EUTECTIC COLLOIDAL CRYSTAL, EUTECTIC COLLOIDAL CRYSTAL SOLIDIFIED BODY, AND METHODS FOR PRODUCING THEM
20170361297 · 2017-12-21
Assignee
Inventors
- Junpei YAMANAKA (Nagoya-shi, Aichi, JP)
- Akiko TOYOTAMA (Nagoya-shi, Aichi, JP)
- Tohru OKUZONO (Nagoya-shi, Aichi, JP)
- Satoshi UDA (Sendai-shi, Miyagi, JP)
- Jun NOZAWA (Sendai-shi, Miyagi, JP)
Cpc classification
C08F222/385
CHEMISTRY; METALLURGY
C08L2205/025
CHEMISTRY; METALLURGY
C08F222/385
CHEMISTRY; METALLURGY
C08L2205/03
CHEMISTRY; METALLURGY
C08F257/02
CHEMISTRY; METALLURGY
International classification
Abstract
[Object] Provided are a “eutectic colloidal crystal” which is an aggregate of plural kinds of colloidal crystals having different lattice constants, a solidified body of the eutectic colloidal crystal, and methods for producing them.
[Resolution means] The eutectic colloidal crystal of the present invention contains two or more kinds of colloidal crystals composed of substantially monodispersed colloidal particles having different particle sizes. This eutectic colloidal crystal is obtained by providing a colloidal dispersion of two or more kinds of colloidal particles having different particle sizes, and a polymer which will not substantially adsorb to the colloidal particles (the coefficient of variation in particle size of these colloidal particles is less than 20%) dissolved in a dispersion medium (dispersion preparation process), and allowing the colloidal dispersion to stand (eutectoid process).
Claims
1-14. (canceled)
15. A eutectic colloidal crystal comprising two or more kinds of opal-type colloidal crystals composed of colloidal particles having a coefficient of particle size variation of less than 20%, the colloidal particles being mixed together at fixed positions.
16. The eutectic colloidal crystal of claim 15, wherein the lattice planes of the colloidal crystals are oriented on the same plane.
17. The eutectic colloidal crystal of claim 15, wherein the colloidal crystals are composed of polymer colloidal particles.
18. The eutectic colloidal crystal of claim 17, wherein the polymer colloidal particles are composed of polystyrene.
19. The eutectic colloidal crystal of claim 15, wherein the average particle size of the colloidal particles is from 1 nm to 50 μm.
20. The eutectic colloidal crystal of claim 15, wherein the colloidal crystals are composed of silica particles.
21. A eutectic colloidal crystal solidified body prepared by immonbilizing the eutectic colloidal crystal of claim 15 by a immonbilizing agent.
22. A method for producing eutectic colloidal crystal comprising: a dispersion preparation process of preparing a colloidal dispersion where two or more kinds of colloidal particles having different particle sizes are dispersed in a dispersion medium which dissolves a polymer, the coefficient of variation of the particle size of the colloidal particles is less than 20%, and the specific gravity of the dispersion medium is smaller than that of the colloidal particles; and a eutectoid process of depositing two or more kinds of opal-type colloidal crystals having different lattice constants by allowing the colloidal dispersion to stand.
23. The method for producing the eutectic colloidal crystal of claim 22, wherein the colloidal crystals are composed of polymer particles.
24. The method for producing the eutectic colloidal crystal of claim 22, wherein the colloidal crystals are composed of polystyrene particles.
25. The method for producing the eutectic colloidal crystal of claim 22, wherein the colloidal crystals are composed of silica particles.
26. The method for producing the eutectic colloidal crystal of claim 22, wherein the average particle size of the colloidal particles is from 1 nm to 50 μm.
27. The method for producing the eutectic colloidal crystal of claim 22, wherein the volume fraction of the colloidal particles to the colloidal dispersion is from 0.001 to 0.1.
28. A method for producing a eutectic colloidal crystal solidified body comprising: a dispersion preparation process of preparing a colloidal dispersion where two or more kinds of colloidal particles having different particle sizes are dispersed in a dispersion medium which dissolves a polymer and a photocurable resin, the coefficient of variation of the particle size of the colloidal particles is less than 20%, and the specific gravity of the dispersion medium is smaller than that of the colloidal particles; a eutectoid process of depositing two or more kinds of opal-type colloidal crystals having different lattice constants by allowing the colloidal dispersion to stand; and a photoirradiation process of immonbilizing the eutectic colloidal crystal formed in the eutectoid process by photoirradiation.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
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[0046] The eutectic colloidal crystal can be produced according to the process shown in
[0047] (Dispersion Preparation Process S1)
[0048] Firstly, as the dispersion preparation process S1, a solution of a polymer dissolved in a dispersion medium is prepared. Two or more kinds of monodispersed colloidal particles (three kinds in
[0049] Examples of the water-soluble nonionic polymer include polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyether, and polyvinyl pyrrolidone. Examples of the water-soluble ionic polymer include cationic polymers such as polyvinylpyridine, polyvinyl benzyl ammonium, and polypeptide; and anionic polymers such as polyacrylic acid, polyacrylamide, polypeptide, and natural polymers such as polysaccharides. In addition, examples of the hydrophobic polymer include polystyrene and polydimethylsiloxane (the solvent for them may be toluene or xylene).
[0050] In the selection of these polymers, the polymers having a charge opposite to that of the surface charge of the colloidal particles are not preferred, because they adsorb to colloidal particles to form a charged colloid. However, even the polymer having a charge opposite to that of the surface charge of the colloidal particles can be used by increasing the salt concentration, which markedly thins the electric double layer, allows the approach of the colloidal particles to each other, forms a hard sphere colloid, and finally, as will be described later, the difference in the polymer concentration causes the difference in the osmotic pressure to generate depletion attraction, and forms opal-type colloidal crystals. Furthermore, this phenomenon can be positively used to adjust the salt concentration in the colloid as appropriate to control the thickness of the electric double layer, which allows the control of, for example, the attraction between the colloidal particles, the growth rate of the opal-type colloidal crystals, and even the half width to the light of the colloidal crystals. Examples of the method for controlling the salt concentration include the control of the abundance of ionic groups (carboxylates, amino groups, etc.) in polymers, and addition of salts.
[0051] Alternatively, the eutectic colloidal crystal may be produced by adding, in addition to the colloidal particles forming opal-type colloidal crystals, the particles finer than the colloidal particles as a polymer, and making the added particles exert the below-described depletion attraction.
[0052] (Eutectoid Process S2)
[0053] In the next place, colloidal dispersion prepared in the dispersion preparation process S1 is taken by a dropper or the like, placed on a glass bottom dish or the like, and allowed to stand (eutectoid process S2). In the eutectoid process S2, the colloidal particles having the same particle size attract each other to flocculate, and a eutectic colloidal crystal composed of three or more kinds of colloidal crystals C1, C2, and C3 having different lattice constants is formed.
[0054] The reason for the attraction of the colloidal particles is presumed as follows. More specifically, the polymer added to the colloidal dispersion is dissolved in the dispersion medium, and intrinsically dispersed in the dispersion medium uniformly. However, as shown in
[0055] In the formation process of the eutectic structure of the colloidal particles, a behavior similar to eutectic formation in the atomic and molecular system is observed. More specifically, the approach between the colloidal particles is made between the particles having the same particle size to form the first colloidal crystals C1, and the colloidal particles having the other particle size gather at the grain boundaries of the first colloidal crystals (left of
[0056] During the formation of the colloidal crystals C1, C2, and C3, the colloidal crystals C1, C2, and C3 composed of the colloidal particles having a higher specific gravity than the dispersion medium keep on sedimentation. And finally they precipitate on the bottom of the container, and form an aggregate (more specifically, eutectic colloidal crystal) at the positions where the colloidal crystals C1, C2, and C3 are fixed. At this time, the colloidal crystals are oriented on the bottom.
[0057] Examples further embodying the present invention are described below.
EXAMPLE 1
[0058] In Example 1, a eutectic colloidal crystal was made using three kinds of monodispersed polystyrene particles. More specifically, the first polystyrene particles were spherical charged polystyrene particles PS600 (Thermo Scientific, purchased in the form of an aqueous dispersion with diameter d=600 nm and volume fraction=0.05, coefficient of variation in particle size: 3%), the second polystyrene particles were spherical green fluorescent charged polystyrene particles G500 (commercial product, diameter d=500 nm, volume fraction=0.1, coefficient of variation in particle size: 5%), and the third polystyrene particles were spherical red fluorescent charged polystyrene particles DR390 (commercial product, diameter d=about 390 nm, volume fraction=0.01, coefficient of variation in particle size: 5%). These particles were purified by a dialysis method and an ion exchange method, mixed at the ratio of the first polystyrene particles: second polystyrene particles: third polystyrene particles=1:0.1:0.05 (volume ratio) (200 μL in total), further 200 μL of a 0.1 w % sodium polyacrylate PAANa (molecular weight: one million, degree of neutralization: 50%) aqueous solution was added, and stirred to make a hard sphere colloid sample. 400 μL of the hard sphere colloid sample was placed in a glass bottom dish container, allowed to stand for several hours to one week, and observed with an inverted optical microscope. The results are shown in
[0059] Furthermore, as shown in
EXAMPLE 2
[0060] In Example 2, a eutectic colloidal crystal was made using two kinds of monodispersed polystyrene particles. More specifically, the first polystyrene particles were spherical charged polystyrene particles PS200 (Thermo Scientific, diameter d=200 nm, volume fraction=0.1, coefficient of variation in particle size: 5%), and the second polystyrene particles were spherical charged polystyrene particles PS250 (synthesized by the inventors, diameter d=250 nm, volume fraction=0.068, coefficient of variation in particle size: 15%).
[0061] The polystyrene particles were synthesized by a soap free emulsion polymerization method. More specifically, 210 mL of water, 100 mL of methanol, 20 mL of styrene monomer, 0.15 g of sodium p-styrenesulfonate as an anionic comonomer, and 1 mL of divinylbenzene were mixed, and stirred for about 30 minutes in a constant temperature bath at 80° C., at a rotation speed of 300 rpm, and in an argon atmosphere. Thereafter, 0.1 g of potassium peroxodisulfate as a radical polymerization initiator was added and stirred for 7 hours, thus synthesizing polystyrene particles.
[0062] These particles were purified by a dialysis method and an ion exchange method, mixed at a ratio of the first polystyrene particles:second polystyrene particles=25:1 (volume ratio) (75 μL in total), further 200 μL of sodium polyacrylate PAANa (molecular weight:million, degree of neutralization:50%, 0.1 w % aqueous solution) was added, and stirred to make a colloid sample. The procedure thereafter is the same as that in Example 1, so that the explanation thereof is omitted.
[0063] The precipitate formed on the glass bottom dish as described above were subjected to optical microphotographing and reflection spectrum measurement (fiber spectrometer, Ocean Optics, USB2000). The results are shown in
EXAMPLE 3
[0064] In Example 3, a eutectic colloidal crystal was made using three kinds of monodispersed polystyrene particles. More specifically, the first polystyrene particles were spherical charged polystyrene particles PS200 (Thermo Scientific, diameter d=200 nm, volume fraction=0.1), the second polystyrene particles were spherical charged polystyrene particles PS250 (synthesized by the inventors (the particles used in Example 2), diameter d=250 nm, volume fraction=0.068), and the third polystyrene particles were spherical charged polystyrene particles PS300 (Thermo Scientific, diameter d=about 300 nm, volume fraction=0.1, coefficient of variation in particle size: 3%). These particles were purified by a dialysis method and an ion exchange method, mixed at the ratio of the first polystyrene particles:second polystyrene particles:third polystyrene particles=4:3:5 (volume ratio) (100 μL in total), further 200 μL of a 0.1 w % sodium polyacrylate PAANa (molecular weight:one million, degree of neutralization 50%) aqueous solution was added, and stirred to make a colloidal dispersion. The procedure thereafter is the same as that in Example 1, so that the explanation thereof is omitted.
[0065] The precipitate formed on the glass bottom dish as described above were subjected to optical microphotographing and reflection spectrum measurement (fiber spectrometer, Ocean Optics, USB2000). The results are shown in
EXAMPLE 4
[0066] <Preparation of Eutectic Colloidal Crystal Solidified Body>
[0067] In Example 4, the eutectic colloidal crystal was fixed by photocurable hydrogel using two kinds of monodispersed polystyrene particles.
[0068] More specifically, spherical charge polystyrene particle PS600 (Thermo Scientific, diameter d=200 nm, volume fraction=0.1) as the first polystyrene particles, and spherical charge polystyrene particle PS430 (synthesized by the inventors (the particles used in Example 2, diameter d=430 nm, volume fraction=0.068) as the second polystyrene particles were purified by a dialysis method and an ion exchange method, mixed at the ratio of the first polystyrene particles:second polystyrene particles=5:1 (volume ratio) (50 μL in total), further 200 μL of a 0.1 wt % aqueous solution of sodium polyacrylate PAANa (molecular weight:one million, degree of neutralization 50%), 250 μL of the following gelling agent, and 500 μL of water were added and stirred to make a colloidal dispersion. The procedure thereafter is the same as that in Example 1; after confirming the formation of the eutectic colloidal crystal by an optical microscope, polymerization of the gelling agent was initiated by ultraviolet irradiation, whereby a eutectic colloidal crystal solidified body was obtained.
[0069] Composition of Gelling Agent
[0070] Gel monomer: N,N′-dimethylol acrylamide (N-MAM) 0.67 mol/L
[0071] Crosslinking agent: methylenebisacrylamide (BIS) 10 mmol/L
[0072] Photopolymerization initiator: [0073] 2,2′-azobis[2-methyl-N-[2-hydroxyethyl]-propionamide 4 mg/mL
[0074] As a result of this, as shown in
[0075] <Influence of Particle Size on Formation of Eutectic Colloidal Crystal>
[0076] In order to determine how much difference in colloidal particle size is necessary for the formation of a eutectic colloidal crystal in the production of a eutectic colloidal crystal composed of different two kinds of monodispersed colloidal particles, the following experiment was carried out using the colloidal particles of various particle sizes.
[0077] More specifically, the polystyrene (PS) particles (Thermo Scientific and others, PS-1 to PS-5) and silica particles (Nippon Shokubai Co., Ltd, S-1 to S-4) having various particle sizes shown in Table 1 were used, and sodium polyacrylate (NaPAA), which had been prepared by adding NaOH to polyacrylic acid (Wako Pure Chemical Industries, Ltd.) to make a sample with a degree of neutralization of 50%, was used as a polymer. In addition, two kinds of colloidal particles dispersions and 0.1 wt % NaPAA were mixed so as to make the total concentration of the two kinds of colloidal particles 3.0 vol %, thus producing a eutectic colloidal crystal. Table 1 shows the particle size d (nm) and the number of surface charges Z (count/particle) of the colloidal particles. Table 2 shows the combination of the two-component colloidal systems and the ratio of the particle size of the two kinds of colloidal particles used in the experiment.
TABLE-US-00001 TABLE 1 Polystyrene PS-1 PS-2 PS-3 PS-4 PS-5 d (nm) 171 205 211 247 282 Z (/particles) 561 649 767 745 1302 Silica S-1 S-2 S-3 S-4 d (nm) 189 204 264 271 Z (/particles) 719 608 1422 1361
TABLE-US-00002 TABLE 2 Particle size Large Small of (L)/particle particles (L) particles (S) size of (S) Example 5 PS-5 PS-1 1.65 Example 6 PS-4 PS-1 1.44 Example 7 PS-3 PS-1 1.23 Example 8 PS-3 PS-2 1.03 Example 9 S-3 S-2 1.29 Example 10 S-2 S-l 1.08 Example 11 S-4 S-3 1.03
[0078] The Case Using Polystyrene Particles as Colloidal Particles
[0079] The reflection spectrum was measured two to four days after the preparation of the eutectic colloidal crystal. As a result of this, in Examples 5 to 8 where polystyrene particles were used as colloidal particles, as shown in
[0080] (Drawing of Phase Diagram)
[0081] Using the four kinds of polystyrene colloidal particles (PS-1 to PS-4) shown in Table 1, colloidal dispersions were prepared at various particle size ratios (r.sub.L/r.sub.S) and various volume fractions, and allowed to stand. Thereafter, the reflection spectra of the precipitates were measured, and the presence or absence of the generation of colloidal crystals was examined, thereby drawing a phase diagram. The result is shown in
[0082] The Case Using Silica Particles as Colloidal Particles
[0083] The reflection spectrum was measured two to four days after the preparation of the eutectic colloidal crystal. As a result of this, in Examples 9 to 11 where silica particles were used as colloidal particles, as shown in
[0084] (Drawing of Phase Diagram)
[0085] Using the four kinds of silica colloidal particles (S-1 to S-4) shown in Table 1, colloidal dispersions were prepared at various particle size ratios (r.sub.L/r.sub.S) and various volume fractions, and allowed to stand. Thereafter, the reflection spectra of the precipitates were measured, and the presence or absence of the generation of colloidal crystals was examined, thereby drawing a phase diagram. The result is shown in
[0086] <Formation of Eutectic Colloidal Crystal Composed of Polystyrene Particles and Silica Particles>
[0087] In Example 12, polystyrene colloidal particles PS-5 (2.5 vol %) and silica colloidal particles S-2 (:0.5 vol %) were mixed to make a colloidal dispersion, and this dispersion was allowed to stand to prepare a eutectic colloidal crystal composed of polystyrene colloidal crystals and silica colloidal crystals.
[0088] On the other hand, in Comparative Example 1, a colloidal dispersion was prepared from polystyrene colloidal particles PS-5 (3 vol %) alone, and the dispersion was allowed to stand to prepare polystyrene colloidal crystals.
[0089] In Comparative Example 2, a colloidal dispersion composed of silica colloidal particles S-2 (3.0 vol %) alone was prepared, and allowed to stand to prepare silica colloidal crystal.
[0090] The eutectic colloidal crystal of Example 12 and the colloidal crystals of Comparative Examples 1 and 2 thus prepared were measured for the reflection spectra 2 to 4 days after preparation.
[0091] As a result of this, as shown in
[0092] According to these results, it was found that a eutectic colloidal crystal was obtained even by mixing colloidal particles of different components, or silica colloidal particles and polystyrene colloidal particles.
[0093] The present invention is not limited to the description of the examples of the invention in any way. The present invention includes various modification aspects capable of being easily conceived by a person skilled in the art without departing from the description of claims.
INDUSTRIAL APPLICABILITY
[0094] The eutectic colloidal crystal of the present invention is useful as a model system of atomic and molecular crystals, and as a technical tool of research and development in the field of crystallography. In particular, since the particles of colloidal crystals can be observed by optical microscopes, they are easier to be observed than atomic and molecular crystals. In addition, since many kinds of colloidal crystals are intermingled, for example, the adjustment of the abundance ratio between them allows the control of the diffraction color. In addition, it is resistant to color fading, and thus is promising as a novel coloring material which develops mixed colors of three primary colors. In addition, it can be used as an electron material for optical filters, or as a decoration material for smartphone covers and nail materials.
REFERENCE SIGNS LIST
[0095] 1, 2, 3 colloidal crystals (eutectic colloidal crystal)