Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/01—Other methods of shaping glass by progressive fusion or sintering of powdered glass onto a shaping substrate, i.e. accretion, e.g. plasma oxidation deposition
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B1/00—Preparing the batches
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
• • 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
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
  • C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
  • C03B5/025—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by arc discharge or plasma heating
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C4/00—Compositions for glass with special properties
  • C03C4/0071—Compositions for glass with special properties for laserable glass
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
  • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
  • H01S3/02—Constructional details
  • H01S3/025—Constructional details of solid state lasers, e.g. housings or mountings
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
  • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
  • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
  • H01S3/16—Solid materials
  • H01S3/163—Solid materials characterised by a crystal matrix
  • H01S3/164—Solid materials characterised by a crystal matrix garnet
  • H01S3/1643—YAG
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B2201/00—Type of glass produced
  • C03B2201/02—Pure silica glass, e.g. pure fused quartz
  • C03B2201/03—Impurity concentration specified
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B2201/00—Type of glass produced
  • C03B2201/02—Pure silica glass, e.g. pure fused quartz
  • C03B2201/03—Impurity concentration specified
  • C03B2201/04—Hydroxyl ion (OH)
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B2201/00—Type of glass produced
  • C03B2201/06—Doped silica-based glasses
  • C03B2201/07—Impurity concentration specified
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B2201/00—Type of glass produced
  • C03B2201/06—Doped silica-based glasses
  • C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
  • C03B2201/23—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2201/00—Glass compositions
  • C03C2201/02—Pure silica glass, e.g. pure fused quartz
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2203/00—Production processes
  • C03C2203/10—Melting processes
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2203/00—Production processes
  • C03C2203/20—Wet processes, e.g. sol-gel process
  • C03C2203/26—Wet processes, e.g. sol-gel process using alkoxides
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2203/00—Production processes
  • C03C2203/40—Gas-phase processes
  • C03C2203/42—Gas-phase processes using silicon halides as starting materials
  • C03C2203/44—Gas-phase processes using silicon halides as starting materials chlorine containing
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

• the present invention relates to an ultraviolet-resistant quartz glass and a method for producing the same.
• the present invention further relates to a harmonic optical member of a YAG laser.
• carbon dioxide lasers have been mainly used for laser processing that cuts and drills metal, ceramics and glass using high-power laser light.
• laser light having a shorter wavelength has begun to be used, and YAG laser harmonics have attracted attention as a light source for an ultraviolet laser processing machine.
• the basic wavelength of oscillation of the YAG laser is 1064 nm, but the second harmonic (532 nm), the third harmonic (355 nm), the fourth harmonic (266 nm), etc. are converted in wavelength and used for processing.
• the second and third harmonics are the mainstream.
• the fourth harmonic is also being put into practical use due to the small processing efficiency and processing alteration, and in the future, the wavelength will be shortened to the fifth harmonic.
• synthetic quartz glass is used as an optical member used for beam processing and beam shaping of a processing machine using higher harmonics after the second harmonic of the YAG laser. This is because synthetic quartz glass is excellent in durability against damage and transmittance. However, at higher harmonic wavelengths, even synthetic quartz glass is not sufficiently durable. It has been found that in the optical system for the harmonic laser after the YAG third harmonic laser, inconvenience occurs if the synthetic quartz glass is used as it is.
• Patent Document 1 a method of removing synthetic oxygen glass having a low impurity concentration and then removing oxygen molecules in the glass
• Patent Document 2 a method of doping hydrogen molecules and then irradiating ultraviolet rays
• Patent Document 3 a method of doping fluorine
• Patent Document 1 Japanese Patent Application Laid-Open No. 04-097922
• Patent Document 2 Japanese Patent Application Laid-Open No. 09-124337
• Patent Document 3 Japanese Patent Application Laid-Open No. 2004-217506 Patent Documents 1 to 3 are particularly disclosed herein. Incorporated as.
• any method it is essential to add a new process to the normal raw material manufacturing method, and the process becomes complicated and the cost increases. Furthermore, the ultraviolet resistance of quartz glass is not sufficient.
• An object of the present invention is to provide an ultraviolet-resistant quartz glass having durability against a harmonic laser, which is further superior to the synthetic quartz glass optical material described in Patent Document 3, and a method for producing the same.
• Another object of the present invention is to provide a harmonic optical member for a YAG laser.
• the inventors of the present invention use a synthetic silica powder as a raw material, and the quartz glass obtained by melting this is a quartz glass excellent in ultraviolet resistance, particularly for the fourth harmonic (266 nm) of a YAG laser.
• the first aspect of the present invention was completed.
• the inventors of the present invention use quartz powder as a raw material, and that the quartz glass obtained by arc plasma melting is quartz glass having excellent ultraviolet resistance, in particular, a fourth harmonic (266 nm) of a YAG laser.
• the second aspect of the present invention has been completed.
• the present invention is as follows.
• Synthetic silica powder is a manufacturing method as described in [1] or [2] which is amorphous.
• the YAG laser irradiation conditions: YAG laser output: 180 mW, pulse width: 20 nsec, frequency: 80 kHz
• the initial transmittance at an optical path length of 30 mm is 100%, and the transmittance is reduced by 3%.
• the irradiation time until is defined as resistance to ultraviolet rays (hereinafter referred to as ultraviolet resistance), and the ultraviolet resistance quartz glass having the ultraviolet resistance of 2500 seconds or more.
• the quartz glass according to [10] wherein the ultraviolet resistance is 5000 seconds or more.
• quartz glass having excellent ultraviolet resistance can be provided.
• the quartz glass of the present invention has high durability against the fourth harmonic (266 nm) of the YAG laser.
• the quartz glass of the present invention exhibits high durability against the fourth harmonic (266 nm) of a YAG laser having a different frequency.
• the 1st aspect of this invention is related with the manufacturing method of the ultraviolet-resistant quartz glass including melting the synthetic silica powder obtained by a specific manufacturing method.
• the second aspect of the present invention relates to a method for producing an ultraviolet-resistant quartz glass including arc plasma melting of silica powder.
• the synthetic silica powder used in the first aspect of the present invention is a silica powder having a low impurity concentration, such as lithium, sodium and potassium alkali metals, magnesium, calcium alkaline earth metals, aluminum, iron, copper and the like.
• the metal concentration is low, preferably each metal concentration is less than 0.1 ppm, more preferably less than 0.05 ppm, and still more preferably less than 0.01 ppm. Most preferably it is substantially 0 ppm, but in practice the lower limit is greater than 0 ppm.
• the synthetic silica powder preferably has a low OH group concentration.
• the OH group concentration is less than 100 ppm, preferably less than 50 ppm, from the viewpoint of obtaining quartz glass having a low OH group concentration.
• Synthetic silica powder is amorphous.
• the synthetic silica powder is (i) a synthetic silica powder prepared by a sol-gel method using alkoxysilane as a raw material, (ii) a synthetic silica powder obtained by hydrolyzing a silicon halide, or (iii) Fumed silica obtained by flame hydrolysis of a silicon compound.
• a synthetic silica powder is obtained by preparing a gel from a solution of alkoxysilane in a solution, drying it and then sintering it into a glass. It is done.
• silicon tetrachloride is hydrolyzed and then dried and powdered.
• synthetic silica powder can be obtained by referring to the method described in Japanese Patent Publication No. 04-75848.
• Fumed silica is obtained by a gas phase reaction such as flame hydrolysis of a silicon compound.
• methods described in Japanese Patent No. 4548625 and Japanese Patent Application Laid-Open No. 2001-220157 can be referred to.
• the synthetic silica powder can be melted by, for example, oxyhydrogen burner melting, arc plasma melting, or electric furnace melting.
• Synthetic silica powder melting methods can be broadly classified into two types: melting by flame and melting by electricity.
• Oxyhydrogen burner melting belongs to melting by flame.
• Synthetic silica powder raw material is supplied and melted in an oxyhydrogen flame.
• Arc plasma melting and electric furnace melting (using a crucible) are electric melting.
• Arc plasma melting is electric melting that uses arc discharge generated by applying a voltage between electrodes.
• Electric furnace melting (using a crucible) is, for example, a method in which a synthetic silica powder raw material is heated and melted with an electric heater in a carbon mold. Compared to melting by flame, melting by electricity is preferred because the OH group concentration in the resulting quartz glass is low.
• the oxyhydrogen burner used in the production method of the first aspect of the present invention is, for example, a method described in Japanese Patent Application Laid-Open No. 2006-8452, from the viewpoint of obtaining a quartz glass with a reduced impurity concentration. preferable.
• Examples of arc plasma melting include the method described in Japanese Patent Application Laid-Open No. 04-325425.
• the existing method can be used as it is for electric furnace melting (using a crucible).
• the silica powder used in the production method of the second aspect of the present invention is not particularly limited, but is preferably either synthetic silica powder or natural quartz powder from the viewpoint of low impurity concentration.
• the synthetic silica powder is the same as that described in the first aspect of the present invention.
• Natural quartz powder is prepared by pulverizing natural quartz. Natural quartz powder has different types and concentrations of impurities depending on the raw quartz. From the viewpoint of using a raw material for quartz glass with high UV resistance, it is preferable that the impurity concentration is low.In particular, the concentration of metal impurities (for example, sodium, calcium, iron, etc.) that affect UV resistance is different for each element. It is preferably 1 ppm or less, more preferably 0.1 ppm or less.
• the arc plasma melting used in the production method of the second aspect of the present invention is an electric melting using an arc discharge generated by applying a voltage between electrodes.
• the existing method described in Kaihei 04-325425 can be used.
• the quartz glass obtained by the production method of the first aspect and the second aspect of the present invention preferably has an OH group concentration of 500 ppm or less from the viewpoint of high ultraviolet resistance, and more preferably 100 ppm or less. More preferably, it is less than 100 ppm.
• the quartz glass obtained by the manufacturing method of the first and second aspects of the present invention is resistant to the harmonics of the YAG laser.
• the harmonic of the YAG laser is a third harmonic, a fourth harmonic, or a fifth harmonic.
• the present invention includes UV resistant quartz glass.
• the ultraviolet resistant quartz glass of the present invention is an ultraviolet resistant quartz glass having an “ultraviolet resistant” of 2500 seconds or more.
• the “ultraviolet light resistance” means that the initial transmittance at an optical path length of 30 mm when irradiated with a fourth harmonic (266 nm) of a YAG laser (irradiation conditions are YAG laser output 180 mW, pulse width 20 nsec, frequency 80 kHz) is 100%. And defined as the irradiation time until the transmittance is reduced by 3%.
• the ultraviolet-resistant quartz glass of the present invention is produced by the production method of the present invention (first aspect or second aspect).
• the ultraviolet resistant quartz glass of the present invention preferably has the ultraviolet resistance of 5,000 seconds or more, more preferably 6,000 seconds or more. The higher the UV resistance, the more preferable and not intended to limit, but the practical upper limit is 15,000 seconds, preferably 20,000 seconds.
• the ultraviolet resistant quartz glass of the present invention preferably has an OH group concentration of 500 ppm or less from the viewpoint of ultraviolet resistance, more preferably an OH group concentration of 300 ppm or less, more preferably 100 ppm or less, More preferably, it is less than 100 ppm, More preferably, it is 50 ppm or less, More preferably, it is 30 ppm or less.
• the ultraviolet-resistant quartz glass of the present invention contains substantially no fluorine.
• the quartz glass of the present invention is prepared by melting synthetic silica powder having a low impurity concentration in the production method of the first aspect, thereby suppressing contamination contamination during melting, Impurity concentration can be suppressed. Also, fluorine is not added as an additive. Even in the production method of the second aspect, the silica glass of the present invention substantially contains fluorine because silica powder containing no fluorine is used as a raw material and there is no step of adding fluorine to the quartz glass in the production process. do not do.
• the present invention includes a YAG laser harmonic optical member made of the quartz glass of the present invention.
• the optical member is a filter, a prism, a lens, or the like.
• the harmonic of the YAG laser is, for example, a third harmonic, a fourth harmonic, or a fifth harmonic.
• the optical member of the present invention has excellent durability for harmonics of YAG laser.
• Sample 1 Quartz glass ingot was manufactured by a direct method using silicon tetrachloride as a raw material. Raw materials are supplied from the central tube of a quartz glass burner, H 2 gas and O 2 gas are supplied from the outer tube of the burner, silica fine particles are synthesized by a dehydration condensation reaction, and deposited on the target at the same time as transparent glass. Got an ingot. The ingot was processed into a 30 mm cube and used as a sample for evaluation.
• Sample 2 A sample produced under the same conditions as Sample 1 except that silicon tetrafluoride was used as a raw material was designated as Sample 2.
• Sample 3 Silica tetrachloride was used as a raw material, and a quartz glass ingot was produced by the soot method.
• the soot body was synthesized by supplying the raw material from the central tube of the quartz glass burner and supplying H 2 gas and O 2 gas from the outer tube of the burner.
• This soot body was heat-treated at 1200 ° C. for 5 hours in a 1 vol% silicon tetrafluoride gas (remaining He gas) atmosphere. Thereafter, a heat treatment was performed in a 100% He gas atmosphere at 1500 ° C. for 5 hours to obtain a transparent ingot.
• the ingot was processed into a 30 mm cube and used as a sample for evaluation.
• Sample 4 A synthetic silica powder was used as a raw material, melted with an oxyhydrogen burner, and deposited in a container composed of refractory bricks to produce a quartz glass ingot. The ingot was processed into a 30 mm cube and used as a sample for evaluation.
• Sample 5 Synthetic silica powder was used as a raw material, arc plasma was generated between the cathode torch and the anode torch, the raw material powder was charged into the plasma and melted and deposited on the target to produce a quartz glass ingot. The ingot was processed into a 30 mm body and used as a sample for evaluation.
• Sample 6 A synthetic silica powder was used as a raw material. After filling the carbon mold with the raw material powder, the mold was set in an electric furnace, and the raw material powder was melted in an electric furnace at 1800 ° C. in a nitrogen atmosphere to produce a quartz glass ingot. The ingot was processed into a 30 mm cube and used as a sample for evaluation.
• Sample 7 A sample manufactured under the same conditions as Sample 4 except that natural quartz powder was used as a raw material was referred to as Sample 7.
• Sample 8 A sample manufactured under the same conditions as Sample 5 except that natural quartz powder was used as a raw material was designated as Sample 8.
• the synthetic silica powder used for Samples 4 to 6 is MKC powder (manufactured by Nippon Kasei Co., Ltd.) manufactured by the sol-gel method using alkoxysilane (tetramethoxysilane Si (OC 2 H 5 ) 4 etc.) as a raw material. It is.
• Table 1 shows the results of impurity analysis of the MKC powder. Table 1 also shows the result of impurity analysis for sample 4 and the result of impurity analysis for natural quartz powder.
• UV resistance test method The UV resistance of the above sample quartz glass was requested by Laser Lab Co., Ltd. and irradiated with a 4th harmonic (266 nm) of YAG laser (irradiation conditions: YAG laser output 180 mW, pulse width 20 nsec, frequency 80 kHz). It was evaluated by the change in transmittance over time. The initial transmittance at an optical path length of 30 mm is taken as 100%, and the resistance is evaluated based on the irradiation time until it decreases by 3%. The results are shown in Table 2.
• UV-resistant quartz glass can be produced by melting synthetic silica powder containing no fluorine. Furthermore, from the comparison between Example 2 and Example 1 and the comparison between Example 4 and Comparative Example 4, when silica powder containing no fluorine is used as a raw material, the plasma is compared with oxyhydrogen burner melting if the raw materials are the same. It can also be seen that the fused glass can produce quartz glass that is superior in UV resistance.
• the present invention is useful in the field related to quartz glass having excellent ultraviolet resistance.

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