CN109721743A - One kind being based on MoS2Color-changing anti-counterfeit material of quantum dot and preparation method thereof - Google Patents
One kind being based on MoS2Color-changing anti-counterfeit material of quantum dot and preparation method thereof Download PDFInfo
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Abstract
The present invention provides one kind to be based on MoS2Color-changing anti-counterfeit material of quantum dot and preparation method thereof, (a) make nano silica microsphere monodisperse in ethyl alcohol；(b) enter nano silica microsphere dispersion liquid in glass capillary and form schemochrome region；(c) preparing evenly dispersed has MoS2Acrylamide pre-polymer solution is placed in glass capillary by the acrylamide pre-polymer solution of quantum dot by capillary effect；(d) glass capillary carries out gel in oxygen-free environment in insulating box；(e) it after the completion of gel, with hydrofluoric acid dissolution glass capillary and nano silica microsphere, takes out gel and impregnates in deionized water, up to color-changing anti-counterfeit material after remaining hydrofluoric acid is removed.Anti-fake material of the invention is that a kind of stability index is high, and color stain is small, and color change interval is wider, and recovery is quicker, and the stronger color-changing anti-counterfeit material of applicability, comprehensive performance is significantly better than existing color-changing anti-counterfeit material.
Description
Technical field
The present invention relates to color-changing anti-counterfeit material technical fields, specifically a kind of to be based on MoS2The color-changing anti-counterfeit of quantum dot
Material and preparation method thereof.
Background technique
The anti-fake material and technology in the present age have very much, but with the development of science and technology, contemporary forgery, personation are also
It being generated in the background of productivity raising and scientific technological advance, scientific and technological content can be very high, even up to mixes the spurious with the genuine,
Degree hard to tell whether it is true or false.So anti-fake material must be more skillful, become " as virtue rises one foot, vice rises ten " as " the magic road Gao Yichi is high
One zhang ".That is, a kind of anti-fake material novel, anti-counterfeit capability is significantly larger than the prior art, there is boundless city
Field space and very large market demand.Root was according to the relevant information, national correlation department was to antifalse material in recent years
The financial support of material puts more effort.The annual output total value in the anti-fake market in the whole world has reached 500,000,000,000 dollars, and domestic anti-fake market is produced per year
Total value has also reached more than 1,000 hundred million yuans.On the whole, the research and development of antifalse material encounter the opportunity of a lifetime.
Based on present, we are badly in need of a kind of new material to break through the existing technical bottleneck of anti-fake material.
The research team of German Leibnitz's polymer research institute has developed a kind of special graphite ene coatings, this stone
Black ene coatings change color when can deform or rupture at it.Researcher believes, the coating or similar that they prepare
Product has certain prospects for commercial application.But the coating disclose material deformation and level of breakage validity in terms of still to
Test, it is also not yet clear whether this coating adapts to rugged environment in real world, therefore, how to prepare a kind of comprehensive
Energy color-changing anti-counterfeit material that is excellent and can adapt to actual application environment becomes important research topic.
Summary of the invention
An object of the present invention is to provide a kind of based on MoS2The color-changing anti-counterfeit material of quantum dot, it is existing anti-fake to solve
The undesirable problem of material comprehensive performance.
It is a kind of based on MoS the second object of the present invention is to provide2The preparation method of the color-changing anti-counterfeit material of quantum dot.
An object of the present invention is achieved through the following technical solutions: a kind of color-changing anti-counterfeit material, and the discoloration is anti-
Pseudo- material is prepared by the following method to obtain:
(a) make nano silica microsphere monodisperse in ethyl alcohol, obtain nano silica microsphere dispersion liquid；
(b) enter nano silica microsphere dispersion liquid in glass capillary, and by ethyl alcohol natural evaporation, make nanometer titanium dioxide
Silicon microballoon forms schemochrome region in glass capillary；
(c) preparing evenly dispersed has MoS2The acrylamide pre-polymer solution of quantum dot, passes through acrylamide pre-polymer solution
Capillary effect, which enters, to be formed in the glass capillary in schemochrome region；
(d) by step (c) glass capillary for being loaded with acrylamide pre-polymer solution Yu Hengwen in oxygen-free environment obtained
Gel is carried out in case；
(e) after the completion of gel, with hydrofluoric acid dissolution glass capillary and nano silica microsphere, gel is taken out and in deionization
It is impregnated in water, up to color-changing anti-counterfeit material after remaining hydrofluoric acid is removed.
In step (b):
Enter nano silica microsphere dispersion liquid in glass capillary by capillary effect, then by glass capillary level
It stands, keeps the ethyl alcohol natural evaporation in glass capillary complete, while nano silica microsphere is formed in glass capillary
Schemochrome region；Or
Nano silica microsphere dispersion liquid is placed in open container, glass capillary is longitudinally inserted into the container,
Nano silica microsphere dispersion liquid passes through capillary effect and enters in glass capillary, and lasting stand keeps container interior and capillary glass
Ethyl alcohol natural evaporation in glass pipe is complete, while nano silica microsphere forms schemochrome region in glass capillary.
In step (c), the preparation process of the acrylamide pre-polymer solution is as follows:
Then n-isopropyl acrylamide and N is added in glassware in taking polyethylene glycol diacrylate into glassware,
N'- methylene-bisacrylamide simultaneously dissolves, and MoS is added later2Quantum dot dispersion liquid adds N, N, N', N'- tetramethyl second two
It is uniformly rear up to third to be finally placed in ultrasonic mixing in ice bath by the ammonium persulfate solution that amine and mass fraction are 5.0% for glassware
Acrylamide pre-polymer solution；Wherein, the n-isopropyl acrylamide and N of addition, the mass ratio of N'- methylene-bisacrylamide are
30: 1, the amount ratio of n-isopropyl acrylamide and polyethyleneglycol diacrylate is 3g: 15 ~ 20mL, N- isopropyl acrylamide
Amine: N, N, N', N'- tetramethylethylenediamine: ammonium persulfate solution=3g: 100 ~ 130uL: 260 ~ 290uL.
In step (c), the MoS2Quantum dot dispersion liquid refers to MoS2Quantum dot is solute, with N-Methyl pyrrolidone is
The dispersion liquid of solvent, wherein MoS2The lateral dimension of quantum dot is 1 ~ 10nm, the MoS2The concentration of quantum dot dispersion liquid is
1mg/mL, MoS2Quantum dot dispersion liquid: n-isopropyl acrylamide=4 ~ 6mL: 3g.
In step (a), the diameter of mono-dispersed nano silicon dioxide microsphere is 251nm；In step (b), the capillary glass
The diameter of glass pipe is 10mm, length 10cm；In step (d), the glass capillary of acrylamide pre-polymer solution will be loaded with
It is fitted into polybag, drains the air in polybag and is filled with nitrogen, plastic bag sealing is placed in 27 DEG C of insulating box later
Middle carry out gel.
The second object of the present invention is to what is be achieved through the following technical solutions: a kind of preparation method of color-changing anti-counterfeit material,
The following steps are included:
(a) make nano silica microsphere monodisperse in ethyl alcohol, obtain nano silica microsphere dispersion liquid；
(b) enter nano silica microsphere dispersion liquid in glass capillary, and by ethyl alcohol natural evaporation, make nanometer titanium dioxide
Silicon microballoon forms schemochrome region in glass capillary；
(c) preparing evenly dispersed has MoS2The acrylamide pre-polymer solution of quantum dot, passes through acrylamide pre-polymer solution
Capillary effect, which enters, to be formed in the glass capillary in schemochrome region；
(d) by step (c) glass capillary for being loaded with acrylamide pre-polymer solution Yu Hengwen in oxygen-free environment obtained
Gel is carried out in case；
(e) after the completion of gel, with hydrofluoric acid dissolution glass capillary and nano silica microsphere, gel is taken out and in deionization
It is impregnated in water, up to color-changing anti-counterfeit material after remaining hydrofluoric acid is removed.
In step (b):
Enter nano silica microsphere dispersion liquid in glass capillary by capillary effect, then by glass capillary level
It stands, keeps the ethyl alcohol natural evaporation in glass capillary complete, while nano silica microsphere is formed in glass capillary
Schemochrome region；Or
Nano silica microsphere dispersion liquid is placed in open container, glass capillary is longitudinally inserted into the container,
Nano silica microsphere dispersion liquid passes through capillary effect and enters in glass capillary, and lasting stand keeps container interior and capillary glass
Ethyl alcohol natural evaporation in glass pipe is complete, while nano silica microsphere forms schemochrome region in glass capillary.
In step (c), the preparation process of the acrylamide pre-polymer solution is as follows:
Then n-isopropyl acrylamide and N is added in glassware in taking polyethylene glycol diacrylate into glassware,
N'- methylene-bisacrylamide simultaneously dissolves, and MoS is added later2Quantum dot dispersion liquid adds N, N, N', N'- tetramethyl second two
It is uniformly rear up to third to be finally placed in ultrasonic mixing in ice bath by the ammonium persulfate solution that amine and mass fraction are 5.0% for glassware
Acrylamide pre-polymer solution；Wherein, the n-isopropyl acrylamide and N of addition, the mass ratio of N'- methylene-bisacrylamide are
30: 1, the amount ratio of n-isopropyl acrylamide and polyethyleneglycol diacrylate is 3g: 15 ~ 20mL, N- isopropyl acrylamide
Amine: N, N, N', N'- tetramethylethylenediamine: ammonium persulfate solution=3g: 100 ~ 130uL: 260 ~ 290uL.
In step (c), the MoS2Quantum dot dispersion liquid refers to MoS2Quantum dot is solute, with N-Methyl pyrrolidone is
The dispersion liquid of solvent, wherein MoS2The lateral dimension of quantum dot is 1 ~ 10nm, the MoS2The concentration of quantum dot dispersion liquid is
1mg/mL, MoS2Quantum dot dispersion liquid: n-isopropyl acrylamide=4 ~ 6mL: 3g.
In step (a), the diameter of mono-dispersed nano silicon dioxide microsphere is 251nm；In step (b), the capillary glass
The diameter of glass pipe is 10mm, length 10cm；In step (d), the glass capillary of acrylamide pre-polymer solution will be loaded with
It is fitted into polybag, drains the air in polybag and is filled with nitrogen, plastic bag sealing is placed in 27 DEG C of insulating box later
Middle carry out gel.
Anti-fake material of the invention is that a kind of stability index is high, and color stain is small, and color change interval is wider, and recovery is more accelerated
Speed, the stronger color-changing anti-counterfeit material of applicability, comprehensive performance are significantly better than existing color-changing anti-counterfeit material.It is provided by the invention
Preparation method is simple, good operability, preparation based on MoS2The color-changing anti-counterfeit material of quantum dot is with good performance.This
Invention has used MoS2Quantum dot makes the performance of anti-fake material more excellent, and unique structure has broad application prospects.
Detailed description of the invention
Fig. 1 is the picture that mono-dispersed nano silicon dioxide microsphere is shot under a scanning electron microscope.Dispersed nano
The diameter of silicon dioxide microsphere is 251nm.
Fig. 2 is the schematic diagram that acrylamide pre-polymer solution is drawn using the capillary effect of glass capillary.In figure, 1 table
Show the glass capillary with schemochrome region, 2 indicate open glass container, and 3 indicate acrylamide pre-polymer solution.
Fig. 3 is prepared by embodiment 2 based on MoS2The color-changing anti-counterfeit material of quantum dot is in Mshot microscope camera MD50
The picture of lower shooting.
Fig. 4 is prepared by embodiment 2 based on MoS2The color-changing anti-counterfeit material of quantum dot is in Mshot metallographic microscope MJ33
Fall penetrate lighting system irradiation under to bendingof light phenomenon schematic diagram.
Fig. 5 is prepared by embodiment 2 based on MoS2The color-changing anti-counterfeit material of quantum dot is in Mshot metallographic microscope MJ33
Fall penetrate lighting system irradiation flowering structure color regionality blue shift when with Mshot microscope camera MD50 shoot picture.
Fig. 6 is the comparison diagram that the stability index of material prepared by embodiment 2 and comparative example 1 is probed into.
Fig. 7 is the comparison diagram that the maximum bend angle of material prepared by embodiment 2 and comparative example 1 is probed into.
Specific embodiment
Following example is for present invention be described in more detail, but embodiment does not do any type of limit to the present invention
It is fixed.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1 has the production of the glass capillary in schemochrome region
As shown in Figure 1, the nano silica microsphere that the present invention uses is that the monodisperse that commercially available diameter is 251nm is received
Rice silicon dioxide microsphere, and it is dispersed in water.It is centrifuged in centrifuge with the revolving speed of 4000r/min, when centrifugation
Between be 5min, later with dropper be sucked out moisture, be then centrifuged again, then moisture is sucked out, so circulation several times after, instill in total
The ethyl alcohol of the moisture same volume of suction, then dispersion (ultrasonic wave is about 1h when dispersing) in ultrasonic wave, scatter until all,
Until no deposition to get arrive nano silica microsphere dispersion liquid of the invention.
Nano silica microsphere dispersion liquid is placed in open glass container, glass capillary is longitudinally inserted into container
In, nano silica microsphere dispersion liquid passes through capillary effect and enters in glass capillary, and lasting stand keeps container interior and hair
Ethyl alcohol natural evaporation in thin glass tube is complete, while nano silica microsphere is formed in glass capillary by self assembly
Schemochrome region；Or
After entering nano silica microsphere dispersion liquid in glass capillary by capillary effect, glass capillary is taken out simultaneously
Horizontal rest keeps the ethyl alcohol natural evaporation in glass capillary complete, while nano silica microsphere is settled and rolled into a ball in physics
Schemochrome region is formed under the action of poly- in glass capillary.
The schemochrome region of above-mentioned formation is to be had by what nano silica microsphere was formed on capillary glass inside pipe wall
The region of striated or other pattern-likes, the diameter of glass capillary are 10mm, length 10cm, glass capillary and nanometer two
Silicon oxide microsphere is easily by hydrofluoric acid dissolution；After forming schemochrome region on capillary glass inside pipe wall, stored spare.
Embodiment 2 is based on MoS2The preparation of the color-changing anti-counterfeit material of quantum dot
(1) prepare the glassware for having lid, for containing acrylamide pre-polymer solution.By the interior table of glassware
The little particles such as the dust of surface attachment first with the sub absorbent cotton wiping for successively dipping acetone, dehydrated alcohol is taken the photograph, are wiped in face, preliminary clear
Except the greasy dirt on its surface, then the glassware is put in acetone with ultrasonic cleaning 10min, is put into alcohol later with super
Sound wave cleans 10min, then is put into deionized water with clip taking-up and uses ultrasonic cleaning 5min, finally takes out from deionized water
And use N2Drying.
(2) acrylamide pre-polymer solution is prepared:
It takes the polyethyleneglycol diacrylate (average molecular weight 600) of 1mL in the glassware of step (1), uses assay balance
The N of n-isopropyl acrylamide (NIPAM, the AR content 98%) and 0.005g of 0.15g, N'- methylene bisacrylamide acyl are weighed respectively
Amine (BIS), is added separately in polyethyleneglycol diacrylate, and the MoS of 0.3mL is then added2Quantum dot dispersion liquid.Later again
The N, N, N' of 6.5uL, the ammonium persulfate solution (matter of N'- tetramethylethylenediamine (TEMED, 99%) and 14.5uL are added with pipettor
Measure score 5%).Wherein, MoS2Quantum dot dispersion liquid refers to MoS2Quantum dot is solute, using N-Methyl pyrrolidone as point of solvent
Dispersion liquid, MoS2The lateral dimension of quantum dot is 1 ~ 10nm, MoS2The concentration of quantum dot dispersion liquid is 1mg/mL.It should be noted that
Ammonium sulfate is initiator, and N, N, N', N'- tetramethylethylenediamine (TEMED) is catalyst, and catalysis ammonium persulfate generates freely
Base, to accelerate the polymerization of acrylamide gel, N, N, N', N'- tetramethylethylenediamine (TEMED, 99%) and ammonium persulfate solution
Amount should strict control, amount is few then to make gel process become abnormal slowly even not gel, and mostly it will cause just for amount
The pre-polymer solution being configured to just completes gel in glassware.Rocking glassware makes each substance tentatively scatter, later
Ultrasonic mixing 1h is mixed to matched pre-polymer solution substantially uniformity in ice bath, is not layered.Ultrasonic mixing process is stringent
Temperature is controlled, the slightly higher pre-polymer solution of temperature will be rapidly condensed into solid.
(3) gel is in oxygen-free environment:
As shown in Fig. 2, acrylamide pre-polymer solution is placed to embodiment 1 and is prepared using the capillary effect of glass capillary
Glass capillary in, and the liquid level in glass capillary is higher than glass container.Make pre-polymer solution full of entire band
There is the region of schemochrome.Later, the glass capillary filled with pre-polymer solution is lain against in culture dish.A polybag is taken,
The air (oxygen can terminate the combination of free radical, to inhibit gel) drained in it is squeezed, then culture dish is pushed into polybag
In, it is full of nitrogen into polybag, then seals with adhesive tape.Polybag after sealing is put into insulating box, temperature is maintained at
27 DEG C, gel 10h.After completing gel, polybag is scratched, culture dish is taken out, glass capillary is impregnated in hydrofluoric acid, until glass
Glass is completely dissolved, and is pressed from both sides out gel with tweezers, is impregnated 10min in deionized water, changes water, then impregnate.After impregnating three times, it will coagulate
Glue takes out and saves in deionized water.It is as shown in Figure 3 to prepare the gel completed.Acrylamide gel is cylinder, bottom surface
Radius and glass capillary used are consistent, and length can be adjusted artificially, and the schemochrome of formation is dispersed in the outer of cylinder
Surface.
The preparation of color-changing anti-counterfeit material of the comparative example 1 based on graphene oxide
(1) prepare the glassware for having lid, for containing acrylamide pre-polymer solution.By the interior table of glassware
The little particles such as the dust of surface attachment first with the sub absorbent cotton wiping for successively dipping acetone, dehydrated alcohol is taken the photograph, are wiped in face, preliminary clear
Except the greasy dirt on its surface, then the glassware is put in acetone with ultrasonic cleaning 10min, is put into alcohol later with super
Sound wave cleans 10min, then is put into deionized water with clip taking-up and uses ultrasonic cleaning 5min, finally takes out from deionized water
And use N2Drying.
(2) acrylamide pre-polymer solution is prepared:
Take the polyethyleneglycol diacrylate (average molecular weight 600) of 1ml in glassware, the N- that 0.15g is successively added is different
The N of propylacrylamide (NIPAM, AR content 98%) and 0.005g, N'- methylene-bisacrylamide (BIS) are then added
The graphene oxide water solution (2mg/ml) of 0.3ml.The N of 6.5ul, N, N', N'- tetramethylethylenediamine are added later
The ammonium persulfate solution (mass fraction 5%) of (TEMED, 99%) and 14.5ul, rocking vessel disperses various substances tentatively, later
Ultrasonic mixing 1h is mixed to matched pre-polymer solution substantially uniformity in ice bath, lamination does not occur.
(3) gel is in oxygen-free environment:
Using the capillary effect of glass capillary, acrylamide pre-polymer solution is placed to capillary glass prepared by embodiment 1
Guan Zhong, and the liquid level in glass capillary is higher than glass container.It is full of pre-polymer solution and entirely has schemochrome
Region.Later, the glass capillary filled with pre-polymer solution is lain against in culture dish.A polybag is taken, extruding drains it
Interior air (oxygen can terminate the combination of free radical, to inhibit gel), then culture dish is pushed into polybag, to polybag
In be full of nitrogen, then seal with adhesive tape.Polybag after sealing is put into insulating box, temperature is maintained at 27 DEG C, gel
10h.After completing gel, polybag is scratched, culture dish is taken out, glass capillary is impregnated in hydrofluoric acid, until glass is completely molten
Solution, presss from both sides out gel with tweezers, impregnates 10min in deionized water, change water, then impregnate.Finally, by gel in a hydrazine hydrate solution
Swelling in (0.33M), to reduce the graphene oxide being dispersed in gel network.Two days later, gel is taken out, is then placed in again
It is impregnated two days in ionized water.
3 performance test of embodiment
Because of MoS2The incorporation of quantum dot imparts some special properties of acrylamide gel.As shown in figure 4, by embodiment 2
The material being made into is placed on the optical microscopy with optical camera that (the bright U.S. of Mshot bright U.S. dollar phase microscope MJ33, Mshot is aobvious
Micro mirror camera MD50), opening microscopical light source, (light penetrates illumination system from falling for the bright U.S. dollar phase microscope MJ33 of Mshot
System), after irradiating a period of time to material, material can be bent as sunflower towards light source, curved with the increase of irradiation time
Bent angle is increasing, eventually stops being bent in some angle.While bending, had using camera MD50 to material
There is the region of schemochrome to be timed candid photograph, discovery also has illuminated schemochrome region while material is to bendingof light
Colour-change phenomena.It is analyzed by a large amount of experimental observation and data, finds the phenomenon that this is a kind of schemochrome regionality blue shift.Cause
For based on MoS2The color-changing anti-counterfeit material of quantum dot has excellent photothermal conversion efficiency, and when illumination, will lead to material generation can
It is inverse to bendingof light, and the change of structure results in the change of schemochrome indirectly, and due to MoS2Special microcosmic of quantum dot
The phenomenon that structure, schemochrome has blue shift, specific phenomenon as shown in figure 5, the number 1 ~ 9 in Fig. 5 to respectively correspond the material curved
The picture shot when 2 °, 4 °, 6 °, 8 °, 10 °, 12 °, 14 °, 16 °, 18 ° bent.And can see by Fig. 5, part-structure color because
For blue shift, it is transferred to nonvisible wavelength, leads to the disappearance of schemochrome.With the phenomenon, we can be fabricated to causes with illumination
The dynamic anti-fake bar code of metachrosis.
By embodiment 2 prepare based on MoS2The discoloration of the material of color-changing anti-counterfeit material and comparative example 1 preparation of quantum dot
Rate is compared.When being irradiated with high-power light, because the power of light itself is excessively high, the photothermal conversion ability of material
It will be saturated, the difference between the different material concentration of same material will amplify, for the difference of more prominent material itself
Performance, we are irradiated using the light of low-power, at this moment it is considered that the requirement capability of photothermal conversion is by light power
It determines, then performance different between material is then determined by the substance adulterated.Ten above two materials of access respectively, and
Each length is 6.5mm, is irradiated that (light is from the bright U.S. dollar phase microscope of Mshot using the light of low-power
Lighting system is penetrated in falling for MJ33), under the premise of guaranteeing that the otherness of experiment is only in that the substance of incorporation, our real-time monitorings
The bending rate of two kinds of materials, and calculate its stability index.It is repeatedly measured using more root timber material and has finally found out representative
The mean value of meaning, it can be deduced that the stability index that two kinds of materials are of universal significance.
In order to describe the anti-interference ability of material, and the stability of material rationally and is clearly expressed in a coordinate system.
It is proposed that stability index, indicates are as follows:
Wherein,
Indicate that aquagel fibre to the curved momentary rate of light source, indicates aquagel fibre in the bending angle of time.
The result of material settling out sex index is shown in Fig. 6.We can clearly compare, and be based on MoS2The discoloration of quantum dot is anti-
Its stability index of pseudo- material is significantly higher than material prepared by comparative example 1.The metachrosis and discrimination of both materials
Relatively strong, in today that imaging technique and color analysis are so flourishing, we can be easy to screen the schemochrome of material
Variation, thus the material that stability index is high, should be just our first choices.Because stability index is high, environment light source is resisted
The ability of pollution is stronger, then its anti-fake accuracy is higher.Furthermore in actual life, it would be desirable to just complete in a short time
The function of anti-counterfeiting detection, so light source should be changed into high-power infrared light supply, but inevitably in light source irradiation time and function
In rate can and ideal situation have certain error, and the material that stability index is high is made to this inevitable error is weakened
At influence have good effect, in this way while guaranteed efficiency, moreover it is possible to greatly improve the accuracy of anti-counterfeiting detection.
To the preparation of embodiment 2 based on MoS2The maximum of the material of color-changing anti-counterfeit material and comparative example 1 preparation of quantum dot
Bending angle is tested, and the result is shown in Fig. 7.With same light source, (light is from the bright U.S. dollar phase microscope MJ33's of Mshot
Fall and penetrate lighting system) measurement of maximum bend angle has been carried out to two kinds of materials.Based on MoS2The color-changing anti-counterfeit material of quantum dot,
Its maximum bend angle is 19.6 degree, and the maximum bend angle of material prepared by comparative example 1 is 40 degree.Because this discoloration is anti-
Its discoloration essence of pseudo- material is also derived from the change of structure, intervenes Gu we can not be bent it.Maximum bend angle
Smaller, in bending, required spatial dimension is with regard to smaller, and its curved invertibity is also stronger, what schemochrome was restored
Speed is also faster.Also, bending angle is smaller, its maximum possessive volume is also with regard to smaller, plasticity in practical Application in Anti-counterfeiting
It is stronger, it is easier in multi-field a wide range of popularization and use.
Embodiment 2 prepare based on MoS2The color-changing anti-counterfeit material of quantum dot, in color change interval and phenomenon also with comparison
The color-changing anti-counterfeit material based on redox graphene of example 1 is different.Initial configuration color used in us is by 251nm
What monodisperse nano silicon dioxide microballoon was formed, initial schemochrome only has red.(the light when we are irradiated material
Lighting system is penetrated from bright the falling for U.S. dollar phase microscope MJ33 of Mshot), the color of material structure color gradually becomes green from red
Color, and then schemochrome goes to black light part, such as Fig. 5.And the color-changing anti-counterfeit material based on graphene oxide of comparative example 1
Material can only occur the transformation from red to green, be not in structure (as red) when initial configuration color only has a kind of color
The phenomenon that color changes to black light part.That is, prepared by us based on MoS2The color-changing anti-counterfeit material of quantum dot,
Its color change interval is wider, and then the ability for storing hiding encoded information is stronger, is expected to replacing present black and white bar code in the future.
When carrying out color analysis, there is color stains for the color-changing anti-counterfeit material of discovery comparative example 1, because of graphite oxide
Alkene is sepia.And it is based on MoS2The color-changing anti-counterfeit material of quantum dot, color stain is relatively small, so its structure color
Accuracy is stronger, and the color zones indexing of schemochrome is also stronger.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of color-changing anti-counterfeit material, which is characterized in that the color-changing anti-counterfeit material is prepared by the following method to obtain:
(a) make nano silica microsphere monodisperse in ethyl alcohol, obtain nano silica microsphere dispersion liquid；
(b) enter nano silica microsphere dispersion liquid in glass capillary, and by ethyl alcohol natural evaporation, make nanometer titanium dioxide
Silicon microballoon forms schemochrome region in glass capillary；
(c) preparing evenly dispersed has MoS2The acrylamide pre-polymer solution of quantum dot, makes acrylamide pre-polymer solution pass through hair
Thin effect, which enters, to be formed in the glass capillary in schemochrome region；
(d) by step (c) glass capillary for being loaded with acrylamide pre-polymer solution Yu Hengwen in oxygen-free environment obtained
Gel is carried out in case；
(e) after the completion of gel, with hydrofluoric acid dissolution glass capillary and nano silica microsphere, gel is taken out and in deionization
It is impregnated in water, up to color-changing anti-counterfeit material after remaining hydrofluoric acid is removed.
2. color-changing anti-counterfeit material according to claim 1, which is characterized in that in step (b):
Enter nano silica microsphere dispersion liquid in glass capillary by capillary effect, then by glass capillary level
It stands, keeps the ethyl alcohol natural evaporation in glass capillary complete, while nano silica microsphere is formed in glass capillary
Schemochrome region；Or
Nano silica microsphere dispersion liquid is placed in open container, glass capillary is longitudinally inserted into the container,
Nano silica microsphere dispersion liquid passes through capillary effect and enters in glass capillary, and lasting stand keeps container interior and capillary glass
Ethyl alcohol natural evaporation in glass pipe is complete, while nano silica microsphere forms schemochrome region in glass capillary.
3. color-changing anti-counterfeit material according to claim 1, which is characterized in that in step (c), the acrylamide prepolymerization
The preparation process of solution is as follows:
Then n-isopropyl acrylamide and N is added in glassware in taking polyethylene glycol diacrylate into glassware,
N'- methylene-bisacrylamide simultaneously dissolves, and MoS is added later2Quantum dot dispersion liquid adds N, N, N', N'- tetramethyl second two
It is uniformly rear up to third to be finally placed in ultrasonic mixing in ice bath by the ammonium persulfate solution that amine and mass fraction are 5.0% for glassware
Acrylamide pre-polymer solution；Wherein, the n-isopropyl acrylamide and N of addition, the mass ratio of N'- methylene-bisacrylamide are
30: 1, the amount ratio of n-isopropyl acrylamide and polyethyleneglycol diacrylate is 3g: 15 ~ 20mL, N- isopropyl acrylamide
Amine: N, N, N', N'- tetramethylethylenediamine: ammonium persulfate solution=3g: 100 ~ 130uL: 260 ~ 290uL.
4. color-changing anti-counterfeit material according to claim 3, which is characterized in that in step (c), the MoS2Quantum dot dispersion
Liquid refers to MoS2Quantum dot is solute, using N-Methyl pyrrolidone as the dispersion liquid of solvent, wherein MoS2The lateral ruler of quantum dot
Very little is 1 ~ 10nm, the MoS2The concentration of quantum dot dispersion liquid is 1mg/mL, MoS2Quantum dot dispersion liquid: N- isopropyl acrylamide
Amine=4 ~ 6mL: 3g.
5. color-changing anti-counterfeit material according to claim 1, which is characterized in that in step (a), mono-dispersed nano titanium dioxide
The diameter of silicon microballoon is 251nm；In step (b), the diameter of the glass capillary is 10mm, length 10cm；Step (d)
In, the glass capillary for being loaded with acrylamide pre-polymer solution is fitted into polybag, the air in polybag is drained and fills
Enter nitrogen, plastic bag sealing is placed in later in 27 DEG C of insulating box and carries out gel.
6. a kind of preparation method of color-changing anti-counterfeit material, which comprises the following steps:
(a) make nano silica microsphere monodisperse in ethyl alcohol, obtain nano silica microsphere dispersion liquid；
(b) enter nano silica microsphere dispersion liquid in glass capillary, and by ethyl alcohol natural evaporation, make nanometer titanium dioxide
Silicon microballoon forms schemochrome region in glass capillary；
(c) preparing evenly dispersed has MoS2The acrylamide pre-polymer solution of quantum dot, makes acrylamide pre-polymer solution pass through hair
Thin effect, which enters, to be formed in the glass capillary in schemochrome region；
(d) by step (c) glass capillary for being loaded with acrylamide pre-polymer solution Yu Hengwen in oxygen-free environment obtained
Gel is carried out in case；
(e) after the completion of gel, with hydrofluoric acid dissolution glass capillary and nano silica microsphere, gel is taken out and in deionization
It is impregnated in water, up to color-changing anti-counterfeit material after remaining hydrofluoric acid is removed.
7. the preparation method of color-changing anti-counterfeit material according to claim 6, which is characterized in that in step (b):
Enter nano silica microsphere dispersion liquid in glass capillary by capillary effect, then by glass capillary level
It stands, keeps the ethyl alcohol natural evaporation in glass capillary complete, while nano silica microsphere is formed in glass capillary
Schemochrome region；Or
Nano silica microsphere dispersion liquid is placed in open container, glass capillary is longitudinally inserted into the container,
Nano silica microsphere dispersion liquid passes through capillary effect and enters in glass capillary, and lasting stand keeps container interior and capillary glass
Ethyl alcohol natural evaporation in glass pipe is complete, while nano silica microsphere forms schemochrome region in glass capillary.
8. the preparation method of color-changing anti-counterfeit material according to claim 6, which is characterized in that in step (c), the propylene
The preparation process of amide pre-polymer solution is as follows:
Then n-isopropyl acrylamide and N is added in glassware in taking polyethylene glycol diacrylate into glassware,
N'- methylene-bisacrylamide simultaneously dissolves, and MoS is added later2Quantum dot dispersion liquid adds N, N, N', N'- tetramethyl second two
It is uniformly rear up to third to be finally placed in ultrasonic mixing in ice bath by the ammonium persulfate solution that amine and mass fraction are 5.0% for glassware
Acrylamide pre-polymer solution；Wherein, the n-isopropyl acrylamide and N of addition, the mass ratio of N'- methylene-bisacrylamide are
30: 1, the amount ratio of n-isopropyl acrylamide and polyethyleneglycol diacrylate is 3g: 15 ~ 20mL, N- isopropyl acrylamide
Amine: N, N, N', N'- tetramethylethylenediamine: ammonium persulfate solution=3g: 100 ~ 130uL: 260 ~ 290uL.
9. the preparation method of color-changing anti-counterfeit material according to claim 8, which is characterized in that in step (c), the MoS2
Quantum dot dispersion liquid refers to MoS2Quantum dot is solute, using N-Methyl pyrrolidone as the dispersion liquid of solvent, wherein MoS2Quantum
The lateral dimension of point is 1 ~ 10nm, the MoS2The concentration of quantum dot dispersion liquid is 1mg/mL, MoS2Quantum dot dispersion liquid: N- is different
Propylacrylamide=4 ~ 6mL: 3g.
10. the preparation method of color-changing anti-counterfeit material according to claim 6, which is characterized in that in step (a), monodisperse
Nano silica microsphere diameter be 251nm；In step (b), the diameter of the glass capillary is 10mm, and length is
10cm；In step (d), the glass capillary for being loaded with acrylamide pre-polymer solution is fitted into polybag, polybag is drained
In air and be filled with nitrogen, plastic bag sealing is placed in later in 27 DEG C of insulating box and carries out gel.
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| CN111799467A (en) * | 2020-07-20 | 2020-10-20 | 陕西科技大学 | MoS for negative electrode of sodium-ion battery2/MoS2Nanocomposite and method for preparing same |
| CN114262466A (en) * | 2022-01-04 | 2022-04-01 | 广东工业大学 | CdTe quantum dot doped structural color composite film, preparation method thereof and application thereof in optical anti-counterfeiting |
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