WO2006125614A1 - A method for the production of solid quartz glass bodies - Google Patents

A method for the production of solid quartz glass bodies Download PDF

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Publication number
WO2006125614A1
WO2006125614A1 PCT/EP2006/004916 EP2006004916W WO2006125614A1 WO 2006125614 A1 WO2006125614 A1 WO 2006125614A1 EP 2006004916 W EP2006004916 W EP 2006004916W WO 2006125614 A1 WO2006125614 A1 WO 2006125614A1
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Prior art keywords
quartz
quartz glass
aforementioned
production
glass body
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Application number
PCT/EP2006/004916
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French (fr)
Inventor
Tatsuhiro Sato
Original Assignee
Heraeus Quarzglas Gmbh & Co. Kg
Shin-Etsu Quartz Products Co. Ltd.
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Publication of WO2006125614A1 publication Critical patent/WO2006125614A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/012—Manufacture of preforms for drawing fibres or filaments
    • C03B37/0128—Manufacture of preforms for drawing fibres or filaments starting from pulverulent glass
    • C03B37/01282—Manufacture of preforms for drawing fibres or filaments starting from pulverulent glass by pressing or sintering, e.g. hot-pressing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C03B19/066—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction for the production of quartz or fused silica articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for

Definitions

  • the invention concerns to a method for the production of a solid quartz glass body and to the quartz glass body manufactured by this method.
  • OVD method outer deposition method
  • silicon tetrachloride is subjected to a flame hydrolysis reaction and the fine quartz powder particles produced are accumulated on a cylindrical target and then the target is taken out and a hollow cylindrical quartz glass porous body is formed.
  • This method is an excellent method of production with which it is possible to produce the bodies in high yield when producing large quartz glass cylinders.
  • the present invention is intended to provide a method for the production of quartz glass bodies with which solid quartz glass bodies can be obtained easily and in high yield, and the quartz glass bodies which are produced by means of the said method.
  • the method for the production of a quartz glass body of this invention is characterized in that a quartz material is packed into the hollow part of a hollow synthetic quartz glass porous body and heated and increased in density and a solid quartz glass body is formed.
  • the aforementioned quartz material is preferably quartz powder.
  • the aforementioned quartz powder is ideally a synthetic quartz powder which has been formed by subjecting glass raw material to a flame hydrolysis reaction.
  • Metal-doped quartz material can be used ideally as the aforementioned quartz ma- terial.
  • the aforementioned metal-doped quartz material is quartz material which contains from 0.1 to 20 wt% jointly of two or more metal elements, and the said metal element preferably comprises at least one type of first metal element selected from group 3B of the periodic table, and preferably Al, and at least one type of metal element selected from among the group comprising Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, the lanthanides and the actinides.
  • the aforementioned synthetic quartz glass porous body is ideally a hollow quartz glass porous body which has been obtained by subjecting glass raw material to a flame hydrolysis reaction to produce fine glass particles, accumulating the said fine glass particles on a substrate and then removing the said substrate.
  • the aforementioned quartz powder is preferably packed by pouring a liquid dispersion obtained by dispersing the aforementioned quartz powder in a liquid medium into the hollow part of the aforementioned synthetic quartz porous body. Furthermore, the aforementioned quartz powder can also be packed with compression.
  • Pure water, an organic solvent or a volatile inorganic solvent which does not contain water can be used ideally as the aforementioned liquid medium.
  • pure water there is preferably a process in which the aforementioned quartz powder is packed and then dried and then subjected to heat treatment in the temperature range from 500 0 C to 1000 0 C in a chlorine- containing gas atmosphere.
  • an organic solvent when used as the aforementioned liquid medium there is preferably a process in which the aforementioned quartz powder is packed and then dried and then subjected to heat treatment in the temperature range from 500 0 C to 1000 0 C in a hydrogen-containing gas atmosphere or in an oxygen-containing gas atmosphere.
  • the quartz glass bodies of this invention are characterized in that they have been produced by means of the method of this invention.
  • the method for the production of a quartz glass body of this invention is characterized in that quartz material is packed into the hollow part of a hollow synthetic quartz glass porous body and heated and increased in density and a solid quartz glass body is formed.
  • the hollow synthetic quartz porous body is preferably obtained by forming fine glass particles by means of flame hydrolysis, for example, using glass raw material and accumulating the said fine glass particles.
  • the known materials can be used for the glass raw material and no particular limitation is imposed, but the use of a silica raw material such as silicon tetrachloride with the conjoint use of a dopant, as required, is ideal.
  • quartz material No particular limitation is imposed upon the aforementioned quartz material provided that it is a material which can form quartz glass, but the use of quartz powder is pre- ferred. It is possible to produce quartz rods which have a quartz part which has different characteristics in the middle part by using a doped quartz material which has been doped with metal, for example, for the aforementioned quartz material, and this is ideal.
  • the dopant No particular limitation is imposed upon the dopant, but the conjoint use of at least one type of first metal element selected from group 3B of the periodic table, and preferably aluminium, and at least one type of second metal element selected from among the group comprising Mg, Ca 1 Sr, Ba, Sc, Y, Ti, Zr, Hf, the lan- thanides and the actinides is preferred.
  • a quartz glass which contains from 0.1 to 20 wt% jointly of these first and second metal elements has excellent plasma erosion resistance and so it is used ideally in quartz materials where plasma erosion resistance is required.
  • a doped quartz material which has been doped with metal is referred to as metal-doped quartz material.
  • Either natural quartz powder or synthetic quartz powder can be used for the aforementioned quartz powder, but synthetic quartz powder is preferred. No particular limitation is imposed upon the aforementioned synthetic quartz powder but use of fine particles which have been obtained by subjecting a silica raw material, such as silicon tetrachloride for example, together with dopant, as required, to a hydrolysis reaction, such as flame hydrolysis for example, is more desirable. Furthermore, mixed powders comprising natural quartz powder or synthetic quartz powder and doping material powder, such as metal or metal oxide powder, may be used. Moreover, in this invention fine particles which have been obtained by subjecting silica raw material to a hydrolysis reaction using metal or metal oxide, as mentioned earlier, as the dopant may be used as the metal doped quartz powder which is used as metal doped quartz material.
  • the particle diameter of the quartz powder which is used in the invention is preferably from 1 nm to 500 ⁇ m, and most desirably from 1 nm to 1 ⁇ m.
  • an organic solvent or an inorganic solvent can be used as the liquid medium for dispersing the aforementioned quartz powder, but the use of pure water, a solution which contains organic material or a volatile inorganic solvent which does not contain water is preferred.
  • a dense quartz glass part is formed in the hollow part when the said solution is poured into the synthetic quartz glass porous body.
  • the pure water which is included is easily removed since the quartz glass porous body which forms the outer perimeter is an especially good absorber and takes up the water, and after the density has been increased a unified quartz glass body with no bubbles at the interface or within the whole region is formed.
  • the quartz powder When the quartz powder is dispersed in pure water and packed into the hollow part, the application of a heat treatment at a temperature within the range from 500 0 C to 1000 0 C in a chlorine-containing gas atmosphere after drying in order to remove the excess moisture is effective for forming a better glass body which has no bubbles.
  • a chlorine-containing gas No particular limitation is imposed upon the chlorine-containing gas, provided that it is a gas which contains chlorine, and examples include Cl 2 , HCI, thionyl chloride and gaseous mixtures of these materials.
  • the quartz powder is packed using a dispersion which contains an organic material, for example a dispersion where the quartz powder has been dispersed in ethanol
  • a dispersion which contains an organic material for example a dispersion where the quartz powder has been dispersed in ethanol
  • the said dispersion is poured into the hollow part of the synthetic quartz glass porous body and the quartz powder is dried after packing, carbon remains within the porous material body and there is a risk that bubbles will be formed on vitrification, but glass with no bubbles can be obtained by reacting the residual carbon with hydrogen or oxygen to convert it to a gas and thus removing the carbon by applying a heat treatment of the porous material body after drying at a temperature within the range from 500°C to 1000 0 C in a hydrogen-containing gas or in an oxygen-containing gas.
  • the quartz powder is packed using a dispersion where the quartz powder has been dispersed in a volatile inorganic solvent which does not contain water it is possible to form a quartz glass body with no bubbles without a process for removing carbon or water which is the cause of bubble formation.
  • Liquid nitrogen for example, is ideal as the aforementioned volatile inorganic solvent.
  • Soot-like synthetic quartz glass fine particles were formed by subjecting silicon tetrachloride to a hydrolysis reaction and a synthetic quartz glass porous body of external diameter 300 mm x internal diameter 100 mm x length 2000 mm was obtained by means of the OVD method. Furthermore, 12.56 kg of fine synthetic quartz glass particles of particle diameter from 0.1 to 2.0 ⁇ m which had been formed in the same way were dispersed in 3.14 kg of pure water to form a dispersion and the aforementioned synthetic quartz glass porous body which had been obtained was stood upright and the said dispersion or solution was poured into the hollow part of the said porous body from the top.
  • Example 2 A similar result was obtained on treatment in the same way as in Example 1 except that the fine synthetic quartz glass particles were dispersed in ethyl alcohol instead of pure water and the heat treatment using chlorine gas after packing into the hollow part and drying was changed to a heat treatment involving being maintained at 800 0 C for 10 hours while passing oxygen gas at a rate of 100 litres/hour.
  • Example 2 A similar result was obtained on treatment in the same way as in Example 2 except that the heat treatment using oxygen gas after drying was changed to heat treat- merit involving being maintained at 800 c C for 10 hours while passing H 2 gas at a rate of 100 litres/hour.
  • Soot-like fine synthetic quartz glass particles were formed by subjecting silicon tetrachloride to a hydrolysis reaction and a synthetic quartz glass porous body of external diameter 300 mm x internal diameter 100 mm x length 2000 mm was obtained by means of the OVD method. Furthermore, using 10 kg of fine synthetic quartz glass particles which had been formed in the same way, these were packed in lengths of 50 mm and compressed (20 kg/cm 2 ) repeatedly in the hollow part and, after packing all of the said fine glass particles in the long hollow part, it was subjected to a density increasing treatment by being maintained at 1400 0 C for 100 hours in the vacuum environment and rendered transparent. After being returned to room temperature it was taken out and a solid quartz glass body with no bubbles throughout the whole of the glass region of diameter 200 mm x length 1500 mm was obtained.
  • Example 1 Each treatment was carried out under the same conditions as in Example 1 except that 15 kg of a mixed powder (metal doped quartz powder) obtained by mixing Y in such a way as to include 0.5 mass% and Al in such a way as to include 1.0 mass% in the same quartz glass powder as used in Example 1 was used as the quartz powder that was packed into the hollow part of the porous body, and the temperature of the density increasing treatment in a vacuum environment was 1800 0 C, and a rod in which the unified hollow part comprised doped quartz was obtained. The size of the rod obtained was the same as in Example 1.
  • a mixed powder metal doped quartz powder obtained by mixing Y in such a way as to include 0.5 mass% and Al in such a way as to include 1.0 mass% in the same quartz glass powder as used in Example 1 was used as the quartz powder that was packed into the hollow part of the porous body, and the temperature of the density increasing treatment in a vacuum environment was 1800 0 C, and a rod in which the unified hollow part comprised doped quartz was obtained.
  • a synthetic quartz glass porous body of external diameter 300 mm x internal diameter 100 mm x length 2000 mm was obtained in the same way as in Example 1.
  • the synthetic quartz glass porous body obtained was stood upright and subjected to a density increasing treatment involving being maintained at 1400 0 C for 100 hours in a vacuum environment and rendered transparent. After returning to room tempera- ture it was taken out and a cylindrical shaped synthetic quartz glass body of external diameter 200 mm x internal diameter 100 mm x length 1500 mm was formed.
  • the glass body obtained was heated and moulded to external diameter 400 mm x internal diameter 180 mm x length 800 mm and split into four, and the external diameter was ground, after which solid quartz glass bodies with no bubbles of diameter 100 mm x length 800 mm were obtained.
  • the synthetic quartz glass bodies obtained had a low yield when compared with Example 1.
  • a synthetic quartz glass porous body of external diameter 300 mm x internal diame- ter 100 mm x length 2000 mm was obtained in the same way as in Example 1.
  • the synthetic quartz glass porous body obtained was stood upright and a quartz glass rod of external diameter 95 mm and length 1500 mm was inserted into the hollow part and it was then subjected to a density increasing treatment involving being maintained at 1400°C for 100 hours in a vacuum environment and rendered trans- parent. After returning to room temperature it was taken out and a cylindrical shaped synthetic quartz glass body of external diameter 200 mm x internal diameter 100 mm x length 1500 mm had been formed, but boundary surface bubbles were seen along the whole length with an internal diameter of some 95 to 100 mm and it could not be used as a unified rod.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

To provide a method for the production of quartz glass bodies with which solid quartz glass bodies can be obtained easily and in high yield with no bubbles and to provide the quartz glass bodies by the said method. Quartz material is packed into the hollow part of a hollow synthetic quartz glass porous body and heated and increased in density in such a way that a solid quartz body is formed. The aforementioned quartz material is preferably quartz powder. Furthermore, the aforementioned quartz powder is preferably packed by pouring a liquid dispersion obtained by dispersing the aforementioned quartz powder in a liquid medium into the hollow part of the aforementioned synthetic quartz glass porous body. The powder can also be packed by compression, may be doped and/or be of synthetic soot origin.

Description

Patent Application
Heraeus Quarzglas GmbH & Co. KG Shin-Etsu Quartz Products Co. Ltd.
A method for the production of solid quartz glass bodies
The invention concerns to a method for the production of a solid quartz glass body and to the quartz glass body manufactured by this method.
One of the methods whereby quartz glass bodies are produced is the so-called OVD method (outer deposition method), a method in which silicon tetrachloride is subjected to a flame hydrolysis reaction and the fine quartz powder particles produced are accumulated on a cylindrical target and then the target is taken out and a hollow cylindrical quartz glass porous body is formed. This method is an excellent method of production with which it is possible to produce the bodies in high yield when producing large quartz glass cylinders.
However, with the abovementioned method, to form a quartz glass rod or plate the cylinder obtained must be subjected to after-processes such as a cutting process and hot moulding, and much time is required and the yield is greatly reduced.
On the other hand, the method in which a glass rod is inserted into the hollow part of a synthetic silica glass tube which has been prepared by way of a soot body and collapsed and formed into a solid is known as a hybrid synthesis method for parent materials for optical fibre purposes (see "Non-crystalline Silica Material Applications Handbook", published by the Rearaizu Co., 31st May 2000, pages 524 to 525). For example, there is disclosed in Japanese Unexamined Patent Application Laid Open 60-210539 a method in which a rod-like porous body is inserted into a tube-like porous body and sintered and transformed into a long narrow rod-like glass body. However, with the method of forming a rod in this way bubbles remain at the inter- face between the tube-like porous body and the rod-like porous body and there are problems with its use as a unified rod.
Problems to be Resolved by the Invention
The present invention is intended to provide a method for the production of quartz glass bodies with which solid quartz glass bodies can be obtained easily and in high yield, and the quartz glass bodies which are produced by means of the said method.
Means of Resolving These Problems
As a result of thorough research carried out with a view to resolving the abovemen- tioned problems, the inventors have devised a method in which quartz material is packed into the hollow part of a hollow quartz glass porous body and heated and the density is raised to form a quartz glass body.
That is to say, the method for the production of a quartz glass body of this invention is characterized in that a quartz material is packed into the hollow part of a hollow synthetic quartz glass porous body and heated and increased in density and a solid quartz glass body is formed.
The aforementioned quartz material is preferably quartz powder. The aforementioned quartz powder is ideally a synthetic quartz powder which has been formed by subjecting glass raw material to a flame hydrolysis reaction.
Metal-doped quartz material can be used ideally as the aforementioned quartz ma- terial. The aforementioned metal-doped quartz material is quartz material which contains from 0.1 to 20 wt% jointly of two or more metal elements, and the said metal element preferably comprises at least one type of first metal element selected from group 3B of the periodic table, and preferably Al, and at least one type of metal element selected from among the group comprising Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, the lanthanides and the actinides.
The aforementioned synthetic quartz glass porous body is ideally a hollow quartz glass porous body which has been obtained by subjecting glass raw material to a flame hydrolysis reaction to produce fine glass particles, accumulating the said fine glass particles on a substrate and then removing the said substrate. The aforementioned quartz powder is preferably packed by pouring a liquid dispersion obtained by dispersing the aforementioned quartz powder in a liquid medium into the hollow part of the aforementioned synthetic quartz porous body. Furthermore, the aforementioned quartz powder can also be packed with compression.
Pure water, an organic solvent or a volatile inorganic solvent which does not contain water can be used ideally as the aforementioned liquid medium. When pure water is used as the aforementioned liquid medium there is preferably a process in which the aforementioned quartz powder is packed and then dried and then subjected to heat treatment in the temperature range from 5000C to 10000C in a chlorine- containing gas atmosphere. Furthermore, when an organic solvent is used as the aforementioned liquid medium there is preferably a process in which the aforementioned quartz powder is packed and then dried and then subjected to heat treatment in the temperature range from 5000C to 10000C in a hydrogen-containing gas atmosphere or in an oxygen-containing gas atmosphere.
The quartz glass bodies of this invention are characterized in that they have been produced by means of the method of this invention.
Effect of the Invention
By means of the invention it is possible to obtain solid quartz glass bodies easily and in high yield. Moreover, by means of this invention it is possible to obtain solid quartz glass bodies which have no bubbles in the whole body from the surface to the inner part.
Embodiment of the Invention
Embodiments of the invention are described below, but these are shown as examples and of course various modifications are possible provided that the technical concept of the invention is not exceeded.
The method for the production of a quartz glass body of this invention is characterized in that quartz material is packed into the hollow part of a hollow synthetic quartz glass porous body and heated and increased in density and a solid quartz glass body is formed. No particular limitation is imposed upon the method by which the aforementioned hollow synthetic quartz porous body is obtained, but the hollow synthetic quartz porous body is preferably obtained by forming fine glass particles by means of flame hydrolysis, for example, using glass raw material and accumulating the said fine glass particles. The known materials can be used for the glass raw material and no particular limitation is imposed, but the use of a silica raw material such as silicon tetrachloride with the conjoint use of a dopant, as required, is ideal. The use of the OVD method in which the fine glass particles are accumulated on a substrate which is being held horizontally and then the said substrate is removed is preferred in practical terms as the method of accumulating the fine glass particles. It is possible to obtain hollow synthetic quartz glass porous bodies in high yield and at low cost by means of the said method.
No particular limitation is imposed upon the aforementioned quartz material provided that it is a material which can form quartz glass, but the use of quartz powder is pre- ferred. It is possible to produce quartz rods which have a quartz part which has different characteristics in the middle part by using a doped quartz material which has been doped with metal, for example, for the aforementioned quartz material, and this is ideal. No particular limitation is imposed upon the dopant, but the conjoint use of at least one type of first metal element selected from group 3B of the periodic table, and preferably aluminium, and at least one type of second metal element selected from among the group comprising Mg, Ca1 Sr, Ba, Sc, Y, Ti, Zr, Hf, the lan- thanides and the actinides is preferred. A quartz glass which contains from 0.1 to 20 wt% jointly of these first and second metal elements has excellent plasma erosion resistance and so it is used ideally in quartz materials where plasma erosion resistance is required. In this invention a doped quartz material which has been doped with metal is referred to as metal-doped quartz material.
Either natural quartz powder or synthetic quartz powder can be used for the aforementioned quartz powder, but synthetic quartz powder is preferred. No particular limitation is imposed upon the aforementioned synthetic quartz powder but use of fine particles which have been obtained by subjecting a silica raw material, such as silicon tetrachloride for example, together with dopant, as required, to a hydrolysis reaction, such as flame hydrolysis for example, is more desirable. Furthermore, mixed powders comprising natural quartz powder or synthetic quartz powder and doping material powder, such as metal or metal oxide powder, may be used. Moreover, in this invention fine particles which have been obtained by subjecting silica raw material to a hydrolysis reaction using metal or metal oxide, as mentioned earlier, as the dopant may be used as the metal doped quartz powder which is used as metal doped quartz material.
No particular limitation is imposed upon the particle diameter of the quartz powder which is used in the invention but it is preferably from 1 nm to 500 μm, and most desirably from 1 nm to 1 μm.
No particular limitation is imposed upon the method whereby the aforementioned quartz material is packed into the hollow part of the synthetic quartz glass porous body, but the packing of the quartz powder using a liquid dispersion obtained by dispersing the quartz powder in a liquid medium by pouring the said liquid dispersion into the hollow part of the synthetic quartz glass porous body and then drying is preferred. Furthermore, a process using methods in which the quartz powder is packed into the hollow part with compression is also very simple and of low cost and these methods are desirable.
No particular limitation is imposed upon the proportion of quartz powder which is included in the aforementioned liquid dispersion but it is preferably from 10 to 90 mass%, and most desirably from 60 to 90 mass%. Furthermore, no particular limita- tion is imposed upon the degree of dispersion of the liquid dispersion but the use of a slurry in which quartz powder of the prescribed particle size is suspended in a liquid is preferred.
No particular limitation is imposed, and either an organic solvent or an inorganic solvent can be used as the liquid medium for dispersing the aforementioned quartz powder, but the use of pure water, a solution which contains organic material or a volatile inorganic solvent which does not contain water is preferred.
For example, when packing quartz powder using a dispersion where quartz powder has been dispersed in pure water, a dense quartz glass part is formed in the hollow part when the said solution is poured into the synthetic quartz glass porous body. In particular, the pure water which is included is easily removed since the quartz glass porous body which forms the outer perimeter is an especially good absorber and takes up the water, and after the density has been increased a unified quartz glass body with no bubbles at the interface or within the whole region is formed. When the quartz powder is dispersed in pure water and packed into the hollow part, the application of a heat treatment at a temperature within the range from 5000C to 10000C in a chlorine-containing gas atmosphere after drying in order to remove the excess moisture is effective for forming a better glass body which has no bubbles. No particular limitation is imposed upon the chlorine-containing gas, provided that it is a gas which contains chlorine, and examples include Cl2, HCI, thionyl chloride and gaseous mixtures of these materials.
Furthermore, when the quartz powder is packed using a dispersion which contains an organic material, for example a dispersion where the quartz powder has been dispersed in ethanol, if the said dispersion is poured into the hollow part of the synthetic quartz glass porous body and the quartz powder is dried after packing, carbon remains within the porous material body and there is a risk that bubbles will be formed on vitrification, but glass with no bubbles can be obtained by reacting the residual carbon with hydrogen or oxygen to convert it to a gas and thus removing the carbon by applying a heat treatment of the porous material body after drying at a temperature within the range from 500°C to 10000C in a hydrogen-containing gas or in an oxygen-containing gas.
Moreover, when the quartz powder is packed using a dispersion where the quartz powder has been dispersed in a volatile inorganic solvent which does not contain water it is possible to form a quartz glass body with no bubbles without a process for removing carbon or water which is the cause of bubble formation. Liquid nitrogen, for example, is ideal as the aforementioned volatile inorganic solvent.
No particular limitation is imposed upon the method of increasing the density by heating in the method of this invention but, for example, a heat treatment at from 13000C to 16000C in a reduced pressure atmosphere is preferred for achieving transparent glass formation. Illustrative Examples
The invention is described in more practical terms below by means of illustrative examples, but these illustrative examples are shown only as examples and they should not of course be interpreted as limiting in any way.
Example 1
Soot-like synthetic quartz glass fine particles were formed by subjecting silicon tetrachloride to a hydrolysis reaction and a synthetic quartz glass porous body of external diameter 300 mm x internal diameter 100 mm x length 2000 mm was obtained by means of the OVD method. Furthermore, 12.56 kg of fine synthetic quartz glass particles of particle diameter from 0.1 to 2.0 μm which had been formed in the same way were dispersed in 3.14 kg of pure water to form a dispersion and the aforementioned synthetic quartz glass porous body which had been obtained was stood upright and the said dispersion or solution was poured into the hollow part of the said porous body from the top. After completely filling the hollow part it was dried for 100 hours at 200°C and then it was heat treated by being maintained at 8000C for 10 hours while passing chlorine gas at a rate of 100 litres/hour. After returning to room temperature it was then subjected to a density increasing treatment by being maintained at 14000C for 100 hours in a vacuum environment and rendered transparent. After returning to room temperature it was taken out and a solid quartz glass body of diameter 200 mm and length 1500 mm with no bubbles in the whole of the glass body was obtained.
Example 2
A similar result was obtained on treatment in the same way as in Example 1 except that the fine synthetic quartz glass particles were dispersed in ethyl alcohol instead of pure water and the heat treatment using chlorine gas after packing into the hollow part and drying was changed to a heat treatment involving being maintained at 8000C for 10 hours while passing oxygen gas at a rate of 100 litres/hour.
Example 3
A similar result was obtained on treatment in the same way as in Example 2 except that the heat treatment using oxygen gas after drying was changed to heat treat- merit involving being maintained at 800cC for 10 hours while passing H2 gas at a rate of 100 litres/hour.
Example 4
Soot-like fine synthetic quartz glass particles were formed by subjecting silicon tetrachloride to a hydrolysis reaction and a synthetic quartz glass porous body of external diameter 300 mm x internal diameter 100 mm x length 2000 mm was obtained by means of the OVD method. Furthermore, using 10 kg of fine synthetic quartz glass particles which had been formed in the same way, these were packed in lengths of 50 mm and compressed (20 kg/cm2) repeatedly in the hollow part and, after packing all of the said fine glass particles in the long hollow part, it was subjected to a density increasing treatment by being maintained at 14000C for 100 hours in the vacuum environment and rendered transparent. After being returned to room temperature it was taken out and a solid quartz glass body with no bubbles throughout the whole of the glass region of diameter 200 mm x length 1500 mm was obtained.
Example 5
Each treatment was carried out under the same conditions as in Example 1 except that 15 kg of a mixed powder (metal doped quartz powder) obtained by mixing Y in such a way as to include 0.5 mass% and Al in such a way as to include 1.0 mass% in the same quartz glass powder as used in Example 1 was used as the quartz powder that was packed into the hollow part of the porous body, and the temperature of the density increasing treatment in a vacuum environment was 18000C, and a rod in which the unified hollow part comprised doped quartz was obtained. The size of the rod obtained was the same as in Example 1.
Comparative Example 1
A synthetic quartz glass porous body of external diameter 300 mm x internal diameter 100 mm x length 2000 mm was obtained in the same way as in Example 1. The synthetic quartz glass porous body obtained was stood upright and subjected to a density increasing treatment involving being maintained at 14000C for 100 hours in a vacuum environment and rendered transparent. After returning to room tempera- ture it was taken out and a cylindrical shaped synthetic quartz glass body of external diameter 200 mm x internal diameter 100 mm x length 1500 mm was formed. The glass body obtained was heated and moulded to external diameter 400 mm x internal diameter 180 mm x length 800 mm and split into four, and the external diameter was ground, after which solid quartz glass bodies with no bubbles of diameter 100 mm x length 800 mm were obtained. The synthetic quartz glass bodies obtained had a low yield when compared with Example 1.
Comparative Example 2
A synthetic quartz glass porous body of external diameter 300 mm x internal diame- ter 100 mm x length 2000 mm was obtained in the same way as in Example 1. The synthetic quartz glass porous body obtained was stood upright and a quartz glass rod of external diameter 95 mm and length 1500 mm was inserted into the hollow part and it was then subjected to a density increasing treatment involving being maintained at 1400°C for 100 hours in a vacuum environment and rendered trans- parent. After returning to room temperature it was taken out and a cylindrical shaped synthetic quartz glass body of external diameter 200 mm x internal diameter 100 mm x length 1500 mm had been formed, but boundary surface bubbles were seen along the whole length with an internal diameter of some 95 to 100 mm and it could not be used as a unified rod.

Claims

Claims
1. Method for the production of a quartz glass body, characterized in that quartz material is packed into the hollow part of a hollow synthetic quartz glass po- rous body and heated and the density is increased and a solid quartz glass body is formed.
2. Method for the production of a quartz glass body, according to Claim 1 , characterized in that the aforementioned quartz material is quartz powder.
3. Method for the production of a quartz glass body, according to Claim 2, characterized in that the aforementioned quartz powder is packed by pouring a liquid dispersion obtained by dispersing the aforementioned quartz powder in a liquid medium into the hollow part of the aforementioned synthetic quartz glass porous body.
4. Method for the production of a quartz glass body, according to Claim 3, characterized in that the aforementioned dispersion medium is pure water.
5. Method for the production of a quartz glass body, according to Claim 4, characterized in that, after packing the aforementioned quartz powder, there is a process in which it is dried and a heat treatment is carried out in the temperature range from 5000C to 10000C in a chlorine-containing gas at- mosphere.
6. Method for the production of a quartz glass body, according to Claim 3, characterized in that the aforementioned liquid dispersion medium is a solution which contains organic material.
7. Method for the production of a quartz glass body, according to Claim 6, characterized in that, after packing the aforementioned quartz powder, there is a process in which it is dried and a heat treatment is carried out in the temperature range from 500°C to 10000C in a hydrogen-containing gas atmosphere.
8. Method for the production of a quartz glass body, according to Claim 6, characterized in that, after packing the aforementioned quartz powder, there is a process in which it is dried and a heat treatment is carried out in the temperature range from 5000C to 10000C in an oxygen-containing gas at- mosphere.
9. Method for the production of a quartz glass body, according to Claim 3, characterized in that the aforementioned liquid medium is a volatile inorganic solvent which does not contain water.
10. Method for the production of a quartz glass body, according to Claim 2, characterized in that the aforementioned packing with quartz material involves the packing of quartz powder with compression.
11. Method for the production of a quartz glass body, according to any one of Claims 2 to 10, characterized in that the aforementioned quartz powder is synthetic quartz powder which has been formed by subjecting glass raw ma- terial to a flame hydrolysis reaction.
12. Method for the production of a quartz glass body, according to any one of Claims 1 to 11 , characterized in that the aforementioned synthetic quartz glass porous body is a hollow quartz glass porous body which has been formed by producing fine quartz glass particles by subjecting glass raw mate- rial to a flame hydrolysis reaction, accumulating the said fine glass particles on a substrate and then removing the substrate.
13. Method for the production of a quartz glass body, according to any one of Claims 1 to 12, characterized in that the aforementioned quartz material is a metal-doped quartz material.
14. Method for the production of a quartz glass body, according to Claim 13, characterized in that the aforementioned metal-doped quartz material is a quartz material which contains from 0.1 to 20 wt% jointly of two or more types of metal element, said metal element comprising at least one type of first metal selected from group 3B of the periodic table and at least one type of second metal element selected from among the group comprising Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, the lanthanides and the actinides.
15. Quartz glass body, characterized in that it has been produced by means of a method disclosed in any one of Claims 1 to 14.
PCT/EP2006/004916 2005-05-26 2006-05-24 A method for the production of solid quartz glass bodies WO2006125614A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60186425A (en) * 1984-03-01 1985-09-21 Furukawa Electric Co Ltd:The Method for forming preform for stepped index-type optical fiber
US5049175A (en) * 1982-11-02 1991-09-17 Heraeus Quarzschmelze Gmbh Method of manufacturing a glass body having a non-uniform refractive index
JPH04295020A (en) * 1991-03-25 1992-10-20 Furukawa Electric Co Ltd:The Method for molding porous quartz glass body
JPH05201736A (en) * 1991-10-25 1993-08-10 Furukawa Electric Co Ltd:The Production of porous parent material for quartz glass
JPH1160260A (en) * 1997-08-08 1999-03-02 Fujikura Ltd Production of optical fiber preform

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5049175A (en) * 1982-11-02 1991-09-17 Heraeus Quarzschmelze Gmbh Method of manufacturing a glass body having a non-uniform refractive index
JPS60186425A (en) * 1984-03-01 1985-09-21 Furukawa Electric Co Ltd:The Method for forming preform for stepped index-type optical fiber
JPH04295020A (en) * 1991-03-25 1992-10-20 Furukawa Electric Co Ltd:The Method for molding porous quartz glass body
JPH05201736A (en) * 1991-10-25 1993-08-10 Furukawa Electric Co Ltd:The Production of porous parent material for quartz glass
JPH1160260A (en) * 1997-08-08 1999-03-02 Fujikura Ltd Production of optical fiber preform

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 010, no. 036 (C - 328) 13 February 1986 (1986-02-13) *
PATENT ABSTRACTS OF JAPAN vol. 017, no. 108 (C - 1032) 5 March 1993 (1993-03-05) *
PATENT ABSTRACTS OF JAPAN vol. 017, no. 638 (C - 1133) 26 November 1993 (1993-11-26) *
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 08 30 June 1999 (1999-06-30) *

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