CN101280455A - Method for self-assembling preparing colloidal photonic crystals and improving mechanical stability - Google Patents

Method for self-assembling preparing colloidal photonic crystals and improving mechanical stability Download PDF

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Publication number
CN101280455A
CN101280455A CNA2008100193992A CN200810019399A CN101280455A CN 101280455 A CN101280455 A CN 101280455A CN A2008100193992 A CNA2008100193992 A CN A2008100193992A CN 200810019399 A CN200810019399 A CN 200810019399A CN 101280455 A CN101280455 A CN 101280455A
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colloidal
particle
crystal
self
assembling
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赵祥伟
赵远锦
扈靖
赵文举
顾忠泽
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Southeast University
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Southeast University
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Abstract

Disclosed is a self-assembly and preparation device of colloidal photonic crystals and the method thereof to improve the mechanical stability; the colloidal particle solution is distributed to a continuous phase and in the formation of colloidal solution droplets. Through the evaporation of the solution in the droplet, the colloidal particle in the solution is self-assembled to become the colloidal photonic crystal while the droplet is taken as a template. For the mechanical stability of the photonic crystal, the mutual cementation of the colloidal particles inside a crystal is greatly enhanced through the heat treatment. The three-dimensional colloidal photonic crystals with high mechanical stability and prepared through such a method has a potential value in the aspects of size exclusion chromatography, enzyme or zymophore, adsorption medium, bio-molecule detection carrier, filter, light switches, photonic paper and so on.

Description

The method of colloidal photon crystal self-assembly preparation and raising mechanical stability thereof
Technical field
The present invention relates to be a kind of be that template is passed through the colloid self-assembly and prepared the three-dimensional colloidal photon crystal mechanical stability of three-dimensional colloidal photon crystal and raising method with the drop.
Background technology
Colloidal crystal is the class material with ordered 3 D structure that is formed by monodispersed micron or submicro inorganic or organic granular (also claiming colloidal particle).Because arranging, the long-range order of colloidal particle make colloidal photon crystal produce photon band gap, so also be called colloidal photon crystal.The ordered 3 D structure of colloidal photon crystal, its repeat cycle, (400~700nm) Bragg diffraction (Bragg diffraction) can take place visible light therein in micron, sub-micrometer scale.The long-range order of colloidal particle is arranged and is made colloidal photon crystal produce the characteristic that has using value such as optical diffraction and optical band gap, maximum tap density, high surface-volume ratio etc.Because the diffraction optics characteristic of colloidal photon crystal makes it have important application prospects as a class photonic crystal at aspects such as spectral filter and photoswitch, high-density magnetic data memory device, chemistry and bio-sensings.Colloidal photon crystal can be used as the ordered porous structural that template preparation has complete photonic band gap in addition, and Jie of this regular arrangement sees porous material in catalysis, absorption with the aspect such as separate and also have important use and be worth.The preparation of colloidal photon crystal at present is the method by the colloidal particle self-assembly mainly, for example: and colloidal particle sedimentation self-assembly, utilize the settlement action of colloidal particle to be assembled in the bottom of container; The self-assembly of space constraint colloidal particle utilizes space constraint to make in the space of colloidal particle self-assembly between two planes; The self-assembly of electrostatic interaction colloidal particle utilizes electrostatic interaction that colloidal particle is assembled in the container; The self-assembly of wicking action colloidal particle utilizes capillary force to make colloidal particle be assembled in surface of substrate etc.But the three-dimensional colloidal photon crystal of these method preparations all is membrane structure basically.In actual application, there are two major causes to limit the application of three-dimensional colloid photonic crystal film.The first, some application examples such as biomolecule carrier preference spherical form, some anisotropy optics devices need annular shape etc., and the colloid photonic crystal film of film shape can not meet the demands.Second, prepare colloidal crystal by the colloidal particle self-assembling method solid phase template or substrate support must be arranged, colloidal crystal has broken away from substrate or template and has been difficult to self-supporting or holds its shape, and the colloidal crystal that obtains is because inside relies on the Van der Waals force between the colloidal particle to be bound up, so its mechanical stability is limited, under the state that breaks away from the template self-supporting, as easy as rolling off a logly damage at the lattice defect place or under external force.Therefore, the expansion of colloidal crystal range of application needs new preparation and improves stable method.
Summary of the invention
Technical problem: the method that the purpose of this invention is to provide a kind of colloidal photon crystal self-assembly preparation and raising mechanical stability thereof, utilize this method can prepare the spherocolloid photonic crystal, and the mechanical stability height of colloidal photon crystal, satisfy the requirement of actually operating and application.
Technical scheme: colloidal photon crystal self-assembly preparation method thereof of the present invention is distributed to colloidal particle solution and forms the colloidal solution drop in the external phase, evaporation colloidal particle wherein by solvent in the drop is that template is self-assembled into the drop is colloidal photon crystal, makes in the crystal colloidal particle bonding mechanical stability that improves photonic crystal greatly mutually by heat treated.
Described colloidal particle is a kind of in monodispersed silicon dioxide granule, zinc oxide particle, gold particle, the TiO 2 particles; Or a kind of in the monodisperse polystyrene particle, polymethylmethacrylate particle, polypyrrole particle, polyaniline particle; Or a kind of in the gold bag silicon dioxide granule of single distributed nuclei shell structure, polystyrene bag silicon dioxide granule, polymethylmethacrylate bag polystyrene particle, polymethylmethacrylate bag silicon dioxide granule.Described colloidal particle solution is disperse phase, is distributed to form the colloidal particle solution droplets in the external phase, and dispersing method adopts homogeneous method or ultrasonic method or droplet generator method.The described colloidal photon crystal that with the drop is template is self-assembled into is spherical or is elliposoidal or is annular.
The raising self-assembly prepares colloidal photon crystal mechanical stability method and is: the mechanical stability of described colloidal crystal makes by heat treated and forms bonding the raising between the colloidal particle; For the colloidal crystal microballoon of silicon dioxide granule assembling, the heat treated temperature is 700 ℃-1100 ℃; For the colloidal crystal microballoon of polystyrene particle, polypyrrole particle, polymethylmethacrylate particle assembling, the heat treated temperature is 100 ℃~130 ℃; For the colloidal crystal microballoon of polyamide particles assembling, the heat treated temperature is 200 ℃~400 ℃; For the colloidal crystal microballoon of TiO 2 particles assembling, the heat treated temperature is 1500 ℃~2000 ℃; For the colloidal crystal microballoon of golden nanometer particle assembling, the temperature of heat treated is 300 ℃~1000 ℃; For the colloidal crystal microballoon of zinc oxide particle assembling, the temperature of heat treated is 1800 ℃~2500 ℃; For the colloidal crystal microballoon of gold bag silicon dioxide granule assembling, the temperature of heat treated is 300 ℃~1000 ℃; For the colloidal crystal microballoon of polystyrene bag silicon dioxide granule, the assembling of polymethylmethacrylate bag silicon dioxide granule, the temperature of heat treated is 100 ℃~150 ℃; For the colloidal crystal microballoon of polymethylmethacrylate bag polystyrene particle assembling, the temperature of heat treated is 100 ℃~130 ℃.Used heating treatment method uses baking oven, retort furnace, or apply nitrogen protection in heat-processed.
Beneficial effect:
1. with the drop be template to carry out the colloidal crystal that the self-assembly of colloidal particle obtains be self supporting structure, for being flexible coupling, the continuous phase solution on flush away colloidal crystal surface just can make colloidal crystal and template break away from, and is simple between colloidal crystal and the template.
2. be that to prepare resulting colloidal photon crystal be globosity to template with the drop, the specific surface area height satisfies the requirement of special use, is particularly suitable as biomolecule carrier, spherical photonic crystal can freely roll, and can show photon crystalline characteristic at three-dimensional.
3. be the template size that can control needed spherocolloid photonic crystal easily with the drop with and uniformity coefficient.
4. be that template prepares colloidal crystal with the drop, the assembling of colloidal particle is at first carried out at two-phase interface, because two-phase is liquid, so the frictional force at interface is minimum, compare with other assemble methods, the crystal long-range order Du Genggao that obtains, plane of crystal is defective still less.
5. colloidal photon crystal is after high-temperature calcination is handled, and mechanical stability increases greatly, can be not broken because of collision, therefore in actual application, can keep spherical, and improved the application quality and the scope of colloidal photon crystal.
Description of drawings
Fig. 1. colloidal particle solution is distributed to the drop synoptic diagram that forms in the external phase,
Fig. 2. colloidal particle is the synoptic diagram that template is self-assembled into colloidal photon crystal with the drop,
Fig. 3. with the drop is the electromicroscopic photograph that template is self-assembled into the colloidal photon crystal microballoon,
Fig. 4. with the drop is the electromicroscopic photograph that template is self-assembled into the colloidal photon crystal microsphere surface,
Fig. 5. the electromicroscopic photograph of high mechanical stability colloidal photon crystal microsphere surface after the calcining.
Embodiment
By the three-dimensional colloidal photon crystal of the high mechanical stability of present method preparation in the size exclusion chromatogram, catalyzer or enzyme carrier, adsorption medium, the biomolecule detection carrier, spectral filter, photoswitch, there is the potential using value aspects such as photon paper.Purpose of the present invention can realize by following scheme:
With the example that is prepared as of silicon dioxide colloid photonic crystal, at first the aqueous solution (disperse phase) with the monodisperse silica colloidal particle is distributed in the insoluble with it oil phase silicone oil (external phase), makes the dioxide/silica gel liquid solution form drop in silicone oil.For preventing to merge mutually between the drop, can add this Pan 80 of an amount of emulsifying agent in the silicone oil in advance.After drop formed, by methods such as heating or seasoninies, the water in the colloidal solution can evaporate, so the concentration of silicon dioxide colloid particle increases gradually in the colloidal solution drop.Along with the continuous increase of concentration, the minimizing gradually of solvent, colloidal particle forms orderly crystalline structure by the self-assembly effect, and this structure meets the Bragg diffraction law, is a kind of colloidal photon crystal therefore.Because from start to finish, the self-assembly of colloidal particle is all among colloidal droplets, so the formed crystal of self-assembly is for being the sphaerocrystal of template with the drop.Collect resulting spherocolloid photonic crystal or colloidal photon crystal microballoon, silicone oil with normal hexane flush away colloidal photon crystal surface, then the silicon dioxide colloid photonic crystal is carried out 2 hours 1000 ℃ of calcination processing, make between the silicon dioxide colloid particle and bond mutually, but be unlikely to merge fully, then can increase exponentially the mechanical stability of colloidal photon crystal microballoon, make it can bear 500 atmospheric pressure.
The method that the present invention provides a kind of very simple spherocolloid photonic crystal self-assembly preparation method thereof and improves the colloidal photon crystal mechanical stability, simple, it is convenient to implement.At first the solution with colloidal particle is distributed to formation colloidal solution drop in the external phase, make solvent evaporates in the colloidal solution drop by the heating or the mode of seasoning, colloidal particle is self-assembled into the spherocolloid photonic crystal, utilize thermal treatment to make between the colloidal particle then and bond mutually, increase the mechanical stability of colloidal crystal.Embodiment is as follows:
The mechanical stability of described colloidal crystal makes by heat treated and forms bonding the raising between the colloidal particle; For the colloidal crystal microballoon of silicon dioxide granule assembling, the heat treated temperature is 700 ℃-1100 ℃; For the colloidal crystal microballoon of polystyrene particle, polypyrrole particle, polymethylmethacrylate particle assembling, the heat treated temperature is 100 ℃~130 ℃; For the colloidal crystal microballoon of polyamide particles assembling, the heat treated temperature is 200 ℃~400 ℃; For the colloidal crystal microballoon of TiO 2 particles assembling, the heat treated temperature is 1500 ℃~2000 ℃; For the colloidal crystal microballoon of golden nanometer particle assembling, the temperature of heat treated is 300 ℃~1000 ℃; For the colloidal crystal microballoon of zinc oxide particle assembling, the temperature of heat treated is 1800 ℃~2500 ℃; For the colloidal crystal microballoon of gold bag silicon dioxide granule assembling, the temperature of heat treated is 300 ℃~1000 ℃; For the colloidal crystal microballoon of polystyrene bag silicon dioxide granule, the assembling of polymethylmethacrylate bag silicon dioxide granule, the temperature of heat treated is 100 ℃~150 ℃; For the colloidal crystal microballoon of polymethylmethacrylate bag polystyrene particle assembling, the temperature of heat treated is 100 ℃~130 ℃.
Embodiment one: the preparation of silicon dioxide colloid photon crystal micro-ball:
1. selecting particle diameter for use is the aqueous solution of the silicon dioxide colloid particle of 200 nanometers, and particle concentration is 10%;
2. by drop generating device the dioxide/silica gel liquid solution is distributed in the silicone oil, forms the silicon dioxide colloid solution droplets;
3. under 90 ℃ of conditions, dried silica colloidal solution drop makes moisture evaporation wherein, and the treatment time is 8 hours, obtains the silicon dioxide colloid photon crystal micro-ball;
4. the silicone oil of flush away colloidal photon crystal microsphere surface was handled 2 hours for 1000 ℃ then, promptly obtained the colloidal photon crystal microballoon of high mechanical stability.
Embodiment two: the preparation of polystyrene colloid photon crystal micro-ball:
1. selecting particle diameter for use is the aqueous solution of the polystyrene colloid particle of 260 nanometers, and particle concentration is 30%;
2. by drop generating device polystyrene colloid solution is distributed in the silicone oil, forms the polystyrene colloid solution droplets;
3. under 60 ℃ of conditions, dry polystyrene colloidal solution drop makes moisture evaporation wherein, and the treatment time is 24 hours, obtains the polystyrene colloid photon crystal micro-ball;
4. the silicone oil of flush away colloidal photon crystal microsphere surface was handled 2 hours for 110 ℃ then, promptly obtained the colloidal photon crystal microballoon of high mechanical stability.
Embodiment three: the preparation of polymethylmethacrylate colloidal photon crystal microballoon:
1. selecting particle diameter for use is the aqueous solution of the polymethylmethacrylate colloidal particle of 240 nanometers, and particle concentration is 24%;
2. by drop generating device polymethylmethacrylate colloidal solution is distributed in the silicone oil, forms polymethylmethacrylate colloidal solution drop;
3. under 80 ℃ of conditions, dry polymethylmethacrylate colloidal solution drop makes moisture evaporation wherein, and the treatment time is 12 hours, obtains polymethylmethacrylate colloidal photon crystal microballoon;
4. the silicone oil of flush away colloidal photon crystal microsphere surface was handled 2 hours for 110 ℃ then, promptly obtained the colloidal photon crystal microballoon of high mechanical stability.

Claims (6)

1. colloidal photon crystal self-assembly preparation method thereof, it is characterized in that: colloidal particle solution is distributed to forms the colloidal solution drop in the external phase, evaporation colloidal particle wherein by solvent in the drop is that template is self-assembled into the drop is colloidal photon crystal, makes in the crystal colloidal particle bonding mechanical stability that improves photonic crystal greatly mutually by heat treated.
2. colloidal photon crystal self-assembly preparation method thereof according to claim 1 is characterized in that described colloidal particle is a kind of in monodispersed silicon dioxide granule, zinc oxide particle, gold particle, the TiO 2 particles; Or a kind of in the monodisperse polystyrene particle, polymethylmethacrylate particle, polypyrrole particle, polyaniline particle; Or a kind of in the gold bag silicon dioxide granule of single distributed nuclei shell structure, polystyrene bag silicon dioxide granule, polymethylmethacrylate bag polystyrene particle, polymethylmethacrylate bag silicon dioxide granule.
3. according to the described colloidal photon crystal self-assembly preparation method thereof of claim 1, it is characterized in that described colloidal particle solution is disperse phase, be distributed to and form the colloidal particle solution droplets in the external phase, dispersing method adopts homogeneous method or ultrasonic method or droplet generator method.
4. colloidal photon crystal self-assembly preparation method thereof according to claim 1 is characterized in that the described colloidal photon crystal that with the drop is template is self-assembled into is spherical or is elliposoidal or is annular.
5. a raising self-assembly as claimed in claim 1 prepares colloidal photon crystal mechanical stability method, it is characterized in that the mechanical stability of described colloidal crystal makes bonding raising of formation between the colloidal particle by heat treated; For the colloidal crystal microballoon of silicon dioxide granule assembling, the heat treated temperature is 700 ℃-1100 ℃; For the colloidal crystal microballoon of polystyrene particle, polypyrrole particle, polymethylmethacrylate particle assembling, the heat treated temperature is 100 ℃~130 ℃; For the colloidal crystal microballoon of polyamide particles assembling, the heat treated temperature is 200 ℃~400 ℃; For the colloidal crystal microballoon of TiO 2 particles assembling, the heat treated temperature is 1500 ℃~2000 ℃; For the colloidal crystal microballoon of golden nanometer particle assembling, the temperature of heat treated is 300 ℃~1000 ℃; For the colloidal crystal microballoon of zinc oxide particle assembling, the temperature of heat treated is 1800 ℃~2500 ℃; For the colloidal crystal microballoon of gold bag silicon dioxide granule assembling, the temperature of heat treated is 300 ℃~1000 ℃; For the colloidal crystal microballoon of polystyrene bag silicon dioxide granule, the assembling of polymethylmethacrylate bag silicon dioxide granule, the temperature of heat treated is 100 ℃~150 ℃; For the colloidal crystal microballoon of polymethylmethacrylate bag polystyrene particle assembling, the temperature of heat treated is 100 ℃~130 ℃.
6. raising self-assembly according to claim 5 prepares colloidal photon crystal mechanical stability method, it is characterized in that used heating treatment method, uses baking oven, retort furnace, or apply nitrogen protection in heat-processed.
CNA2008100193992A 2008-01-08 2008-01-08 Method for self-assembling preparing colloidal photonic crystals and improving mechanical stability Pending CN101280455A (en)

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Cited By (16)

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CN103143303A (en) * 2013-03-01 2013-06-12 东南大学 Wide-visual-angle colloid crystal film and preparation method thereof
CN103226277A (en) * 2013-04-02 2013-07-31 东南大学 Angle unbiased color display device based on photonic crystal fibers
CN104458705A (en) * 2014-12-31 2015-03-25 黑龙江大学 Preparing method of surface enhancing Raman chip
CN106040114A (en) * 2016-05-24 2016-10-26 华中科技大学 Hydrogel photonic crystal microspheres, and preparation method and application thereof
CN106423000A (en) * 2016-09-28 2017-02-22 武汉纺织大学 Preparation method for core-shell TiO2-SiO2 microsphere self-assembled structural color film
CN107442045A (en) * 2017-09-06 2017-12-08 蚌埠玻璃工业设计研究院 A kind of method that micro-nano particle emulsion droplets add standby layer-controllable colloidal crystal
CN107604442A (en) * 2017-09-06 2018-01-19 蚌埠玻璃工业设计研究院 A kind of method that emulsion suspension prepares colloidal crystal
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CN109932760A (en) * 2019-04-02 2019-06-25 上海第二工业大学 A kind of preparation method of transparent colloid crystal film with photon
CN110344038A (en) * 2019-07-11 2019-10-18 江苏省肿瘤医院 One kind is based on photonic crystal template gold or silver-colored counter opal microballoon and preparation method thereof
CN111349351A (en) * 2020-04-17 2020-06-30 南京鼓楼医院 Preparation method of photonic crystal microspheres based on multi-shell nanoparticles
CN111996583A (en) * 2020-08-28 2020-11-27 河南理工大学 Self-assembly method of polystyrene colloidal particle crystals in aqueous medium
CN112892427A (en) * 2021-01-22 2021-06-04 海昌隐形眼镜有限公司 Method for preparing silica colloid photonic crystal microspheres in batch
CN113359217A (en) * 2021-05-27 2021-09-07 北京理工大学 Device and method for rapidly preparing three-dimensional photonic crystal
CN113877787A (en) * 2021-08-18 2022-01-04 航天特种材料及工艺技术研究所 Photonic crystal infrared stealth material and preparation method thereof
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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103143303A (en) * 2013-03-01 2013-06-12 东南大学 Wide-visual-angle colloid crystal film and preparation method thereof
CN103143303B (en) * 2013-03-01 2015-05-20 东南大学 Wide-visual-angle colloid crystal film and preparation method thereof
CN103226277A (en) * 2013-04-02 2013-07-31 东南大学 Angle unbiased color display device based on photonic crystal fibers
CN103226277B (en) * 2013-04-02 2016-01-27 东南大学 A kind of angle based on photonic crystal fiber is without inclined chromatic display
CN104458705A (en) * 2014-12-31 2015-03-25 黑龙江大学 Preparing method of surface enhancing Raman chip
CN104458705B (en) * 2014-12-31 2017-01-18 黑龙江大学 Preparing method of surface enhancing Raman chip
CN106040114A (en) * 2016-05-24 2016-10-26 华中科技大学 Hydrogel photonic crystal microspheres, and preparation method and application thereof
CN106423000A (en) * 2016-09-28 2017-02-22 武汉纺织大学 Preparation method for core-shell TiO2-SiO2 microsphere self-assembled structural color film
CN107442045A (en) * 2017-09-06 2017-12-08 蚌埠玻璃工业设计研究院 A kind of method that micro-nano particle emulsion droplets add standby layer-controllable colloidal crystal
CN107604442A (en) * 2017-09-06 2018-01-19 蚌埠玻璃工业设计研究院 A kind of method that emulsion suspension prepares colloidal crystal
CN108004590A (en) * 2017-12-12 2018-05-08 中国工程物理研究院激光聚变研究中心 Nano-porous surface plasmon crystal and preparation method thereof
CN109932760A (en) * 2019-04-02 2019-06-25 上海第二工业大学 A kind of preparation method of transparent colloid crystal film with photon
CN109932760B (en) * 2019-04-02 2021-05-25 上海第二工业大学 Preparation method of transparent colloid photonic crystal film
CN110344038A (en) * 2019-07-11 2019-10-18 江苏省肿瘤医院 One kind is based on photonic crystal template gold or silver-colored counter opal microballoon and preparation method thereof
CN111349351A (en) * 2020-04-17 2020-06-30 南京鼓楼医院 Preparation method of photonic crystal microspheres based on multi-shell nanoparticles
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CN112892427A (en) * 2021-01-22 2021-06-04 海昌隐形眼镜有限公司 Method for preparing silica colloid photonic crystal microspheres in batch
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CN113359217B (en) * 2021-05-27 2022-09-23 北京理工大学 Device for rapidly preparing three-dimensional photonic crystal
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CN114839702A (en) * 2022-04-27 2022-08-02 中国科学院力学研究所 Method and system for rapidly preparing photonic crystal through low-pressure auxiliary evaporation

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