WO2017004842A1 - 反蛋白石胶体晶体纤维的制备方法 - Google Patents

反蛋白石胶体晶体纤维的制备方法 Download PDF

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WO2017004842A1
WO2017004842A1 PCT/CN2015/084030 CN2015084030W WO2017004842A1 WO 2017004842 A1 WO2017004842 A1 WO 2017004842A1 CN 2015084030 W CN2015084030 W CN 2015084030W WO 2017004842 A1 WO2017004842 A1 WO 2017004842A1
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mma
crystal fiber
microspheres
colloidal crystal
inverse opal
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French (fr)
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张克勤
丁晨
袁伟
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南通纺织丝绸产业技术研究院
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Priority to US15/745,800 priority Critical patent/US20180237957A1/en
Publication of WO2017004842A1 publication Critical patent/WO2017004842A1/zh
Priority to US16/802,942 priority patent/US20200190704A1/en

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    • D—TEXTILES; PAPER
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    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/6224—Fibres based on silica
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    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/1225—Basic optical elements, e.g. light-guiding paths comprising photonic band-gap structures or photonic lattices
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/52—Constituents or additives characterised by their shapes
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    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
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  • the invention relates to a method for preparing an inverse opal colloidal crystal fiber.
  • the colloidal crystals prepared from the dielectric material silica and the polymer monodisperse spheres are commonly used to obtain controllable three-dimensional dielectric periodic materials, such as photonic crystals, which have a certain structure on the length scale and can change light due to Bragg diffraction.
  • the extension of these materials has a blocking effect on light of a specific wavelength, so that light is reflected and interfered multiple times in the crystal, so that the photonic crystal exhibits a photonic band gap property for light of a specific wavelength.
  • This property allows photonic crystals to have a large number of applications, such as enhancing or suppressing simultaneous emission of light, light filtering and conversion, and controlling the transmission of visible and infrared light. Because the inverse opal structure photonic crystal has full bandgap properties, it is widely used in the fields of waveguide, optical storage and optical filtering.
  • the templating method mainly uses photolithography to obtain microchannels, and then fills the microchannels with a polymer colloidal crystal template, fills the intergranular pores with inorganic particles such as silica or titania particles, and finally sinters the polymer colloidal crystal template. Remove, leaving the inverse opal colloidal crystal fibers regularly arranged by air balls. This method is complicated and costly, with low yield and limited size.
  • the capillary carrier method fills or coats the polymer colloid solution onto the inner surface of the capillary and then goes to the template as in the templating method.
  • the capillary carrier method has a low yield and forms crack defects on the surface, which are disadvantageous for the transmission of light waves.
  • an object of the present invention is to provide a high-yield, controllable size, internal A method for preparing crack-free inverse opal colloidal crystal fibers.
  • the preparation method of the inverse opal colloidal crystal fiber of the invention comprises the steps of:
  • step (1) 2 ml of methyl methacrylate, 2 ml of acrylic acid, 38 ml of polystyrene, 200 ml of deionized water, and 0 to 0.033 g of dodecylbenzenesulfonic acid (SDS) are added to the flask. 1 g of sodium hydrogencarbonate, and stirred uniformly. After stirring at 70 ° C for half an hour, 2 ml of ammonium persulfate solution was added, the temperature was raised to 80 ° C, and the reaction was stirred for 10 hours to synthesize the P-(St- with a size of 190-450 nm. MMA-AA) Microspheres.
  • SDS dodecylbenzenesulfonic acid
  • the P-(St-MMA-AA) microsphere dispersion is prepared by taking the P-(St-MMA-AA) microspheres having a size of 300 nm.
  • the silica particles have an average particle size of 10 to 20 nm.
  • the P-(St-MMA-AA) microsphere dispersion having a mass volume fraction of 0.4% to 0.6% is taken, and the P-(St-MMA-AA) is micro.
  • the spherical dispersion and the silica sol nanosphere are uniformly mixed to form a colloidal solution at a mass ratio of 1:0.4 to 0.6, and the P-(St-MMA-AA) microsphere and the silica sol nanosphere are vertically settled from After assembly, it is baked at 50 ° C
  • the colloidal crystal fiber is obtained by drying in a box.
  • a strip-shaped inverse opal structure photonic crystal fiber with a full optical band gap can be obtained by a simple vertical sedimentation method
  • a photonic crystal fiber strip having a length of more than 3 cm and a width of between 20 micrometers and 300 micrometers can be obtained;
  • the yield is high, and hundreds to thousands can be prepared at a time.
  • Figure 2 is a structural color fiber strip of different colors made in accordance with the present invention.
  • a method for preparing an inverse opal colloidal crystal fiber is as follows:
  • step (1) 2 ml of methyl methacrylate, 2 ml of acrylic acid, 38 ml of polystyrene, 200 ml of deionized water, 0 to 0.033 g of dodecylbenzenesulfonic acid (SDS), and 1 g are added to the flask.
  • SDS dodecylbenzenesulfonic acid
  • Sodium bicarbonate and stirred uniformly.
  • 2 ml of ammonium persulfate solution was added, the temperature was raised to 80 ° C, and the reaction was stirred for 10 hours to synthesize P-(St-MMA-AA) having a size of 190-450 nm. Microspheres.
  • the particle size was 190 nm
  • the mass was 60 mg of P-(St-MMA-AA) microspheres and 18 mg of silica particles
  • the P-(St-MMA-AA) microspheres were formulated to have a mass fraction of 0.3%, P-( St-MMA-AA) 20ml of microspheres and silica sol in a mass ratio of 1:0.3, placed in a 25ml beaker, ultrasonically mixed to make the two evenly mixed, and then placed in an oven at 50 ° C to dry
  • a colloidal crystal fiber strip was obtained, and the colloidal crystal fiber strip was placed in an oven at 500 ° C for 2 h to remove P-(St-MMA-AA) microspheres to form an inverse protein structure photonic crystal fiber strip.
  • P-(St-MMA-AA) microspheres with a size of 300 nm and a mass of 80 mg and 32 mg of silica particles, and prepare a P-(St-MMA-AA) mass volume fraction of 0.4%, P-(St- MMA-AA) 20ml dispersion of microspheres and silica sol particles with a mass ratio of 1:0.4.
  • the dispersion is placed in a 25ml beaker.
  • the mixture is evenly mixed by ultrasonication and then dried in an oven at 50 ° C to obtain colloidal crystals.
  • the fiber strips were placed in a 500 ° C oven for 2 h to remove P-(St-MMA-AA) microspheres to form an inverse protein structure photonic crystal fiber strip.
  • P-(St-MMA-AA) microspheres with a size of 400 nm and a mass of 100 mg and 50 mg of silica particles, and prepare a P-(St-MMA-AA) mass volume fraction of 0.5%, P-(St- MMA-AA) 20ml dispersion of microspheres and silica sol particles with a mass ratio of 1:0.5; the dispersion is placed in a 25ml beaker, sonicated and uniformly mixed, and then dried in an oven at 50 ° C to obtain colloidal crystals.
  • the fiber strips were placed in a 500 ° C oven for 2 h to remove P-(St-MMA-AA) microspheres to form an inverse protein structure photonic crystal fiber strip.
  • P-(St-MMA-AA) microspheres with a size of 448 nm and a mass of 80 mg and 48 mg of silica particles were prepared to prepare a P-(St-MMA-AA) mass fraction of 0.6%, P-(St- MMA-AA) 20ml dispersion of microspheres and silica sol particles with a mass ratio of 1:0.6; the dispersion is placed in a 25ml beaker, sonicated and uniformly mixed, and then dried in an oven at 50 ° C to obtain colloidal crystals.
  • the fiber strips were placed in a 500 ° C oven for 2 h to remove P-(St-MMA-AA) microspheres to form an inverse protein structure photonic crystal fiber strip.
  • the silica particles in the above four examples are all irregular solid particles having a size of 10-20 nm.
  • Anti-protein structured photonic crystal fiber strips of silicon oxide particles, different sizes of P-(St-MMA-AA) microspheres are used to obtain inverse color photonic crystal fiber strips of different colors.
  • the preparation method of the inverse opal colloidal crystal fiber of the present invention has a P-(St-MMA-AA) microsphere size of 300 nm, and the mass fraction of the dispersion liquid is 0.4% to 0.6%, and When the silica sol has a mass ratio of 1:0.4-0.6, an inverse-protein structure photonic crystal fiber strip of the best length and width is obtained; 300-nm P-(St-MMA-AA) microspheres are used for self-assembly.
  • the vertical sedimentation process it can be uniformly and reacted with the silica particles to obtain the inverse opal colloidal crystal fiber with no crack on the surface and the inside, and the obtained inverse opal colloidal crystal fiber can be peeled off from the surface of the slide glass for convenient use. .

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Abstract

一种反蛋白石胶体晶体纤维的制备方法，通过垂直沉降两种组分胶体球(微米或者纳米尺寸)，即聚苯乙烯壳核结构球和二氧化硅颗粒，得到3.5cm左右长，宽度和厚度可调的条状反蛋白石胶体晶体纤维，产量高，尺寸可控，方法快捷方便，纤维表面与内部均无裂纹，且制得的反蛋白石胶体晶体纤维条可以从载玻片表面剥离，方便取用。

Description

反蛋白石胶体晶体纤维的制备方法 技术领域
本发明涉及一种反蛋白石胶体晶体纤维的制备方法。
背景技术
介电材料二氧化硅和聚合物单分散球制备得到的胶体晶体通常用于获得可控三维介电周期性材料，如光子晶体，这些材料在长度尺度上具有一定结构，由于布拉格衍射可以改变光的延伸，这些材料对于特定波长的光具有阻挡作用，因此光在晶体中会被多次反射和干扰，这样光子晶体对特定波长的光呈现光子禁带性质。这一性质使得光子晶体具有大量的应用，如增强或抑制光的同步发射、光过滤和转换，可以控制可见光和红外光的传递。由于反蛋白石结构光子晶体具有全禁带性质而广泛应用于波导，光存储和光过滤等领域。
由于反结构光子晶体纤维具有光子传播的优势，受到人们极大的关注。目前，反结构光子晶体的制备方法主要有两种，模板法和毛细管载体法。模板法主要是利用光刻蚀技术得到微通道，随后在微通道中填充聚合物胶体晶体模板，在胶体晶体空隙间填充无机颗粒如二氧化硅或二氧化钛颗粒，最后通过烧结将聚合物胶体晶体模板去除，留下由空气球规则排列的反蛋白石胶体晶体纤维。这种方法较复杂且成本高昂，产量低，尺寸受限。毛细管载体法即将聚合物胶体溶液填充或涂覆到毛细管内表面，随后与模板法一样去模板。毛细管载体法产量低且会在表面形成裂纹缺陷，裂纹缺陷对光波的传输是不利的。
发明内容
为解决上述技术问题，本发明的目的是提供一种产量高、尺寸可控、内部 无裂纹的反蛋白石胶体晶体纤维的制备方法。
本发明的反蛋白石胶体晶体纤维的制备方法，包括步骤：
(1)利用微乳液法在聚苯乙烯(St)微球的表面共聚一层聚丙烯酸甲酯(MMA)与聚丙烯酸(AA)的共聚物，形成核为聚苯乙烯的壳核结构的P-(St-MMA-AA)微球；
(2)取质量体积分数为0.3％～1.0％的所述P-(St-MMA-AA)微球分散液，将所述P-(St-MMA-AA)微球分散液与二氧化硅溶胶纳米球按质量比为1：0.3～0.6混合均匀形成胶体溶液，所述P-(St-MMA-AA)微球与所述二氧化硅纳米球垂直沉降自组装后置于50℃烘箱中烘干得到条状胶体晶体纤维；
(3)将所述胶体晶体纤维条置于500℃烘箱中烧结2h除去P-(St-MMA-AA)微球，形成反蛋白结构光子晶体纤维。
进一步的，所述步骤(1)中于烧瓶中加入2ml甲基炳烯酸甲脂、2ml丙烯酸、38ml聚苯乙烯、200ml去离子水、0～0.033g十二烷基苯磺酸(SDS)、1g碳酸氢钠，并搅拌均匀，在70℃下搅拌半小时后加入2ml过硫酸铵溶液，将温度升到80℃继续搅拌反应10小时合成尺寸在190～450nm的所述P-(St-MMA-AA)微球。
进一步的，所述步骤(2)中取尺寸为300nm的所述P-(St-MMA-AA)微球配制所述P-(St-MMA-AA)微球分散液。
进一步的，所述二氧化硅溶胶中二氧化硅颗粒平均尺寸为10～20nm。
进一步的，所述步骤(2)中取质量体积分数为0.4％～0.6％的所述P-(St-MMA-AA)微球分散液，将所述P-(St-MMA-AA)微球分散液与二氧化硅溶胶纳米球按质量比为1：0.4～0.6混合均匀形成胶体溶液，所述P-(St-MMA-AA)微球与所述二氧化硅溶胶纳米球垂直沉降自组装后置于50℃烘 箱中烘干得到胶体晶体纤维。
借由上述方案，本发明的反蛋白石胶体晶体纤维的制备方法有益效果如下：
1、用简单的垂直沉降方法即可得到全光带间隙的条状反蛋白石结构光子晶体纤维；
2、通过改变制备体系分散液容积，可制得长度3cm以上，宽度20微米到300微米之间的光子晶体纤维条；
3、光子晶体纤维内部无裂缝，有利于光的传导；
4、产率较高，一次可以制备数百到上千根。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1是本发明的反蛋白石结构胶体晶体纤维的制备流程；
图2是本发明制得的不同颜色的结构色纤维条。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
参见图1，一种反蛋白石胶体晶体纤维的制备方法，步骤如下：
(1)利用微乳液法在聚苯乙烯(St)微球的表面共聚一层聚丙烯酸甲酯(MMA)与聚丙烯酸(AA)的共聚物，合成核为聚苯乙烯的壳核结构的P-(St-MMA-AA)微球；
(2)取质量体积分数为0.3％～1.0％的P-(St-MMA-AA)微球，将P- (St-MMA-AA)微球与硅溶胶纳米球按质量比为1：0.3～0.6混合均匀形成胶体溶液，P-(St-MMA-AA)微球与硅溶胶纳米球垂直沉降自组装后置于50℃烘箱中烘干得到胶体晶体纤维；
(3)将胶体晶体纤维条置于500℃烘箱中烧结2h除去P-(St-MMA-AA)微球，形成反蛋白结构光子晶体纤维。
具体的，步骤(1)中于烧瓶中加入2ml甲基炳烯酸甲脂、2ml丙烯酸、38ml聚苯乙烯、200ml去离子水、0～0.033g十二烷基苯磺酸(SDS)、1g碳酸氢钠，并搅拌均匀，在70℃下搅拌半小时后加入2ml过硫酸铵溶液，将温度升到80℃继续搅拌反应10小时合成尺寸在190～450nm的P-(St-MMA-AA)微球。
实施例1：
取粒径为190nm，质量为60mg P-(St-MMA-AA)微球以及18mg二氧化硅颗粒，配制成P-(St-MMA-AA)微球质量体积分数为0.3％，P-(St-MMA-AA)微球与二氧化硅溶胶按质量比为1：0.3的分散液20ml，盛放于25ml烧杯中，超声混合使两者混合均匀后将其放于50℃烘箱中烘干得到胶体晶体纤维条，将胶体晶体纤维条置于500℃烘箱中烧结2h除去P-(St-MMA-AA)微球，形成反蛋白结构光子晶体纤维条。
实施例2：
取尺寸为300nm、质量为80mg的P-(St-MMA-AA)微球以及32mg二氧化硅颗粒，配制成P-(St-MMA-AA)质量体积分数为0.4％，P-(St-MMA-AA)微球与二氧化硅溶胶颗粒质量比为1:0.4的分散液20ml，分散液盛放于25ml烧杯中，超声使两者混合均匀后置于50℃烘箱中烘干得到胶体晶体纤维条，将胶体晶体纤维条置于500℃烘箱中烧结2h除去P-(St-MMA-AA)微球，形成反蛋白结构光子晶体纤维条。
实施例3：
取尺寸为400nm、质量为100mg的P-(St-MMA-AA)微球以及50mg二氧化硅颗粒，配制成P-(St-MMA-AA)质量体积分数为0.5％，P-(St-MMA-AA)微球与二氧化硅溶胶颗粒质量比为1:0.5的分散液20ml；分散液盛放于25ml烧杯中，超声使两者混合均匀后置于50℃烘箱中烘干得到胶体晶体纤维条，将胶体晶体纤维条置于500℃烘箱中烧结2h除去P-(St-MMA-AA)微球，形成反蛋白结构光子晶体纤维条。
实施例4：
取尺寸为448nm、质量为80mg的P-(St-MMA-AA)微球以及48mg二氧化硅颗粒，配制成P-(St-MMA-AA)质量体积分数为0.6％，P-(St-MMA-AA)微球与二氧化硅溶胶颗粒质量比为1:0.6的分散液20ml；分散液盛放于25ml烧杯中，超声使两者混合均匀后置于50℃烘箱中烘干得到胶体晶体纤维条，将胶体晶体纤维条置于500℃烘箱中烧结2h除去P-(St-MMA-AA)微球，形成反蛋白结构光子晶体纤维条。
以上四个实施例中二氧化硅颗粒均为不规则固体颗粒，其尺寸为10-20nm。
如图2所示，P-(St-MMA-AA)微球与二氧化硅自组装垂直沉降后置于50℃烘箱中烘干，制得的胶体晶体纤维条的长度在3.5cm左右，宽度在50微米-200微米之间；将胶体晶体纤维条置于500℃烘箱中烧结2h除去P-(St-MMA-AA)微球，得到空气球密堆的间隙填有折射率为1.56的二氧化硅颗粒的反蛋白结构光子晶体纤维条，用不同尺寸的P-(St-MMA-AA)微球得到不同颜色的反蛋白结构光子晶体纤维条。
由上述各实施例可见，本发明的反蛋白石胶体晶体纤维的制备方法在P-(St-MMA-AA)微球尺寸为300nm，其分散液质量体积分数为0.4％～0.6％、与 二氧化硅溶胶按质量比为1：0.4～0.6时，获得最佳长度与宽度的反蛋白结构光子晶体纤维条；采用300nm的P-(St-MMA-AA)微球，是为了在自组装垂直沉降过程中，能够较均匀地与二氧化硅颗粒作用，获得表面与内部均无裂纹的反蛋白石胶体晶体纤维，且制得的反蛋白石胶体晶体纤维可以从载玻片表面剥离，方便取用。
以上所述仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (5)

  1. 一种反蛋白石胶体晶体纤维的制备方法，其特征在于，包括步骤：
    (1)利用微乳液法在聚苯乙烯(St)微球的表面共聚一层聚丙烯酸甲酯(MMA)与聚丙烯酸(AA)的共聚物，形成核为聚苯乙烯的壳核结构的P-(St-MMA-AA)微球；
    (2)取质量体积分数为0.3％～1.0％的所述P-(St-MMA-AA)微球分散液，将所述P-(St-MMA-AA)微球分散液与二氧化硅溶胶纳米球按质量比为1：0.3～0.6混合均匀形成胶体溶液，所述P-(St-MMA-AA)微球与所述二氧化硅纳米球垂直沉降自组装后置于50℃烘箱中烘干得到条状胶体晶体纤维；
    (3)将所述胶体晶体纤维条置于500℃烘箱中烧结2h除去P-(St-MMA-AA)微球，形成反蛋白结构光子晶体纤维。
  2. 根据权利要求1所述的反蛋白石胶体晶体纤维的制备方法，其特征在于：所述步骤(1)中于烧瓶中加入2ml甲基炳烯酸甲脂、2ml丙烯酸、38ml聚苯乙烯、200ml去离子水、0～0.033g十二烷基苯磺酸(SDS)、1g碳酸氢钠，并搅拌均匀，在70℃下搅拌半小时后加入2ml过硫酸铵溶液，将温度升到80℃继续搅拌反应10小时合成尺寸在190～450nm的所述P-(St-MMA-AA)微球。
  3. 根据权利要求2所述的反蛋白石胶体晶体纤维的制备方法，其特征在于：所述步骤(2)中取尺寸为300nm的所述P-(St-MMA-AA)微球配制所述P-(St-MMA-AA)微球分散液。
  4. 根据权利要求3所述的反蛋白石胶体晶体纤维的制备方法，其特征在于：所述二氧化硅溶胶中二氧化硅颗粒平均尺寸为10～20nm。
  5. 根据权利要求4所述的反蛋白石胶体晶体纤维的制备方法，其特征在于：所述步骤(2)中取质量体积分数为0.4％～0.6％的所述P-(St-MMA-AA)微球分散液，将所述P-(St-MMA-AA)微球分散液与二氧化硅溶胶纳米球按质量比 为1：0.4～0.6混合均匀形成胶体溶液，所述P-(St-MMA-AA)微球与所述二氧化硅溶胶纳米球垂直沉降自组装后置于50℃烘箱中烘干得到胶体晶体纤维。
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