CN103464356A - Method for wrinkling hydrogen bond membranes on PDMS (Polydimethysiloxane) elastic body through layer-by-layer self-assembly - Google Patents
Method for wrinkling hydrogen bond membranes on PDMS (Polydimethysiloxane) elastic body through layer-by-layer self-assembly Download PDFInfo
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- CN103464356A CN103464356A CN2013102822699A CN201310282269A CN103464356A CN 103464356 A CN103464356 A CN 103464356A CN 2013102822699 A CN2013102822699 A CN 2013102822699A CN 201310282269 A CN201310282269 A CN 201310282269A CN 103464356 A CN103464356 A CN 103464356A
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Abstract
The invention discloses a method for wrinkling hydrogen bond membranes on a PDMS (Polydimethysiloxane) elastic body through layer-by-layer self-assembly. The method is characterized in that a compound system is formed by PDMS which is used as a substrate and the hydrogen bond membranes which are obtained through layer-by-layer self-assembly, no wrinkles exist as the modulus of the hydrogen bond membranes is lower after the compound system is dried, the modulus of the hydrogen bond membranes is increased after the compound system is heated, and a wrinkling phenomenon happens after the compound system is cooled. The PDMS is low in cost, is good in elasticity and light transmission, capable of maintaining the natural flexibility and the elasticity of the PDMS in a wider temperature range, non-toxic and easy to process. A layer-by-layer self-assembly technology is widely researched long ago and has multiple advantages, the experiment method is simple, and the uniformity and the stability of the hydrogen bond membranes are good. The modulus of the hydrogen bond membranes is greatly changed along with the change of the humidity and the temperature of environment. A linear relation is formed by the number of assembling layers and the period of wrinkles. According to the method disclosed by the invention, the layer-by-layer self-assembly technology and the wrinkling phenomenon are combined, and the advantages of the layer-by-layer self-assembly are retained.
Description
Technical field
The present invention relates to the layer-by-layer of hydrogen bond film, be specifically related to the PDMS elastomer and form the wrinkling research of soft or hard compound system as substrate and hydrogen bond film.
Background technology
Ultra-thin film formed this soft/hard compound system that the PDMS of take constructs on substrate and surface thereof is object, study this system and be subject to environmental stimuli to do the used time, the controlled preparation of the generation of soft or hard interface stress and the lax chill mark micro-structural formed thereof becomes one of focus of research work in recent years.The self-assembling method layer by layer of film is simple, and simple to operate, and the stability of the film obtained is higher, and image conversion, mechanical performance and application study technique are very ripe.The crosslinked front and back of the hydrogen bond film character that hydrogen bond self assembly layer by layer obtains has very large difference, and solvent pH value is had to response, and experimental technique is easy.Do substrate with PDMS, the hydrogen bond film is assembled into to PDMS upper, heat at a certain temperature certain hour, the highly cross-linked modulus of hydrogen bond film increases, cooling rear formation labyrinth wrinkle.Along with the increase of the number of plies, the fold wavelength is along with increase, and therefore, under the same visual field, the striped number of seeing tails off.In addition, these novel slackness structures as the structuring template in selective absorption and the growth of regulating cell and other materials, at aspects such as wetability, micro flow chip and electronic devices, obtained extensive use.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of on the PDMS elastomer the wrinkling method of self assembly hydrogen bond film layer by layer.Be to using the hydrogen bond film that dimethyl silicone polymer (be called for short PDMS) obtains as substrate and self assembly layer by layer to form compound system, hydrogen bond film modulus is low after dry does not have wrinkle to form, and after heating, its modulus increases, cooling rear wrinkling phenomenon.(PDMS) is cheap for dimethyl silicone polymer, has well good elasticity, light transmission, can keep its natural pliability and elasticity in wider temperature range, nontoxic, easy processing.And layer-by-layer just is widely studied before very early, a lot of advantages is arranged, experimental technique is easy, film homogeneity and good stability.The modulus of hydrogen bond film produces very large variation with the change of ambient humidity and temperature.It is substrate that dimethyl silicone polymer (PDMS) is take in the present invention, utilizes self-assembly method layer by layer to prepare high molecular hard film layer, has obtained corresponding soft or hard system; Aspect the wrinkle processing of surface of elastomer, wait and process the generation of inducing soft or hard interface stress by heating, when stress reaches critical value, system discharges stress with the form of wrinkle or crackle, successfully makes dimethyl silicone polymer surface and produces the labyrinth-like pleated pattern.By changing the thickness of hard film layer, find that the periodicity of wrinkle has linear relationship with bed thickness, thereby realize the controlled preparation of fold.Cover the wrinkling thought of a skim in soft substrate also just is suggested before very early.
In order to solve the problems of the technologies described above, the present invention a kind of on the PDMS elastomer the wrinkling method of self assembly hydrogen bond film layer by layer, comprise the following steps:
Step 3, above-mentioned PDMS elastomer is cut into after sheet material to the acid solution of putting into polyacrylic acid and PEO, the hydrogen bond film of the different numbers of plies in assembling, the process of assembling every one deck hydrogen bond film is: first above-mentioned PDMS elastomer sheet is used to oxygen plasma treatment 30 seconds; Then the PDMS elastomer sheet is put into successively to polyacrylic acid solution 10 minutes, the acid solution 2 minutes that concentration is 2mg/mL, PEO solution 10 minutes, the acid solution 2 minutes that concentration is 2mg/mL, in the process of assembling hydrogen bond film, the pH value of all solution is 2.5～3; The pH value of solution is regulated with HCL solution.For the film homogeneous is compacted, after the assembling one-period finishes, with hair-dryer cold wind, blow to film surface dripless.By that analogy, circulate repeatedly, multilayer hydrogen bond film in assembling.
It is dry that step 4, the PDMS elastomer sheet that will assemble the hydrogen bond film of the different numbers of plies are put into the vavuum pump of silica gel, then is placed under 200 ℃ heating 1 hour, is formed with the labyrinth-like wrinkle on PDMS elastomer sheet surface after being cooled to room temperature.
Compared with prior art, the invention has the beneficial effects as follows:
Method of the present invention has good repeatability, and the modulus of hydrogen bond film produces very large variation with the change of ambient humidity and temperature, by changing the modulus of self assembly hydrogen bond film, sample surface morphology difference.Wrinkle size of the present invention can reach micron level, in wetability, microfluidic device, selective deposition, has very large using value.
The accompanying drawing explanation
Fig. 1 is the light microscope picture that Comparative Examples obtains sample surfaces;
Fig. 2 is the labyrinth-like wrinkle light microscope picture that the embodiment of the present invention 2 obtains;
The light microscope picture that Fig. 3 is the constituency wrinkle structure that obtains of the embodiment of the present invention 3;
The light microscope picture that Fig. 4 is the constituency wrinkle structure that obtains of the embodiment of the present invention 4;
Fig. 5 is the embodiment of the present invention 5 wrinkle cycle obtained and the graph of a relation of assembling the number of plies.
The specific embodiment
Below in conjunction with preferred specific embodiment, the present invention is described in further detail, but enforcement of the present invention is not limited to this.
Comparative Examples:
By PDMS performed polymer and crosslinking agent in mass ratio 10:1 mix, pour in vessel and fully stir the formation prepolymer with glass bar;
2. in the prepolymer mixed, minute bubbles are arranged, need to pass through the multiplex vavuum pump of circulating water type degassed, in the present embodiment, the degassed time is set as 2 hours; After degassed completing, put it into constant temperature blast drying oven, then solidify under 70 ℃, solidify after 4 hours and form the PDMS elastomer;
3. above-mentioned PDMS elastomer is cut into to the sheet material of 1cm * 1cm, put into the acid solution of polyacrylic acid PAA and PEO PEO, multilayer hydrogen bond film on its surface-assembled;
4. the process of each circulation is: first above-mentioned PDMS elastomer sheet is used to oxygen plasma treatment 30 seconds; Then put into successively PAA solution, the acid solution of concentration 2mg/mL, PEO solution and the acid solution of 2mg/mL, time in above-mentioned solution is followed successively by 10 minutes, 2 minutes, 10 minutes and 2 minutes, in said process, the pH value of each solution is adjusted in 2.5 left and right with HCL solution.For the film homogeneous is compacted, after the assembling one-period finishes, with hair-dryer cold wind, blow to film surface dripless;
5. the process according to above-mentioned steps 4 so circulates 12 times, 12 layers of hydrogen bond film in the assembling of PDMS surface of elastomer; The PDMS elastomer sheet of the upper 12 layers of hydrogen bond film of assembling is put into to dry 12 hours of the vavuum pump of silica gel, now surface does not have wrinkle to produce.The hydrogen bond film assembling that this assembling is 12 layers finishes dry rear surface pattern light microscope picture as shown in Figure 1.
Embodiment 1:
A kind of on the PDMS elastomer 6 layers of wrinkling method of hydrogen bond film of self assembly layer by layer, wherein step 1 to 4 the same with in Comparative Examples, then according to the so circulation 6 times of the process of above-mentioned steps 4,6 layers of hydrogen bond film in the assembling of PDMS surface of elastomer; The PDMS elastomer sheet of the upper 6 layers of hydrogen bond film of assembling is put into to dry 12 hours of the vavuum pump of silica gel, then heating 1 hour under 200 ℃, be formed with the labyrinth-like wrinkle on PDMS elastomer sheet surface after being cooled to room temperature.This surface labyrinth-like wrinkle light microscope picture as shown in Figure 2.
Embodiment 2:
A kind of on the PDMS elastomer 12 layers of wrinkling method of hydrogen bond film of self assembly layer by layer, wherein step 1 to 4 the same with in embodiment 1, then according to the so circulation 12 times of the process of above-mentioned steps 4,12 layers of hydrogen bond film in the assembling of PDMS surface of elastomer; The PDMS elastomer sheet of the upper 12 layers of hydrogen bond film of assembling is put into to dry 12 hours of the vavuum pump of silica gel, then heating 1 hour under 200 ℃, be formed with the labyrinth-like wrinkle on PDMS elastomer sheet surface after being cooled to room temperature.12 layers of hydrogen bond film heat and labyrinth-like wrinkle light microscope picture within 1 hour, occurs as shown in Figure 3 under 200 ℃.Can find out, this labyrinth-like wrinkle is compared the labyrinth-like wrinkle of embodiment 1, and its cycle is larger.
Embodiment 3:
A kind of on the PDMS elastomer 18 layers of wrinkling method of hydrogen bond film of self assembly layer by layer, wherein step 1 to 4 the same with in embodiment 1, then according to the so circulation 18 times of the process of above-mentioned steps 4,18 layers of hydrogen bond film in the assembling of PDMS surface of elastomer; The PDMS elastomer sheet of the upper 18 layers of hydrogen bond film of assembling is put into to dry 12 hours of the vavuum pump of silica gel, then heating 1 hour under 200 ℃, be formed with the labyrinth-like wrinkle on PDMS elastomer sheet surface after being cooled to room temperature.18 layers of hydrogen bond film heat and labyrinth-like wrinkle light microscope picture within 1 hour, occurs as shown in Figure 4 under 200 ℃, can find out, this labyrinth-like wrinkle is compared the labyrinth-like wrinkle of embodiment 2, and its cycle increases.
Above-described embodiment the 1,2, the 3rd is assembled respectively the hydrogen bond film of 6,12,18 layers on the PDMS elastomer, forms the labyrinth-like wrinkle after heating.Fig. 5 shows the graph of a relation of wrinkle cycle and the assembling number of plies, can find out the increase along with the assembling number of plies, and the labyrinth-like wrinkle cycle also increases simultaneously.
To sum up, the present invention assembles the hydrogen bond film that polyacrylic acid and PEO form in the PDMS substrate, and heating 1 hour under 200 ℃ after assembling finishes the labyrinth-like wrinkle occurs after cooling.The number of plies that can assemble by regulation and control in experiment, the cycle of regulation and control wrinkle.The number of plies of assembling and the cycle of wrinkle are linear.The inventive method combines layer-by-layer and wrinkling, has retained the advantage of self assembly layer by layer, and experimental technique is easy, film homogeneity and good stability.
Although top, in conjunction with figure, invention has been described; but the present invention is not limited to the above-mentioned specific embodiment; the above-mentioned specific embodiment is only schematic; rather than restrictive; those of ordinary skill in the art is under enlightenment of the present invention; in the situation that do not break away from aim of the present invention, can also make a lot of distortion, within these all belong to protection of the present invention.
Claims (3)
1. the wrinkling method of self assembly hydrogen bond film layer by layer on the PDMS elastomer comprises the following steps:
Step 1, by PDMS performed polymer and crosslinking agent in mass ratio for after 10:1 mixes, pour in culture dish and fully stir and form prepolymer;
Step 2, to prepolymer carry out successively degassed, dry, form the PDMS elastomer after solidifying;
Step 3, above-mentioned PDMS elastomer is cut into after sheet material to the acid solution of putting into polyacrylic acid and PEO, the hydrogen bond film of the different numbers of plies in assembling, the process of assembling every one deck hydrogen bond film is: first above-mentioned PDMS elastomer sheet is used to oxygen plasma treatment 30 seconds; Then the PDMS elastomer sheet is put into successively to polyacrylic acid solution 10 minutes, the acid solution 2 minutes that concentration is 2mg/mL, PEO solution 10 minutes, the acid solution 2 minutes that concentration is 2mg/mL, in the process of assembling hydrogen bond film, the pH value of all solution is 2.5～3;
It is dry that step 4, the PDMS elastomer sheet that will assemble the hydrogen bond film of the different numbers of plies are put into the vavuum pump of silica gel, then is placed under 200 ℃ heating 1 hour, is formed with the labyrinth-like wrinkle on PDMS elastomer sheet surface after being cooled to room temperature.
2. the wrinkling method of self assembly hydrogen bond film layer by layer on the PDMS elastomer according to claim 1, wherein, in step 3, after the every one deck hydrogen bond film of assembling, blow to film surface dripless with cold wind.
3. the wrinkling method of self assembly hydrogen bond film layer by layer on the PDMS elastomer according to claim 1, wherein, regulate the pH value of all solution with HCL solution in step 3.
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Cited By (3)
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| CN104401933A (en) * | 2014-11-04 | 2015-03-11 | 天津大学 | Method for constructing multistage ordered microstructure through combination of wetting removal process and template process |
| CN105061731A (en) * | 2015-07-31 | 2015-11-18 | 天津大学 | Method for constructing multistage morphology polypyrrole membrane based on in situ wrinkling and thermal expansion |
| CN110835418A (en) * | 2019-11-14 | 2020-02-25 | 哈尔滨工业大学 | Construction method of flexible two-dimensional fold structure on surface of elastic base material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401933A (en) * | 2014-11-04 | 2015-03-11 | 天津大学 | Method for constructing multistage ordered microstructure through combination of wetting removal process and template process |
| CN104401933B (en) * | 2014-11-04 | 2016-04-20 | 天津大学 | A kind of wetting removal and template combine and construct the method for multilevel ordered micro-structural |
| CN105061731A (en) * | 2015-07-31 | 2015-11-18 | 天津大学 | Method for constructing multistage morphology polypyrrole membrane based on in situ wrinkling and thermal expansion |
| CN110835418A (en) * | 2019-11-14 | 2020-02-25 | 哈尔滨工业大学 | Construction method of flexible two-dimensional fold structure on surface of elastic base material |
| CN110835418B (en) * | 2019-11-14 | 2022-04-22 | 哈尔滨工业大学 | Construction method of flexible two-dimensional fold structure on surface of elastic base material |
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Application publication date: 20131225 |