CN109754043A - A kind of preparation method of micro-nano structure antifalsification label - Google Patents
A kind of preparation method of micro-nano structure antifalsification label Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 36
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 30
- 239000010931 gold Substances 0.000 claims description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 18
- 229910052681 coesite Inorganic materials 0.000 claims description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims description 16
- 229910052682 stishovite Inorganic materials 0.000 claims description 16
- 229910052905 tridymite Inorganic materials 0.000 claims description 16
- 238000010041 electrostatic spinning Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 10
- 239000005695 Ammonium acetate Substances 0.000 claims description 10
- 229940043376 ammonium acetate Drugs 0.000 claims description 10
- 235000019257 ammonium acetate Nutrition 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000005253 cladding Methods 0.000 claims description 9
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 8
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 230000009514 concussion Effects 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 3
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005457 optimization Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000012876 topography Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- DCRZVUIGGYMOBI-UHFFFAOYSA-N 2-sulfanylidene-1,3-dihydrobenzimidazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2NC(=S)NC2=C1 DCRZVUIGGYMOBI-UHFFFAOYSA-N 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- -1 nanometer rods Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
Abstract
The present invention relates to a kind of preparation methods of micro-nano structure antifalsification label, assemble to obtain by the nano particle of electrospun fibers and nucleocapsid structure.Nano particle contains specific Raman molecular, has special Raman fingerprint peaks, the intensity of fingerprint peaks and position can be exchanged into specific bar code.The material can be firmly secured at glass surface, and by repeatedly washing, Raman signal still keeps well, can be used as the antifalsification label of glass.The label has special " topography ", i.e. micron order electrospun fibers and nanoscale nucleocapsid structure, the pore structure of perforation, unique bar code and stable performance.
Description
Technical field
The present invention relates to a kind of preparation methods of micro-nano structure antifalsification label, belong to optical material and its anti-counterfeit field, special
Not Shi Yongyu glass matrix true and false identification.
Background technique
Vehicle glass is a part indispensable in automobile construction.Good glass can keep out wind and rain sandstone, be to protect
Demonstrate,prove the first barrier of life security.Fake and forged glass not only influences driver's vision and degree of fatigue, but will be to occupant's
Life constitutes a serious threat.Fake and forged glass is sought exorbitant profit to illegal businessman, but can make consumer's person, property right by
To infringement, the image of expanding economy and brand marketers is seriously constrained.In order to identify counterfeit and shoddy goods, maintenance is regulated the market
Order, anti-counterfeiting technology are come into being.The true and false of substance can be identified by preparing anti-fake product according to anti-counterfeiting technology, this progress in the mankind
There is important research significance in development with society.
Antifalsification label currently on the market is broadly divided into laser tag, query formulation from technical characteristic and function evolution angle
Numerical code anti-fake label, texture anti-fake label etc..For example, Fu Yao halogen in combination China Telecom produces a kind of laser lithography holography
Anti-fake product, from 2008, the accessory paste List anti-counterfeiting mark of group production.Query formulation numerical code anti-fake label is will to produce
Product confidence input database, by phone or network, the heart or information bank are inquired in queries.Texture label is with material
Expect that the speckle mark having in itself is a kind of anti-counterfeiting technology of anti-counterfeit recognition label.The speckle of nature is always multifarious,
Such as the textures such as fingerprint, zebra-stripe be all it is random, unique, can not be there are two duplicate, the information of texture carries out
Inquiry and identification.Anti-fake product need to meet that identity uniqueness, stability is good and safety height etc. requires.
Anti-fake spectrogram is a kind of important anti-fake approach.Common spectrum includes fluorescence spectrum and Raman spectrum, fluorescence light
Spectrum has emission spectrum wide, and the spectrogram that Color tunable control is poor, color is different has the spies such as certain overlapping, bleach-resistant performance difference
Sign, this is subject to certain restrictions it in anti-fake.Raman spectrum belongs to molecular vibration spectrum, can reflect the feature knot of molecule
Structure, but Raman scattering is a very weak process, so signal is very weak, to carry out Raman spectrum to adsorption Raman molecular
Research is employed to certain enhancement effect substantially, and Surface enhanced Raman scattering (SERS) is wherein important one kind.Surface enhanced
The common substrate of Raman scattering is gold, silver, copper etc..It is of various shapes to receive with the continuous development of nanotechnology and nano science
Rice material is come out one after another, such as nano particle, nanometer rods, nano wire and nanotube etc..Since the size of nano material is small, surface
Can be big, it is easy to that aggregation occurs between particle and particle or merges.After particle aggregation or fusion, the Raman molecular on surface
Signal there is relatively unstable phenomenon.If using gold, silver nano particle as the absorption carrier of Raman molecular, by it
Cladding can effectively avoid the generation of above situation.Although the nano particle being wrapped by can save the regular hour in the solution,
But it is detrimental to save for a long time, and inconvenient to use, be unfavorable for as label in kind.
Summary of the invention
A kind of system of micro-nano structure antifalsification label is proposed the purpose of the invention is to improve the deficiencies in the prior art
Preparation Method, the method that the invention is simple and feasible, the micro-nano structure material of preparation are novel, efficient and stable.
The technical solution of the present invention is as follows: material prepared by the present invention is by the pore structure and nanometer of electrospun fibers
The core-shell structure and Raman spectrum of grain combine, and the signal of Raman molecular is converted to bar code, as a kind of novel
Optical anti-counterfeiting label.Firstly, by Raman molecular modification to the surface Au NPs；Then, Au NPs is carried out by sol-gal process
Cladding obtains Au@SiO2NPs.It can be acted on by Au-S key between Raman molecular and Au NPs, it is contemplated that Raman molecular is in Au
The surface NPs exists simultaneously the state of adsorption and de-adsorption, and coated with silica on the surface Au NPs, is made Raman point by the present invention
Steadily there is the surface Au NPs in son.At the same time, silica can be effectively avoided Au NPs's to the cladding of Au NPs
Assemble and merges.The material is using electrospun fibers as carrier, by Au@SiO2NPs is evenly dispersed in fiber surface, by adding
The mode of heat makes Au@SiO2NPs is partly embedded into fiber, obtains a kind of new material.The material has novel micro-nano knot
Structure, special hole, stable surface Raman enhancement signal, convert unique bar code for the material, can be used as a kind of light
Learn antifalsification label.
The specific technical proposal of the invention is: a kind of preparation method of micro-nano structure antifalsification label, the specific steps of which are as follows:
(1) hydrophobic polymer and hydrophilic polymer are added separately to stir to dissolve in corresponding solvent, it will
Two kinds of solution mix to arrive polymer dope in proportion；Optimization electrostatic spinning machine injects speed, receives distance, voltage
Parameter obtains the fiber that diameter is evenly distributed；
(2) Raman molecular is modified on the surface gold nano grain Au NPs, by sol-gal process by coated with silica
On the surface Au NPs, the coated with silica gold nano grain Au@SiO with core-shell structure is obtained2NPs；
(3) the Au@SiO for obtaining step (2)2NPs is dispersed in the mixed solution of acetic acid and ammonium acetate, then by Static Spinning
Silk fiber is immersed in above-mentioned solution, makes electrospun fibers and Au@SiO2NPs assembling, by Au@SiO2NPs inhales evenly dispersedly
It is attached to fiber surface；
(4) step (3) Au@SiO has been adsorbed into2The fiber of NPs is laid in carrier surface, and then putting it in baking oven makes
Au@SiO2NPs is embedded in fiber, obtains rough micro-nano structure antifalsification label.
Hydrophobic polymer is polymethyl methacrylate (PMMA) in preferred steps (1)；Hydrophilic polymer is poly- 4-
Vinylpyridine (P4VP)；The mass concentration of polymer dope hydrophobic polymer and hydrophilic polymer is 12%-38%；
Hydrophobic polymer and hydrophilic polymer 0.5-2 in mass ratio mixing.
Solvent described in preferred steps (1) is N,N-dimethylformamide (DMF) and acetone is 0.25-3 by volume:
The solvent of 1 ratio mixing.
The speed of injecting of electrostatic spinning machine is 0.05-0.5mm/min in preferred steps (1)；Receiving distance is 10-30cm；
Positive pressure is 8-25kV；Negative pressure is -5 to -1kV.
The partial size of Au NPs is 40-80nm in preferred steps (2)；The Raman molecular be mercaptobenzoic acid (4-MBA) or
One or two kinds of mixing of 2-mercaptobenzimidazole -5- carboxylic acid (MBIA), the concentration of the two are 0.01mM-10mM, the two
Isoconcentration mixed volume ratio 0.1-10.In step (2) solvent used in sol-gal process be water and isopropanol mixed solvent, two
The volume ratio of person is 0.2-5, Au@SiO2NPs partial size is 50-200nm；Cladding is with a thickness of 10-70nm.
The pH value of acetic acid and ammonium acetate mixed solution is 2-10 in preferred steps (3)；Au@SiO2NPs be dispersed in acetic acid and
Concentration is 200 μm of ol/L-200pmol/L in the mixed solution of ammonium acetate.
Make electrospun fibers and Au@SiO in preferred steps (3)2NPs assembling is using one in static, concussion or vortex
Kind or two kinds of control assembling speeds and degree of scatter.The heating temperature of baking oven is 60 DEG C -200 DEG C in preferred steps (4).
The utility model has the advantages that
This method assembles micron-sized electrospun fibers and Core-shell Structure Nanoparticles, and nano particle is embedded to
In electrospun fibers.The preparation method simple process, abundant raw material are easy to get, structure novel, Raman signal are stablized, fingerprint peaks
Intensity and position, which are converted into bar code, can be used as a kind of novel antifalsification label.The label can be stablized on glass carrier surface to be deposited
Surface Raman enhancement signal can be obtained in tow sides, the advantages that having safety coefficient high, identity identifiability concurrently.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of 4 micro-nano structure antifalsification label of embodiment；
Fig. 2 is the Raman spectrum of 4 antifalsification label of embodiment and its bar code that is converted into.
Specific embodiment
Embodiment 1
(1) prepare PMMA the and P4VP spinning solution of 12wt%, the mass ratio of two kinds of polymer is 1:2, solvent be acetone and
DMF mixed solvent, volume ratio 2:1.The parameter that electrostatic spinning machine is arranged is as follows: positive pressure 25kV, and negative pressure -5kV injects speed
0.20mm/min receives distance 20cm.
(2) the Au NPs that partial size is about 40nm is prepared, the 4-MBA of 0.01mM is modified on the surface Au NPs, colloidal sol is passed through
Gel method is by coated with silica on the surface Au NPs, and wherein the volume ratio of water and isopropanol is 1:5, and obtaining partial size is about
The Au@SiO of 60nm2NPs, cladding thickness is about 10nm.
(3) the Au@SiO for being 200 μm of ol/L by concentration2NPs is dispersed in the acetic acid of pH=2 and the mixed solution of ammonium acetate
In, 2cm × 2cm electrospun fibers are immersed in above-mentioned solution, which remain stationary state and continue 10min, makes electrostatic
Spinning fibre and Au@SiO2NPs assembling.Finally, Au@SiO will be adsorbed2The fiber of NPs takes out from solution.
(4) Au@SiO has been adsorbed by above-mentioned2The fiber of NPs is spread on glass carrier, is heated, is obtained under conditions of 60 DEG C
To flexible anti-counterfeiting label.
(5) Raman is tested: the label, which is placed on Raman spectrometer test, can be obtained 4-MBA Raman spectrogram.By 4-
MBA fingerprint peaks are converted to bar code, and peak position and peak intensity respectively correspond position and the width of bar code black line, middle ware away from for
Its input database is used as the antifalsification label of the materials such as glass by white spaces in turn.
Embodiment 2
(1) prepare PMMA the and P4VP spinning solution of 20wt%, the mass ratio of two kinds of polymer is 2:1, solvent be acetone and
DMF mixed solvent, volume ratio 1:3.The parameter that electrostatic spinning machine is arranged is as follows: positive pressure 18kV, and negative pressure -1kV injects speed
0.45mm/min receives distance 15cm.
(2) the Au NPs that partial size is about 60nm is prepared, by the MBIA modification of 8.9mM on the surface Au NPs, is coagulated by colloidal sol
Glue method is by coated with silica on the surface Au NPs, and wherein the volume ratio of water and isopropanol is 2.5:1, and obtaining partial size is about
The Au@SiO of 100nm2NPs, cladding thickness is about 20nm.
(3) the Au@SiO for being 200pmol/L by concentration2NPs is dispersed in the acetic acid of pH=4 and the mixed solution of ammonium acetate
In, 2cm × 2cm electrospun fibers are immersed in above-mentioned solution, which keeps concussion state to continue 10min, makes electrostatic
Spinning fibre and Au@SiO2NPs assembling.Finally, Au@SiO will be adsorbed2The fiber of NPs takes out from solution.
(4) Au@SiO has been adsorbed by above-mentioned2The fiber of NPs is spread on glass carrier, is heated, is obtained under conditions of 90 DEG C
To flexible anti-counterfeiting label.
(5) Raman is tested: the label, which is placed on Raman spectrometer test, can be obtained MBIA Raman spectrogram.By MBIA
Fingerprint peaks are converted to bar code, and peak position and peak intensity respectively correspond position and the width of bar code black line, and middle ware is away from being white
Its input database is used as the antifalsification label of the materials such as glass by color space in turn.
Embodiment 3
(1) prepare PMMA the and P4VP spinning solution of 38wt%, the mass ratio of two kinds of polymer is 1:2, solvent be acetone and
DMF mixed solvent, volume ratio 4:1.The parameter that electrostatic spinning machine is arranged is as follows: positive pressure 15kV, and negative pressure -1kV injects speed
0.25mm/min receives distance 30cm.
(2) the Au NPs that partial size is about 80nm is prepared, the MBIA (volume ratio 1:10) of the 4-MBA of 5mM and 5mM is mixed and is repaired
Decorations are on the surface Au NPs, by sol-gal process by coated with silica on the surface Au NPs, the wherein volume of water and isopropanol
Than obtaining the Au@SiO that partial size is about 200nm for 5:12NPs, cladding thickness is about 60nm.
It (3) is 1pmol/LAu@SiO by concentration2NPs is dispersed in the acetic acid of pH=9 and the mixed solution of ammonium acetate, will
2cm × 2cm electrospun fibers are immersed in above-mentioned solution, which keeps vorticity to continue 10min, keep electrostatic spinning fine
Dimension and Au@SiO2NPs assembling.Finally, Au@SiO will be adsorbed2The fiber of NPs takes out from solution.
(4) Au@SiO has been adsorbed by above-mentioned2The fiber of NPs is spread on glass carrier, is heated under conditions of 120 DEG C,
Obtain flexible anti-counterfeiting label.
(5) Raman is tested: the label, which is placed on Raman spectrometer test, can be obtained MBIA Raman spectrogram.By MBIA
Fingerprint peaks are converted to bar code, and peak position and peak intensity respectively correspond position and the width of bar code black line, and middle ware is away from being white
Its input database is used as the antifalsification label of the materials such as glass by color space in turn.
Embodiment 4
(1) PMMA the and P4VP spinning solution of 26.5wt% is prepared, the mass ratio of two kinds of polymer is 2:1, and solvent is acetone
With DMF mixed solvent, volume ratio 1:1.The parameter that electrostatic spinning machine is arranged is as follows: positive pressure 15kV, and negative pressure -2kV injects speed
0.05mm/min receives distance 10cm.
(2) the Au NPs that partial size is about 60nm is prepared, the MBIA (volume ratio 1:1) of the 4-MBA of 4.5mM and 4.5mM is mixed
Modification is closed on the surface Au NPs, by sol-gal process by coated with silica on the surface Au NPs, wherein water and isopropanol
Volume ratio is 1:2, obtains the Au@SiO that partial size is about 130nm2NPs, cladding thickness is about 35nm.
It (3) is 150pmol/LAu@SiO by concentration2NPs is dispersed in the acetic acid of pH=6 and the mixed solution of ammonium acetate,
2cm × 2cm electrospun fibers are immersed in above-mentioned solution, which keeps concussion state to continue 10min, makes electrostatic spinning
Fiber and Au@SiO2NPs assembling.Finally, Au@SiO will be adsorbed2The fiber of NPs takes out from solution.
(4) Au@SiO has been adsorbed by above-mentioned2The fiber of NPs is spread on glass carrier, is heated under conditions of 150 DEG C
It is as shown in Figure 1 the scanning electron microscope (SEM) photograph of concaveconvex structure antifalsification label to flexible anti-counterfeiting label.
(5) Raman is tested: the label, which is placed on Raman spectrometer test, can be obtained MBIA Raman spectrogram (such as Fig. 2 a
It is shown).MBIA fingerprint peaks are converted to bar code (as shown in Figure 2 b), peak position and peak intensity respectively correspond bar code black line
Position and width, middle ware by its input database and then are used as the antifalsification labels of the materials such as glass away from for white spaces.
Claims (8)
1. a kind of preparation method of micro-nano structure antifalsification label, the specific steps of which are as follows:
(1) hydrophobic polymer and hydrophilic polymer are added separately to stir to dissolve in corresponding solvent, by two kinds
Solution mixes to arrive polymer dope in proportion；Optimization electrostatic spinning machine injects speed, receives distance, voltage parameter,
Obtain the fiber that diameter is evenly distributed；
(2) Raman molecular is modified on the surface gold nano grain Au NPs, by sol-gal process by coated with silica in Au
The surface NPs obtains the coated with silica gold nano grain Au@SiO with core-shell structure2NPs；
(3) the Au@SiO for obtaining step (2)2NPs is dispersed in the mixed solution of acetic acid and ammonium acetate, then electrostatic spinning is fine
Dimension is immersed in above-mentioned solution, makes electrospun fibers and Au@SiO2NPs assembling, by Au@SiO2NPs is adsorbed evenly dispersedly
In fiber surface；
(4) step (3) Au@SiO has been adsorbed into2The fiber of NPs is laid in carrier surface, and then putting it in baking oven makes Au@
SiO2NPs is embedded in fiber, obtains rough micro-nano structure antifalsification label.
2. preparation method according to claim 1, it is characterised in that hydrophobic polymer is polymethyl in step (1)
Sour methyl esters；Hydrophilic polymer is poly- 4-vinylpyridine；The matter of polymer dope hydrophobic polymer and hydrophilic polymer
Measuring concentration is 12%-38%；Hydrophobic polymer and hydrophilic polymer 0.5-2 in mass ratio mixing.
3. preparation method according to claim 1, it is characterised in that solvent described in step (1) is N, N- dimethyl methyl
Amide and acetone are the solvent of the ratio mixing of 0.25-3:1 by volume.
4. preparation method according to claim 1, it is characterised in that the speed of injecting of electrostatic spinning machine is in step (1)
0.05-0.5mm/min；Receiving distance is 10-30cm；Positive pressure is 8-25kV；Negative pressure is -5 to -1kV.
5. preparation method according to claim 1, it is characterised in that the partial size of Au NPs is 40-80nm in step (2)；Step
Suddenly Au@SiO in (2)2NPs partial size is 50-200nm；Cladding is with a thickness of 10-70nm.
6. preparation method according to claim 1, it is characterised in that the pH of acetic acid and ammonium acetate mixed solution in step (3)
Value is 2-10；Au@SiO2It is 200 μm of ol/L-200pmol/L that NPs, which is dispersed in concentration in the mixed solution of acetic acid and ammonium acetate,.
7. preparation method according to claim 1, it is characterised in that make electrospun fibers and Au@SiO in step (3)2
NPs assembling using it is static, concussion or be vortexed one of or.
8. preparation method according to claim 1, it is characterised in that the heating temperature of baking oven is 60 DEG C -200 in step (4)
℃。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110907423A (en) * | 2019-10-30 | 2020-03-24 | 南京工业大学 | Method for preparing silver nanosheet composite fiber material |
| CN113514446A (en) * | 2021-05-26 | 2021-10-19 | 哈尔滨工业大学 | Method for rapidly matching and identifying SERS spectrogram |
| CN113763802A (en) * | 2021-09-09 | 2021-12-07 | 天津工业大学 | SERS anti-counterfeit label based on ternary Raman reporter molecule |
| CN114863790A (en) * | 2022-04-13 | 2022-08-05 | 四川大学 | Chiral nano anti-counterfeit label |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001027365A1 (en) * | 1999-10-08 | 2001-04-19 | The University Of Akron | Electrospun fibers and an apparatus therefor |
| US20010002275A1 (en) * | 1997-03-12 | 2001-05-31 | Oldenburg Steven J. | Metal nanoshells |
| US20120058697A1 (en) * | 2009-04-01 | 2012-03-08 | Strickland Aaron D | Conformal particle coatings on fiber materials for use in spectroscopic methods for detecting targets of interest and methods based thereon |
| CN103243408A (en) * | 2013-05-21 | 2013-08-14 | 苏州大学 | Preparation method of porous fiber with surface-enhanced Raman scattering effect |
| CN104907019A (en) * | 2015-04-29 | 2015-09-16 | 复旦大学 | Magnetic fluorescent Raman double-encoding composite microspheres and preparation method and application thereof |
| US20160059517A1 (en) * | 2014-08-26 | 2016-03-03 | Council Of Scientific And Industrial Research | High performance light weight carbon fiber fabric-electrospun carbon nanofibers hybrid polymer composites |
| CN105869516A (en) * | 2016-06-12 | 2016-08-17 | 王连杰 | Visible nanometer anti-counterfeit label |
| CN106544788A (en) * | 2016-11-03 | 2017-03-29 | 苏州科技大学 | The synthetic method of nanometer silver/silicon dioxide Raman surface enhanced film and application |
-
2018
- 2018-12-28 CN CN201811617691.4A patent/CN109754043B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010002275A1 (en) * | 1997-03-12 | 2001-05-31 | Oldenburg Steven J. | Metal nanoshells |
| WO2001027365A1 (en) * | 1999-10-08 | 2001-04-19 | The University Of Akron | Electrospun fibers and an apparatus therefor |
| US20120058697A1 (en) * | 2009-04-01 | 2012-03-08 | Strickland Aaron D | Conformal particle coatings on fiber materials for use in spectroscopic methods for detecting targets of interest and methods based thereon |
| CN103243408A (en) * | 2013-05-21 | 2013-08-14 | 苏州大学 | Preparation method of porous fiber with surface-enhanced Raman scattering effect |
| US20160059517A1 (en) * | 2014-08-26 | 2016-03-03 | Council Of Scientific And Industrial Research | High performance light weight carbon fiber fabric-electrospun carbon nanofibers hybrid polymer composites |
| CN104907019A (en) * | 2015-04-29 | 2015-09-16 | 复旦大学 | Magnetic fluorescent Raman double-encoding composite microspheres and preparation method and application thereof |
| CN105869516A (en) * | 2016-06-12 | 2016-08-17 | 王连杰 | Visible nanometer anti-counterfeit label |
| CN106544788A (en) * | 2016-11-03 | 2017-03-29 | 苏州科技大学 | The synthetic method of nanometer silver/silicon dioxide Raman surface enhanced film and application |
Non-Patent Citations (1)
| Title |
|---|
| 廖佳: "《基于贵金属纳米粒子的SERS活性基底研究进展》", 《分析科学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110907423A (en) * | 2019-10-30 | 2020-03-24 | 南京工业大学 | Method for preparing silver nanosheet composite fiber material |
| CN110907423B (en) * | 2019-10-30 | 2022-08-30 | 南京工业大学 | Method for preparing silver nanosheet composite fiber material |
| CN113514446A (en) * | 2021-05-26 | 2021-10-19 | 哈尔滨工业大学 | Method for rapidly matching and identifying SERS spectrogram |
| CN113763802A (en) * | 2021-09-09 | 2021-12-07 | 天津工业大学 | SERS anti-counterfeit label based on ternary Raman reporter molecule |
| CN114863790A (en) * | 2022-04-13 | 2022-08-05 | 四川大学 | Chiral nano anti-counterfeit label |
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