WO2023218938A1 - Verre perméable aux ultraviolets - Google Patents
Verre perméable aux ultraviolets Download PDFInfo
- Publication number
- WO2023218938A1 WO2023218938A1 PCT/JP2023/016202 JP2023016202W WO2023218938A1 WO 2023218938 A1 WO2023218938 A1 WO 2023218938A1 JP 2023016202 W JP2023016202 W JP 2023016202W WO 2023218938 A1 WO2023218938 A1 WO 2023218938A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- content
- transmittance
- ultraviolet
- mass
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 120
- 238000002834 transmittance Methods 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 230000007423 decrease Effects 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 238000004031 devitrification Methods 0.000 description 8
- 239000006060 molten glass Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000006066 glass batch Substances 0.000 description 5
- 238000007500 overflow downdraw method Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000003280 down draw process Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- 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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/02—Details
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/02—Details
- G01J1/04—Optical or mechanical part supplementary adjustable parts
Definitions
- the present invention relates to ultraviolet-transparent glass.
- a flame sensor that detects ultraviolet light with a wavelength of 185 to 260 nm that is generated by flames has been developed, and a method has been proposed that uses this flame sensor to detect fires and flames from combustion devices.
- Ultraviolet transmitting glass for example, Patent Document 1
- Patent Document 1 which has high transmittance in the deep ultraviolet region, is used for containers and window materials that house such flame sensors.
- ultraviolet-transmissive glass As the outer cylinder of the flame sensor, high detection sensitivity can be achieved continuously.
- conventional ultraviolet transmitting glasses have a problem in that their transmittance is low, especially in the deep ultraviolet region of wavelengths from 200 to 250 nm.
- the present invention aims to obtain a glass having higher transmittance than conventional products in the deep ultraviolet region.
- the F content at a depth of 15 ⁇ m from the glass surface is x (mass%)
- the F content at a depth of 1 ⁇ m from the glass surface is y (mass%)
- y /x is 0.8 or more.
- the "F content” can be measured with a commercially available electron beam microanalyzer (for example, EPMA-1720H manufactured by Shimadzu Corporation).
- the transmittance (%) at a thickness of 0.5 mm and a wavelength of 200 nm is T200 , it is preferable that T200 ⁇ 69.
- the "transmittance at a wavelength of 200 nm” can be measured with a commercially available spectrophotometer (for example, UV-3100PC manufactured by Shimadzu Corporation).
- the ultraviolet transmitting glass of the present invention preferably has a thickness of 0.2 to 2 mm and is tubular.
- the ultraviolet transmitting glass of the present invention has, as a glass composition, SiO 2 55 to 75%, Al 2 O 3 1 to 10%, B 2 O 3 10 to 30%, CaO 0 to 5%, BaO 0 to 5%, Li 2 O+Na 2 O+K 2 O 1-15%, TiO 2 0-0.001%, Fe 2 O 3 0-0.001%, and F 0.5-7%.
- A+B+C refers to the total amount of component A, component B, and component C.
- Li2O + Na2O + K2O refers to the total amount of Li2O , Na2O and K2O .
- the ultraviolet transmitting glass of the present invention is preferably used for flame sensors.
- the method for producing ultraviolet transmitting glass of the present invention is characterized by forming glass into a tubular shape and then immersing the tubular glass in an acid solution for etching.
- y/x is 0.8 or more, preferably 0.85 or more, particularly 0.9 or more. If y/x is too small, Fe 3+ contained near the glass surface will be difficult to reduce, and the transmittance in the deep ultraviolet region will tend to decrease. Note that the upper limit value of y/x is not particularly limited, but is realistically 1.2 or less. Moreover, the specific numerical value of y/x is as follows.
- x is 0.5 to 7%, 0.6 to 5%, particularly 0.7 to 3%. If x is too small, the content of F inside the glass will decrease, Fe 3+ contained inside the glass will be difficult to reduce, and the transmittance in the deep ultraviolet region will tend to decrease. On the other hand, if x is too large, it becomes difficult to vitrify.
- y is 0.4 to 8.4%, 0.45 to 6%, 0.5 to 5%, particularly 0.6 to 3%. If y is too small, the content of F near the glass surface will decrease, making it difficult for Fe 3+ contained near the glass surface to be reduced, and the transmittance in the deep ultraviolet region will tend to decrease. On the other hand, if y is too large, it becomes difficult to vitrify.
- the transmittance (%) at a thickness of 0.5 mm and a wavelength of 200 nm is T 200
- T 220 is the transmittance (%) at a thickness of 0.5 mm and a wavelength of 220 nm
- T 220 ⁇ 79, particularly T 220 ⁇ 80 If the transmittance at a thickness of 0.5 mm and a wavelength of 220 nm is too low, it will be difficult for ultraviolet light to pass through, and the performance of the light source or device mounted thereon will likely deteriorate.
- T 250 is the transmittance (%) at a thickness of 0.5 mm and a wavelength of 250 nm
- T 250 ⁇ 87, particularly T 250 ⁇ 88 it is preferable that T 250 ⁇ 87, particularly T 250 ⁇ 88. If the transmittance at a thickness of 0.5 mm and a wavelength of 250 nm is too low, it will be difficult for ultraviolet light to pass through, and the performance of the light source or device mounted thereon will likely deteriorate.
- the strain point of the ultraviolet transmitting glass of the present invention is preferably 400°C or higher, 410°C or higher, particularly 415°C or higher. If the strain point of the ultraviolet-transmitting glass is too low, for example, when forming a functional film on the surface, the glass is likely to undergo unintended deformation during a high-temperature film-forming process. Note that the upper limit of the strain point is not particularly limited, but realistically it is 600° C. or less.
- the softening point of the ultraviolet transmitting glass of the present invention is preferably 850°C or lower, 800°C or lower, or 750°C or lower, particularly 700°C or lower. If the softening point is too high, it will be difficult to reheat the glass. Note that the lower limit of the softening point is not particularly limited, but realistically it is 600°C or higher.
- the temperature at which the ultraviolet transmitting glass of the present invention has a viscosity of 10 2.5 dPa ⁇ s is preferably 1540°C or lower, 1520°C or lower, 1500°C or lower, particularly 1480°C or lower. If the temperature at 10 2.5 dPa ⁇ s is too high, the load on the glass melting furnace increases, the meltability decreases, and the manufacturing cost of glass tends to rise.
- the "temperature at 10 2.5 dPa ⁇ s" can be measured by the platinum ball pulling method. Note that the lower limit of the temperature at 10 2.5 dPa ⁇ s is not particularly limited, but realistically it is 1300° C. or higher.
- the average linear thermal expansion coefficient of the ultraviolet transmitting glass of the present invention in the temperature range of 30 to 380°C is preferably 30 x 10 -7 /°C or more, particularly 35 x 10 -7 /°C or more, and 95 x 10 -7 /°C or less, particularly preferably 80 ⁇ 10 -7 /°C or less. If the average linear thermal expansion coefficient is too low, it will be difficult to match the thermal expansion coefficients of various members such as sensor terminals. On the other hand, if the average linear thermal expansion coefficient is too high, the glass will be easily damaged by thermal shock.
- the liquidus temperature of the ultraviolet transmitting glass of the present invention is preferably 1120°C or lower, 1100°C or lower, 1080°C or lower, 1050°C or lower, 1000°C or lower, 950°C or lower, 900°C or lower, particularly 850°C or lower.
- the viscosity at the liquidus temperature is 10 4.0 dPa ⁇ s or more, 10 4.3 dPa ⁇ s or more, 10 4.5 dPa ⁇ s or more, 10 4.8 dPa ⁇ s or more, 10 5.1 dPa ⁇ s
- it is preferably 10 5.3 dPa ⁇ s or more, particularly 10 5.5 dPa ⁇ s or more. In this way, the devitrification resistance is improved and it becomes easier to mold by a down-draw method, particularly an overflow down-draw method, so that it becomes easier to produce glass in a desired shape.
- the Young's modulus of the ultraviolet transmitting glass of the present invention is preferably 40 GPa or more, particularly 45 GPa or more. If the Young's modulus is too low, it will be difficult for the glass to maintain its rigidity on the conveyance line in the device manufacturing process, and the glass will be more likely to deform, warp, or break.
- the ultraviolet transmitting glass of the present invention has, as a glass composition, SiO 2 55-75%, Al 2 O 3 1-10%, B 2 O 3 10-30%, CaO 0-5%, BaO 0-0. 5%, Li 2 O+Na 2 O+K 2 O 1-15%, TiO 2 0-0.001%, Fe 2 O 3 0-0.001%, and F 0.5-7%.
- SiO 2 is the main component that forms the skeleton of glass.
- the content of SiO 2 is preferably 55-75%, 58-70%, particularly 65-69%. If the content of SiO 2 is too low, Young's modulus and acid resistance tend to decrease. On the other hand, if the content of SiO 2 is too high, the high-temperature viscosity becomes high and the meltability tends to decrease, and in addition, devitrification crystals such as cristobalite tend to precipitate, and the liquidus temperature tends to increase. Become.
- Al 2 O 3 is a component that increases Young's modulus and also suppresses phase separation and devitrification.
- the content of Al 2 O 3 is preferably 1 to 10%, 2 to 9%, particularly 3 to 8%. If the content of Al 2 O 3 is too small, the Young's modulus tends to decrease, and the glass tends to undergo phase separation and devitrification. On the other hand, if the content of Al 2 O 3 is too large, the high temperature viscosity will increase and the meltability will tend to decrease.
- B 2 O 3 is a component that improves melting properties and devitrification resistance, and also improves susceptibility to scratches and increases strength.
- the content of B 2 O 3 is preferably 10 to 30%, 13 to 28%, particularly 15 to 25%. If the content of B 2 O 3 is too small, meltability and devitrification resistance tend to decrease, and resistance to hydrofluoric acid-based chemicals tends to decrease. On the other hand, if the content of B 2 O 3 is too large, Young's modulus and acid resistance tend to decrease.
- CaO is a component that lowers high temperature viscosity and increases meltability. Moreover, among alkaline earth metal oxides, since the raw material to be introduced is relatively inexpensive, it is a component that reduces raw material costs.
- the content of CaO is preferably 0 to 5%, 0.01 to 1%, particularly 0.1 to 0.8%. If the content of CaO is too high, the glass tends to devitrify.
- BaO is a component that increases resistance to devitrification.
- the content of BaO is preferably 0 to 5%, 0.1 to 3%, particularly 0.5 to 1.5%. If the BaO content is too high, the glass will easily devitrify.
- Li 2 O, Na 2 O, and K 2 O are alkali metal oxide components that lower high-temperature viscosity, significantly increase meltability, and contribute to initial melting of the glass raw material.
- the content of Li 2 O+Na 2 O+K 2 O is preferably 1 to 15%, 2 to 10%, particularly 3 to 6%. If the content of Li 2 O + Na 2 O + K 2 O is too small, the meltability tends to decrease. On the other hand, if the content of Li 2 O+Na 2 O+K 2 O is too large, the coefficient of thermal expansion may become unduly high.
- Li 2 O is a component that lowers high-temperature viscosity, significantly increases meltability, and contributes to initial melting of the glass raw material.
- the content of Li 2 O is preferably 0 to 5%, 0 to 3%, particularly 0.1 to 1.2%. If the content of Li 2 O is too large, the glass tends to undergo phase separation.
- Na 2 O is a component that lowers high-temperature viscosity, significantly increases meltability, and contributes to initial melting of the glass raw material. It is also a component for adjusting the coefficient of thermal expansion.
- the content of Na 2 O is preferably 0 to 10%, 0 to 8%, 1 to 5%, particularly 1 to 3%. If the content of Na 2 O is too large, the coefficient of thermal expansion may become unduly high.
- K 2 O is a component that lowers high temperature viscosity, significantly increases meltability, and contributes to the initial melting of the glass raw material. It is also a component for adjusting the coefficient of thermal expansion.
- the content of K 2 O is preferably 0 to 10%, 0.1 to 5%, particularly 0.5 to 3%. If the content of K 2 O is too large, the coefficient of thermal expansion may become unduly high.
- TiO 2 is a component that reduces transmittance in the deep ultraviolet region.
- the content of TiO 2 is preferably 0.001% or less, 0.0008% or less, particularly 0.0001 to 0.0006%. If the content of TiO 2 is too large, the glass becomes colored and the transmittance in the deep ultraviolet region tends to decrease.
- Fe 2 O 3 is a component that reduces transmittance in the deep ultraviolet region.
- the content of Fe 2 O 3 is preferably 0.001% or less, 0.0001 to 0.0009%, particularly 0.00001 to 0.0008%. If the content of Fe 2 O 3 is too large, the glass becomes colored and the transmittance in the deep ultraviolet region tends to decrease.
- Fe ions in iron oxide exist in the state of Fe 2+ or Fe 3+ . If the proportion of Fe 2+ is too small, the transmittance in deep ultraviolet rays tends to decrease. Therefore, the mass ratio of Fe 2+ /(Fe 2+ +Fe 3+ ) in the iron oxide contained in the ultraviolet transmitting glass of the present invention is 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, especially It is preferable that it is 0.5 or more.
- F is a component that reduces Fe 3+ contained in the glass and improves the transmittance in the deep ultraviolet region. It is also a component that lowers viscosity and increases meltability.
- the content of F is preferably 0.5 to 7%, 0.6 to 5%, particularly 0.7 to 3%. If the F content is too low, it will be difficult to obtain the above effects. On the other hand, if the F content is too high, it becomes difficult to vitrify.
- SrO is a component that increases resistance to devitrification.
- the content of SrO is preferably 0 to 7%, 0 to 5%, 0 to 3%, particularly 0 to 1%. If the content of SrO is too large, the glass tends to devitrify.
- ZrO 2 is a component that improves acid resistance, but if it is included in a large amount in the glass composition, the glass tends to devitrify. Therefore, the content of ZrO 2 is preferably 0.1% or less, 0.001 to 0.02%, particularly 0.0001 to 0.01%.
- MoO 3 is a component that is contained as an impurity from within the furnace during production, but if it is contained in a large amount in the glass composition, there is a risk of reducing the transmittance in the deep ultraviolet region. Therefore, the content of MoO 3 is preferably 0.05% or less, 0.005 to 0.001%, particularly 0.0001 to 0.0005%.
- the shape of the ultraviolet transmitting glass of the present invention can be set arbitrarily.
- the shape of the ultraviolet transmitting glass of the present invention can be, for example, a flat plate, a curved plate, a straight tube, a curved tube, a rod, a sphere, a container, or a block.
- the thickness of the ultraviolet transmitting glass is preferably 0.2 to 2 mm, particularly 0.25 to 1.9 mm, and preferably has a tubular shape such as a straight tube shape or a curved tube shape. preferable.
- the ultraviolet transmittance decreases as the thickness of the glass increases, but since the ultraviolet transmitting glass of the present invention has high transmittance in the wavelength region of 250 nm or less, even if the thickness is increased compared to conventional products. High transmittance can be maintained in the same wavelength range.
- the surface roughness Ra of the surface of the ultraviolet transmitting glass of the present invention is preferably 10 nm or less, 9 nm or less, 8 nm or less, 7 nm or less, 6 nm or less, 5 nm or less, 4 nm or less, 3 nm or less, 2 nm or less, particularly 1 nm or less. . If the surface roughness Ra of the surface is too large, the transmittance in deep ultraviolet rays tends to decrease.
- the ultraviolet transmitting glass of the present invention can be produced, for example, by mixing various glass raw materials to obtain a glass batch, then melting this glass batch, clarifying and homogenizing the obtained molten glass, and molding it into a predetermined shape. It can be made with
- a reducing agent as part of the glass raw material.
- Fe 3+ contained in the glass is reduced and the transmittance of deep ultraviolet rays is improved.
- materials such as wood powder, carbon powder, metal aluminum, metal silicon, and aluminum fluoride can be used, and among these, metal silicon and aluminum fluoride are preferred.
- metal silicon as a part of the glass raw material, and the amount added is 0.001 to 3% by mass, 0.005% by mass based on the total mass of the glass batch. -2% by weight, preferably 0.01-1% by weight, particularly 0.05-0.75% by weight. If the amount of metal silicon added is too small, Fe 3+ contained in the glass will not be reduced, and the transmittance in deep ultraviolet rays will tend to decrease. On the other hand, if the amount of metal silicon added is too large, the glass tends to be colored brown.
- AlF 3 aluminum fluoride
- the amount added is 0.01 to 2% by mass in terms of F, 0.05% by mass based on the total mass of the glass batch. It is preferably from 1.5% by weight, particularly from 0.3 to 1.5% by weight. If the amount of aluminum fluoride added is too small, Fe 3+ contained in the glass will not be reduced, and the transmittance in deep ultraviolet rays will tend to decrease. On the other hand, if the amount of aluminum fluoride added is too large, there is a possibility that F gas will remain in the glass as bubbles.
- the method for producing ultraviolet-transparent glass of the present invention when forming the ultraviolet-transparent glass into a flat plate shape, it is preferable to use a down-draw method or an overflow down-draw method.
- molten glass overflows from both sides of a heat-resistant gutter-like structure, and the overflowing molten glass joins at the bottom end of the gutter-like structure, stretching downward to form a glass plate. This is the way to do it.
- the surface of the glass plate that is to become the surface does not come into contact with the trough-like refractories and is formed as a free surface.
- the structure and material of the gutter-like structure are not particularly limited as long as desired dimensions and surface accuracy can be achieved.
- the method of applying force when performing downward stretch molding is not particularly limited. For example, a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated while in contact with the glass, or a plurality of pairs of heat-resistant rolls are brought into contact only near the end surface of the glass. You may adopt the method of stretching.
- the method for producing ultraviolet-transparent glass of the present invention when forming the ultraviolet-transparent glass into a tubular shape, it is preferable to use a down-draw method, a bellows method, a Danner method, or the like.
- the Danner method is a method in which molten glass is rolled down and wound around the upper end of a heat-resistant sleeve-like structure arranged at an angle, and the molten glass that has flowed down to the lower end is stretched and formed to form a glass tube.
- a slot-down method for example, a slot-down method, a redraw method, a float method, etc. can also be adopted.
- the content of F in the surface layer of the glass tends to decrease in some cases.
- it is possible to increase the F content near the glass surface by immersing the glass in an acid solution and etching it to remove the surface layer where the F content has decreased.
- the acid used for the etching treatment nitric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid with a concentration of 3 to 50% by mass, or a mixed acid consisting of at least two of the above-mentioned acids with an acid concentration of 3 to 50% by mass, etc. can be used.
- the immersion time is preferably 1 minute or more, 3 minutes or more, particularly 5 minutes or more.
- the immersion time is too short, etching may be insufficient and the F content near the glass surface may not increase.
- the upper limit of the immersion time is not particularly limited, but realistically it is 20 minutes or less.
- the temperature of the acid is preferably 20°C or higher, 25°C or higher, particularly 30°C or higher. If the temperature of the acid is too low, etching may be insufficient and the F content near the glass surface may not increase.
- the upper limit of the temperature of the acid is not particularly limited, it is realistically 95°C or lower. Note that it is also possible to remove the surface layer portion where the F content has decreased by physical polishing or the like.
- Table 1 shows Examples (Samples No. 1 to 5) of the present invention and Comparative Examples (Sample No. 6).
- a glass batch prepared by mixing the glass raw materials shown in the table so as to have the glass composition shown in the table was placed in a platinum crucible and melted at 1600°C for 6 hours.
- the obtained molten glass was stirred using a platinum stirrer to homogenize it.
- the molten glass was poured onto a carbon plate, formed into a flat plate shape, and then slowly cooled from a temperature approximately 20°C higher than the annealing point to room temperature at a rate of 3°C/min, and then etched under the conditions shown in the table. I did it.
- Transmittance was measured for each sample obtained.
- the transmittance is a value obtained by measuring the spectral transmittance in the thickness direction using a double beam spectrophotometer (UV-3100PC manufactured by Shimadzu Corporation).
- UV-3100PC manufactured by Shimadzu Corporation
- samples having the thicknesses listed in Table 1 and polished on both sides to optically polished surfaces (mirror surfaces) were used.
- the surface roughness Ra of the surfaces of these measurement samples was measured by AFM, it was 0.5 to 1.0 nm in a measurement area of 10 ⁇ m ⁇ 10 ⁇ m.
- the F content x (mass %) at a depth of 15 ⁇ m from the glass surface, and the F content y (mass %) at a depth of 1 ⁇ m from the glass surface are It was measured by line analysis using a microanalyzer (EPMA-1720H manufactured by Shimadzu Corporation).
- sample No. with y/x of 0.81 or more had high transmittance for ultraviolet light with a wavelength of 200 to 250 nm.
- sample No. with a small y/x of 0.71 No. 6 had a low transmittance of ultraviolet light with a wavelength of 200 to 250 nm. It was also found that the larger y/x, the higher the transmittance of ultraviolet light with a wavelength of 200 to 250 nm.
- the molten glass was poured out and formed into a flat plate shape.
- it is formed into a flat plate shape using an overflow down-draw method, etc., with both surfaces unpolished. It is preferable to use it.
- it is preferable to shape
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
L'invention fournit un verre perméable aux ultraviolets dont la perméabilité aux ultraviolets est élevée dans une région d'ultraviolets profonds, tout particulièrement entre 200 et 250nm de longueur d'ondes. Le verre perméable aux ultraviolets de l'invention est caractéristique en ce que y/x est supérieur ou égal à 0,8, dans le cas où la teneur en F à une profondeur de 15μm depuis la surface du verre est représentée par x (en % en masse), et la teneur en F à une profondeur de 1μm depuis la surface du verre est représentée par y (en % en masse).
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JP2022-167700 | 2022-10-19 | ||
JP2022167700A JP2023168201A (ja) | 2022-05-13 | 2022-10-19 | 紫外線透過ガラス |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH07187706A (ja) * | 1993-10-15 | 1995-07-25 | Jenaer Glaswerk Gmbh | 改良された紫外線透過性及び加水分解安定性を有する還元溶融ホウケイ酸ガラス及びその利用法 |
JP2005247598A (ja) * | 2004-03-01 | 2005-09-15 | Hoya Corp | 精密プレス成形用プリフォームの製造方法および光学素子の製造方法 |
JP2009023898A (ja) * | 2007-06-20 | 2009-02-05 | Asahi Glass Co Ltd | 合成石英ガラス体、その製造方法、光学素子および光学装置 |
JP2013095619A (ja) * | 2011-10-28 | 2013-05-20 | Olympus Corp | ガラス製光学素子 |
JP2019099414A (ja) * | 2017-12-01 | 2019-06-24 | クアーズテック株式会社 | シリカガラス部材及びシリカガラス部材の製造方法 |
JP2019147722A (ja) * | 2018-02-28 | 2019-09-05 | 日本電気硝子株式会社 | 紫外線透過ガラス及びその製造方法 |
WO2021070707A1 (fr) * | 2019-10-07 | 2021-04-15 | 日本電気硝子株式会社 | Verre transmettant les ultraviolets |
-
2023
- 2023-04-25 WO PCT/JP2023/016202 patent/WO2023218938A1/fr unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH07187706A (ja) * | 1993-10-15 | 1995-07-25 | Jenaer Glaswerk Gmbh | 改良された紫外線透過性及び加水分解安定性を有する還元溶融ホウケイ酸ガラス及びその利用法 |
JP2005247598A (ja) * | 2004-03-01 | 2005-09-15 | Hoya Corp | 精密プレス成形用プリフォームの製造方法および光学素子の製造方法 |
JP2009023898A (ja) * | 2007-06-20 | 2009-02-05 | Asahi Glass Co Ltd | 合成石英ガラス体、その製造方法、光学素子および光学装置 |
JP2013095619A (ja) * | 2011-10-28 | 2013-05-20 | Olympus Corp | ガラス製光学素子 |
JP2019099414A (ja) * | 2017-12-01 | 2019-06-24 | クアーズテック株式会社 | シリカガラス部材及びシリカガラス部材の製造方法 |
JP2019147722A (ja) * | 2018-02-28 | 2019-09-05 | 日本電気硝子株式会社 | 紫外線透過ガラス及びその製造方法 |
WO2021070707A1 (fr) * | 2019-10-07 | 2021-04-15 | 日本電気硝子株式会社 | Verre transmettant les ultraviolets |
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