CN106444099A - Magneto-chromic self-orienting photonic crystal ball and preparation method thereof - Google Patents
Magneto-chromic self-orienting photonic crystal ball and preparation method thereof Download PDFInfo
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- CN106444099A CN106444099A CN201611184159.9A CN201611184159A CN106444099A CN 106444099 A CN106444099 A CN 106444099A CN 201611184159 A CN201611184159 A CN 201611184159A CN 106444099 A CN106444099 A CN 106444099A
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- photonic crystal
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 239000011246 composite particle Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 239000011805 ball Substances 0.000 claims description 56
- 239000013078 crystal Substances 0.000 claims description 24
- 238000002845 discoloration Methods 0.000 claims description 23
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
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- 238000006073 displacement reaction Methods 0.000 claims description 6
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- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
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- 125000002252 acyl group Chemical group 0.000 claims description 2
- 229960002233 benzalkonium bromide Drugs 0.000 claims description 2
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052751 metal Inorganic materials 0.000 claims description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
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- 229940113124 polysorbate 60 Drugs 0.000 claims description 2
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- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 claims 1
- 229920000307 polymer substrate Polymers 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
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- 230000005426 magnetic field effect Effects 0.000 abstract 1
- 239000002159 nanocrystal Substances 0.000 abstract 1
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- 238000000985 reflectance spectrum Methods 0.000 description 9
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- 238000007711 solidification Methods 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- 230000002708 enhancing effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
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- 229920001219 Polysorbate 40 Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000008358 core component Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
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- 238000010926 purge Methods 0.000 description 1
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- 238000010025 steaming Methods 0.000 description 1
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- 150000003462 sulfoxides Chemical class 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/09—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on magneto-optical elements, e.g. exhibiting Faraday effect
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nonlinear Science (AREA)
- Power Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a magneto-chromic self-orienting photonic crystal ball and a preparation method thereof. Pre-polymerized liquid prepared from monodispersed superparamagnetic nano crystal druse colloid core-shell composite particles, a polymerization monomer, a cross-linking agent, a photoinitiator, a surface active agent and dispersion liquid is dropwise added to an oil phase, liquid drops are cured under the effects of an externally applied magnetic field and ultraviolet light, the photonic crystal ball is taken out after reaction, and washing and solvent replacement are performed. The magneto-chromic self-orienting photonic crystal ball has the advantages that the preparation, regulation and control method is simple and good in repeatability; a solid-liquid coexisting structure is always kept, the magneto-chromic self-orienting performance can be also kept; the mass center of the photonic crystal ball does not coincide with the center of the ball, so that the photonic crystal ball show self-developing characteristics without an externally applied magnetic field effect, more energy is saved by adopting self development compared with traditional magnetic field induced developing, and controllability is good.
Description
Technical field
The present invention relates to display material preparation field, more particularly to a kind of can magneto discoloration auto-orientation photonic crystal ball
And preparation method thereof.
Background technology
The photon crystal micro-ball being made up of monodisperse particle produces beautiful because of the wherein periodic arrangement of monodisperse particle
Schemochrome.Especially, the 1-D photon crystal ball being assembled by superparamagnetic nanoparticle is easy to assembly because of it, and brightness is high, band
The advantages of gap regulation and control facilitate causes the extensive concern of domestic and international researcher.For example with four oxygen of superparamagnetic Silica-coated
The research changing the 1-D photon crystal ball that three-iron core-shell particles are primitive achieves impressive progress.As document
[J.Am.Chem.Soc.2009, volume 131, page 15687] obtain assuming solid color by emulsion polymerization one-step solidification
One-dimensional solid photonic crystal ball, the acquisition of other color photonic crystal balls can only be by changing externally-applied magnetic field in preparation process
Magnetic field intensity obtaining.Document [Small, 2011, volume 9, page 1163] by applying in microfluidic channel different parts
The magnetic field one-step solidification of varying strength can obtain the one-dimensional solid photonic crystal ball assuming different colours, compared to the former, this
Preparation technology more optimizes, and prepared photonic crystal ball monodispersity is good, size tunable.Additionally, with ferroso-ferric oxide particle being
The research of the 1-D photon crystal ball of primitive also achieves impressive progress.As patent【Using micro-reaction device and externally-applied magnetic field system
The method of standby colour developing photon crystal micro-ball】These spherical drop shells are solidified by the method using uv photopolymerization, photonic crystal
The colour developing shell of structure is preserved, and places a period of time, and prepared photon crystal micro-ball can be fully cured.The method is simple
Easy, the photonic crystal ball structure-controllable of preparation, the preparation controlling photon crystal structure to magnetic field has important value.These
Although 1-D photon crystal ball can show beautiful schemochrome under the influence of a magnetic field, and there is magneto discoloration performance.But with
When there is also two aspect problems, one：The display of photonic crystal ball color depends on magnetic field；It two：Its magneto discoloration performance is subject to
Surrounding medium and magnetic direction affect larger, poor controllability.
Content of the invention
The technical problem to be solved is：There is provided a kind of can the auto-orientation photonic crystal ball of magneto discoloration and its system
Preparation Method.Gained photonic crystal ball has auto-orientation colour developing and the performance characteristics along auto-orientation direction magneto discoloration, preparation method
Simply, favorable repeatability, controls preparing of photon crystal structure significant in magnetic field.
The present invention solves its technical problem and adopts following technical scheme：A kind of can magneto discoloration auto-orientation photonic crystal
Ball, it is the asymmetric heterojunction structure of solid phase shell and liquid phase kernel, and described solid phase shell is by polymeric matrix and fixation
Form one-dimensional catenary structure by monodispersed superparamagnetic nanometer crystal druse colloid Core-shell Composite Particles in the polymer matrix to form, institute
The liquid phase kernel stated is made up of monodispersed superparamagnetic nanometer crystal druse colloid Core-shell Composite Particles dispersion liquid, and described photon is brilliant
Body ball barycenter is misaligned with the centre of sphere.
Described can magneto discoloration auto-orientation photonic crystal ball, its unsymmetric structure refers to that solid phase shell thickness is uneven
Even, its heterojunction structure refers to have solid-liquid concurrently biphase, and described liquid phase kernel will not solidify during storage.
By such scheme, described polymeric matrix is to be changed by one or more of Organic substance containing acrylic acid groups
Learn the gel network being cross-linked into.
A kind of can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that will be by monodispersed super suitable
Magnetic nanometer crystal druse colloid Core-shell Composite Particles, polymerized monomer, cross-linking agent, light trigger, surfactant and dispersion liquid composition
Pre-polymerization drop enters in oil phase, and drop solidifies under externally-applied magnetic field and action of ultraviolet light, takes out gained photonic crystal after the completion of reaction
Ball, washs and carries out solvent displacement.
By such scheme, described polymerized monomer is one of Organic substance containing acrylic acid groups or their group
Close.
By such scheme, described cross-linking agent is N-N methylene-bisacrylamide, ethylene glycol dimethacrylate, ring
Oxosilane, poly- carbodiimide, methylene diacrylamide, diisocyanate.
By such scheme, described light trigger is 2- hydroxy-2-methyl -1- phenylacetone, diethoxy acetophenone, 2,
4,6- trimethylbenzoyl phenyl phosphonate esters, 1- hydroxycyclohexylphenylketone, 2- methyl -2- (4- morpholinyl) -1- [4- (4-
Morpholinyl) phenyl] -1- butanone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, methyl benzoylformate, azodiisobutyronitrile,
Peroxidating two acyl or persulfate.
By such scheme, described surfactant is Triton X-100, alkaling earth metal base, benzalkonium bromide,
Fatty glyceride, polysorbas20, polysorbate40, polysorbate60, Tween 80, polysorbate85；Described dispersion liquid is ethylene glycol, water, diformazan
Sulfoxide, dimethylformamide, acetic acid, alkanol, dichloromethane.
By such scheme, the viscosity of described oil phase is 3000cP～6000cP；A length of 250～the 400nm of described ultraviolet light wave,
Hardening time is 30～90s.
By such scheme, solvent displacement solvent for use is water, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, tetrahydrochysene
Furan or their mixture.
The present invention passes through to control the ultraviolet light polymerization time, and displaces uncured region after the completion of preparation in time except single point
Component beyond scattered superparamagnetic nanometer crystal druse colloid Core-shell Composite Particles, obtained a kind of can magneto discoloration auto-orientation photon
Crystal ball.This photonic crystal ball is the liquid-solid asymmetric nucleocapsid structure coexisting, including the photonic crystal shell being cured and not by
The liquid core of solidification.In no externally-applied magnetic field, auto-orientation shows shell color to described photonic crystal ball；Apply magnetic along auto-orientation direction
During field, in liquid core, the chaining colour developing of nanoparticle orientation, shows kernel and shell dual-visualization and magneto discoloration characteristic.These are special
Property not only gives photonic crystal ball more superior color developing, also makes photonic crystal ball have unique magneto discoloration
Energy (to realize moreover it is possible to not change its deflection angle not only by its deflection angle of flux control by the change of its color
In the case of, to realize only by the photon band gap adjusting chain structure in liquid core.).With current gained 1-D photon crystal ball
Compare, the photonic crystal ball in the present invention has the advantages that preparation method is simple, structure-controllable, from colour developing, Color tunable, aobvious
Show that the fields such as device, sensor, dc-dc converter and security devices have broad application prospects.
Beneficial effects of the present invention：
(1) prepare photonic crystal ball with reference to microemulsion method and uv-light polymerization method, its preparation and regulation and control method simple,
Favorable repeatability.
(2) photonic crystal ball of gained replaced by solvent, removes and removes monodispersed superparamagnetic nanometer crystal druse colloid core in liquid core
Component beyond shell compound particle, it is to avoid spheroid uncured region cured later so as to be always maintained at solid-liquid structure, namely
Keep its can magneto discoloration auto-orientation performance.
(3) barycenter of photonic crystal ball is misaligned with the centre of sphere, causes it to show from colour developing under the effect of no externally-applied magnetic field
Feature, more energy efficient with respect to classical magnetic field inducing color development from colour developing.
(4) make by applying outfield kernel nanoparticle be orientated chaining Show Color, and variable color is difficult by surrounding medium
And the impact of magnetic direction, controllability is good.
Brief description
Fig. 1 is the field emission scanning electron microscope figure of products therefrom in embodiment 1.
Fig. 2～3 be in embodiment 2 products therefrom in the digital photograph figure not plus during magnetic field and field emission scanning electron microscope figure.
Fig. 4 is that in embodiment 3, products therefrom does not add digital photograph figure during magnetic field.
Fig. 5 is the field emission scanning electron microscope figure of products therefrom in embodiment 4.
Fig. 6 is the digital photograph that in embodiment 5, products therefrom acts on the collection of lower edge auto-orientation direction in different magnetic field intensity
Figure.
Fig. 7 is the reflectance spectrum that in embodiment 5, products therefrom acts on the collection of lower edge auto-orientation direction in different magnetic field intensity
Figure.
Fig. 8 is the field emission scanning electron microscope image of products therefrom in embodiment 6.
Fig. 9 is the field emission scanning electron microscope image of products therefrom in embodiment 7.
Figure 10 (a)～(c) is the digital photograph figure of products therefrom in embodiment 8～embodiment 10.
Figure 11 is the reflectance spectrum figure of products therefrom in embodiment 8～embodiment 10.
Specific embodiment
For a better understanding of the present invention, it is further elucidated with present disclosure with reference to embodiment.It should be understood that these
Embodiment is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that reading instruction of the present invention
Content after, those skilled in the art can make various changes or modifications to the present invention, and these equivalent form of values equally fall within this
Application appended claims limited range.
Embodiment 1
Tannic acid and Polyvinylpyrrolidone are added in ethylene glycol and configures uniformly mixed solution, tannin acid concentration is
3.33g/L, polyvinylpyrrolidoneconcentration concentration is 400g/L.Then ferric chloride hexahydrate is added in mixed solution, stir to complete
CL, concentration 4.1g/L of ferric ion or 8.6g/L in solution.It is eventually adding anhydrous sodium acetate and adjust pH to 9.0.So
After put in reactor, airtight heating is to 200 DEG C, and is incubated 24 hours, is then cooled to room temperature, with ethanol purge separate 2～3
Secondary, obtain product after solidss vacuum drying.As shown in the field emission scanning electron microscope image of the present embodiment product in Fig. 1, institute
The product obtaining is 150nm monodisperse colloid particle.
Embodiment 2
By 0.5g NIPA (NIPAM), 28.6mg N-N methylene-bisacrylamide (BIS), 22.8mg
2- hydroxy-2-methyl -1- phenylacetone (HMPP), 84.3mg Triton X-100 (Triton X-100) is added to
Ethylene glycol (EG) dispersion liquid of the monodispersed superparamagnetic nanometer crystal druse colloid Core-shell Composite Particles of 5.0mg/mL embodiment 1 gained
In, ultrasonic disperse uniformly, forms pre-polymerization liquid standby.
It is 1mL with capacity, pre-polymerization liquid is added dropwise to and fills viscosity by the micro-syringe of syringe needle model 27G is 5000cP oil phase
Glass drying oven in, now emulsion droplets are in suspended state in oil phase, after standing half a minute, it are just gone up as circular magnet
Side, regulating magnet and sample interval, make magnetic field intensity be 260Gs, stand 30 seconds, and then opening power is 1000W, and wavelength is
365nm uviol lamp is solidified, and hardening time is 52s.Take out products therefrom after the completion of reaction and use N,N-dimethylformamide
Washing, removes the oil phase of its surface remaining, then uses distilled water wash 3 times, the photonic crystal ball cleaned is transferred to and fills steaming
Carry out solvent displacement in the centrifuge tube of distilled water, after 1 day, then with distilled water wash 2 times and product storage is standby in distilled water
With.Digital photograph under the effect of no externally-applied magnetic field for the products therefrom is as shown in Fig. 2 its display is uniformly orange-yellow.By gained light
Sub- crystal ball is cut open along auto-orientation direction, discards core liquid lyophilization, and gained section observes under scanning electron microscope
Pattern is as shown in figure 3, the magnetic particle that this photonic crystal spherical shell layer has an asymmetry and shell includes is consolidated in the form of chain
Determine in the base.
Embodiment 3
Identical with embodiment 2 step, after the oil phase of photonic crystal ball surface cleans up, the photonic crystal ball cleaned is turned
Move to and in the centrifuge tube fill ethanol, carry out solvent displacement, after 1 day, then with washing with alcohol 2 times, and by product storage in ethanol
Standby.Digital photograph under no externally-applied magnetic field for the products therefrom is as shown in figure 4, its display is uniformly orange red.Retouch with embodiment 2
The Fig. 2 stating is the same, and it remains to assume homogeneous schemochrome in the case of breaking away from magnetic field.The replacement of replacement solvent is described, not shadow
Ring the auto-orientation performance of photonic crystal ball.
Embodiment 4
Identical with embodiment 2 step, monomer is 0.5g acrylic acid (AA).Monomer is acrylic acid and NIPA
When photonic crystal ball structure be consistent.As shown in figure 5, the structure of explanation this method photonic crystal ball of preparing gained is not subject to
The impact of monomeric species.
Embodiment 5
Products therefrom in above-described embodiment 2 is placed in distilled water, applies the magnetic field of varying strength along auto-orientation direction, adopt
The digital photograph figure of collection photonic crystal ball is as shown in Figure 6 and reflectance spectrum figure is as shown in fig. 7, from digital photograph Fig. 6, with
The enhancing of magnetic field intensity, the color that shell photon crystal structure is presented does not change, and liquid core nanoparticle is orientated chaining institute
Gradually there is blue shift in the color presenting, color is rhodo successively, orange, dark green.From reflectance spectrum Fig. 7, with magnetic field intensity
Enhancing, the reflection peak peak position of shell photon crystal structure is not moved, and liquid core nanoparticle is orientated the reflection peak-to-peak of chaining
Position gradually blue shift.
Embodiment 6
Identical with embodiment 2 step, but hardening time be 30s.Gained photonic crystal ball is cut open along auto-orientation direction, abandons
Go core liquid lyophilization, the pattern that gained section observes under scanning electron microscope as shown in figure 8, as seen from the figure, photon
The shell thickness of crystal ball is very thin, and it places easily rupturable in water for a long time.
Embodiment 7
Identical with embodiment 2 step, but hardening time be 90s.Gained photonic crystal ball is cut open along auto-orientation direction, cold
After lyophilizing is dry, as shown in figure 9, as seen from the figure, photonic crystal ball is cured for the pattern that gained section observes under scanning electron microscope
Completely, become a solid spheroid.
Embodiment 8
Identical with embodiment 2 step, but magnetic field intensity is 600Gs.Products therefrom is placed in the digital photograph figure in distilled water
As shown in Figure 10 (a) with reflectance spectrum figure as shown in figure 11, this photonic crystal ball can be observed from digital photograph Figure 10 (a) and present
Bottle green, understands in conjunction with reflectance spectrum Figure 11, its reflection peak peak position is located at 535nm.
Embodiment 9
Identical with embodiment 2 step, but magnetic field intensity is 330Gs.Products therefrom is placed in the digital photograph figure in distilled water
As shown in Figure 10 (b) with reflectance spectrum figure as shown in figure 11, this photonic crystal ball can be observed from digital photograph Figure 10 (b) and present
Yellow, understands in conjunction with reflectance spectrum Figure 11, its reflection peak peak position is located at 625nm.
Embodiment 10
Identical with embodiment 2 step, but magnetic field intensity is 280Gs.Products therefrom is placed in the digital photograph figure in distilled water
As shown in Figure 10 (c) with emission spectrum as shown in figure 11, this photonic crystal ball can be observed from digital photograph Figure 10 (c) and assume Fructus Citri tangerinae
Redness, understands in conjunction with reflectance spectrum Figure 11, its reflection peak peak position is located at 670nm.
Claims (10)
1. a kind of can magneto discoloration auto-orientation photonic crystal ball, it is the asymmetric hetero-junctions of solid phase shell and liquid phase kernel
Structure, described solid phase shell is by polymeric matrix and to fix in the polymer matrix by monodispersed superparamagnetic nanometer crystal druse glue
Body Core-shell Composite Particles form one-dimensional catenary structure composition, and described liquid phase kernel is by monodispersed superparamagnetic nanometer crystal druse glue
Body Core-shell Composite Particles dispersion liquid forms, and described photonic crystal ball barycenter is misaligned with the centre of sphere.
2. according to claim 1 can magneto discoloration auto-orientation photonic crystal ball it is characterised in that described polymer
Substrate is the gel network being chemically crosslinked by one or more of Organic substance containing acrylic acid groups.
3. a kind of can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that will be by monodispersed superparamagnetic
It is pre- that nanometer crystal druse colloid Core-shell Composite Particles, polymerized monomer, cross-linking agent, light trigger, surfactant and dispersion liquid form
Poly- drop enters in oil phase, and drop solidifies under externally-applied magnetic field and action of ultraviolet light, takes out gained photonic crystal ball after the completion of reaction,
Wash and carry out solvent displacement.
4. according to claim 3 can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that institute
The polymerized monomer stated is one of Organic substance containing acrylic acid groups or combinations thereof.
5. according to claim 3 can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that institute
The cross-linking agent stated is N-N methylene-bisacrylamide, ethylene glycol dimethacrylate, epoxy silane, poly- carbodiimide, methene
Bisacrylamide, diisocyanate.
6. according to claim 3 can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that institute
The light trigger stated is 2- hydroxy-2-methyl -1- phenylacetone, diethoxy acetophenone, 2,4,6- trimethylbenzoyl benzene
Base phosphonate ester, 1- hydroxycyclohexylphenylketone, 2- methyl -2- (4- morpholinyl) -1- [4- (4- morpholinyl) phenyl] -1- butanone,
2- hydroxy-2-methyl -1- phenyl -1- acetone, methyl benzoylformate, azodiisobutyronitrile, peroxidating two acyl or persulfate.
7. according to claim 3 can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that institute
The surfactant stated is Triton X-100, alkaling earth metal base, benzalkonium bromide, fatty glyceride, and polysorbas20 is told
Temperature 40, polysorbate60, Tween 80, polysorbate85；Described dispersion liquid is ethylene glycol, water, dimethyl sulfoxide, dimethylformamide, acetic acid,
Alkanol, dichloromethane.
8. according to claim 3 can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that institute
The viscosity stating oil phase is 3000cP～6000cP；A length of 250～the 400nm of described ultraviolet light wave, hardening time is 30～90s.
9. according to claim 3 can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that molten
Agent displacement solvent for use is water, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, oxolane or their mixture.
10. according to claim 3 can magneto discoloration auto-orientation photonic crystal ball preparation method it is characterised in that institute
The range of accommodation of the magnetic field intensity stated is 200～700Gs.
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