CN110003717A - A kind of steganography material and steganography method based on surface-enhanced Raman nano particle - Google Patents
A kind of steganography material and steganography method based on surface-enhanced Raman nano particle Download PDFInfo
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- CN110003717A CN110003717A CN201910183338.8A CN201910183338A CN110003717A CN 110003717 A CN110003717 A CN 110003717A CN 201910183338 A CN201910183338 A CN 201910183338A CN 110003717 A CN110003717 A CN 110003717A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a kind of steganography materials and steganography method based on surface-enhanced Raman nano particle, are related to Material Field and information security field.Steganography material based on surface-enhanced Raman nano particle of the invention, is the mixing material that surface-enhanced Raman nano particle is added in common material.Surface-enhanced Raman nano particle is made of metal nano substrate and Characteristic Raman molecule, and metal nano substrate is gold.Steganography method of the invention is distinguished information-recording using one or more steganography materials and common material, is encrypted.The Raman spectral information for reading the steganography material and the common material is scanned or is imaged using Raman spectrometer, it is extracted with algorithm and optimizes the coefficient of different component to obtain optimal fitting spectrum, the combination that ambient noise is excluded with the Bu Tong steganography material is completed to select, hiding information is obtained, decryption is completed.The present invention has the characteristics that safe, at low cost, signal is strong, light is stable and ambient stable performance is good, is able to carry out information combination multiplex.
Description
Technical field
The present invention relates to Material Field and information security fields, more particularly to one kind to be based on surface-enhanced Raman nano particle
Steganography material and steganography method.
Background technique
With the development of information technology, information security issue becomes increasingly conspicuous.Information leakage can not only damage personal, enterprise
Privacy, in some instances it may even be possible to state secret and safety can be seriously threatened.Therefore, very urgent need are become to the protection of important information
It wants.Steganography is a kind of common information protective technology, refers to by the Information hiding of desired transmitting in other information, does not allow pre-
Anyone except phase recipient knows the transmitting and content of information.With another conventional information protection technique-cryptography phase
It is that the information of transmitting will not cause others attention or suspection than the advantages of, Steganography.Steganography ink is normal in steganography
A kind of steganography material.The information naked eyes write with the ink are invisible, only can just be showed by certain visualization way
Come.According to visualization way can there are many types, including heat development ink, chemical development ink, photodevelopment by steganography ink
Ink etc..Compared with the first two, photodevelopment mode has safety, to the advantage of information lossless, the information combination that complexity can be achieved.
Photodevelopment ink is mainly fluorescent ink, issues fluorescence under the irradiation of certain wavelength laser, shows hiding information.However fluorescence
Ink has its disadvantage.Traditional easy photobleaching of organic fluorescent dye ink, light stability is poor, and fluorescence colour contamination phenomenon limits
The multiplex of information combination；And although the quantum dot or rare earth ink light stability that new development is got up are preferable, spectral peak is relatively narrow,
To human body, environment there may be toxicity, and higher cost.
Therefore, those skilled in the art is dedicated to developing a kind of steganography material based on surface-enhanced Raman nano particle
And steganography method, it is not only safe, at low cost, signal is strong, light is stable and ambient stable performance is good, but also have information combination multiple
Change ability.
Summary of the invention
In view of the above drawbacks of the prior art, the technical problem to be solved by the present invention is to how to seek it is a kind of safety,
It is at low cost, signal is strong, light is stable and ambient stable performance is good, with information combination multiplex ability steganography material and steganography side
Method.
To achieve the above object, the present invention provides a kind of steganography materials based on surface-enhanced Raman nano particle, should
Surface-enhanced Raman nano particle is added in steganography material.
Further, the surface-enhanced Raman nano particle is made of metal nano substrate and Characteristic Raman molecule.
Further, the metal in the metal nano substrate is gold.
Further, the structure of the metal nano substrate includes nano core-shell grain structure, nano flower, nanometer triangle
Piece, nanosphere, nanometer rods, nanometer star, Nano dendritic crystal and nano particle dimer.
Further, the Characteristic Raman molecule include to thioresorcin (Isosorbide-5-Nitrae-BDT), 4- nitrobenzenethiol (4-NBT),
Ortho-nitrophenyl thiophenol (2-NBT), 2- sulfydryl -5- nitrobenzimidazole (2-M-5-NBI), 2- sulfydryl -6- nitrobenzene thiazole (2-
M-6-NBT), two mercaptan of biphenyl -4,4'- (4,4'-BPDT), 4- thiocresol (4-MBT), adjacent chlorothio-phenol (2-CBT), 4- chlorine
Benzenethiol (4-CBT) and 2- naphthyl mercaptan (2-NT).
Optionally, steganography material includes but is not limited to steganography ink, steganography ink, steganography ink powder, steganography pigment or steganography
Coating.Such as steganography fountain pen ink, steganography writing brush ink, steganography printing ink, steganography printing color etc..
The present invention also provides a kind of steganography sides using the steganography material based on surface-enhanced Raman nano particle
Method, comprising the following steps:
Step 1, Party A use steganography materials based on surface-enhanced Raman nano particle and general
Logical material records information respectively, is encrypted；
Cipher mode and combination are passed to Party B by step 2, the Party A；
The record information is passed to the Party B by step 3, the Party A；
Step 4, the Party B are scanned using Raman spectrometer or the imaging reading one or more are described is based on table
Face enhances the steganography material of Raman nano particle and the Raman spectral information of the common material；
Step 5, the Party B pass through optimization different component using special algorithm to the Raman spectral information of acquisition
Coefficient obtains optimal fitting spectrum；
Step 6, the Party B are combined the optimal fitting spectrum according to the cipher mode and combination,
Decryption obtains hiding information.
Further, the common material in the step 1 and the step 4 include ordinary ink, it is common ink, general
Logical ink powder, common pigments or common coating.
Further, the special algorithm used in the step 5 includes Classical Least-Squares.
It further, include that sample stage is mobile, sharp using the scanning mode of Raman spectrometer imaging process in the step 4
Light hot spot is mobile and both moves；The shape of laser facula in the scanning mode includes point hot spot, linear light spot and face light
Spot；The Raman spectrometer imaging process uses 10 × camera lens of Confocal laser-scanning microscopy instrument, laser excitation wavelength 785nm, institute
Stating laser power density is 4.6 × 104W/cm2, acquisition time is 1 second.
Further, the mode of written information described in the step 1 include it is hand-written, printing, coating and printing.
The present invention also provides as described above based on the steganography material of surface-enhanced Raman nano particle in information security
Application in field.
In better embodiment of the invention, steganography ink is by the surface-enhanced Raman nanometer of the embedded 4-NBT synthesized
Particulate condensation takes 100 μ L to be centrifuged, the heroic board fountain pen ink that 200 μ L dilute 10 times is added after sucking supernatant, ultrasound to 2.5nM
It mixes, obtains 4-NBT steganography ink.And the gold that the surface-enhanced Raman nano particle of embedded 4-NBT is synthesized by seed mediated growth method
Based on core solution, absorption after 4-NBT ethanol solution is added, centrifuge washing and disperses again, it is raw followed by gold ion reduction method
Long golden shell is made.It can be seen that surface-enhanced Raman nano particle manufacturing process is simple in steganography ink and material utilization amount is small, because
This has highly-safe, at low cost feature.
In another better embodiment of the invention, written information is mixed using a variety of steganography inks and ordinary ink,
The reading and extraction for row information of going forward side by side.Comparing can by the spectrum of steganography ink written information and the spectrum of ordinary ink written information
To know, steganography ink contains the characteristic peak of Raman molecular, and it is obvious with ordinary ink difference, encryption and non-encrypted information can be distinguished,
Has the strong characteristic of signal.The raman spectra of each steganography ink is relatively narrow simultaneously, can choose different Raman spectrum peaks,
Obtain the ability of steganography ink information combination multiplex.
In another better embodiment of the invention, multiple Raman test is carried out to the information write by steganography ink,
Timing node is respectively to write the same day, one week, two weeks, one month, two months and three months, is usually saved in the dark.Steganography
Although the Raman signal of ink is weakened over time, considerable signal is still maintained after three months,
The writing profile that can clearly identify steganography ink illustrates that steganography ink prepared by the present invention has good long-time stability.
Therefore the invention has the benefit that the present invention provides a kind of steganography based on surface-enhanced Raman nano particle
Material and steganography method have safe, at low cost, signal is strong, light is stable and ambient stable performance is good, is able to carry out information to combine
The characteristics of multiplex.
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific structure and generation, with
It is fully understood from the purpose of the present invention, feature and effect.
Detailed description of the invention
Fig. 1 is a better embodiment of the invention, is received with the surface-enhanced Raman of embedded 4-NBT Raman reporter molecules
The photograph via bright field for the information that the steganography ink of rice grain is write chooses 1310-1365cm in its Raman spectrum-1The integral of Raman peaks
The Raman spectrum of three points in the Raman image figure and image that intensity is drawn；
Fig. 2 be it is of the invention based on surface-enhanced Raman nano particle structural schematic diagram；
Fig. 3 is another better embodiment of the invention, is drawn with the surface enhanced of embedded Isosorbide-5-Nitrae-BDT Raman reporter molecules
The photograph via bright field of steganography ink and ordinary ink the mixing written information of graceful nano particle chooses 1030- in its Raman spectrum
1090cm-1Five in Raman image figure that the integrated intensities of Raman peaks is drawn, image and image after algorithm process
The Raman spectrum of a point；
Fig. 4 is another better embodiment of the invention, with the surface-enhanced Raman of embedded 4-NBT Raman reporter molecules
The steganography ink of nano particle, embedded 1,4-BDT Raman reporter molecules surface-enhanced Raman nano particle steganography ink and
Ordinary ink mixes the photograph via bright field of written information, chooses Raman image figure and pass through algorithm process that different Raman peaks are drawn
The image for the different information combination extracted afterwards；
Fig. 5 is another better embodiment of the invention, to the surface-enhanced Raman of embedded 4-NBT Raman reporter molecules
The Raman image figure of the long term stability tests for the information that the steganography ink of nano particle is write chooses 1310- in Raman spectrum
1365cm-1The integrated intensity of Raman peaks is drawn；
Fig. 6 is another better embodiment of the invention, to the surface-enhanced Raman of embedded 4-NBT Raman reporter molecules
The Raman image figure of the sunshine stability test for the information that the steganography ink of nano particle is write chooses 1310- in Raman spectrum
1365cm-1The integrated intensity of Raman peaks is drawn.
Specific embodiment
Multiple preferred embodiments of the invention are introduced below with reference to Figure of description, keep its technology contents more clear and just
In understanding.The present invention can be emerged from by many various forms of embodiments, and protection scope of the present invention not only limits
The embodiment that Yu Wenzhong is mentioned.
In the accompanying drawings, the identical component of structure is indicated with same numbers label, everywhere the similar component of structure or function with
Like numeral label indicates.The size and thickness of each component shown in the drawings are to be arbitrarily shown, and there is no limit by the present invention
The size and thickness of each component.Apparent in order to make to illustrate, some places suitably exaggerate the thickness of component in attached drawing.
Embodiment one: the steganography ink based on embedded 1,4-BDT Raman molecular
Step 1, the surface-enhanced Raman nano particle (embedded Isosorbide-5-Nitrae-BDT Raman molecular) of golden core-shell structure is prepared
Step 1.1, (particle diameter 25nm, is scattered in the golden core solution for taking 2mL 1nmol/L seed mediated growth method to synthesize
In the hexadecyltrimethylammonium chloride solution (CTAC) of 100mmol/L) centrifuge washing is primary, CTAC concentration is reduced to
20mmol/L is scattered in original volume.
Step 1.2, the Isosorbide-5-Nitrae-BDT solution of 100 μ L is slowly added in the pond Yu Chaosheng, solution concentration is generally higher than 2mmol/L,
Such as 3mmol/L, 4mmol/L, 5mmol/L, standing adsorption 2-4 hours, be then centrifuged for washing repeatedly (such as 2 times, 3 times, 4
It is secondary), it is scattered in the CTAC of 1mL 50mmol/L again, obtains the golden nuclear particle for being coated with Isosorbide-5-Nitrae-BDT molecule.
Step 1.3, by CTAC the and 1mL 3-7mmol/L of 20mL 50mmol/L (such as 3.42mmol/L, 4.86mmol/L,
6.30mmol/L etc.) four hydration chlorauric acid solutions mixing.
Step 1.4,600 μ L 0.025-0.055mol/L (such as 0.03mol/L, 0.04mol/L, 0.05mol/ are separately added into
L etc.) ascorbic acid solution and 1mL by the golden core solution for being coated with molecule that is synthesized in step 1.2, Yu Chaosheng quickly shakes in pond
It swings, finally obtains the surface-enhanced Raman nano particle with core-shell structure of embedded Isosorbide-5-Nitrae-BDT molecule.Grain structure figure is as schemed
Shown in 2.
Step 2, steganography ink is prepared.
By the surface-enhanced Raman nanoparticle concentration of the embedded Isosorbide-5-Nitrae-BDT synthesized in step 1 to 4nM, take 200 μ L from
The heroic board fountain pen ink that 100 μ L dilute 10 times is added after sucking supernatant in the heart, and ultrasound mixes, and obtains Isosorbide-5-Nitrae-BDT ink.
Embodiment two: the steganography ink based on embedded 4-NBT Raman molecular
Step 1, the surface-enhanced Raman nano particle (embedded 4-NBT Raman molecular) of golden core-shell structure is prepared
Step 1.1, (particle diameter 25nm, is scattered in the golden core solution for taking 2mL 0.47nmol/L seed mediated growth method to synthesize
In the hexadecyltrimethylammonium chloride solution (CTAC) of 100mmol/L) centrifuge washing is primary, CTAC concentration is reduced to
20mmol/L is scattered in original volume.
Step 1.2, the 4-NBT solution of 100 μ L is slowly added in the pond Yu Chaosheng, solution concentration is generally higher than 8mmol/L, such as
9mmol/L, 10mmol/L, 11mmol/L etc. standing adsorption 5-20 minutes, are then centrifuged for washing repeatedly, are scattered in 1mL again
In the CTAC of 50mmol/L, the golden nuclear particle for being coated with 4-NBT is obtained.
Step 1.3, by the CTAC of 16mL 50mmol/L and 800 μ L 3-7mmol/L (such as 3.42mmol/L, 4.86mmol/
L, 6.30mmol/L etc.) four hydration chlorauric acid solutions mixing.
Step 1.4,480 μ L 0.025-0.055mol/L (such as 0.03mol/L, 0.04mol/L, 0.05mol/ are separately added into
L etc.) ascorbic acid solution and the golden core solution for being coated with molecule that is synthesized by step 1.2 of 960 μ L, Yu Chaosheng quickly shake in pond
It swings, finally obtains the surface-enhanced Raman nano particle with core-shell structure of embedded 4-NBT molecule.Grain structure figure such as Fig. 2
It is shown.
Step 2, steganography ink is prepared.
The surface-enhanced Raman nanoparticle concentration for the embedded 4-NBT that step 1 is synthesized takes 100 μ L to be centrifuged to 2.5nM,
The heroic board fountain pen ink that 200 μ L dilute 10 times is added after sucking supernatant, ultrasound mixes, and obtains 4-NBT ink.
Embodiment three: it using steganography ink written information and is read out, as shown in Figure 1.
Using the steganography ink based on embedded 4-NBT Raman molecular synthesized in embodiment two, is dipped with pen and existed in right amount
" dragon " is write on paper, as shown in the upper left Fig. 1.
Choose 6.25 × 6.5mm2Region is divided into 25 × 26 pixel, using Confocal laser-scanning microscopy 10 × camera lens of instrument
The spectrum of the information, excitation wavelength 785nm are tested, laser power density is 4.6 × 104W/cm2, acquisition time is 1 second, is obtained
To the Raman spectrum of each pixel, 4-NBT 1310-1365cm is chosen-1The integrated intensity of Raman peaks draws Raman image figure, such as
The lower-left Fig. 1.The Raman image and photograph via bright field of visible written information coincide fine.Three spectrum on the right of Fig. 1 respectively correspond
Three points in Raman image: 1 is the spectrum of paper, 2 and 3 are the spectrum of 4-NBT ink, it is seen that paper does information reading
It disturbs less.
Example IV: written information, the reading and extraction of row information of going forward side by side are mixed using steganography ink and ordinary ink.Such as
Shown in Fig. 3.
Using the steganography ink based on embedded Isosorbide-5-Nitrae-BDT Raman molecular synthesized in embodiment one, dipped in right amount with pen
Isosorbide-5-Nitrae-BDT ink writes " format " in " information " on paper, remaining letter is write by ordinary ink, such as the left side Fig. 3
Shown on.
Choose 24.4 × 6.8mm2Region is divided into 61 × 17 pixel, using Confocal laser-scanning microscopy 10 × camera lens of instrument
The spectrum of the information, excitation wavelength 785nm are tested, laser power density is 4.6 × 104W/cm2, acquisition time is 1 second, is obtained
To the Raman spectrum of each pixel, Isosorbide-5-Nitrae-BDT 1030-1090cm is chosen-1The integrated intensity of Raman peaks draws Raman image figure,
As Fig. 3 it is left shown in.As shown, the information only write with the steganography ink of the nano particle containing surface-enhanced Raman could be
It shows, has obtained and different information in light field in Raman image.Therefore real information is able to carry out with steganography ink
Hide.
5 Raman spectrums on the right side of Fig. 3 respectively correspond the upper left Fig. 3 and 5 left points: 1 is the spectrum of paper, and 2 and 4 are
The spectrum of ordinary ink, 3 and 5 be the weaker and stronger spectrum of Isosorbide-5-Nitrae-BDT ink signal respectively.Compare No. 5 spectrum and 2, No. 4 light
Spectrum is it is found that Isosorbide-5-Nitrae-BDT ink contains the characteristic peak of Raman molecular, obviously with ordinary ink difference.
Since paper is uneven, some places background is higher, leads to occur false positive signal in Raman image figure (such as
Point 4 in Fig. 3), therefore these signals are removed using Classical Least-Squares (CLS).
Pass through using the spectrum of paper, ordinary ink, Isosorbide-5-Nitrae-BDT ink and higher background signal as component, algorithm is referred to
Optimize the coefficient of different component to obtain optimal fitting spectrum.By paper, the signal of ordinary ink and higher these three components of background
It is indicated with dark color, the signal of Isosorbide-5-Nitrae-BDT ink is indicated with light color.The color of each pixel is by highest group of coefficient in image
The color divided determines.The imaging obtained after processing is as shown in the lower-left Fig. 3, it can be observed that false positive signal has removed, leaves behind
The signal of 1,4-BDT ink.
Embodiment five: mixing written information using different steganography inks and ordinary ink, the reading for row information of going forward side by side and
It extracts.As shown in Figure 4.
With pen dip appropriate embodiment two made from 4-NBT ink " aei " in " abcdefghi " is write on paper,
" bdfh " in the writing of Isosorbide-5-Nitrae-BDT ink made from appropriate embodiment one " abcdefghi " is dipped, alphabetical " cg " is by ordinary ink
It writes, sees the 1-1 of Fig. 4.
Choose 11.1 × 12.3mm2Region is divided into 37 × 41 pixel, using Confocal laser-scanning microscopy 10 × camera lens of instrument
The spectrum of the information, excitation wavelength 785nm are tested, laser power density is 4.6 × 104W/cm2, acquisition time is 1 second, is obtained
To the Raman spectrum of each pixel.
Different information combination in order to obtain, is imaged using different Raman peaks.
Choose 1310-1365cm-1The integrated intensity of Raman peaks draws Raman image figure, represents the information of 4-NBT ink, sees
The 2-1 of Fig. 4；
Since 1,4-BDT ink and 4-NBT ink are in 1030-1090cm-1There is the overlapping at peak, therefore only chooses 1030-
1070cm-1The integrated intensity of Raman peaks draws the information that Raman image represents Isosorbide-5-Nitrae-BDT ink, sees the 2-2 of Fig. 4, as seen from the figure
Information profile is unobvious；
Choose 1110-1165cm-1The integrated intensity of Raman peaks draws Raman image figure, represents the information of ordinary ink, sees
The 2-3 of Fig. 4, the surface-enhanced Raman nano particle due to embedding Isosorbide-5-Nitrae-BDT molecule enhance the signal of molecular ink simultaneously, therefore
Shown here is the information that 1,4-BDT ink is write；
Choose 1030-1090cm-1The integrated intensity of Raman peaks draws Raman image figure, represents Isosorbide-5-Nitrae-BDT ink and 4-NBT
The information of ink mixing, is shown in the 2-4 of Fig. 4；
Choose 1310-1365cm-1The integrated intensity of Raman peaks draws Raman image figure, adjusts threshold value, represents ordinary ink
With the information of 4-NBT ink mixing, the 2-5 of Fig. 4 is seen, due to embedding the surface-enhanced Raman nano particle pair of Isosorbide-5-Nitrae-BDT molecule
The enhancing of molecular ink, what is obtained is actually the information of Isosorbide-5-Nitrae-BDT ink and the mixing of 4-NBT ink；
Choose 1540-1600cm-1The integrated intensity of Raman peaks draws Raman image figure, represents the letter of three kinds of inks mixing
Breath, is shown in the 2-6 of Fig. 4, does not see the information of ordinary ink actually.
Based on the limitation being imaged in the above results with single Raman peaks, using the Classical Least-Squares based on spectral shape
(CLS) separate and extract information.Using the spectrum of paper, ordinary ink, 4-NBT ink and Isosorbide-5-Nitrae-BDT ink as refer to component,
Algorithm obtains optimal fitting spectrum by optimizing the coefficient of different component.The information for needing to show certain component, is just joined
It examines spectrum and is set as light color, remaining is set as dark color, and the color of each pixel is determined by the color of the highest component of coefficient in image.
3-1 is the written information of 4-NBT ink in Fig. 4, and 3-2 is the written information of Isosorbide-5-Nitrae-BDT ink, and 3-3 is common ink
The written information of water, 3-4 are the combination written informations of 4-NBT ink and Isosorbide-5-Nitrae-BDT ink, and 3-5 is 4-NBT ink and common ink
The combination written information of water, 3-5 are the combination written informations of Isosorbide-5-Nitrae-BDT ink and ordinary ink, and 3-7 is three kinds of combination of inks books
Write information.It can be seen that based on surface-enhanced Raman nano particle steganography ink combination algorithm can be realized information hide and
Combination.
Embodiment six: the long term stability tests of steganography ink.As shown in Figure 5.
Multiple Raman test is carried out to " dragon " write in embodiment three, timing node is respectively to write same day 1-1, one week
1-2, two weeks 1-3, a month 1-4, two months 1-5 and three months 1-6, test parameter are usually protected in the dark with embodiment three
It deposits.Choose 4-NBT 1310-1365cm-1The integrated intensity of Raman peaks draws corresponding Raman image figure and sees Fig. 5.As shown,
The Raman signal of steganography ink is weakened over time, but still maintains considerable signal after three months,
The profile that can clearly identify " dragon " illustrates that steganography ink prepared by the present invention has good long-time stability.
Embodiment seven: the sunshine stability test of steganography ink.As shown in Figure 6.
The 4-NBT ink prepared in appropriate embodiment two is dipped with pen and writes " sun " on paper, chooses 7.8 × 4mm2
Region is divided into 39 × 20 pixel, and the spectrum of the information, excitation wavelength are tested using Confocal laser-scanning microscopy 10 × camera lens of instrument
For 785nm, laser power density is 4.6 × 104W/cm2, acquisition time is 1 second, obtains the Raman spectrum of each pixel, chooses
4-NBT 1310-1365cm-1The integrated intensity of Raman peaks draws Raman image figure and sees Figure 61-1.
Then place it within continuous two days under 10 points of morning to 4 points of sunlight in afternoon and irradiate 6 hours, daily with it is above-mentioned
Identical parameters carry out Raman image to it.Imaging after first solarization is shown in that Fig. 6 1-2, the imaging after solarization in second day are shown in Fig. 6
1-3.As seen from the figure, the signal of steganography ink shined upon lower without significant change at continuous two days, illustrated its sunshine stability
Preferably.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that the ordinary skill of this field is without wound
The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be within the scope of protection determined by the claims.
Claims (10)
1. a kind of steganography material based on surface-enhanced Raman nano particle, which is characterized in that be added in the steganography material
Surface-enhanced Raman nano particle.
2. as described in claim 1 based on the steganography material of surface-enhanced Raman nano particle, which is characterized in that the surface
Enhancing Raman nano particle is made of metal nano substrate and Characteristic Raman molecule.
3. as claimed in claim 2 based on the steganography material of surface-enhanced Raman nano particle, which is characterized in that the metal
The structure of nanometer substrate includes nano core-shell grain structure, nano flower, nanometer triangular plate, nanosphere, nanometer rods, nanometer star, receives
Rice dendrite and nano particle dimer.
4. as claimed in claim 2 based on the steganography material of surface-enhanced Raman nano particle, which is characterized in that the feature
Raman molecular includes to thioresorcin (1,4-BDT), 4- nitrobenzenethiol (4-NBT), ortho-nitrophenyl thiophenol (2-NBT), 2- mercapto
Base -5- nitrobenzimidazole (2-M-5-NBI), 2- sulfydryl -6- nitrobenzene thiazole (2-M-6-NBT), two sulphur of biphenyl -4,4'-
Alcohol (4,4'-BPDT), 4- thiocresol (4-MBT), adjacent chlorothio-phenol (2-CBT), 4- chlorothio-phenol (4-CBT) and 2- naphthyl mercaptan
(2-NT)。
5. as described in claim 1 based on the steganography material of surface-enhanced Raman nano particle, which is characterized in that the steganography
Material includes steganography ink, steganography ink, steganography ink powder, steganography pigment or steganography coating.
6. a kind of steganography method using the steganography material based on surface-enhanced Raman nano particle as described in claim 1,
It is characterized in that, comprising the following steps:
Step 1, Party A use one or more kinds of the steganography materials and common material based on surface-enhanced Raman nano particle
Material records information respectively, is encrypted；
Cipher mode and combination are passed to Party B by step 2, the Party A；
Step 3, the Party A pass to the Party B for information is recorded；
Step 4, the Party B are scanned using Raman spectrometer or imaging reading is one or more kinds of described based on surface enhanced drawing
The steganography material of graceful nano particle and the Raman spectral information of the common material；
Step 5, the Party B pass through the coefficient of optimization different component using special algorithm to the Raman spectral information of acquisition
To obtain optimal fitting spectrum；
Step 6, the Party B are combined the optimal fitting spectrum according to the cipher mode and combination, decryption
Obtain hiding information.
7. steganography method as claimed in claim 6, which is characterized in that the common material in the step 1 and the step 4
Material includes ordinary ink, common ink, common ink powder, common pigments or common coating.
8. steganography method as claimed in claim 6, which is characterized in that the special algorithm used in the step 5 includes
Classical Least-Squares；It using the scanning mode of Raman spectrometer imaging process include that sample stage is mobile, laser in the step 4
Hot spot is mobile and both moves；The shape of laser facula in the scanning mode includes point hot spot, linear light spot and face hot spot；
The Raman spectrometer imaging process uses 10 × camera lens of Confocal laser-scanning microscopy instrument, and laser excitation wavelength 785nm is described to swash
Optical power density is 4.6 × 104W/cm2, acquisition time is 1 second.
9. steganography method as claimed in claim 6, which is characterized in that the mode of information-recording described in the step 1 includes
Hand-written, printing, coating and printing.
10. as described in claim 1 based on the steganography material of surface-enhanced Raman nano particle in information security field
Using.
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| CN111311700A (en) * | 2020-01-20 | 2020-06-19 | 首都师范大学 | Method for correcting error of information encryption read-write by using nanotechnology |
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