CN105273213B - A method of regulating and controlling surface wrinkling or wrinkle-chasing using redox environment - Google Patents
A method of regulating and controlling surface wrinkling or wrinkle-chasing using redox environment Download PDFInfo
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- CN105273213B CN105273213B CN201510801458.1A CN201510801458A CN105273213B CN 105273213 B CN105273213 B CN 105273213B CN 201510801458 A CN201510801458 A CN 201510801458A CN 105273213 B CN105273213 B CN 105273213B
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Abstract
It is to regulate and control the solvent swelling state of the surfaces PDMS PANI films with redox environment, and then regulate and control the surface topography of PANI films the invention discloses a kind of method regulating and controlling surface wrinkling or wrinkle-chasing using redox environment.Dimethyl silicone polymer (PDMS) the elastomer strip sample of surface with corrugation polyaniline (PANI) film is placed in sodium borohydride solution, chill mark disappears, the sample that the wrinkle disappears is placed in hydrogen peroxide solution, chill mark reappears.And thering are the PDMS strip samples of corrugation PANI films to be initially positioned in the potassium persulfate solution of strong oxidizing property on surface, wrinkle can equally disappear, and the sample of the wrinkle-chasing is immersed again in hydrochloric acid solution, and wrinkle can occur again.For the present invention in the way of shirtsleeve operation, novel redox means realize the reversible regulation and control to wrinkle pattern, and prepared by the surface for intelligent response and regulation and control open new approach, are constructed for functional response interface and provide new thinking.
Description
Technical field
The present invention relates to picture on surface technologies of preparing, and in particular to a kind of technique side of regulation and control polyaniline chill mark pattern
Method.
Background technology
Derived from interfacial stress relaxation film surface corrugation be used as a kind of novel surface patterning technique, in recent years by
The very big concern of people, and it is widely used in the fields such as flexible electrode, sensor, optical device and membrane material physical property characterization.And
In specific application field, such as interface cohesion, wetability, optical property and microchannel field, need reversibly to control wrinkle
The appearance and disappearance of line, to change the interface binding power of device, wetability, the switch of translucency and microchannel.Currently, right
The reversible regulation and control of surface wrinkling/wrinkle-chasing focus primarily upon mechanical means, complex steps.How to develop a kind of simple and quick effective
Mode realizes that the reversible regulation and control of corrugation/wrinkle-chasing are still a great problem of current research.The redox environment of system is chemical anti-
An important parameter in answering.Currently, the materials most with redox response is applied in drug release, actuator is urged
The fields such as agent do not relate at the aspect of constructing of Intelligent interfaces.Exploitation has good stimulating responsive to redox environment
There is potential application prospect on surface in fields such as environmental monitorings.
Invention content
For the above-mentioned prior art, the present invention provides a kind of side regulating and controlling surface wrinkling or wrinkle-chasing using redox environment
Method.It is substrate that the present invention, which selects PDMS, and on the surfaces PDMS, one layer of corrugated PANI of deposition is thin by way of adsorpting polymerization in situ
Film.The reversible regulation and control of PANI films corrugation/wrinkle-chasing are realized in the way of simple immersion treatment.
In order to solve the above-mentioned technical problem, a kind of side regulating and controlling surface wrinkling or wrinkle-chasing using redox environment of the present invention
Method is to regulate and control the solvent swelling state of the surfaces PDMS PANI films with redox environment, and then regulate and control the surface topography of PANI films.
Further, one of following two kinds of processing procedures may be used, make the surfaces PDMS PANI wrinkles film successively wrinkle-chasing and
Again it wrinkles：
1) uniformly growth there is into the boron hydrogen that the PDMS elastomer strip samples of one layer of PANI wrinkle film are placed in 0.1M
Change and taken out after 2 seconds in sodium solution, obtains the PANI films of wrinkle pattern disappearance in PDMS elastomer strip specimen surfaces, this is carried
The PDMS elastomer strip samples for the PANI films that wrinkle pattern disappears are placed in the hydrogen peroxide solution of mass fraction 15wt% 1 minute
After take out, retrieve corrugated PANI wrinkles film in PDMS elastomer strip specimen surfaces；
2) uniformly growth there is into the over cure that the PDMS elastomer strip samples of one layer of PANI wrinkle film are placed in 0.1M
It is taken out after 5 seconds in sour potassium solution, obtains the PANI films of wrinkle pattern disappearance in PDMS elastomer strip specimen surfaces, obtain wrinkle
The PDMS elastomer strip samples of the PANI films with the disappearance of wrinkle pattern are placed in the hydrochloric acid of 1M by the PANI films that pattern disappears
It is taken out after 1 minute in solution, corrugated PANI wrinkles film is retrieved in PDMS elastomer strip specimen surfaces.
Used uniformly growth has the preparation process of the PDMS elastomer strip samples of one layer of PANI wrinkle film
It is as follows：
Step 1: PDMS performed polymers are mixed with crosslinking agent by certain mass ratio, pour into a vessel, it is abundant with glass bar
Stirring, obtains uniform performed polymer；
Step 2: after the performed polymer that step 1 is obtained deaerates 1 hour in vacuum desiccator, it is placed in constant temperature forced air drying
It heats 4 hours and is cured under 70 degrees Celsius of case, obtain PDMS elastomers；
Step 3: the PDMS elastomeric shears that step 2 is obtained are standby at the PDMS elastomer strip samples of 3cm × 1cm
With；
Step 4: the aniline hydrochloric acid solution of 0.1M and the ammonium persulfate hydrochloric acid solution of 0.1M are prepared respectively, respectively by aniline
Hydrochloric acid solution and ammonium persulfate hydrochloric acid solution are placed in 0-5 degrees Celsius 30 minutes；
Step 5: prepared in step 4 two kinds of solution are quickly mixed into mixed solution, and will be made from step 3
PDMS elastomer strip samples immerse the mixed solution, and after being reacted 15 minutes in 0-5 degrees Celsius of environment, it is long to take out PDMS elastomers
Bar sample, which, which equably grows, one layer of PANI wrinkle film.
Compared with prior art, the beneficial effects of the invention are as follows：
The method of the present invention has easy operability, good repeatability, it can be achieved that chill mark quick, reversible tune
Control.The stimulating responsive PANI films constructed have huge application prospect in sensor, the fields such as smart window.The present invention relates to
Using redox means regulate and control picture on surface method, other materials system can be extended to, to construct intelligent surface and interface
Provide new thinking.
Description of the drawings
Fig. 1 is that embodiment 1-3 grows to obtain the optical microscope picture of corrugated PANI films in PDMS surface in situ；
Fig. 2 is the optical microscope picture to disappear through sodium borohydride processing PANI film wrinkles in embodiment 2；
Fig. 3 is the optical microscope picture to disappear through potassium peroxydisulfate processing PANI film wrinkles in embodiment 3.
Specific implementation mode
A kind of mentality of designing for the method regulating and controlling surface wrinkling or wrinkle-chasing using redox environment of the present invention is with oxidation
Reducing environment regulates and controls the solvent swelling state of the surfaces PDMS PANI films, and then regulates and controls the surface topography of PANI films.
The corrugated polyaniline of growth in situ (PANI) film first in dimethyl silicone polymer (PDMS) substrate is formed
The dual layers of corrugated system of PDMS/PANI.
Then the specimen sample is placed in the sodium borohydride solution of reproducibility after a certain period of time, chill mark disappears, will
The PDMS/PANI compound systems of wrinkle-chasing are placed in the hydrogen peroxide solution of oxidisability after a certain period of time, and chill mark occurs again.Tool
Body step is：Uniformly growth there is into the hydroboration that the PDMS elastomer strip samples of one layer of PANI wrinkle film are placed in 0.1M
It is taken out after 2 seconds in sodium solution, the PANI films of wrinkle pattern disappearance is obtained in PDMS elastomer strip specimen surfaces, by this with wrinkle
The PDMS elastomer strip samples for the PANI films that line pattern disappears were placed in the hydrogen peroxide solution of mass fraction 15wt% after 1 minute
It takes out, corrugated PANI wrinkles film is retrieved in PDMS elastomer strip specimen surfaces；
Similarly, the PANI films of surface wrinkling are placed in the potassium persulfate solution of strong oxidizing property, wrinkle disappears after a certain period of time
It loses, this sample is immersed hydrochloric acid solution certain time again, wrinkle can equally occur again.It is as follows：Surface is uniform
Ground growth has the PDMS elastomer strip samples of one layer of PANI wrinkle film to be placed in the potassium persulfate solution of 0.1M to take out after 5 seconds,
The PANI films of wrinkle pattern disappearance are obtained in PDMS elastomer strip specimen surfaces, obtain the PANI films of wrinkle pattern disappearance, it will
The PDMS elastomer strip samples of the PANI films to disappear with wrinkle pattern are placed in the hydrochloric acid solution of 1M to be taken out after 1 minute,
Corrugated PANI wrinkles film is retrieved in PDMS elastomer strip specimen surfaces.
In above-mentioned redox regulatory, PANI films suffer from good corrugation/wrinkle-chasing invertibity.The present invention is using simply
Mode of operation, novel redox means realize the reversible regulation and control to wrinkle pattern, are prepared by the surface of intelligent response
And regulation and control open new approach, are constructed for functional response interface and provide new thinking.
Technical solution of the present invention is described in further detail in the following with reference to the drawings and specific embodiments, it is described specific
Embodiment is only explained the present invention, is not intended to limit the invention.
Embodiment 1：
The corrugated PANI films for being equably grown in the surfaces PDMS are prepared, are included the following steps：
Step 1: PDMS performed polymers are mixed with crosslinking agent by certain mass ratio, pour into a vessel, it is abundant with glass bar
Stirring, obtains uniform performed polymer；
Step 2: after the performed polymer that step 1 is obtained deaerates 1 hour in vacuum desiccator, it is placed in constant temperature forced air drying
It heats 4 hours and is cured under 70 degrees Celsius of case, obtain PDMS elastomers；
Step 3: the PDMS elastomeric shears that step 2 is obtained are standby at the PDMS elastomer strip samples of 3cm × 1cm
With；
Step 4: the aniline hydrochloric acid solution of 0.1M and the ammonium persulfate hydrochloric acid solution of 0.1M are prepared respectively, respectively by aniline
Hydrochloric acid solution and ammonium persulfate hydrochloric acid solution are placed in 0-5 degrees Celsius 30 minutes；
Step 5: prepared in step 4 two kinds of solution are quickly mixed into mixed solution, and will be made from step 3
PDMS elastomer strip samples immerse the mixed solution, and after being reacted 15 minutes in 0-5 degrees Celsius of environment, it is long to take out PDMS elastomers
Bar sample, which, which equably grows, one layer of PANI wrinkle film, and optical microscope picture is such as
Shown in Fig. 1.
Embodiment 2：
A method of regulating and controlling surface wrinkling or wrinkle-chasing using redox environment, is the PANI wrinkles for obtaining embodiment 1
Line film is placed in the sodium borohydride solution of 0.1M reproducibilities and is taken out after 2 seconds, obtains the PANI films of wrinkle pattern disappearance, optical microphotograph
Mirror picture is as shown in Figure 2.The PANI films of above-mentioned no wrinkle are placed in the oxidisability hydrogen peroxide solution of mass fraction 15wt% 1 point
It is taken out after clock, it is as shown in Figure 1 to retrieve corrugated PANI films optical microscope picture.
Embodiment 3：
A method of regulating and controlling surface wrinkling or wrinkle-chasing, the PANI wrinkles that embodiment 1 is obtained using redox environment
Film is placed in the potassium persulfate solution of 0.1M oxidisability and is taken out after 5 seconds, obtains the PANI films of wrinkle pattern disappearance, light microscope
Picture is as shown in Figure 3.The PANI films of above-mentioned no wrinkle were placed in the hydrochloric acid solution of 1M after 1 minute and are taken out, corrugation is retrieved
PANI film optical microscope pictures it is as shown in Figure 1.
To sum up, the method for the present invention is mainly in the corrugated PANI films of PDMS substrate growth in situ, and utilizes different oxidations
Reducing environment goes to realize the reversible regulation and control to chill mark.Since in different environment, the swelling that PANI films are in different is received
Contracting state causes volume that reversible variation occurs, and then realizes the reversible change of corrugation/wrinkle-chasing of pattern.The present invention utilizes letter
Single mode of operation, novel redox means quickly, effectively, reversibly regulate and control wrinkle pattern, and it is with cyclicity
Good advantage.
Although above in conjunction with attached drawing, invention has been described, and the invention is not limited in above-mentioned specific implementations
Mode, the above mentioned embodiment is only schematical, rather than restrictive, and those skilled in the art are at this
Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to the present invention's
Within protection.
Claims (2)
1. a kind of method regulating and controlling PDMS surface wrinklings or wrinkle-chasing using redox environment regulates and controls PDMS with redox environment
The solvent swelling state of surface PANI films, and then regulate and control the surface topography of PANI films, which is characterized in that use following two kinds of processing procedures
One of, make the surfaces PDMS PANI wrinkle film wrinkle-chasings and wrinkles again：
1) uniformly growth there is into the sodium borohydride that the PDMS elastomer strip samples of one layer of PANI wrinkle film are placed in 0.1M
It is taken out after 2 seconds in solution, obtains the PANI films of wrinkle pattern disappearance in PDMS elastomer strip specimen surfaces, this is carried into wrinkle
The PDMS elastomer strip samples for the PANI films that pattern disappears are placed in the hydrogen peroxide solution of mass fraction 15wt% to be taken after 1 minute
Go out, corrugated PANI wrinkles film is retrieved in PDMS elastomer strip specimen surfaces；
2) uniformly growth there is into the potassium peroxydisulfate that the PDMS elastomer strip samples of one layer of PANI wrinkle film are placed in 0.1M
It is taken out after 5 seconds in solution, obtains the PANI films of wrinkle pattern disappearance in PDMS elastomer strip specimen surfaces, this is carried into wrinkle
The PDMS elastomer strip samples for the PANI films that pattern disappears are placed in the hydrochloric acid solution of 1M to be taken out after 1 minute, in PDMS elasticity
Body strip specimen surface retrieves corrugated PANI wrinkles film.
2. the method for utilizing redox environment regulation and control surface wrinkling or wrinkle-chasing according to claim 1, which is characterized in that institute
The uniformly growth used has the PDMS elastomer strips of one layer of PANI wrinkle film, the preparation process of sample as follows：
Step 1: PDMS performed polymers are mixed with crosslinking agent by certain mass ratio, pour into a vessel, is fully stirred with glass bar
It mixes, obtains uniform performed polymer；
Step 2: after the performed polymer that step 1 is obtained deaerates 1 hour in vacuum desiccator, it is placed in constant temperature blast drying oven 70
It heats 4 hours and is cured under degree Celsius, obtain PDMS elastomers；
Step 3: the PDMS elastomeric shears that step 2 is obtained are spare at the PDMS elastomer strip samples of 3cm × 1cm；
Step 4: the aniline hydrochloric acid solution of 0.1M and the ammonium persulfate hydrochloric acid solution of 0.1M are prepared respectively, respectively by aniline hydrochloric acid
Solution and ammonium persulfate hydrochloric acid solution are placed in 0-5 degrees Celsius 30 minutes；
Step 5: prepared in step 4 two kinds of solution are quickly mixed into mixed solution, and by PDMS bullets made from step 3
Property body strip sample immerse the mixed solution, after being reacted 15 minutes in 0-5 degrees Celsius of environment, take out PDMS elastomer strips examination
Sample, which, which equably grows, one layer of PANI wrinkle film.
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| CN107057093B (en) * | 2017-02-24 | 2019-07-05 | 天津大学 | A kind of method that ultraviolet lighting eliminates Degradable high polymer film chill mark |
| CN107043471B (en) * | 2017-03-22 | 2020-01-21 | 天津大学 | Method for preparing polymer multilevel pattern through ultrasonic-assisted treatment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467764A (en) * | 2013-07-05 | 2013-12-25 | 天津大学 | Method used for realizing wrinkle evolution of layer-by-layer self-assembled hydrogen bond films on PDMS elastomers |
| CN103466540A (en) * | 2013-07-05 | 2013-12-25 | 天津大学 | Method used for preparing wrinkles of multilayer composite silver film on PDMS elastomer substrate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467764A (en) * | 2013-07-05 | 2013-12-25 | 天津大学 | Method used for realizing wrinkle evolution of layer-by-layer self-assembled hydrogen bond films on PDMS elastomers |
| CN103466540A (en) * | 2013-07-05 | 2013-12-25 | 天津大学 | Method used for preparing wrinkles of multilayer composite silver film on PDMS elastomer substrate |
Non-Patent Citations (2)
| Title |
|---|
| "Large-Area Patterning of Polyaniline Film Based on in Situ Self-Wrinkling and Its Reversible Doping/Dedoping Tunability";Jixun Xie等;《Macromolecules》;20150128;第48卷;663-671 * |
| "皱纹化聚苯胺膜的可逆响应性研究及应用";谢继勋等;《2015年全国高分子学术论文报告会》;20151021;第1299页 * |
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Address after: 300350 Haijing garden, Haihe Education Park, Jinnan, Tianjin, 135, Tianjin University. Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |
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Granted publication date: 20181019 Termination date: 20201119 |