CN104611762A - Crack-free colloidal crystal, crack-free inverse colloidal crystal and preparing method of the crack-free colloidal crystal and the crack-free inverse colloidal crystal - Google Patents
Crack-free colloidal crystal, crack-free inverse colloidal crystal and preparing method of the crack-free colloidal crystal and the crack-free inverse colloidal crystal Download PDFInfo
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- CN104611762A CN104611762A CN201410797914.5A CN201410797914A CN104611762A CN 104611762 A CN104611762 A CN 104611762A CN 201410797914 A CN201410797914 A CN 201410797914A CN 104611762 A CN104611762 A CN 104611762A
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Abstract
The invention provides a method of preparing a crack-free colloidal crystal and a crack-free inverse colloidal crystal through self assembly by adding a proper amount of sodium silicate, potassium silicate or a mixture of the sodium silicate and the potassium silicate into a microsphere emulsion. The method includes following steps of: (1) adding a proper amount of the sodium silicate, the potassium silicate or a mixture of the sodium silicate and the potassium silicate into the colloid microsphere emulsion, and after full dissolution, adding the obtained mixture into a container; (2) inserting a substrate vertically or obliquely into the container; and (3) allowing the container to stand at room temperature or in an oven, and allowing microspheres to perform self-assembly. By addition of the silicate or the sillicates, gaps among the microspheres are filled with silicate hydrolyzates, so that microsphere distance reduction caused by solvent evaporation is effectively inhibited, thus avoiding generation of cracks in colloidal crystal films. The method also includes (4) removing the silicate hydrolyzates among the microspheres through a chemical or physical method to obtain the crack-free colloidal crystal, or removing the microspheres to obtain the crack-free inverse colloidal crystal.
Description
Technical field
The present invention relates to a kind of flawless colloidal crystal, anti-phase colloidal crystal and preparation method thereof, belong to colloidal crystal self-assembly and preparing technical field thereof.
Background technology
Colloidal crystal is the regular ordered 3 D structure with certain crystal formation of arrangement formed by self-assembly by colloid micro ball, because its specific refraction periodically converts, create and the light intensity of a certain specific band is reflected and the effect of the light-transmissive of its all band, utilize colloidal crystal for template, the anti-phase colloidal crystal with photonic band-gap can be prepared, i.e. photonic crystal.In addition, colloidal crystal, due to the pore structure of its rule, also has huge application prospect in the field such as chromatogram and catalysis.The preparation method of current colloidal crystal mainly contains gravity deposition, vertical deposition method, level deposition method, spin-coating method, liquid-gas interface self-assembly, ink-jet printing process etc.Wherein the most frequently used is vertical deposition method, and the method becomes the method for widespread use the most in research and production because preparation cycle is relatively short, the colloidal crystal compound with regular structure of preparation, defect are less.But in the method, microballoon arrange on substrate regular after, along with the volatilization of solvent between microballoon, microballoon spacing diminishes gradually, is difficult to invariably occur crackle after dry in micro-sphere array.
Chinese patent application CN102502659A and CN103145134A proposes one and is at high temperature calcined by silicon dioxide microsphere, prepares the method for flawless colloidal crystal afterwards for self-assembly.The method needs to carry out redispersion to microballoon after high-temperature calcination, and the thorough degree of redispersion has a strong impact on the degree of order of the colloidal crystal that self assembling process is formed, and affects the productive rate of colloidal crystal.In addition, the method be not suitable for the self-assembly of polymer microballoon such as polystyrene or poly (methyl methacrylate) micro-sphere, because these microballoons cannot bear higher calcining temperature.
Summary of the invention
The object of the invention is to propose a kind of by adding appropriate water glass, potassium silicate or the mixture of the two in microballoon emulsion, thus avoid the method that cracks in colloidal crystal preparation process.
Method proposed by the invention comprises following steps:
(1) in the emulsion of colloid micro ball, add appropriate water glass, potassium silicate or the mixture of the two, after dissolving completely, insert in container;
(2) insert substrate in a reservoir, the vertical or slant setting of substrate is among emulsion;
(3) container is statically placed in room temperature or baking oven, due to solvent naturally volatilize, the machinery lift of the extraction of emulsion or substrate makes emulsion liquid level counter substrate decline, thus along the direction of the inswept substrate of liquid level, microballoon self-assembly on substrate forms the colloidal crystal film of regular arrangement.Due to the interpolation of silicate, its hydrolysate is filled between microballoon, makes the microballoon spacing produced by solvent evaporates reduce to obtain effective suppression, thus avoids the appearance of crackle in colloidal crystal film;
(4) the silicate cement hydrolysis products removed between microballoon finally by chemistry or physical method can obtain colloidal crystal, or can also remove microballoon and obtain anti-phase colloidal crystal.
In step 1, the weight of the water glass added in colloid micro ball emulsion, potassium silicate or the mixture of the two is the 0.02-8% of emulsion weight, is preferably the 0.05-3% of emulsion weight.
Colloid micro ball described in step 1 can be polymer microballoon or inorganic microspheres, polymer microballoon preferred self-polystyrene microballoon, crosslinked polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyethyl methacrylate microballoon, inorganic microspheres is preferably silicon dioxide microsphere; In emulsion, the particle diameter of microballoon is 80nm-2000nm.The disperse phase forming emulsion is generally water or ethanol.
In above-mentioned preparation method, in step 2, substrate is generally glass, silica glass, silicon chip etc.Substrate vertically or slant setting among emulsion.
When emulsion disperse phase used is water, be generally positioned among baking oven, temperature controls as 30-95 DEG C, preferred 40-60 DEG C, constant temperature 24h, thus along with the volatilization of solvent, microballoon is self-assembly on substrate.If disperse phase used is ethanol, general temperature controls between 0-70 DEG C, preferred 10-40 DEG C.
In above-mentioned preparation method's step (3), by the silicate cement hydrolysis products between the method removal microballoon of hydrofluoric acid etch, thus flawless colloidal crystal can be obtained; If when microballoon is polymkeric substance in addition, by being fired to more than 450 DEG C or by selecting suitable organic solvent to dissolve microballoon under aerobic environment, thus flawless anti-phase colloidal crystal can be obtained.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of the colloidal crystal of being filled by silicate cement hydrolysis products that Fig. 1 obtains for embodiment 1.
The scanning electron microscope (SEM) photograph of the colloidal crystal obtained after silicate cement hydrolysis products between the removal microballoon that Fig. 2 obtains for embodiment 1.
Embodiment
The experimental technique used in the following stated embodiment if no special instructions, is ordinary method.
The raw material used in the following stated example, reagent etc., if no special instructions, be and can buy from commercial channels.
Embodiment 1, SiO
2add water glass in microballoon emulsion and prepare flawless colloidal crystal by self-assembly.
From buying the SiO that particle diameter is 290nm on the market
2(disperse phase is H to microballoon emulsion
2o), with deionized water, emulsion being diluted to weight percent is 0.05%, gets 15ml emulsion and is positioned in 25ml beaker, add 0.15g water glass wherein subsequently, and by ultrasonic vibration, each component is mixed.
The silicon chip of 1cm × 2cm is placed in Piranha solution (98% vitriol oil and mass percentage concentration be 30% aqueous hydrogen peroxide solution be by volume 3:1 preparation mixing solutions; This solution has strong oxidizing property, and meeting organic solvent may be explosion caused, answers rigorous concentration safety in using) in, 90 DEG C of heat treated 30min, then use washed with de-ionized water, and dry up with nitrogen.Afterwards, vertically inserted by silicon chip and be equipped with in the beaker of emulsion, upper end stays 0.5cm to expose emulsion liquid level.
Beaker is positioned in 60 DEG C of baking ovens, place after 24 hours, due to the volatilization of moisture content, liquid level is down under silicon chip, on silicon chip, silicon dioxide microsphere self-assembly forms colloidal crystal film, because water glass hydrolysate is filled between microballoon, not there is crackle in colloidal crystal film, and its scanning electron microscope (SEM) photograph as shown in Figure 1.
Thereafter, by the silicon chip with colloidal crystal film, a capacity of inserting is in the polyethylene bottle of 1L, puts into the open polyethylene bottle that the capacity that 5ml 50%HF is housed is 10ml afterwards, cover lid in bottle, places 3 minutes.Because water glass hydrolysate is comparatively loose, fallen very soon, and silicon dioxide microsphere still remains by HF vapor etch, form flawless colloidal crystal, its scanning electron microscope (SEM) photograph as shown in Figure 2.
Embodiment 2, by preparing flawless polystyrene colloid crystal adding of potassium silicate.
First prepare by the method for letex polymerization the polystyrene colloid microballoon that particle diameter is 480nm: successively 500ml deionized water and 18ml vinylbenzene are added and be equipped with in the 1L there-necked flask of mechanical stirrer and reflux condensing tube, water-bath there-necked flask being placed in 60 DEG C is carried out heating and leads to nitrogen stirring, mechanical stirring speed is 300r/min, after 60 minutes, 0.25g Potassium Persulphate is added as letex polymerization initiator in there-necked flask, after reaction 25h, obtain the emulsion that particle diameter is 480nm polystyrene colloid microballoon, the standard deviation of this polystyrene microsphere particle diameter is less than 3%.
Microspheres amount mensuration is carried out to the above-mentioned colloid micro ball emulsion prepared, and by adding of deionized water, the weight percent of microballoon in emulsion is adjusted to 0.08%, getting 25ml is positioned in the flat centrifuge tube of 50ml capacity, add 0.18g potassium silicate wherein subsequently, and by ultrasonic vibration, each component is mixed.
The sheet glass of 1cm × 2cm is placed in Piranha solution, and 90 DEG C of heat treated 30min, then use washed with de-ionized water, and dry up with nitrogen.Afterwards, vertically inserted in centrifuge tube by sheet glass, upper end stays 0.5cm to expose emulsion liquid level.
Flat centrifuge tube is positioned in 60 DEG C of baking ovens, after 24 hours, due to the volatilization of moisture content, liquid level is down under sheet glass, on sheet glass, polystyrene microsphere is self-assembled into as colloidal crystal film, and because potassium silicate hydrolysate is filled between microballoon, colloidal crystal film does not occur crackle.
Finally, by the sheet glass soaking at room temperature with colloidal crystal film among dimethyl formamide, place 12 hours, thereafter sheet glass is taken out, after residual toluene volatilization, flawless anti-phase colloidal crystal film can be obtained.
Claims (4)
1. a flawless colloidal crystal, anti-phase colloidal crystal and preparation method thereof, the method passes through the method adding water glass, potassium silicate or the mixture of the two in the colloid micro ball emulsion used in self assembling process, avoid the colloidal crystal film prepared to crack, comprise the steps:
(1) in the emulsion of colloid micro ball, add appropriate water glass, potassium silicate or the mixture of the two, fully mix, insert in container;
(2) insert substrate in a reservoir, the vertical or slant setting of substrate is among emulsion;
(3) container is statically placed in room temperature or baking oven, due to solvent naturally volatilize, the machinery lift of the extraction of emulsion or substrate makes emulsion liquid level counter substrate decline, thus along the direction of the inswept substrate of liquid level, microballoon self-assembly on substrate forms the colloidal crystal film of regular arrangement, simultaneously because water glass hydrolysate is filled between microballoon, thus avoid the generation of crackle in colloidal crystal;
(4) prepare flawless colloidal crystal by chemistry or the silicate cement hydrolysis products that can remove between microballoon of physical method, or microballoon can also be removed obtain the anti-phase colloidal crystal of flawless.
2. preparation method according to claim 1, it is characterized in that: in step (1), in colloid micro ball emulsion, add water glass or potassium silicate, the water glass added or the weight of potassium silicate are the 0.02-8% of emulsion weight, are preferably the 0.05-3% of emulsion weight.
3. the colloid micro ball emulsion according to claim 1-2, colloid micro ball is polymer microballoon or inorganic microspheres, the preferred self-polystyrene microballoon of polymer microballoon, the polystyrene microsphere of divinyl benzene crosslinked, poly (methyl methacrylate) micro-sphere, polyethyl methacrylate microballoon, inorganic microspheres is preferably silicon dioxide microsphere; In emulsion, the particle diameter of microballoon is 80nm-2000nm.
4. the method as described in right 1, is characterized in that, substrate is vertical or tilt to be inserted among emulsion, and the angle angle of substrate and emulsion liquid level is 5-175 degree.
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|---|---|---|---|
| CN201410797914.5A CN104611762A (en) | 2014-12-19 | 2014-12-19 | Crack-free colloidal crystal, crack-free inverse colloidal crystal and preparing method of the crack-free colloidal crystal and the crack-free inverse colloidal crystal |
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| CN201410797914.5A CN104611762A (en) | 2014-12-19 | 2014-12-19 | Crack-free colloidal crystal, crack-free inverse colloidal crystal and preparing method of the crack-free colloidal crystal and the crack-free inverse colloidal crystal |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338447A (en) * | 2008-08-29 | 2009-01-07 | 哈尔滨工业大学 | Method for self-assembling photonic crystal |
| US20110144253A1 (en) * | 2009-12-14 | 2011-06-16 | Chan Chih-Chieh | Method for Making a 3D Photonic Crystal |
| CN102732942A (en) * | 2011-03-31 | 2012-10-17 | 中国科学院化学研究所 | Preparation method of self-supporting crack-free photonic crystal |
| CN102995101A (en) * | 2012-11-28 | 2013-03-27 | 中国科学技术大学 | Slope-induced self-assembly colloidal crystal based on industrialized application and preparation method thereof |
-
2014
- 2014-12-19 CN CN201410797914.5A patent/CN104611762A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338447A (en) * | 2008-08-29 | 2009-01-07 | 哈尔滨工业大学 | Method for self-assembling photonic crystal |
| US20110144253A1 (en) * | 2009-12-14 | 2011-06-16 | Chan Chih-Chieh | Method for Making a 3D Photonic Crystal |
| CN102732942A (en) * | 2011-03-31 | 2012-10-17 | 中国科学院化学研究所 | Preparation method of self-supporting crack-free photonic crystal |
| CN102995101A (en) * | 2012-11-28 | 2013-03-27 | 中国科学技术大学 | Slope-induced self-assembly colloidal crystal based on industrialized application and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BENJAMIN HATTON ET AL.: "Assembly of large-area, highly ordered, crack-free inverse opal films", 《PNAS》 * |
| LIKUI WANG ET AL.: "Fabrication of Crack-Free Colloidal Crystals Using a Modified Vertical Deposition Method", 《J. PHYS. CHEM. C》 * |
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