CN103514823A - Structure with colors changing along with visual angles - Google Patents
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- CN103514823A CN103514823A CN201210225740.6A CN201210225740A CN103514823A CN 103514823 A CN103514823 A CN 103514823A CN 201210225740 A CN201210225740 A CN 201210225740A CN 103514823 A CN103514823 A CN 103514823A
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Abstract
A structure with colors changing along with visual angles comprises multi-hole template material and nanotubes / nanowires which are composited on the inner walls or at the bottoms of multi-hole template material hole channels. On the basis of the multi-hole template material, the structure with the colors changing along with the visual angles comprises hole channel inner wall composite metal nanotubes, a multi-hole alumina template of the metallic oxide and metallic nitride nanotubes and a flexible transparent multi-hole organic polymer template, and optical angle color changing is achieved through an optical interference structure. The composite magnetic metal or alloy nanowires can be provided for magnetic detection, and abundant semiconductor properties can be provided through the composite semiconductor oxide nanotubes. The structure has the advantages that the effect of optical angle color changing is easy to observe through the design of the optical interference structure; a multi-functional composite structure can be formed through compositing of other functional materials such as magnetic materials and semiconductor materials, and can be widely applied to many fields such as indication signs, labels, anti-forgery technologies and sensor technologies.
Description
Technical field
The present invention relates to the structure with light angle color changing effect that a class is comprised of porosint, metal and metal oxide, metal nitride materials, particularly relate to based on organic polymer foraminous die plate, there is flexible angular color change structured material.
Background technology
Optical interference structure is present in occurring in nature widely, if wing of the feather of birds and butterfly etc. is exactly some examples, in structure like that, due to refraction, reflection of light and the interference of light of light, can be created in the visual effect of observing different colours under different angles.Particularly the holographic imaging of the light in artificial synthetic optical medium material and under coherent light modulation, can produce the effect of 3 D stereoscopic image and change especially.Any factor that affects medium refraction index variation, all can cause the optical property of optical interference structure to change, thereby its angular color change character is changed.
As everyone knows, anti-counterfeiting technology is because its special role has extensively been approved and has been applied to every field, the anti-counterfeiting technology based on optical principle as chromatography anti-forge paper, colored anti-forgery ink etc. be one of them important application.The material with light angle color changing effect because it is convenient to identification and has obtained development rapidly, has just been used this anti-counterfeiting technology in 100 yuans, China's the 5th cover for false proof.Existing angular color change technology is mostly based on the camouflage paint ink such as cholesteric liquid crystal or application laser rainbow hologram plate-making technology and moulding replication technology, when its anti-counterfeiting characteristic is to change printed matter viewing angle, color can change, and prior art exists the technological deficiencies such as antiforge function is single, character is stable not.
Because the character of angular color change structure is relevant with the refractive index of structure, and in humidity sensor, due to humidity increase, can cause the gas molecule adsorbances such as material surface water vapor to increase, thereby certain variation occurs the refractive index that causes material, thereby can reflect that using the change of optical property as indicator signal measured is the variation of humidity.Therefore, such material also can be under certain condition for the detection technique of humidity.
Summary of the invention
The object of this invention is to provide the structure that a kind of color changes with visual angle, by the various nanotubes of compound preparation and nano-material in foraminous die plate, its optical property (as angular color change) is regulated and controled.
For achieving the above object, the present invention proposes the structure that a kind of color changes with visual angle, comprises foraminous die plate material and the nanowires/nanotubes that is compound in described foraminous die plate material.
Wherein, described nanowires/nanotubes is compound in duct inwall or the bottom of described foraminous die plate material.
Wherein, described foraminous die plate material is rigidity foraminous die plate material or flexible foraminous die plate material.
Wherein, described rigidity foraminous die plate material consists of inorganic porous mould material.
Wherein, the porous alumina formwork of described inorganic porous mould material for preparing by anodic oxidation.
Wherein, described porous alumina formwork is for being used the anodic oxidation preparation under voltage conditions of sulfuric acid, phosphoric acid or oxalic acid, and described voltage comprises direct current and alternating voltage, and voltage swing is in 20V-200V scope.
Wherein, described flexible foraminous die plate material consists of organic polymer porosint, and described organic polymer porosint comprises porous organic film prepared by track etching polycarbonate membrane, track etching polyester film, polymethylmethacrylate and polystyrene and organic flexible and transparent foraminous die plate material of preparing by micro-processing technology;
Wherein, described track etching polycarbonate membrane and track etching polyester film, first be to utilize nuclear fission fragment or heavy ion accelerator to bombard polycarbonate macromolecule membrane or polyester macromolecule film, then the cracking molecule at track place is by the corrosion formation of the chemical reagent duct vertical with face, and pore diameter range is 10nm-8 μ m; Porous organic film prepared by described polymethylmethacrylate and polystyrene, by utilizing the different etch rate of polymethylmethacrylate and polystyrene, obtains porous organic film material; Organic flexible and transparent foraminous die plate material prepared by described micro-processing technology, for preparing on the basis of mylar, in conjunction with micro-processing masking process electron beam lithography, mylar is processed, finally with strong oxidizer, corrode and obtain porous polyester film, by controlling irradiation dose, etching time and temperature, obtain aperture, hole Density Distribution, the controlled organic flexible and transparent porous polymer membraneous material of film thickness.
Wherein, described color comprises following several types with visual angle change structure:
(a) duct inwall composite magnetic metal or alloy nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(b) the compound nonmagnetic metal of duct inwall or alloy nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire;
(c) duct inwall composite magnetic metal or alloy nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire;
(d) the compound nonmagnetic metal of duct inwall or alloy nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(e) duct inwall composite metal oxide or metal nitride nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(f) duct inwall composite metal oxide or metal nitride nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire.
Wherein, the nanowires/nanotubes that is compound in described foraminous die plate material duct inwall or bottom comprises: nanotube, nano wire form by magnetic metal or alloy; Nanotube, nano wire form by nonmagnetic metal or alloy; Nanotube consists of magnetic metal or alloy, and nano wire consists of nonmagnetic metal or alloy; Nanotube consists of nonmagnetic metal or alloy, and nano wire consists of magnetic metal or alloy; Nanotube consists of metal oxide, nitride, and nano wire consists of magnetic metal or alloy; Nanotube consists of metal oxide, nitride, and nano wire consists of nonmagnetic metal or alloy.
Wherein, described magnetic metal consists of transition element and alloy cpd Fe, Co, Ni, Mn, CoFe, NiFe, CoNi, FeCoNi, CoPt, CoPd, FePt, FePd, NiMn, FeMn, NiFeCr, 15 kinds of simple substance rare-earth metals La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Te, Dy, Ho, Er, Tm, Yb, Lu or rare earth-magnesium-yttrium-transition metals alloy or compound form; Nonmagnetic metal or alloy consist of Cu, Cr, V, Nb, Mo, Ru, Pd, Ta, W, Pt, Ag, Au and their alloy; Metal oxide, nitride are by MgO, InO, SnO
2, CuO, CdO, HfO
2, TiO
2, Cr
2o
3, FeO
x, ZnO, V
2o
5, InN, AlN form.
Wherein, described magnetic and nonmagnetic metal or alloy nanotube/nano wire are realized by the Chemical self-assembly method of electrochemical deposition, electroless deposition, ald, sol-gel process; Described metal oxide/nitride nano pipe is prepared by sol-gel process, electrochemical deposition, ald, template vapour deposition.
Wherein, be also included in composite magnetic metal or alloy nanowires/nanotubes before by the graphical treatment of masking process, make the angular color change structure with anti-counterfeiting mark.
Wherein, described foraminous die plate material thickness is less than 10 μ m, the aperture 20nm-500nm in described duct; Described magnetic or nonmagnetic metal or alloy nano line length are 20nm-400nm.
The structure that novel color provided by the invention changes with visual angle, can produce a class nano structural material of optical interference based on foraminous die plate compound substance, it utilizes foraminous die plate material composite nano tube/nano-material, thereby realize optical interference and obtain light angle color changing effect, and, when obtaining light angle color changing effect, can also there is the character such as other magnetics and semiconductor etc.
Accompanying drawing explanation
Below, describe by reference to the accompanying drawings embodiments of the invention in detail:
Figure 1A is the embodiment of the present invention 1 Zhong duct inwall composite magnetic metal or alloy nanotube, the structural representation of bottom, duct composite magnetic metal or alloy nano wire.
Figure 1B is the embodiment of the present invention 1 compound nonmagnetic metal of Zhong duct inwall or alloy nanotube, the structural representation of the duct compound nonmagnetic metal in bottom or alloy nano-wire.
Fig. 1 C is the embodiment of the present invention 1 Zhong duct inwall composite magnetic metal or alloy nanotube, the structural representation of the duct compound nonmagnetic metal in bottom or alloy nano-wire.
Fig. 1 D is the embodiment of the present invention 1 compound nonmagnetic metal of Zhong duct inwall or alloy nanotube, the structural representation of bottom, duct composite magnetic metal or alloy nano wire.
Fig. 2 A is the embodiment of the present invention 2 Zhong duct inwall composite metal oxide or metal nitride nanotubes, bottom, duct composite magnetic metal or alloy nano thread structure schematic diagram.
Fig. 2 B is the embodiment of the present invention 2 Zhong duct inwall composite metal oxide or metal nitride nanotubes, the duct compound nonmagnetic metal in bottom or alloy nano-wire structural representation.
Fig. 3 A adopts micro fabrication to prepare the schematic diagram that flexible and transparent porous polyester (PET) film is used mask plate in the embodiment of the present invention 4.
Fig. 3 B adopts micro fabrication to prepare the schematic diagram of flexible and transparent porous polyester (PET) thin-film process in the embodiment of the present invention 4.
Fig. 4 makes the anti-counterfeit structure process schematic diagram with special graph in the embodiment of the present invention 5.
Wherein, Reference numeral:
10, nanotube 20, nano wire
30, foraminous die plate material 1, electron beam
2, mask plate 3, polyester (PET) film
4, the polyester of local irradiation (PET) film 5, porous polyester PET membraneous material
Embodiment
Utilization of the present invention has the porosint of regular texture as template, prepares the nano structural materials such as nanowires/nanotubes of metal, alloy and metal oxide by self assembly pattern.By controlling the aperture of porosint, the condition of chemical reaction etc. can realize the regulation and control to the composition of nanowires/nanotubes and structure, thereby obtain the controlled nano material of performance.
The present invention is based on composite porous material, the nanostructured that the color of design changes with visual angle, its principle is foraminous die plate surface reflection light and through repeatedly reflecting and passing through the interference effect between the light of metal nanometer line surface reflection, its preparation technology is simple, and manufacturing cost is lower; According to different application, can choose corresponding porosint; By kinds of processes, can regulate and control the refractive index of optical interference structure, transmission film thickness etc.Nanostructured based on this kind of angular color change can be widely used in many fields such as anti-counterfeiting technology, sensor technology, label trade mark.
In the situation that utilizing various magnetic metals to prepare nano wire and nanotube, not only can obtain the nano structural material of angular color change, this kind of material also has magnetic mark or the false proof dual-use function of magnetic simultaneously; Particularly, if nonmagnetic metal nano wire/non magnetic nanotube and magnetic metal nano wire/magnetic metal nanotube are alternately changed to even patternization use, can, simultaneously for photoimaging and magnetic image mark and false proof, there is very high practical value.
The structure that color of the present invention changes with visual angle, nanotube 10/ nano wire 20 that comprises foraminous die plate material 30 and be compound in described foraminous die plate material portion.Described nanotube 10/ nano wire 20 is compound in duct inwall or the bottom of described foraminous die plate material.
Wherein, the structure that color of the present invention changes with visual angle, is also included in composite magnetic metal or alloy nanowires/nanotubes before by the graphical treatment of masking process, makes the angular color change structure with anti-counterfeiting mark.
And, foraminous die plate material thickness of the present invention between 100nm to 1000 μ m,, the aperture 20nm-500nm in described duct; Described magnetic or nonmagnetic metal or alloy nano line length are 20nm-400nm.
According to an aspect of the present invention, provide a kind of foraminous die plate material, comprise rigidity foraminous die plate material and the large class of flexible foraminous die plate material two, the thickness of foraminous die plate material is between 100nm to 1000 μ m.
In technique scheme, rigidity foraminous die plate material mainly consists of inorganic porous mould material, the porous alumina formwork that described inorganic porous mould material refers generally to prepare by anodic oxidation.
Described porous alumina formwork comprises the porous alumina formworks that under different voltage conditions prepared by anodic oxidation such as using sulfuric acid, phosphoric acid, oxalic acid; Described voltage conditions comprises direct current and alternating voltage, and voltage swing is in 20V-200V scope.
In technique scheme, flexible foraminous die plate material consists of various organic polymer porosints, and described organic polymer foraminous die plate material comprises porous organic film prepared by track etching polycarbonate membrane and polyester film, polymethylmethacrylate and polystyrene and organic flexible and transparent foraminous die plate material of preparing by micro-processing technology (electron beam exposure, etching etc.).
Described track etching polycarbonate membrane and polyester film, first utilize nuclear fission fragment or heavy ion accelerator to bombard macromolecule membrane (polycarbonate, polyester etc.), then the cracking molecule at track place is by the corrosion formation of the chemical reagent duct vertical with face, and pore diameter range is 10nm-8 μ m.
Porous organic film prepared by described polymethylmethacrylate and polystyrene, by utilizing polymethylmethacrylate (PMMA) and the different etch rate of polystyrene (PS), can obtain porous organic film material.
Organic flexible and transparent foraminous die plate material prepared by described micro-processing technology, preparing on the basis of polyester (PET) film, in conjunction with micro-processing masking process electron beam lithography, PET film is processed, finally use strong oxidizer (as the corrosive liquid being formed by potassium dichromate, sulfuric acid) to corrode and obtain porous polyester film, by controlling irradiation dose, etching time and temperature, can obtain aperture, hole Density Distribution, the controlled organic flexible and transparent porous polymer membraneous material of film thickness.Wherein, irradiation measures as 300kGy, and corrosive liquid temperature is as 65 ℃, and etching time is as 6h, and irradiation dose is larger, the higher required etching time of corrosive liquid temperature is shorter).
According to another aspect of the present invention, in foraminous die plate, compound various nanotubes and nano-material regulate and control its optical property, and in foraminous die plate, compound nanotube, nano wire can have following several situation: composite nano tube, nano wire form by magnetic metal or alloy; Composite nano tube, nano wire form by nonmagnetic metal or alloy; Composite nano tube/nano wire consists of magnetic metal or alloy, and composite nano-line/nanotube consists of nonmagnetic metal or alloy; Composite nano tube consists of metal oxide, nitride, and composite nano-line consists of metal or alloy.The length 20nm-400nm of nano wire.
Further, the structure that color of the present invention changes with visual angle, comprises following several types:
(a) duct inwall composite magnetic metal or alloy nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(b) the compound nonmagnetic metal of duct inwall or alloy nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire;
(c) duct inwall composite magnetic metal or alloy nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire;
(d) the compound nonmagnetic metal of duct inwall or alloy nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(e) duct inwall composite metal oxide or metal nitride nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(f) duct inwall composite metal oxide or metal nitride nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire.
Described magnetic metal or the alloy nano-wire of growing in template duct can be prepared by magnetron sputtering, electron beam evaporation, laser deposition, solution reaction method or electrochemical deposition, preferably electrochemical deposition method.
Describedly at porous alumina formwork inwall Nano tube of composite oxides, can pass through ald (ALD), chemical vapor deposition (CVD) or sol-gal process (Sol-Gel) is realized, composite metal nanotube is realized by electro-deposition or electroless deposition chemical reaction.
In technique scheme, magnetic metal by transition element (T) and alloy cpd thereof as Fe, Co, Ni, Mn, CoFe, NiFe, CoNi, FeCoNi, CoPt, CoPd, FePt, FePd, NiMn, FeMn, NiFeCr etc. and 15 kinds of simple substance thuliums (R=La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Te, Dy, Ho, Er, Tm, Yb and Lu) and the formation such as the R-T alloy that forms of rare earth-magnesium-yttrium-transition metal or compound; Nonmagnetic metal or alloy consist of Cu, Cr, V, Nb, Mo, Ru, Pd, Ta, W, Pt, Ag, Au and their alloy; Metal oxide, nitride are by MgO, InO, SnO
2, CuO, CdO, HfO
2, TiO
2, Cr
2o
3, FeO
x, ZnO, V
2o
5, the formation such as InN, AlN, by controlling composition, structure, the pattern of magnetic material, can control magnetic.
Described magnetic and nonmagnetic metal or alloy nanotube/nano wire are realized by Chemical self-assembly method, as electrochemical deposition, electroless deposition, ald, sol-gel process (Sol-Gel) etc.; Described metal oxide nanotubes/nitride nano pipe is by preparations such as sol-gel process, electrochemical deposition, ald, template vapour depositions.
Described electrochemical deposition of metal or alloy nanotube/nano wire can, by controlling electrodeposition condition (deposition potential, sedimentation time, deposit fluid formula etc.) and selecting different mould materials, be realized the preparation of heterogeneity metal or alloy nanowires/nanotubes.
Described electroless deposition is prepared metal or alloy nanowires/nanotubes material, by controlling the condition (agent prescription, reagent concentration etc.) of chemical reaction, can control pattern and the character of the nanowires/nanotubes of preparation.
Described sol-gel process is the common basic skills of preparing metal/metal oxide block, membraneous material, combine with foraminous die plate material, the nanowires/nanotubes that obtains metal oxide that can be easy, is processed and can be obtained metal, alloy nanotube/nano wire by follow-up hydrogen reducing;
Described template vapour deposition is to adopt and the general similar method of chemical vapor deposition, in conjunction with mould plate technique, grows pattern by the nano material of template contral in template.
In accordance with a further aspect of the present invention, compound by selecting suitable nano material and foraminous die plate to carry out, thereby the character that makes it there are other more abundant Gong controls, survey when obtaining light angle color changing effect, nanowires/nanotubes in foraminous die plate material, except optical property is regulated and controled, due to other characteristics of himself, as magnetic, semiconductor property etc., can also utilize other character of nano material self and optical property compound, form multi-functional composite nanostructure.
Color of the present invention is with visual angle change structure, and it is for to realize light angle color changing effect by the optical interference effects of foraminous die plate, magnetic or nonmagnetic metal or alloy nano-wire special construction.Realize in the optical interference effects structure of angular color change, porous film material can be selected the porous alumina formwork of composite metal nanotube or metal oxide, nitride nano pipe, the porous organic polymer template of porous organic polymer template and composite metal nanotube or metal oxide, nitride nano pipe.The porous alumina formwork of preferred rigid composite metal nano-tube or metal oxide, nitride nano pipe in fields such as trademark, signs; Need material to there is the field preferably clear porous organic formwork of better flexibility, comprise the porous organic film of the preparations such as track etching polycarbonate membrane and polyester film, polymethylmethacrylate and polystyrene and porous polyester (PET) film etc.
And by nanowires/nanotubes compound in foraminous die plate material, one or both are all chosen as magnetic metal or alloy, can realize when obtaining light angle color changing effect and make this structure have magnetic;
Described magnetic metal by transition element (T) and alloy cpd thereof as Fe, Co, Ni, Mn, CoFe, NiFe, CoNi, FeCoNi, CoPt, CoPd, FePt, FePd, NiMn, FeMn, NiFeCr etc. and 15 kinds of simple substance thuliums (R=La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Te, Dy, Ho, Er, Tm, Yb and Lu) and the formation such as the R-T alloy that forms of rare earth-magnesium-yttrium-transition metal or compound; By controlling composition, structure, the pattern of magnetic material, can control magnetic;
In technique scheme, composite nano tube in foraminous die plate material is chosen as to the metal oxide materials with semiconductor property, can realizes when obtaining light angle color changing effect and make this structure there is semiconductor property;
Described metal oxide is by ZnO, CdO, SnO
2, Fe
2o
3, Cr
2o
3etc. formation, by selecting different oxide semiconductor materials can realize the compound of semiconductor property.
[embodiment 1]:
Incorporated by reference to accompanying drawing 1A to Fig. 1 D.
First porous alumina formwork 30 one sides that are less than 10 μ m at thickness grow layer of metal (copper or gold) as electrode material by magnetically controlled sputter method, then by electrochemical deposition method, in alumina formwork duct, deposit magnetic or nonmagnetic metal or alloy nano-wire 20, concrete technology parameter is as follows:
1, plated metal nickel SO
47H
2o 120g/L, H
3bO
340g/L, usings saturated calomel electrode (SCE) as contrast electrode, and sedimentation potential is-1.0V, room temperature deposition;
2, plated metal cobalt CoSO
47H
2o 120g/L, H
3bO
340g/L, usings saturated calomel electrode (SCE) as contrast electrode, and sedimentation potential is-1.0V, room temperature deposition;
3, plated metal iron FeSO
47H
2o 120g/L, H
3bO
340g/L, usings saturated calomel electrode (SCE) as contrast electrode, and sedimentation potential is-1.1V, room temperature deposition;
4, deposition magnetic metal Multilayered Nanowires, Co/Cu Multilayered Nanowires CoSO
47H
2o 120g/L, CuSO
47H
2o 1.6g/L, H
3bO
340g/L, usings saturated calomel electrode (SCE) as contrast electrode, pulsed deposition, be respectively-1.0V of sedimentation potential and-0.5V, room temperature deposition;
5, plated metal copper CuSO
45H
2o 120g/L, H
3bO
340g/L, usings saturated calomel electrode (SCE) as contrast electrode, and sedimentation potential is-0.4V, room temperature deposition;
6, plated metal silver AgNO3 0.01mol/L, usings Ag/AgCl electrode as contrast electrode, and sedimentation potential is-0.5V, room temperature deposition;
On this basis, by selecting suitable mode of deposition,, deposit the top, duct of magnetic or nonmagnetic metal or alloy nano-wire, continue by electrochemical deposition or electroless deposition methods growth magnetic or nonmagnetic metal or alloy nanotube 10, concrete technology parameter is as follows:
7, plated metal nickel SO
47H
2o 2g/L, adds proper amount of surfactant, usings saturated calomel electrode (SCE) as contrast electrode, and sedimentation potential is-1.0V, room temperature deposition;
8, plated metal Co CoSO
47H
2o 2g/L, adds proper amount of surfactant, usings saturated calomel electrode (SCE) as contrast electrode, and sedimentation potential is-1.0V, room temperature deposition;
9, the complex [Ag (NH of electroless deposition of metals silver silver
3)
2+, 4.25 * 10
-3mol/L], [glucose and tartrate, concentration is respectively 2.27 * 10 to reductive agent
-2mol/L and 2.67 * 10
-3mol/L], soaking at room temperature;
10, electrodeposit metals gold HAuCl
42.1 * 10-3mol/L, usings saturated calomel electrode as contrast electrode, and sedimentation potential is-0.7V, room temperature deposition.
Obtain by the interference effect of two bundle coherent light A, B, realizing light angle color changing effect by the porosint of composite metal nanotube, the false proof foundation structure of magneto-optic that metal nanometer line forms.
[embodiment 2]:
Incorporated by reference to accompanying drawing 2A to Fig. 2 B.
At thickness, be less than in the porous alumina formwork 30 of 10 μ m, first can adopt the nanotube 10 of the composite metal oxides such as sol-gel process, electrochemical deposition or nitride.
For example, adopt sol-gel process (Sol-Gel) Qi duct inwall to prepare one deck oxide nano (as zinc oxide nano mitron etc.), concrete technology parameter is as follows:
The colloidal sol precursor of making ZnO, usings ethylene glycol monomethyl ether as solvent, Zinc diacetate dihydrate 8.26g, and appropriate stabilizing agent, adds ethylene glycol monomethyl ether to 50mL, in 70 ℃ of constant temperature, stirs and within 1 hour, forms colloidal sol; Then porous alumina formwork is entered in colloidal sol, fully submergence, with 200 ℃ of baking 10min in baking oven, finally 500 ℃ of thermal treatment 1 hour in tubular furnace.
At duct inwall, be compounded with in the porous alumina formwork of zinc oxide nano mitron, by electro-deposition method, prepare magnetic or nonmagnetic metal or alloy nano-wire 20, concrete technology is with embodiment 1.
[embodiment 3]
At track etching polycarbonate membrane and polyester film, simultaneously utilize Grown by Magnetron Sputtering layer of metal (copper or gold) as electrode material, then adopt the method for electrochemical deposition in organic polymer template duct, to deposit magnetic or nonmagnetic metal or alloy nano-wire, concrete deposition process parameters is with embodiment 1.Make and there is flexible angular color change structure.
[embodiment 4]:
Incorporated by reference to accompanying drawing 3A to Fig. 3 B.
First adopt micro fabrication to prepare flexible and transparent porous polyester (PET) film, concrete technology is as follows:
Making has the graphic array mask plate 2 of aperture 20nm-400nm, and polyester (PET) film 3 that is 10 μ m by thickness is used above-mentioned mask plate 2, utilizes masking process, carries out polyester (PET) film 4 that electron beam irradiation obtains local irradiation; Then use the corrosive liquid being formed by potassium dichromate, sulfuric acid to carry out corrosive liquid corrosion to the polyester through electron beam 1 irradiation (PET) film 4, obtain ordered porous polyester PET thin film material 5, wherein, irradiation metering 300kGy, 65 ℃ of corrosive liquid temperature, corrosion 6h.
Then, by electrochemical deposition, in porous PET film duct, grow magnetic metal or alloy nano-wire, concrete technology parameter is with embodiment 1.The nanostructured making like this, except having light angle color changing effect, can also utilize the magnetic of magnetic nanometer as composite magnetic functional material, thereby in field of anti-counterfeit technology, provides a kind of novel magneto-optic anti-counterfeit structure.
[embodiment 5]:
Incorporated by reference to accompanying drawing 4.
In the structure of common light angle color changing effect, by making such as photoetching technique, simple graph processing, there is the structure of special graph, can be applied to the fields such as trademark, sign, concrete technology is as follows:
At duct inwall, be compounded with the alumina formwork of metal nano-tube (technological parameter is with embodiment 1) or metal oxide nanotubes (technological parameter is with embodiment 2), track etching polycarbonate membrane and polyester film, the surperficial spin coating photoresist (step 1) of porous PET template (technological parameter is with embodiment 4), by thering is special graph, the masking process uv-exposure of word is processed (step 2) development treatment (step 3), then according to the electro-deposition process parameter in embodiment 1, carry out the deposition (step 4) of magnetic metal or alloy nano-wire, the part of being stopped up by photoresist in duct is just owing to cannot carrying out electro-deposition, and form, there is special graph, the angular color change structure of word.
Effect of the present invention:
The structure that a kind of novel color provided by the invention changes with visual angle, utilizes foraminous die plate material composite nano tube/nano-material, thereby realize optical interference, obtains light angle color changing effect.It is a kind of magnetosensitive or photochromics based on nano wire and nano tube structure, is that a kind of to take self assembly metal nanometer line and nanotube in foraminous die plate material be magneto or the photosensitive nano structural material that can be used to indicate the various fields such as sign, label trade mark, anti-counterfeiting technology, sensor technology on basis.
Compare with other angular color change structures, one aspect of the present invention is by the selection of various template material, the measures such as composite nano tube/nano-material can be modulated optical property more flexibly, for example, rigidity foraminous die plate is more suitable in the application in the fields such as hard commecial label, Warning Mark, and flexible foraminous die plate is more suitable for the application in the fields such as anti-counterfeiting technology, sensor technology, and can modulate optical property equally by the compound of different refractivity, reflectivity nano material; Pass through on the other hand the compound of the nano materials such as magnetic, semiconductor, can be so that this structure has the more physicochemical characteristics of horn of plenty, for example, in field of anti-counterfeit technology, it is simple that light angle color changing effect has identification, be convenient to consumer's raising and distinguish the advantages such as rate, by composite magnetic nano material, by simultaneously for magnetic anti-counterfeit provide basis, thereby having the simple while of identification concurrently, compound by magnetics anti-counterfeiting technology, greatly improve imitated threshold, realization is identified simply, extremely difficult imitated New Type Magneto anti-counterfeiting technology.
Certainly; the present invention also can have other various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art can make according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection domain of the claims in the present invention.
1, the structure that color changes with visual angle, is characterized in that, comprises foraminous die plate material and the nanowires/nanotubes that is compound in described foraminous die plate material.
2, the structure that color according to claim 1 changes with visual angle, is characterized in that, described nanowires/nanotubes is compound in duct inwall or the bottom of described foraminous die plate material.
3, the structure that color according to claim 1 changes with visual angle, is characterized in that, described foraminous die plate material is rigidity foraminous die plate material or flexible foraminous die plate material.
4, the structure that color according to claim 3 changes with visual angle, is characterized in that, described rigidity foraminous die plate material consists of inorganic porous mould material.
5, the structure that color according to claim 4 changes with visual angle, is characterized in that, the porous alumina formwork of described inorganic porous mould material for preparing by anodic oxidation.
6, the structure that color according to claim 5 changes with visual angle, it is characterized in that, described porous alumina formwork is for being used the anodic oxidation preparation under voltage conditions of sulfuric acid, phosphoric acid or oxalic acid, and described voltage comprises direct current and alternating voltage, and voltage swing is in 20V-200V scope.
7, the structure that color according to claim 3 changes with visual angle, it is characterized in that, described flexible foraminous die plate material consists of organic polymer porosint, and described organic polymer porosint comprises porous organic film prepared by track etching polycarbonate membrane, track etching polyester film, polymethylmethacrylate and polystyrene and organic flexible and transparent foraminous die plate material of preparing by micro-processing technology;
8, the structure that color according to claim 7 changes with visual angle, it is characterized in that, described track etching polycarbonate membrane and track etching polyester film, first be to utilize nuclear fission fragment or heavy ion accelerator to bombard polycarbonate macromolecule membrane or polyester macromolecule film, then the cracking molecule at track place is by the corrosion formation of the chemical reagent duct vertical with face, and pore diameter range is 10nm-8 μ m;
Porous organic film prepared by described polymethylmethacrylate and polystyrene, by utilizing the different etch rate of polymethylmethacrylate and polystyrene, obtains porous organic film material;
Organic flexible and transparent foraminous die plate material prepared by described micro-processing technology, for preparing on the basis of mylar, in conjunction with micro-processing masking process electron beam lithography, mylar is processed, finally with strong oxidizer, corrode and obtain porous polyester film, by controlling irradiation dose, etching time and temperature, obtain aperture, hole Density Distribution, the controlled organic flexible and transparent porous polymer membraneous material of film thickness.
9, color according to claim 2, with visual angle change structure, is characterized in that, comprises following several types:
(a) duct inwall composite magnetic metal or alloy nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(b) the compound nonmagnetic metal of duct inwall or alloy nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire;
(c) duct inwall composite magnetic metal or alloy nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire;
(d) the compound nonmagnetic metal of duct inwall or alloy nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(e) duct inwall composite metal oxide or metal nitride nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(f) duct inwall composite metal oxide or metal nitride nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire.
10, the structure that color according to claim 2 changes with visual angle, is characterized in that, the nanowires/nanotubes that is compound in described foraminous die plate material duct inwall or bottom comprises: nanotube, nano wire form by magnetic metal or alloy; Nanotube, nano wire form by nonmagnetic metal or alloy; Nanotube consists of magnetic metal or alloy, and nano wire consists of nonmagnetic metal or alloy; Nanotube consists of nonmagnetic metal or alloy, and nano wire consists of magnetic metal or alloy; Nanotube consists of metal oxide, nitride, and nano wire consists of magnetic metal or alloy; Nanotube consists of metal oxide, nitride, and nano wire consists of nonmagnetic metal or alloy.
11, the structure changing with visual angle according to the color described in claim 9 or 10, it is characterized in that, alloy or compound that described magnetic metal consists of transition element and alloy cpd Fe, Co, Ni, Mn, CoFe, NiFe, CoNi, FeCoNi, CoPt, CoPd, FePt, FePd, NiMn, FeMn, NiFeCr, 15 kinds of simple substance rare-earth metals La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Te, D y, Ho, Er, Tm, Yb, Lu or rare earth-magnesium-yttrium-transition metals form; Nonmagnetic metal or alloy consist of Cu, Cr, V, Nb, Mo, Ru, Pd, Ta, W, Pt, Ag, Au and their alloy; Metal oxide, nitride are by MgO, InO, SnO
2, CuO, CdO, HfO
2, TiO
2, Cr
2o
3, FeO
x, ZnO, V
2o
5, InN, AlN form.
12, the structure changing with visual angle according to the color described in claim 9 or 10, it is characterized in that, described magnetic and nonmagnetic metal or alloy nanotube/nano wire are realized by the Chemical self-assembly method of electrochemical deposition, electroless deposition, ald, sol-gel process; Described metal oxide/nitride nano pipe is prepared by sol-gel process, electrochemical deposition, ald, template vapour deposition.
13, the structure that color according to claim 1 changes with visual angle, is characterized in that, is also included in composite magnetic metal or alloy nanowires/nanotubes before by the graphical treatment of masking process, makes the angular color change structure with anti-counterfeiting mark.
14, the structure that color according to claim 2 changes with visual angle, is characterized in that, described foraminous die plate material thickness is less than 10 μ m, the aperture 20nm-500nm in described duct; Described magnetic or nonmagnetic metal or alloy nano line length are 20nm-400nm.
The structure that a kind of color changes with visual angle, the nanowires/nanotubes that comprises foraminous die plate material and be compound in described foraminous die plate material duct inwall or bottom, the structure that this color changes with visual angle be take foraminous die plate material as basis, comprise porous alumina formwork and the flexible and transparent porous organic polymer template of duct inwall composite metal nanotube and metal oxide, nitride nano pipe, and realize angular color change by this optical interference structure.By composite magnetic metal or alloy nano wire, magnetic detection can be supplied, by composite semiconductor oxide nano, abundant semiconductor property can be provided.The invention has the advantages that: the light angle color changing effect of realizing by design optical interference structure, is simply easy to observation; Can form a kind of multi-functional composite structure by compound other functional materials as magnetic material, semiconductor material etc., can be widely used in the various fields such as Warning Mark, label trade mark, anti-counterfeiting technology, sensor technology.
Claims (14)
1. the structure that color changes with visual angle, is characterized in that, comprises foraminous die plate material and the nanowires/nanotubes that is compound in described foraminous die plate material.
2. the structure that color according to claim 1 changes with visual angle, is characterized in that, described nanowires/nanotubes is compound in duct inwall or the bottom of described foraminous die plate material.
3. the structure that color according to claim 1 changes with visual angle, is characterized in that, described foraminous die plate material is rigidity foraminous die plate material or flexible foraminous die plate material.
4. the structure that color according to claim 3 changes with visual angle, is characterized in that, described rigidity foraminous die plate material consists of inorganic porous mould material.
5. the structure that color according to claim 4 changes with visual angle, is characterized in that, the porous alumina formwork of described inorganic porous mould material for preparing by anodic oxidation.
6. the structure that color according to claim 5 changes with visual angle, it is characterized in that, described porous alumina formwork is for being used the anodic oxidation preparation under voltage conditions of sulfuric acid, phosphoric acid or oxalic acid, and described voltage comprises direct current and alternating voltage, and voltage swing is in 20V-200V scope.
7. the structure that color according to claim 3 changes with visual angle, it is characterized in that, described flexible foraminous die plate material consists of organic polymer porosint, and described organic polymer porosint comprises porous organic film prepared by track etching polycarbonate membrane, track etching polyester film, polymethylmethacrylate and polystyrene and organic flexible and transparent foraminous die plate material of preparing by micro-processing technology.
8. the structure that color according to claim 7 changes with visual angle, it is characterized in that, described track etching polycarbonate membrane and track etching polyester film, first be to utilize nuclear fission fragment or heavy ion accelerator to bombard polycarbonate macromolecule membrane or polyester macromolecule film, then the cracking molecule at track place is by the corrosion formation of the chemical reagent duct vertical with face, and pore diameter range is 10nm-8 μ m;
Porous organic film prepared by described polymethylmethacrylate and polystyrene, by utilizing the different etch rate of polymethylmethacrylate and polystyrene, obtains porous organic film material;
Organic flexible and transparent foraminous die plate material prepared by described micro-processing technology, for preparing on the basis of mylar, in conjunction with micro-processing masking process electron beam lithography, mylar is processed, finally with strong oxidizer, corrode and obtain porous polyester film, by controlling irradiation dose, etching time and temperature, obtain aperture, hole Density Distribution, the controlled organic flexible and transparent porous polymer membraneous material of film thickness.
9. color according to claim 2, with visual angle change structure, is characterized in that, comprises following several types:
(a) duct inwall composite magnetic metal or alloy nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(b) the compound nonmagnetic metal of duct inwall or alloy nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire;
(c) duct inwall composite magnetic metal or alloy nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire;
(d) the compound nonmagnetic metal of duct inwall or alloy nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(e) duct inwall composite metal oxide or metal nitride nanotube, bottom, duct composite magnetic metal or alloy nano wire;
(f) duct inwall composite metal oxide or metal nitride nanotube, the duct compound nonmagnetic metal in bottom or alloy nano-wire.
10. the structure that color according to claim 2 changes with visual angle, is characterized in that, the nanowires/nanotubes that is compound in described foraminous die plate material duct inwall or bottom comprises: nanotube, nano wire form by magnetic metal or alloy; Nanotube, nano wire form by nonmagnetic metal or alloy; Nanotube consists of magnetic metal or alloy, and nano wire consists of nonmagnetic metal or alloy; Nanotube consists of nonmagnetic metal or alloy, and nano wire consists of magnetic metal or alloy; Nanotube consists of metal oxide, nitride, and nano wire consists of magnetic metal or alloy; Nanotube consists of metal oxide, nitride, and nano wire consists of nonmagnetic metal or alloy.
11. structures that change with visual angle according to the color described in claim 9 or 10, it is characterized in that, alloy or compound that described magnetic metal consists of transition element and alloy cpd Fe, Co, Ni, Mn, CoFe, NiFe, CoNi, FeCoNi, CoPt, CoPd, FePt, FePd, NiMn, FeMn, NiFeCr, 15 kinds of simple substance rare-earth metals La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Te, D y, Ho, Er, Tm, Yb, Lu or rare earth-magnesium-yttrium-transition metals form; Nonmagnetic metal or alloy consist of Cu, Cr, V, Nb, Mo, Ru, Pd, Ta, W, Pt, Ag, Au and their alloy; Metal oxide, nitride are by MgO, InO, SnO
2, CuO, CdO, HfO
2, TiO
2, Cr
2o
3, FeO
x, ZnO, V
2o
5, InN, AlN form.
12. structures that change with visual angle according to the color described in claim 9 or 10, it is characterized in that, described magnetic and nonmagnetic metal or alloy nanotube/nano wire are realized by the Chemical self-assembly method of electrochemical deposition, electroless deposition, ald, sol-gel process; Described metal oxide/nitride nano pipe is prepared by sol-gel process, electrochemical deposition, ald, template vapour deposition.
The structure that 13. colors according to claim 1 change with visual angle, is characterized in that, is also included in composite magnetic metal or alloy nanowires/nanotubes before by the graphical treatment of masking process, makes the angular color change structure with anti-counterfeiting mark.
The structure that 14. colors according to claim 2 change with visual angle, is characterized in that, described foraminous die plate material thickness is less than 10 μ m, the aperture 20nm-500nm in described duct; Described magnetic or nonmagnetic metal or alloy nano line length are 20nm-400nm.
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