WO2021135882A1 - 一种微光学玻璃器件的制备方法 - Google Patents

一种微光学玻璃器件的制备方法 Download PDF

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WO2021135882A1
WO2021135882A1 PCT/CN2020/135096 CN2020135096W WO2021135882A1 WO 2021135882 A1 WO2021135882 A1 WO 2021135882A1 CN 2020135096 W CN2020135096 W CN 2020135096W WO 2021135882 A1 WO2021135882 A1 WO 2021135882A1
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micro
optical glass
silica
glass device
sol
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PCT/CN2020/135096
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English (en)
French (fr)
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刘莹莹
李乾
陈雨叁
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深圳市绎立锐光科技开发有限公司
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Priority to EP20909100.8A priority Critical patent/EP3995460A4/en
Priority to JP2022502226A priority patent/JP2023507698A/ja
Publication of WO2021135882A1 publication Critical patent/WO2021135882A1/zh

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    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
    • 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
    • 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
    • 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
    • C03C2203/20—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
    • C03C2203/50—After-treatment
    • C03C2203/52—Heat-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the invention relates to the technical field of glass preparation, in particular to a method for preparing a micro-optical glass device.
  • micro-optical devices such as microlens arrays
  • the method of processing microstructures such as grinding
  • the sol-gel method is relatively More economical preparation method.
  • the traditional sol-gel process with high solid content and low shrinkage rate is suitable for the preparation of large-sized glass devices. Due to the influence of the mold processing size, it is impossible to directly produce micron-level fine optical structures. For this reason, in patent CN1761626A, a method for preparing fine glass structure by multiple transfer printing is proposed. A large-size aluminum alloy mold is precisely processed by a high-precision diamond lathe, and then the antisymmetric structure is copied by silicon rubber embossing.
  • the present invention provides a low-cost, simple process for the preparation of micro-optical glass devices, including the following steps: Step 1: Obtain a silica dispersion, and add an acid solution Add the silica dispersion to adjust the pH of the silica dispersion and stir; Step 2: Add tetraethylorthosilicate to the silica dispersion and stir to obtain a sol.
  • Alkaline solution is added to the sol to adjust the pH value of the sol, stirring and standing; Step 3: Injecting the standing sol into a mold and aging to obtain a wet gel; Step 4: Adding the sol The wet gel is demolded, cleaned, and dried to obtain a dry gel; step 5: sintering the dry gel to obtain a micro-optical glass device; wherein the solid content of silica in the raw material is not more than 25.5%.
  • the solid content of silica in the raw material is not more than 25%.
  • the solid content of silica in the raw material is not more than 20.3%.
  • the step one includes: obtaining a silica dispersion stock solution with a preset molar volume, and mixing the silica dispersion stock solution with deionized water to obtain the silica dispersion
  • the deionized water is used to adjust the solid content of the silica.
  • the molar ratio of silica contained in the silica dispersion to the ethyl orthosilicate is 2.8 to 4.7.
  • the molar ratio of the silica contained in the silica dispersion liquid to the ethyl orthosilicate is 3.8 to 4.7.
  • the acidic solution is a hydrochloric acid solution
  • the silica dispersion has a pH value of 1.3 to 2.8 after adjusting the pH value.
  • the alkaline solution is an aqueous ammonia solution
  • the pH of the sol is 2.5-5 after the pH is adjusted.
  • the mold is a silicone mold.
  • the sintering temperature is not higher than 1100°C.
  • the present invention includes the following beneficial effects: by using a low silica solid content raw material to prepare a micro-optical glass device by a sol-gel method, the preparation of glass with a large shrinkage rate is realized, and the belt
  • the glass device with surface micro-optical structure avoids the way of multiple transfers with low shrinkage, which greatly reduces the cost and simplifies the process.
  • Figure 1 is a schematic flow chart of the method for preparing the micro-optical glass device of the present invention.
  • the main inventive concept is to control the raw materials for preparing glass devices by the sol-gel method.
  • the solid content of silica is controlled at the same time, so that the solid content of the raw materials is relatively high.
  • the low value realizes the large shrinkage rate of sol-gel preparation and breaks through the limitation of sol-gel preparation under high solid content in the past. Further, by controlling the ratio of the two silica sources, the yield problem of the preparation under low solid content is solved.
  • the solid content in the present invention refers to the mass percentage of silicon dioxide in the raw materials (including silicon dioxide after the hydrolysis of ethyl orthosilicate) in the total raw materials.
  • Figure 1 is a schematic flow chart of the method for preparing the micro-optical glass device of the present invention, including: step one, obtaining a silica dispersion, and adjusting the pH; step two, preparing a sol; step three, preparing a wet gel ; Step four, preparing dry gel; step five, sintering, to obtain micro-optical glass devices. Each step is described in detail below.
  • This step includes obtaining a silica dispersion liquid, adding an acidic solution to the silica dispersion liquid to adjust the pH value of the silica dispersion liquid, and stirring, and finally obtain a silica dispersion liquid with a preset pH value as the second A source of silica.
  • the initial silica dispersion (that is, the pH value is not adjusted) can be obtained by mixing and stirring fumed silica and deionized water, and dispersing by magnetic stirring, homogenizer and/or ultrasonic, so that the gas phase Silica is evenly dispersed in water. Then, the silica dispersion is filtered to remove impurities and undispersed agglomerated particles.
  • the fumed silica in the present invention selects a particle size with a D50 in the range of 20 nm to 150 nm, and has a larger specific surface area.
  • a large amount of silica dispersion stock solution with a preset molar volume is prepared in advance, and a certain amount of silica dispersion stock solution is obtained during each production, and mixed and diluted with deionized water.
  • deionized water is used to adjust the solid content of silica, so as to obtain the silica dispersion of the production batch.
  • the acidic solution is added to the silica dispersion and stirred uniformly.
  • the acidic solution can be, for example, a dilute hydrochloric acid solution, so that the silica dispersion is adjusted to a pH value of 1.3-2.8. It can be understood that the acidic solution may also be other acidic solutions for adjusting the pH value.
  • ethyl orthosilicate is added to the silica dispersion and stirred, and the ethyl orthosilicate is hydrolyzed to obtain a sol, and an alkaline solution is further added to the sol to adjust the sol The pH value, stir and let stand.
  • the sol begins to gradually form a gel. The process should not be too long, and it only needs to stand for a short time to expel the bubbles in the stirring process.
  • the alkaline solution may be an aqueous ammonia solution. After the pH value of the sol is adjusted, the pH value increases, and finally is 2.5-5. It can be understood that the alkaline solution may also be other alkaline solutions for adjusting the pH value.
  • the static sol is poured into a mold and aged to obtain a wet gel.
  • the mold can be of various shapes and sizes as required, so that glass optical devices of various shapes and sizes can be obtained.
  • the wet gel has a certain strength and can be demolded from the mold.
  • the present invention preferably adopts a silicone mold to peel off the wet gel within a certain deformation range of the silicone mold. If a rigid mold is used, on the one hand, it may damage the fine optical surface structure, causing burrs and cracks, and on the other hand, it is not easy to remove the wet gel.
  • the wet gel is demolded, washed and dried to obtain a dry gel.
  • the temperature should not be too high, otherwise it may cause excessive dehydration and cause the sample to crack.
  • the dry gel is sintered to obtain a micro-optical glass device.
  • the sample gets a second volume shrinkage, and changes from opaque to transparent glass device.
  • sintering needs to be performed at a temperature above 1200°C.
  • the inventor found that sintering at high temperatures will damage the edges and surfaces of optical glass devices, causing them to slightly deform or even deform. Cracked.
  • traditional larger-sized optical glass devices such as millimeter-level optical devices
  • such surface defects have little effect, but in micro-optical glass devices, this will seriously affect the optical performance of the device.
  • the inventor found that by reducing the solid content of silica in the raw material, an optical device with high transparency can be obtained even if the sintering temperature is lowered.
  • the sintering temperature is not higher than 1100°C, which not only protects the micro-optical structure of the glass surface from cracking, but also reduces the risk of internal crystallization and decreased transparency at low solid content, and improves the product yield. .
  • the reduction of sintering temperature can also reduce energy consumption and production costs.
  • Second, weigh the fumed silica particles and deionized water, mix and stir, use a homogenizer to disperse evenly; add dilute hydrochloric acid, adjust pH 2, after stirring, add ethyl orthosilicate, stir to form a sol solution, and then add ammonia Adjust the pH of the sol to 4, stir and put it aside, pour it into a mold with a microstructure, it will gel after 10 hours, and demold after 48 hours.
  • the ratio is the substance of silica (SiO 2) contained in the fumed silica particles or silica dispersion stock solution
  • the shrinkage rate is the volume shrinkage rate of the sintered glass device relative to the gel after demolding, which can be measured by the Archimedes method
  • yield rate Refers to defective products with cracks, scratches, dirt, bubbles, and extremely low transmittance.
  • the solid content has a significant effect on the shrinkage rate.
  • the solid content of silica in the raw material is not more than 25.5%.
  • the solid content of silica in the raw material is not more than 25%.
  • the solid content of silica in the raw material is not more than 20.3%, so that the shrinkage rate can reach more than 89%.
  • the ratio of the two different silica sources has a huge impact on the yield of the product and the production time.
  • n SiO2 /n TEOS 3.8
  • the solid content has little effect on the yield of the product, all around 60%, which only has a significant impact on the shrinkage rate. Therefore, determining the ratio of the two silica sources is of great significance to the actual mass production of products.
  • Ethyl orthosilicate contributes to the gel process. If only silica dispersion is used as the silica source, the gel formation process is extremely slow and cannot be used in mass production of products. The amount of ethyl orthosilicate, the required gel time is gradually shortened. According to the inventor's research, the molar ratio n SiO 2 /n TEOS of silicon dioxide to ethyl orthosilicate contained in the silicon dioxide dispersion liquid is below 4.7, which can meet mass production requirements.
  • the solution that does not require a 100% yield rate is adopted.
  • the yield rate and production time need to be considered comprehensively.
  • a higher yield rate often represents a longer gel time, as long as the number of good products per unit time is higher. That's it.
  • the molar ratio of silica to tetraethylorthosilicate contained in the silica dispersion is 2.8 to 4.7.
  • the molar ratio of silicon dioxide to ethyl orthosilicate contained in the silicon dioxide dispersion is 3.8 to 4.7 to ensure a yield rate of more than 60%.

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

一种低成本、工艺简单的微光学玻璃器件的制备方法，包括：步骤一：获取二氧化硅分散液，将酸性溶液加入二氧化硅分散液，以调节二氧化硅分散液的pH值，并搅拌；步骤二：将正硅酸乙酯加入二氧化硅分散液，并搅拌，得到溶胶，将碱性溶液加入溶胶，以调节溶胶的pH值，搅拌并静置；步骤三：将静置后的溶胶注入模具，陈化，得到湿凝胶；步骤四：将湿凝胶脱模，清洗、干燥，得到干凝胶；步骤五：将干凝胶烧结，得到微光学玻璃器件；其中，原料中的二氧化硅固含量不大于25.5％。通过采用低二氧化硅固含量的原料以溶胶凝胶法制备微光学玻璃器件，实现了大收缩率，可以一次性制得带有表面微光学结构的玻璃器件，降低了成本和简化了工艺。

Description

一种微光学玻璃器件的制备方法 技术领域
本发明涉及玻璃制备技术领域，特别涉及一种微光学玻璃器件的制备方法。
背景技术
近年来，随着投影领域的光学设计技术的飞速发展，大而笨重的投影机逐渐为结构精巧、体积小的便携投影机所取代，而且投影技术有着进一步向智能终端如手机、智能眼镜迁移的趋势。伴随而来的是，光机体积的减小及光斑尺寸的减小对光束精细化整形和调制提出了越来越高的要求。而且，随着高亮度激光光源的普及，在满足上述精细化光整形调制的条件下，光学元件也要承受越来越高的热能，从而对耐热性也有了更高的要求，树脂类光学器件已不能满足当前的光机设计，玻璃光学器件已经成为必选项。
当制备微光学器件(如微透镜阵列)时，在整块玻璃上进行微结构加工(如打磨)的方法，设备成本高且工艺难度大，不利于大规模生产，而溶胶凝胶法是相对较为经济的制备方法。传统的高固含量、低收缩率方案的溶胶凝胶工艺适合制备大尺寸的玻璃器件，受模具加工尺寸的影响，无法直接制得微米级的精细光学结构。为此，在专利CN1761626A中提出了一种多次转印制备精细玻璃结构的方法，通过高精密的金刚石车床精密加工一个较大尺寸的铝合金模具，再采用硅橡胶压印复制反对称结构，注入溶胶到该硅橡胶模具中成型，烧结成型的玻璃品(与铝合金模具相比体积收缩一定倍数)，再作为模具，压印硅橡胶的形成反对称结构的硅橡胶模具，如此类推，经过多次转印，从而实现微米级的精细玻璃结构。然而，该技术方案耗费的材料成本、时间成本过于巨大，对于薄利多销的消费级微型投影系统难以承受。因此，一种更为经济的微光学玻璃器件的制备方法亟待开发。
发明内容
针对上述现有技术的高成本、工艺复杂的缺陷，本发明提供一种低成本、工艺简单的微光学玻璃器件的制备方法，包括以下步骤：步骤一：获取二氧化硅分散液，将酸性溶液加入所述二氧化硅分散液，以调节所述二氧化硅分散液的pH值，并搅拌；步骤二：将正硅酸乙酯加入所述二氧化硅分散液，并搅拌，得到溶胶，将碱性溶液加入所述溶胶，以调节所述溶胶的pH值，搅拌并静置；步骤三：将静置后的所述溶胶注入模具，陈化，得到湿凝胶；步骤四：将所述湿凝胶脱模，清洗、干燥，得到干凝胶；步骤五：将所述干凝胶烧结，得到微光学玻璃器件；其中，原料中的二氧化硅固含量不大于25.5％。
在一个实施方式中，原料中的二氧化硅固含量不大于25％。
在一个实施方式中，原料中的二氧化硅固含量不大于20.3％。
在一个实施方式中，在所述步骤一中，包括：获取预设摩尔体积的二氧化硅分散液原液，将所述二氧化硅分散液原液与去离子水混合，得到所述二氧化硅分散液，所述去离子水用于调节所述二氧化硅固含量。
在一个实施方式中，在所述原料中，所述二氧化硅分散液所含的二氧化硅与所述正硅酸乙酯的摩尔比为2.8～4.7。
在一个实施方式中，所述二氧化硅分散液所含的二氧化硅与所述正硅酸乙酯的摩尔比为3.8～4.7。
在一个实施方式中，在所述步骤一中，所述酸性溶液为盐酸溶液，所述二氧化硅分散液经调节pH值后的pH值为1.3～2.8。
在一个实施方式中，在所述步骤二中，所述碱性溶液为氨水溶液，所述溶胶经调节pH值后的pH值为2.5～5。
在一个实施方式中，所述模具为硅胶模具。
在一个实施方式中，在所述步骤五中，烧结温度不高于1100℃。
与现有技术相比，本发明包括如下有益效果：通过采用低二氧化硅固含量的原料以溶胶凝胶法制备微光学玻璃器件，实现了大收缩率的玻璃制备，可以一次性制得带有表面微光学结构的玻璃器件，避免了低收缩率多次转印的方式，大大降低了成本和简化了工艺。
附图说明
图1为本发明的微光学玻璃器件的制备方法的流程示意图。
具体实施方式
下面结合附图和实施方式对本发明实施例进行详细说明。
在本发明中，主要的发明构思在于对溶胶凝胶法制备玻璃器件的原料控制，通过采用两种二氧化硅源结合的方式，同时控制二氧化硅的固含量，使得原料的固含量处于较低的数值，从而实现了溶胶凝胶制备的大收缩率，突破了以往高固含量下溶胶凝胶制备的限制。进一步地，通过对两种二氧化硅源的比例的控制，解决了低固含量下的制备的良率问题。
本发明所述的固含量，是指原料中的二氧化硅(包括正硅酸乙酯水解后的二氧化硅)占全部原料的质量百分比。
请参见图1，为本发明的微光学玻璃器件的制备方法的流程示意图，包括：步骤一，获取二氧化硅分散液，并调节pH值；步骤二，制备溶胶；步骤三，制备湿凝胶；步骤四，制备干凝胶；步骤五，烧结，得到微光学玻璃器件。下面对各个步骤进行详细描述。
<步骤一>
本步骤包括，获取二氧化硅分散液，将酸性溶液加入二氧化硅分散液，以调节二氧化硅分散液的pH值，并搅拌，最终得到预设pH值的二氧化硅分散液，作为第一二氧化硅源。
在本发明中，初始的二氧化硅分散液(即未调节pH值的)可以通过将气相二氧化硅与去离子水混合搅拌获得，通过磁力搅拌、均质机和/或超声分散，使得气相二氧化硅在水中分散均匀。而后，还要将二氧化硅分散液进行过滤，去除杂质和未被分散的团聚颗粒。
本发明中的气相二氧化硅选择D50在20nm～150nm范围内的粒径尺寸，具有较大的比表面积。
通常，要保证二氧化硅分散液的均匀性，需要较长时间的上述处理 过程，导致每次生产的时间较长。因此，在本发明的一个实施方式中，事先大量配置预设摩尔体积的二氧化硅分散液原液，每次生产时并获取一定量的二氧化硅分散液原液，将其与去离子水混合稀释，其中，去离子水用于调节二氧化硅固含量，从而得到该生产批次的二氧化硅分散液。该技术方案使得对二氧化硅固含量的调节变得简单，而且减少了混合均匀所需的时间，不必每次过滤除杂，提高了生产效率，提高了不同批次生产中的原料稳定性。
将酸性溶液加入二氧化硅分散液搅拌均匀，酸性溶液可以例如是稀盐酸溶液，使得二氧化硅分散液经调节pH值后为1.3～2.8。可以理解，酸性溶液也可以是其他用于调节pH值的酸性溶液。
<步骤二>
获得酸性的二氧化硅分散液后，将正硅酸乙酯加入到该二氧化硅分散液中，并搅拌，正硅酸乙酯水解，得到溶胶，进一步将碱性溶液加入溶胶，以调节溶胶的pH值，搅拌并静置。在静置过程中，溶胶开始逐渐形成凝胶，该过程不宜过长，只需短时间静置以排出搅拌过程中的气泡即可。
在本发明的实施方式中，碱性溶液可以为氨水溶液，溶胶经调节pH值后，pH值上升，最终为2.5～5。可以理解，碱性溶液也可以是其他用于调节pH值的碱性溶液。
<步骤三>
将静置后的溶胶注入模具，陈化，得到湿凝胶。
在该步骤中，模具根据需要可以是各种形状、各种尺寸，从而可以得到各种形状、尺寸的玻璃光学器件。经陈化后，湿凝胶具有一定强度，可以从模具中脱模，为了便于脱模，本发明优选地采用硅胶模具，可以在硅胶模具一定的形变范围内将湿凝胶剥离出来。如果采用刚性模具，一方面可能损坏精细的光学表面结构，造成毛刺、裂痕，另一方面不易将湿凝胶脱出。
<步骤四>
将湿凝胶脱模，清洗、干燥，得到干凝胶。
脱模后，得到带有转印精细结构的湿凝胶块。将该湿凝胶块可能存 在一定的不均匀杂质，对其进行清洗，除去表面杂质，有利于得到透明度更高的产品。
在对湿凝胶块进行干燥时，温度不宜过高，否则可能导致脱水过于激烈而导致样品开裂。
干燥后，得到相对于湿凝胶块体积缩小的干凝胶块。该步骤是制备微光学玻璃器件过程中体积收缩的主要部分。
<步骤五>
将干凝胶烧结，得到微光学玻璃器件。该步骤中，样品得到第二次体积收缩，并由不透明转为透明玻璃器件。
通常地，在现有技术的溶胶凝胶法制备光学玻璃的技术方案中，烧结需要在1200℃以上进行，发明人发现，高温下烧结会损坏光学玻璃器件的边缘、表面，使其轻微变形甚至开裂。在传统的较大尺寸的光学玻璃器件中(如毫米级光学器件)，这类表面缺陷影响不大，但是在微光学玻璃器件中，这会严重影响器件的光学性能。在本发明中，发明人发现，通过降低原料中二氧化硅的固含量，即使降低烧结温度也可以获得透明度高的光学器件。在本发明的优选实施方式中，烧结温度不高于1100℃，不但保护了玻璃表面的微光学结构不开裂，还能够降低低固含量下内部晶化、透明度下降的风险，提升了产品良率。此外，烧结温度的降低还能够降低能耗和生产成本呢。
以上，对制备步骤进行了详细说明，下面请参考具体实施例，为便于对各技术方案效果进行对比，选择相同实验条件下的不同固含量、二氧化硅源比例进行对比分析。
实施例
首先称取气相二氧化硅颗粒和去离子水，混合搅拌，使用均质机分散均匀；加入稀盐酸，调节pH＝2，搅拌后，加入正硅酸乙酯，搅拌形成溶胶溶液，接着加入氨水调节溶胶pH＝4，搅拌后静置，注入带有微结构模具中，10h后已凝胶，48h后脱模。
将上述带有微结构的湿凝胶放入纯去离子水中，进行循环水洗，水洗后放入温度为45℃恒温恒湿箱中进行干燥，样品干燥后经过1050℃保温12h烧结得到具有微结构的光学元件。
各实施例、对比例的数据表见下图，其中，固含量的解释参见上文说明；比例是气相二氧化硅颗粒或二氧化硅分散液原液中含有的二氧化硅(SiO 2)的物质的量与正硅酸乙酯(TEOS)的物质的量的比；收缩率为烧结后的玻璃器件相对于脱模后的凝胶的体积收缩率，可通过阿基米德法测量；良率是指开裂、划痕、脏污、气泡以及透过率极低的情况为不良品。
固含量 比例(n SiO2/n TEOS) 收缩率 良率
35.0％ 5.0 73.43％ 100％
25.5％ 3.8 86.80％ 60％
25.3％ 4.7 86.88％ 100％
25.3％ 4.1 86.88％ 90％
25.0％ 3.8 87.50％ 60％
24.3％ 4.1 88.03％ 89％
20.3％ 3.8 89.10％ 60％
15.3％ 2.8 90.30％ 40％
根据列表数据可以看出，固含量对收缩率的影响显著，想要获得尽可能精细尺寸的光学玻璃器件，需要降低原料中二氧化硅的固含量。在本发明中，原料中的二氧化硅固含量不大于25.5％。优选地，原料中的二氧化硅固含量不大于25％。进一步优选地，原料中的二氧化硅固含量不大于20.3％，以使得收缩率能够达到89％以上。
发明人发现，在本发明中，两种不同的二氧化硅源的比例，对产品的良率以及生产时间具有巨大影响。在同样的比例下，例如n SiO2/n TEOS＝3.8，固含量对产品的良率影响不大，都在60％左右，只对收缩率产生明显影响。因此，确定两种二氧化硅源的比例，对实际产品量产意义重要。
正硅酸乙酯(TEOS)有助于凝胶过程，如果仅采用二氧化硅分散液作为二氧化硅源，其形成凝胶的过程极其缓慢，不能够应用于产品量产中，随着增加正硅酸乙酯的量，所需的凝胶时间逐渐缩短。经发明人研究，二氧化硅分散液所含的二氧化硅与正硅酸乙酯的摩尔比n SiO2/n TEOS在4.7以下时可满足量产要求。
然而过多的正硅酸乙酯可能导致凝胶收缩时开裂。从表中数据看出，随着n SiO2/n TEOS的减小，良率逐渐降低，当n SiO2/n TEOS达到低至2.8时，良率已降低至40％，再小的比值的经济价值不大。
在本发明中，并非要求良率100％的方案才被采纳，需要综合考虑良率和生产时间，较高的良率往往代表更长的凝胶时间，只要在单位时间内的良品数量较高即可。
因此，在本发明中，二氧化硅分散液所含的二氧化硅与正硅酸乙酯的摩尔比为2.8～4.7。优选地，二氧化硅分散液所含的二氧化硅与正硅酸乙酯的摩尔比为3.8～4.7，以保证60％以上的良品率。
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。
以上所述仅为本发明的实施方式，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (10)

  1. 一种微光学玻璃器件的制备方法，包括以下步骤：
    步骤一：获取二氧化硅分散液，将酸性溶液加入所述二氧化硅分散液，以调节所述二氧化硅分散液的pH值，并搅拌；
    步骤二：将正硅酸乙酯加入所述二氧化硅分散液，并搅拌，得到溶胶，将碱性溶液加入所述溶胶，以调节所述溶胶的pH值，搅拌并静置；
    步骤三：将静置后的所述溶胶注入模具，陈化，得到湿凝胶；
    步骤四：将所述湿凝胶脱模，清洗、干燥，得到干凝胶；
    步骤五：将所述干凝胶烧结，得到微光学玻璃器件；
    其特征在于，原料中的二氧化硅固含量不大于25.5％。
  2. 根据权利要求1所述的微光学玻璃器件的制备方法，其特征在于，原料中的二氧化硅固含量不大于25％。
  3. 根据权利要求2所述的微光学玻璃器件的制备方法，其特征在于，原料中的二氧化硅固含量不大于20.3％。
  4. 根据权利要求1所述的微光学玻璃器件的制备方法，其特征在于，在所述步骤一中，包括：获取预设摩尔体积的二氧化硅分散液原液，将所述二氧化硅分散液原液与去离子水混合，得到所述二氧化硅分散液，所述去离子水用于调节所述二氧化硅固含量。
  5. 根据权利要求1所述的微光学玻璃器件的制备方法，其特征在于，在所述原料中，所述二氧化硅分散液所含的二氧化硅与所述正硅酸乙酯的摩尔比为2.8～4.7。
  6. 根据权利要求5所述的微光学玻璃器件的制备方法，其特征在于，所述二氧化硅分散液所含的二氧化硅与所述正硅酸乙酯的摩尔比为3.8～4.7。
  7. 根据权利要求1～6中任一项所述的微光学玻璃器件的制备方法，其特征在于，在所述步骤一中，所述酸性溶液为盐酸溶液，所述二氧化硅分散液经调节pH值后的pH值为1.3～2.8。
  8. 根据权利要求1～6中任一项所述的微光学玻璃器件的制备方法，其特征在于，在所述步骤二中，所述碱性溶液为氨水溶液，所述溶胶经 调节pH值后的pH值为2.5～5。
  9. 根据权利要求1～6中任一项所述的微光学玻璃器件的制备方法，其特征在于，所述模具为硅胶模具。
  10. 根据权利要求1～6中任一项所述的微光学玻璃器件的制备方法，其特征在于，在所述步骤五中，烧结温度不高于1100℃。
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