CN107219194B - The preparation method and application for having the compound polyelectrolyte of the patterning micro nano structure of response - Google Patents
The preparation method and application for having the compound polyelectrolyte of the patterning micro nano structure of response Download PDFInfo
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- CN107219194B CN107219194B CN201710306274.7A CN201710306274A CN107219194B CN 107219194 B CN107219194 B CN 107219194B CN 201710306274 A CN201710306274 A CN 201710306274A CN 107219194 B CN107219194 B CN 107219194B
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Abstract
Has the preparation method and application of the compound polyelectrolyte of the patterning micro nano structure of response, it is related to a kind of preparation method and application of compound polyelectrolyte.The invention aims to solve the problem of that the expensive compound sensor of existing humidity sensor can not achieve industrialized production and compound sensor without relative humidity, acidity and other Testing index.Preparation method: one, patterned PDMS seal is prepared；Two, the preparation of compound polyelectrolyte；Three, it presses, keep the temperature, transfer, obtaining the compound polyelectrolyte for the patterning micro nano structure for having response.Have scattering medium application of the compound polyelectrolyte of the patterning micro nano structure of response as intelligence super perspective material, response, is detected for life food quality, for humidity sensor, be used for humidity sensor.The present invention can get the compound polyelectrolyte for having the patterning micro nano structure of response.
Description
Technical field
The present invention relates to a kind of preparation method and applications of compound polyelectrolyte.
Background technique
With the development either scientific research or industrial production of modernization, be difficult to find out one it is unrelated with humidity sensor
Field come.In real life, cell culture also or food and battery production be required to control humidity lower than 70-80% with
Prevent the growth of mushroom microorganism from polluting, relative air humidity appropriate can increase life comfort and promote health,
And relative air humidity is too low will cause chapped skin and itch phenomenon.Measurement and control despite degree is especially heavy to the mankind
Want, up to the present fast response time, the hygrometer that small in size, the linearity is good, more stable mainly from the U.S. Honeywell
(Honeywell Inc.) and price price are expensive.And the Jenner based on electron tunneling effect and test resistance value of latest report
The organic crosslinking compound sensor of rice grain-can not achieve industrialized production always.In May, 2015 France and Germany in succession put into effect method
Case forbids food waste, forbids supermarket to abandon as first in the world or destroys the French relevant law for the food that do not sell
Through clear stipulaties: if food fails to sell, supermarket has to food is donated to charity organization or food bank, allows Xiang Guanji
Structure is sent to food on poor manpower.As long as supermarket's area has been more than 400 square metres, boss is had to and these mechanism label
It concludes an agreement, otherwise can face the fine of 3750 Euros (2.79 ten thousand RMB).It will not be to human health so how to detect food
Threaten again ensure food do not waste, mutually cope with supermarket in food (potato chips, meat, vegetables etc.) Testing index such as: phase
To humidity, the sensor of acidity or other indexs will possess huge market prospects.
Summary of the invention
Expensive the invention aims to solve existing humidity sensor, compound sensor can not achieve industrial metaplasia
It produces and the problem of compound sensor without relative humidity, acidity and other Testing index, and provides and have response
Pattern the preparation method and application of the compound polyelectrolyte of micro nano structure.
Has the preparation method of the compound polyelectrolyte of the patterning micro nano structure of response, specifically by following
What step was completed:
One, patterned PDMS seal is prepared:
The prepolymer A of dimethyl silicone polymer and curing agent B are mixed, first low whipping speed be 200r/min~
Under 500r/min stir 5min~8min, then centrifugal speed be 3000r/min~4000r/min under be centrifuged 5min~
8min obtains mixed solution；Mixed solution is poured in the culture dish equipped with patterned silicon substrate, then by culture dish in temperature
Degree is vacuum solidification 1h~3h at 60 DEG C~80 DEG C, obtains patterned PDMS seal on a silicon substrate；The PDMS that will be patterned into
Seal is removed from silicon substrate, obtains patterned PDMS seal；
The mass ratio of the prepolymer A and curing agent B of dimethyl silicone polymer described in step 1 are 10:1；
Two, the preparation of compound polyelectrolyte:
It by polyelectrolyte electronics to being added in container, then is 70 DEG C~80 DEG C in temperature and mixing speed is 300r/min
Magnetic agitation 15min~25min under~800r/min, obtains the compound polyelectrolyte of flocculent structure in the solution；
Mixed liquor of the polyelectrolyte electronics described in step 2 to mixed liquor or PAA/PAH for PSS/PDDA；It is described
PSS/PDDA mixed liquor be kayexalate sodium chloride solution and polyacrylate sodium chloride solution according to body
Product is mixed than 1:1；The mixed liquor of the PAA/PAH is the sodium chloride solution of polyacrylic acid and the sodium chloride of polycyclic aromatic hydrocarbon
Solution is mixed according to volume ratio 1:1；
Three, the compound polyelectrolyte of flocculent structure is taken out from solution, then the polyelectrolyte of flocculent structure is compound
Object covers on the patterned PDMS seal obtained in step 1, then to the figure for the compound polyelectrolyte for being covered with flocculent structure
Apply 20kPa~130kPa on the PDMS seal of case, then in the case where temperature is 60 DEG C~75 DEG C and pressure is 20kPa~130kPa
Pressure maintaining 5min~15min, then transferred, transfer time are 5min~15min, then by compound polyelectrolyte with it is patterned
The separation of PDMS seal obtains the compound polyelectrolyte for the patterning micro nano structure for having response；
Thermal transfer is transferred as described in step 3, transfer temperature is 60 DEG C~100 DEG C；
Have described in step 3 response patterning micro nano structure compound polyelectrolyte with a thickness of
0.1 μm~30 μm.
The compound polyelectrolyte for having the patterning micro nano structure of response is based on optical diffraction effect for judging
Irritability reaction to external environment.
The compound polyelectrolyte for having the patterning micro nano structure of response is answered as the super perspective material of intelligence
With.
The compound polyelectrolyte for having the patterning micro nano structure of response is applied in super resolution technologies.
Have scattering medium of the compound polyelectrolyte of the patterning micro nano structure of response as response
Using.
The compound polyelectrolyte for having the patterning micro nano structure of response is based on reaction color under stressed condition
And the change of scattering is detected for life food quality.
The compound polyelectrolyte for having the patterning micro nano structure of response, which is based on microbial degradation, to be tied
The principle that structure changes can be used in optical sensor, can be used for humidity sensor based on the principle that irritability response occurs to humidity
In, it can be used in acidity-basicity sensor based on the principle that irritability response occurs to pH value.
Advantages of the present invention:
One, the compound polyelectrolyte of the patterning micro nano structure prepared by the present invention for having response has to wet
It is high can to efficiently solve existing humidity sensor price for degree, pH and the reaction highly sensitive to other organic chemicals
Expensive, compound sensor can not achieve industrialized production and the composite sensing without relative humidity, acidity and other Testing index
The problem of device.The compound polyelectrolyte of the patterning micro nano structure prepared by the present invention for having response to containing on the market
There is the food of polyelectrolyte food additives, accurate fast and low-cost detection can be carried out；In addition, for lower relative humidity
Also very sensitive, relative humidity can be down to 20%, can be by visually seeing this hair when relative humidity is 20%~100%
The variation of the compound polyelectrolyte color of the patterning micro nano structure for having response of bright preparation comes, and learns opposite
The change of humidity, this is that many hygrometers on the market can not be accomplished；
Two, it is prepared by the present invention have response patterning micro nano structure compound polyelectrolyte for pH,
Temperature or hydrophobic chemical ingredient are very sensitive, are more advantageous to and are used widely as sensor.Even in aqueous solution,
Ionic strength in polyelectrolyte (Polyelectrolyte) can be obtained by calculating.Due to tool prepared by the present invention
The compound polyelectrolyte of the patterning micro nano structure of standby response has biodegradability, therefore can detecte out bacterium
Growth or food deterioration itself；
Three, whether the present invention effectively detects the preservation condition of food for convenience and still can be made safely by people
With we are compound by the polyelectrolyte that microcontact printing techniques are prepared for having the patterning micro nano structure of response
Object.It possesses many phenomenons such as Meta Materials, can sensitively make a response to humidity, temperature, pH value and ionic strength and
Change structure, then by laser or natural light irradiation, the pattern for having response of variation structure is read by spectrum
Change the compound polyelectrolyte of micro nano structure instantly under the effect of external stressed condition reflected value or absorption value judge
The fine or not degree of food.
The present invention can get the compound polyelectrolyte for having the patterning micro nano structure of response.
Detailed description of the invention
Fig. 1 is the work of the compound polyelectrolyte of the patterning micro nano structure for having response prepared by embodiment one
Skill flow chart, in Fig. 11 be flocculent structure compound polyelectrolyte, 2 be patterned PDMS seal, and 3 be patterned PDMS
The square of array on seal, 4 be transfer pressure, heat preservation, and 5 are for the height of the square of array on patterned PDMS seal
10 μm, 6 for the width of the square of array on patterned PDMS seal be 10 μm, and 7 be that polyelectrolyte after transferring is compound
Object, 8 separate for compound polyelectrolyte with patterned PDMS seal, and 9 be the patterning micro nano structure for having response
Compound polyelectrolyte；
Fig. 2 is that the laser pen of two kinds of different wave lengths in embodiment one has response through what is prepared in embodiment one
The schematic device scattered after the compound polyelectrolyte of micro nano structure is patterned, 1 is red green laser in Fig. 2
Pen, 2 compound polyelectrolyte for patterning micro nano structure for having response to prepare in embodiment one, 3 be white
Screen；
Fig. 3 is the SEM figure of patterned PDMS seal obtained in one step 1 of embodiment；
Fig. 4 is that the polyelectrolyte for having the patterning micro nano structure of response obtained in one step 3 of embodiment is answered
Close the SEM figure of object；
Fig. 5 is green laser pen through the scatter diagram that patterned PDMS seal generates obtained in one step 1 of embodiment
Piece；
Fig. 6 is the surface texture for the true PDMS for obtaining Fig. 4 progress Fourier transform；
Fig. 7 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared in embodiment one is put
Set the picture that green laser irradiating sample scatters under 35% damp condition；
Fig. 8 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared in embodiment one is put
Set the picture that green laser irradiating sample scatters under 100% damp condition；
Fig. 9 is the compound polyelectrolyte for the patterning micro nano structure for having response being calculated by Fig. 7
Characteristic size 1/Q curve, 1 is that the compound polyelectrolyte for having the patterning micro nano structure of response is placed in Fig. 9
Characteristic size 1/Q curve under 35% damp condition, 2 be the poly- electrolysis for having the patterning micro nano structure of response
Matter compound is placed on the characteristic size 1/Q curve under 100% damp condition；
Figure 10 is the enlarged drawing at the place A in Fig. 9, and 1 is the poly- electricity for patterning micro nano structure for having response in Figure 10
Solution matter compound is placed on the characteristic size 1/Q curve under 35% damp condition, and 2 be the patterning micro-nano for having response
The compound polyelectrolyte of rice structure is placed on the characteristic size 1/Q curve under 100% damp condition；
Figure 11 is the compound polyelectrolyte for the patterning micro nano structure for having response being calculated by Fig. 7
Q value curve, 1 is that the compound polyelectrolyte for having the patterning micro nano structure of response is placed on 35% in Figure 11
Q value curve under damp condition, 2 be that the compound polyelectrolyte for having the patterning micro nano structure of response is placed on
Q value curve under 100% damp condition；
Figure 12 is the polyelectrolyte by heating the patterning micro nano structure for having response for be crosslinked preparation
The laser confocal scanning microscope picture in the channel FITC of compound；
Figure 13 is the polyelectrolyte by heating the patterning micro nano structure for having response for be crosslinked preparation
The laser confocal scanning microscope picture in RITC channel of the compound under 100% damp condition after 30min；
Figure 14 is the polyelectrolyte by heating the patterning micro nano structure for having response for be crosslinked preparation
The laser confocal scanning microscope picture in the channel RITC of compound；
Figure 15 is the poly- electrolysis for not carrying out the patterning micro nano structure for having response for being crosslinked preparation by heating
The laser confocal scanning microscope picture of matter compound light field after 30min under 100% damp condition；
Figure 16 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared by embodiment one is put
Set the picture that green laser irradiating sample scatters under 35% damp condition；
Figure 17 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared by embodiment one is put
Set the picture that green laser irradiating sample scatters under 100% damp condition；
Figure 18 is that the polyelectrolyte for the patterning micro nano structure for having response being calculated by Figure 16 is compound
The characteristic size 1/Q curve of object, in Figure 16 1 for the patterning micro nano structure for having response of embodiment one poly- electrolysis
Matter compound is placed on the characteristic size 1/Q curve under 35% damp condition, and 2 have response for prepared by embodiment one
The compound polyelectrolyte of patterning micro nano structure be placed on the characteristic size 1/Q curve under 100% damp condition；
Figure 19 is the enlarged drawing at the place A in Figure 18, in Figure 19 1 be embodiment one the patterning for having response it is micro-nano
The compound polyelectrolyte of structure is placed on the characteristic size 1/Q curve under 35% damp condition, and 2 be the preparation of embodiment one
The compound polyelectrolyte for having the patterning micro nano structure of response is placed on feature ruler under 100% damp condition
Very little 1/Q curve；
Figure 20 is the patterning micro nano structure for having response prepared by the embodiment one being calculated by Figure 17
Compound polyelectrolyte Q value curve, the 1 micro-nano knot of patterning for having response prepared for embodiment one in Figure 20
The compound polyelectrolyte of structure is placed on the Q value curve under 35% damp condition, and 2 have and stress ring for prepared by embodiment one
The compound polyelectrolyte for the patterning micro nano structure answered is placed on the Q value curve under 100% damp condition；
Figure 21 is that the polyelectrolyte of the obtained patterning micro nano structure for having response prepared by embodiment three is multiple
Close the ordinary optical microscope picture of object；
Figure 22 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared by embodiment three is put
Set the ordinary optical microscope figure under 100% damp condition after 15min clock；
Figure 23 carries out the comparison diagram that light dissipates measurement for compound polyelectrolyte, and 1 is to obtain in one step 3 of embodiment in Figure 23
The ultraviolet-visible absorption spectroscopy of the patterned film of the compound polyelectrolyte arrived, 2 be smooth compound polyelectrolyte film
Ultraviolet-visible absorption spectroscopy.
Specific embodiment
Specific embodiment 1: present embodiment is that the polyelectrolyte for having the patterning micro nano structure of response is answered
The preparation method for closing object, is specifically realized by the following steps:
One, patterned PDMS seal is prepared:
The prepolymer A of dimethyl silicone polymer and curing agent B are mixed, first low whipping speed be 200r/min~
Under 500r/min stir 5min~8min, then centrifugal speed be 3000r/min~4000r/min under be centrifuged 5min~
8min obtains mixed solution；Mixed solution is poured in the culture dish equipped with patterned silicon substrate, then by culture dish in temperature
Degree is vacuum solidification 1h~3h at 60 DEG C~80 DEG C, obtains patterned PDMS seal on a silicon substrate；The PDMS that will be patterned into
Seal is removed from silicon substrate, obtains patterned PDMS seal；
The mass ratio of the prepolymer A and curing agent B of dimethyl silicone polymer described in step 1 are 10:1；
Two, the preparation of compound polyelectrolyte:
It by polyelectrolyte electronics to being added in container, then is 70 DEG C~80 DEG C in temperature and mixing speed is 300r/min
Magnetic agitation 15min~25min under~800r/min, obtains the compound polyelectrolyte of flocculent structure in the solution；
Mixed liquor of the polyelectrolyte electronics described in step 2 to mixed liquor or PAA/PAH for PSS/PDDA；It is described
PSS/PDDA mixed liquor be kayexalate sodium chloride solution and polyacrylate sodium chloride solution according to body
Product is mixed than 1:1；The mixed liquor of the PAA/PAH is the sodium chloride solution of polyacrylic acid and the sodium chloride of polycyclic aromatic hydrocarbon
Solution is mixed according to volume ratio 1:1；
Three, the compound polyelectrolyte of flocculent structure is taken out from solution, then the polyelectrolyte of flocculent structure is compound
Object covers on the patterned PDMS seal obtained in step 1, then to the figure for the compound polyelectrolyte for being covered with flocculent structure
Apply 20kPa~130kPa on the PDMS seal of case, then in the case where temperature is 60 DEG C~75 DEG C and pressure is 20kPa~130kPa
Pressure maintaining 5min~15min, then transferred, transfer time are 5min~15min, then by compound polyelectrolyte with it is patterned
The separation of PDMS seal obtains the compound polyelectrolyte for the patterning micro nano structure for having response；
Thermal transfer is transferred as described in step 3, transfer temperature is 60 DEG C~100 DEG C；
Have described in step 3 response patterning micro nano structure compound polyelectrolyte with a thickness of
0.1 μm~30 μm.
Prepolymer A and curing agent the B purchase of dimethyl silicone polymer described in present embodiment are (beautiful from Dow Corning Corporation
State), model Poly (dimethylsiloxane) PDMS kit (Sylgard 184).
The advantages of present embodiment:
One, the compound polyelectrolyte of the patterning micro nano structure for having response of present embodiment preparation has
To humidity, pH and the reaction highly sensitive to other organic chemicals, existing humidity sensor valence can be efficiently solved
Lattice are expensive, and compound sensor can not achieve industrialized production and without the compound of relative humidity, acidity and other Testing index
The problem of sensor.The compound polyelectrolyte pair of the patterning micro nano structure for having response of present embodiment preparation
Food on the market containing polyelectrolyte food additives can carry out accurate fast and low-cost detection；In addition, for lower
Relative humidity is also very sensitive, and relative humidity, when relative humidity is 20%~100%, can pass through naked eyes down to 20%
See that the variation of the compound polyelectrolyte color of the patterning micro nano structure prepared by the present invention for having response comes, and
Learn the change of relative humidity, this is that many hygrometers on the market can not be accomplished；
Two, present embodiment preparation have response patterning micro nano structure compound polyelectrolyte for
PH, temperature or hydrophobic chemical ingredient are very sensitive, are more advantageous to and are used widely as sensor.Even in aqueous solution
In, the ionic strength in polyelectrolyte (Polyelectrolyte) can be obtained by calculating.Due to present embodiment system
The compound polyelectrolyte of the standby patterning micro nano structure for having response has biodegradability, therefore can detecte
The growth of bacterium or food deterioration itself out；
Three, whether present embodiment effectively detects the preservation condition of food for convenience and still can be pacified by people
It entirely uses, we are multiple by the polyelectrolyte that microcontact printing techniques are prepared for having the patterning micro nano structure of response
Close object.It possesses many phenomenons such as Meta Materials, can sensitively make a response to humidity, temperature, pH value and ionic strength
And change structure, then by laser or natural light irradiation, the figure for having response of variation structure is read by spectrum
The compound polyelectrolyte of case micro nano structure instantly under the effect of external stressed condition reflected value or absorption value sentence
The fine or not degree of jejunitas object.
Present embodiment can get the compound polyelectrolyte for having the patterning micro nano structure of response.
Specific embodiment 2: the difference of present embodiment and specific embodiment one is: figure described in step 1
The PDMS seal of case is the square that the side length of array is 10 μm.Other are same as the specific embodiment one.
Specific embodiment 3: the difference of present embodiment and specific embodiment one or two is: described in step 2
Kayexalate sodium chloride solution be kayexalate, sodium chloride and distilled water mixed liquor, polystyrene
The concentration of kayexalate is 2mg/mL in the sodium chloride solution of sodium sulfonate, and the concentration of sodium chloride is 2mol/L；Described
The sodium chloride solution of polyacrylate is the mixed liquor of polyacrylate, sodium chloride and distilled water, the sodium chloride of polyacrylate
The concentration of polyacrylate is 2mg/mL in solution, and the concentration of sodium chloride is 2mol/L.Other and specific embodiment one or two
It is identical.
Specific embodiment 4: the difference of present embodiment and specific embodiment one to three is: described in step 2
Polyacrylic acid sodium chloride solution be polyacrylic acid, sodium chloride and distilled water mixed liquor, the sodium chloride solution of polyacrylic acid
The concentration of middle polyacrylic acid is 2mg/mL, and the concentration of sodium chloride is 2mol/L；The sodium chloride solution of the polycyclic aromatic hydrocarbon is more
The mixed liquor of cycloaromatics, sodium chloride and distilled water, polycyclic aromatic hydrocarbon concentration is 2mg/mL, chlorination in the sodium chloride solution of polycyclic aromatic hydrocarbon
The concentration of sodium is 2mol/L.Other are identical as specific embodiment one to three.
Specific embodiment 5: present embodiment is that the polyelectrolyte for having the patterning micro nano structure of response is answered
It closes object and is used to judge to react the irritability of external environment based on optical diffraction effect.
Specific embodiment 6: present embodiment is that the polyelectrolyte for having the patterning micro nano structure of response is answered
Object is closed as the super perspective material application of intelligence.
Specific embodiment 7: present embodiment is that the polyelectrolyte for having the patterning micro nano structure of response is answered
Object is closed to be applied in super resolution technologies.
Specific embodiment 8: present embodiment is that the polyelectrolyte for having the patterning micro nano structure of response is answered
Close scattering medium application of the object as response.
Specific embodiment 9: present embodiment is that the polyelectrolyte for having the patterning micro nano structure of response is answered
Change of the object based on reaction color under stressed condition and scattering is closed to detect for life food quality.
Specific embodiment 10: present embodiment is that the polyelectrolyte for having the patterning micro nano structure of response is answered
Close object based on microbial degradation can recurring structure change principle can be used in optical sensor, based on to humidity occur irritability
The principle of response can be used in humidity sensor, can be used for pH value sensing based on the principle that irritability response occurs to pH value
In device.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: have the preparation method of the compound polyelectrolyte of the patterning micro nano structure of response, tool
Body is completed by the following steps:
One, patterned PDMS seal is prepared:
The prepolymer A of dimethyl silicone polymer and curing agent B is mixed, low whipping speed is to stir under 300r/min first
Then 5min is centrifuged 5min in the case where centrifugal speed is 3000r/min, obtains mixed solution；Mixed solution is poured over equipped with figure
In the culture dish of the silicon substrate of case, then by culture dish temperature be 70 DEG C at vacuum solidification 2h, obtain pattern on a silicon substrate
The PDMS seal of change；The PDMS seal that will be patterned into is removed from silicon substrate, obtains patterned PDMS seal；
The mass ratio of the prepolymer A and curing agent B of dimethyl silicone polymer described in step 1 are 10:1；
Patterned PDMS seal described in step 1 is the square that the side length of array is 10 μm；
Two, the preparation of compound polyelectrolyte:
By polyelectrolyte electronics to being added in container, then the magnetic force in the case where temperature is 75 DEG C and mixing speed is 500r/min
20min is stirred, obtains the compound polyelectrolyte of flocculent structure in the solution；
Polyelectrolyte electronics is to the mixed liquor for PAA/PAH described in step 2；The mixed liquor of the PAA/PAH is
The sodium chloride solution of polyacrylic acid and the sodium chloride solution of polycyclic aromatic hydrocarbon are mixed according to volume ratio 1:1；The polypropylene
The sodium chloride solution of acid is the mixed liquor of polyacrylic acid, sodium chloride and distilled water, polypropylene in the sodium chloride solution of polyacrylic acid
The concentration of acid is 2mg/mL, and the concentration of sodium chloride is 2mol/L；The sodium chloride solution of the polycyclic aromatic hydrocarbon is polycyclic aromatic hydrocarbon, chlorine
Change the mixed liquor of sodium and distilled water, polycyclic aromatic hydrocarbon concentration is 2mg/mL, the concentration of sodium chloride in the sodium chloride solution of polycyclic aromatic hydrocarbon
For 2mol/L；
Three, the compound polyelectrolyte of flocculent structure is taken out from solution, then the polyelectrolyte of flocculent structure is compound
Object covers on the patterned PDMS seal obtained in step 1, then to the figure for the compound polyelectrolyte for being covered with flocculent structure
Apply 75kPa, then the pressure maintaining 10min in the case where temperature is 60 DEG C and pressure is 75kPa on the PDMS seal of case, then transferred,
Transfer time is 10min, then compound polyelectrolyte is separated with patterned PDMS seal, obtains the figure for having response
The compound polyelectrolyte of case micro nano structure；
Thermal transfer is transferred as described in step 3, transfer temperature is 60 DEG C；
Have described in step 3 response patterning micro nano structure compound polyelectrolyte with a thickness of
10μm。
Prepolymer A and curing agent the B purchase of the dimethyl silicone polymer described in step 1 of embodiment one are public from DOW CORNING
It takes charge of in (U.S.), model Poly (dimethylsiloxane) PDMS kit (Sylgard 184).
Embodiment two: the present embodiment and the difference of embodiment one are: being transferred as thermal transfer described in step 3, transfer
Temperature is 100 DEG C.Other steps are the same as example 1 with parameter.
Embodiment three: the present embodiment and the difference of embodiment one are: polyelectrolyte electronics described in step 2 to for
The mixed liquor of PSS/PDDA；The mixed liquor of the PSS/PDDA is the sodium chloride solution and polyacrylic acid of kayexalate
The sodium chloride solution of ester is mixed according to volume ratio 1:1；The sodium chloride solution of the kayexalate is polyphenyl second
The mixed liquor of alkene sodium sulfonate, sodium chloride and distilled water, kayexalate in the sodium chloride solution of kayexalate
Concentration is 2mg/mL, and the concentration of sodium chloride is 2mol/L；The sodium chloride solution of the polyacrylate is polyacrylate, chlorine
Change the mixed liquor of sodium and distilled water, the concentration of polyacrylate is 2mg/mL, sodium chloride in the sodium chloride solution of polyacrylate
Concentration be 2mol/L.Other steps are the same as example 1 with parameter.
Fig. 1 is the work of the compound polyelectrolyte of the patterning micro nano structure for having response prepared by embodiment one
Skill flow chart, in Fig. 11 be flocculent structure compound polyelectrolyte, 2 be patterned PDMS seal, and 3 be patterned PDMS
The square of array on seal, 4 be transfer pressure, heat preservation, and 5 are for the height of the square of array on patterned PDMS seal
10 μm, 6 for the width of the square of array on patterned PDMS seal be 10 μm, and 7 be that polyelectrolyte after transferring is compound
Object, 8 separate for compound polyelectrolyte with patterned PDMS seal, and 9 be the patterning micro nano structure for having response
Compound polyelectrolyte.
Electron microscope picture involved in the present invention by electron microscope (model: Quanta 3D ESEM,
Hillsboro, the U.S.) test；Optical photograph is by Red Green laser pen (wavelength is respectively 523,650nm, Britain)
Test；
With red green laser, (wavelength of the laser pen with dual wavelength, feux rouges is 650nm, and the wavelength of green light is respectively
532nm) tool irradiate the patterning micro nano structure of standby response compound polyelectrolyte (fixed sample apart from laser pen with
And the distance of sample distance scattering picture white screen), utilize trigonometric function (formula 1) calculating corresponding after obtaining scattering picture
Scattering angle numerical value.
Q indicates 1/nm, and λ value is the wavelength of laser, and θ is sample illuminated laser spot and scattering center line and illuminated laser spot
Angle between pattern scattering point line.As shown in Figure 2.
Fig. 2 is that the laser pen of two kinds of different wave lengths in embodiment one has response through what is prepared in embodiment one
The schematic device scattered after the compound polyelectrolyte of micro nano structure is patterned, 1 is red green laser in Fig. 2
Pen, 2 compound polyelectrolyte for patterning micro nano structure for having response to prepare in embodiment one, 3 be white
Screen；
Fig. 3 is the SEM figure of patterned PDMS seal obtained in one step 1 of embodiment；
As can be seen from Figure 3, use PDMS casting method that can replicate the pattern of silicon substrate with negative sense, from the The Small Well figure of micron level
Case obtains the small raised design of identical size array.
Fig. 4 is that the polyelectrolyte for having the patterning micro nano structure of response obtained in one step 3 of embodiment is answered
Close the SEM figure of object；
As can be seen from Figure 4, array patterning compound polyelectrolyte film, shape can be prepared by micro-contact-printing
It is regular.
Patterned PDMS seal obtained in laser pen irradiation one step 1 of embodiment with green, the scatter diagram of generation
Piece, as shown in Figure 5；
Fig. 5 is green laser pen through the scatter diagram that patterned PDMS seal generates obtained in one step 1 of embodiment
Piece；
Laser beam has dispersion effect by patterned PDMS seal as can be seen from Figure 5.
The surface texture for the PDMS seal that Fig. 5 progress Fourier transform is obtained, as shown in Figure 6；
Fig. 6 is the surface texture for the true PDMS for obtaining Fig. 4 progress Fourier transform；
As can be seen from Figure 6, patterned PDMS seal obtained in one step 1 of embodiment is that array-like micro/nano level is other
Square protrusion.
The compound polyelectrolyte for patterning micro nano structure for having response that we will prepare in embodiment one
It is placed under the different wave length test environment of laser pen, different air humiditys compares, as shown in Figure 7 and Figure 8；
Fig. 7 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared in embodiment one is put
Set the picture that green laser irradiating sample scatters under 35% damp condition；
Fig. 8 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared in embodiment one is put
Set the picture that green laser irradiating sample scatters under 100% damp condition；
From Fig. 7 and Fig. 8 it is found that under different relative humidity conditions, patterned compound polyelectrolyte film is to passing through
The scattering pattern of green laser be different.
Fig. 9 is the compound polyelectrolyte for the patterning micro nano structure for having response being calculated by Fig. 7
Characteristic size 1/Q curve, 1 is that the compound polyelectrolyte for having the patterning micro nano structure of response is placed in Fig. 9
Characteristic size 1/Q curve under 35% damp condition, 2 be the poly- electrolysis for having the patterning micro nano structure of response
Matter compound is placed on the characteristic size 1/Q curve under 100% damp condition；
Laser scattering intensity and characteristic pattern are by the relationship between size as can be seen from Figure 9.
Figure 10 is the enlarged drawing at the place A in Fig. 9, and 1 is the poly- electricity for patterning micro nano structure for having response in Figure 10
Solution matter compound is placed on the characteristic size 1/Q curve under 35% damp condition, and 2 be the patterning micro-nano for having response
The compound polyelectrolyte of rice structure is placed on the characteristic size 1/Q curve under 100% damp condition；
As can be seen from Figure 10, the patterning compound polyelectrolyte characteristic pattern of preparation is pressed having a size of 10 microns.
Figure 11 is the compound polyelectrolyte for the patterning micro nano structure for having response being calculated by Fig. 7
Q value curve, 1 is that the compound polyelectrolyte for having the patterning micro nano structure of response is placed on 35% in Figure 11
Q value curve under damp condition, 2 be that the compound polyelectrolyte for having the patterning micro nano structure of response is placed on
Q value curve under 100% damp condition；
As can be seen from Figure 11, identical patterning compound polyelectrolyte in different humidity, deposit by the Q value being calculated
In significant difference.
Transfer temperature is 100 DEG C in embodiment two, i.e., by heat cross-linking, is carried out to prepared by embodiment two by heating
The compound polyelectrolyte for being crosslinked the patterning micro nano structure for having response of preparation is tested, such as the institute of Figure 12~15
Show；
Figure 12 is the polyelectrolyte by heating the patterning micro nano structure for having response for be crosslinked preparation
The laser confocal scanning microscope picture in the channel FITC of compound；
As can be seen from Figure 12, compound polyelectrolyte (PAA/PAH) passes through the PEC shape that after heat cross-linking, is fluorescently labeled
It is regular.
Figure 13 is the polyelectrolyte by heating the patterning micro nano structure for having response for be crosslinked preparation
The laser confocal scanning microscope picture in RITC channel of the compound under 100% damp condition after 30min；
As can be seen from Figure 13, patterned compound polyelectrolyte film, after heat cross-linking, even if it is opposite to improve environment
Humidity, the patterning that can still keep relative stability.
Figure 14 is the polyelectrolyte by heating the patterning micro nano structure for having response for be crosslinked preparation
The laser confocal scanning microscope picture in the channel RITC of compound；
As can be seen from Figure 14, the compound polyelectrolyte pattern of preparation is regular.
Figure 15 is the poly- electrolysis for not carrying out the patterning micro nano structure for having response for being crosslinked preparation by heating
The laser confocal scanning microscope picture of matter compound light field after 30min under 100% damp condition；
From figure 15, it can be known that not passing through the patterning compound polyelectrolyte film of heat cross-linking, envionmental humidity is being improved
Under conditions of, it is more difficult to maintain the integrality of pattern.
Figure 16 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared by embodiment one is put
Set the picture that green laser irradiating sample scatters under 35% damp condition；
As can be seen from Figure 16, under conditions of relative humidity is 35%, available more complete laser light scattering picture.
Figure 17 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared by embodiment one is put
Set the picture that green laser irradiating sample scatters under 100% damp condition；
As can be seen from Figure 17, under conditions of being 35% compared to relative humidity, 100% relative humidity can destroy micrometer structure
Pattern, so as to by laser light scattering pattern, showing envionmental humidity at that time, i.e. performance response material
Effect.
Figure 18 is that the polyelectrolyte for the patterning micro nano structure for having response being calculated by Figure 16 is compound
The characteristic size 1/Q curve of object, in Figure 16 1 for the patterning micro nano structure for having response of embodiment one poly- electrolysis
Matter compound is placed on the characteristic size 1/Q curve under 35% damp condition, and 2 have response for prepared by embodiment one
The compound polyelectrolyte of patterning micro nano structure be placed on the characteristic size 1/Q curve under 100% damp condition；
Figure 19 is the enlarged drawing at the place A in Figure 18, in Figure 19 1 be embodiment one the patterning for having response it is micro-nano
The compound polyelectrolyte of structure is placed on the characteristic size 1/Q curve under 35% damp condition, and 2 be the preparation of embodiment one
The compound polyelectrolyte for having the patterning micro nano structure of response is placed on feature ruler under 100% damp condition
Very little 1/Q curve；
From Figure 18 and Figure 19 it is found that by uncrosslinked compound polyelectrolyte different relative humidity characteristic size
Compare, it can be seen that when relative humidity is larger, significant change occurs for the pattern of micron level, loses characteristic size.
Figure 20 is the patterning micro nano structure for having response prepared by the embodiment one being calculated by Figure 17
Compound polyelectrolyte Q value curve, the 1 micro-nano knot of patterning for having response prepared for embodiment one in Figure 20
The compound polyelectrolyte of structure is placed on the Q value curve under 35% damp condition, and 2 have and stress ring for prepared by embodiment one
The compound polyelectrolyte for the patterning micro nano structure answered is placed on the Q value curve under 100% damp condition；
As can be seen from Figure 20, the compound polyelectrolyte laser light scattering pattern for not passing through heat cross-linking, in different relative humidity meters
Obtained Q value.Compared to the compound polyelectrolyte of crosslinking, humidity variation is become apparent.
Figure 21 is that the polyelectrolyte of the obtained patterning micro nano structure for having response prepared by embodiment three is multiple
Close the ordinary optical microscope picture of object；
As can be seen from Figure 21, uncrosslinked PSS/PDDA compound polyelectrolyte, when relative humidity is 35%, pattern form
It is more complete.
Figure 22 is that the compound polyelectrolyte of the patterning micro nano structure for having response prepared by embodiment three is put
Set the ordinary optical microscope figure under 100% damp condition after 15min clock；
As can be seen from Figure 22, uncrosslinked PSS/PDDA compound polyelectrolyte patterned film loses original micro- completely
Rice structure.
Figure 23 carries out the comparison diagram that light dissipates measurement for compound polyelectrolyte, and 1 is to obtain in one step 3 of embodiment in Figure 23
The ultraviolet-visible absorption spectroscopy of the patterned film of the compound polyelectrolyte arrived, 2 be smooth compound polyelectrolyte film
Ultraviolet-visible absorption spectroscopy；
It as can be seen from Figure 23, is the basis of laser light scattering pattern formation for micro-nano patterning.
Claims (10)
1. the preparation method for having the compound polyelectrolyte of the patterning micro nano structure of response, it is characterised in that the party
What method was specifically realized by the following steps:
One, patterned PDMS seal is prepared:
The prepolymer A of dimethyl silicone polymer and curing agent B is mixed, low whipping speed is 200r/min~500r/min first
Then lower stirring 5min~8min is centrifuged 5min~8min in the case where centrifugal speed is 3000r/min~4000r/min, is mixed
Close solution；Mixed solution is poured in the culture dish equipped with patterned silicon substrate, then by culture dish temperature be 60 DEG C~
Vacuum solidification 1h~3h at 80 DEG C obtains patterned PDMS seal on a silicon substrate；The PDMS seal that will be patterned into is from silicon substrate
It is removed on plate, obtains patterned PDMS seal；
The mass ratio of the prepolymer A and curing agent B of dimethyl silicone polymer described in step 1 are 10:1；
Two, the preparation of compound polyelectrolyte:
By polyelectrolyte electronics to being added in container, then temperature be 70 DEG C~80 DEG C and mixing speed be 300r/min~
Magnetic agitation 15min~25min under 800r/min obtains the compound polyelectrolyte of flocculent structure in the solution；
Mixed liquor of the polyelectrolyte electronics described in step 2 to mixed liquor or PAA/PAH for PSS/PDDA；Described
The mixed liquor of PSS/PDDA is the sodium chloride solution of kayexalate and the sodium chloride solution of polyacrylate according to volume
It is mixed than 1:1；The mixed liquor of the PAA/PAH is molten for the sodium chloride solution of polyacrylic acid and the sodium chloride of polycyclic aromatic hydrocarbon
Liquid is mixed according to volume ratio 1:1；
Three, the compound polyelectrolyte of flocculent structure is taken out from solution, then by the compound polyelectrolyte lid of flocculent structure
On the patterned PDMS seal obtained in step 1, then to the patterning for the compound polyelectrolyte for being covered with flocculent structure
PDMS seal on apply 20kPa~130kPa, then the pressure maintaining in the case where temperature is 60 DEG C~75 DEG C and pressure is 20kPa~130kPa
5min~15min, then transferred, transfer time are 5min~15min, then by compound polyelectrolyte and patterned PDMS
Seal separation obtains the compound polyelectrolyte for the patterning micro nano structure for having response；
Thermal transfer is transferred as described in step 3, transfer temperature is 60 DEG C~100 DEG C；
Have described in step 3 response patterning micro nano structure compound polyelectrolyte with a thickness of 0.1 μm
~30 μm.
2. the preparation of the compound polyelectrolyte of the patterning micro nano structure according to claim 1 for having response
Method, it is characterised in that patterned PDMS seal described in step 1 is the square that the side length of array is 10 μm.
3. the preparation of the compound polyelectrolyte of the patterning micro nano structure according to claim 1 for having response
Method, it is characterised in that the sodium chloride solution of kayexalate described in step 2 is kayexalate, chlorination
The mixed liquor of sodium and distilled water, the concentration of kayexalate is 2mg/mL in the sodium chloride solution of kayexalate,
The concentration of sodium chloride is 2mol/L；The sodium chloride solution of the polyacrylate is polyacrylate, sodium chloride and distilled water
Mixed liquor, the concentration of polyacrylate is 2mg/mL in the sodium chloride solution of polyacrylate, and the concentration of sodium chloride is 2mol/
L。
4. the preparation of the compound polyelectrolyte of the patterning micro nano structure according to claim 1 for having response
Method, it is characterised in that the sodium chloride solution of polyacrylic acid described in step 2 is polyacrylic acid, sodium chloride and distilled water
Mixed liquor, the concentration of polyacrylic acid is 2mg/mL in the sodium chloride solution of polyacrylic acid, and the concentration of sodium chloride is 2mol/L；It is described
Polycyclic aromatic hydrocarbon sodium chloride solution be polycyclic aromatic hydrocarbon, sodium chloride and distilled water mixed liquor, the sodium chloride solution of polycyclic aromatic hydrocarbon
Middle polycyclic aromatic hydrocarbon concentration is 2mg/mL, and the concentration of sodium chloride is 2mol/L.
5. have the application of the compound polyelectrolyte of the patterning micro nano structure of response as described in claim 1,
It is characterized in that the compound polyelectrolyte for having the patterning micro nano structure of response is based on optical diffraction effect for sentencing
The disconnected irritability to external environment is reacted.
6. have the application of the compound polyelectrolyte of the patterning micro nano structure of response as described in claim 1,
It is characterized in that having the compound polyelectrolyte of the patterning micro nano structure of response as the super perspective material of intelligence
Using.
7. have the application of the compound polyelectrolyte of the patterning micro nano structure of response as described in claim 1,
It is characterized in that the compound polyelectrolyte for having the patterning micro nano structure of response is applied to super resolution technologies
In.
8. have the application of the compound polyelectrolyte of the patterning micro nano structure of response as described in claim 1,
It is characterized in that having scattering matchmaker of the compound polyelectrolyte of the patterning micro nano structure of response as response
Be situated between application.
9. have the application of the compound polyelectrolyte of the patterning micro nano structure of response as described in claim 1,
It is characterized in that the compound polyelectrolyte for having the patterning micro nano structure of response is based on reacting face under stressed condition
The change of color and scattering is detected for life food quality.
10. have the application of the compound polyelectrolyte of the patterning micro nano structure of response as described in claim 1,
It is characterized in that the compound polyelectrolyte for having the patterning micro nano structure of response, which is based on microbial degradation, to be occurred
The principle that structure changes can be used in optical sensor, can be used for humidity sensor based on the principle that irritability response occurs to humidity
In device, it can be used in acidity-basicity sensor based on the principle that irritability response occurs to pH value.
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| CN102217072A (en) * | 2008-09-19 | 2011-10-12 | 南洋理工大学 | Electronic device with channel, electrodes and semiconductor formed on respective bonded substrates |
| CN104736725A (en) * | 2012-08-13 | 2015-06-24 | 加利福尼亚大学董事会 | Methods and systems for detecting biological components |
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| CN102217072A (en) * | 2008-09-19 | 2011-10-12 | 南洋理工大学 | Electronic device with channel, electrodes and semiconductor formed on respective bonded substrates |
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