CN109721743B - Based on MoS2Color-changing anti-counterfeiting material of quantum dots and preparation method thereof - Google Patents
Based on MoS2Color-changing anti-counterfeiting material of quantum dots and preparation method thereof Download PDFInfo
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Abstract
The invention provides a method based on MoS2The color-changing anti-counterfeiting material of the quantum dot and the preparation method thereof, (a) the nano silicon dioxide microspheres are monodisperse in ethanol; (b) enabling the nano silicon dioxide microsphere dispersion liquid to enter a capillary glass tube and forming a structural color area; (c) preparation of a uniformly dispersed MoS2The method comprises the following steps of (1) preparing an acrylamide prepolymerization solution of quantum dots, and putting the acrylamide prepolymerization solution into a capillary glass tube through a capillary effect; (d) gelling the capillary glass tube in an oxygen-free environment in a thermostat; (e) and after the gelation is finished, dissolving the capillary glass tube and the nano silicon dioxide microspheres by using hydrofluoric acid, taking out the gel, soaking the gel in deionized water, and removing residual hydrofluoric acid to obtain the color-changing anti-counterfeiting material. The anti-counterfeiting material disclosed by the invention is a color-changing anti-counterfeiting material with high stability index, small color pollution, wider color-changing range, quicker recovery and stronger applicability, and the comprehensive performance of the anti-counterfeiting material is obviously superior to that of the existing color-changing anti-counterfeiting material.
Description
Technical Field
The invention relates to the technical field of color-changing anti-counterfeiting materials, in particular to a color-changing anti-counterfeiting material based on MoS2A color-changing anti-counterfeiting material of quantum dots and a preparation method thereof.
Background
The anti-counterfeiting materials and the technology of the current generation are many, but along with the development of the scientific technology, the current generation of counterfeiting and counterfeit also occurs on the background of the improvement of productivity and the development of the scientific technology, and the technological content of the anti-counterfeiting materials and the technology can be very high, even to the extent of being false or misgenuine and being indistinguishable. Therefore, the anti-counterfeiting material must be technically high, namely, the magic height is changed into a ruler which is higher than the ruler. Namely, the novel anti-counterfeiting material has far higher anti-counterfeiting capacity than that of the anti-counterfeiting material in the prior art, and has very wide market space and very large market demand. According to the relevant data display, the financial support of the related national departments on the novel anti-counterfeiting material is increased in recent years. The annual output total value of the global anti-counterfeiting market reaches 5000 billion dollars, and the annual output total value of the domestic anti-counterfeiting market also reaches more than 1000 billion yuan RMB. Generally speaking, the research and development of novel anti-counterfeiting materials meet a huge and difficult opportunity. Based on the prior art, a new material is urgently needed to break through the existing technical bottleneck of the anti-counterfeiting material.
A research team at the leibraz polymer institute, germany, developed a special graphene coating that can change color when it deforms or ruptures. Researchers believe that coatings or products similar to them produced by them have some industrial application prospects. However, the effectiveness of the coating in revealing the degree of deformation and cracking of the material is still tested, and it is not clear whether the coating can adapt to the severe environment in the real world, so that how to prepare a color-changing anti-counterfeiting material which has excellent comprehensive performance and can adapt to the practical application environment becomes an important research subject.
Disclosure of Invention
One of the purposes of the invention is to provide a MoS-based method2The color-changing anti-counterfeiting material of the quantum dots solves the problem that the comprehensive performance of the existing anti-counterfeiting material is not ideal.
Another object of the present invention is to provide a method for manufacturing a semiconductor device based on MoS2A preparation method of a color-changing anti-counterfeiting material of quantum dots.
One of the purposes of the invention is realized by the following technical scheme: the color-changing anti-counterfeiting material is prepared by the following method:
(a) monodisperse the nano silicon dioxide microspheres in ethanol to obtain nano silicon dioxide microsphere dispersion liquid;
(b) enabling the nano silicon dioxide microsphere dispersion liquid to enter a capillary glass tube, and naturally evaporating ethanol to enable the nano silicon dioxide microspheres to form a structural color area in the capillary glass tube;
(c) preparation of a uniformly dispersed MoS2The method comprises the following steps of (1) pre-polymerizing an acrylamide solution of quantum dots, and enabling the pre-polymerizing acrylamide solution to enter a capillary glass tube with a structural color region through a capillary effect;
(d) gelling the capillary glass tube filled with the acrylamide prepolymerization solution prepared in the step (c) in a thermostat in an oxygen-free environment;
(e) and after the gelation is finished, dissolving the capillary glass tube and the nano silicon dioxide microspheres by using hydrofluoric acid, taking out the gel, soaking the gel in deionized water, and removing residual hydrofluoric acid to obtain the color-changing anti-counterfeiting material.
In step (b):
enabling the nano-silica microsphere dispersion to enter a capillary glass tube through a capillary effect, then horizontally standing the capillary glass tube to enable ethanol in the capillary glass tube to be completely evaporated naturally, and simultaneously forming a structural color area in the capillary glass tube by the nano-silica microsphere; or
Placing the nano-silica microsphere dispersion liquid in an open container, longitudinally inserting the capillary glass tube into the container, enabling the nano-silica microsphere dispersion liquid to enter the capillary glass tube through a capillary effect, continuously standing to enable ethanol in the container and the capillary glass tube to be completely and naturally evaporated, and enabling the nano-silica microspheres to form a structural color region in the capillary glass tube.
In the step (c), the acrylamide prepolymerization solution is prepared as follows:
putting polyethylene glycol diacrylate into a glass ware, adding N-isopropylacrylamide and N, N' -methylene bisacrylamide into the glass ware, dissolving, and adding MoS2Adding N, N, N ', N' -tetramethylethylenediamine and 5.0 mass percent ammonium persulfate solution into the quantum dot dispersion solution, and finally placing a glassware in an ice bath for ultrasonic mixing uniformly to obtain an acrylamide prepolymerization solution; the mass ratio of the added N-isopropylacrylamide to the N, N ' -methylene bisacrylamide is 30: 1, the dosage ratio of the N-isopropylacrylamide to the polyethylene glycol diacrylate is 3 g: 15-20 mL, and the ratio of the N-isopropylacrylamide to the N, N, N ', N ' -tetramethyl ethylenediamine to the ammonium persulfate solution is =3 g: 100-130 uL: 260-290 uL.
In step (c), the MoS2Quantum dot dispersion refers to MoS2A dispersion liquid with quantum dots as solute and N-methyl pyrrolidone as solvent, wherein MoS2The transverse size of the quantum dots is 1-10 nm, and the MoS2The concentration of the quantum dot dispersion liquid is 1mg/mL, MoS2The mass ratio of the quantum dot dispersion liquid to the N-isopropyl acrylamide = 4-6 mL: 3 g.
In the step (a), the diameter of the monodisperse nano silicon dioxide microspheres is 251 nm; in the step (b), the diameter of the capillary glass tube is 10mm, and the length of the capillary glass tube is 10 cm; in the step (d), the capillary glass tube filled with the acrylamide prepolymerization solution is filled into a plastic bag, the air in the plastic bag is exhausted and filled with nitrogen, and then the plastic bag is sealed and placed in a thermostat at 27 ℃ for gelation.
The second purpose of the invention is realized by the following technical scheme: a preparation method of a color-changing anti-counterfeiting material comprises the following steps:
(a) monodisperse the nano silicon dioxide microspheres in ethanol to obtain nano silicon dioxide microsphere dispersion liquid;
(b) enabling the nano silicon dioxide microsphere dispersion liquid to enter a capillary glass tube, and naturally evaporating ethanol to enable the nano silicon dioxide microspheres to form a structural color area in the capillary glass tube;
(c) preparation of a uniformly dispersed MoS2The method comprises the following steps of (1) pre-polymerizing an acrylamide solution of quantum dots, and enabling the pre-polymerizing acrylamide solution to enter a capillary glass tube with a structural color region through a capillary effect;
(d) gelling the capillary glass tube filled with the acrylamide prepolymerization solution prepared in the step (c) in a thermostat in an oxygen-free environment;
(e) and after the gelation is finished, dissolving the capillary glass tube and the nano silicon dioxide microspheres by using hydrofluoric acid, taking out the gel, soaking the gel in deionized water, and removing residual hydrofluoric acid to obtain the color-changing anti-counterfeiting material.
In step (b):
enabling the nano-silica microsphere dispersion to enter a capillary glass tube through a capillary effect, then horizontally standing the capillary glass tube to enable ethanol in the capillary glass tube to be completely evaporated naturally, and simultaneously forming a structural color area in the capillary glass tube by the nano-silica microsphere; or
Placing the nano-silica microsphere dispersion liquid in an open container, longitudinally inserting the capillary glass tube into the container, enabling the nano-silica microsphere dispersion liquid to enter the capillary glass tube through a capillary effect, continuously standing to enable ethanol in the container and the capillary glass tube to be completely and naturally evaporated, and enabling the nano-silica microspheres to form a structural color region in the capillary glass tube.
In the step (c), the acrylamide prepolymerization solution is prepared as follows:
putting polyethylene glycol diacrylate into a glass ware, adding N-isopropylacrylamide and N, N' -methylene bisacrylamide into the glass ware, dissolving, and adding MoS2Adding N, N, N ', N' -tetramethylethylenediamine and 5.0 mass percent ammonium persulfate solution into the quantum dot dispersion solution, and finally placing a glassware in an ice bath for ultrasonic mixing uniformly to obtain an acrylamide prepolymerization solution; the mass ratio of the added N-isopropylacrylamide to the N, N ' -methylene bisacrylamide is 30: 1, the dosage ratio of the N-isopropylacrylamide to the polyethylene glycol diacrylate is 3 g: 15-20 mL, and the ratio of the N-isopropylacrylamide to the N, N, N ', N ' -tetramethyl ethylenediamine to the ammonium persulfate solution is =3 g: 100-130 uL: 260-290 uL.
In step (c), the MoS2Quantum dot dispersion refers to MoS2A dispersion liquid with quantum dots as solute and N-methyl pyrrolidone as solvent, wherein MoS2The transverse size of the quantum dots is 1-10 nm, and the MoS2The concentration of the quantum dot dispersion liquid is 1mg/mL, MoS2The mass ratio of the quantum dot dispersion liquid to the N-isopropyl acrylamide = 4-6 mL: 3 g.
In the step (a), the diameter of the monodisperse nano silicon dioxide microspheres is 251 nm; in the step (b), the diameter of the capillary glass tube is 10mm, and the length of the capillary glass tube is 10 cm; in the step (d), the capillary glass tube filled with the acrylamide prepolymerization solution is filled into a plastic bag, the air in the plastic bag is exhausted and filled with nitrogen, and then the plastic bag is sealed and placed in a thermostat at 27 ℃ for gelation.
The anti-counterfeiting material disclosed by the invention is a color-changing anti-counterfeiting material with high stability index, small color pollution, wider color-changing range, quicker recovery and stronger applicability, and the comprehensive performance of the anti-counterfeiting material is obviously superior to that of the existing color-changing anti-counterfeiting material. The preparation method provided by the invention is simple and easy to implement, has good operability, and the prepared MoS-based material2The color-changing anti-counterfeiting material of the quantum dots has good performance. Hair brushObviously use MoS2The quantum dots enable the performance of the anti-counterfeiting material to be more excellent, the structure is unique, and the application prospect is wide.
Drawings
Fig. 1 is a picture of monodisperse nano silica microspheres taken under a scanning electron microscope. The diameter of the monodisperse nano silicon dioxide microsphere is 251 nm.
FIG. 2 is a schematic view of the sucking of the acrylamide prepolymerization solution by the capillary effect of a capillary glass tube. In the figure, 1 denotes a capillary glass tube having a structural color region, 2 denotes an open glass container, and 3 denotes an acrylamide prepolymerization solution.
FIG. 3 shows MoS-based samples prepared in example 22And (3) taking pictures of the color-changing anti-counterfeiting material of the quantum dots under an Mshot microscope camera MD 50.
FIG. 4 shows MoS-based samples prepared in example 22And (3) a schematic diagram of the phenomenon that the color-changing anti-counterfeiting material of the quantum dot bends towards light under the irradiation of an epi-illumination system of a Mshot metallurgical microscope MJ 33.
FIG. 5 shows MoS-based samples prepared in example 22And (3) taking pictures of the color-changing anti-counterfeiting material of the quantum dots by using an Mshot microscope MD50 when the structural color regionally blue-shifts under the irradiation of an epi-illumination system of an Mshot metallographic microscope MJ 33.
Fig. 6 is a comparative graph of the stability index studies for the materials prepared in example 2 and comparative example 1.
Fig. 7 is a comparison of the maximum bend angle studies for the materials prepared in example 2 and comparative example 1.
Detailed Description
The following examples are intended to illustrate the present invention in further detail, but the present invention is not limited thereto in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
EXAMPLE 1 production of a capillary glass tube having a structured color region
As shown in fig. 1, the nano silica microspheres used in the present invention are monodisperse nano silica microspheres with a diameter of 251nm, which are commercially available and dispersed in water. Centrifuging the mixture in a centrifuge at the rotating speed of 4000r/min for 5min, sucking out water by a dropper, centrifuging again, sucking out water again, repeating the steps for several times, dripping ethanol with the same volume as the total sucked water, and dispersing in ultrasonic waves (the ultrasonic dispersion time is about 1 h) until the dispersion is completely dispersed and no deposition exists, thus obtaining the nano silicon dioxide microsphere dispersion liquid.
Placing the nano-silica microsphere dispersion liquid into an open glass container, longitudinally inserting the capillary glass tube into the container, enabling the nano-silica microsphere dispersion liquid to enter the capillary glass tube through a capillary effect, continuously standing to enable ethanol in the container and the capillary glass tube to be completely evaporated naturally, and simultaneously forming a structural color region by self-assembling nano-silica microspheres in the capillary glass tube; or
After the nano silicon dioxide microsphere dispersion liquid enters the capillary glass tube through the capillary effect, the capillary glass tube is taken out and horizontally placed, so that the ethanol in the capillary glass tube is naturally and completely evaporated, and meanwhile, the nano silicon dioxide microspheres form a structural color area in the capillary glass tube under the action of physical sedimentation and agglomeration.
The formed structural color area is an area which is formed on the inner wall of the capillary glass tube by the nano silicon dioxide microspheres and has a stripe shape or other pattern shapes, the diameter of the capillary glass tube is 10mm, the length of the capillary glass tube is 10cm, and both the capillary glass tube and the nano silicon dioxide microspheres are easily dissolved by hydrofluoric acid; after the structural color area is formed on the inner wall of the capillary glass tube, the capillary glass tube is stored for standby.
Example 2 MoS-based2Preparation of color-changing anti-counterfeiting material of quantum dot
(1) A glass vessel with a lid was prepared to hold the acrylamide prepolymerization solution. Sequentially dipping absorbent cotton of acetone and absolute ethyl alcohol on the inner surface of a glass ware by using a forceps to wipe off small particles such as dust and the like attached to the surface, preliminarily removing oil stains on the surface of the glass ware, putting the glass ware into acetone to be cleaned for 10min by using ultrasonic waves, putting the glass ware into alcohol to be cleaned for 10min by using the ultrasonic waves, taking the glass ware out by using a clamp, putting the glass ware into deionized water to be cleaned by using the ultrasonic wavesCleaning for 5min, taking out from deionized water and adding N2And (5) drying.
(2) Preparation of acrylamide prepolymerization solution:
taking 1mL of polyethylene glycol diacrylate (average molecular weight 600) into the glassware in the step (1), respectively weighing 0.15g of N-isopropylacrylamide (NIPAM, AR content 98%) and 0.005g of N, N' -methylenebisacrylamide (BIS) by using an analytical balance, respectively adding the weighed materials into the polyethylene glycol diacrylate, and then adding 0.3mL of MoS2A quantum dot dispersion. Then 6.5uL of N, N, N ', N' -tetramethylethylenediamine (TEMED, 99%) and 14.5uL of ammonium persulfate solution (5% by mass) were added by a pipette. Wherein, MoS2Quantum dot dispersion refers to MoS2Dispersion of quantum dots as solute and N-methylpyrrolidone as solvent, MoS2The transverse size of the quantum dots is 1-10 nm, MoS2The concentration of the quantum dot dispersion was 1 mg/mL. It should be noted that ammonium persulfate solution is the initiator, N '-Tetramethylethylenediamine (TEMED) is the catalyst, catalyzing ammonium persulfate to generate free radicals, thus accelerating the polymerization of acrylamide gel, and the amounts of N, N' -tetramethylethylenediamine (TEMED, 99%) and ammonium persulfate solution should be strictly controlled, with small amounts causing the gelling process to become abnormally slow or even non-gelling, and large amounts causing the freshly prepared prepolymerization solution to complete gelling in glassware. Shaking a glassware to disperse the substances initially, and then ultrasonically mixing for 1h in an ice bath until the prepared prepolymerization solution is completely and uniformly mixed without layering. The temperature of the ultrasonic mixing process is strictly controlled, and the prepolymerization solution can be quickly coagulated into solid at a slightly higher temperature.
(3) Gel in oxygen-free environment:
as shown in FIG. 2, the acrylamide prepolymerization solution was placed in the fine glass tube prepared in example 1 by utilizing the capillary effect of the fine glass tube, and the liquid level in the fine glass tube was higher than that of the glass container. The prepolymerization solution was allowed to fill the entire area with the structural color. Thereafter, the capillary glass tube filled with the prepolymerization solution was placed in a petri dish. A plastic bag is taken, the air inside the bag is exhausted by squeezing (oxygen stops the combination of free radicals, so that gel is inhibited), the culture dish is pushed into the plastic bag, the plastic bag is filled with nitrogen, and then the plastic bag is sealed by using an adhesive tape. And (4) putting the sealed plastic bag into a thermostat, and keeping the temperature at 27 ℃ for gelling for 10 h. After the gel is finished, the plastic bag is scratched, the culture dish is taken out, the capillary glass tube is soaked in hydrofluoric acid until the glass is completely dissolved, the gel is clamped out by a pair of tweezers, the gel is soaked in deionized water for 10min, water is changed, and then the gel is soaked again. After three dips, the gel was removed and stored in deionized water. The finished gel was prepared as shown in FIG. 3. The acrylamide gel is cylindrical, the radius of the bottom surface is consistent with that of a capillary glass tube used, the length of the acrylamide gel can be adjusted manually, and the formed structural color is dispersed on the outer surface of the cylinder.
Comparative example 1 preparation of color-changing anti-counterfeiting material based on graphene oxide
(1) A glass vessel with a lid was prepared to hold the acrylamide prepolymerization solution. Sequentially dipping absorbent cotton of acetone and absolute ethyl alcohol on the inner surface of a glass ware by using a forceps to wipe off small particles such as dust and the like attached to the surface, preliminarily removing oil stains on the surface of the glass ware, putting the glass ware into acetone to be cleaned for 10min by ultrasonic waves, putting the glass ware into alcohol to be cleaned for 10min by ultrasonic waves, taking the glass ware out by a clamp to be put into deionized water to be cleaned for 5min by ultrasonic waves, taking the glass ware out of the deionized water and using N2And (5) drying.
(2) Preparation of acrylamide prepolymerization solution:
1ml of polyethylene glycol diacrylate (average molecular weight 600) was put into a glass vessel, 0.15g of N-isopropylacrylamide (NIPAM, AR content 98%) and 0.005g of N, N' -methylenebisacrylamide (BIS) were added in succession, and then 0.3ml of an aqueous graphene oxide solution (2 mg/ml) was added. Then 6.5ul of N, N, N ', N' -tetramethylethylenediamine (TEMED, 99%) and 14.5ul of ammonium persulfate solution (mass fraction of 5%) were added, the vessel was shaken to disperse the various substances initially, and then ultrasonic mixing was carried out in an ice bath for 1h until the prepared prepolymerization solution was completely and uniformly mixed without delamination.
(3) Gel in oxygen-free environment:
the acrylamide prepolymerization solution was placed in the capillary glass tube prepared in example 1 by utilizing the capillary effect of the capillary glass tube, and the liquid level in the capillary glass tube was higher than that of the glass container. The prepolymerization solution was allowed to fill the entire area with the structural color. Thereafter, the capillary glass tube filled with the prepolymerization solution was placed in a petri dish. A plastic bag is taken, the air inside the bag is exhausted by squeezing (oxygen stops the combination of free radicals, so that gel is inhibited), the culture dish is pushed into the plastic bag, the plastic bag is filled with nitrogen, and then the plastic bag is sealed by using an adhesive tape. And (4) putting the sealed plastic bag into a thermostat, and keeping the temperature at 27 ℃ for gelling for 10 h. After the gel is finished, the plastic bag is scratched, the culture dish is taken out, the capillary glass tube is soaked in hydrofluoric acid until the glass is completely dissolved, the gel is clamped out by a pair of tweezers, the gel is soaked in deionized water for 10min, water is changed, and then the gel is soaked again. Finally, the gel was swollen in hydrazine monohydrate solution (0.33M) to reduce the graphene oxide dispersed in the gel network. After two days, the gel was removed and then placed in deionized water for two days.
Example 3 Performance testing
Because of the MoS2The addition of quantum dots endows the acrylamide gel with some special properties. As shown in fig. 4, the material prepared in example 2 was placed on an optical microscope with an optical camera (Mshot mingmuim phase microscope MJ33, Mshot mingmuim phase microscope MD 50), a light source of the microscope (light from an epi-illumination system of the Mshot mingmuim phase microscope MJ 33) was turned on, and after a certain period of time of irradiation, the material was bent toward the light source like a sunflower, and the bending angle became larger with the increase of the irradiation time, and finally the bending was stopped at a certain angle. While the material was bent, the area of the material having the structural color was captured at regular time intervals using the camera MD50, and it was found that the material was bent to the light and also had a color change phenomenon of the irradiated structural color area. Through a large number of experimental observations and data analysis, the phenomenon of regional blue shift of structural color is found. Because of being based on MoS2The color-changing anti-counterfeiting material of the quantum dots has excellent photo-thermal conversion efficiency, and can cause the material to be reversibly bent to light during illumination, so that the structureThe change in (2) indirectly leads to a change in structural color, again due to MoS2The special microstructure of the quantum dot has a phenomenon of blue shift in structural color, and the specific phenomenon is shown in fig. 5, wherein numbers 1-9 in fig. 5 respectively correspond to pictures shot when the material is bent by 2 degrees, 4 degrees, 6 degrees, 8 degrees, 10 degrees, 12 degrees, 14 degrees, 16 degrees and 18 degrees. And as can be seen from fig. 5, part of the structural color shifts to invisible wavelengths due to blue shift, resulting in disappearance of the structural color. By applying the phenomenon, the dynamic anti-counterfeiting bar code with the photochromic capability can be manufactured.
MoS-based prepared in example 22The color change rate of the quantum dot color-changing anti-counterfeiting material is compared with that of the material prepared in comparative example 1. When high-power light is used for irradiation, the photothermal conversion capacity of the material is saturated due to the fact that the power of the light is too high, the difference between different raw material concentrations of the same material is amplified, in order to highlight different performances of the material, low-power light is used for irradiation, the required capacity of photothermal conversion is determined by the power of the light, and the different performances of the materials are determined by doped substances. Taking tens of the two materials, each having a length of 6.5mm, irradiating the two materials with low-power light (the light is from an epi-illumination system of Mshot Mingmei gold phase microscope MJ 33), monitoring the bending rates of the two materials in real time on the premise of ensuring that the experimental difference is only in the doped substances, and calculating the stability index of the two materials. The average value with representative significance is finally obtained by measuring a plurality of materials for a plurality of times, and the stability index with common significance of the two materials can be obtained.
In order to describe the interference resistance of the material and to express the stability of the material reasonably and clearly in a coordinate system. We propose a stability index, expressed as:
wherein,
the instantaneous rate of bending of the hydrogel fiber toward the light source is shown, and the bending angle of the hydrogel fiber over time is shown.
The results of the material stability index are shown in fig. 6. We can clearly compare, based on MoS2The stability index of the color-changing anti-counterfeiting material of the quantum dot is obviously higher than that of the material prepared in the comparative example 1. The two materials have strong color change capability and discrimination, and the structural color change of the materials can be easily discriminated at present when the imaging technology and color analysis are developed, so that the materials with high stability index are the first choice. Because the stability index is high, the stronger the capability of resisting the pollution of an environmental light source, the higher the anti-counterfeiting accuracy of the anti-counterfeiting ink is. In addition, in real life, the function of anti-counterfeiting detection needs to be completed in a short time, so the light source is replaced by a high-power infrared light source, but certain errors can be generated between the irradiation time and the power of the light source and the ideal situation, and the material with high stability index has a good effect on weakening the influence caused by the inevitable errors, so that the efficiency is ensured, and the accuracy of anti-counterfeiting detection can be greatly improved.
MoS-based prepared for example 22The color-changeable anti-counterfeiting material of the quantum dot and the material prepared in comparative example 1 were tested for the maximum bending angle, and the results are shown in fig. 7. The maximum bend angle was measured for both materials using the same light source (light from the epi-illumination system of Mshot Mingmei gold phase microscope MJ 33). Based on MoS2The maximum bending angle of the color-changing anti-counterfeiting material of the quantum dots is 19.6 degrees, and the maximum bending angle of the material prepared in the comparative example 1 is 40 degrees. Because the color-changing nature of the color-changing anti-counterfeiting material is still caused by the change of the structure, the color-changing anti-counterfeiting material cannot interfere in the bending. The smaller the maximum bending angle, the smaller the spatial extent required for bending, and the more reversible the bending, and the faster the structural color recovery. Moreover, the smaller the bending angle is, the maximum occupied volume of the anti-counterfeiting paper in practical anti-counterfeiting application isThe smaller the size is, the stronger the plasticity is, and the wide-range popularization and use in multiple fields are easier.
MoS-based preparation of example 22The color-changing anti-counterfeiting material of the quantum dots is different from the color-changing anti-counterfeiting material based on the reduced graphene oxide in the comparative example 1 in the color-changing range and phenomenon. The initial structural color we used was formed from 251nm monodisperse nanosilica microspheres, which were only red in color. When we illuminated the material (light from the epi-illumination system of Mshot mingmuim gold phase microscope MJ 33), the color of the structural color of the material gradually changed from red to green, and then the structural color turned to the invisible part, as shown in fig. 5. In contrast, when the initial structural color of the graphene oxide-based color-changing anti-counterfeiting material of comparative example 1 is only one color (such as red), only the transition from red to green occurs, and the phenomenon that the structural color changes to the invisible light partially does not occur. That is, we prepared MoS-based2The color-changing anti-counterfeiting material of the quantum dots has a wider color-changing range, further has stronger capability of storing hidden coded information, and is expected to replace the existing black and white bar codes in the future.
When color analysis was performed, the color-changeable anti-counterfeit material of comparative example 1 was found to have color contamination because the graphene oxide was dark brown. Based on MoS2The color pollution of the color-changing anti-counterfeiting material of the quantum dots is relatively small, so that the accuracy of the structural color is higher, and the color discrimination of the structural color is also higher.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The color-changing anti-counterfeiting material is characterized by being prepared by the following method:
(a) monodisperse the nano silicon dioxide microspheres in ethanol to obtain nano silicon dioxide microsphere dispersion liquid;
(b) enabling the nano silicon dioxide microsphere dispersion liquid to enter a capillary glass tube, and naturally evaporating ethanol to enable the nano silicon dioxide microspheres to form a structural color area in the capillary glass tube;
(c) preparation of a uniformly dispersed MoS2The method comprises the following steps of (1) pre-polymerizing an acrylamide solution of quantum dots, and enabling the pre-polymerizing acrylamide solution to enter a capillary glass tube with a structural color region through a capillary effect; the preparation process of the acrylamide prepolymerization solution is as follows:
putting polyethylene glycol diacrylate into a glass ware, adding N-isopropylacrylamide and N, N' -methylene bisacrylamide into the glass ware, dissolving, and adding MoS2Adding N, N, N ', N' -tetramethylethylenediamine and 5.0 mass percent ammonium persulfate solution into the quantum dot dispersion solution, and finally placing a glassware in an ice bath for ultrasonic mixing uniformly to obtain an acrylamide prepolymerization solution; wherein the mass ratio of the added N-isopropylacrylamide to the N, N ' -methylenebisacrylamide is 30: 1, the dosage ratio of the N-isopropylacrylamide to the polyethylene glycol diacrylate is 3 g: 15-20 mL, and the ratio of the N-isopropylacrylamide to the N, N, N ', N ' -tetramethylethylenediamine to the ammonium persulfate solution is =3 g: 100-130 uL: 260-290 uL;
the MoS2Quantum dot dispersion refers to MoS2A dispersion liquid with quantum dots as solute and N-methyl pyrrolidone as solvent, wherein MoS2The transverse size of the quantum dots is 1-10 nm, and the MoS2The concentration of the quantum dot dispersion liquid is 1mg/mL, MoS2The mass ratio of the quantum dot dispersion liquid to the N-isopropyl acrylamide = 4-6 mL: 3 g;
(d) gelling the capillary glass tube filled with the acrylamide prepolymerization solution prepared in the step (c) in a thermostat in an oxygen-free environment;
(e) and after the gelation is finished, dissolving the capillary glass tube and the nano silicon dioxide microspheres by using hydrofluoric acid, taking out the gel, soaking the gel in deionized water, and removing residual hydrofluoric acid to obtain the color-changing anti-counterfeiting material.
2. The color-changing security material according to claim 1, wherein in step (b):
enabling the nano-silica microsphere dispersion to enter a capillary glass tube through a capillary effect, then horizontally standing the capillary glass tube to enable ethanol in the capillary glass tube to be completely evaporated naturally, and simultaneously forming a structural color area in the capillary glass tube by the nano-silica microsphere; or
Placing the nano-silica microsphere dispersion liquid in an open container, longitudinally inserting the capillary glass tube into the container, enabling the nano-silica microsphere dispersion liquid to enter the capillary glass tube through a capillary effect, continuously standing to enable ethanol in the container and the capillary glass tube to be completely and naturally evaporated, and enabling the nano-silica microspheres to form a structural color region in the capillary glass tube.
3. The color-changing security material according to claim 1, wherein in step (a), the diameter of the monodisperse nano silica microspheres is 251 nm; in the step (b), the diameter of the capillary glass tube is 10mm, and the length of the capillary glass tube is 10 cm; in the step (d), the capillary glass tube filled with the acrylamide prepolymerization solution is filled into a plastic bag, the air in the plastic bag is exhausted and filled with nitrogen, and then the plastic bag is sealed and placed in a thermostat at 27 ℃ for gelation.
4. The preparation method of the color-changing anti-counterfeiting material is characterized by comprising the following steps of:
(a) monodisperse the nano silicon dioxide microspheres in ethanol to obtain nano silicon dioxide microsphere dispersion liquid;
(b) enabling the nano silicon dioxide microsphere dispersion liquid to enter a capillary glass tube, and naturally evaporating ethanol to enable the nano silicon dioxide microspheres to form a structural color area in the capillary glass tube;
(c) preparation of a uniformly dispersed MoS2The method comprises the following steps of (1) pre-polymerizing an acrylamide solution of quantum dots, and enabling the pre-polymerizing acrylamide solution to enter a capillary glass tube with a structural color region through a capillary effect; the preparation process of the acrylamide prepolymerization solution is as follows:
putting polyethylene glycol diacrylate into a glass ware, adding N-isopropylacrylamide and N, N' -methylene bisacrylamide into the glass ware, dissolving, and adding MoS2Adding N, N, N ', N' -tetramethylethylenediamine and 5.0 mass percent ammonium persulfate solution into the quantum dot dispersion solution, and finally placing a glassware in an ice bath for ultrasonic mixing uniformly to obtain an acrylamide prepolymerization solution; wherein the mass ratio of the added N-isopropylacrylamide to the N, N ' -methylenebisacrylamide is 30: 1, the dosage ratio of the N-isopropylacrylamide to the polyethylene glycol diacrylate is 3 g: 15-20 mL, and the ratio of the N-isopropylacrylamide to the N, N, N ', N ' -tetramethylethylenediamine to the ammonium persulfate solution is =3 g: 100-130 uL: 260-290 uL;
the MoS2Quantum dot dispersion refers to MoS2A dispersion liquid with quantum dots as solute and N-methyl pyrrolidone as solvent, wherein MoS2The transverse size of the quantum dots is 1-10 nm, and the MoS2The concentration of the quantum dot dispersion liquid is 1mg/mL, MoS2The mass ratio of the quantum dot dispersion liquid to the N-isopropyl acrylamide = 4-6 mL: 3 g;
(d) gelling the capillary glass tube filled with the acrylamide prepolymerization solution prepared in the step (c) in a thermostat in an oxygen-free environment;
(e) and after the gelation is finished, dissolving the capillary glass tube and the nano silicon dioxide microspheres by using hydrofluoric acid, taking out the gel, soaking the gel in deionized water, and removing residual hydrofluoric acid to obtain the color-changing anti-counterfeiting material.
5. The method for preparing a color-changing security material according to claim 4, wherein in the step (b):
enabling the nano-silica microsphere dispersion to enter a capillary glass tube through a capillary effect, then horizontally standing the capillary glass tube to enable ethanol in the capillary glass tube to be completely evaporated naturally, and simultaneously forming a structural color area in the capillary glass tube by the nano-silica microsphere; or
Placing the nano-silica microsphere dispersion liquid in an open container, longitudinally inserting the capillary glass tube into the container, enabling the nano-silica microsphere dispersion liquid to enter the capillary glass tube through a capillary effect, continuously standing to enable ethanol in the container and the capillary glass tube to be completely and naturally evaporated, and enabling the nano-silica microspheres to form a structural color region in the capillary glass tube.
6. The method for preparing a color-changing anti-counterfeiting material according to claim 4, wherein in the step (a), the diameter of the monodisperse nano silica microspheres is 251 nm; in the step (b), the diameter of the capillary glass tube is 10mm, and the length of the capillary glass tube is 10 cm; in the step (d), the capillary glass tube filled with the acrylamide prepolymerization solution is filled into a plastic bag, the air in the plastic bag is exhausted and filled with nitrogen, and then the plastic bag is sealed and placed in a thermostat at 27 ℃ for gelation.
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