WO2008028341A1 - Verre flint dense du type non polluant à indice de réfraction élevé et dispersion élevée, et procédé et dispositif permettant sa préparation - Google Patents
Verre flint dense du type non polluant à indice de réfraction élevé et dispersion élevée, et procédé et dispositif permettant sa préparation Download PDFInfo
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- WO2008028341A1 WO2008028341A1 PCT/CN2006/002483 CN2006002483W WO2008028341A1 WO 2008028341 A1 WO2008028341 A1 WO 2008028341A1 CN 2006002483 W CN2006002483 W CN 2006002483W WO 2008028341 A1 WO2008028341 A1 WO 2008028341A1
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- Prior art keywords
- refractive index
- environmentally
- optical glass
- glass
- glass according
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- 239000006185 dispersion Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000007613 environmental effect Effects 0.000 title abstract description 3
- 239000005308 flint glass Substances 0.000 title abstract 2
- 239000011521 glass Substances 0.000 claims abstract description 62
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000005304 optical glass Substances 0.000 claims description 45
- 238000004519 manufacturing process Methods 0.000 claims description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- 238000002485 combustion reaction Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 12
- 239000003345 natural gas Substances 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000006060 molten glass Substances 0.000 claims description 8
- 230000033228 biological regulation Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 238000012937 correction Methods 0.000 claims 1
- 238000005194 fractionation Methods 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 11
- 238000002834 transmittance Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000000156 glass melt Substances 0.000 abstract 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000002893 slag Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012824 chemical production Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
Classifications
-
- 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
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/18—Stirring devices; Homogenisation
- C03B5/187—Stirring devices; Homogenisation with moving elements
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
Definitions
- the invention relates to an optical glass and a production method and equipment thereof, in particular to a high refractive index (Nd) high dispersion environmental protection heavy flint optical glass and a production method and equipment thereof.
- Nd refractive index
- the content of components such as Ti0 2 and Nb 2 0 5 in the glass component is correspondingly large, and these components cause the viscosity of the molten glass during the production process to be dilute, the crystallization is severe, and the constant fluctuation is large. Difficult to form, the quality of the glass stripe is not high, and the production is very difficult.
- optical glass manufacturers generally use a pool furnace to produce secondary materials.
- the production process is: After the prepared raw materials are thoroughly mixed, they are melted into glass slag of suitable particle size at a high temperature by a single crucible, and the glass slag is tested.
- the refractive index of the glass slag with acceptable refractive index is re-introduced into a high-temperature smelting furnace to form a molten glass, which is clarified and sufficiently homogenized to form a glass strip. Since the production method undergoes two high temperatures, the optical transmission performance of the glass is affected, and the number of steps is large, the production cycle is long, and the production cost is high.
- the technical problem to be solved by the present invention is to provide a high refractive index and high dispersion environmentally friendly heavy flint optical glass, which does not contain Pb0, As 2 0 3 and Gd0.
- the present invention also provides a method for producing the above optical glass.
- the method has a high optical temperature, a glass having good optical transmission performance, a small number of steps, and a short cycle.
- the present invention also provides a production apparatus for the above optical glass.
- the technical solution adopted by the invention to solve the technical problem is: high refractive index and high dispersion environment-friendly heavy flint optical glass, the weight percentage composition thereof is: Si0 2 : 20-44%, Ti0 2 : 22-34%, Nb 2 0 5 : 5 - 22%, ⁇ 3 ⁇ 40: 7-18°/. , BaO: 9-17°/. , K 2 0: 0 - 9%, CaO: 0-3%, Zr0 2 : 0-3%, SrO: 0-0. 5%, Sb 2 0 3 : 0-0. 5%.
- High refractive index high dispersion environmentally friendly heavy flint optical glass production method comprises the following steps: 1) thoroughly mixing the prepared raw materials to ensure uniformity thereof; 2) melting in a pool furnace at a high temperature of 1150-1300 ° C The glass liquid is made to make the refractive index consistency of the glass liquid good; 3) After the clarified and fully homogenized glass liquid is clarified and sufficiently homogenized, it is formed into a glass strip; 4) The glass strip is annealed in an annealing furnace.
- the production equipment of high refractive index and high dispersion environmentally-friendly heavy flint optical glass comprises a pool furnace and an annealing furnace, and the melting furnace of the pool furnace is connected with an automatic combustion control system.
- Vd (Abbe number) is 23.
- the optical glass of the present invention does not contain Pb0, As 2 0 ⁇ n GdO environmentally polluting components, the Nd is 1. 7-1.
- Vd (Abbe number) is 23. 5-28. 5, is a high refractive index and high dispersion environmentally friendly heavy flint optical glass.
- the invention adopts a pool furnace to produce optical glass in a single material manner, the production process is coherent and simple, the number of high-temperature melting times is reduced, the optical transmission performance can be improved under the condition of the same raw material quality, and the process is small and the production cycle is short. , reducing production costs.
- Figure 1 is a flow chart of a conventional secondary chemical production method.
- Fig. 2 is a flow chart showing the production mode of the primary chemical material of the present invention.
- Figure 3 is a schematic view of a frame stirrer.
- Figure 4 is a schematic view of a disc agitator. (Where: Fig. 4a is a front view of the disc agitator; Fig. 4b is a side view of the disc agitator; and Fig. 4c is a partial cross-sectional view of the disc agitator.)
- Figure 5 is a schematic view showing the configuration of a production apparatus of the present invention.
- the optical glass of the present invention contains 20-44% of the glass forming body Si0 2 . If the Si0 content is too high, the glass transmittance and the dispersion index cannot meet the requirements, and the melting temperature becomes high and is not easily melted; if Si0 2 If the content ratio is too low, the crystallization property and chemical stability are lowered, and the preferable SiO 2 content is 23-44%, and the particularly preferable SiO 2 content is 25 - 37%.
- the flux in the glass N3 ⁇ 40 + K 2 0 A total content of 7-27%, wherein the content of N is 7-18% 0, 2 0 content of 0-9%; preferred content of Na 2 0 10-16%, the content of K 2 0 is from 0 8%; particularly preferred ⁇ 0 content is 12-15%, ⁇ 20 content is 0-8%
- the ratio of the glass former Si0 2 and the fluxes Na 2 0 and ⁇ 20 is limited, and the preferred Si0 2 + Na
- the total content of 2 0+ 2 0 is 50%, and the total content of Si0 2 + Na 2 0+K 2 0 is particularly preferably 45%.
- the alkaline earth metal oxides Ba0, CaO and SrO can adjust the microstructure of the glass and improve the chemical stability of the glass.
- the preferred content of BaO+CaO+SrO is 10-20%, wherein the BaO content is 9-17%.
- the content of CaO is 0-3%, and the content of SrO is 0-0. 5%; the total content of Ba0+Ca0+Sr0 is particularly preferably 12-18°/. 5% ⁇
- the content of BaO is 12-16%, the content of CaO is 0-3%, and the content of SrO is 0-0. 5%.
- Ti0 2 can make the glass have a high refractive index, but if the content is too high, the dispersion coefficient will be greatly reduced and the crystallization tendency will be greatly increased; if the content is too small to achieve the required high refractive index, the Ti0 2 content is 22-34%, preferably 27-34%, particularly preferably 28-32%.
- Nb 2 0 5 can make the glass have a high refractive index, and replacing the Ti0 2 with an appropriate amount of Nb 2 0 5 can ensure that the glass has a high refractive index and at the same time reduce the tendency of crystallization, but an excessive Nb 2 0 5 content causes a refractive index,
- the dispersion coefficient cannot simultaneously meet the requirements, so the Nb 2 0 5 content is 5-22%, preferably 10-22%, particularly preferably 12-20%.
- Zr0 2 can make the glass have a high refractive index, and at the same time improve the chemical stability and swelling properties of the glass.
- the Zr0 2 part can be used instead of Ti0 2 to make the optical index meet the requirements, but the ⁇ ]:0 2 content will increase the crystallization. 5% ⁇
- the tendency to lower the refractive index, so Zr0 2 content is 0-3%, preferably 0-2%, particularly preferably 0-1. 5%.
- Sb 2 0 3 is a clarifying agent, which can reversibly absorb and release gas with other gases in different temperature zones of the glass melting stage, and accumulates a small gas into a larger gas, which is floated to the surface by buoyancy in the glass liquid to eliminate but excess Sb 2 0 3 content will affect the glass color and reduce the life of the platinum container, so Sb 2 0 3 content of 0-0. 5%, preferably 0-0. 3%, particularly preferably 0-0. 15%.
- Table 1 shows nine examples of the optical glass of the present invention.
- the optical glass of the present invention does not contain PbO, As 2 3 and GdO which are polluting to the environment, and the optical properties are: Nd is 1. 7-1. 85, Vd is 23. 5-28. 5.
- 1 is a flow chart of a conventional secondary chemical production mode, which comprises the following steps: batching; melting glass slag in a single crucible; testing constant and batching; qualified glass slag melting glass in pool furnace Liquid; clarification; homogenization; molding; annealing furnace annealing.
- the production method of the primary chemical material of the present invention is a flow chart of the production method of the primary chemical material of the present invention, and the specific steps of the production method are as follows: 1. The prepared raw materials are thoroughly mixed to ensure uniformity thereof.
- the glass furnace of the present invention is melted into a molten glass at a high temperature of 1,150 to 1,300 Torr to make the refractive index of the molten glass uniform.
- Fig. 4 is a schematic view of a disc agitator, the discs 2 being joined together by a shaft, and the bezel 3 is disposed on both sides of the outer edge of the disc 2 and is raised in a stair shape.
- the principle of the agitating of the disc-shaped agitator is to change the flow direction of the glass liquid through the disc 2, and the frame 3 is cut, and the width of the frame 3 is large.
- the viscosity of the glass is very small, the resistance to the rotating agitator is small, and the disc-shaped agitator having a relatively large frame width is relatively more resistant and has a high stirring ability, and can better stir the glass of the dilute viscosity.
- the glass liquid with acceptable refractive index is clarified and fully homogenized, and then formed into a glass strip.
- the glass strip is annealed in an annealing furnace.
- the advantage of the production method of the primary chemical material relative to the production method of the secondary chemical material is that the single-melting glass slag is eliminated, and the main purpose of this step is to ensure the refractive index consistency of the glass liquid.
- the key to the production method of using the primary furnace material is to take effective measures to ensure the uniformity of the raw materials from the preparation of raw materials to the melting process, and to increase the consistency of the refractive index of the molten glass by adding auxiliary devices in the molten glass.
- the technical indexes of the high refractive index and high dispersion environmentally-friendly heavy flint optical glass produced by the production method of the invention all reach the product technical index, and the optical transmission performance is better.
- the production method of the second material produced H-ZF 52A color, the standard lens in 0HARA upper limit of the present invention using the production process of the color produced H- ZF 52A, in the lens Lower limit of the standard value (+10 dish); H-ZF 7LA strip color and internal transmittance produced by the same raw material, using the secondary chemical production method, H-ZF 7 LA produced by the production method of the present invention
- the chromaticity and internal permeability are about 10 nm, which is the lower limit of the standard value (-10 nm).
- the production equipment of the present invention is shown in Fig. 5, including a pool furnace and an annealing furnace.
- the melting tank of the pool furnace is connected to an automatic combustion control system, wherein the connection relationship of the automatic combustion control system is accordingly: natural gas inlet, filter adjustment Pressure regulation automatic cut-off system, natural gas flow measurement control system, proportional adjustment system; combustion air inlet, pressure regulation automatic cut-off system, combustion air flow measurement control The system and the proportional adjustment system; wherein there is a temperature controller between the natural gas flow measurement control system and the melting pool of the pool furnace, the proportional adjustment system is connected to the burner of the melting pool.
- the working principle of the production equipment of the invention is: setting the ratio of natural gas and air on the proportional adjustment system to ensure the full combustion of the natural gas, and measuring the actual temperature value of the melting pool of the furnace by the temperature controller and setting The constant temperature value is compared, a control command is issued to the natural gas flow measurement control system to adjust the flow of the natural gas, and the signal of the natural gas flow change is transmitted to the combustion air flow measurement control system through the proportional adjustment system, and the combustion air flow measurement control system will assist combustion The air flow is adjusted to match the natural gas flow, so that the flow rate of the two reaches the set value, and finally the temperature is maintained at the set temperature to maintain the stability of the process.
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- Life Sciences & Earth Sciences (AREA)
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Description
高折射率高色散环保重火石光学玻璃及其生产方法和设备 所属技术领域
本发明涉及一种光学玻璃及其生产方法和设备,特别是涉及一种高折 射率 (Nd) 高色散环保重火石光学玻璃及其生产方法和设备。
背景技术
随着人们生活水平的提高, 为了满足高档数码产品高像数、小型轻便 的要求, 具有高折射率、 高色散(低阿贝数)、 密度小等优点的重火石光学 玻璃的需求越来越大, 但光学玻璃中含有的 Pb0、 As203和 GdO对环境造成 严重污染, 为此, 光学设备生产厂商要求具有相同光学特性的玻璃中不含 Pb0、 As203和 GdO成份。
为了使光学玻璃具有高折射率,玻璃组份中的 Ti02和 Nb205等成分的含 量相应也很大, 由于这些组份导致生产过程中玻璃液粘度稀、 析晶严重、 常数波动大和成型困难, 使玻璃条紋质量不高, 生产难度很大。
目前的光学玻璃生产厂家一般采用池炉以二次化料的方式生产, 生产 工艺过程是: 将配制好的原料经充分混合后用单坩埚在高温下熔化成粒度 合适的玻璃渣, 测试玻璃渣的折射率, 将折射率合格的玻璃渣再投入到高 温熔炼池炉中熔制成玻璃液, 经过澄清和充分均化后成型成玻璃条料。 由 于该生产方法经过两次高温, 影响了玻璃的光学透过性能, 而且工序较多、 生产周期长、 生产成本高。
发明内容
本发明所要解决的技术问题是提供一种高折射率高色散环保重火石光 学玻璃, 该光学玻璃组份中不含 Pb0、 As203和 Gd0。
本发明还要提供一种上述光学玻璃的生产方法, 该方法只经过一次高 温, 玻璃的光学透过性能好, 工序少, 周期短。
本发明还要提供一种上述光学玻璃的生产设备。
本发明解决技术问题所采用的技术方案是: 高折射率高色散环保重火 石光学玻璃,其重量百分比组成为: Si02 : 20-44%、 Ti02: 22-34%、 Nb205 : 5 - 22%、 Ν¾0: 7—18°/。、 BaO: 9-17°/。、 K20: 0 - 9%、 CaO : 0—3%、 Zr02: 0-3%,
SrO: 0-0. 5%、 Sb203: 0-0. 5%。
高折射率高色散环保重火石光学玻璃的生产方法, 该方法包括以下步 骤: 1 ) 将配制好的原料充分混合, 保证其均匀性; 2 ) 在 1150- 1300°C的 高温下用池炉熔化成玻璃液, 使玻璃液的折射率一致性良好; 3)将折射率 合格的玻璃液经过澄清和充分均化后, 成型为玻璃条料; 4)将玻璃条料在 退火炉中退火。
高折射率高色散环保重火石光学玻璃的生产设备,包括池炉和退火炉, 所述池炉的溶化池与自动燃烧控制系统相连。
本发明的有益效果是: 本发明的光学玻璃不含 Pb0、 As20^n GdO对环 境造成污染的组份, 其 Nd为 1. 7-1. 85、 Vd (阿贝数) 为 23. 5-28. 5, 是 高折射率高色散环保重火石光学玻璃。 本发明采用池炉以一次化料的方式 生产光学玻璃, 生产流程连贯、 简洁, 减少了高温熔制次数, 在原料质量 相同的条件下, 能提高光学透过性能, 而且工序少, 生产周期短, 降低了 生产成本。
附图说明
图 1是现有的二次化料生产方式的流程图。
图 2是本发明一次化料生产方式的流程图。
图 3是框式搅拌器示意图。
图 4是圆盘搅拌器示意图。 (其中: 图 4a是圆盘搅拌器的主视图; 图 4b是圆盘搅拌器的侧视图; 图 4c是圆盘搅拌器的局部剖视附视图。)
图 5 是本发明的生产设备配置示意图。
具体实施方式
本发明的光学玻璃中含有 20- 44%的玻璃形成体 Si02, 若 Si0 含量过 高, 则玻璃的^射率、 色散指标不能达到要求, 同时熔制温度变高, 不易 熔化; 若 Si02的含量比例过低, 则会降低结晶性能和化学稳定性, 优选的 Si02含量为 23-44%, 特别优选的 Si02含量为 25 - 37%。
除了玻璃形成体, 还需要一定比例的助熔剂用来降低熔制温度较高的 高折射率组份, 助熔剂的含量过高, 则影响玻璃的研磨性能、 化学稳定性; 助熔剂的含量过低, 则高折射率组份难熔。 因此玻璃中助熔剂 N¾0 +K20的
总含量为 7-27%, 其中 N 0的含量为 7-18%, 20的含量为 0-9%; 优选的 Na20 的含量为 10-16%, K20 的含量为 0-8%; 特别优选的 Ν 0 的含量为 12-15%, Κ20的含量为 0-8%
为了使玻璃的光学指标达到要求, 必须含有较高比例的高折射率的组 份, 因此玻璃形成体 Si02和助熔剂 Na20和 Κ20的比例就受到限制, 优选的 Si02+Na20+ 20的总含量 50%, 特别优选的 Si02 +Na20+K20的总含量 45%。
碱土金属氧化物 Ba0、 CaO和 SrO可以调整玻璃的微观结构, 改善玻璃 的化学稳定性, 优选的 BaO+CaO+SrO的总含量为 10-20%, 其中, BaO 的含 量为 9-17%, CaO的含量为 0-3%, SrO的含量为 0-0. 5%; 特别优选的 Ba0+ Ca0+Sr0的总含量为 12-18°/。, 其中 BaO的含量为 12-16%, CaO 的含量为 0-3% , SrO的含量为 0-0. 5%。
Ti02可以使玻璃具有高折射率, 但含量过高会大大降低色散系数并且 大大增加析晶倾向; 含量过小又无法达到要求的高折射率, 因此 Ti02含量 为 22-34%, 优选的 27-34%, 特别优选的 28-32%。
Nb205可以使玻璃具有高折射率,用适量的 Nb205替代 Ti02可以保证玻璃 具有高折射率, 同时减少析晶倾向, 但过多的 Nb205含量会使折射率、 色散 系数不能同时达到要求, 因此 Nb205含量为 5-22%, 优选 10-22%, 特别优选 12-20%。
Zr02可以使玻璃具有高折射率, 同时改善玻璃化学稳定性能、 膨胀性 能, 可以用 Zr02部分的替代 Ti02, 使光性指标达到要求, 但∑]:02含量过高 会增加析晶倾向、 降低折射率, 因此 Zr02含量为 0-3%, 优选 0-2%, 特别优 选 0-1. 5%。
Sb203是澄清剂, 在玻璃熔制阶段的不同温度区可与其它气体发生可逆 的吸收和放出气体, 将微小的气体积聚成较大气体, 在玻璃液中靠浮力上 浮到表面后消除, 但 Sb203含量过多会影响玻璃色度并降低铂金容器的使用 寿命, 因此 Sb203含量为 0-0. 5%, 优选 0-0. 3%, 特别优选 0-0. 15%。
表 1是本发明的光学玻璃的 9个实施例。
表 1
从表 1可以看出: 本发明的光学玻璃不含 PbO、 As203和 GdO对环境造 成污染的组份, 其光性指标为: Nd为 1. 7-1. 85、 Vd为 23. 5-28. 5。
图 1是现有的二次化料生产方式的流程图,该生产方法包括以下几步: 配料 ; 在单坩埚中熔制玻璃渣 ; 检验常数并组批; 合格玻渣在池炉熔制 玻璃液; 澄清; 均化; 成型 ; 退火炉退火。
图 2是本发明一次化料生产方式的流程图,该生产方法的具体步骤是- 一: 将配制好的原料充分混合, 保证其均匀性。
1 )采用快速水分测试仪, 加强原料尤其是易吸潮原料的水分监控, 符 合光学玻璃原料标准的才能使用, 不合格禁用; 2 )配料采用少量多次称量 方法, 每次秤量不大于 30千克玻璃的粉料; 称量设备使用高精度称量设备 (如电子秤), 精度为 0. 01kg; 3 ) 采用搅拌器混合均匀; 4) 为了防止原 料分层严重, 采用少量装箱, 每次装箱的玻璃粉料不超过 30千克; 5 ) 由 于是人工定时加料, 为减少运输、 存放过程的分层, 每次加料前再采用手 工搅拌。
二: 用本发明的池炉在 1150- 1300Ό的高温下熔化成玻璃液, 使玻璃液 的折射率一致性良好。
1 ) 增加熔化池的鼓泡器, 从 1只变为 2— 4只鼓泡器; 2 ) 采用自动燃
烧控制系统, 保持燃烧火焰的氧化气氛并自动调节温度, 保证熔化温度和 气氛符合工艺要求的稳定性; 3 )增加测试熔化池玻璃液的折射率次数, 每 4 小时一次, 必要时及时校正。 采用折射率不同的同系列玻璃牌号或原料 校正, 保证校正料不引入被校正玻璃中没有的成份; 4)用圆盘状搅拌器代 替框式搅拌器。 图 3是框式搅拌器示意图, 框式搅拌器的搅拌原理是依靠 边框 1来搅动和切割, 边框 1的宽度较小。 图 4是圆盘搅拌器示意图, 圆 盘 2通过轴连接在一起, 边框 3设置在圆盘 2的外边缘两侧, 并呈楼梯状 上升。 圆盘状搅拌器的搅拌原理是通过圆盘 2来改变玻璃液的流向, 边框 3来切割, 边框 3 的宽度较大。 因为玻璃粘度很小, 对转动的搅拌器阻力 很小, 相对来说边框宽度较大的圆盘状搅拌器受到的阻力大些, 搅拌能力 强, 能更好的对稀粘度玻璃进行搅拌。
三: 将折射率合格的玻璃液经过澄清和充分均化后, 成型为玻璃条料。 四: 将玻璃条料在退火炉中退火。
一次化料的生产方法相对于二次化料的生产方法的优点在于: 取消了 单坩埚熔制玻璃渣环节, 此环节的主要目的是保证玻璃液折射率一致性。 采用池炉一次化料的生产方法的关键是, 从配制原料到熔制环节采取有效 措施保证原料的均匀性, 并在熔制玻璃液环节增加辅助装置提高玻璃液折 射率的一致性。
采用本发明的生产方法生产出来的高折射率高色散环保重火石光学玻 璃的各项技术指标均达到产品技术指标, 而且光学透过性能更优。 用同样 的原料, 采用二次化料的生产方法生产的 H-ZF52A色度、 内透都在 0HARA 标准的上限,采用本发明的生产方法生产的 H- ZF52A色度、 内透都在标准值 的下限(+10皿);用同样的原料,采用二次化料的生产方法生产的 H-ZF7LA 条料色度、 内透比采用本发明的生产方法生产的 H-ZF7LA色度、 内透高约 10nm, 在标准值的下限 (-10 nm) 。
本发明的生产设备如图 5所示, 包括池炉和退火炉, 池炉的溶化池与 自动燃烧控制系统相连, 其中自动燃烧控制系统的连接关系依此为: 天燃 气进气口、 过滤调压稳压自动截止系统、 天燃气流量测量控制系统、 比例 调节系统; 助燃风进气口、 调压稳压自动截止系统、 助燃风流量测量控制
系统、 比例调节系统; 其中天燃气流量测量控制系统与池炉的熔化池之间 还有温控仪, 所述比例调节系统与溶化池的烧咀相连。
本发明的生产设备工作时的工作原理是: 在比例调节系统上设定好天 燃气和空气的比例来保证天燃气的充分燃烧, 温控仪测量池炉的熔化池的 实际温度值并与设定温度值对比, 发出控制指令到天燃气流量测量控制系 统来调节天燃气的流量, 同时天燃气流量变化的信号通过比例调节系统传 输到助燃风流量测量控制系统, 助燃风流量测量控制系统将助燃风流量调 节到与天燃气流量相匹配, 使二者流量达到设定值, 最终使温度保持在设 定温度, 维持工艺的稳定。
Claims
1、 高折射率高色散环保重火石光学玻璃, 其特征在于: 其重量百分比 组成为: Si02: 20-44%、 Ti02 : 22-34%、 Nb205 : 5-22%、 Na20: 7-18%、 BaO: 9-17%、 K20: 0-9%、 CaO : 0-3%、 Zr02: 0-3%、 SrO: 0-0. 5%和 Sb203: 0-0. 5%。
2、如权利要求 1所述的高折射率高色散环保重火石光学玻璃, 其特征 在于: Si02 、 Na20和 K20的重量百分比之和 50%, Ba0、 CaO和 SrO的重 量百分比之和为 10-20%。
3、如权利要求 1所述的高折射率高色散环保重火石光学玻璃, 其特征 在于: 其重量百分比组成为: Si02: 23 - 44%、 Ti02 : 27-34%、 Nb205: 10-22%、 Na20: 10-16%、 BaO: 12-16%、 K20: 0-8%; CaO : 0-3% 、 Zr02: 0-2%、 SrO: 0-0. 5%和 Sb203: 0-0. 3%。
4、如权利要求 1所述的高折射率高色散环保重火石光学玻璃, 其特征 在于: 其重量百分比组成为: Si02: 25-37%、 Ti02、 28-32%、 Nb205: 12-20%、 Na20: 12-15%、 BaO: 12-16%、 K20: 0-8%、 CaO : 0-3% 、 Zr02: 0-1. 5%、 SrO: 0-0. 5%和 Sb203: 0-0. 15%。
5、如权利要求 4所述的高折射率高色散环保重火石光学玻璃, 其特征 在于: 所述 Si02 、 Na20和 K20的重量百分比之和 45%, 所述 Ba0、 CaO 和 SrO的重量百分比之和为 12-18%。
6、 权利要求 1 所述的高折射率高色散环保重火石光学玻璃的生产方 法, 其特征在于: 该方法包括以下步骤: 1 )将配制好的原料 分混合, 保 证其均匀性; 2)在 1150-1300°C的高温下用池炉熔化成玻璃液, 使玻璃液 的折射率一致性良好; 3)将折射率合格的玻璃液经过澄清和充分均化后, 成型为玻璃条料; 4) 将玻璃条料在退火炉中退火。
7、如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产方 法, 其特征在于: 步骤 1所述充分混合是: 配料采用少量多次称量方法。
8、如权利要求 7所述的高折射率高色散环保重火石光学玻璃的生产方 法, 其特征在于: 所述少量多次称量方法是: 每次秤量不大于 30千克玻璃 的粉料, 称量设备使用高精度称量设备。
9、如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产方 法, 其特征在于: 步骤 1所述充分混合是: 采用搅拌器混合均匀。
10、 如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产 方法, 其特征在于: 步骤 1所述充分混合是: 采用少量装箱。
11、如权利要求 10所述的高折射率高色散环保重火石光学玻璃的生产 方法,其特征在于:所述少量装箱是:每次装箱的玻璃粉料不超过 30千克。
12、 如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产 方法, 其特征在于: 步骤 1所述充分混合是: 每次加料前采用手工搅拌。
13、 如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产 方法, 其特征在于: 进行所述步骤 1时, 采用快速水分测试仪对光学玻璃 原料进行水分监控, 符合光学玻璃原料标准的才能使用, 不合格禁用。
14、 如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产 方法, 其特征在于: 步骤 2所述池炉的鼓泡器为 2— 4只。
15、 如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产 方法, 其特征在于: 步骤 2所述池炉采用自动燃烧控制系统, 保持燃烧火 焰的氧化气氛并自动调节温度, 保证熔化温度和气氛符合工艺要求的稳定 性。
16、 如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产 方法, 其特征在于: 步骤 2所述使玻璃液的折射率一致性良好是: 每 4小 时测试一次熔化池玻璃液的折射率, 及时校正。
17、如权利要求 16所述的高折射率高色散环保重火石光学玻璃的生产 方法, 其特征在于: 所述校正采用折射率不同的同系列玻璃牌号或原料校 正。
18、 如权利要求 6所述的高折射率高色散环保重火石光学玻璃的生产 方法, 其特征在于: 步骤 2所述池炉采用圆盘状搅拌器。
19、 权利要求 1所述的高折射率高色散环保重火石光学玻璃的生产设 备, 包括池炉和退火炉, 其特征在于: 所述池炉的溶化池与自动燃烧控制 系统相连。
20、如权利要求 19所述的高折率高色散环保重火石光学玻璃的生产设
备, 其特征在于: 所述自动燃烧控制系统的连接关系依此为: 天燃气进气 口、 过滤调压稳压自动截止系统、 天燃气流量测量控制系统、 比例调节系 统; 助燃风进气口、 调压、 稳压、 自动截止系统、 助燃风流量测量控制系 统、 比例调节系统; 其中助燃风流量测量控制系统与池炉的熔化池之间还 有温控仪; 所述比例调节系统与溶化池的烧咀相连。
21、如权利要求 19所述的高折射率高色散环保重火石光学玻璃的生产 设备, 其特征在于: 所述池炉釆用 2— 4只鼓泡器。
22、如权利要求 19所述的高折射高色散环保重火石光学玻璃的生产设 备, 其特征在于: 所述池炉采用圆盘状搅拌器, 圆盘(2)通过轴连接在一 起, 边框 (3) 设置在圆盘 (2) 的外边缘两侧。
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JP4074568B2 (ja) * | 2003-08-19 | 2008-04-09 | Hoya株式会社 | 光学ガラスの製造方法 |
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JP5044573B2 (ja) | 2012-10-10 |
CN1915875B (zh) | 2010-08-18 |
JP2009527442A (ja) | 2009-07-30 |
CN1915875A (zh) | 2007-02-21 |
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