CN109735036A - One kind being based on WS2Color-changing anti-counterfeit material of nanometer sheet and preparation method thereof - Google Patents
One kind being based on WS2Color-changing anti-counterfeit material of nanometer sheet and preparation method thereof Download PDFInfo
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Abstract
The present invention provides one kind to be based on WS2Color-changing anti-counterfeit material of nanometer sheet 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 WS2Acrylamide pre-polymer solution is placed in glass capillary by the acrylamide pre-polymer solution of nanometer sheet 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 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 WS2The color-changing anti-counterfeit of nanometer sheet
Material and preparation method thereof.
Background technique
Current anti-fake situation very severe, fake products have been directed to the every aspect of people's lives.Long-living vacation not long ago
Vaccine event, has shocked compatriots.It has no longer been single for having events, the fake products problems such as the former false milk powder, false pork, false egg again
Pure cost problem, many fake products have breached the lowest permissible level of virtue of the mankind., cannot be forbearing and conciliatory again for fake products, it cannot be ambiguous again
It is all right one way or the other, it is necessary to accomplish zero tolerance vividly.
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 WS2The color-changing anti-counterfeit material of nanometer sheet, it is existing anti-fake to solve
The undesirable problem of material comprehensive performance.
It is a kind of based on WS the second object of the present invention is to provide2The preparation method of the color-changing anti-counterfeit material of nanometer sheet.
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 WS2The acrylamide pre-polymer solution of nanometer sheet, 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.
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 WS is added later2Nanometer sheet 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 WS2Nanometer sheet dispersion liquid refers to WS2Nanometer sheet is solute, with the mixed liquor of water and ethyl alcohol is
The dispersion liquid of solvent, wherein WS2The lateral dimension of nanometer sheet is 0.05 ~ 1um；The WS2The concentration of nanometer sheet dispersion liquid is
1mg/mL, WS2Nanometer sheet 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 WS2The acrylamide pre-polymer solution of nanometer sheet, 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.
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 WS is added later2Nanometer sheet 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 WS2Nanometer sheet dispersion liquid refers to WS2Nanometer sheet is solute, with the mixed liquor of water and ethyl alcohol is
The dispersion liquid of solvent, wherein WS2The lateral dimension of nanometer sheet is 0.05 ~ 1um；The WS2The concentration of nanometer sheet dispersion liquid is
1mg/mL, WS2Nanometer sheet 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 index of stability is high, structural stability is strong, color stain is small, restores and more accelerate
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 WS2The color-changing anti-counterfeit material of nanometer sheet is with good performance.This
Invention has used WS2Nanometer sheet makes the performance of anti-fake material more excellent, unique structure, can really be applied to the anti-of reality
In puppet detection, have 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 WS2The color-changing anti-counterfeit material of nanometer sheet is in Mshot microscope camera MD50
The picture of lower shooting.
Fig. 4 is prepared by embodiment 2 based on WS2The color-changing anti-counterfeit material of nanometer sheet 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 WS2The color-changing anti-counterfeit material of nanometer sheet 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 WS2The preparation of the color-changing anti-counterfeit material of nanometer sheet
(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 WS of 0.3mL is then added2Nanometer sheet 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, WS2Nanometer sheet dispersion liquid refers to WS2Nanometer sheet is solute, (contains 20vol% with the mixed liquor of water and ethyl alcohol
Ethyl alcohol) be solvent dispersion liquid, WS2The lateral dimension of nanometer sheet is 0.05 ~ 1um, WS2Nanometer sheet with a thickness of 1 ~ 10 layer；
The WS2The concentration of nanometer sheet dispersion liquid be 1mg/mL, inactive dose.It should be noted that ammonium persulfate solution is initiator, N, N,
N', N'- tetramethylethylenediamine (TEMED) are catalyst, and catalysis ammonium persulfate generates free radicals, to accelerate acrylamide gel
Polymerization, N, N, N', the amount of N'- tetramethylethylenediamine (TEMED, 99%) and ammonium persulfate solution should strict control, amount is few then
Gel process can be made to become abnormal slowly even not gel, mostly it will cause the pre-polymer solutions being just configured in glass for amount
Gel is just completed in vessel.Rocking glassware makes each substance tentatively scatter, later in ice bath ultrasonic mixing 1h to being matched
The mixing of pre-polymer solution substantially uniformity, is not layered.Ultrasonic mixing process wants strict temperature control, and the slightly higher prepolymerization of temperature is molten
Liquid 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 WS2The incorporation of nanometer sheet imparts some special properties of acrylamide gel.As shown in figure 4, by embodiment 2
The material being made into is placed on the Mshot metallographic microscope MJ33 with Mshot microscope camera MD50, is opened above microscope
Light source (light penetrates lighting system from falling for Mshot metallographic microscope MJ33), after irradiating a period of time to gel, gel meeting
It is bent as sunflower towards light source, with the increase of irradiation time, curved angle is increasing, eventually at some
Angle stops bending.While bending, we there is the region of schemochrome to be timed material and grab using microscope camera
It claps, discovery is while material is to bendingof light, also with the colour-change phenomena in illuminated schemochrome region, the visible figure of specific phenomenon
5.Number 1 ~ 9 in Fig. 5 respectively corresponds what the material was shot when being bent 2 °, 4 °, 6 °, 8 °, 10 °, 12 °, 14 °, 16 °, 17 °
Picture.Wherein, number 1 ~ 5 indicates that the schemochrome of material is red, and because of WS2The effect of nanometer sheet strong room temperature luminescence generated by light,
Schemochrome is deeper and deeper with curved progress color.Number 6 ~ 7 indicates that the schemochrome overwhelming majority of material is green, only remaining
Partial red.Number 8 ~ 9 indicates that the schemochrome of material has all become green, and remains schemochrome color burn
The phenomenon that.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.Because of base
In WS2The acrylamide gel of nanometer sheet has excellent photothermal conversion efficiency, when illumination, will lead to gel occur it is reversible to
Bendingof light, and the change of structure results in the change of schemochrome, and because WS indirectly2The special microstructure of nanometer sheet, knot
The phenomenon that the phenomenon that structure color has blue shift, this strong room temperature luminescence generated by light effect leads to the colouring intensity increase of schemochrome, be pair
Ratio is unexistent.With the phenomenon, we can be fabricated to the dynamic anti-fake bar code that metachrosis is caused with illumination.
By embodiment 2 prepare based on WS2The discoloration speed of the material of color-changing anti-counterfeit material and comparative example 1 preparation of nanometer sheet
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 is just
It can be saturated, the difference between the different material concentration of same material will amplify, for the dissimilarity of more prominent material itself
Can, we are irradiated using the light of low-power, at this moment it is considered that the requirement capability of photothermal conversion is determined by light power
Fixed, then performance different between material is then determined by the substance adulterated.We fetch ten above two materials respectively, and
And each length is 6.5mm, is irradiated that (light is from the bright U.S. metallography microscope of Mshot using the light of low-power
Lighting system is penetrated in falling for mirror MJ33), under the premise of guaranteeing that the otherness of experiment is only in that the substance of incorporation, we supervise in real time
The bending rate of two kinds of materials is surveyed, and calculates its stability index.It is repeatedly measured using more root timber material and has finally found out generation
The mean value for justice of expressing the 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,
V indicates aquagel fibre to the curved momentary rate of light source, and x 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 WS2The discoloration of nanometer sheet is anti-
Its stability index of pseudo- material is significantly higher than the material of the preparation of comparative example 1.The metachrosis and discrimination of both materials compared with
By force, today so flourishing in imaging technique and color analysis, we can be easy to screen the structure color change of material,
The thus high material of stability index, should be just our first choice.Because stability index is high, environment light source pollution is resisted
Ability is stronger, then its anti-fake accuracy is higher.Furthermore in actual life, it would be desirable to just complete anti-fake inspection in a short time
The function of survey, so light source should be changed into high-power infrared light supply, but the inevitably meeting in light source irradiation time and on power
There is certain error with ideal situation, and the material that stability index is high, the shadow caused by weakening this inevitable error
Ringing has 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 WS2The maximum of the material of color-changing anti-counterfeit material and comparative example 1 preparation of nanometer sheet is curved
Bent angle is tested, and the result is shown in Fig. 7.With same light source, (light is fallen from the bright U.S. dollar phase microscope MJ33's of Mshot
Penetrate lighting system) measurement of maximum bend angle has been carried out to two kinds of materials.Based on WS2The color-changing anti-counterfeit material of nanometer sheet,
Maximum bend angle is 17 degree, and the maximum bend angle of comparative example 1 is 40 degree.Because of its discoloration sheet of this color-changing anti-counterfeit material
Matter is also derived from the change of structure, intervenes Gu we can not be bent it.Maximum bend angle is smaller, in bending,
Required spatial dimension is with regard to smaller, and its curved invertibity is also stronger, and the speed that schemochrome is restored is also faster.And
And bending angle is smaller, its maximum possessive volume is also just smaller in practical Application in Anti-counterfeiting, and plasticity is stronger, it is easier to more
It promotes the use of on a large scale in field.
When carrying out color analysis, there is color stains for the material of discovery comparative example 1, because graphene oxide is brown
Color.And it is based on WS2The color-changing anti-counterfeit material of nanometer sheet, color stain is relatively small, so its structure color accuracy is more
By force, 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 WS2The acrylamide pre-polymer solution of nanometer sheet, 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 WS is added later2Nanometer sheet 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 WS2Nanometer sheet dispersion liquid
Refer to WS2Nanometer sheet is solute, using the mixed liquor of water and ethyl alcohol as the dispersion liquid of solvent, wherein WS2The lateral dimension of nanometer sheet
For 0.05 ~ 1um；The WS2The concentration of nanometer sheet dispersion liquid is 1mg/mL, WS2Nanometer sheet dispersion liquid: n-isopropyl acrylamide=
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 WS2The acrylamide pre-polymer solution of nanometer sheet, 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 WS is added later2Nanometer sheet 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 WS2It receives
Rice piece dispersion liquid refers to WS2Nanometer sheet is solute, using the mixed liquor of water and ethyl alcohol as the dispersion liquid of solvent, wherein WS2Nanometer sheet
Lateral dimension be 0.05 ~ 1um；The WS2The concentration of nanometer sheet dispersion liquid is 1mg/mL, WS2Nanometer sheet dispersion liquid: N- isopropyl
Base acrylamide=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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| CN110982011A (en) * | 2019-11-29 | 2020-04-10 | 河北大学 | Light-directing bending material and preparation method thereof |
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| 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 |
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| SHIVANI SHARMA ET AL.,: "Size-tunable photoluminescence from WS2 nanostructures", 《MATERIALS RESEARCH EXPRESS》 * |
| ZE ZHAO ET AL.,: "Bioinspired Heterogeneous Structural Color Stripes from Capillaries", 《ADVANCED MATERIALS COMMUNICATION》 * |
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