CN103276439A - Preparation method of molecular colloidal photonic crystal microbeads - Google Patents
Preparation method of molecular colloidal photonic crystal microbeads Download PDFInfo
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Abstract
The invention discloses a preparation method of molecular colloidal photonic crystal microbeads, which have the characteristics of adjustable particle size, controllable appearance, excellent monodispersity and the like. The method of the invention comprises the following steps: the method comprises the steps of building a three-phase microfluidic channel, preparing a double-sided liquid drop template, preparing Janus particles with solid and liquid coexisting and preparing molecular colloidal photonic crystal microbeads.
Description
Technical field
The present invention relates to a kind of preparation method of crystal microballon, more specifically to a kind of preparation method of molecule-type colloidal photon crystal microballon.
Background technology
The colloidal photon crystal microballon not only has the hexagonal closs packing structure of long-range order because of its unique assembly mechanism, the more important thing is that embodying non-dependence of angle in macroscopical optical property is comprehensive optics consistence.The photon band gap feature of this uniqueness makes it become intelligent material of new generation, has great application prospect at aspects such as biological detection, optics and chemical sensors.Up to now, the photonic crystal microballon of having reported has many structures such as sphere, ring property, crescent, yet the colloidal photon crystal microballon of this class formation can only allow the simple grain microballon to have a kind of photon crystal structure look, it is the unicity of schemochrome, limited the practical application of colloidal photon crystal microballon greatly, microballon therefore how to construct the many structural units of one becomes the key of expanding photonic crystal microballon Application Areas.
At present, prepare high performance functional materials by assembled unit is one of focus of research both at home and abroad always, and has been penetrated into a plurality of ambits.And different with the assembly mechanism of colloidal particle, atom or the building block principle of molecule are based on valence bond theory, therefore by molecule or the macro morphology of the target object of atomic building than horn of plenty.If the assembling field that this concept of constructing by valence link is introduced the colloidal photon crystal microballon, will certainly expand the pattern of colloidal photon crystal microballon greatly, (for example: complex constructions such as point-like, wire, planar, positive tetrahedron, the two hammers of triangle) obtain being similar to the colloidal photon crystal microballon of molecule pattern.Microflow control technique is package technique with the fastest developing speed in recent years, not only can prepare the colloidal photon crystal microballon of homogeneous phase by microflow control technique, also can prepare anisotropic microballon, for example the Janus colloidal photon crystal microballon of symmetrical configuration.This type of Janus microballon can be given the photon band gap characteristic characteristic opposite with another side of a photonic crystal of particle.Therefore how to construct such as the most senior assembled unit of Janus microballon by microflow control technique, further the high performance functional materials of preparation has very important meaning again.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of molecule-type colloidal photon crystal microballon, characteristics such as the prepared molecule-type colloidal photon crystal microballon of this method has adjustable grain, and pattern is controlled, monodispersity is superior.Simultaneously the preparation method have cost low, be easy to advantages such as monodispersity integrated and microminiaturized, the preparation microballon is good, favorable repeatability.
The present invention mainly is achieved through the following technical solutions:
The preparation method of molecule-type colloidal photon crystal microballon of the present invention, it may further comprise the steps:
Building of three-phase microfluidic channel: adopt photoetching or soft quarter micro-processing technology set up the microchannel network, perhaps set up a T shape passage, this T shape passage has 3 openings, and one of them mouthful is two disperse phase entrances, a mouth is the external phase entrance, also has 1 mouth to be outlet;
The preparation of two-sided drop template: three kinds of solution of two disperse phase and external phase are respectively charged into syringe and are connected with separately entrance, flow velocity with numerical control micro-injection pump control three-phase solution obtains particle diameter stabilized uniform bilateral structure drop template from exporting out;
The preparation of solid-liquid coexistence Janus particulate: with the drop template dry solidification of bilateral structure, obtain having concurrently solid hemisphere and drop hemisphere in the solid-liquid coexistence Janus of one particulate;
The preparation of molecule-type colloidal photon crystal microballon: be construction unit with solid-liquid coexistence Janus particulate, by impressed field the Janus particulate carried out precision and control, finish the controllable operating of single drop template, be assembled into molecule-type colloidal photon crystal microballon.
The preparation method of molecule-type colloidal photon crystal microballon of the present invention, its further technical scheme is that described T shape passage is made up of parallel double passage draw point, polymkeric substance flexible rubber hose, threeway, wherein parallel double passage draw point is the disperse phase passage, and the polymkeric substance flexible rubber hose is the external phase passage; Further technical scheme is that described polymkeric substance flexible rubber hose is polydimethylsiloxane pipe, polyvinyl chloride pipe, polyfluortetraethylene pipe or polyether-ether-ketone pipe.
The preparation method of molecule-type colloidal photon crystal microballon of the present invention, its further technical scheme can also be that described microchannel network using quartz plate, sheet glass, polymethylmethacrylate or polydimethylsiloxane micro-fluid chip are made.
The preparation method of molecule-type colloidal photon crystal microballon of the present invention, its further technical scheme can also be that one in described two disperse phase of the preparation of face drop template are water, the another one disperse phase is cross-linked resin monomer and the mixing solutions that can produce the nanoparticle of responsiveness to impressed field, external phase is oil phase, and water, mixing solutions and oil phase can form stable three phase boundary, and wherein water is single dispersoid solution of massfraction 20-50%.Wherein said single dispersoid solution is preferably a kind of in polystyrene colloid particle solution, polymethylmethacrylate colloidal particle solution, silicon dioxide colloid particle solution and the colloidal tio 2 particle solution.Described cross-linked resin monomer is preferably ethoxylated trimethylolpropane triacrylate (EO
3-TMPTA), trimethylolpropane trimethacrylate (TMPTMA), propoxylation Viscoat 295 (PO
3-TMPTA), a kind of in tri (propylene glycol) diacrylate (TPGDA) and the propylene glycol diacrylate (DPGDA); The described nanoparticle that can produce responsiveness to impressed field is a kind of or its combination in graphite, iron, four oxidation trisomes, ferric oxide, cobalt, nickel, silver, copper, the golden nanometer particle, also its alloy nano particle.Described oil phase is preferably a kind of in methyl-silicone oil, paraffin oil and the toluene.
The preparation method of molecule-type colloidal photon crystal microballon of the present invention, the diameter of the bilateral structure drop described in the preparation that its further technical scheme can also be two-sided drop template reduces size droplet diameter by increasing the external phase flow velocity or reducing the disperse phase flow velocity, increases size droplet diameter by reducing the external phase flow velocity or increasing the disperse phase flow velocity.
The preparation method of molecule-type colloidal photon crystal microballon of the present invention, its further technical scheme can also be in the preparation of solid-liquid coexistence Janus particulate, and the solid hemisphere of described solid-liquid coexistence Janus particulate is by the spontaneous colloidal photon crystal that is assembled into of single dispersoid solution in the drying process; The liquid hemisphere of described solid-liquid coexistence Janus particulate can produce by the cross-linked resin monomer with to impressed field that the mixing solutions of the nanoparticle of responsiveness forms, and it still keeps original liquid form without any variation in drying process.
The preparation method of molecule-type colloidal photon crystal microballon of the present invention, wherein during the preparation of molecule-type colloidal photon crystal microballon, described impressed field is preferably a kind of in magnetic field, the electric field or its compound.
The present invention has following beneficial effect:
1, preparation cost is low, can realize from putting the preparation of a series of molecule-type colloidal photon crystal microballons such as line, face, positive rectangular pyramid, trigonal bipyramid as long as build once the cover micro fluidic device.
2, since the size of microfluidic channel all at micron order, solution is by the control of numerical control micro-injection pump, therefore device is that very easy realization is integrated with microminiaturization.
3, raw materials cost is low, and the size of microfluidic channel is all at micron order, and micro-injection originally can realize the injection speed of μ L/min, and experiment needs raw material few, has solved raw materials cost greatly.
4, because two-sided drop is to generate by the shear force between fluid, therefore to have size distribution even for the drop of preparation, characteristics such as size adjustable, and resulting solid-liquid is also deposited the Janus construction unit and is also had monodispersity preferably.
5, because the size of two-sided drop is relevant with stability with the speed of fluid, have nothing to do with the material behavior of device, so identical at fluid, under the certain situation of injection speed, can keep good repeatability.
6, because the adding of magnetic or conductive nanometer particle can realize impressed field accurately controlling single Janus construction unit.
7, prepared colloidal photon crystal microballon is similar to molecular configuration on pattern, can realize from putting the preparation of some row molecule-type colloidal photon crystal microballons such as line, face, positive rectangular pyramid, trigonal bipyramid.
Description of drawings
Fig. 1 indicates discontinuous phase entrance 1,2 for the three-phase microfluidic channel synoptic diagram that the present invention designs among the figure, external phase entrance 3, outlet 4.
Fig. 2 is the molecule-type colloidal photon crystal microballon SEM sem photograph of the dots structure (being similar to argon molecule) of embodiment 1 preparation.
Fig. 3 is the molecule-type colloidal photon crystal microballon SEM sem photograph of the linear structure (being similar to hydrogen molecule) of embodiment 1 preparation.
Fig. 4 is the molecule-type colloidal photon crystal microballon SEM sem photograph of the planar structure (being similar to the boron trifluoride molecule) of embodiment 1 preparation.
Fig. 5 is the molecule-type colloidal photon crystal microballon SEM sem photograph of the positive tetrahedron structure (being similar to the tetracol phenixin molecule) of embodiment 1 preparation.
Fig. 6 is the molecule-type colloidal photon crystal microballon SEM sem photograph of the trigonal bipyramid structure (being similar to the phosphorus pentafluoride molecule) of embodiment 1 preparation.
Embodiment
Below by specific embodiment explanation the present invention, but the present invention not only is defined in these embodiment.
Three-phase microfluidic channel design: as shown in Figure 1, adopt two channels syringe needle, polydimethylsiloxane flexible rubber hose, threeway junction T type passage.This passage has three entrances: 1,2 entrances are disperse phase, are external phase, an outlet.This three-phase microfluidic system to the effects such as shearing force of disperse phase, generates the drop with bilateral structure by three alternate interfacial tensions and external phase.By numerical control micro-injection pump control flow rate of fluid.
Embodiment 1
1. the configuration particle diameter is 226nm, and massfraction is that the dispersion liquid of 30% monodisperse polystyrene microsphere is first disperse phase, is 0.2mL h with being connected the setting flow velocity with micro-injection pump behind the dispersion liquid inhalation syringe
-1
Configuration be mixed with the 0.2wt% ferriferrous oxide nano-particle EO3-TMPTA solution as second disperse phase, be 0.2mL h with is connected the setting flow velocity behind the solution inhalation syringe with micro-injection pump
-1
3. select for use methyl-silicone oil as continuous phase solution, and be connected with micro-injection pump behind the inhalation syringe that to set flow velocity be 2mL h
-1
4. start the three-phase micro fluidic device: treat that the external phase methyl-silicone oil is full of the syringe pump that starts two disperse phase behind the flexible rubber hose simultaneously fully, treats to obtain the drop template that stabilized uniform has bilateral structure behind the flow speed stability
5. the PE plastic cup that adopts the methyl-silicone oil shop fixtures is as collection container and keep having between the drop certain distance to prevent the drop cohesion, collector is statically placed in the ventilating kitchen under the room temperature, treats namely to have formed the Janus hydridization microballon assembled unit that has solid-liquid and deposit after solvent in the dispersion liquid hemisphere of polystyrene microsphere volatilizees fully.
6. because the adding of ferriferrous oxide nano-particle, make Janus hydridization microballon have certain responsiveness in magnetic field to external world, therefore using the effect of extraneous needle induces the Janus assembled unit directed mobile, and the Janus unit of control some amount is adjacent to each other combines together to liquid hemisphere, forms a function microballon that independently is similar to molecular structure
7. the solid-liquid of control different quantities and deposit the Janus assembled unit can obtain being similar to the composite structure of point-like, wire, planar, positive tetrahedron, trigonal bipyramid type, corresponds respectively to the argon molecule of monatomic structure, the hydrogen molecule of diatomic structure, boron trifluoride, tetracol phenixin, phosphorus pentafluoride.
1. the configuration particle diameter is 300nm, and massfraction is that the dispersion liquid of 30% monodisperse silica microspheres is first disperse phase, is 0.2mL h with being connected the setting flow velocity with micro-injection pump behind the dispersion liquid inhalation syringe
-1
Configuration be mixed with the 0.2wt% ferriferrous oxide nano-particle EO3-TMPTA solution as second disperse phase, be 0.2mL h with is connected the setting flow velocity behind the solution inhalation syringe with micro-injection pump
-1
3. select for use basic silicone oil as continuous phase solution, and be connected with micro-injection pump behind the inhalation syringe that to set flow velocity be 2mL h
-1
4. start the three-phase micro fluidic device: treat that the external phase methyl-silicone oil is full of the syringe pump that starts two disperse phase behind the flexible rubber hose simultaneously fully, treats to obtain the drop template that stabilized uniform has bilateral structure behind the flow speed stability
5. the PE plastic cup that adopts basic silicone oil shop fixtures is as collection container and keep having between the drop certain distance to prevent the drop cohesion, collector is statically placed in the ventilating kitchen under the room temperature, treats namely to have formed the Janus hydridization microballon assembled unit that has solid-liquid and deposit after solvent in the dispersion liquid hemisphere of polystyrene microsphere volatilizees fully.
6. because the adding of ferriferrous oxide nano-particle, make Janus hydridization microballon have certain responsiveness in magnetic field to external world, therefore using the effect of extraneous needle induces the Janus assembled unit directed mobile, and the Janus unit of control some amount is adjacent to each other combines together to liquid hemisphere, forms a function microballon that independently is similar to molecular structure
7. the solid-liquid of control different quantities and deposit the Janus assembled unit can obtain being similar to the composite structure of point-like, wire, planar, positive tetrahedron, trigonal bipyramid type, corresponds respectively to the argon molecule of monatomic structure, the hydrogen molecule of diatomic structure, boron trifluoride, tetracol phenixin, phosphorus pentafluoride.
Claims (10)
1. the preparation method of a molecule-type colloidal photon crystal microballon is characterized in that may further comprise the steps:
Building of three-phase microfluidic channel: adopt photoetching or soft quarter micro-processing technology set up the microchannel network, perhaps set up a T shape passage, this T shape passage has 3 openings, and one of them mouthful is two disperse phase entrances, a mouth is the external phase entrance, also has 1 mouth to be outlet;
The preparation of two-sided drop template: three kinds of solution of two disperse phase and external phase are respectively charged into syringe and are connected with separately entrance, flow velocity with numerical control micro-injection pump control three-phase solution obtains particle diameter stabilized uniform bilateral structure drop template from exporting out;
The preparation of solid-liquid coexistence Janus particulate: with the drop template dry solidification of bilateral structure, obtain having concurrently solid hemisphere and drop hemisphere in the solid-liquid coexistence Janus of one particulate;
The preparation of molecule-type colloidal photon crystal microballon: be construction unit with solid-liquid coexistence Janus particulate, by impressed field the Janus particulate carried out precision and control, finish the controllable operating of single drop template, be assembled into molecule-type colloidal photon crystal microballon.
2. according to the preparation method of claims 1 described molecule-type colloidal photon crystal microballon, it is characterized in that described T shape passage is made up of parallel double passage draw point, polymkeric substance flexible rubber hose, threeway, wherein parallel double passage draw point is the disperse phase passage, and the polymkeric substance flexible rubber hose is the external phase passage.
3. according to the preparation method of claims 2 described molecule-type colloidal photon crystal microballons, it is characterized in that described polymkeric substance flexible rubber hose is polydimethylsiloxane pipe, polyvinyl chloride pipe, polyfluortetraethylene pipe or polyether-ether-ketone pipe.
4. according to the preparation method of claims 1 described molecule-type colloidal photon crystal microballon, it is characterized in that described microchannel network using quartz plate, sheet glass, polymethylmethacrylate or polydimethylsiloxane micro-fluid chip are made.
5. according to the preparation method of claims 1 described molecule-type colloidal photon crystal microballon, one in described two disperse phase of preparation that it is characterized in that face drop template are water, the another one disperse phase is cross-linked resin monomer and the mixing solutions that can produce the nanoparticle of responsiveness to impressed field, external phase is oil phase, and water, mixing solutions and oil phase can form stable three phase boundary, and wherein water is single dispersoid solution of massfraction 20-50%.
6. according to the preparation method of claims 5 described molecule-type colloidal photon crystal microballons, it is characterized in that described single dispersoid solution is a kind of in polystyrene colloid particle solution, polymethylmethacrylate colloidal particle solution, silicon dioxide colloid particle solution and the colloidal tio 2 particle solution.
7. according to the preparation method of claims 5 described molecule-type colloidal photon crystal microballons, it is characterized in that described cross-linked resin monomer is ethoxylated trimethylolpropane triacrylate (EO
3-TMPTA), trimethylolpropane trimethacrylate (TMPTMA), propoxylation Viscoat 295 (PO
3-TMPTA), a kind of in tri (propylene glycol) diacrylate (TPGDA) and the propylene glycol diacrylate (DPGDA); The described nanoparticle that can produce responsiveness to impressed field is a kind of or its combination in graphite, iron, four oxidation trisomes, ferric oxide, cobalt, nickel, silver, copper, the golden nanometer particle.
8. according to the preparation method of claims 5 described molecule-type colloidal photon crystal microballons, it is characterized in that described oil phase is a kind of in methyl-silicone oil, paraffin oil and the toluene.
9. according to the preparation method of claims 1 described molecule-type colloidal photon crystal microballon, the diameter that it is characterized in that the bilateral structure drop described in the preparation of two-sided drop template reduces size droplet diameter by increasing the external phase flow velocity or reducing the disperse phase flow velocity, increases size droplet diameter by reducing the external phase flow velocity or increasing the disperse phase flow velocity.
10. according to the preparation method of claims 1 described molecule-type colloidal photon crystal microballon, it is characterized in that in the preparation of solid-liquid coexistence Janus particulate that the solid hemisphere of described solid-liquid coexistence Janus particulate is by the spontaneous colloidal photon crystal that is assembled into of single dispersoid solution in the drying process; The liquid hemisphere of described solid-liquid coexistence Janus particulate can produce by the cross-linked resin monomer with to impressed field that the mixing solutions of the nanoparticle of responsiveness forms, and it still keeps original liquid form without any variation in drying process.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103846067A (en) * | 2014-03-19 | 2014-06-11 | 中国科学技术大学 | Magnetic isomerism Janus microsphere with controllable grain size and morphology as well as preparation method thereof and used microfluid control device |
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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 |
| CN113349436A (en) * | 2021-06-17 | 2021-09-07 | 武汉市昱宸峰科技有限公司 | Heating non-combustion cigarette with fuming blasting beads |
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| CN103846067A (en) * | 2014-03-19 | 2014-06-11 | 中国科学技术大学 | Magnetic isomerism Janus microsphere with controllable grain size and morphology as well as preparation method thereof and used microfluid control device |
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| CN111481680A (en) * | 2020-05-29 | 2020-08-04 | 南京鼓楼医院 | Adhesive microcarrier imitating boston ivy and preparation method thereof |
| CN112625281A (en) * | 2020-12-18 | 2021-04-09 | 南京鼓楼医院 | Janus structural color film for visual sensing and preparation method thereof |
| CN112625281B (en) * | 2020-12-18 | 2023-05-12 | 南京鼓楼医院 | Janus structural color film for visual sensing and preparation method thereof |
| 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 |
| CN113349436A (en) * | 2021-06-17 | 2021-09-07 | 武汉市昱宸峰科技有限公司 | Heating non-combustion cigarette with fuming blasting beads |
| CN114720683A (en) * | 2022-05-20 | 2022-07-08 | 南京鼓楼医院 | Preparation method and application of magnetic Janus microcarrier for bladder cancer exosome multivariate analysis |
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