly preferably in a range from 220 to 270 μm. Furthermore, preferably, the silicon dioxide granulate I has a particle size D10 in a range from 50 to 150 μm, for example in a range from 80 to 150 μm, particularly preferably in a range from 100 to 150 μm. Furthermore, preferably, the silicon dioxide granulate I has a particle size D90 in a range from 250 to 620 μm, for example in a range from 280 to 550 μm, particularly preferably in a range from 300 to 450 μm.
Particle size means the size of the particles of aggregated primary particles, which am present in a silicon dioxide powder, in a slurry or in a silicon dioxide granulate. The mean particle size means the arithmetic mean of all particle sizes of the indicated material. The D50 value indicates that 50% of the particles, based on the total number of particles, am smaller than the indicated value. The D10 value indicates that 10% of the particles, based on the total number of particles, am smaller than the indicated value. The Do value indicates that 90% of the particles, based on the total number of particles, am smaller than the indicated value. The particle size is measured by the dynamic photo analysis process according to ISO 13322-2:2006-11.
Preferably, the granules of the silicon dioxide granulate I have a spherical morphology. Spherical morphology means a round or oval form of the particle. The granules of the silicon dioxide granulate I preferably have a mean sphericity in a range from 0.7 to 1.3 SPHT3, for example a mean sphericity in a range from 0.8 to 1.2 SPHT3, particularly preferably a mean sphericity in a range from 0.85 to 1.1 SPHT3. The feature SPHT3 is described in the test methods.
Furthermore, the granules of the silicon dioxide granulate I preferably have a mean symmetry in a range from 0.7 to 1.3 Symm3, for example a mean symmetry in a range from 0.8 to 1.2 Symm3, particularly preferably a mean symmetry in a range from 0.85 to 1.1 Symm3. The feature of the mean symmetry Symm3 is described in the test methods.
Preferably, the silicon dioxide granulate I has a metal content of metals different to aluminium of less than 1000 ppb, for example of less than 500 ppb, particularly preferably of less than 100 ppb, in each case based on the total weight of the silicon dioxide granulate I. Often however, the silicon dioxide granulate I has a content of metals different to aluminium of at least 1 ppb. Often, the silicon dioxide granulate I has a metal content of metals different to aluminium of less than 1 ppm, preferably in a range from 40 to 900 ppb, for example in a range from 50 to 700 ppb, particularly preferably in a range from 60 to 500 ppb, in each case based on the total weight of the silicon dioxide granulate I. Such metals are for example sodium, lithium, potassium, magnesium, calcium, strontium, germanium, copper, molybdenum, titanium, iron and chromium. These can for example be present as an element, as part of a molecule or of an ion or of a complex.
The silicon dioxide granulate I can comprise further constituents, for example in the form of molecules, ions or elements. Preferably, the silicon dioxide granulate I comprises less than 500 ppm of further constituents, for example less than 300 ppm, particularly preferably less than 100 ppm, in each case based on the total weight of the silicon dioxide granulate I. Often, at least 1 ppb of further constituents are comprised. The further constituents can in particular be selected from the group consisting of carbon, fluoride, iodide, bromide, phosphorus or a mixture of at least two thereof.
Preferably, the silicon dioxide granulate I comprises less than 100 ppm of other constituents, for example less than 80 ppm, particularly preferably less than 70 ppm, in each case based on the total weight of the silicon dioxide granulate I. Often, however, at least 1 ppb of the other constituents is comprised.
The silicon dioxide granulate I preferably has the feature combination [A]/[B]/[C] or [A]/[B]/[E] or [A]/[B]/[G], further preferred the feature combination [A]/[B]/[C]/[E] or [A]/[B]/[C]/[G] or [A]/[B]/[E]/[G], further preferably the feature combination [A]/[B]/[C]/[E]/[G].
The silicon dioxide granulate I preferably has the feature combination [A]/[B]/[C], wherein the BET surface area is in a range from 20 to 40 m2/g, the mean particle size is in a range from 180 to 300 μm and the bulk density is in a range from 0.6 to 1.1 g/mL.
The silicon dioxide granulate I preferably has the feature combination [A]/[B]/[E], wherein the BET surface area is in a range from 20 to 40 m2/g, the mean particle size is in a range from 180 to 300 μm and the aluminium content is in a range from 1 to 50 ppb.
The silicon dioxide granulate I preferably has the feature combination[A]/[B]/[G], wherein the BET surface area is in a range from 20 to 40 m2/g, the mean particle size is in a range from 180 to 300 μm and the pore volume is in a range from 0.2 to 0.8 mL/g.
The silicon dioxide granulate I preferably has the feature combination [A]/[B]/[C]/[E], wherein the BET surface area is in a range from 20 to 40 m2/g, the mean particle size is in a range from 180 to 300 μm, the bulk density is in a range from 0.6 to 1.1 g/mL and the aluminium content is in a range from 1 to 50 ppb.
The silicon dioxide granulate I preferably has the feature combination [A]/[B]/[C]/[G], wherein the BET surface area is in a range from 20 to 40 m2/g, the mean particle size is in a range from 180 to 300 μm, the bulk density is in a range from 0.6 to 1.1 g/mL and the pore volume is in a range from 0.2 to 0.8 mL/g.
The silicon dioxide granulate I preferably has the feature combination [A]/[B]/[E]/[G], wherein the BET surface area is in a range from 20 to 40 m2/g, the mean particle size is in a range from 180 to 300 μm, the aluminium content is in a range from 1 to 50 ppb and the pore volume is in a range from 0.2 to 0.8 mL/g.
The silicon dioxide granulate I preferably has the feature combination [A]/[B]/[C]/[E]/[G], wherein the BET surface area is in a range from 20 to 40 m2/g, the mean particle size is in a range from 180 to 300 μm, the bulk density is in a range from 0.6 to 1.1 g/mL, the aluminium content is in a range from 1 to 50 ppb and the pore volume is in a range from 0.2 to 0.8 mL/g.
Step ii.)
The silicon dioxide is treated with a reactant at a temperature in a range from 1000 to 1300° C. Preferably, the silicon dioxide granulate I can additionally be subjected to a mechanical treatment.
Chemical
According to a preferred embodiment of the first aspect of the invention, the silicon dioxide granulate I comprises at least two particles. Preferably, the at least two particles can carry out a motion relative to each other. As means for bringing about the relative motion, in principle all means known to the skilled man and which appear to him to be suitable can be considered. Particular preferred is a mixing. A mixing can in principle be carried out in any manner. Preferably, a feed-oven is selected for this. Accordingly, the at least two particles can preferably perform a motion relative to each other by being agitated in a feed oven, for example in a rotary kiln.
Feed ovens mean ovens for which loading and unloading of the oven, so-called charging, is carried out continuously. Examples of feed-ovens are rotary kilns, roll-over type furnaces, belt conveyor ovens, conveyor ovens, continuous pusher-type furnaces. Preferably, for treatment of the silicon dioxide granulate I, rotary kilns am used.
According to the invention, the silicon dioxide granulate I is treated with a reactant to obtain a silicon dioxide granulate II. The treatment is carried out in order to change the concentration of certain materials in the silicon dioxide granulate. The silicon dioxide granulate I can have impurities or certain functionalities, the content of which should be reduced, such as for example: OH groups, carbon containing compounds, transition metals, alkali metals and alkali earth metals. The impurities and functionalities can originate from the starting materials or can be introduced in the course of the process. The treatment of the silicon dioxide granulate I can serve various purposes. For example, employing treated silicon dioxide granulate I, i.e. silicon dioxide granulate II, can simplify the processing of the silicon dioxide granulate to obtain quartz glass bodies. Furthermore, this selection can be employed to tune the properties of the resulting quartz glass body. For example, the silicon dioxide granulate I can be purified or surface modified.
Preferably, a gas or a combination of multiple gases is suitable as reactant. This is also referred to as a gas mixture. In principle, all gases known to the skilled man can be employed, which are known for the specified treatment and which appear to be suitable. Preferably, a gas selected from the group consisting of HCl, Cl2, F2, O2, O3, H2, C2F4, C2F, HClO4, air, inert gas, e.g. N2, He, Ne, Ar, Kr, or combinations of two or more thereof is employed. Preferably, the treatment is carried out in the presence of a gas or a combination of two or more gases. Preferably, the treatment is carried out in a gas counter flow or a gas co-flow.
Preferably, the reactant is selected from the group consisting of HCl, Cl2, F2, O2, O3 or combinations of two or more thereof. Preferably, mixtures of two or more of the above-mentioned gases are used for the treatment of silicon dioxide granulate I. Through the presence of F, Cl or both, metals which are contained in silicon dioxide granulates I as impurities, such as for example transition metals, alkali metals and alkali earth metals, can be removed. In this connection, the above mentioned metals can be converted along with constituents of the gas mixture under the process conditions to obtain gaseous compounds which are subsequently drawn out and thus am no longer present in the granulate. Furthermore, preferably, the OH content in the silicon dioxide granulate I can be decreased by the treatment of the silicon dioxide granulate I with these gases.
Preferably, a gas mixture of HCl and Cl2 is employed as reactant. Preferably, the gas mixture has an HCl content in a range from 1 to 30 vol.-%, for example in a range from 2 to 15 vol.-%, particularly preferably in a range from 3 to 10 vol.-%. Likewise, the gas mixture preferably has a Cl2 content in a range from 20 to 70 vol.-%, for example in a range from 25 to 65 vol.-%, particularly preferably in a range from 30 to 60 vol.-%. The remainder up to 100 vol.-% can be made up of one or more inert gases, e.g. N2, He, Ne, Ar, Kr, or of air. Preferably, the proportion of inert gas in the reactants is in a range from 0 to less than 50 vol.-%, for example in a range from 1 to 40 vol.-% or from 5 to 30 vol.-%, particularly preferably in a range from 10 to 20 vol.-%, in each case based on the total volume of the reactants.
O2, C2F2, or mixtures thereof with Cl2 are preferably used for purifying silicon dioxide granulate I which has been prepared from a siloxane or from a mixture of multiple siloxanes.
The reactant in the form of a gas or of a gas mixture is preferably contacted with the silicon dioxide granulate as a gas flow or as part of a gas flow with a throughput in a range from 50 to 2000 L/h, for example in a range from 100 to 1000 L/h, particularly preferably in a range from 200 to 500 L/h. A preferred embodiment of the contacting is a contact of the gas flow and silicon dioxide granulate in a feed oven, for example in a rotary kiln. Another preferred embodiment of the contacting is a fluidised bed process.
Through treatment of the silicon dioxide granulate I with the reactant, a silicon dioxide granulate II with a carbon content wC(2) is obtained. The carbon content wC(1) of the silicon dioxide granulate II is less than the carbon content wC(1) of the silicon dioxide granulate I, based on the total weight of the respective silicon dioxide granulate. Preferably, wC(2) is 0.5 to 99%, for example 20 to 80% or 50 to 95%, particularly preferably 60 to 99% less than wC(1).
Thermal
According to the invention, the silicon dioxide granulate I is additionally subjected to a thermal treatment. One or more of these additional treatments can be carried out before or during the treatment with the reactant. Additionally, the additional treatment can also be carried out on the silicon dioxide granulate II. The following description of the preferred conditions under which a thermal treatment can take place therefore also represents the preferred conditions of an optional thermal treatment of the silicon dioxide granulate II.
The thermal treatment of the silicon dioxide granulate I can serve various purposes. For example, this treatment facilitates the processing of the silicon dioxide granulate II to obtain quartz glass bodies. The treatment can also influence the properties of the resulting glass body. For example, the silicon dioxide granulate II can be compactified, purified, surface modified or dried. In this connection, the specific surface area (BET) can decrease. Likewise, the bulk density and the mean particle size can increase due to agglomerations of silicon dioxide particles. The thermal treatment can be carried out dynamically or statically.
For the dynamic thermal treatment, all ovens in which the silicon dioxide granulate can be thermally treated whilst being agitated are in principle suitable. For the dynamic thermal treatment, preferably feed ovens are used.
A preferred mean holding time of the silicon dioxide granulate in the dynamic thermal treatment is quantity dependent. Preferably, the mean holding time of the silicon dioxide granulate in the dynamic thermal treatment is in the range from 10 to 180 min, for example in the range from 20 to 120 min or from 30 to 90 min. Particularly preferably, the mean holding time of the silicon dioxide granulate in the dynamic thermal treatment is in the range from 30 to 90 min.
In the case of a continuous process, a defined portion of the flow of silicon dioxide granulate is used as a sample load for the measurement of the holding time, e.g. a gram, a kilogram or a tonne. The start and end of the holding time are determined by the introduction into and exiting from the continuous oven operation.
Preferably, the throughput of the silicon dioxide granulate in a continuous process for dynamic thermal treatment is in the range from 1 to 50 kg/h, for example in the range from 5 to 40 kg/h or from 8 to 30 kg/h. Particularly preferably, the throughput here is in the range from 10 to 20 kg/h.
In the case of a discontinuous process for dynamic thermal treatment, the treatment time is given as the period of time between the loading and subsequent unloading of the oven.
In the case of a discontinuous process for dynamic thermal treatment, the throughput is in a range from 1 to 50 kg/h, for example in the range from 5 to 40 kg/h or from 8 to 30 kg/h. Particularly preferably, the throughput is in the range from 10 to 20 kg/h. The throughput can be achieved using a sample load of a determined amount which is treated for an hour. According to another embodiment, the throughput can be achieved through a number of loads per hour, wherein the weight of a single load corresponds to the throughput per hour divided by the number of loads. In this event, time of treatment corresponds to the fraction of an hour which is given by 60 minutes divided by the number of loads per hour.
According to the invention, the dynamic thermal treatment of the silicon dioxide granulate is carried out at an oven temperature in a range from 1000 to 1300° C., for example in a range from 1050 to 1250° C., particularly preferably in a range from 1100 to 1200° C.
Preferably, the temperature at a measuring point in the oven deviates from the set temperature by less than 10% downwards or upwards, based on the entire treatment period and the entire length of the oven as well as at every point in time in the treatment as well as at every position in the oven. Furthermore, preferably, temperatures measured from the set temperature also lie at a measuring point within the range indicated above.
Alternatively, in particular the continuous process of a dynamic thermal treatment of the silicon dioxide granulate can by carried out at differing oven temperatures. For example, the oven can have a constant temperature over the treatment period, wherein the temperature varies in section over the length of the oven. Such sections can be of the same length or of different lengths. Preferably, in this case, the temperature increases from the entrance of the oven to the exit of the oven. Preferably, the temperature at the entrance is at least 100° C. lower than at the exit, for example 150° C. lower or 200° C. lower or 300° C. lower or 400° C. lower. Furthermore, preferably, the temperature at the exit is preferably 1000 to 1300° C., for example 1050 to 1250° C., particularly preferably 1100 to 1200° C.
Furthermore, preferably, the temperature at the entrance is preferably at least 600° C., for example 700 to 1200° C. or 800 to 1100° C., particularly preferably 900 to 1000° C. Furthermore, each of the temperature ranges given at the oven entrance can be combined with each of the temperature ranges given at the oven exit. Preferred combinations of oven entrance temperature ranges and oven exit temperature ranges are:
For the static thermal treatment of the silicon dioxide granulate, crucibles arranged in an oven are preferably used. Suitable as crucibles are sinter crucibles or metal sheet crucibles. Preferred are rolled metal sheet crucibles made out of multiple sheets which are riveted together. Examples of crucible materials are refractory metals, in particular tungsten, molybdenum and tantalum. The crucibles can furthermore be made of graphite or, in the case of the crucibles of refractory metals, can be lined with graphite foil. Furthermore, preferably, the crucibles can be made of silicon dioxide. Particularly preferably, silicon dioxide crucibles are employed.
The mean holding time of the silicon dioxide granulate in the static thermal treatment is quantity dependent. Preferably, the mean holding time of the silicon dioxide granulate in the static thermal treatment for a 60 kg amount of silicon dioxide granulate I is in a range from 1 to 60 h, for example in a range from 5 to 50 h or from 10 to 40 h, particularly preferably in a range from 20 to 30 h.
For the static thermal treatment of the silicon dioxide granulate crucibles arranged in an oven am preferably used. Suitable crucibles are sinter crucibles or metal sheet crucibles. Preferred are rolled metal sheet crucibles made out of multiple sheets which are riveted together. Examples of crucible materials are refractory metals, in particular tungsten, molybdenum and tantalum. The crucible can furthermore be made of graphite or in the case of the crucible of refractory metals can be lined with graphite foil. Furthermore, preferably, the crucibles can be made of silicon dioxide. Particularly preferably, silicon dioxide crucibles are employed.
The mean holding time of the silicon dioxide granulate in the static thermal treatment is quantity dependent. Preferably, the mean holding time of the silicon dioxide granulate in the static thermal treatment for a 20 kg amount of silicon dioxide granulate I is in the range from 10 to 180 min, for example in the range from 20 to 120 min, particularly preferably in the range from 30 to 90 min.
According to the invention, the static thermal treatment of the silicon dioxide granulate is carried out at an oven temperature in a range from 1000 to 1300° C., for example in a range from 1050 to 1250° C., particularly preferably in a range from 1100 to 1200° C.
Preferably, the static thermal treatment of the silicon dioxide granulate I is carried out at constant oven temperature. The static thermal treatment can also be carried out at a varying oven temperature. Preferably, in this case, the temperature increases during the treatment, wherein the temperature at the start of the treatment is at least 50° C. lower than at the end, for example 70° C. lower or 80° C. lower or 100° C. lower or 110° C. lower, and wherein the temperature at the end is 1000 to 1300° C., for example 1050 to 1250° C., particularly preferably 1100 to 1200° C.
Mechanical
According to a further preferred embodiment, the silicon dioxide granulate I can additionally be mechanically treated. The mechanical treatment can be carried out for increasing the bulk density. The mechanical treatment can be combined with the above mentioned thermal or chemical treatment or with both. A mechanical treatment can avoid the agglomerates in the silicon dioxide granulate and therefore the mean particle size of the individual, treated silicon dioxide granules in the silicon dioxide granulate becoming too large. An enlargement of the agglomerates can hinder the further processing or have disadvantageous impacts on the properties of the quartz glass bodies prepared by the inventive process, or a combination of both effects. A mechanical treatment of the silicon dioxide granulate also promotes a uniform contact of the surfaces of the individual silicon dioxide granules with the gas or gases. This is in particular achieved by concurrent mechanical and chemical treatment with a reactant. In this way, the effect of the chemical treatment can be improved.
The mechanical treatment of the silicon dioxide granulate I can be carried out by moving two or more silicon dioxide granules relative to each other, for example by rotating the tube of a rotary kiln.
Preferably, the silicon dioxide granulate I is treated with a reactant, thermally and mechanically. Preferably, a simultaneous treatment with a reactant, thermal and mechanical treatment of the silicon dioxide granulate I is carried out.
In the treatment with a reactant, the content of impurities in the silicon dioxide granulate I is reduced. For this, the silicon dioxide granulate I can be treated in a rotary kiln at raised temperature and under a chlorine and oxygen containing atmosphere. Water present in the silicon dioxide granulate I evaporates, organic materials react to form CO and CO2. Metal impurities can be converted to volatile chlorine containing compounds.
Preferably, the silicon dioxide granulate I is treated in a chlorine and oxygen containing atmosphere in a rotary kiln at a temperature of at least 500° C., preferably in a temperature range from 550 to 1300° C. or from 600 to 1260° C. or from 650 to 1200° C. or from 700 to 1000° C., particularly preferably in a temperature range from 700 to 900° C. The chlorine containing atmosphere contains for example HCl or Cl2 or a combination of both. This treatment causes a reduction of the carbon content.
Furthermore, preferably alkali and iron impurities are reduced. Preferably, a reduction of the number of OH groups is achieved. At temperatures under 700° C., treatment periods can be long, at temperatures above 1100° C. there is a risk that pores of the granulate close, trapping chlorine or gaseous chlorine compounds.
Preferably, it is also possible to carry out sequentially multiple treatments with a reactant, each concurrent with thermal and mechanical treatment. For example, the silicon dioxide granulate I can first be treated in a chlorine containing atmosphere and subsequently in an oxygen containing atmosphere. The low concentrations of carbon, hydroxyl groups and chlorine resulting therefrom facilitate the melting down of the silicon dioxide granulate II.
According to a further preferred embodiment, step II.2) is characterised by at least one, for example by at least two or at least three, particularly preferably by a combination of all of the following features:
Preferably, the silicon dioxide granulate I has a particle diameter which is greater than the particle diameter of the silicon dioxide powder. Preferably, the particle diameter of the silicon dioxide granulate I is up to 300 times as great as the particle diameter of the silicon dioxide powder, for example up to 250 times as great or up to 200 times as great or up to 150 times as great or up to 100 times as great or up to 50 times as great or up to 20 times as great or up to 10 times as great, particularly preferably 2 to 5 times as great.
According to the invention, the silicon dioxide granulate II has a carbon content wC(2). The carbon content wC(2) of the silicon dioxide granulate II is less than the carbon content wC(1) of the silicon dioxide granulate I. Preferably, wC(2) is 0.5 to 50%, for example 1 to 45%, particularly preferably 1.5 to 40% less than wC(1). The carbon content wC(2) is preferably less than 5 ppm, for example less than 3 ppm, particularly preferably less than 1 ppm, in each case based on the total weight of silicon dioxide granulate II. Often the silicon dioxide granulate II has a carbon content wC(2) of 1 ppb or more.
According to the invention, the silicon dioxide granulate II has a content of alkaline earth metal wM(2). The content of alkaline earth metal wM(2) of the silicon dioxide granulate II is less than the content of alkaline earth metal wM(1) of the silicon dioxide granulate I. Preferably, wM(2) is 0.5 to 50%, for example 1 to 45%, particularly preferably 1.5 to 40% less than wM(1). The content of alkaline earth metal wM(2) is preferably less than 500 ppb, for example less than 450 ppb or 400 ppb or 350 ppb, particularly preferably less than 300 ppb, in each case based on the total weight of silicon dioxide granulate II. Often the silicon dioxide granulate II has a content of alkaline earth metal wM(2) of 1 ppb or more.
Preferably, the silicon dioxide granulate II has at least one, for example at least two or at least three or at least four, particularly preferably at least five of the following features:
Preferably, the silicon dioxide granulate II has a micro pore proportion in a range from 1 to 2 m2/g, for example in a range from 1.2 to 1.9 m2/g, particularly preferably in a range from 1.3 to 1.8 m2/g.
The silicon dioxide granulate II preferably has a density in a range from 0.5 to 2.0 g/cm3, for example from 0.6 to 1.5 g/cm3, particularly preferably from 0.8 to 1.2 g/cm3. The density is measured according to the method described in the test methods.
The silicon dioxide granulate II preferably has a particle size D50 in a range from 150 to 250 μm, for example in a range from 180 to 250 μm, particularly preferably in a range from 200 to 250 μm. Furthermore, preferably, the silicon dioxide granulate II has a particle size D10 in a range from 50 to 150 μm, for example in a range from 80 to 150 μm, particularly preferably in a range from 100 to 150 μm. Furthermore, preferably, the silicon dioxide granulate II has a particle size D50 in a range from 250 to 450 μm, for example in a range from 280 to 420 μm, particularly preferably in a range from 300 to 400 μm.
Preferably, the granules of the silicon dioxide granulate II have a spherical morphology. Spherical morphology means a round or oval form of the particle. The granules of the silicon dioxide granulate II preferably have a mean sphericity in a range from 0.7 to 1.3 SPHT3, for example a mean sphericity in a range from 0.8 to 1.2 SPHT3, particularly preferably a mean sphericity in a range from 0.85 to 1.1 SPHT3. The feature SPHT3 is described in the test methods.
Furthermore, the granules of the silicon dioxide granulate II preferably have a mean symmetry in a range from 0.7 to 1.3 Symm3, for example a mean symmetry in a range from 0.8 to 1.2 Symm3, particularly preferably a mean symmetry in a range from 0.85 to 1.1 Symm3. The feature of the mean symmetry Symm3 is described in the test methods.
Preferably, the silicon dioxide granulate II has a metal content of metals different to aluminium of less than 1000 ppb, for example of less than 500 ppb, particularly preferably of less than 100 ppb, in each case based on the 30 total weight of the silicon dioxide granulate II. Often however, the silicon dioxide granulate II has a content of metals different to aluminium of at least 1 ppb. Often, the silicon dioxide granulate I has a metal content of metals different to aluminium of less than 1 ppm, preferably in a range from 40 to 900 ppb, for example in a range from 50 to 700 ppb, particularly preferably in a range from 60 to 500 ppb, in each case based on the total weight of the silicon dioxide granulate II. Such metals are for example sodium, lithium, potassium, magnesium, calcium, strontium, germanium, copper, molybdenum, titanium, iron and chromium. These can for example be present as an element, as part of a molecule or of an ion or of a complex.
The silicon dioxide granulate II can comprise further constituents, for example in the form of molecules, ions or elements. Preferably, the silicon dioxide granulate II comprises less than 500 ppm of further constituents, for example less than 300 ppm, particularly preferably less than 100 ppm, in each case based on the total weight of the silicon dioxide granulate II. Often, at least 1 ppb of further constituents am comprised. The further constituents can in particular be selected from the group consisting of carbon, fluoride, iodide, bromide, phosphorus or a mixture of at least two thereof.
Preferably, the silicon dioxide granulate II comprises less than 100 ppm of other constituents, for example less than 80 ppm, particularly preferably less than 70 ppm, in each case based on the total weight of the silicon dioxide granulate II. Often, however, at least 1 ppb of the other constituents is comprised.
The silicon dioxide granulate II preferably has the feature combination (A)/(B)/(C) or (A)/(B)/(D) or (A)/(B)/(H), further preferred the feature combination (A)/(B)/(C)/(D) or (A)/(B)/(C)/(H) or (A)/(B)/(D)/(H), further preferably the feature combination (A)/(B)/(C)/(D)/(H).
The silicon dioxide granulate II preferably has the feature combination (A)/(B)/(C), wherein the chlorine content is less than 330 ppm, the aluminium content is less than 100 ppb and the metal content of metals which am different to aluminium is in a range from 1 to 100 ppb.
The silicon dioxide granulate II preferably has the feature combination (A)/(B)/(D), wherein the chlorine content is less than 330 ppm, the aluminium content is less than 100 ppb and the BET surface area is in a range from 10 to 30 m2/g.
The silicon dioxide granulate II preferably has the feature combination (A)/(B)/(H), wherein the chlorine content is less than 330 ppm, the aluminium content is less than 100 ppb and The tamped density is in a range from 0.8 to 1.0 g/mL.
The silicon dioxide granulate II preferably has the feature combination (A)/(B)/(C)/(D), wherein the chlorine content is less than 330 ppm, the aluminium content is less than 100 ppb, the metal content of metals which am different to aluminium is in a range from 1 to 100 ppb and the BET surface area is in a range from 10 to 30 m2/g.
The silicon dioxide granulate II preferably has the feature combination (A)/(B)/(C)/(H), wherein the chlorine content is less than 330 ppm, the aluminium content is less than 100 ppb, the metal content of metals which are different to aluminium is in a range from 1 to 100 ppb and The tamped density is in a range from 0.8 to 1.0 g/mL.
The silicon dioxide granulate II preferably has the feature combination (A)/(B)/(D/(H), wherein the chlorine content is less than 330 ppm, the aluminium content is less than 100 ppb, the BET surface area is in a range from 10 to 30 m2/g and The tamped density is in a range from 0.8 to 1.0 g/mL.
The silicon dioxide granulate II preferably has the feature combination (A)/(B)/(C)/(D)/(H), wherein the chlorine content is less than 330 ppm, the aluminium content is less than 100 ppb, the metal content of metals which are different to aluminium is in a range from 1 to 100 ppb, the BET surface area is in a range from 10 to 30 m2/g and The tamped density is in a range from 0.8 to 1.0 g/mL.
Step iii.)
According to step iii.), a glass melt is formed out of the silicon dioxide granulate. Normally, the silicon dioxide granulate is warmed until a glass melt is obtained. The warming of the silicon dioxide granulate to obtain a glass melt can in principle by carried out by any way known to the skilled man for this purpose.
Preparation of a Glass Melt
The formation of a glass melt from the silicon dioxide granulate, for example by warming, can be carried out by a continuous process. In the process according to the invention for the preparation of a quartz glass body, the silicon dioxide granulate can preferably be introduced continuously into an oven or the glass melt can be removed continuously from the oven, or both. Particularly preferably, the silicon dioxide granulate is introduced continuously into the oven and the glass melt is removed continuously from the oven.
For this, an oven which has at least one inlet and at least one outlet is in principle suitable. An inlet means an opening through which silicon dioxide and optionally further materials can be introduced into the oven. An outlet means an opening through which at least a part of the silicon dioxide can be removed from the oven. The oven can for example be arranged vertically or horizontally. Preferably, the oven is arranged vertically. Preferably, at least one inlet is located above at least one outlet. “Above” in connection with fixtures and features of an oven means, in particular in connection with an inlet and outlet, that the fixture or the features which is arranged “above” another has a higher position above the zero of absolute height. “Vertical” means that the line directly joining the inlet and the outlet of the oven deviates not more than 30° from the direction of gravity.
According to a preferred embodiment of the first aspect of the invention, the oven comprises a hanging metal sheet crucible. Into the hanging metal sheet crucible is introduced the silicon dioxide granulate and warmed to obtain a glass melt. A metal sheet crucible means a crucible which comprises at least one rolled metal sheet. Preferably, a metal sheet crucible has multiple rolled metal sheets. A hanging metal sheet crucible means a metal sheet crucible as previously described which is arranged in an oven in a hanging position.
The hanging metal sheet crucible can in principle be made of all materials which are known to the skilled man and which are suitable for melting silicon dioxide. Preferably, the metal sheet of the hanging metal sheet crucible comprises a sintered material, for example a sinter metal. Sinter metals means metals or alloys which are obtained by sintering of metal powders.
Preferably, the metal sheet of the metal sheet crucible comprises at least one item selected from the group consisting of the refractory metals. Refractory metals means metals of group 4 (Ti, Zr, Hf), of group 5 (V, Nb, Ta) and of group 6 (Cr, Mo, W).
Preferably, the metal sheet of the metal sheet crucible comprises a sinter metal selected from the group consisting of molybdenum, tungsten or a combination thereof. Furthermore, preferably, the metal sheet of the metal sheet crucible comprises at least one further refractory metal, particularly preferably rhenium, osmium, iridium, ruthenium or a combination of two or more thereof.
Preferably, the metal sheet of the metal sheet crucible comprises an alloy of molybdenum with a refractory metal, or tungsten with a refractory metal. Particularly preferred alloy metals are rhenium, osmium, iridium, ruthenium or a combination of two or more thereof. According to a further example, the metal sheet of the metal sheet crucible is an alloy of molybdenum with tungsten, rhenium, osmium, iridium, ruthenium or a combination of two or more thereof. For example the metal sheet of the metal sheet crucible can be an alloy of tungsten with molybdenum, rhenium, osmium, iridium, ruthenium or a combination of two or more thereof.
Preferably, the above described metal sheet of the metal sheet crucible can be coated with a refractory metal. According to a preferred example, the metal sheet of the metal sheet crucible is coated with rhenium, osmium, iridium, ruthenium, molybdenum or tungsten, or a combination of two or more thereof.
Preferably, the metal sheet and the coating have different compositions. For example a molybdenum metal sheet can be coated with one or multiple coats of rhenium, osmium, iridium, ruthenium, tungsten or a combination of two or more thereof. According to another example, a tungsten metal sheet is coated with one or multiple layers of rhenium, osmium, iridium, ruthenium, molybdenum or a combination of two or more thereof. According to a further example, the metal sheet of the metal sheet crucible can be made of molybdenum alloyed with rhenium or of tungsten alloyed with rhenium, and be coated on the inner side of the crucible with one or multiple layers comprising rhenium, osmium, iridium, ruthenium or a combination of two or more thereof.
Preferably, the metal sheet of the hanging metal sheet crucible has a density % % or greater of the theoretical density, for example from 96% to 98% More preferable are higher theoretical densities, in particular in the range from 98 to 99.95% The theoretical density of a basic material corresponds to the density of a pow free and 100% dense material. A density of the metal sheet of the metal sheet crucible of more than 96% of the theoretical density can for example be obtained by sintering a sinter metal and subsequent compactification of the sintered metal.
Particularly preferably, a metal sheet crucible is obtainable by sintering of a sinter metal, rolling to obtain a metal sheet and processing the metal sheet to obtain a crucible.
Preferably, the metal sheet crucible has at least a lid, a wall and a base plate. Preferably, the hanging metal sheet crucible has at least one, for example at least two or at least three or at least four, particularly preferably at least five or all of the following features:
The hanging metal sheet crucible can in principle be heated in any way which is known to the skilled person and which seems to him to be suitable. The hanging metal sheet crucible can for example be heated by means of electrical heating elements (resistive) or by induction. In the case of resistive heating, the solid surface of the metal sheet crucible is warmed from the outside and delivers the energy from there to its inner side.
According to a preferred embodiment of the present invention, the energy transfer into the melting crucible is not performed by warming the melting crucible, or a bulk material present therein, or both, using a flame, such as for example a burner flame directed into the melting crucible or onto the melting crucible.
By means of the hanging arrangement, the hanging metal sheet crucible can be moved in the oven. Preferably, the crucible can be at least partially moved into and moved out of the oven. If different heating zones am present in the oven, their temperature profile will be transferred to the crucible which is present in the oven. By changing the position of the crucible in the oven, multiple heating zones, varying heating zones or multiple varying heating zones can be produced in the crucible.
The metal sheet crucible has a nozzle. The nozzle is made of a nozzle material. Preferably, the nozzle material comprises a pre-compactified material, for example with a density in a range of more than 95%, for example from 98 to 100%, particularly preferably from 99 to 99.999%, in each case based on the theoretical density of the nozzle material. Preferably, the nozzle material comprises a refractory metal, for example molybdenum, tungsten or a combination thereof with a further refractory metal. Molybdenum is a particularly preferred nozzle material. Preferably, a nozzle comprising molybdenum can have a density of 100% of the theoretical density.
Preferably, the base plate comprised in a metal sheet crucible is thicker than the sides of the metal sheet crucible. Preferably, the base plate is made of the same material as the sides of the metal sheet crucible. Preferably, the base plate of the metal sheet crucible is not a rolled metal sheet. The base plate is for example 1.1 to 5000 times as thick or 2 to 1000 times as thick or 4 to 500 times as thick, particularly preferably 5 to 50 times as thick, each time compared with a wall of the metal sheet crucible.
According to a preferred embodiment of the first aspect of the invention, the oven comprises a hanging or a standing sinter crucible. The silicon dioxide granulate is introduced into the hanging or standing sinter crucible and warmed to obtain a glass melt.
A sinter crucible means a crucible which is made from a sinter material which comprises at least one sinter metal and has a density of not more than 96% of the theoretical density of the metal. Sinter metal means metals of alloys which am obtained by sintering of metal powders. The sinter material and the sinter metal in a sinter crucible are not rolled.
Preferably, the sinter material of the sinter crucible has a density of 85% or more of the theoretical density of the sinter material, for example a density from 85% to 95% or from 90% to 94%, particularly preferably from 91% to 93%.
The sinter material can in principle be made of any material which is known to the skilled person and which is suitable for melting silicon dioxide. Preferably, the sinter material is made of at least one of the elements selected from the group consisting of refractory metals, graphite or materials lined with graphite foil.
Preferably, the sinter material comprises a first sinter metal selected from the group consisting of molybdenum, tungsten and a combination thereof. Furthermore, preferably, the sinter material additionally comprises at least one further refractory metal which is different to the first sinter metal particularly preferably selected from the group consisting of molybdenum, tungsten, rhenium, osmium, iridium, ruthenium or a combination of two or mom thereof.
Preferably, the sinter material comprises an alloy of molybdenum with a refractory metal, or tungsten with a refractory metal. Particularly preferable alloy metals are rhenium, osmium, iridium, ruthenium or a combination of two or more thereof. According to a further example, the sinter material comprises an alloy of molybdenum with tungsten, rhenium, osmium, iridium, ruthenium or a combination of two or more thereof. For example the sinter material can comprise an alloy of tungsten with molybdenum, rhenium, osmium, iridium, ruthenium or a combination of two or more thereof.
According to a further preferred embodiment, the above described sinter material can comprise a coating which comprises a refractory metal, in particular rhenium, osmium, iridium, ruthenium or a combination of two or more thereof. According to a preferred example, the coating comprises rhenium, osmium, iridium, ruthenium, molybdenum or tungsten, or a combination of two or more thereof.
Preferably, the sinter material and its coating have different compositions. An example is a sinter material comprising molybdenum which is coated with one or more layers of rhenium, osmium, iridium, ruthenium, tungsten or of a combination of two or more thereof. According to another example, a sinter material comprising tungsten is coated with one or more layers of rhenium, osmium, iridium, ruthenium, molybdenum or of a combination of two or more thereof. According to another example, the sinter material can be made of molybdenum alloyed with rhenium or of tungsten alloyed with rhenium, and coated on the inner side of the crucible with one or multiple layers comprising rhenium, osmium, iridium, ruthenium or comprising a combination of two or more thereof.
Preferably, a sinter crucible is made by sintering the sinter material to obtain a mould. The sinter crucible can be made in a mould as a whole. It is also possible for individual parts of the sinter crucible to be made in a mould and subsequently processed to obtain the sinter crucible. Preferably, the crucible is made out of more than one part, for example a base plate and one or more side parts. The side parts are preferably made in one piece, based on the circumference of the crucible. Preferably, the sinter crucible can be made of multiple side parts arranged on top of each other. Preferably, the side parts of the sinter crucible are sealed by means of screwing or by means of a tongue and groove connection. A screwing is preferably achieved by making side parts which have a thread at the borders.
In the case of a tongue and groove connection, two side parts which am to be joined each have a notch at the borders into which tongue is introduced as the connecting third part, such that a form-closed connection is formed perpendicular to the plane of the crucible wall. Particularly preferably, a sinter crucible is made of more than one side part, for example of two or more side parts, particularly preferably of three or more side parts. Particularly preferably, the parts of the hanging sinter crucible am screwed. Particularly preferably, the parts of the standing sinter crucible am connected by means of a tongue and groove connection.
The base plate can in principle be connected with the crucible wall by any means known to the skilled person and which is suitable for this purpose. According to a preferred embodiment, the base plate has an outward thread and the base plate is connected with the crucible wall by being screwed into it. According to a further preferred embodiment, the base plate is connected with the crucible wall by means of screws. According to a further preferred embodiment, the base plate is suspended in the sinter crucible, for example by laying the base plate on an inward flange of the crucible wall. According to a further preferred embodiment, at least a part of the crucible wall and a compactified base plate are sintered in one piece. Particularly preferably, the base plate and the crucible wall of the hanging sinter crucible are screwed. Particularly preferably, the base plate and the crucible wall of the standing sinter crucible are connected by means of a tongue and groove connection.
Preferably, the base plate comprised by a sinter crucible is thicker than the sides, for example 1.1 to 20 times as thick or 1.2 to 10 times as thick or 1.5 to 7 times as thick, particularly preferably 2 to 5 times as thick. Preferably, the sides have a constant wall thickness over the circumference and over the height of the sinter crucible.
The sinter crucible has a nozzle. The nozzle is made of a nozzle material. Preferably, the nozzle material comprises a pre-compactified material, for example with a density in a range of more than 95%, for example from 98 to 100%, particularly preferably from 99 to 99.999%, in each case based on the theoretical density of the nozzle material. Preferably, the nozzle material comprises a refractory metal, for example molybdenum, tungsten or a combination therefrom with a refractory metal. Molybdenum is a particularly preferred nozzle material. Preferably, a nozzle comprising molybdenum can have a density of 100% of the theoretical density.
The hanging sinter crucible can be heated in any way known to the skilled person and which appears to him to be suitable. The hanging sinter crucible can for example be heated inductively or resistively. In the case of inductive heating, the energy is introduced directly via coils in the side wall of the sinter crucible and delivered from there to the inside of the crucible. In the case of resistive heating, the energy is introduced by radiation, whereby the solid surface is warmed from the outside and the energy is delivered from there to the inside. Preferably, the sinter crucible is heated inductively.
Preferably, the sinter crucible has one or more than one heating zones, for example one or two or three or more than three heating zones, preferably one or two or three heating zones, particularly preferably one heating zone. The heating zones of the sinter crucible can be brought up to the same temperature or different temperatures. For example, all heating zones can be brought up to one temperature, or all heating zones can be brought up to different temperatures, or two or more heating zones can be brought up to one temperature and one or more heating zones can, independently of each other, be brought up to other temperatures. Preferably, all heating zones am brought up to the different temperatures, for example the temperature of the heating zones increases in the direction of the material transport of the silicon dioxide granulate.
A hanging sinter crucible means a sinter crucible as previously described which is arranged hanging in an oven.
Preferably, the hanging sinter crucible has at least one, for example at least two or at least three or at least four, particularly preferably all of the following features:
The hanging assembly is preferably a hanging assembly which is installed during the construction of the hanging sinter crucible, for example a hanging assembly which is provided as an integral component of the crucible, particularly preferably a hanging assembly which is provided out of the sinter material as an integral component of the crucible. Furthermore, the hanging assembly is preferably a hanging assembly which is installed onto the sinter crucible and which is made of a material which is different to the sinter material, for example of aluminium, steel, iron, nickel or copper, preferably of copper, particularly preferably a cooled, for example a water cooled, hanging assembly made of copper which is installed on the sinter crucible.
By virtue of the hanging assembly, the hanging sinter crucible can be moved in the oven. Preferably, the crucible can be at least partially introduced and withdrawn from the oven. If different heating zones are present in the oven, their temperature profile will be transferred to the crucible which is present in the oven. By changing the position of the crucible in the oven, multiple heating zones, varying heating zones or multiple varying heating zones can be produced in the crucible.
A standing sinter crucible means a sinter crucible of the type previously described which is arranged standing in an oven.
Preferably, the standing sinter crucible has at least one, for example at least two or at least three or at least four, particularly preferably all of the following features:
The standing sinter crucible preferably has a separation of the gas compartments in the oven and in the region underneath the oven. The region underneath the oven means the region underneath the nozzle, in which the removed glass melt is present. Preferably, the gas compartments are separated by the surface on which the crucible stands. Gas which is present in the gas compartment of the oven between the inner wall of the oven and the outer wall of the crucible, can not leak down into the region underneath the oven. The removed glass melt does not contact the gases from the gas compartment of the oven. Preferably, glass melts removed from an oven with a sinter crucible in a standing arrangement and quartz glass bodies formed therefrom have a higher surface purity than melts removed from an oven with a sinter crucible in a hanging arrangement and quartz glass bodies formed therefrom.
Preferably, the crucible is connected with the inlet and the outlet of the oven in such a way that silicon dioxide granulate can enter into the crucible via the crucible inlet and through the inlet of the oven and glass melt can be removed through the outlet of the crucible and the outlet of the oven.
Preferably, the crucible comprises, in addition to the at least one inlet, at least one opening, preferably multiple openings, through which the gas can be introduced and removed. Preferably, the crucible comprises at least two openings, whereby at least one can be used as a gas inlet and at least one can be used as a gas outlet. Preferably, the use of at least one opening as gas inlet and at least one opening as gas outlet leads to a gas flow in the crucible.
The silicon dioxide granulate is introduced into the crucible through the inlet of the crucible and subsequently warmed in the crucible. The warming can be carried out in the presence of a gas or of a gas mixture of two or mom gases. Furthermore, during the warming, water attached to the silicon dioxide granulate can transfer to the gas phase and form a further gas. The gas or the mixture of two or more gases is present in the gas compartment of the crucible. The gas compartment of the crucible means the region inside the crucible which is not occupied by a solid or liquid phase. Suitable gases are for example hydrogen, inert gases as well as two or more thereof. Inert gases mean those gases which up to a temperature of 2400° C. do not react with the materials present in the crucible. Preferred inert gases are nitrogen, helium, neon, argon, krypton and xenon, particularly preferably argon and helium. Preferably, the warming is carried out in reducing atmosphere. This can be provided by means of hydrogen or a combination of hydrogen and an inert gas, for example a combination of hydrogen and helium, or of hydrogen and nitrogen, or of hydrogen and argon, particularly preferably a combination of hydrogen and helium.
Preferably, an at least partial gas exchange of air, oxygen and water in exchange for hydrogen, at least one inert gas, or in exchange for a combination of hydrogen and at least one inert gas is carried out on the silicon dioxide granulate. The at least partial gas exchange is carried out on the silicon dioxide granulate during introduction of the silicon dioxide granulate, or before the warming, or during the warming, or during at least two of the aforementioned activities. Preferably, the silicon dioxide granulate is warmed to melting in a gas flow of hydrogen and at least one inert gas, for example argon or helium.
Preferably, the dew point of the gas on exiting through the gas outlet is less than 0° C. The dew point means the temperature beneath which at fixed pressure a part of the gas or gas mixture in question condenses. In general, this means the condensation of water. The dew point is measured with a dew point mirror hygrometer according to the test method described in the methods section.
Preferably, the oven has at least one gas outlet, as does preferably also a melting crucible found therein, through which gas introduced into the oven and gas formed during the running of the oven is removed. The oven can additionally have at least one dedicated gas inlet. Alternatively or additionally, gas can be introduced through the inlet, also referred to as the solids inlet, for example together with the silicon dioxide particles, or beforehand, afterwards, or by a combination of two or more of the aforementioned possibilities.
Preferably, the gas which is removed from the oven through the gas outlet has a dew point of less than 0° C., for example of less than −10° C., or less than −20° C. on exiting from the oven through the gas outlet. The dew point is measured according to the test method described in the methods section at a slight overpressure of 5 to 20 mbar. A suitable measuring device is for example an “Optidew” device from the company Michell Instruments GmbH, D-61381 Friedrichsdorf.
The dew point of the gas is preferably measured at a measuring location at a distance of 10 cm or more from the gas outlet of the oven. Often, this distance is between 10 cm and 5 m. In this range of distances—here referred to as “on exiting”—the distance of the measuring location from the gas outlet of the oven is insignificant for the result of the dew point measurement. The gas is conveyed to the measurement location by fluid connection, for example in a hose or a tube. The temperature of the gas at the measurement location is often between 10 and 60° C., for example 20 to 50° C., in particular 20 to 30° C.
Suitable gases and gas mixtures have already been described. It was established in the context of separate tests that the above disclosed values apply to each of the named gases and gas mixtures.
According to a further preferred embodiment, the gas or gas mixture has a dew point of less than −50° C. prior to entering into the oven, in particular into the melting crucible, for example less than −60° C., or less than −70° C., or less than −80° C. A dew point commonly does not exceed −60° C. Also, the following ranges for the dew point upon entering into the oven are preferred: from −50 to −100° C.; from −60 to −100° C. and from −70 to −100° C.
According to a further preferred embodiment, the dew point of the gas prior to entering into the oven is at least 50° C. less than on exiting from the melting crucible, for example at least 60° C., or even 80° C. For measuring the dew point on exiting from the melting crucible, the above disclosures apply. For measuring the dew point prior to entry into the oven, the disclosures apply analogously. Since no source of contribution to moisture is present and there is no possibility of condensing out between the measuring location and the oven, the distance of the measuring location to the gas inlet of the oven is not relevant.
According to a preferred embodiment, the oven, in particular the melting crucible, is operated with a gas exchange rate in a range from 200 to 3000 L/h.
According to a preferred embodiment, the dew point is measured in a measuring cell, the measuring cell being separated by a membrane from the gas passing through the gas outlet. The membrane is preferably permeable to moisture. By these means, the measuring cell can be protected from dust and other particles present in the gas flow and which are conveyed out of the melting oven, in particular out of a melting crucible, along with the gas flow By these means, the working time of a measuring probe can be increased considerably. The working time means the time period of operation of the oven during which neither replacement of the measuring probe, nor cleaning of the measuring probe is required.
According to a preferred embodiment, a dew point mirror measuring device is employed.
The dew point at the gas outlet of the oven can be configured. Preferably, a process for configuring the dew point at the outlet of the oven comprises the following steps:
Preferably, this process can be used to configure the dew point to a range of less than 0° C., for example less than −10° C., particularly preferably less than −20° C. Further preferably, the dew point can be configured to a range of less than 0° C. to −100° C., for example less than −10° C. to −80° C., particularly preferably less than −20° C. to −60° C.
For the preparation of a quartz glass body, “Input material” means silicon dioxide particles which are provided, preferably silicon dioxide granulate, silicon dioxide grain, or combinations thereof. The silicon dioxide particles, the granulate and the grain are preferably characterised by the features described in the context of the first aspect.
The oven and the gas flow are preferably characterised by the features described in the context of the first aspect. Preferably, the gas flow is formed by introducing a gas into the oven through an inlet and by removing a gas out of the oven through an outlet. The “gas replacement rate” means the volume of gas which is passed out of the oven through the outlet per unit time. The gas replacement rate is also called the throughput of the gas flow or volume throughput.
The configuration of the dew point can in particular be performed by varying the residual moisture of the input material or the gas replacement rate of the gas flow. For example, the dew point can be increased by increasing residual moisture of the input material. By decreasing the residual moisture of the input material, the dew point can be reduced. An increase in the gas replacement rate can lead to a reduction in the dew point. A reduced gas replacement rate on the other hand can yield an increased dew point.
Preferably, the gas replacement rate of the gas flow is in a range from 200 to 3000 L/h, for example 200 to 2000 L/h, particularly preferably 200 to 1000 L/h.
The residual moisture of the input material is preferably in a range from 0.001 wt. % to 5 wt. %, for example from 0.01 to 1 wt. %, particularly preferably 0.03 to 0.5 wt. %, in each case based on the total weight of the input material.
Preferably, the dew point can also be affected by further factors. Examples of such means are the dew point of the gas flow on entry into the oven, the oven temperature and the composition of the gas flow. A reduction of the dew point of the gas flow on entry into the oven, a reduction of the oven temperature or a reduction of the temperature of the gas flow at the outlet of the oven can lead to a reduction of the dew point of the gas flow at the outlet. The temperature of the gas flow at the outlet of the oven has no effect on the dew point, as long as it is above the dew point.
Particularly preferably, the dew point is configured by varying the gas replacement rate of the gas flow.
Preferably, the process is characterised by at least one, for example at least two or at least three, particularly preferably at least four of the following feature:
It is particularly preferred, when employing a silicon dioxide granulate with a high residual moisture, to employ a gas flow with a high gas replacement rate and a low dew point at the inlet of the oven. By contrast, when employing a silicon dioxide granulate with a low residual moisture, a gas flow with a low gas replacement rate and a high dew point at the inlet of the oven can be used.
Particularly preferably, when employing a silicon dioxide granulate with a residual moisture of less than 3 wt. %, the gas replacement rate of a gas flow comprising helium and hydrogen can be in a range from 200 to 3000 L/h.
If a silicon dioxide granulate with a residual moisture of 0.1% is fed to the oven at 30 kg/h, a gas replacement rate of the gas flow in a range from 2800 to 3000 lf is selected in the case of He/H2=50:50 and in a range from 2700 to 2900l/h is selected in the case of He/H2=30:70, and a dew point of the gas flow before entry into the oven of −90° C. is selected. A dew point of less than 0° C. is thereby obtained at the gas outlet.
If a silicon dioxide granulate with a residual moisture of 0.05% is fed to the oven at 30 kg/h, a gas replacement rate of the gas flow in a range from 1900 to 2100l/h is selected in the case of He/H2=50:50 and in a range from 1800 to 2000l/h is selected in the case of He/H2=30:70, and a dew point of the gas flow before entry into the oven of −90° C. is selected. A dew point of less than 0° C. is thereby obtained at the gas outlet.
If a silicon dioxide granulate with a residual moisture of 0.03% is fed to the oven at 30 kg/h, a gas replacement rate of the gas flow in a range from 1400 to 1600 I/h is selected in the case of He/H2=50:50 and in a range from 1200 to 1400 I/h is selected in the case of He/H2=30:70, and a dew point of the gas flow before entry into the oven of −90° C. is selected. A dew point of less than 0° C. is thereby obtained at the gas outlet.
The oven temperature for melting the silicon dioxide granulate is preferably in the range from 1700 to 2500° C., for example in the range from 1900 to 2400° C., particularly preferably in the range from 2100 to 2300° C.
Preferably, the holding time in the oven is in a range from 1 hour to 50 hours, for example 1 to 30 hours, particularly preferably 5 to 20 hours. In the context of the present invention, the holding time means the time which is required, when carrying out the process according to the invention, to remove the fill quantity of the melting oven from the melting oven in which the glass melt is formed, in a manner according to the invention. The fill quantity is the entire mass of silicon dioxide in the melting oven. In this connection, the silicon dioxide can be present as a solid and as a glass melt.
Preferably, the oven temperature increases over the length in the direction of the material transport. Preferably, the oven temperature increases over the length in the direction of the material transport by at least 100° C., for example by at least 300° C. or by at least 500° C. or by at least 700° C., particularly preferably by at least 1000° C. Preferably, the maximum temperature in the oven is 1700 to 2500° C., for example 1900 to 2400° C., particularly preferably 2100 to 2300° C. The increase of the oven temperature can proceed uniformly or according to a temperature profile.
Preferably, the oven temperature decreases before the glass melt is removed from the oven. Preferably, the oven temperature decreases before the glass melt is removed from the oven by 50 to 500° C., for example by 100° C. or by 400° C., particularly preferably by 150 to 300° C. Preferably, the temperature of the glass melt on removal is 1750 to 2100° C., for example 1850 to 2050° C., particularly preferably 1900 to 2000° C.
Preferably, the oven temperature increases over the length in the direction of the material transport and decreases before the glass melt is removed from the oven. In this connection, the oven temperature preferably increases over the length in the direction of the material transport by at least 100° C., for example by at least 300° C. or by at least 500° C. or by at least 700° C., particularly preferably by at least 1000° C. Preferably, the maximum temperature in the oven is 1700 to 2500° C., for example 1900 to 2400° C., particularly preferably 2100 to 2300° C. Preferably, the oven temperature decreases before the glass melt is removed from the oven by 50 to 500° C., for example by 100° C. or by 400° C., particularly preferably by 150 to 300° C.
Pre-Heating Section
Preferably, the oven has at least a first and a further chamber joined to each other by a passage, the first and the further chamber having a different temperature, the temperature of the first chamber being lower than the temperature of the further chamber. In one of the further chamber, a glass melt is formed from the silicon dioxide granulate. This chamber is referred to as melting chamber in the following. A chamber which is joined to the melting chamber via a duct but which is upstream of it is also referred to as pre-heating section. An example is those in which at least one outlet is directly connected with the inlet of the melting chamber. The arrangement above may also be made in independent ovens, in which case the melting chamber is a melting oven. In the further description, however, the term ‘melting oven’ may be taken as being identical to the term ‘melting chamber’: so what is said concerning the melting oven may also be taken as applying to the melting chamber and vice versa. The term ‘pre-heating section’ means the same in both cases.
Preferably, the silicon dioxide granulate has a temperature in a range from 20 to 1300° C. on entry into the oven.
According to a first embodiment, the silicon dioxide granulate is not tempered prior to entry into the melting chamber. The silicon dioxide granulate has for example a temperature in a range from 20 to 40° C. on entry into the oven, particularly preferably from 20 to 30° C. If silicon dioxide granulate II is provided according to step i.), it preferably has a temperature on entry into the oven in a range from 20 to 40° C., particularly preferably from 20 to 30° C.
According to another embodiment, the silicon dioxide granulate is tempered up to a temperature in a range from 40 to 1300° C. prior to entry into the oven. Tempering means setting the temperature to a selected value. The tempering can in principle be carried out in any way known to the skilled person and known for the tempering of silicon dioxide granulate. For example, the tempering can be carried out in an oven arranged separate from the melting chamber or in an oven connected to the melting chamber.
Preferably, the tempering is carried out in a chamber connected to the melting chamber. Preferably, the oven thus comprises a pre-heating section in which the silicon dioxide can be tempered. Preferably, the pre-heating section is itself a feed oven, particularly preferably a rotary kiln. A feed oven means a heated chamber which, in operation, effects a movement of the silicon dioxide from an inlet of the feed oven to an outlet of the feed oven. Preferably, the outlet is directly connected to an inlet of the melting oven. In this way, the silicon dioxide granulate can arrive from the pre-heating section into the melting oven without further intermediate steps or means.
It is further preferred that the pre-heating section comprises at least one gas inlet and at least one gas outlet. Through the gas inlet, the gas can arrive in the interior, the gas chamber of the pre-heating section, and through the gas outlet it can be removed. It is also possible to introduce gas into the pre-heating section via the inlet of the pre-heating section for the silicon dioxide granulate. Also, gas can be removed via the outlet of the pre-heating section and subsequently separated from the silicon dioxide granulate. Furthermore, preferably, the gas can be introduced via the inlet for the silicon dioxide granulate and a gas inlet of the pre-heating section, and removed via the outlet of the pre-heating section and a gas outlet of the pre-heating section.
Preferably, a gas flow is produced in the pre-heating section by use of the gas inlet and of the gas outlet. Suitable gases am for example hydrogen, inert gases as well as two or more thereof. Preferred inert gases am nitrogen, helium, neon, argon, krypton and xenon, particularly preferably nitrogen and helium. Preferably, a reducing atmosphere is present in the pre-heating section. This can by provided in the form of hydrogen or a combination of hydrogen and an inert gas, for example a combination of hydrogen and helium or of hydrogen and nitrogen, particularly preferably a combination of hydrogen and helium. Furthermore, preferably, an oxidising atmosphere is present in the pre-heating section. This can preferably be provided in the form of oxygen or a combination of oxygen and one or more further gases, air being particularly preferable. Further preferably, it is possible of the silicon dioxide to be tempered at reduced pressure in the pre-heating section.
For example, the silicon dioxide granulate can have a temperature on entry into the oven in a range from 100 to 1100° C. or from 300 to 1000 or from 600 to 900° C. If silicon dioxide granulate II is provided according to step i.), it preferably has a temperature on entry into the oven in a range from 100 to 1100° C. or from 300 to 1000 or from 600 to 900° C.
According to a preferred embodiment of the first aspect of the invention, the oven comprises at least two chambers. Preferably, the oven comprises a first and at least one further chamber. The first and the further chamber are connected to each other by a passage.
The at least two chambers can in principle be arranged in the oven in any manner, preferably vertical or horizontal, particularly preferably vertical. Preferably, the chambers are arranged in the oven in such as way that on carrying out the process according to the first aspect of the invention, silicon dioxide granulate passes through the first chamber and is subsequently heated in the further chamber to obtain a glass melt. The further chamber preferably has the above described features of the melting oven and of the crucible arranged therein.
Preferably, each of the chambers comprises an inlet and an outlet. Preferably, the inlet of the oven is connected to the inlet of the first chamber via a passage. Preferably, the outlet of the oven is connected to the outlet of the further chamber via a passage. Preferably, the outlet of the first chamber is connected to the inlet of the further chamber via a passage.
Preferably, the chambers are arranged in such a manner that the silicon dioxide granulate can arrive in the first chamber through the inlet of the oven. Preferably, the chambers are arranged in such a manner that a silicon dioxide glass melt can be removed from the further chamber through the outlet of the oven. Particularly preferably, the silicon dioxide granulate can arrive in the first chamber through the inlet of the oven and a silicon dioxide glass melt can be removed from a further chamber through the outlet of the oven.
The silicon dioxide, in the form of granulate or powder, can go from a first into a further chamber through the passage in the direction of material transport as defined by the process. Reference to chambers connected by a passage includes arrangements in which further intermediate elements arrange in the direction of the material transport between a first and a further chamber. In principle, gases, liquids and solids can pass through the passage. Preferably, silicon dioxide powder, slurries of silicon dioxide powder and silicon dioxide granulate can pass through the passage between a first and a further chamber. Whilst the process according to the invention is carried out, all of the materials introduced into the first chamber can arrive in the further chamber via the passage between the first and the further chamber. Preferably, only silicon dioxide in the form of granulate or powder arrive in the further chamber via the passage between the first and the further chamber. Preferably, the passage between the first and the further chamber is closed up by the silicon dioxide, such that the gas chamber of the first and the further chamber am separated from each other, preferably such that in different gases or gas mixtures, different pressures or both can be present in the gas chambers. According to another preferred embodiment, the passage is formed of a gate, preferably a rotary gate valve.
Preferably, the first chamber of the oven has at least one gas inlet and at least one gas outlet. The gas inlet can in principle have any form which is known to the skilled person and which is suitable for introduction of a gas, for example a nozzle, a vent or a tube. The gas outlet can in principle have any form known to the skilled person and which is suitable for removal of a gas, for example a nozzle, a vent or a tube.
Preferably, silicon dioxide granulate is introduced into the first chamber through the inlet of the oven and warmed. The warming can be carried out in the presence of a gas or of a combination of two or more gases. To this end, the gas or the combination of two or more gases is present in the gas chamber of the first chamber. The gas chamber of the first chamber means the region of the first chamber which is not occupied by a solid or liquid phase. Suitable gases are for example hydrogen, oxygen, inert gases as well as two or more thereof. Preferred inert gases are nitrogen, helium, neon, argon, krypton and xenon, particularly preferred are nitrogen, helium and a combination thereof. Preferably, the warming is carried out in a reducing atmosphere. This can preferably be provided in the form of hydrogen or a combination of hydrogen and helium. Preferably, the silicon dioxide granulate is warmed in the first chamber in a flow of the gas or of the combination of two or more gases.
It if further preferred that the silicon dioxide granulate is warmed in the first chamber at reduced pressure, for example at a pressure of less than 500 mbar or less than 300 mbar, for example 200 mbar or less.
Preferably, the first chamber has at least one device with which the silicon dioxide granulate is moved. In principle, all devices can be selected which am known to the skilled person for this purpose and which appear suitable. Preferably, stirring, shaking and slewing devices.
According to a preferred embodiment of the first aspect of the invention, the temperatures in the first and in the further chamber am different. Preferably, the temperature in the first chamber is lower than the temperature in the further chamber. Preferably, the temperature difference between the first and the further chamber is in a range from 600 to 2400° C., for example in a range from 1000 to 2000° C. or from 1200 to 1800° C., particularly preferably in a range from 1500 to 1700° C. Furthermore, preferably, the temperature the first chamber is 600 to 2400° C., for example 1000 to 2000° C. or 1200 to 1800° C., particularly preferably 1500 to 1700° C. lower than the temperature in the further chamber.
According to a preferred embodiment, the first chamber of the oven is a pre-heating section, particularly preferably a pre-heating section as described above, which has the features as described above. Preferably, the pre-heating section is connected to the further chamber via a passage. Preferably, silicon dioxide goes from the pre-heating section via a passage into the further chamber. The passage between the pre-heating section and the further chamber can be closed off, so that no gases introduced into the pre-heating section go through the passage into the further chamber. Preferably, the passage between the pre-heating section and the further chamber is closed off, so that the silicon dioxide does not come into contact with water. The passage between the pre-heating section and the further chamber can be closed off, so that the gas chamber of the pre-heating section and the first chamber are separated from each other in such a way that different gases or gas mixtures, different pressures or both can be present in the gas chambers. A suitable passage is preferably as per the above described embodiments.
According to a further preferred embodiment, the first chamber of the oven is not a pre-heating section. For example, the first chamber can be a levelling chamber. A levelling chamber is a chamber of the oven in which variations in throughput in a pre-heating section upstream thereof, or throughput differences between a pre-heating section and the further chamber are levelled. For example, as described above a rotary kiln can be arranged upstream of the first chamber. This commonly has a throughput which can vary by an amount up to 6% of the average throughput. Preferably, silicon dioxide is held in a levelling chamber at the temperature at which it arrives in the levelling chamber.
It is also possible for the oven to have a first chamber and more than one further chambers, for example two further chambers or three further chambers or four further chambers or five further chambers or more than five further chambers, particularly preferably two further chambers. If the oven has two further chambers, the first chamber is preferably a pre-heating section, the first of the further chambers a levelling chamber and the second of the further chambers the melting chamber, based on the direction of the material transport.
According to a further preferred embodiment, an additive is present in the first chamber. The additive is preferably selected from the group consisting of halogens, inert gases, bases, oxygen or a combination of two or more thereof.
In principle, halogens in elemental form and halogen compounds am suitable additives. Preferred halogens am selected from the group consisting of chlorine, fluorine, chlorine containing compounds and fluorine containing compounds. Particularly preferable are elemental chlorine and hydrogen chloride.
In principle, all inert gases as well as mixtures of two or more thereof are suitable additives. Preferred inert gases am nitrogen, helium or a combination thereof.
In principle bases am also suitable additives. Preferred bases for use as additives am inorganic and organic bases.
Further, oxygen is a suitable additive. The oxygen is preferably present as an oxygen containing atmosphere, for example in combination with an inert gas or a mixture of two or more inert gases, particularly preferably in combination with nitrogen, helium or nitrogen and helium.
The first chamber can in principle comprise any material which is known to the skilled person and which is suitable for heating silicon dioxide. Preferably, the first chamber comprises at least one element selected from the group consisting of quartz glass, a refractory metal, aluminium and a combination of two or more thereof, particularly preferably, the first chamber comprises quartz glass or aluminium.
Preferably, the temperature in the first chamber does not exceed 600° C. if the first chamber comprises a polymer or aluminium. Preferably, the temperature in the first chamber is 100 to 1100° C., if the first chamber comprises quartz glass. Preferably, the first chamber comprises mainly quartz glass.
In the transportation of the silicon dioxides from the first chamber to the further chamber through the passage between the first and the further chamber, the silicon dioxide can in principle be present in any state. Preferably, the silicon dioxide is present as a solid, for example as particles, powder or granulate. According to a preferred embodiment of the first aspect of the invention, the transportation of the silicon dioxides from the first to the further chamber is carried out as granulate.
According to a further preferred embodiment the further chamber is a crucible made of a metal sheet or of a sinter material, wherein the sinter material comprises a sinter metal, wherein the metal sheet or the sinter metal is selected from the group consisting of molybdenum, tungsten and a combination thereof.
The glass melt is removed from the oven through the outlet, preferably via a nozzle.
Step iv.)
A quartz glass body is made out of at least a part of the glass melt. For this, preferably at least a part of the glass melt made in step iii) is removed and the quartz glass body is made out of it.
The removal of the part of the glass melt made in step iii) can in principle be carried out continuously from the melting oven or from the melting chamber or after the production of the glass melt has been finished. Preferably, a part of the glass melt is removed continuously. The glass melt is removed through the outlet of the oven, or from the outlet of the melting chamber, in each case preferably via a nozzle.
The glass melt can be cooled before, during or after the removal, to a temperature which enables the forming of the glass melt. A rise in the viscosity of the glass melt is connected to the cooling of the glass melt. The glass melt is preferably cooled to such an extent that in the forming, the produced form holds and the forming is at the same time as easy and reliable as possible and can be carried out with little effort. The skilled person can easily establish the viscosity of the glass melt for forming by varying the temperature of the glass melt at the forming tool. Preferably, the glass melt has a temperature on removal in the range from 1750 to 2100° C., for example 1850 to 2050° C., particularly preferably 1900 to 2000° C. Preferably, the glass melt is cooled to a temperature of less than 500° C. after removal, for example of less than 200° C. or less than 100° C. or less than 50° C., particularly preferably to a temperature in the range from 20 to 30° C.
The quartz glass body which is formed can be a solid body or a hollow body. A solid body means a body which is mainly made out of a single material. Nevertheless, a solid body can have one or more inclusions, e.g. gas bubbles. Such inclusions in a solid body commonly have a size of 65 mm3 or less, for example of less than 40 mm3, or of less than 20 mm3, or of less than 5 mm3, or of less than 2 mm3, particularly preferably of less than 0.5 mm3. Preferably, a solid body comprises less than 0.02 vol.-% of its volume as inclusion, for example less than 0.01 vol.-% or less than 0.001 vol.-%, in each case based on the total volume of the solid body.
The quartz glass body has an exterior form. The exterior form means the form of the outer edge of the cross section of the quartz glass body. The exterior form of the quartz glass body in cross-section is preferably round, elliptical or polygonal with three or more corners, for example 4, 5, 6, 7 or 8 corners, particularly preferably the quartz glass body is round.
Preferably, the quartz glass body has a length in the range from 100 to 10000 mm, for example from 1000 to 4000 mm, particularly preferably from 1200 to 3000 mm.
Preferably, the quartz glass body has an exterior diameter in the range from 1 to 500 mm, for example in a range from 2 to 400 mm, particularly preferably in a range from 5 to 300 mm.
The forming of the quartz glass body is performed by means of a nozzle. The glass melt is sent through the nozzle. The exterior form of a quartz glass body formed through the nozzle is determined by the form of the nozzle opening. If the opening is round, a cylinder will be made in forming the quartz glass body. If the opening of the nozzle has a structure, this structure will be transferred to the exterior form of the quartz glass body. A quartz glass body which is made by means of a nozzle with structure at the opening, has an image of the structure in the length direction along the glass strand.
The nozzle is integrated in the melting oven. Preferably, it is integrated in the melting oven as part of the crucible, particularly preferably as part of the outlet of the crucible.
Preferably, the at least part of the glass melt is removed through the nozzle. The exterior form of the quartz glass body is formed by the removal of the at least part of the glass melt through the nozzle.
Preferably, the quartz glass body is cooled after the forming, so that it maintains its form. Preferably, the quartz glass body is cooled after the forming to a temperature which is at least 1000° C. below the temperature of the glass melt in the forming, for example at least 1500° C. or at least 1800° C., particularly preferably 1900 to 1950° C. Preferably, the quartz glass body is cooled to a temperature of less than 500° C., for example of less than 200° C. or less than 100° C. or less than 50° C., particularly preferably to a temperature in the range from 20 to 30° C.
According to a preferred embodiment of the first aspect of the invention, the obtained quartz glass body can be treated with at least one procedure selected from the group consisting of chemical, thermal or mechanical treatment.
Preferably, the quartz glass body is chemically post treated. Post treatment relates to treatment of a quartz glass body which has already been made. Chemical post treatment of the quartz glass body means in principle any procedure which is known to the skilled person and appears suitable for employing materials for changing the chemical structure or the composition of the surface of the quartz glass body, or both. Preferably, the chemical post treatment comprises at least one means selected from the group consisting of treatment with fluorine compounds and ultrasound cleaning.
Possible fluorine compounds are in particular hydrogen fluoride and fluorine containing acids, for example hydrofluoric acid. The liquid preferably has a content of fluorine compounds in a range from 35 to 55 wt.-%, preferably in a range from 35 to 45 wt.-%, the wt.-% in each case based on the total amount of liquid. The remainder up to 100 wt.-% is usually water. Preferably, the water is fully desalinated water or deionised water.
Ultrasound cleaning is preferably performed in a liquid bath, particularly preferably in the presence of detergents. In the case of ultrasound cleaning, commonly no fluorine compounds, for example neither hydrofluoric acid nor hydrogen fluoride.
The ultrasound cleaning of the quartz glass body is preferably carried out under at least one, for example at least two or at least three or at least four or at least five, particularly preferably all of the following conditions:
Preferably, the quartz glass body is thermally post treated. Thermal post treatment of the quartz glass body means in principle a procedure known to the skilled person and which appears suitable for changing the form or structure or both of the quartz glass body by means of temperature. Preferably, the thermal post treatment comprises at least a one means selected from the group consisting of tempering, compressing, inflating, drawing, welding, and a combination of two or more thereof. Preferably, the thermal post treatment is not performed for the purpose of removing material.
The tempering is preferably performed by heating the quartz glass body in an oven, preferably at a temperature in a range from 900 to 1300° C., for example in a range from 900 to 1250° C. or from 1040 to 1300° C., particularly preferably in a range from 1000 to 1050° C. or from 1200 to 1300° C. Preferably, in the thermal treatment, a temperature of 1300° C. is not exceeded for continuous period of more than 1 h, particularly preferably a temperature of 1300° C. is not exceeded during the entire duration of the thermal treatment. The tempering can in principle be performed at reduced pressure, at normal pressure or at increased pressure, preferably at reduced pressure, particularly preferably in a vacuum.
The compressing is preferably performed by heating the quartz glass body, preferably to a temperature of about 2100° C., and subsequent forming during a rotating turning motion, preferably with a rotation speed of about 60 rpm. For example, a quartz glass body in the form of a rod can be formed into a cylinder.
Preferably, a quartz glass body can be inflated by injecting a gas into the quartz glass body. For example, a quartz glass body can by formed into a large-diameter tube by inflating. For this, preferably the quartz glass body is heated to a temperature of about 2100° C., whilst a rotating turning motion is performed, preferably with a rotation speed of about 60 rpm, and the interior is flushed with a gas, preferably at a defined and controlled inner pressure of up to about 100 mbar. A large-diameter tube means a tube with an outer diameter of at least 500 mm.
A quartz glass body can preferably be drawn. The drawing is preferably performed by heating the quartz glass body, preferably to a temperature of about 2100° C., and subsequently pulling with a controlled pulling speed to the desired outer diameter of the quartz glass body. For example lamp tubes can be formed from quartz glass bodies by drawing.
Preferably, the quartz glass body is mechanically post treated. A mechanic post treatment of the quartz glass body means in principle any procedure known to the skilled person and which appears suitable for using an abrasive means to change the shape of the quartz glass body or to split the quartz glass body into multiple pieces. In particular, the mechanical post treatment comprises at least one means selected from the group consisting of grinding, drilling, honing, sawing, waterjet cutting, laser cutting, roughening by sandblasting, milling and a combination of two or more thereof.
Preferably, the quartz glass body is treated with a combination of these procedures, for example with a combination of a chemical and a thermal post treatment or a chemical and a mechanical post treatment or a thermal and a mechanical post treatment, particularly preferably with a combination of a chemical, a thermal and a mechanical post treatment. Furthermore, preferably, the quartz glass body can subjected to several of the above mentioned procedures, each independently from the others.
According to an embodiment of the first aspect of the invention, the process comprises the following process step:
The hollow body which is made has an interior and an exterior form. Interior form means the form of the inner edge of the cross section of the hollow body. The interior and exterior form in cross section of the hollow body can be the same or different. The interior and exterior form of the hollow body in cross section can be round, elliptical or polygonal with three or more corners, for example 4, 5, 6, 7 or 8 corners.
Preferably, the exterior form of the cross section corresponds to the interior form of the hollow body. Particularly preferably, the hollow body has in cross section a round interior and a round exterior form.
In another embodiment, the hollow body can differ in the interior and exterior form. Preferably, the hollow body has in cross section a round exterior form and a polygonal interior form. Particularly preferably, the hollow body in cross section has a round exterior form and a hexagonal interior form.
Preferably, the hollow body has a length in the range from 100 to 10000 mm, for example from 1000 to 4000 mm, particularly preferably from 1200 to 2000 mm.
Preferably, the hollow body has a wall thickness in a range from 0.8 to 50 mm, for example in a range from 1 to 40 mm or from 2 to 30 mm or from 3 to 20 mm, particularly preferably in a range from 4 to 10 mm.
Preferably, the hollow body has an outer diameter of 2.6 to 400 mm, for example in a range from 3.5 to 450 mm, particularly preferably in a range from 5 to 300 mm.
Preferably, the hollow body has an inner diameter of 1 to 300 mm, for example in a range from 5 to 280 mm or from 10 to 200 mm, particularly preferably in a range from 20 to 100 mm.
The hollow body comprises one or more openings. Preferably, the hollow body comprises one opening. Preferably, the hollow body has an even number of openings, for example 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 openings. Preferably, the hollow body comprises two openings. Preferably, the hollow body is a tube. This form of the hollow body is particularly preferred if the light guide comprises only one core. The hollow body can comprise more than two openings. The openings am preferably located in pairs situated opposite each other at the ends of the quartz glass body. For example, each end of the quartz glass body can have 2, 3, 4, 5, 6, 7 or more than 7 openings, particularly preferably 5, 6 or 7 openings. Preferred forms are for example tubes, twin tubes, i.e. tubes with two parallel channels, and multi channel tubes, i.e. Tubes with more than two parallel channels.
The hollow body can in principle be formed by any method known to the skilled person. Preferably, the hollow body is formed by means of a nozzle. Preferably, the nozzle comprises in the middle of its opening a device which deviates the glass melt in the forming. In this way, a hollow body can be formed from a glass melt.
A hollow body can be made by the use a nozzle and subsequent post treatment. Suitable post treatments am in principle all process known to the skilled person for making a hollow body out of a solid body, for example compressing channels, drilling, honing or grinding. Preferably, a suitable post treatment is to send the solid body over one or multiple mandrels, whereby a hollow body is formed. Also, the mandrel can be introduced into the solid body to make a hollow body. Preferably, the hollow body is cooled after the forming.
Preferably, the hollow body is cooled to a temperature of less than 500° C. after the forming, for example less than 200° C. or less than 100° C. or less than 50° C., particularly preferably to a temperature in the range from 20 to 30° C.
Pre-Compacting
It is in principle possible to subject the silicon dioxide granulate II provided in step ii.) to one or multiple pre treatment steps, before it is warmed in step iii.) to obtain a glass melt. Possible pre treatment steps are for example thermal or mechanical treatment steps. For example the silicon dioxide granulate can be compactified before the warming in step iii.). “Compacting” means a reduction in the BET surface area and a reduction of the pore volume.
The silicon dioxide granulate is preferably compactified by heating the silicon dioxide granulate or mechanically by exerting a pressure to the silicon dioxide granulate, for example rolling or pressing of the silicon dioxide granulate. Preferably, the silicon dioxide granulate is compactified by heating. Particularly preferably, the compacting of the silicon dioxide granulate is performed by heating by means of a pre-heating section which is connected to the melting oven.
Preferably, the silicon dioxide is compactified by heating at a temperature in a range from 800 to 1400° C., for example at a temperature in a range from 850 to 1300° C., particularly preferably at a temperature in a range from 900 to 1200° C.
In a preferred embodiment of the first aspect of the invention, the BET surface area of the silicon dioxide granulate is not reduced to less than 5 m2/g prior to the warming in step iii.), preferably not to less than 7 m2/g or not to less than 10 m2/g, particularly preferably not to less than 15 m2/g. Furthermore, it is preferred, that the BET surface area of the silicon dioxide granulate is not reduced prior to the warming in step iii.) compared with the silicon dioxide granulate II provided in step ii.).
In a preferred embodiment of the first aspect of the invention, the BET surface area of the silicon dioxide granulate is reduced to less than 20 m2/g, for example to less than 15 m2/g, or to less than 10 m2/g, or to a range of more than 5 to less than 20 m2/g or from 7 to 15 m2/g, particularly preferably to a range of 9 to 12 m2/g. Preferably, the BET surface area of the silicon dioxide granulate is reduced prior to the heating in step iii.) in comparison to the silicon dioxide granulate II provided in step ii.) by less than 40 m2/g, for example by 1 to 20 m2/g or by 2 to 10 m2/g, particularly preferably by 3 to 8 m2/g, the BET surface area after the compactification being more than 5 m2/g.
The compactified silicon dioxide granulate is referred to in the following as silicon dioxide granulate III. Preferably, the silicon dioxide granulate III has at least one, for example at least two or at least three or at least four, particularly preferably at least five of the following features:
The silicon dioxide granulate III preferably has the feature combination A./F./G. or A./F./H. or A./G./H., further preferably the feature combination A./F./G./H.
The silicon dioxide granulate III preferably has the feature combination A./F./G., wherein the BET surface area is in a range from 10 to 30 m2/g, The tamped density is in a range from 1.15 to 1.35 g/mL and the carbon content is less than 4 ppm.
The silicon dioxide granulate III preferably has the feature combination A./F./H., wherein the BET surface area is in a range from 10 to 30 m2/g, The tamped density is in a range from 1.15 to 1.35 g/mL and the chlorine content is in a range from 1 ppb to 200 ppm.
The silicon dioxide granulate III preferably has the feature combination A./G./H., wherein the BET surface area is in a range from 10 to 30 m2/g, the carbon content is less than 4 ppm and the chlorine content is in a range from 1 ppb to 200 ppm.
The silicon dioxide granulate III preferably has the feature combination A./F./G./H., wherein the BET surface area is in a range from 10 to 30 m2/g, The tamped density is in a range from 1.15 to 1.35 g/mL, the carbon content is less than 4 ppm and the chlorine content is in a range from 1 ppb to 200 ppm.
Preferably, in at least one process step, a silicon component different to silicon dioxide is introduced. The introduction of silicon components different to silicon dioxide is also referred to in the following as Si-doping. In principle, the Si-doping can be performed in any process step. Preferably, the Si-doping is performed in step i.), ii.) or iii.).
The silicon component which is different to silicon dioxide can in principle be introduced in any form, for example as a solid, as a liquid, as a gas, in solution or as a dispersion. Preferably, the silicon component different to silicon dioxide is introduced as a powder. Also, preferably, the silicon component different to silicon dioxide can be introduced as a liquid or as a gas.
The silicon component which is different to silicon dioxide is preferably introduced in an amount in a range from 1 to 100,000 ppm, for example in a range from 10 to 10,000 ppm or from 30 to 1000 ppm or in a range from 50 to 500 ppm, particularly preferably in a range from 80 to 200 ppm, further particularly preferably in a range from 200 to 300 ppm, in each case based on the total weight of silicon dioxide.
The silicon component which is different to silicon dioxide can be solid, liquid or gaseous. If it is solid, it preferably has a mean particle size of up to 10 mm, for example of up to 1000 μm of up to 400 μm or in a range from 1 to 400 μm, for example 2 to 200 μm or 3 to 100 μm, particularly preferably in a range from 5 to 50 μm. The particle size values am based on the state of the silicon component which is different to silicon dioxide at room temperature.
The silicon component preferably has a purity of at least 99.5 wt.-%, for example at least 99.8 wt.-% or at least 99.9 wt.-%, or at least 99.99 wt.-%, particularly preferably at least 99.999 wt.-%, in each case based on the total weight of the silicon component. Preferably, the silicon component has a carbon content of not more than 10 ppm, for example not more than 50 ppm, particularly preferably not more than 1 ppm, in each case based on the total weight the silicon component. Particularly preferably, this applies to silicon employed as the silicon component. Preferably, the silicon component has an amount of impurities selected from the group consisting of Al, Ca, Co, Cr, Cu, Fe, Ge, Hf, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Ti, V, W, Zn, Zr of not more than 250 ppm, for example not more than 150 ppm, particularly preferably not more than 100 ppm, in each case based on the total weight of the silicon component. Particularly preferably, this applies where silicon is employed as the silicon component.
Preferably, a silicon component which is different to silicon dioxide is introduced in process step i.). Preferably, the silicon component which is different to silicon dioxide is introduced during the processing of the silicon dioxide powder to obtain a silicon dioxide granulate (step II.). For example the silicon component which is different to silicon dioxide can be introduced before, during or after the granulation.
Preferably, the silicon dioxide can be Si-doped by introducing the silicon component which is different to silicon dioxide to the slurry comprising silicon dioxide powder. For example, the silicon component which is different to silicon dioxide can be mixed with silicon dioxide powder and subsequently slurried, or the silicon component which is different to silicon dioxide can be introduced into a slurry of silicon dioxide powder a liquid and then slurried, or the silicon dioxide powder can be introduced into a slurry or solution of the silicon component which is different to silicon dioxide in a liquid and then slurried.
Preferably, the silicon dioxide can be Si-doped by introduction of the silicon component which is different to silicon dioxide during granulation. It is in principle possible to introduce the silicon component which is different to silicon dioxide at any point in time during the granulation. In the case of spray granulation, the silicon component which is different to silicon dioxide can for example be sprayed through the nozzle into the spray tower together with the slurry. In the case of roll granulation, the silicon component which is different to silicon dioxide can preferably be introduced in solid form or as a slurry, for example after introducing the slurry into the stirring vessel.
Furthermore, preferably, the silicon dioxide can be Si-doped by introduction of the silicon component which is different to silicon dioxide after the granulation. For example, the silicon dioxide can be doped in step ii.) during the treatment of the silicon dioxide granulate I to obtain silicon dioxide granulate II, preferably by introducing the silicon component which is different to silicon dioxide during the thermal and optionally the mechanical treatment of the silicon dioxide granulate I.
Preferably, the silicon dioxide granulate II is doped with the silicon component which is different to silicon dioxide.
Furthermore, preferably, the silicon component which is different to silicon dioxide can also be introduced during several of the above mentioned sections, in particular during and after the thermal or mechanical treatment of the silicon dioxide granulate I to obtain the silicon dioxide granulate II.
The silicon component which is different to silicon dioxide can in principle be silicon or any silicon containing compound known to the skilled person and which has a reducing effect. Preferably, the silicon component which is different to silicon dioxide is silicon, a silicon-hydrogen compound, for example a silane, a silicon-oxygen compound, for example silicon monoxide, or a silicon-hydrogen-oxygen compound, for example disiloxane. Examples of preferred silanes are monosilane, disilane, trisilane, tetrasilane, pentasilane, hexasilane, heptasilane higher homologous compounds as well as isomers of the aforementioned, and cyclic silanes like cyclo-pentasilane.
Preferably, a silicon component which is different to silicon dioxide is introduced in process step iii.).
Preferably, the silicon component which is different to silicon dioxide can be introduced directly into the melting crucible with the silicon dioxide granulate. Preferably, silicon as the silicon component which is different from silicon dioxide can be introduced into the melting crucible with the silicon dioxide granulate. The silicon is preferably introduced as powder, in particular with the particle size previously given for the silicon component which is different to silicon dioxide.
Preferably, the silicon component which is different to silicon dioxide is added to the silicon dioxide granulate before introduction into the melting crucible. The addition can in principle be performed at any time after the formation of the granulate, for example in the pre-heating section, before or during the pre-compacting of the silicon dioxide granulate II, or to the silicon dioxide granulate III.
A silicon dioxide granulate obtained by addition of a silicon component which is different to silicon dioxide is referred to in the following as “Si-doped granulate”. Preferably, the Si-doped granulate has at least one, for example at least two or at least three or at least four, particularly preferably at least five of the following features:
In a preferred embodiment of the first aspect of the invention, the melting energy is transferred to the silicon dioxide granulate via a solid surface.
A solid surface means a surface which is different to the surface of the silicon dioxide granulate and which does not melt or collapse at the temperatures to which the silicon dioxide granulate is heated for melting. Suitable materials for the solid surface am for example the materials which are suitable as crucible material.
The solid surface can in principle be any surface which is known to the skilled person and which is suitable for this purpose. For example the crucible or a separate component which is not the crucible can be used as the solid surface.
The solid surface can in principle be heated in any manner known to the skilled person and which is suitable for this purpose, in order to transfer the melting energy to the silicon dioxide granulate. Preferably, the solid surface is heated by resistive heating or inductive heating. In the case of inductive heating, the energy is directly coupled into the solid surface by means of coils and delivered from there to its inner side. In the case of resistive heating, the solid surface is warmed from the outer side and passes the energy from them to its inner side. In this connection, a heating chamber gas with low heat capacity is advantageous, for example an argon atmosphere or an argon containing atmosphere. For example, the solid surface can be heated electrically or by firing the solid surface with a flame from the outside. Preferably, the solid surface is heated to a temperature which can transfer an amount of energy to the silicon dioxide granulate and/or part melted silicon dioxide granulate which is sufficient for melting the silicon dioxide granulate.
If a separate component is used as the solid surface, this can be brought into contact with the silicon dioxide granulate in any manner, for example by laying the component on the silicon dioxide granulate or by introducing the component between the granules of the silicon dioxide granulate or by inserting the component between the crucible and the silicon dioxide granulate or by a combination of two or more thereof. The component can be heated before, or during or before and during the transfer of the melting energy.
Preferably, the melting energy is transferred to the silicon dioxide granulate via the inner side of the crucible. In this case, the crucible is heated enough so that the silicon dioxide granulate melts. The crucible is preferably heated resistively or inductively. The warmth is transferred from the outer side to the inner side of the crucible. The solid surface of the inner side of the crucible transfers the melting energy to the silicon dioxide granulate.
According to a further preferred embodiment of the present invention, the melting energy is not transferred to the silicon dioxide granulate via a gas compartment. Furthermore, preferably, the melting energy is not transferred to the silicon dioxide granulate by firing of the silicon dioxide granulate with a flame. Examples of these excluded means of transferring energy are directing one or multiple burner flames from above in the melting crucible, or onto the silicon dioxide, or both.
The above described process according to the first aspect of the invention relates to the preparation of a quartz glass body.
Preferably, the quartz glass body has at least one of the following features, for example at least two or at least three or at least four, particularly preferably at least five of the following features:
Preferably, the quartz glass body has a metal content of metals different to aluminium of less than 1000 ppb, for example of less than 500 ppb, particularly preferably of less than 100 ppb, in each case based on the total weight of the quartz glass body. Often however, the quartz glass body has a content of metals different to aluminium of at least 1 ppb. Such metals am for example sodium, lithium, potassium, magnesium, calcium, strontium, germanium, copper, molybdenum, titanium, iron and chromium. This can for example be present as an element, as an ion, or as part of a molecule or of an ion or of a complex.
The quartz glass body can comprise further constituents. Preferably, the quartz glass body comprises less than 500 ppm, for example less than 450 ppm, particularly preferably less than 400 ppm of further constituents, the ppm in each case being base on the total weight of the quartz glass body. Possible other constituents am for example carbon, fluorine, iodine, bromine and phosphorus. These can for example be present as an element, as an ion or as part of a molecule, an ion or a complex. Often however, the quartz glass body has a content of further constituents of at least 1 ppb.
Preferably, the quartz glass body comprises less than 5 ppm carbon, for example less than 4.5 ppm, particularly preferably less than 4 ppm, in each case based on the total weight of the quartz glass body. Often however, the quartz glass body has a carbon content of at least 1 ppb.
Preferably, the quartz glass body has a homogeneously distributed OH content, Cl content or Al content. An indicator of the homogeneity of the quartz glass body can be expressed as the standard deviation of OH content, Cl content or Al content. The standard deviation is the measure of the spread of the values of a variable from their arithmetic mean, here the OH content, chlorine content or aluminium content. For measuring the standard deviation, the content in the sample of the component in question e.g. OH, chlorine or aluminium, is measured at least seven measuring locations.
The quartz glass body preferably has the feature combination A]/B]/C] or A]/B]/D] or A]/B]/F], further preferred the feature combination A]/B]/C]/D] or A]/B]/C]/F] or A]/B]/D]/F], further preferably the feature combination A]/B]/C]/D]/F].
The quartz glass body preferably has the feature combination A]/B]/C], wherein The OH content is less than 400 ppm, the chlorine content is less than 100 ppm and the aluminium content is less than 80 ppb.
The quartz glass body preferably has the feature combination A]/B]/D], The OH content is less than 400 ppm, the chlorine content is less than 100 ppm and the ODC content is in a range from 0.1·1015 to 3·1015/cm3.
The quartz glass body preferably has the feature combination A]/B]/F], wherein The OH content is less than 400 ppm, the chlorine content is less than 100 ppm and the viscosity (p=1013 hPa) is in a range from log10 (η (1250° C.)/dPas)=11.4 to log10 (η (1250° C.)/dPas)=12.9.
The quartz glass body preferably has the feature combination A]/B]/C]/D], wherein The OH content is less than 400 ppm, the chlorine content is less than 100 ppm, the aluminium content is less than 80 ppb and the ODC content is in a range from 0.1·1015 to 3·1015/cm3.
The quartz glass body preferably has the feature combination A]/B]/C]/F], wherein The OH content is less than 400 ppm, the chlorine content is less than 100 ppm, the aluminium content is less than 80 ppb and the viscosity (p=1013 hPa) is in a range from log10 (η (1250° C.)/dPas)=11.4 to log10 (η (1250° C.)/dPas)=12.9.
The quartz glass body preferably has the feature combination A]/B]/D]/F], wherein The OH content is less than 400 ppm, the chlorine content is less than 100 ppm, the ODC content is in a range from 0.1·1015 to 3·1015/cm3 and the viscosity (p=1013 hPa) is in a range from log10 (η (1250° C.)/dPas)=11.4 to log10 (η (1250° C.)/dPas)=12.9.
The quartz glass body preferably has the feature combination A]/B]/C]/D]/F], wherein The OH content is less than 400 ppm, the chlorine content is less than 100 ppm, the aluminium content is less than 80 ppb and the ODC content is in a range from 0.1·1015 to 3·1015/cm3 and the viscosity (p=1013 hPa) is in a range from log10 (η (1250° C.)/dPas)=11.4 to log10 (η (1250° C.)/dPas)=12.9.
A second aspect of the invention is a process for the preparation of a silicon dioxide granulate II comprising the following process steps:
Preferably, the silicon dioxide granulate I additionally has the features described in the context of the first aspect of the invention. Preferably, the silicon dioxide granulate I is prepared as described in the context of the first aspect of the invention.
Preferably, the silicon dioxide granulate II additionally has the features described in the context of the first aspect of the invention. Preferably, the treatment of the silicon dioxide granulate II with a reactant takes place at a temperature in a range from 1000 to 1300° C. as described in the context of the first aspect of the invention.
Particularly preferably, the silicon dioxide granulate II has a carbon content wC(2). The carbon content wC(2) of the silicon dioxide granulate II is less than the carbon content wC(1) of the silicon dioxide granulate I. Preferably, wC(2) is 0.5 to 50%, for example 1 to 45%, particularly preferably 1.5 to 40% less than wC(1). The carbon content wC(2) is preferably less than 5 ppm, for example less than 3 ppm, particularly preferably less than 1 ppm, in each case based on the total weight of silicon dioxide granulate II. Often, the silicon dioxide granulate II has a carbon content of at least 1 ppm.
According to the invention, the silicon dioxide granulate II has a content of alkaline earth metal wM(2). The content of alkaline earth metal wM(2) of the silicon dioxide granulate II is less than the content of alkaline earth metal wM(1) of the silicon dioxide granulate I. Preferably, wM(2) is 0.5 to 50%, for example 1 to 45%, particularly preferably 1.5 to 40% less than wM(1). The content of alkaline earth metal wM(2) is preferably less than 500 ppb, for example less than 450 ppb or 400 ppb or 350 ppb, particularly preferably less than 300 ppb, in each case based on the total weight of silicon dioxide granulate II. Often, the silicon dioxide granulate II has a content of alkaline earth metal wM(2) of 1 ppb or more.
The silicon dioxide granulate II preferably has at least one, preferably at least two or at least three or at least four, particularly preferably all of the following features:
A third aspect of the present invention is a quartz glass body obtainable by the process according to the first aspect of the invention.
Preferably, the quartz glass body has at least one of the following features, for example at least two or at least three or at least four, particularly preferably at least five of the following features:
A fourth aspect of the present invention is a process for the preparation of a light guide comprising the following steps
Step A/
The quartz glass body provided in step A/ is a hollow body with at least one opening. The quartz glass body provided in step A/ is preferably characterised by the features according to the third aspect of the invention. The quartz glass body provided in step A/ is preferably obtainable by a process according to the first aspect of the invention comprising as step iv.) the preparation of a hollow body out of the quartz glass body. Particularly preferably, the quartz glass body thus obtained has the features according to the third aspect of the invention.
Step B/
One or multiple core rods are introduced through the at least one opening of the quartz glass body (step B/). A core rod in the context of the present invention means an object which is designed to be introduced into a jacket, for example a jacket M1, and processed to obtain a light guide. The core rod has a core of quartz glass. Preferably, the core rod comprises a core of quartz glass and jacket layer M0 which surrounds the core.
Each core rod has a form which is selected such that it fits into the quartz glass body. Preferably, the exterior form of the core rod corresponds to the form of the opening of the quartz glass body. Particularly preferably, the quartz glass body is a tube and the core rod is a rod with a round cross section.
The diameter of the core rod is smaller than the inner diameter of the hollow body. Preferably, the diameter of the core rod is 0.1 to 3 mm smaller than the inner diameter of the hollow body, for example 0.3 to 2.5 mm smaller or 0.5 to 2 mm smaller or 0.7 to 1.5 mm smaller, particularly preferably 0.8 to 1.2 mm smaller.
Preferably, the ratio of the inner diameter of the quartz glass body to the diameter of the core rod is in the range from 2:1 to 1.0001:1, for example in the range from 1.8:1 to 1.01:1 or in the range from 1.6:1 to 1.005:1 or in the range from 1.4:1 to 1.01:1, particularly preferably in the range from 1.2:1 to 1.05:1.
Preferably, a region inside the quartz glass body which is not filled by the core rod can be filled with at least one further component, for example with a silicon dioxide powder or with a silicon dioxide granulate.
It is also possible for a core rod which is already present in a further quartz glass body to be introduced into a quartz glass body. The further quartz glass body in this case has an outer diameter which is smaller than the inner diameter of the quartz glass body. The core rod which is introduced into the quartz glass body can also be present in two or more further quartz glass bodies, for example in 3 or 4 or 5 or 6 or more further quartz glass bodies.
A quartz glass body with one or multiple core rods obtainable in this way will be referred to in the following as “precursor”.
Step C/
The precursor is drawn in the warm (step C/). The obtained product is a light guide with one or multiple cores and at least one jacket M1.
Preferably, the drawing of the precursor is performed with a speed in the range from 1 to 100 m/h, for example with a speed in the range from 2 to 50 m/h or from 3 to 30 m/h. Particularly preferably, the drawing of the quartz glass body is performed with a speed in the range from 5 to 25 m/h.
Preferably, the drawing is performed in the warm at a temperature of up to 2500° C., for example at a temperature in the range from 1700 to 2400° C., particularly preferably at a temperature in the range from 2100 to 2300° C.
Preferably, the precursor is sent through an oven which heats the precursor from the outside.
Preferably, the precursor is stretched until the desired thickness of the light guide is achieved. Preferably, the precursor is stretched to 1,000 to 6,000,000 times the length, for example to 10,000 to 500,000 times the length or to 30,000 to 200,000 times the length, in each case based on the length of the quartz glass body provided in step A/. Particularly preferably, the precursor is stretched to 100,000 to 10,000,000 times the length, for example to 150,000 to 5,800,000 times the length or to 160,000 to 640,000 times the length or to 1,440,000 to 5,760,000 times the length or to 1,440,000 to 2,560,000 times the length, in each case based on the length of the quartz glass body provided in step A/.
Preferably, the diameter of the precursor is reduced by the stretching by a factor in a range from 100 to 3,500, for example in a range from 300 to 3,000 or from 400 to 800 or from 1,200 to 2,400 or from 1,200 to 1,600, in each case based on the diameter of the quartz glass body provided in step A/.
The light guide, also referred to as light wave guide, can comprises any material which is suitable for conducting or guiding electromagnetic radiation, in particular light.
Conducting or guiding radiation means propagating the radiation over the length extension of the light guide without significant obstruction or attenuation of the intensity of the radiation. For this, the radiation is coupled into the guide via one end of the light guide. Preferably, the light guide conducts electromagnetic radiation in a wavelength range from 170 to 5000 nm. Preferably, the attenuation of the radiation by the light guide in the wavelength range in question is in a range from 0.1 to 10 dB/km. Preferably, the light guide has a transfer rate of up to 50 Tbit/s.
The light guide preferably has a curl parameter of more than 6 m. The curl parameter in the context of the invention means the bending radius of a fibre, e.g. of a light guide or of a jacket M1, which is present as a freely moving fibre free from external forces.
The light guide is preferably made to be pliable. Pliable in the context of the invention means that the light guide is characterised by a bending radius of 20 mm or less, for example of 10 mm or less, particularly preferably less than 5 mm or less. A bending radius means the smallest radius which can be formed without fracturing the light guide and without impairing the ability of the light guide to conduct radiation. An impairment is present where them is attenuation of more than 0.1 dB of light sent through a bend in the light guide. The attenuation is preferably mentioned at a reference wavelength of 1550 nm.
Preferably, the quartz is composed of silicon dioxide with less than 1 wt.-% of other substances, for example with less than 0.5 wt.-% of other substances, particularly preferably with less than 0.3 wt.-% of other substances, in each case based on the total weight of the quartz. Furthermore, preferably, the quartz comprises at least 99 wt.-% silicon dioxide, based on the total weight of the quartz.
The light guide preferably has an elongate form. The form of the light guide is defined by its length extension L and its cross section Q. The light guide preferably has a round outer wall along its length extension L. A cross section Q of the light guide is always determined in a plane which is perpendicular to the outer wall of the light guide. If the light guide is curved in the length extension L, then the cross section Q is determined perpendicular to the tangent at a point on the outer wall of the light guide. The light guide preferably has a diameter d in a range from 0.04 to 1.5 mm. The light guide preferably has a length in a range from 1 m to 100 km.
According to the invention, the light guide comprises one or multiple cores, for example one core or two cores or three cores or four cores or five cores or six cores or seven cores or more than seven cores, particularly preferably one core. Preferably, more than 90%, for example more than 95%, particularly preferably more than 98%, of the electromagnetic radiation which is conducted through the light guide is conducted in the cores. For the transport of light in the cores, the preferred wavelength ranges apply, as already given for the light guide. Preferably, the material of the core is selected from the group consisting of glass or quartz glass, or a combination of both, particularly preferably quartz glass. The cores can, independently of each other, be made of the same material or of different materials. Preferably, all of the cores are made of the same material, particularly preferably of quartz glass.
Each core has a, preferably round, cross section QK and has an elongate form with length LK. The cross section QK of a core is independent from the cross section QK of each other core. The cross section QK of the cores can be the same or different. Preferably, the cross sections QK of all the cores are the same. A cross section QK of a core is always determined in a plane which is perpendicular to the outer wall of the core or the outer wall of the light guide. If the core is curved in length extension, then the cross section QK will be perpendicular to the tangent at a point on the outer wall of the core. The length LK of a core is independent of the length LK of each other core. The lengths LK of the cores can be the same or different. Preferably, the lengths LK of all the cores are the same. Each core preferably has a length LK in a range from 1 in to 100 km. Each core has a diameter dr. The diameter dx of a core is independent of the diameter dx of each other core. The diameters dK of the cores can be the same or different. Preferably, the diameters dK of all the cores are the same. Preferably, the diameter dK of each core is in a range from 0.1 to 1000 μm, for example from 0.2 to 100 μm or from 0.5 to 50 μm, particularly preferably from 1 to 30 μm.
Each core has at least one distribution of refractive index perpendicular to the maximum extension of the core. “Distribution of refractive index” means the refractive index is constant or changes in a direction perpendicular to the maximum extension of the core. The preferred distribution of refractive index corresponds to a concentric distribution of refractive index, for example to a concentric profile of refractive index in which a first region with the maximum refractive index is present in the centre of the core and which is surrounded by a further region with a lower refractive index. Preferably, each core has only one refractive index distribution over its length LK. The distribution of refractive index of a core is independent of the distribution of refractive index in each other core. The distributions of refractive index of the cores can be the same or different. Preferably, the distributions of refractive index of all the cores are the same. In principle, it is also possible for a core to have multiple different distributions of refractive index.
Each distribution of refractive index perpendicular to the maximum extension of the core has a maximum refractive index nK. Each distribution of refractive index perpendicular to the maximum extension of the core can also have further lower refractive indices. The lowest refractive index of the distribution of refractive index is preferably not mom than 0.5 smaller than the maximum refractive index nK of the distribution of refractive index. The lowest refractive index of the distribution of refractive index is preferably 0.0001 to 0.15, for example 0.0002 to 0.1, particularly preferably 0.0003 to 0.05, less than the maximum refractive index nK of the distribution of refractive index.
Preferably, the core has a refractive index nK in a range from 1.40 to 1.60, for example in a range from 1.41 to 1.59, particularly preferably in a range from 1.42 to 1.58, in each case measured at a reference wavelength of λr=589 nm (sodium D-line), at a temperature of 20° C. and at normal pressure (p=1013 hPa). For further details in this regard, see the test methods section. The refractive index nK of a cow is independent of the refractive index nK of each other core. The refractive indices nK of the cores can be the same or different. Preferably, the refractive indices nK of all the cores are the same.
Preferably, each core of the light guide has a density in a range from 1.9 to 2.5 g/cm3, for example in a range from 2.0 to 2.4 g/cm3, particularly preferably in a range from 2.1 to 2.3 g/cm3. Preferably, the cores have a residual moisture content of less than 100 ppb, for example of less than 20 ppb or of less than 5 ppb, particularly preferably of less than 1 ppb, in each case based on the total weight of the core. The density of a core is independent of the density of the each other core. The densities of the cores can be the same or different. Preferably, the densities of all cows are the same.
If a light guide comprises more than one core, then each core is, independently of the other cores, characterised by the above features. It is preferred for all cores to have the same features.
According to the invention, the coms are surrounded by at least one jacket M1. The jacket M1 preferably surrounds the coms over the entire length of the coms. Preferably, the jacket M1 surrounds the coms for at least 95%, for example at least 98% or at least 99%, particularly preferably 100% of the exterior surface, that is to say the entire outer wall, of the coms. Often, the coms am entirely surrounded by the jacket M1 up until the ends (in each case the last 1-5 cm). This serves to protect the coms from mechanical impairment.
The jacket M1 can comprise any material, including silicon dioxide, which has a lower refractive index than at least one point P along the profile of the cross section QK of the core. Preferably, this at least one point in the profile of the cross section QK of the core is the point which lies at the centre of the core. Furthermore, preferably, the point P in the profile of the cross section of the core is the point which has a maximum refractive index nKmax in the core. Preferably, the jacket M1 has a refractive index nm which is at least 0.0001 lower than the refractive index of the core nK at the at least one point in the profile of the cross section Q of the core. Preferably, the jacket M1 has a refractive index nm which is lower than the refractive index of the core nK by an amount in the range from 0.0001 to 0.5, for example in a range from 0.0002 to 0.4, particularly preferably in a range from 0.0003 to 0.3.
The jacket M1 preferably has a refractive index nm in a range from 0.9 to 1.599, for example in a range from 1.30 to 1.59, particularly preferably in a range from 1.40 to 1.57. Preferably, the jacket M1 forms a region of the light guide with a constant refractive index nm. A region with constant refractive index means a region in which the refractive index does not deviate from the mean of nm by more than 0.0001.
In principle, the light guide can comprise further jackets. Particularly preferably at least one of the further jackets, preferably several or all of them, a refractive index which is lower than the refractive index nK of each core. Preferably, the light guide has one or two or three or four or more than four further jackets which surround the jacket M1. Preferably, the further jackets which surround the jacket M1 have a refractive index which is lower than the refractive index nm of the jacket M1.
Preferably, the light guide has one or two or three or four or more than four further jackets which surround the cores and which are surrounded by the jacket M1, i.e. situated between the cores and the jacket M1. Furthermore, preferably, the further jackets situated between the cores and the jacket M1 have a refractive index which is higher than the refractive index nM1 of the jacket M1.
Preferably, the refractive index decreases from the core of the light guide to the outermost jacket. The reduction in the refractive index from the core to the outermost jacket can occur in steps or continuously. The reduction in the refractive index can have different sections. Furthermore, preferably, the refractive index can be stepped in at least one section and be continuous in at least one other section. The steps can be of the same or different height. It is certainly possible to arrange sections with increasing refractive index between sections with decreasing refractive index.
The different refractive indices of the different jackets can for example be configured by doping of the jacket M1, of the further jackets and/or of the cores.
Depending on the manner of preparation of a core, a core can already have a first jacket layer M0 following it preparation. This jacket layer M0 which directly neighbours the core is sometimes also called an integral jacket layer. The jacket layer M0 is situated closer to the middle point of the core than the jacket M1 and, if they are present, the further jackets. The jacket layer M0 commonly does not serve for light conduction or radiation conduction. Rather, the jacket layer M0 serves more to keep the radiation inside the core where it is transported. The radiation which is conducted in the core is thus preferably reflected at the interface from the core to the jacket layer M0. This interface from the core to the jacket layer M0 is preferably characterised by a change in refractive index. The refractive index of the jacket layer M0 is preferably lower than the refractive index n of the core. Preferably, the jacket layer M0 comprises the same material as the core, but has a lower refractive index to the core on account of doping or of additives.
Preferably, at least the jacket M1 is made out of silicon dioxide and has at least one, preferably several or all of the following features:
Preferably, the jacket has a refractive index homogeneity of less than 1×10−4. The refractive index homogeneity indicates the maximum deviation of the refractive index at each position of a sample, for example of a jacket M1 or of a quartz glass body, based on the mean value of all the refractive indices measured in the sample. For measuring the mean value, the refractive index is measured at least seven measuring locations.
Preferably, the jacket M1 has a metal content of metals different to aluminium of less than 1000 ppb, for example of less than 500 ppb, particularly preferably of less than 100 ppb, in each case based on the total weight of the jacket M1. Often however, the jacket M1 has a content of metals different to aluminium of at least 1 ppb. Such metals am for example sodium, lithium, potassium, magnesium, calcium, strontium, germanium, copper, molybdenum, titanium, iron and chromium. These can be present, for example, as an element, as an ion or as part of a molecule or of an ion or of a complex.
The jacket M1 can comprise further constituents. Preferably, the jacket comprises less than 500 ppm, for example less than 450 ppm, particularly preferably less than 400 ppm of further constituents, the ppm in each case based on the total weight of the jacket M1. Possible further constituents am for example carbon, fluorine, iodine, bromine and phosphorus. These can be present for example as an element, as an ion or as part of a molecule, of an ion or of a complex. Often however, the jacket M1 has a content of further constituents of at least 1 ppb.
Preferably, the jacket M1 comprises less than 5 ppm carbon, for example less than 4 ppm or less than 3 ppm, particularly preferably less than 2 ppm, in each case based on the total weight of the jacket M1. Often however, the jacket M1 has a carbon content of at least 1 ppb.
Preferably, the jacket M1 has a homogeneous distribution of OH content, Cl content or Al content.
In a preferred embodiment of the light guide, the jacket M1 contributes by weight at least 80 wt.-%, for example at least 85 wt.-%, particularly preferably at least 90 wt.-%, in each case based on the total weight of the jacket M1 and the cores. Preferably, the jacket M1 contributes by weight at least 80 wt.-%, for example at least 85 wt.-%, particularly preferably at least 90 wt.-%, in each case based on the total weight of the jacket M1, the cores and the further jackets situated between the jacket M1 and the cores. Preferably, the jacket M1 contributes by weight at least 80 wt.-%, for example at least 85 wt.-%, particularly preferably at least 90 wt.-%, in each case based on the total weight of the light guide.
Preferably, the jacket M1 has a density in a range from 2.1 to 2.3 g/cm3, particularly preferably in a range from 2.18 to 2.22 g/cm3.
A further aspect relates to a light guide, obtainable by a process comprising the following steps:
The steps A/, B/ and C/ are preferably characterised by the features described in the context of the third aspect of the invention.
The light guide is preferably characterised by the features described in the context of the third aspect of the invention.
A fifth aspect of the present invention relates to a process for the preparation of an illuminant comprising the following steps:
Step (i)
In step (i), a hollow body is provided. The hollow body provided in step (i) comprises at least one opening, for example one opening or two opening or three openings or four opening, particularly preferably one opening or two openings.
Preferably, a hollow body with at least one opening is provided in step (i) which is obtainable by a process according to the first aspect of the invention comprising step iv.), (step (i-1)). Preferably, the hollow body has the features described in the context of the first or third aspect of the invention.
Preferably, a hollow body is provided in step (i) which is obtainable from a quartz glass body according to the third aspect of the invention, (step (i-2)). There are many possibilities for processing a quartz glass body according to the third aspect of the invention to obtain a hollow body.
Preferably, a hollow body with two openings can be formed out of a quartz glass body analogue to step iv.) of the first aspect of the invention.
The processing of the quartz glass body to obtain a hollow body with an opening can in principle be performed by means of any process known to the skilled person and which are suitable for the preparation of glass hollow bodies with an opening. For example, processes comprising a pressing, blowing, sucking or a combination thereof are suitable. It is also possible to form a hollow body with one opening from a hollow body with two openings by closing an opening, for example by melting shut.
The obtained hollow body preferably has the features described in the context of the first and third aspect of the invention.
The hollow body is made of a material which comprises silicon dioxide, preferably in a range from 98 to 100 wt.-%, for example in a range from 99.9 to 100 wt.-%, particularly preferably 100 wt.-%, in each case based on the total weight of the hollow body.
The material out of which the hollow body is prepared preferably has at least one, preferably several, for example two, or preferably all of the following features:
Step (ii)
Preferably, the hollow body of step (i) is fitted with electrodes, preferably with two electrodes, before filling with a gas. Preferably, the electrodes are connected to a source of electrical current. Preferably, the electrodes are connected to an illuminant socket.
The material of the electrodes is preferably selected from the group of metals. In principle the electrode material can be selected from any metal which does not oxidise, corrode, melt or otherwise become impaired in its form or conductivity as electrode under the operative conditions of the illuminant. The electrode material is preferably selected from the group consisting of iron, molybdenum, copper, tungsten, rhenium, gold and platinum or at least two selected therefrom, tungsten, molybdenum or rhenium being preferred.
Step (iii)
The hollow body provided in step (i) and optionally fitted with electrodes in step (ii) is filled with a gas.
The filling can be performed in any process known to the skilled person and which is suitable for the filling. Preferably, a gas is fed into the hollow body through the at least one opening.
Preferably, the hollow body is evacuated prior to filling with the gas, preferably evacuated to a pressure of less than 2 mbar. By subsequent introduction of a gas, the hollow body is filled with the gas. These steps can be repeated in order to reduce air impurities, in particular oxygen. Preferably, these steps are repeated at least twice, for example at least thrice or at least four times, particularly preferably at least five times until the amount of other gas impurities such as air, in particular oxygen, is sufficiently low. This procedure is particularly preferred for filling hollow bodies with one opening.
In the hollow body comprises two or more openings, the hollow body is preferably filled through one of the openings. The air present in the hollow body prior to filling with the gas can exit through the at least one further opening. The gas is fed through the hollow body until the amount of other gas impurities such as air, in particular oxygen, is sufficiently low.
Preferably, the hollow body is filled with an inert gas or with a combination of two or more inert gases, for example with nitrogen, helium, neon, argon, krypton, xenon or a combination of two or more thereof, particularly preferably with krypton, xenon or a combination of nitrogen and argon. Further preferred filling materials for the hollow body of illuminants are deuterium and mercury.
Preferably, the hollow body is closed after filling a gas, so that the gas does not exit during the further processing, so that no air enters from outside during the further processing, or both. The closing can be performed by melting or placing a cap. Suitable caps are for example quartz glass caps, which are for example melted onto the hollow body, or illuminant sockets. Preferably, the hollow body is closed by melting.
The illuminant according to the fifth aspect of the invention comprises a hollow body and optionally electrodes. The illuminant preferably has at least one, for example at least two or at least three or at least four, particularly preferably at least five of the following features:
A further aspect relates to an illuminant, obtainable by a process comprising the following steps:
The steps (i), (ii) and (iii) am preferably characterised by the features described in the context of the fifth aspect.
The illuminant is preferably characterised by the features described in the context of the fifth aspect.
A sixth aspect of the present invention relates to a process for the preparation of a formed body comprising the following steps:
The quartz glass body provided in step (1) is a quartz glass body according to the third aspect of the invention or obtainable by a process according to the first aspect of the invention. Preferably, the provided quartz glass body has the features of the first or third aspect of the invention.
Step (2)
For forming the quartz glass body provided in step (1), in principle any processes known to the skilled person and which are suitable for forming quartz glass are possible. Preferably, the quartz glass body is formed as described in the context of the first, fourth and fifth aspect of the invention to obtain a formed body. Furthermore, preferably, the formed body can be formed by means of techniques known to glass blowers.
The formed body can in principle take any shape which is formable out of quartz glass. Preferred formed bodies are for example:
According to a preferred embodiment, the formed body can be treated after the forming. For this, in principle all processes described in connection with the first aspect of the invention which am suitable for post treatment of the quartz glass body am possible. Preferably, the formed body can be mechanically processed, for example by drilling, honing, external grinding, reducing in size or drawing.
A further aspect relates to a formed body obtainable by a process comprising the following steps:
The steps (1) and (2) are preferably characterised by the features described in the context of the sixth aspect.
The formed body is preferably characterised by the features described in the context of the sixth aspect.
A seventh aspect of the invention is the use of carbon to reduce the alkaline earth metal content of silicon dioxide granulate. Preferred is the use of carbon to reduce the alkaline earth metal content and the carbon content of silicon dioxide granulate. Furthermore, the use of carbon to reduce the alkaline earth metal content of pyrogenically produced silicon dioxide granulate is preferred.
An eighth aspect of the invention is the use of a silicon dioxide granulate for the preparation of quartz glass and of products selected from the group consisting of a light guide, an illuminant and a formed body, wherein the silicon dioxide granulate has a carbon content of less than 5 ppm, wherein the ppm am based on the total weight of the silicon dioxide granulate:
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.
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 am 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.
In
In
The crucible 901 is filled with silicon dioxide granulate 905 via the inlet 903. In operation, silicon dioxide granulate 905 is present in the upper region of the crucible, whilst a glass melt 906 is present in the lower region of the crucible. The crucible can be heated by heating elements 907 which are arranged on the outer side of the crucible wall 910. The oven also has an insulation layer 909 between the heating elements 907 and the outer wall 908. The space between the insulation layer 909 and the crucible wall 910 can be filled with a gas and for this purpose has a gas inlet 911 and a gas outlet 912. A quartz glass body 913 can be removed from the crucible 901 through the nozzle 904.
In
In
The extraction strength of the screening device 1104 can be configured to correspond to the particle size of the particles to be extracted. Particles above a defined particle size are sieved off by the sieving device 1105 and removed through the discharge 1107. The sieve permeability of the sieving device 1105 can be selected to correspond to the particle size to be sieved off. The remaining particles, a silicon dioxide granulate having the desired particle size, is removed through the outlet 1108.
In
Test Methods
a. Fictive Temperature
The fictive temperature is measured by Raman spectroscopy using the Raman scattering intensity at about 606 cm−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.
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−1 or on the absorption band at ca. 7200 cm−1. The selection of the band is made on the basis that the transmission loss through OH absorption is between 10 and 90%.
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
wherein the effective cross section is set to σ=7.5·10−17 cm2 (from L. Skuja, “Color Centers and Their Transformations in Glassy SiO2”, Lectures of the summer school “Photosensitivity in optical Waveguides and glasses”, Jul. 13-18 1998, Vitznau, Switzerland).
d. Elemental Analysis
d-1) Solid samples am 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 am 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 HNO3 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 am 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 am introduced into the extraction flask. No conversion based on the original sample weight is made.
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 am measured. The density is given as the difference between the two weight measurements divided by the volume of the liquid introduced.
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 Na2CO3 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 am taken and transferred to a 100 ml measuring flask, 0.75 ml of glacial acetic acid and 60 ml TISAB am 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 Werkstätten GmbH. With the fluoride concentration in the solution, the dilution factor and the sample weight, the fluoride concentration in the quartz glass is calculated.
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 FIFE insert is removed and the solution is transferred entirely to a 100 ml measuring flask. There, 10 ml HNO3 (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 CI-500 and a reference electrode of type R-503/D attached to a pMX 3000/pH/ION from Wissenschaftlich-Technische Werkstätten GmbH.
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 am 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.
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=I0/I.
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 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.
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 dish. The sample is bathed in pure oxygen and heated for 180 seconds to 900° C. The CO2 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).
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”).
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 k=1550 nm.
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.
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 MΩcm). 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.
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 HNO3 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.
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 HNO3 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.
r. DH Value of the Slurry
The pH value of the slurry is measured using a WTW 3210 from Wissenschaftlich-Technische-Werkstätten GmbH. The pH 3210 Set 3 from WTW is employed as electrode. The measurement is made at a temperature of 23° C.
s. Solids Content
A weighed portion m, of a sample is heated for 4 hours to 500° C. reweighed after cooling (m2). The solids content w is given as m2/m1*100 [Wt. %].
t. Bulk Density
The bulk 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.
u. Tanned Density (Granulate)
The tamped density is measured according to the standard DIN ISO 787:1995-10.
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-Nr. 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).
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.
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.
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.
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 m2 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=nett 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 m2 g.
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 & heigt=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).
zb. Dew Point Measurement
The dew point is measured using a dew point mirror hygrometer called “Optidew” of the company Michell Instruments 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.
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 t 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.).
The example is further illustrated in the following through examples. The invention is not limited by the examples.
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 am given in table 1 and the specifications of the resulting product am given in table 2. Experimental data for this example am indicated with A1-x.
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 am indicated with A2-x.
B. 1. Preparation of Silicon Dioxide Powder (Silicon Source: SiCl4)
A portion of silicon tetrachloride (SiCl4) 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.
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.
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.
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.
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 am 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.
E. 1. Preparation of Silicon Dioxide Granulate from Silicon Dioxide Powder
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 am dried in a spray tower and collect on the floor of the tower. The process parameters am given in Table 9 and the properties of the obtained granulate in Table 10. Experimental data for this example am indicated with E1-x.
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 am indicated with E2-x.
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 am identified with E3-1.
The granulates are all open pored, have a uniform and spherical shape (all by microscopic investigation).
They tend wtf to stick together or cement.
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.
1)For the rotary kilns, 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).
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.
1)For the rotary kilns, 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).
Due to this treatment, G3-1 and G3-2 exhibit a significantly reduced alkaline earth metal content in comparison to before (F3-1 & F3-2 respectively).
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
In Example H7-1, a gas distributing ring is arranged in the melting crucible, with which the flushing gas is fed close to the surface of the glass melt. An example of such an arrangement is shown in
In Example H8-x, the dew point is measured at the gas outlet. The measuring principle is shown in
I. Post Processing of a Quartz Glass Body
J. “Used Acid” (HF Bath after Use)
K. Service Life of Glass Reactors
L. Temperature Variation Stability
| Number | Date | Country | Kind |
|---|---|---|---|
| 15201145 | Dec 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/081462 | 12/16/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/103131 | 6/22/2017 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2155131 | Hanlein | Apr 1939 | A |
| 3043660 | Hughes et al. | Jul 1962 | A |
| 3127289 | Beall | Mar 1964 | A |
| 3212871 | Vatterodt | Oct 1965 | A |
| 3261676 | Morelock | Jul 1966 | A |
| 3320045 | Weiss et al. | May 1967 | A |
| 3331673 | Bour | Jul 1967 | A |
| 3359098 | Teaford | Dec 1967 | A |
| 3370921 | Wagstaff | Feb 1968 | A |
| 3401017 | Burke, Jr. | Sep 1968 | A |
| 3523096 | Burke, Jr. | Aug 1970 | A |
| 3686113 | Burke, Jr. | Aug 1972 | A |
| 3694398 | Burke, Jr. | Sep 1972 | A |
| 3711262 | Schultz et al. | Jan 1973 | A |
| 3717450 | Loughridge et al. | Feb 1973 | A |
| 3764286 | Antczak et al. | Oct 1973 | A |
| 3944713 | Plumat et al. | Mar 1976 | A |
| 4033780 | Baumgartner et al. | Jul 1977 | A |
| 4038370 | Fokimoto et al. | Jul 1977 | A |
| 4042361 | Bihuniak et al. | Aug 1977 | A |
| 4047966 | Bihuniak et al. | Sep 1977 | A |
| 4113459 | Mattmuller | Sep 1978 | A |
| 4195982 | Coucoulas et al. | Apr 1980 | A |
| 4224295 | Brandt et al. | Sep 1980 | A |
| 4336048 | van der Steen et al. | Jun 1982 | A |
| 4358306 | Okamoto et al. | Nov 1982 | A |
| 4372771 | Coucoulas et al. | Feb 1983 | A |
| 4546484 | Meerman | Oct 1985 | A |
| 4650511 | Koya et al. | Mar 1987 | A |
| 4828593 | Morishita et al. | May 1989 | A |
| 4828594 | Morishita et al. | May 1989 | A |
| 4828595 | Morishita et al. | May 1989 | A |
| 4871695 | Seki et al. | Oct 1989 | A |
| 4888036 | Clasen | Dec 1989 | A |
| 4923497 | Leber et al. | May 1990 | A |
| 4938788 | Segawa et al. | Jul 1990 | A |
| 4979973 | Takita et al. | Dec 1990 | A |
| 4985275 | Takemura et al. | Jan 1991 | A |
| 5063179 | Menashi et al. | Nov 1991 | A |
| 5141786 | Shimizu et al. | Aug 1992 | A |
| 5145507 | Kyoto et al. | Sep 1992 | A |
| 5196759 | Parham et al. | Mar 1993 | A |
| 5240488 | Chandross et al. | Aug 1993 | A |
| 5244485 | Hihara et al. | Sep 1993 | A |
| 5262610 | Huang et al. | Nov 1993 | A |
| 5302556 | Shimizu et al. | Apr 1994 | A |
| 5364432 | Leber | Nov 1994 | A |
| 5364433 | Nishimura | Nov 1994 | A |
| 5516350 | Onoda et al. | May 1996 | A |
| 5540782 | Miyagi et al. | Jul 1996 | A |
| 5541826 | Sandell | Jul 1996 | A |
| 5547482 | Chalk et al. | Aug 1996 | A |
| 5585173 | Kamo et al. | Dec 1996 | A |
| 5601428 | Okoshi et al. | Feb 1997 | A |
| 5631522 | Scott et al. | May 1997 | A |
| 5637284 | Sato et al. | Jun 1997 | A |
| 5651827 | Aoyama et al. | Jul 1997 | A |
| 5665133 | Orii et al. | Sep 1997 | A |
| 5674792 | Moritz et al. | Oct 1997 | A |
| 5713979 | Nicholson et al. | Feb 1998 | A |
| 5736206 | Englisch et al. | Apr 1998 | A |
| 5772714 | Sato et al. | Jun 1998 | A |
| 5776240 | Deller et al. | Jul 1998 | A |
| 5807418 | Chamberland et al. | Sep 1998 | A |
| 5837334 | Yokokawa et al. | Nov 1998 | A |
| 5851253 | Pet et al. | Dec 1998 | A |
| 5855860 | Nishimine et al. | Jan 1999 | A |
| 5904817 | Berger | May 1999 | A |
| 5924216 | Takahashi | Jul 1999 | A |
| 5928397 | Bihuniak et al. | Jul 1999 | A |
| 5972488 | Nagata et al. | Oct 1999 | A |
| 5976480 | Mangold et al. | Nov 1999 | A |
| 5979186 | Koppler et al. | Nov 1999 | A |
| 6071838 | Endo et al. | Jun 2000 | A |
| 6127295 | Yoon et al. | Oct 2000 | A |
| 6129899 | Katsuro et al. | Oct 2000 | A |
| 6133178 | Kamada et al. | Oct 2000 | A |
| 6136736 | Rajaram et al. | Oct 2000 | A |
| 6143676 | Ohashi et al. | Nov 2000 | A |
| 6162552 | Bewlay et al. | Dec 2000 | A |
| 6235669 | Antczak et al. | May 2001 | B1 |
| 6263704 | Tomita et al. | Jun 2001 | B1 |
| 6257737 | Marshall et al. | Jul 2001 | B1 |
| 6260563 | Lordo et al. | Jul 2001 | B1 |
| 6291377 | Komine et al. | Sep 2001 | B1 |
| 6360563 | Gerhardt et al. | Mar 2002 | B1 |
| 6368175 | Horiuchi et al. | Apr 2002 | B1 |
| 6380110 | Werdecker et al. | Apr 2002 | B1 |
| 6399526 | Tomita et al. | Jun 2002 | B2 |
| 6422861 | Antczak et al. | Jul 2002 | B1 |
| 6484540 | Shimada et al. | Nov 2002 | B1 |
| 6632086 | Antczak et al. | Oct 2003 | B1 |
| 6653786 | Fukushima et al. | Nov 2003 | B2 |
| 6679945 | Oswald et al. | Jan 2004 | B2 |
| 6684664 | Werdecker et al. | Feb 2004 | B2 |
| 6739155 | Giddings et al. | May 2004 | B1 |
| 6752864 | Meyer et al. | Jun 2004 | B2 |
| 6763682 | Sayce et al. | Jul 2004 | B1 |
| 6826927 | Fukui et al. | Dec 2004 | B2 |
| 6849242 | Koeppler et al. | Feb 2005 | B1 |
| 7255843 | Kobayashi et al. | Aug 2007 | B2 |
| 7427387 | Katsuro et al. | Sep 2008 | B2 |
| 7452518 | Hansen et al. | Nov 2008 | B2 |
| 7506521 | Bookbinder et al. | Mar 2009 | B2 |
| 7629391 | Jacquinot et al. | Dec 2009 | B2 |
| 7641969 | Fletcher, III | Jan 2010 | B2 |
| 7645335 | Lortz et al. | Jan 2010 | B2 |
| 7722849 | Moerters et al. | May 2010 | B2 |
| 7785560 | Schumacher et al. | Aug 2010 | B2 |
| 7803341 | Ohara et al. | Sep 2010 | B2 |
| 7841211 | Sato et al. | Nov 2010 | B2 |
| 7955715 | Trommer et al. | Jun 2011 | B2 |
| 7998558 | Chen et al. | Aug 2011 | B2 |
| 8017536 | Weber et al. | Sep 2011 | B2 |
| 8053080 | Fukui et al. | Nov 2011 | B2 |
| 8132429 | Pedrido | Mar 2012 | B2 |
| 8211817 | Arai et al. | Jul 2012 | B2 |
| 8268740 | Fiacco et al. | Sep 2012 | B2 |
| 8316671 | Huenermann | Nov 2012 | B2 |
| 8426778 | Bolt | Apr 2013 | B1 |
| 8529651 | Lortz et al. | Sep 2013 | B2 |
| 8541326 | Morita et al. | Sep 2013 | B2 |
| 8764992 | Wursche et al. | Jul 2014 | B2 |
| 8899732 | Reinten et al. | Dec 2014 | B2 |
| 8940266 | Yamada et al. | Jan 2015 | B2 |
| 9108876 | Dawes et al. | Aug 2015 | B2 |
| 9120678 | Ueda | Sep 2015 | B2 |
| 9272942 | Trommer et al. | Mar 2016 | B2 |
| 9359263 | Hartmann | Jun 2016 | B2 |
| 9446959 | Ueda | Sep 2016 | B2 |
| 9481108 | Sowa | Nov 2016 | B2 |
| 9505651 | Gu et al. | Nov 2016 | B2 |
| 9580348 | Lehmann et al. | Feb 2017 | B2 |
| 9625213 | Uibel et al. | Apr 2017 | B2 |
| 9701561 | Coapes et al. | Jul 2017 | B2 |
| 9732180 | Burckhardt et al. | Aug 2017 | B2 |
| 9745201 | Ueda | Aug 2017 | B2 |
| 9797068 | Sakurada et al. | Oct 2017 | B2 |
| 9914265 | Bauer et al. | Mar 2018 | B2 |
| 9957431 | Scheich et al. | May 2018 | B2 |
| 10173917 | Yamazaki et al. | Jan 2019 | B2 |
| 20010008366 | Nishida | Jul 2001 | A1 |
| 20010025001 | Oda et al. | Sep 2001 | A1 |
| 20020041963 | Konya et al. | Apr 2002 | A1 |
| 20020044903 | Oswald et al. | Apr 2002 | A1 |
| 20020046992 | Inaki et al. | Apr 2002 | A1 |
| 20020071871 | Snyder et al. | Jun 2002 | A1 |
| 20020134108 | Werdecker et al. | Sep 2002 | A1 |
| 20020144517 | Fujiwara et al. | Oct 2002 | A1 |
| 20030000458 | Marumo et al. | Jan 2003 | A1 |
| 20030041623 | Werdecker et al. | Mar 2003 | A1 |
| 20030089279 | Meyer et al. | May 2003 | A1 |
| 20030101748 | Ezaki et al. | Jun 2003 | A1 |
| 20030119648 | Werdecker et al. | Jun 2003 | A1 |
| 20030121283 | Yu | Jul 2003 | A1 |
| 20030124045 | Kobayashi et al. | Jul 2003 | A1 |
| 20030129153 | Moerters et al. | Jul 2003 | A1 |
| 20030158297 | Sano et al. | Aug 2003 | A1 |
| 20030159464 | Bowden et al. | Aug 2003 | A1 |
| 20030159466 | Bowden et al. | Aug 2003 | A1 |
| 20030159468 | Zeng et al. | Aug 2003 | A1 |
| 20030169315 | Pickrell | Sep 2003 | A1 |
| 20030175649 | Oosterlaken et al. | Sep 2003 | A1 |
| 20030185739 | Mangold et al. | Oct 2003 | A1 |
| 20030226377 | Barrett et al. | Dec 2003 | A1 |
| 20040115440 | Werdecker et al. | Jun 2004 | A1 |
| 20040116270 | Oswald et al. | Jun 2004 | A1 |
| 20040118155 | Brown et al. | Jun 2004 | A1 |
| 20040253164 | Mangold et al. | Dec 2004 | A1 |
| 20050000250 | Humbach et al. | Jan 2005 | A1 |
| 20050039490 | Zeng et al. | Feb 2005 | A1 |
| 20050072191 | Giddings et al. | Apr 2005 | A1 |
| 20050103231 | Geisselmann et al. | May 2005 | A1 |
| 20050129603 | Szillat et al. | Jun 2005 | A1 |
| 20050129605 | Unger et al. | Jun 2005 | A1 |
| 20050220692 | Mangold et al. | Oct 2005 | A1 |
| 20050232571 | Fabian | Oct 2005 | A1 |
| 20050258758 | Boehme | Nov 2005 | A1 |
| 20050272588 | Sato et al. | Dec 2005 | A1 |
| 20050272826 | Mangold et al. | Dec 2005 | A1 |
| 20060055300 | Janos et al. | Mar 2006 | A1 |
| 20060059948 | Sato et al. | Mar 2006 | A1 |
| 20060117801 | Saitou et al. | Jun 2006 | A1 |
| 20060122450 | Kim et al. | Jun 2006 | A1 |
| 20060137400 | Hansen et al. | Jun 2006 | A1 |
| 20060137401 | Fabian | Jun 2006 | A1 |
| 20060176701 | Shemit et al. | Aug 2006 | A1 |
| 20060183623 | Ikuta et al. | Aug 2006 | A1 |
| 20060201647 | Schumacher et al. | Sep 2006 | A1 |
| 20060204189 | Sasaki et al. | Sep 2006 | A1 |
| 20060246363 | Kikugawa et al. | Nov 2006 | A1 |
| 20060281623 | Winnen et al. | Dec 2006 | A1 |
| 20070015652 | Mangold et al. | Jan 2007 | A1 |
| 20070145332 | Koeppler et al. | Jun 2007 | A1 |
| 20070178329 | Trommer et al. | Aug 2007 | A1 |
| 20070180862 | Takahashi | Aug 2007 | A1 |
| 20070199659 | Landsmeer | Aug 2007 | A1 |
| 20080066497 | Weber et al. | Mar 2008 | A1 |
| 20080075949 | Kirst et al. | Mar 2008 | A1 |
| 20080107385 | Ohga et al. | May 2008 | A1 |
| 20080113174 | Sato et al. | May 2008 | A1 |
| 20080193715 | Weber et al. | Aug 2008 | A1 |
| 20080203625 | Oswald et al. | Aug 2008 | A1 |
| 20080213591 | Meyer et al. | Sep 2008 | A1 |
| 20080268201 | Fiacco et al. | Oct 2008 | A1 |
| 20080282743 | Xu et al. | Nov 2008 | A1 |
| 20080290317 | Hille et al. | Nov 2008 | A1 |
| 20090139265 | Sato et al. | Jun 2009 | A1 |
| 20090151848 | Werdecker et al. | Jun 2009 | A1 |
| 20090208760 | Kuwahara et al. | Aug 2009 | A1 |
| 20090311159 | Gray | Dec 2009 | A1 |
| 20100005881 | Broedel et al. | Jan 2010 | A1 |
| 20100041538 | Arai et al. | Feb 2010 | A1 |
| 20100048376 | Oswald et al. | Feb 2010 | A1 |
| 20100071421 | Dawes et al. | Mar 2010 | A1 |
| 20100091360 | Kuehn et al. | Apr 2010 | A1 |
| 20100107700 | Dawes et al. | May 2010 | A1 |
| 20100162759 | Duran et al. | Jul 2010 | A1 |
| 20100178509 | Schumacher et al. | Jul 2010 | A1 |
| 20100179269 | Schachtely et al. | Jul 2010 | A1 |
| 20100196243 | Meyer et al. | Aug 2010 | A1 |
| 20100221501 | Chen et al. | Sep 2010 | A1 |
| 20100251771 | Langner et al. | Oct 2010 | A1 |
| 20100316858 | Sato et al. | Dec 2010 | A1 |
| 20100319582 | Fischer | Dec 2010 | A1 |
| 20110092757 | Akagishi et al. | Apr 2011 | A1 |
| 20110100063 | Desorcie et al. | May 2011 | A1 |
| 20110113829 | Leber et al. | May 2011 | A1 |
| 20110183138 | Trommer et al. | Jul 2011 | A1 |
| 20110226020 | Xu et al. | Sep 2011 | A1 |
| 20110244387 | Katusic et al. | Oct 2011 | A1 |
| 20110272322 | Yamagata et al. | Nov 2011 | A1 |
| 20110281227 | Franz et al. | Nov 2011 | A1 |
| 20120052297 | Pech et al. | Mar 2012 | A1 |
| 20120056106 | Neumann | Mar 2012 | A1 |
| 20120103017 | Ludwig | May 2012 | A1 |
| 20120174629 | Leber | Jul 2012 | A1 |
| 20120213685 | Morita et al. | Aug 2012 | A1 |
| 20120288716 | Ueda | Nov 2012 | A1 |
| 20120297837 | Ishihara | Nov 2012 | A1 |
| 20120324958 | Yang | Dec 2012 | A1 |
| 20130047669 | Annamalai | Feb 2013 | A1 |
| 20130133377 | Fabian et al. | May 2013 | A1 |
| 20130219963 | Lehmann et al. | Aug 2013 | A1 |
| 20130319321 | Winnicka et al. | Dec 2013 | A1 |
| 20130340483 | Takahashi | Dec 2013 | A1 |
| 20140041575 | Yamagata | Feb 2014 | A1 |
| 20140072803 | Panz et al. | Mar 2014 | A1 |
| 20140349830 | Trommer et al. | Nov 2014 | A1 |
| 20150052948 | Lehmann et al. | Feb 2015 | A1 |
| 20150059407 | Lehmann et al. | Mar 2015 | A1 |
| 20150086462 | Such et al. | Mar 2015 | A1 |
| 20150114284 | Yamagata | Apr 2015 | A1 |
| 20150325836 | Neumann | Nov 2015 | A1 |
| 20160002092 | Kuehn | Jan 2016 | A1 |
| 20160009586 | Bookbinder et al. | Jan 2016 | A1 |
| 20160090319 | Hofmann et al. | Mar 2016 | A1 |
| 20160168005 | Gromann et al. | Jun 2016 | A1 |
| 20180057391 | Kuhn | Mar 2018 | A1 |
| 20180362385 | Arndt et al. | Dec 2018 | A1 |
| 20180370835 | Otter et al. | Dec 2018 | A1 |
| 20180370838 | Otter et al. | Dec 2018 | A1 |
| 20190031554 | Otter et al. | Jan 2019 | A1 |
| 20190055150 | Fabian et al. | Feb 2019 | A1 |
| 20190062193 | Otter et al. | Feb 2019 | A1 |
| 20190062194 | Otter et al. | Feb 2019 | A1 |
| 20190062197 | Otter et al. | Feb 2019 | A1 |
| 20190062198 | Hunermann et al. | Feb 2019 | A1 |
| 20190071342 | Otter et al. | Mar 2019 | A1 |
| 20190071344 | Otter et al. | Mar 2019 | A1 |
| 20190077672 | Otter et al. | Mar 2019 | A1 |
| 20190077688 | Otter et al. | Mar 2019 | A1 |
| 20190077691 | Otter et al. | Mar 2019 | A1 |
| 20190092672 | Gromann et al. | Mar 2019 | A1 |
| 20190092674 | Otter et al. | Mar 2019 | A1 |
| 20190092675 | Whippey et al. | Mar 2019 | A1 |
| 20190092676 | Otter et al. | Mar 2019 | A1 |
| 20190119141 | Whippey et al. | Apr 2019 | A1 |
| 20190152827 | Otter et al. | May 2019 | A1 |
| 20200123039 | Gromann et al. | Apr 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 2575799 | Mar 2006 | CA |
| 420 502 | Sep 1966 | CH |
| 1051528 | May 1991 | CN |
| 1757598 | Apr 2006 | CN |
| 201348619 | Nov 2009 | CN |
| 101723387 | Jun 2010 | CN |
| 101723388 | Jun 2010 | CN |
| 202063820 | Dec 2011 | CN |
| 102753493 | Oct 2012 | CN |
| 102762362 | Oct 2012 | CN |
| 202594940 | Dec 2012 | CN |
| 103011552 | Apr 2013 | CN |
| 103011567 | Apr 2013 | CN |
| 202989330 | Jun 2013 | CN |
| 103717531 | Apr 2014 | CN |
| 103771690 | May 2014 | CN |
| 103925791 | Jul 2014 | CN |
| 203976973 | Dec 2014 | CN |
| 104368272 | Feb 2015 | CN |
| 104402197 | Mar 2015 | CN |
| 108218194 | Jun 2018 | CN |
| 543 957 | Feb 1932 | DE |
| 671 626 | Feb 1937 | DE |
| 854 073 | Oct 1952 | DE |
| 1927851 | Dec 1969 | DE |
| 2904199 | Aug 1980 | DE |
| 2909815 | Sep 1980 | DE |
| 144 868 | Nov 1980 | DE |
| 3028364 | Feb 1982 | DE |
| 3227785 | Jan 1984 | DE |
| 3227786 | Jan 1984 | DE |
| 248 928 | Aug 1987 | DE |
| 1237107 | May 1994 | DE |
| 19706556 | Aug 1998 | DE |
| 199 50 496 | Apr 2001 | DE |
| 10058558 | Jun 2002 | DE |
| 102 00 234 | Apr 2003 | DE |
| 10243953 | Apr 2004 | DE |
| 10243953 | Apr 2004 | DE |
| 10329806 | Oct 2004 | DE |
| 102004038602 | Dec 2005 | DE |
| 102005016732 | Oct 2006 | DE |
| 102005061274 | Jun 2007 | DE |
| 102007049158 | Apr 2009 | DE |
| 102009059016 | Jun 2011 | DE |
| 102010008162 | Aug 2011 | DE |
| 102011121153 | Mar 2013 | DE |
| 102011120412 | Jun 2013 | DE |
| 102012008123 | Oct 2013 | DE |
| 102012011946 | Dec 2013 | DE |
| 0015315 | Sep 1980 | EP |
| 0129015 | Dec 1984 | EP |
| 0335875 | Oct 1989 | EP |
| 0463045 | Jan 1992 | EP |
| 0574642 | Dec 1993 | EP |
| 0627390 | Dec 1994 | EP |
| 0629580 | Dec 1994 | EP |
| 0709340 | May 1996 | EP |
| 0715342 | Jun 1996 | EP |
| 0729918 | Sep 1996 | EP |
| 1182168 | Feb 2002 | EP |
| 1201610 | May 2002 | EP |
| 1304313 | Apr 2003 | EP |
| 1361195 | Nov 2003 | EP |
| 1717202 | Nov 2006 | EP |
| 1197271 | Jul 1970 | GB |
| 1254492 | Nov 1971 | GB |
| 2044738 | Oct 1980 | GB |
| 2049641 | Dec 1980 | GB |
| S53-4027 | Jan 1978 | JP |
| 6158822 | Mar 1986 | JP |
| 61068340 | Apr 1986 | JP |
| 6230633 | Feb 1987 | JP |
| 6230634 | Feb 1987 | JP |
| 62202826 | Sep 1987 | JP |
| 62212233 | Sep 1987 | JP |
| 62212235 | Sep 1987 | JP |
| 62212236 | Sep 1987 | JP |
| S62-212234 | Sep 1987 | JP |
| S62-246834 | Oct 1987 | JP |
| 63166791 | Jul 1988 | JP |
| H02-9783 | Jan 1990 | JP |
| 0264645 | Mar 1990 | JP |
| H02-80329 | Mar 1990 | JP |
| 02199015 | Aug 1990 | JP |
| 02283015 | Nov 1990 | JP |
| 031528 | Jan 1991 | JP |
| 0455332 | Feb 1992 | JP |
| 04182322 | Jun 1992 | JP |
| H04219333 | Aug 1992 | JP |
| 0532429 | Feb 1993 | JP |
| H05-24856 | Feb 1993 | JP |
| H05-32429 | Feb 1993 | JP |
| 0587403 | Apr 1993 | JP |
| 3061215 | Apr 1993 | JP |
| H05-32432 | May 1993 | JP |
| H05-229839 | Sep 1993 | JP |
| 07133131 | May 1995 | JP |
| 07277725 | Oct 1995 | JP |
| 07277751 | Oct 1995 | JP |
| H07-277751 | Oct 1995 | JP |
| H08-081226 | Jan 1996 | JP |
| H0840737 | Feb 1996 | JP |
| 08100411 | Apr 1996 | JP |
| H08-119664 | May 1996 | JP |
| 08165131 | Jun 1996 | JP |
| H08-143329 | Jun 1996 | JP |
| 09012325 | Jan 1997 | JP |
| H09-12325 | Jan 1997 | JP |
| 0940434 | Feb 1997 | JP |
| H09-40434 | Feb 1997 | JP |
| H09-80005 | Mar 1997 | JP |
| 09165214 | Jun 1997 | JP |
| 10265259 | Oct 1998 | JP |
| 10287416 | Oct 1998 | JP |
| H11-1331 | Jan 1999 | JP |
| 4014724 | Oct 1999 | JP |
| 11302081 | Nov 1999 | JP |
| 11310423 | Nov 1999 | JP |
| 2000-290026 | Oct 2000 | JP |
| 2001048571 | Feb 2001 | JP |
| 2001048571 | Feb 2001 | JP |
| 2001072427 | Mar 2001 | JP |
| 2001-089168 | Apr 2001 | JP |
| 2001089125 | Apr 2001 | JP |
| 2001155680 | Jun 2001 | JP |
| 2001-220157 | Aug 2001 | JP |
| 2001-220158 | Aug 2001 | JP |
| 2001220126 | Aug 2001 | JP |
| 4889141 | Apr 2002 | JP |
| 2002114510 | Apr 2002 | JP |
| 4371565 | May 2002 | JP |
| 2002145633 | May 2002 | JP |
| 2002291253 | Oct 2002 | JP |
| 2003-112933 | Apr 2003 | JP |
| 2003137571 | May 2003 | JP |
| 2003-192331 | Jul 2003 | JP |
| 2005008519 | Jan 2005 | JP |
| 2005067913 | Mar 2005 | JP |
| 2005056692 | Mar 2005 | JP |
| 2005-162535 | Jun 2005 | JP |
| 2005145812 | Jun 2005 | JP |
| 2005170706 | Jun 2005 | JP |
| 2006-335577 | Dec 2006 | JP |
| 2007520408 | Jul 2007 | JP |
| 2008063157 | Mar 2008 | JP |
| 2009216373 | Sep 2009 | JP |
| 5075703 | Oct 2009 | JP |
| 2010018470 | Jan 2010 | JP |
| 2010150096 | Jul 2010 | JP |
| 2011132073 | Jul 2011 | JP |
| 2011184210 | Sep 2011 | JP |
| 2011207719 | Oct 2011 | JP |
| 2012066947 | Apr 2012 | JP |
| 2013-091812 | May 2013 | JP |
| 2014088298 | May 2014 | JP |
| 2014-201501 | Oct 2014 | JP |
| 662 507 | May 1979 | SU |
| 1675244 | Sep 1991 | SU |
| 8803914 | Jun 1988 | WO |
| 9507269 | Mar 1995 | WO |
| 9902459 | Jan 1999 | WO |
| 2006015763 | Feb 2006 | WO |
| 2006021416 | Mar 2006 | WO |
| 2006024440 | Mar 2006 | WO |
| 2009071465 | Jun 2009 | WO |
| 2010150586 | Dec 2010 | WO |
| WO-2010150586 | Dec 2010 | WO |
| 2011106221 | Sep 2011 | WO |
| 2013149882 | Oct 2013 | WO |
| 2015137340 | Apr 2017 | WO |
| Entry |
|---|
| JP2001048571A Google Patents Machine Translation—Performed Jul. 6, 2020. (Year: 2020). |
| DE10243953A1 Google Patents Machine Translation—Performed Jul. 6, 2020. (Year: 2020). |
| Non-Final Office Action dated Oct. 3, 2019 in U.S. Appl. No. 16/061,929. |
| Non-Final Office Action dated Oct. 29, 2019 in U.S. Appl. No. 16/061,122. |
| Karstensen, H. “Fabrication Techniques of Optical Fibres”, Journal of Electronics and Telecom, Engrs., vol. 32, No. 4, Feb. 1986. |
| The Office Action for U.S. Appl. No. 16/062,705 dated May 16, 2019 (9 pgs.). |
| Non-Final Office Action in U.S. Appl. No. 16/062,280 dated Sep. 9, 2020. |
| Non-Final Office Action in U.S. Appl. No. 16/061,185 dated Sep. 3, 2020. |
| Notice of Allowance dated Feb. 25, 2020 in U.S. Appl. No. 16/061,122. |
| Notice of Allowance dated Mar. 23, 2020 in U.S. Appl. No. 16/061,929. |
| Notice of Allowance dated Dec. 26, 2019 in U.S. Appl. No. 16/062,705. |
| Shinetsu Quartz, “Intrinsic Optical Properties of Synthetic Fused Silica for 193 nm Immersion Lithography,” (1 page). Oct. 2006. |
| Functionsbeschreibung, “Theory of Operation,” (1 page) 2014. |
| McPherson Inc., “Vuvas 2000 Vacuum UV Analytical Spectrophotometer,” (4 pages) Sep. 7, 2009. |
| Dodd and Fraser, “Optical Determinations of QH in Fused Silica,” (1 page). |
| PMX 3000/ION, User's Manual, Microprocessor Controlled High Performance-pH-ion-meter (71 pgs) Mar. 20, 2003. |
| Goodfellow, Carbon Powder (1 pg.) Dec. 4, 2015. |
| Telecommunication Standardization Sector of ITU, “Series G: Transmission Systems and Media Digital Systems and Networks,” Oct. 2012, (24 pages). |
| Agilent Technologies, “Agilent 7500 ICP-MS ChemStation (G1834B) Operator's Manual,” 2005, (659 pages). |
| Agilent Technologies, “Agilent 7500 Series ICP-MS,” 2008, (334 pages). |
| Din, “Modeme Rheologische Prufverfahren,” Sep. 2012, (62 pages). |
| International Standard, “Particle Size Analysis—Laser Diffraction Methods,” Oct. 2009, (60 pages). |
| Indian Standard, “Optical Fibres, Fibre Curl,” 2006, (23 pages). |
| Indian Standard, “Optical Fibres, Attenuation,” 2001, (29 pages). |
| International Standard, “Particle Size Analysis—Image Analysis Methods,” May 2014, (32 pages). |
| International Standard, “Particle Size Analysis—Image Analysis Methods,” Nov. 2006, (32 pages). |
| Wacker Polysilicon, “Product Specification,” Aug. 2013, (3 pages). |
| Perkinelmer, “WinLab32 for ICP Instrument Control Software,” 2010, (569 pages). |
| Journal of Non-Crystalline Solids, “The UV-induced 210 nm absorption band in fused silica with different thermal history and stoichiometry,” May 1992, (9 pages). |
| J. Appl. Phys. 51, “Reaction of Hydrogen with Hydroxyl-Free Vitreous Silica,” Jan. 1980, (5 pages). |
| Institute of Solid State Physics, University of Latvia, “Color Centers and Their Transformations in Glassy SiO2,” Jul. 10, 1998, (16 pages). |
| International Telecommunication Union, “Series G: Transmission Systems and Media, Digital Systems and Networks: Transmission media and optical systems charateristics—Optical Fibre cables,” Oct. 2012, (24 pages). |
| R. Bruckner, “Silicon Dioxide,” Encyclopedia of Applied Physics, vol. 18, 1997, (31 pages). |
| ASTM International, “Standard Test Method for Linear Thermal Expansion of Rigid Solids with Interferometry,” 2016, (9 pages). |
| Photon Kinetics, “Optical Fiber Preform Analyzers from Photon Kinetics,” Aug. 17, 2015, (1 page). |
| DM 100, Heraeus, Aug. 2013 (2 pgs). |
| R 503/P R503/D, WTW, Operating Manual Aug. 2007 (21 pgs). |
| CI 500 DIN, CI 500 BNC, Operating Manual Mar. 2015 (52 pgs.). |
| F500 DIN, F500 BNC, Operating Manual Mar. 2015 (52 pgs.). |
| Non-Final Office Action dated Oct. 22, 2020 for U.S. Appl. No. 16/062,243. |
| Non-Final Office Action dated Nov. 10, 2020 for U.S. Appl. No. 16/062,234. |
| Non-Final Office Action dated Nov. 30, 2020 for U.S. Appl. No. 16/061,558. |
| Non-Final Office Action dated Nov. 18, 2020 for U.S. Appl. No. 16/062,290. |
| Non-Final Office Action dated Nov. 27, 2020 for U.S. Appl. No. 16/062,658. |
| Pilachowski, Tim “111, Section 8.5 The Normal Distribution”, Lecture Notes, Apr. 12, 2015, 8 pgs. |
| “A Review on the Angle of Repose of Granular Materials”, Hamzah M. Beakawi Al-Hasheimi, et al., Department of Civil and Environmental Engineering, Feb. 2, 2018. |
| “Analytical Devices for the Measurement of Water Vapor and Hydrocarbon Dew-Point in Natural Gas”, D.R. Potter, AMETEK Process Instruments, NGSTech 2011. |
| Non-Final Office Action dated Dec. 15, 2020 in U.S. Appl. No. 16/062,348. |
| Non-Final Office Action dated Dec. 16, 2020 in U.S. Appl. No. 16/062,366. |
| Non-Final Office Action dated Jan. 8, 2021 in U.S. Appl. No. 16/062,685. |
| Non-Final Office Action dated Jan. 14, 2021 in U.S. Appl. No. 16/062,303. |
| Non-Final Office Action dated Jan. 15, 2021 in U.S. Appl. No. 16/062,382. |
| Final Office Action dated Feb. 1, 2021 in U.S. Appl. No. 16/062,280. |
| Final Office Action dated Mar. 10, 2021 in U.S. Appl. No. 16/062,243. |
| Notice of Allowance dated Mar. 11, 2021 in U.S. Appl. No. 16/061,185. |
| Final Office Action dated Apr. 2, 2021 in U.S. Appl. No. 16/062,234. |
| Final Office Action dated Apr. 5, 2021 in U.S. Appl. No. 16/061,927. |
| Final Office Action dated Apr. 19, 2021 in U.S. Appl. No. 16/062,290. |
| Non-Final Office Action dated Apr. 30, 2021 in U.S. Appl. No. 16/062,387. |
| Non-Final Office Action dated May 3, 2021 in U.S. Appl. No. 16/061,451. |
| Notice of Allowance dated May 5, 2021 in U.S. Appl. No. 16/062,366. |
| Non-Final Office Action dated May 5, 2021 in U.S. Appl. No. 16/062,280. |
| Non-Final Office Action dated May 14, 2021 in U.S. Appl. No. 16/062,248. |
| Final Office Action dated May 19, 2021 in U.S. Appl. No. 16/062,348. |
| Final Office Action dated Jun. 1, 2021 in U.S. Appl. No. 16/062,382. |
| Final Office Action dated Jun. 2, 2021 in U.S. Appl. No. 16/061,558. |
| Zhang, et al. “Characterization of Spray Granulated Nd: YAG Particles for Transparent Ceramics”, (8 pgs). |
| Final Office Action dated Jun. 16, 2021 in U.S. Appl. No. 16/062,658. |
| Final Office Action dated Jun. 30, 2021 in U.S. Appl. No. 16/062,303. |
| Non-Final Office Action dated Jul. 20, 2021 in U.S. Appl. No. 16/062,234. |
| Advisory Action dated Jul. 23, 2021 in U.S. Appl. No. 16/062,348. |
| “How to Produce Glass Fiber Using an Indigenous Method”, the first edition, Construction Engineering Bureau, Shaanzi People's Publishing House, Oct. 31, 1959. |
| Hongyong Xie, et al. “Powder Mechanics and Engineering”, Chemical Industry Press, p. 186, Jul. 31, 2007. |
| Non-Final Office Action dated Aug. 30, 2021 in U.S. Appl. No. 16/062,243. |
| Non-Final Office Action dated Sep. 27, 2021 in U.S. Appl. No. 16/062,348. |
| Advisory Action dated Sep. 23, 2021 in U.S. Appl. No. 16/062,658. |
| Notice of Allowance dated Oct. 4, 2021 in U.S. Appl. No. 16/062,303. |
| Li, Gongyang, et al. “The Characteristic of Spray Drying”, The Design of Common Chemical Unit Equipment, Second Edition, Aug. 31, 2009. |
| Final Office Action dated Oct. 18, 2021 in U.S. Appl. No. 16/061,451. |
| Final Office Action dated Oct. 20, 2021 in U.S. Appl. No. 16/062,387. |
| Non-Final Office Action dated Oct. 21, 2021 in U.S. Appl. No. 16/061,558. |
| Notice of Allowance dated Nov. 1, 2021 in U.S. Appl. No. 16/062,303. |
| Non-Final Office Action dated Nov. 16, 2021 in U.S. Appl. No. 16/062,382. |
| Number | Date | Country | |
|---|---|---|---|
| 20180370835 A1 | Dec 2018 | US |
