CN104692321B - A kind of method that mode utilizing orthogonal impressing induction prepares ordered porous membrane - Google Patents
A kind of method that mode utilizing orthogonal impressing induction prepares ordered porous membrane Download PDFInfo
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- CN104692321B CN104692321B CN201510056658.9A CN201510056658A CN104692321B CN 104692321 B CN104692321 B CN 104692321B CN 201510056658 A CN201510056658 A CN 201510056658A CN 104692321 B CN104692321 B CN 104692321B
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Abstract
The invention discloses a kind of method that mode utilizing orthogonal impressing induction prepares ordered porous membrane, PDMS performed polymer and cross-linking agent prepare prepolymer；Degassing, be dried, solidification after formed PDMS elastomer；Mechanical stretching method is used to prepare the PDMS wrinkle template with bar shaped wrinkle of different cycles；Prepare the substrate with polymeric membrane；It is mutually perpendicular to contact face-to-face with both wrinkle directions with substrate by wrinkle template, it is then placed into 1h at polymeric membrane glass transition temperature or somewhat higher temperature and is cooled to room temperature, throw off wrinkle template, the micron-sized crepe structure surface of substrate film defines nano level ordered porous structural.The present invention utilizes PDMS wrinkle template to be prepared for ordered porous membrane by the way of orthogonal impressing, achieve the combination of micron order wrinkle and nanoscale hole, the simple instrument and equipment is used to can be obtained by loose structure, it is to avoid the use of the instrument that cost is high and the operating procedure of very complicated.
Description
Technical field
The present invention designs a kind of polymeric membrane surface micro-structure process technology, has particularly related to be attached to one hole one table
Technology in the structure of face.
Background technology
Not only in field of polymer technology, in metal material and field of inorganic materials, the research of porous material also obtains more and more extensive
Concern, be classified largely into three classes according to the size porous material of hole: poromerics, mesoporous material, macrovoid material,
It stores at gas and has potential application prospect in terms of detection, catalysis, heavy metal analysis and drug release.Same wrinkle
Micro structure as a kind of prepare micron, submicron-scale group technological means be different from conventional etch means, have simple, fast
The advantage of speed, and wrinkle size has controllability, preparing large-area reticulation patterns becomes current research tendency the most in the world.Wrinkle
Stricture of vagina patterning be widely applied by many, as the advanced low-k materials in sensor and catalyst carrier, microelectronic component,
Medicine transmission and slow-release material etc..But the research that the micro structure that both has excellent properties combines but rarely has report,
And existing loose structure to prepare big multipair raw materials used requirement strict, and experiment condition is harsh.Meanwhile, porous material
In material, the ordering of porous and controllability have also been obtained the attention of academia in recent years.
Summary of the invention
For above-mentioned technology, the invention provides a kind of by micron order wrinkle with nanometer porous combine prepare ordered porous
The method of film.The present invention is spin coating polymer solutions in PDMS unidirectional wrinkle template, thus obtains a floor height in template and divides
Sub-film, can regulate and control the thickness of polymeric membrane by the concentration of regulation rotating speed with polymer solution in spin coating process；After the spin-coating
Unidirectional wrinkle template on cover another direction PDMS normal thereto unidirectional wrinkle template, and certain load,
Then room is slowly cooled to after being placed on uniform temperature (higher than the glass transition temperature of polymer) heating certain time
Temperature, take off load and PDMS wrinkle template above is opened, in the process can by change heating condition and heating time
Between regulate and control the surface topography of polymeric membrane, thus avoid the use of the high instrument of cost and the operation step of very complicated
Suddenly.
In order to solve above-mentioned technical problem, a kind of mode utilizing orthogonal impressing induction that the present invention proposes prepares ordered porous membrane
Method, comprise the following steps:
Step one, PDMS performed polymer and cross-linking agent are mixed for 10:1 in mass ratio after, pour in culture dish, use Glass rod
It is sufficiently stirred for forming uniform prepolymer；
Step 2, prepolymer step one prepared deaerate successively, be dried, solidify after form PDMS elastomer；
Step 3, PDMS elastomeric shear step 2 prepared become sheet material；
Step 4, use mechanical stretching method, and according to one of following process technique prepare different cycles with bar shaped wrinkle
PDMS wrinkle template: sheet material step 3 obtained, processes 15-60 when prestretched 10% with oxygen plasma
Min, afterwards, bounces back with the speed of 0.5%/min and obtains the PDMS wrinkle with bar shaped wrinkle that the wrinkle cycle is 6～15 microns
Stricture of vagina template；Or: the sheet material that step 3 is obtained, process 55min when prestretched 30% by UV ozone, afterwards,
Bounce back with the speed of 1%/min and obtain the PDMS wrinkle template with bar shaped wrinkle that the wrinkle cycle is 30～40 microns；
Step 5, the polymer solution that concentration is 30～60mg/ml is spin-coated on the PDMS wrinkle template that step 4 prepares
On one surface, wherein, the polymer solution of spin coating 30 μ l on the PDMS wrinkle template area of every 1c, then, take out true
Empty 1-2h volatilizees completely to solvent, thus obtains polymeric membrane in described PDMS wrinkle template；
Step 6, using the PDMS wrinkle template after step 5 processes as substrate, by step 4 gained wrinkle template with
This substrate contacts with the wrinkle direction of substrate face-to-face according to the wrinkle direction of template wrinkle, is perpendicular to contact
Direction, face applies 0～30g load with the contact surface of every 1c, at above-mentioned polymeric membrane glass transition temperature to polymeric membrane glass
In the temperature of glass transition temperature+50 DEG C, both cool to room temperature with the furnace after contacting 1h, take off load and by wrinkle template from
Throw off in substrate, thus on the micron-sized crepe structure surface of substrate polymeric membrane, be formed with nano level ordered porous knot
Structure.
Further, described polymer solution is that polystyrene/tetrahydrofuran solution, styrene methyl methacrylate are randomly total to
One in polymers/tetrahydrofuran solution and (polystyrene+Polyethylene Glycol)/oxolane mixed solution.
Compared with prior art, the invention has the beneficial effects as follows:
Present invention achieves the combination of wrinkle and porous, and can be by the kind of regulation polymer solution used and concentration
And the cycle of wrinkle template regulates the size of many hole dimensions, the order of porous obtains greatly under the restriction of wrinkle template
Improvement, the present invention has the biggest motility to the selection of polymeric material simultaneously.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) picture of the ordered porous pattern that the embodiment of the present invention 1 obtains；
Fig. 2 is scanning electron microscope (SEM) picture of the ordered porous pattern that the embodiment of the present invention 2 obtains；
Fig. 3 is scanning electron microscope (SEM) picture of the ordered porous pattern that the embodiment of the present invention 3 obtains；
Fig. 4 is scanning electron microscope (SEM) picture of the ordered porous pattern that the embodiment of the present invention 5 obtains；
Fig. 5 is scanning electron microscope (SEM) picture of the ordered porous pattern that the embodiment of the present invention 6 obtains.
Detailed description of the invention
Being described in further detail technical solution of the present invention with specific embodiment below in conjunction with the accompanying drawings, described is embodied as
The present invention is only explained by example, not in order to limit the present invention.
Embodiment 1, utilize the mode induction of orthogonal impressing to prepare ordered porous membrane, comprise the following steps:
Step one, PDMS performed polymer and cross-linking agent are mixed for 10:1 in mass ratio after, pour in culture dish, use Glass rod
It is sufficiently stirred for forming uniform prepolymer；
Step 2, performed polymer step one mixed deaerate after 1h in the multiplex vacuum pump of circulating water type, add at 70 DEG C
Hot 4h is dried, solidify after form PDMS elastomer；
Step 3, PDMS elastomeric shear step 2 prepared become the rectangle of 6cm × 2cm；
Step 4, sheet material step 3 obtained, process 30min when prestretched 10% with oxygen plasma, it
After, bouncing back with the speed of 0.5%/min and obtain the PDMS wrinkle template with bar shaped wrinkle, its wrinkle cycle is about 7 microns；
Step 5, the PDMS wrinkle template with bar shaped wrinkle step 4 prepared just are cutting into 1cm × 1cm
Square, polystyrene (PS)/oxolane (THF) solution taking the 40mg/ml of 30 μ l is spin-coated on the band sheared completely
Having in the one side of PDMS wrinkle template of bar shaped wrinkle, evacuation 1h to solvent volatilization is complete, thus at described PDMS
Polystyrene film is obtained in wrinkle template；
Step 6, using the PDMS wrinkle template after step 5 processes as substrate, by step 4 gained wrinkle template with
This substrate contacts with the wrinkle direction of substrate face-to-face according to the wrinkle direction of template wrinkle, is placed on 140
Cool to room temperature with the furnace after both contact 1h at a temperature of DEG C, wrinkle template is thrown off from substrate, thus at substrate film
Being formed with nano level ordered porous structural on the surface of micron order crepe structure, the aperture of this porous is about 900 ran.
Fig. 1 be the PS/THF solution spin coating sample of the present embodiment 40mg/ml at 140 degrees Celsius after minor cycle wrinkle template-mediated
SEM schemes.
Embodiment 2: utilize the mode induction of orthogonal impressing to prepare ordered porous membrane, comprise the following steps:
Step one to step 4 with embodiment 1；
Step 5, the PDMS wrinkle template with bar shaped wrinkle step 4 prepared just are cutting into 1cm × 1cm
Square, the PS/THF solution of the 50mg/ml taking 30 μ l is spin-coated on the PDMS wrinkle with bar shaped wrinkle sheared completely
In the one side of template, evacuation 1.5h to solvent volatilization completely, thus obtains polystyrene in described PDMS wrinkle template
Film；
Step 6, with embodiment 1, finally, being formed on the surface of the micron order crepe structure of substrate film nano level has
Sequence loose structure, the aperture of this porous is about 600 ran.Fig. 2 is the PS/THF solution rotation of the present embodiment 50mg/ml
It is coated with sample at 140 degrees Celsius of SEM figures after minor cycle wrinkle template-mediated.
Embodiment 3: utilize the mode induction of orthogonal impressing to prepare ordered porous membrane, comprise the following steps:
Step one to step 4 with embodiment 1；
Step 5, the PDMS wrinkle template with bar shaped wrinkle step 4 prepared just are cutting into 1cm × 1cm
Square, the PS/THF solution of the 60mg/ml taking 30 μ l is spin-coated on the PDMS wrinkle with bar shaped wrinkle sheared completely
In the one side of template, evacuation 2h to solvent volatilization completely, thus obtains polystyrene in described PDMS wrinkle template
Film；
Step 6, using the PDMS wrinkle template after step 5 processes as substrate, by step 4 gained wrinkle template with
This substrate contacts with the wrinkle direction of substrate face-to-face according to the wrinkle direction of template wrinkle, is placed on 130
Cool to room temperature with the furnace after both contact 1h at a temperature of DEG C, wrinkle template is thrown off from substrate, thus at substrate film
Being formed with nano level ordered porous structural on the surface of micron order crepe structure, the aperture of this porous is about 500 ran.
Fig. 3 be the PS/THF solution spin coating sample of the present embodiment 60mg/ml at 130 degrees Celsius after minor cycle wrinkle template-mediated
SEM schemes.
Embodiment 4: utilize the mode induction of orthogonal impressing to prepare ordered porous membrane, comprise the following steps:
Step one to step 4 with embodiment 1；
Step 5, the PDMS wrinkle template with bar shaped wrinkle step 4 prepared just are cutting into 1cm × 1cm
Square, take the styrene methyl methacrylate random copolymer/oxolane (PS-r-PMMA/THF of the 50mg/ml of 30 μ l
Random copolymer) solution be spin-coated on completely sheared with in the one side of the PDMS wrinkle template of bar shaped wrinkle, evacuation
2h to solvent volatilization completely, thus obtains styrene methyl methacrylate random copolymerization in described PDMS wrinkle template
Thing thin film；
Step 6, with embodiment 1, finally, being formed on the surface of the micron order crepe structure of substrate film nano level has
Sequence loose structure, the aperture of this porous is about 400 ran.
Embodiment 5: utilize the mode induction of orthogonal impressing to prepare ordered porous membrane, comprise the following steps:
Step one to step 3 with embodiment 1；
Step 4, sheet material step 3 obtained, process 55min when prestretched 30% by UV ozone, afterwards,
Bouncing back with the speed of 1%/min and obtain the PDMS wrinkle template of band bar shaped wrinkle, its wrinkle cycle is about 30 microns；
Step 5, the PDMS wrinkle template with bar shaped wrinkle step 4 prepared just are cutting into 1cm × 1cm
Square, the PS-r-PMMA/THF random copolymer solution of the 30mg/ml taking 30 μ l be spin-coated on completely sheared with bar
In the one side of the PDMS wrinkle template of shape wrinkle, evacuation 1h to solvent volatilization is complete, thus at described PDMS wrinkle
Styrene methyl methacrylate random copolymer thin film is obtained in template；
Step 6, using the PDMS wrinkle template after step 5 processes as substrate, by step 4 gained wrinkle template with
This substrate contacts with the wrinkle direction of substrate face-to-face according to the wrinkle direction of template wrinkle, is perpendicular to contact
Direction, face applies 20g load, is placed at a temperature of 120 DEG C and cools to room temperature with the furnace after both contact 1h, takes off load also
Wrinkle template is thrown off from substrate, thus be formed on the micron order crepe structure surface of substrate film nano level in order
Loose structure, and formed ordered porous above have smaller size of hole to generate, the size in the biggest hole is about 1.5
Microns, the size in less hole is about 200 ran.Fig. 4 is the PS/THF solution rotation of the present embodiment 30mg/ml
It is coated with sample at 120 degrees Celsius of SEM figures after large period wrinkle template-mediated.
Embodiment 6: utilize the mode induction of orthogonal impressing to prepare ordered porous membrane, comprise the following steps:
Step one is to step four-way embodiment 1；
Step 5, the PDMS wrinkle template with bar shaped wrinkle step 4 prepared just are cutting into 1cm × 1cm
Square, take 30 μ l 5% (polystyrene+Polyethylene Glycol)/oxolane mixed solution (wherein polystyrene and poly-second
The proportioning of glycol is 4:1) be spin-coated on completely sheared with in the one side of the PDMS wrinkle template of bar shaped wrinkle, evacuation
2h to solvent volatilization completely, thus obtains polystyrene and Polyethylene Glycol bipolar mixture thin film in described PDMS wrinkle template；
Step 6, using the PDMS wrinkle template after step 5 processes as substrate, by step 4 gained wrinkle template with
This substrate contacts with the wrinkle direction of substrate face-to-face according to the wrinkle direction of template wrinkle, is placed on 120
Cool to room temperature with the furnace after both contact 1h at a temperature of DEG C, wrinkle template is thrown off from substrate, thus at substrate film
Nano level ordered porous structural it is formed with on the surface of micron order crepe structure, and on the ordered porous structural formed
Having smaller size of hole to generate, the size in the biggest hole is about 250 ran, and the size in less hole about 40 is received
About meter.Fig. 5 be the spin coating sample of the mixed solution of the present embodiment 5% (PS+PEG)/THF at 120 degrees Celsius through Xiao Zhou
SEM figure after phase template-mediated.
To sum up, the present invention utilizes the mode of orthogonal impressing induction to prepare ordered porous membrane preparation method and achieves wrinkle and porous
Organically combine, and can be come by the kind of regulation polymer used and concentration and the cycle of wrinkle template and heating-up temperature
Regulating the size of many hole dimensions, the order of porous is greatly improved under the restriction of wrinkle template, simultaneously the present invention couple
The selection of polymeric material has the biggest motility.
Although above in conjunction with accompanying drawing, invention has been described, but the invention is not limited in above-mentioned detailed description of the invention,
Above-mentioned detailed description of the invention is only schematic rather than restrictive, and those of ordinary skill in the art is in the present invention
Enlightenment under, without deviating from the spirit of the invention, it is also possible to make many variations, these belong to the guarantor of the present invention
Within protecting.
Claims (1)
1. the method that the mode utilizing orthogonal impressing induction prepares ordered porous membrane, it is characterised in that comprise the following steps:
Step one, PDMS performed polymer and cross-linking agent are mixed for 10:1 in mass ratio after, pour in culture dish, use Glass rod
It is sufficiently stirred for forming uniform prepolymer；
Step 2, prepolymer step one prepared deaerate successively, be dried, solidify after form PDMS elastomer；
Step 3, PDMS elastomeric shear step 2 prepared become sheet material；
Step 4, use mechanical stretching method, and according to one of following process technique prepare different cycles with bar shaped wrinkle
PDMS wrinkle template:
Sheet material step 3 obtained, processes 15-60min when prestretched 10% with oxygen plasma, afterwards,
Bounce back with the speed of 0.5%/min and obtain the PDMS wrinkle template with bar shaped wrinkle that the wrinkle cycle is 6～15 microns；
Or:
Sheet material step 3 obtained, processes 55min when prestretched 30% by UV ozone, afterwards, with
The speed retraction of 1%/min obtains the PDMS wrinkle template with bar shaped wrinkle that the wrinkle cycle is 30～40 microns；
Step 5, the polymer solution that concentration is 30～60mg/ml is spin-coated on the PDMS wrinkle template that step 4 prepares
On one surface, wherein, on the PDMS wrinkle template area of every 1c, the polymer solution of spin coating 30 μ l, then, takes out
Vacuum 1-2h is volatilized completely to solvent, thus obtains polymeric membrane in described PDMS wrinkle template；Wherein, described poly-
Polymer solution be polystyrene/tetrahydrofuran solution, styrene methyl methacrylate random copolymer/tetrahydrofuran solution and
One in (polystyrene+Polyethylene Glycol)/oxolane mixed solution；
Step 6, using the PDMS wrinkle template after step 5 processes as substrate, by step 4 gained wrinkle template with
This substrate contacts with the wrinkle direction of substrate face-to-face according to the wrinkle direction of template wrinkle, is perpendicular to contact
Direction, face applies 0～30g load with the contact surface of every 1c, at above-mentioned polymeric membrane glass transition temperature to polymeric membrane glass
In the temperature of glass transition temperature+50 DEG C, both cool to room temperature with the furnace after contacting 1h, take off load and by wrinkle template from
Throw off in substrate, thus on the micron-sized crepe structure surface of substrate polymeric membrane, be formed with nano level ordered porous knot
Structure.
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| CN104914494A (en) * | 2015-06-13 | 2015-09-16 | 复旦大学 | A method for obtaining full-color-spectrum structural color through preparing metal holes having a chassis by utilizing nano-imprint lithography |
| CN105000532B (en) * | 2015-06-17 | 2016-08-24 | 清华大学 | The preparation of film-based system unstability speckle figure and the regulation and control method under wavelength dimension |
| 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 |
| CN106393726B (en) * | 2016-09-30 | 2019-03-05 | 大连海洋大学 | In the method for the striated micro-structure of elastomer PDMS surface construction morphology controllable |
| CN111071983A (en) * | 2019-12-23 | 2020-04-28 | 大连海洋大学 | Rapid preparation method of elastomer PDMS (polydimethylsiloxane) multistage wrinkled surface |
| CN115260764A (en) * | 2022-08-25 | 2022-11-01 | 哈尔滨工业大学 | Preparation method of flexible oxygen sensing film based on microstructure |
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| CN102795595A (en) * | 2012-07-13 | 2012-11-28 | 天津大学 | Preparation method of wrinkles by combining selected area ultraviolet ozonization and solvent swelling and application thereof |
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