CN109735036B - Based on WS2Color-changing anti-counterfeiting material of nanosheet and preparation method thereof - Google Patents
Based on WS2Color-changing anti-counterfeiting material of nanosheet and preparation method thereof Download PDFInfo
- Publication number
- CN109735036B CN109735036B CN201811554194.4A CN201811554194A CN109735036B CN 109735036 B CN109735036 B CN 109735036B CN 201811554194 A CN201811554194 A CN 201811554194A CN 109735036 B CN109735036 B CN 109735036B
- Authority
- CN
- China
- Prior art keywords
- glass tube
- capillary glass
- nano
- capillary
- color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Paper (AREA)
Abstract
The invention provides a WS-based method2The color-changing anti-counterfeiting material of the nano-sheet and the preparation method thereof, (a) nano-silica 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 homogeneously dispersed organic WS2Placing the acrylamide prepolymerization solution of the nanosheets 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, less color pollution, 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 WS-based color-changing anti-counterfeiting material2A color-changing anti-counterfeiting material of a nano-sheet and a preparation method thereof.
Background
The current anti-counterfeiting situation is very severe, and the counterfeit goods relate to the aspects of people's life. The problem of counterfeit goods is no longer a simple manufacturing cost problem, and many counterfeit goods break through the moral bottom line of human beings. For counterfeit goods, no allowance can be made, no ambiguity can be made, and zero tolerance must be made truly.
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. 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 objectives of the present invention is to provide a WS-based solution2The color-changing anti-counterfeiting material of the nano-sheet 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 WS-based method2A preparation method of a color-changing anti-counterfeiting material of a nano-sheet.
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 homogeneously dispersed organic WS2The acrylamide pre-polymerization solution of the nanosheets is made 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' -methylenebisacrylamide into the glass ware, dissolving, and adding WS2Adding N, N, N ', N' -tetramethylethylenediamine and 5.0 mass percent ammonium persulfate solution into the nanosheet dispersion, 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 WS2The nanosheet dispersion is denoted as WS2A dispersion liquid with nanosheet as solute and a mixed liquid of water and ethanol as solvent, wherein WS2The transverse size of the nano sheet is 0.05-1 um; the WS2The concentration of the nano-sheet dispersion is 1mg/mL, WS2Nano meterThe tablet dispersion liquid is N-isopropylacrylamide = 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 homogeneously dispersed organic WS2The acrylamide pre-polymerization solution of the nanosheets is made 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' -methylenebisacrylamide into the glass ware, dissolving, and adding WS2Adding N, N, N ', N' -tetramethylethylenediamine and 5.0 mass percent ammonium persulfate solution into the nanosheet dispersion, 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 WS2The nanosheet dispersion is denoted as WS2A dispersion liquid with nanosheet as solute and a mixed liquid of water and ethanol as solvent, wherein WS2The transverse size of the nano sheet is 0.05-1 um; the WS2The concentration of the nano-sheet dispersion is 1mg/mL, WS2The ratio of the nanosheet dispersion to N-isopropylacrylamide is = 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 is a color-changing anti-counterfeiting material with high stability index, strong structural stability, small color pollution, quicker recovery and stronger applicability, and the comprehensive performance of the anti-counterfeiting material is obviously superior to that of the prior color-changing anti-counterfeiting materialA material. The preparation method provided by the invention is simple and easy to implement, has good operability, and is based on WS2The color-changing anti-counterfeiting material of the nano-sheet has good performance. The invention uses WS2The nano-sheet enables the performance of the anti-counterfeiting material to be more excellent, has a unique structure, can be really applied to actual anti-counterfeiting detection, and has a wide application prospect.
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 is WS-based prepared in example 22And (3) taking pictures of the color-changing anti-counterfeiting material of the nanosheets under Mshot microscope camera MD 50.
FIG. 4 shows WS-based samples prepared in example 22Schematic diagram of the phenomenon that the color-changing anti-counterfeiting material of the nanosheets bends towards light under the irradiation of an epi-illumination system of a Mshot metallographic microscope MJ 33.
FIG. 5 WS-based preparation prepared in example 22And (3) taking pictures of the color-changing anti-counterfeiting material of the nanosheets by using an Mshot microscope camera 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 based on WS2Preparation of color-changing anti-counterfeiting material of nanosheet
(1) A glass vessel with a lid was prepared to hold the acrylamide prepolymerization solution. Wiping the inner surface of glassware with absorbent cotton dipped with acetone and anhydrous alcohol in sequence, and wiping off small particles such as dust attached to the surfaceRemoving oil stain on the surface of glassware primarily, cleaning glassware in acetone for 10min, cleaning in alcohol for 10min, taking out with clamp, cleaning in deionized water for 5min, taking out from deionized water, and cleaning with 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 WS2A nanosheet 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 WS2The nanosheet dispersion is denoted as WS2Dispersion liquid using nanosheet as solute and mixed liquid of water and ethanol (containing 20vol% of ethanol) as solvent, WS2The transverse dimension of the nano sheet is 0.05-1 um, WS2The thickness of the nano sheet is 1-10 layers; the WS2The concentration of the nano-sheet dispersion liquid is 1mg/mL, and no active agent is used. 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 WS2The incorporation of the nanosheets imparts some special properties to the acrylamide gel. As shown in fig. 4, the material made in example 2 is placed on a Mshot metalloscope MJ33 with a Mshot microscopic camera MD50, a light source (light from an epi-illumination system of the Mshot metalloscope MJ 33) on the microscope is turned on, after the gel is irradiated for a period of time, the gel bends towards the light source like a sunflower, the bending angle becomes larger and larger with the increase of the irradiation time, and finally the bending stops at a certain angle. When the material is bent, a microscope camera is used for regularly capturing the area of the material with the structural color, the color change phenomenon of the irradiated structural color area is found when the material is bent to light,the specific phenomenon can be seen in fig. 5. Numbers 1-9 in fig. 5 correspond to pictures taken of the material at 2 °, 4 °, 6 °, 8 °, 10 °, 12 °, 14 °, 16 °, 17 ° bends, respectively. Wherein the numbers 1-5 represent that the structural color of the material is red, and because WS2The nano-sheet has strong room-temperature photoluminescence effect, and the structural color becomes darker and darker along with the bending. The numbers 6-7 show that most of the structural colors of the materials are green, and only the residual red is red. The numbers 8-9 show that the structural color of the material is changed into green, and the structural color is deepened. Through a large number of experimental observations and data analysis, the phenomenon of regional blue shift of structural color is found. Because based on WS2The acrylamide gel of the nano-sheet has excellent photo-thermal conversion efficiency, when the acrylamide gel is illuminated, the gel can be reversibly bent to light, and the structural change indirectly causes the structural color change due to WS2The special microstructure of the nano-sheet has the phenomenon of blue shift of the structural color, and the phenomenon that the color intensity of the structural color is increased due to the strong room-temperature photoluminescence effect is not possessed by the comparative example. By applying the phenomenon, the dynamic anti-counterfeiting bar code with the photochromic capability can be manufactured.
WS-based prepared in example 22The color change rate of the color change anti-counterfeiting material of the nanosheet 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. Using a plurality of materialsThe average value with representative significance is finally obtained through multiple measurements, 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 content of the first and second substances,
v represents the instantaneous rate of bending of the hydrogel fiber toward the light source, and x represents the bending angle of the hydrogel fiber over time.
The results of the material stability index are shown in fig. 6. We can clearly compare based on WS2The stability index of the color-changing anti-counterfeiting material of the nano-sheet 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.
WS-based preparation of example 22The color-changing anti-counterfeiting material of the nanosheet and the material prepared in comparative example 1 were tested for maximum bending angle, and the results are shown in fig. 7. Using the same light source (light from Mshot BrightEpi-illumination system of meijin phase microscope MJ 33) performed maximum bend angle measurements for both materials. Based on WS2The maximum bending angle of the color-changing anti-counterfeiting material of the nano-sheet is 17 degrees, while the maximum bending angle of the color-changing anti-counterfeiting material of 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. And the smaller the bending angle is, the smaller the maximum occupied volume of the anti-counterfeiting product in practical anti-counterfeiting application is, the stronger the plasticity is, and the anti-counterfeiting product is easier to popularize and use in a large range in multiple fields.
Upon color analysis, the material of comparative example 1 was found to have color contamination because the graphene oxide was tan. Based on WS2The color-changing anti-counterfeiting material of the nano-sheet has relatively small color pollution, so that the accuracy of the structural color is stronger, and the color discrimination of the structural color is also stronger.
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 homogeneously dispersed organic WS2The preparation method comprises the following steps of (1) preparing an acrylamide prepolymerization solution of a nanosheet, wherein the preparation process comprises the following steps:
putting polyethylene glycol diacrylate into a glass ware, adding N-isopropylacrylamide and N, N' -methylenebisacrylamide into the glass ware, dissolving, and adding WS2Adding N, N, N ', N' -tetramethylethylenediamine and 5.0 mass percent ammonium persulfate solution into the nanosheet dispersion, 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;
enabling the acrylamide prepolymerization solution to enter a capillary glass tube with a structural color area through a capillary effect; the WS2The nanosheet dispersion is denoted as WS2A dispersion liquid with nanosheet as solute and a mixed liquid of water and ethanol as solvent, wherein WS2The transverse size of the nano sheet is 0.05-1 um; the WS2The concentration of the nano-sheet dispersion is 1mg/mL, WS2N-isopropylacrylamide and N-isopropyl acrylamide = 4-6 mL and 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 homogeneously dispersed organic WS2The preparation method comprises the following steps of (1) preparing an acrylamide prepolymerization solution of a nanosheet, wherein the preparation process comprises the following steps:
putting polyethylene glycol diacrylate into a glass ware, adding N-isopropylacrylamide and N, N' -methylenebisacrylamide into the glass ware, dissolving, and adding WS2Adding N, N, N ', N' -tetramethylethylenediamine and 5.0 mass percent ammonium persulfate solution into the nanosheet dispersion, 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' -methylene bisacrylamide is 30: 1, and the N-isopropylacrylamide and the polyethylene glycol dipropylene areThe dosage ratio of the alkenoic acid ester is 3 g: 15-20 mL, N-isopropylacrylamide: N, N, N ', N' -tetramethylethylenediamine: ammonium persulfate solution =3 g: 100-130 uL: 260-290 uL;
enabling the acrylamide prepolymerization solution to enter a capillary glass tube with a structural color area through a capillary effect; the WS2The nanosheet dispersion is denoted as WS2A dispersion liquid with nanosheet as solute and a mixed liquid of water and ethanol as solvent, wherein WS2The transverse size of the nano sheet is 0.05-1 um; the WS2The concentration of the nano-sheet dispersion is 1mg/mL, WS2N-isopropylacrylamide and N-isopropyl acrylamide = 4-6 mL and 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811554194.4A CN109735036B (en) | 2018-12-18 | 2018-12-18 | Based on WS2Color-changing anti-counterfeiting material of nanosheet and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811554194.4A CN109735036B (en) | 2018-12-18 | 2018-12-18 | Based on WS2Color-changing anti-counterfeiting material of nanosheet and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109735036A CN109735036A (en) | 2019-05-10 |
| CN109735036B true CN109735036B (en) | 2021-06-25 |
Family
ID=66360554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811554194.4A Active CN109735036B (en) | 2018-12-18 | 2018-12-18 | Based on WS2Color-changing anti-counterfeiting material of nanosheet and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109735036B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982011B (en) * | 2019-11-29 | 2021-08-03 | 河北大学 | Light-directing bending material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106199770A (en) * | 2016-09-27 | 2016-12-07 | 大连理工大学 | A kind of 1-D photon crystal structure chromogenic materials and preparation method thereof |
-
2018
- 2018-12-18 CN CN201811554194.4A patent/CN109735036B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106199770A (en) * | 2016-09-27 | 2016-12-07 | 大连理工大学 | A kind of 1-D photon crystal structure chromogenic materials and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Bioinspired Heterogeneous Structural Color Stripes from Capillaries;Ze Zhao et al.,;《ADVANCED MATERIALS COMMUNICATION》;20171017;第29卷(第46期);第1704569(1-8)页，supporting information部分第1-3页 * |
| Size-tunable photoluminescence from WS2 nanostructures;Shivani Sharma et al.,;《Materials Research Express》;20180427;第5卷(第4期);第045047(1-9)页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109735036A (en) | 2019-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | MOF-derived nanoporous carbons with diverse tunable nanoarchitectures | |
| CN109721743B (en) | Based on MoS2Color-changing anti-counterfeiting material of quantum dots and preparation method thereof | |
| Wu et al. | Three-dimensional basswood-based membrane with well-designed multilevel/hierarchical imprinting surface: A high-efficiency selective separation system | |
| CN102005609A (en) | Composite gel polymer electrolyte membrane and application thereof | |
| JPH01158051A (en) | Thin membrane electrolyte | |
| CN110982011B (en) | Light-directing bending material and preparation method thereof | |
| CN109060198A (en) | The double cross-linked network self-healing hydrogel capacitance pressure transducer,s of PAA class | |
| Yang et al. | Swelling and diffusion model of a hydrophilic film coating on controlled-release urea particles | |
| CN104037432A (en) | High polymer-modified metal organic framework material composite membrane, and preparation and application thereof | |
| CN109735036B (en) | Based on WS2Color-changing anti-counterfeiting material of nanosheet and preparation method thereof | |
| CN110102248A (en) | A kind of surface oxygen defect porous metal oxide material and its preparation and application | |
| CN108807687A (en) | A kind of preparation method of nickel oxide film | |
| CN107221447A (en) | A kind of graphene flexible compound electrode, its preparation method and flexible super capacitor | |
| Zhang et al. | Microorganism inspired hydrogels: hierarchical super/macro-porous structure, rapid swelling rate and high adsorption | |
| CN111426674B (en) | Sunflower nano array structure for enhancing SERS activity and preparation method thereof | |
| CN106841344B (en) | The preparation and application of a kind of poroid single-walled carbon nanotube and its modified electrode | |
| CN109535454B (en) | Lead ion response type intelligent membrane, preparation method thereof and detection method of lead ions in water sample | |
| CN105860102B (en) | The preparation method of P (PVIS-AA)/Sodium Alginate Hydrogel Films and its application in the catalyst | |
| CN108226123B (en) | Method for preparing surface enhanced Raman scattering substrate by femtosecond laser | |
| CN109762113B (en) | Method for rapidly preparing high-quality acrylamide gel film | |
| CN104888626A (en) | Preparation method of degradable polylactic acid microporous membrane | |
| Ma et al. | Hydrophilic–hydrophobic hybrid gel for effective humidity capture and response | |
| Soler-Illia et al. | Chemical methods to produce mesoporous thin films with tunable properties | |
| CN106830704A (en) | The preparation method of the super hydrophilic porous super infiltration boundary material of superhydrophobic patternization | |
| Xu et al. | Thermo-sensitive hydrogels for forward osmosis with NIR light-induced freshwater recovery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |