CN112812565B - Magnetic response color-changing photonic crystal ink for 3D printing and preparation method thereof - Google Patents

Magnetic response color-changing photonic crystal ink for 3D printing and preparation method thereof Download PDF

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CN112812565B
CN112812565B CN202110088419.7A CN202110088419A CN112812565B CN 112812565 B CN112812565 B CN 112812565B CN 202110088419 A CN202110088419 A CN 202110088419A CN 112812565 B CN112812565 B CN 112812565B
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photonic crystal
color
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ink
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CN112812565A (en
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汪长春
方怡权
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Fudan University
Zhuhai Fudan Innovation Research Institute
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Zhuhai Fudan Innovation Research Institute
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • B33Y70/10Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2265Oxides; Hydroxides of metals of iron
    • C08K2003/2275Ferroso-ferric oxide (Fe3O4)
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
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Abstract

The invention belongs to the technical field of photonic crystal materials, and particularly relates to magnetic response color-changing photonic crystal ink for 3D printing and a preparation method thereof. The preparation method comprises the following steps: preparing superparamagnetic colloidal particles, and dispersing the superparamagnetic colloidal particles in a polar solvent to obtain a magnetic response color-changing photonic crystal solution; mixing and emulsifying the solution and a curable polymer precursor to obtain a magnetic response emulsion; and adding a thixotropic agent or a resin reinforcing agent into the emulsion to obtain the magnetic response color-changing photonic crystal ink. The excellent thixotropy of the ink enables the magnetic response photonic crystal device in any shape to be manufactured in a 3D printing mode, and the device can still show dynamic reversible bright structural color along with the change of the strength of a magnetic field after being cured. The invention effectively improves the application convenience and the degree of freedom of the magnetic response type photonic crystal, and has great application prospect in the fields of anti-counterfeiting, information storage, magnetic field sensors and the like.

Description

Magnetic response color-changing photonic crystal ink for 3D printing and preparation method thereof
Technical Field
The invention belongs to the technical field of photonic crystal materials, and particularly relates to magnetic response color-changing photonic crystal ink for 3D printing and a preparation method thereof.
Background
Photonic crystals are a class of materials with periodic dielectric constant structures that can modulate the propagation of light of a particular wavelength by changing the physical structure and refractive properties of the material. The photonic band gap structure of the stimulus-response photonic crystal can change along with the change of the external environment (such as steam, temperature, strain, pH and electromagnetic field), and the diffraction wavelength of the stimulus-response photonic crystal can be modulated within the visible light wavelength range, so that the stimulus-response photonic crystal can intuitively reflect specific structural color, and has great application prospects in various fields such as chemical sensing, biological sensing, anti-counterfeiting marking, encryption storage and the like.
The magnetic response photonic crystal with magnetic nano microspheres (such as ferroferric oxide nano cluster colloid) as structural units is an important stimulus response type photonic crystal. Only under the action of an external magnetic field, the magnetic nano-microsphere can be magnetized, can be rapidly assembled into an ordered one-dimensional nano-chain photonic crystal structure, and can show a corresponding color. According to the Bragg formula, the structural color can be controlled by adjusting the distance between the magnetic nano microspheres. With the enhancement of the magnetic field, the magnetized particles are closer under a stronger magnetic field and have smaller particle spacing, so that light with shorter wavelength is diffracted; when the magnetic field is weaker, due to electrostatic repulsion or steric hindrance repulsion, the magnetic nano-microspheres are relatively loose during assembly and accumulation, the particle spacing becomes larger, and light with longer wavelength is diffracted.
Chinese patent CN 101794652 relates to a carbon-coated magnetic nanoparticle with controllable and uniform size. Further, chinese patent CN 108147470 proposes that a water-soluble magnetic-responsive photonic crystal is prepared by coating it with a silica shell. Chinese patents CN110787743 and CN 105738975 disclose methods for preparing magnetic nanoparticles with stable poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, the products of which can realize full spectrum color change in various solvents, and the preparation methods are simple, convenient and easy to scale. Chinese patent CN 111063500A develops an organic silicon modification method on the surface of the magnetic nano microsphere, so that the magnetic response photonic crystal can keep bright structural color in various polar solvents and non-polar solvents, and the optical stability of the magnetic response photonic crystal is widened. The assembly of the photonic crystal structure of the magnetic-response photonic crystal is beneficial to the free movement capability in a good solvent, however, the magnetic-response photonic crystal must exist in a dispersion liquid form, and the magnetic-response photonic crystal is easy to flow and deform during the use process, the solvent is easy to volatilize, and the encapsulation has great difficulty, so that the application scene of the magnetic-response photonic crystal is greatly limited.
Therefore, how to obtain a stable application form of the magnetic response photonic crystal is a great challenge. The american chemical society has reported a method for combining magnetic nanoparticles with hydrogel microspheres, which realizes optical structure color conversion under a dynamic magnetic field by controlling the rotation of polyethylene glycol diacrylate microspheres with magnetic-responsive photonic crystals immobilized therein (j. AM. chem. soc. 2009, 131, 15687-. Chinese patent CN 107988657 proposes a method for combining magnetic colloidal microsphere dispersion with sodium alginate hydrogel, which prepares magnetic field responsive photonic crystal fiber in capillary, but the reflectivity of the magnetic field responsive photonic crystal fiber is greatly lost compared with the original magnetic response photonic crystal dispersion, and the weaker mechanical property of the thinner hydrogel fiber is not beneficial to practical application. Therefore, how to prepare stable magnetic-response photonic crystal materials with fixed macroscopic morphology on the premise of maintaining the magnetic-response color-changing performance remains an important problem in the field.
Disclosure of Invention
The invention aims to provide magnetic response color-changing photonic crystal ink and a preparation method thereof.
The invention provides a preparation method of magnetic response color-changing photonic crystal ink, which comprises the following specific steps:
(1) preparing superparamagnetic colloidal particles, and dispersing the superparamagnetic colloidal particles in a polar solvent to obtain a magnetic response color-changing photonic crystal solution;
(2) mixing and emulsifying the crystal solution and a curable polymer precursor to obtain a water-in-oil emulsion;
(3) and adding a thixotropic agent or a resin reinforcing agent into the emulsion to obtain the magnetic response color-changing photonic crystal ink.
In the step (1), the superparamagnetic colloidal particles are ferroferric oxide nanoclusters with the particle size of 50-300 nm and are prepared by a solvothermal method. The ferroferric oxide nanocluster has a chemically or physically modified shell layer which can be functional SiO (silicon dioxide) prepared by hydrolyzing organic silane by carbon, poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, polyvinylpyrrolidone, polyacrylic acid and sodium citrate2One or more of.
In the step (1), the concentration of the obtained magnetic response color-changing photonic crystal solution is 5-20 mg/ml, the obtained magnetic response color-changing photonic crystal solution can show a bright structural color under a magnetic field of 200-2000 Gs, and the maximum reflectivity of the obtained magnetic response color-changing photonic crystal solution is not lower than 30%. In a visible spectrum wave band, the structural color of the material generates blue shift along with the enhancement wavelength of a magnetic field and generates red shift along with the weakening of the magnetic field, and the material has good color change reversibility.
Preferably, in step (1), the polar solvent used is water, ethanol or ethylene glycol.
Preferably, in the step (2), the curable polymer precursor is selected from one or more of polydimethylsiloxanes, acrylics and epoxies. Polydimethylsiloxane, i.e. PDMS silicone rubber, is preferred.
Preferably, in the step (2), an appropriate amount of a water-in-oil emulsifier can be optionally added in the mixing process.
Preferably, in the step (3), the thixotropic agent or the resin reinforcing agent is selected from one or more of silicon oxide powder, metal oxide powder and chopped glass fiber. The addition amount is 3-10% of the mass of the emulsion. Hydrophobic fumed silica is preferred.
The magnetic response color-changing photonic crystal ink prepared by the invention can be used for custom printing at normal temperature by using a commercial 3D printer, can still respond to the strength of an external magnetic field after being cured and molded, changes the structural color of the ink, and realizes the effect of designing and manufacturing various macroscopic magnetic response color-changing devices according to needs.
The invention has the advantages of
(1) The invention solves the defect that the original magnetic response type photonic crystal is limited by a solvent, and the photonic crystal ink with the magnetic response color change effect is stored in emulsion liquid drops through the construction of a secondary structure of a water-in-oil emulsion. As the polymer matrix in the continuous phase can be solidified, the magnetic colloid particles in the liquid drop can still keep the magnetic response photonic crystal assembly behavior similar to that in the original solution state, thereby showing bright color. In addition, the photonic crystal ink also has good thixotropy, can be conveniently molded and processed, can be used for preparing a magnetic response type photonic crystal material with a certain macroscopic form without complex packaging, and greatly expands the application range of the magnetic response type photonic crystal.
(2) The ink designed by the invention is oriented to a commercialized 3D printer, gets rid of the limitation of a mold to processing in a common method, can be extruded and stacked at room temperature for molding, and has simple, convenient and safe flow and high processing freedom. The ink prepared by the method can be used for preparing solid photonic crystal devices in any forms according to specific requirements on the premise of keeping the magnetic response color change performance and higher reflectivity, and the color change effect can be observed by naked eyes.
(3) The method has universality in the aspect of preparing the ink magnetic response color-changing photonic crystal ink for 3D printing. The preparation method of the emulsion ink can be compatible with various common magnetic response type colloidal particles (such as Fe)3O4@C、Fe3O4@PSSMA、Fe3O4@PVP、Fe3O4@SiO2Etc.) and various transparent polymer precursors from plastics to rubber can be used as emulsified continuous phases to obtain macroscopic magnetic response photonic crystal devices with different properties. Those skilled in the art will be able to formulate a variety of different types of magnetically responsive color-changing inks in accordance with the spirit of the present invention.
The magnetic response color-changing photonic crystal ink prepared by the invention has excellent thixotropy, so that magnetic response photonic crystal devices in any shapes can be manufactured in a 3D printing mode, and the devices can still show dynamic reversible bright structural color along with the change of the strength of a magnetic field after being cured. The invention effectively improves the application convenience and the degree of freedom of the magnetic response type photonic crystal, and has huge application prospects in the fields of anti-counterfeiting, information storage, magnetic field sensors and the like.
Drawings
FIG. 1 is a histogram of the particle size distribution of the product prepared in example 1, with the corresponding transmission electron microscope picture (scale: 500 nm) being inset.
FIG. 2 is a histogram of the particle size distribution of the product prepared in example 2, with the corresponding transmission electron microscope picture (scale: 500 nm) being inset.
FIG. 3 is a reflection spectrum curve of the prepared ferroferric oxide magnetic nanocluster in aqueous dispersion. Wherein (a) is the product prepared in example 1 (the magnetic field of a 24V DC electromagnet is applied). (b) The product was prepared for example 2 (applying a 24V magnetic field of a dc electromagnet).
FIG. 4 is a digital photograph of the prepared ferroferric oxide magnetic nanocluster in an aqueous dispersion under an applied magnetic field. Wherein (a) is the product prepared in example 1; FIG. 4 (b) shows the product prepared in example 2.
FIG. 5 is a digital photograph of the prepared magnetic response color-changing photonic crystal ink under an applied magnetic field. Wherein (a) is the product prepared in example 3; (b) the product prepared in example 4.
Fig. 6 is a magnetic-responsive color-changing photonic crystal butterfly solid state device manufactured by 3D printing using the inks prepared in examples 3 and 4.
Detailed Description
The above-described scheme is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The experimental conditions used in the examples can be further adjusted according to actual conditions, and the conditions in the conventional experiments (deionized water, room temperature, etc.) are not generally indicated. Specific implementation processes of the present invention are described below by examples, wherein examples 1 to 2 are processes for preparing monodisperse ferroferric oxide magnetic nanoclusters, and examples 3 to 4 are processes for preparing magnetic response color-changing photonic crystal inks.
Example 1 Synthesis of monodisperse ferroferric oxide magnetic nanoclusters
40 mL of anhydrous ethylene glycol is weighed and added into a 150 mL conical flask, 0.65 g of anhydrous ferric trichloride, 3g of anhydrous sodium acetate, 1.5 g of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (PSSMA) and 400 mu L of distilled water are sequentially added, and after the materials are fully dispersed into a uniform solution in an ultrasonic, stirring or heating mode, 0.6 g of sodium hydroxide is added, and stirring and dissolving are continued for 1 hour. The solution is transferred into a 50 ml polytetrafluoroethylene inner container, sealed in a stainless steel reaction kettle and placed in a constant temperature oven at 190 ℃ for heating reaction for 9 hours. And after the reaction is finished, performing magnetic adsorption separation by using a magnet, washing the product for two to three times by using ethanol, and finally dispersing the product into 15 ml of distilled water to obtain the aqueous dispersion of the ferroferric oxide magnetic nanocluster, wherein the particle size of the aqueous dispersion is about 136 nm under an electron microscope, and the aqueous dispersion can be assembled under the magnetic field of a 24V direct current electromagnet to show the structural color of orange yellow.
Example 2 Synthesis of monodisperse ferroferric oxide magnetic nanoclusters
40 mL of anhydrous ethylene glycol is weighed and added into a 150 mL conical flask, 0.65 g of anhydrous ferric trichloride, 3g of anhydrous sodium acetate, 1.5 g of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (PSSMA) and 300 mu L of distilled water are sequentially added, and after the materials are fully dispersed into a uniform solution in an ultrasonic, stirring or heating mode, 0.6 g of sodium hydroxide is added, and stirring and dissolving are continued for 1 hour. The solution is transferred into a 50 ml polytetrafluoroethylene inner container, sealed in a stainless steel reaction kettle and placed in a constant temperature oven at 190 ℃ for heating reaction for 9 hours. And after the reaction is finished, performing magnetic adsorption separation, washing the product with ethanol for two to three times, and finally dispersing the product into 15 ml of distilled water to obtain the aqueous dispersion of the ferroferric oxide magnetic nanocluster, wherein the particle size of the aqueous dispersion is about 143 nm under an electron microscope, and the aqueous dispersion can be assembled under the magnetic field of a 24V direct current electromagnet to show the structural color of orange.
Example 3 preparation of magnetically responsive color-changing Photonic Crystal ink
1ml of the aqueous dispersion of the ferroferric oxide magnetic nanocluster (example 1) is separated by strong magnetic adsorption, then water is absorbed, and the aqueous dispersion is dispersed in 1ml of ethylene glycol again by ultrasonic. 2g of a prepolymer and 0.2 g of a crosslinking agent were mixed with 2g of Polydimethylsiloxane (PDMS) by stirring to obtain a silicone rubber precursor. Adding 2 drops (about 0.04 g) of ethoxy silicone surfactant and 1ml of ethylene glycol dispersion into the precursor, fully stirring until the mixture is emulsified to be viscous, and fully mixing 0.15g of hydrophobic gas-phase nano silicon dioxide with the emulsion to obtain the magnetic response color-changing photonic crystal ink. The ink can show structural color similar to that of the aqueous dispersion liquid of the ink under the magnetic field, and can be directly loaded in a cylinder of a commercial 3D printer for extrusion printing.
Example 4 preparation of magnetically responsive color-changing Photonic Crystal ink
1ml of the aqueous dispersion of the ferroferric oxide magnetic nanocluster (example 2) is separated by strong magnetic adsorption, then water is absorbed, and the aqueous dispersion is dispersed in 1ml of ethylene glycol again by ultrasonic. 2g of a prepolymer and 0.2 g of a crosslinking agent were mixed with 2g of Polydimethylsiloxane (PDMS) by stirring to obtain a silicone rubber precursor. Adding 2 drops (about 0.04 g) of ethoxy silicone surfactant and 1ml of ethylene glycol dispersion into the precursor, fully stirring until the mixture is emulsified to be viscous, and fully mixing 0.15g of hydrophobic gas-phase nano silicon dioxide with the emulsion to obtain the magnetic response color-changing photonic crystal ink. The ink can show structural color similar to that of the aqueous dispersion liquid of the ink under the magnetic field, and can be directly loaded in a cylinder of a commercial 3D printer for extrusion printing.
A magnetically responsive color-changing photonic crystal butterfly-shaped solid-state device fabricated by 3D printing using the inks prepared in example 3 and example 4 together is shown in fig. 6. In the series of butterfly patterns, the red ink in example 4 is used for the butterfly body, and the green ink in example 3 is used for the butterfly stripe. In fig. 6, the left-most picture shows the dark brown color of the magnetite without the magnetic field, and the brown dark and light contrast of the butterfly body and the stripes is caused by the difference of the particle sizes of the randomly distributed magnetite in the ink; then, the magnetic field is enhanced by gradually approaching the NbFeB permanent magnet to the butterfly pattern, and the body of the butterfly gradually shows dark red and gradually deepens along with the enhancement of the magnetic field (the wavelength is blue-shifted); the speckled part of the butterfly appears bright emerald green under magnetic field and gradually turns deep blue (blue-shifted wavelength) with increasing magnetic field. The whole process is dynamically reversible, the response time is rapid (less than 1 s) and the process can be observed by naked eyes. When the external magnetic field is removed, the color can be restored to the original state, and the change of the structural color can be reproduced by repeatedly applying the magnetic field. The emulsion structure of the composite ink designed by the invention can effectively retain the excellent magnetic response color change property of the ferroferric oxide magnetic nano cluster in the original dispersion liquid. The magnetic response photonic crystal color-changing device manufactured by 3D printing of the ink takes silicon rubber or other polymers as a substrate, is a solid with a certain thickness and capable of bearing peeling and bending, and has a certain mechanical strength. In addition, the magnetic field can be constructed by an electromagnet, controllable and accurate magnetic field intensity can be conveniently obtained by only adjusting the current, and great convenience is further provided for the application of the ink in the fields of anti-counterfeiting, information storage, magnetic field sensors and the like.
It should be noted that the above-mentioned examples are only for illustrating the technical concepts and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and to implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (7)

1. The magnetic-response color-changing photonic crystal ink for 3D printing is characterized by being prepared by the following preparation method:
(1) preparing superparamagnetic colloidal particles, and dispersing the superparamagnetic colloidal particles in a polar solvent to obtain a magnetic response color-changing photonic crystal solution;
(2) mixing and emulsifying the crystal solution and a curable polymer precursor to obtain a water-in-oil emulsion;
(3) adding a thixotropic agent or a resin reinforcing agent into the emulsion to obtain the magnetic response color-changing photonic crystal ink;
the superparamagnetic colloidal particles in the step (1) are ferroferric oxide nanoclusters with the particle size of 50-300 nm and are prepared by a solvothermal method; the ferroferric oxide nanocluster has a chemically or physically modified shell layer which can be functional SiO (silicon dioxide) prepared by hydrolyzing organic silane by carbon, poly (4-styrenesulfonic acid-co-maleic acid) sodium salt, polyvinylpyrrolidone, polyacrylic acid and sodium citrate2One or more of.
2. The magnetic-response color-changing photonic crystal ink for 3D printing according to claim 1, wherein the concentration of the magnetic-response color-changing photonic crystal solution obtained in step (1) is 5-20 mg/ml, which shows vivid structural color under the magnetic field of 200-2000 Gs, and the maximum reflectivity is not lower than 30%; in a visible spectrum wave band, the structural color of the material generates blue shift along with the enhancement wavelength of a magnetic field and generates red shift along with the weakening of the magnetic field, and the material has good color change reversibility.
3. The magnetically-responsive color-changing photonic crystal ink for 3D printing according to claim 2, wherein the polar solvent used in step (1) is water, ethanol or ethylene glycol.
4. The magnetically-responsive color-changing photonic crystal ink for 3D printing according to claim 3, wherein the curable polymer precursor in step (2) is selected from one or more of polydimethylsiloxanes, acrylics, epoxies.
5. The magnetically-responsive color-changing photonic crystal ink for 3D printing according to claim 4, wherein an appropriate amount of water-in-oil emulsifier is selectively added during the mixing in step (2).
6. The magnetic-response color-changing photonic crystal ink for 3D printing according to claim 5, wherein the thixotropic agent or the resin reinforcing agent in the step (3) is selected from one or more of silicon oxide powder, metal oxide powder and chopped glass fiber, and the addition amount is 3-10% of the mass of the emulsion.
7. The application of the magnetic response color-changing photonic crystal ink as claimed in one of claims 1 to 6, wherein a commercial 3D printer is used for custom printing at normal temperature, and the self structural color can be changed in response to the intensity of an external magnetic field after curing and forming, so that various magnetic response color-changing devices in macroscopic forms can be designed and manufactured as required.
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