CN114515516A - High-flux corrugated PDMS nanofiber composite membrane and preparation method thereof - Google Patents
High-flux corrugated PDMS nanofiber composite membrane and preparation method thereof Download PDFInfo
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- CN114515516A CN114515516A CN202210098880.5A CN202210098880A CN114515516A CN 114515516 A CN114515516 A CN 114515516A CN 202210098880 A CN202210098880 A CN 202210098880A CN 114515516 A CN114515516 A CN 114515516A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/08—Patterned membranes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a high-flux corrugated PDMS nanofiber composite membrane, which comprises a substrate and a surface layer, wherein the surface layer is a corrugated PDMS membrane, the substrate is a porous nanofiber material with a plurality of randomly distributed strip-shaped protruding structures, and the plurality of protruding structures are mutually crossed to form a plurality of concave regions. The invention can easily manufacture a defect-free submicron thin PDMS membrane by coating the PDMS membrane casting solution on the electrospinning nanofiber substrate, wherein the convex structure and the concave region on the surface of the substrate can transfer the structural shape of the bottom layer to the PDMS membrane, so that the PDMS membrane is corrugated, the prepared corrugated PDMS composite membrane has the advantages of high flux, no need of a specific substrate mould and low transmission resistance, and the preparation process is simple.
Description
Technical Field
The invention belongs to the technical field of fiber composite membranes, and particularly relates to a high-flux corrugated PDMS nanofiber composite membrane and a preparation method thereof.
Background
Polydimethylsiloxane (PDMS) is a standard membrane material used for permeation, gas separation and nanofiltration, and has wide applications in pervaporation, gas separation and nanofiltration processes. For practical applications, high-throughput PDMS membranes are always needed to improve the efficiency of the separation process. Currently, efforts are being made to modify the membrane geometry to increase flux, and two methods are currently available to control the geometric appearance of the membrane.
The first method is to make the film as thin as possible, and to manufacture an ultra-thin film having a thickness of about 100 nm, but it tends to cause a decrease in selectivity, causing defects in the film. The second approach is to pattern the surface of the composite membrane, which can increase the permeate flux by increasing the membrane surface roughness or membrane effective area. Referring to "Mass transfer in corrected membranes" in Journal of Membrane Science ", Cussler et al manufactured highly corrugated PDMS membranes for pervaporation experiments and verified that an improved Thiele model was used for Membrane Mass transfer, it was found that the corrugated Membrane structure resulted in a doubling of flux compared to the flat sheet Membrane, however, no selective permeation was reported in such PDMS membranes, which could not exclude the effect of defects on Membrane flux increase. In addition, such high throughput PDMS membranes do not effectively separate mixtures of molecules. Referring to "Fabrication and characterization of micro-patterned PDMS composite membranes for enhanced ethanol recovery" in Journal of Membrane Science ", Lei.e., Lei.J.prepared PDMS selective layers by using different crosslinkers (p-tolyltriethoxysilane, p-TTES; triethoxyvinylsilane, VTES; tetraethyl orthosilicate, TEOS), it was found that the TEOS-crosslinked Membrane had the largest pattern size (3.78 μm), and the high flux of the patterned Membrane was attributed to the increase in effective Membrane area compared to the non-patterned Membrane.
It follows that the fabrication of high throughput PDMS membranes consists in depositing thinner membrane layers and, where possible, creating patterned membrane surfaces, however, the implementation of sub-micron thin PDMS membranes using traditional macroporous substrates (e.g. average pore size >100 nm) remains a huge challenge, as the penetration of the PDMS coating into the substrate macropores often leads to too thick transition layers or membrane layer defects, reducing the membrane separation performance, and furthermore, the current methods of fabricating patterned PDMS membranes are complicated or fail to show good separation performance for molecular mixtures. In view of this, it is necessary to research a high-throughput corrugated PDMS nanofiber composite membrane and a method for preparing the same.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a high-flux corrugated PDMS nanofiber composite membrane and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical solutions:
the high-flux corrugated PDMS nanofiber composite membrane comprises a substrate and a surface layer, wherein the surface layer is a corrugated PDMS membrane, the substrate is a porous nanofiber material with a plurality of randomly distributed strip-shaped protruding structures, and the protruding structures are mutually crossed to form a plurality of concave regions.
Preferably, the height of the protruding structure is 230 to 260nm, and the average diameter of the recessed region is 160 to 280 nm.
More preferably, the thickness of the surface layer is 0.5 to 2.5 μm.
A preparation method of a high-flux corrugated PDMS nanofiber composite membrane comprises the following specific steps:
s1, obtaining a substrate;
and S2, dissolving PDMS, a catalyst and a cross-linking agent in a solvent, applying the solution on the surface of a substrate, and performing film forming treatment to obtain the composite film.
Preferably, the aforementioned substrate is prepared by the following method: dissolving a polymer in an organic solvent to obtain a spinning solution; and preparing the electrospinning nanofiber substrate from the spinning solution by an electrostatic spinning method, and carrying out hot pressing treatment to obtain the substrate.
Still preferably, the polymer is one of polyvinylidene fluoride, polyethersulfone, polysulfone or polyacrylonitrile, and the organic solvent is one or a mixture of acetone, dichloromethane, N-dimethylformamide or tetrahydrofuran.
More preferably, the organic solvent is N, N-dimethylformamide and acetone according to a volume ratio of (4-6): (1-2).
More preferably, the mass fraction of the polymer in the spinning solution is 8 to 15 wt%; the injection speed of the injector is kept at 0.1-1 mL/min; the speed of the rotary collector is 300 rpm, the voltage is set to be 5-20 kV, the distance between the collector and the metal needle is 10-20 cm, the temperature of the electrostatic spinning process is 25-50 ℃, and the relative humidity is 40-50%; the hot pressing temperature is 25-80 ℃, and the hot pressing pressure is 1-9 Mpa.
Specifically, the catalyst is one of dibutyltin dilaurate or dimethyl phthalate, the crosslinking agent is one of ethyl orthosilicate, vinyl trimethoxy silane or phenyl triethoxy silane, and the solvent is one or a mixture of n-heptane, n-hexane, n-octane, acetone or triethanolamine.
Preferably, the mass ratio of the catalyst to the crosslinking agent to the PDMS is (1-3): (10-16): (100-120).
The invention has the advantages that: the invention can easily manufacture a defect-free submicron thin PDMS membrane by coating the PDMS membrane casting solution on the electrospinning nanofiber substrate, wherein the convex structures and the concave regions on the surface of the substrate can transfer the structural shape of the bottom layer to the PDMS membrane, so that the PDMS membrane is corrugated, meanwhile, a plurality of strip-shaped convex structures on the surface of the substrate are mutually crossed, the PDMS solvent can be effectively prevented from excessively permeating into the concave regions of the substrate, the prepared corrugated PDMS composite membrane has the advantages of high flux, no need of a specific substrate mold and low transmission resistance, and the preparation process is simple; the corrugated form of the PDMS membrane effectively increases the surface area of the composite membrane, thereby effectively improving the separation performance of the membrane.
Drawings
FIG. 1 is an SEM image of a substrate after hot pressing post-treatment of S1-S9 in test 1 of the present invention;
FIG. 2 is a graph of pervaporation performance measurements of PDMS composite membranes prepared under a substrate with recessed regions of different average diameters in test 2 of the present invention;
fig. 3 is SEM surface (a, d), cross-sectional view (b, e) and Si element EDX map (c, f) images of (a, c) defect-free PDMS film layer formed on a substrate having different average diameter depression regions in experiment 2 of the present invention;
fig. 4 is SEM images of the surface (a, c) and cross-section (d, f) of the PDMS nanofiber composite membrane in experiment 3 of the present invention;
FIG. 5 is an AFM image of the smooth PDMS film (a) and the corrugated PDMS film (b, c) in experiment 3 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
The high-flux corrugated PDMS nanofiber composite membrane comprises a substrate and a surface layer, wherein the surface layer is a corrugated PDMS membrane, the substrate is a porous nanofiber material with a plurality of randomly distributed strip-shaped protruding structures, and the protruding structures are mutually crossed to form a plurality of concave regions. The height of the protruding structure is 230-260 nm, the average diameter of the recessed area is 160-280 nm, and the thickness of the surface layer is 0.5-2.5 μm.
A preparation method of a high-flux corrugated PDMS nanofiber composite membrane comprises the following specific steps:
s1, obtaining a substrate;
and S2, dissolving PDMS, a catalyst and a cross-linking agent in a solvent, applying the solution on the surface of a substrate, and performing film forming treatment to obtain the composite film.
The substrate is prepared by the following method: dissolving a polymer in an organic solvent to obtain a spinning solution; and preparing the electrospinning nanofiber substrate from the spinning solution by an electrostatic spinning method, and carrying out hot pressing treatment to obtain the substrate. Wherein the polymer is one of polyvinylidene fluoride, polyethersulfone, polysulfone or polyacrylonitrile, and the organic solvent is one or a mixture of acetone, dichloromethane, N-dimethylformamide or tetrahydrofuran. The organic solvent is N, N-dimethylformamide and acetone according to a volume ratio (4-6): (1-2). The mass fraction of the polymer in the spinning solution is 8-15 wt%; the injection speed of the injector is kept at 0.1-1 mL/min; the speed of the rotary collector is 300 rpm, the voltage is set to be 5-20 kV, the distance between the collector and the metal needle is 10-20 cm, the temperature of the electrostatic spinning process is 25-50 ℃, and the relative humidity is 40-50%; the hot pressing temperature is 25-80 ℃, and the hot pressing pressure is 1-9 Mpa.
The film forming treatment in S2 is drying treatment, the catalyst is one of dibutyltin dilaurate or dimethyl phthalate, the crosslinking agent is one of ethyl orthosilicate, vinyl trimethoxy silane or phenyl triethoxy silane, and the solvent is one or a mixture of n-heptane, n-hexane, n-octane, acetone or triethanolamine. The mass ratio of the catalyst to the crosslinking agent to the PDMS is (1-3): (10-16): (100-120).
Performance test
1. Effect of Hot pressing conditions on substrate Properties
In order to adjust the strip-shaped protruding structures and the recessed regions of the substrate and improve the mechanical strength, the electrospinning nanofiber substrate was subjected to hot pressing treatment under different pressures and temperatures, the performance of the substrate prepared under different hot pressing conditions was tested, and a comparative example C1 was set, the comparative example selected the electrospinning nanofiber substrate without hot pressing treatment, and referring to table 1 for the characteristics and operating conditions of the substrates in S1 to S9 and C1, it was observed that the increase in hot pressing pressure and temperature resulted in a more compact and rigid substrate structure, achieving a reduction in the average diameter of the recessed regions, which however resulted in an increase in transmission resistance, and if the average of the recessed regions of the substrate was too large, it was difficult to produce a defect-free film on the substrate surface. In addition, through the hot-pressing post-treatment at different pressures and temperatures, the water contact angle of the substrate is basically unchanged, the surface of the substrate has strong hydrophobicity, the water contact angle is 120 degrees, the surface of the substrate can cause non-polar liquid (such as PDMS/n-heptane coating solution) to be easy to wet, and a defect-free film layer can be formed, so that the PDMS casting solution can be directly coated on the surface of the substrate to form the defect-free and thin PDMS film layer.
The surface morphology of the substrate in S1-S9 is shown in figure 1, and it can be seen that the substrate has a plurality of strip-shaped protruding structures which are crossed and interpenetrated to form a recessed region and do not have a thick skin layer, and the structure of the substrate is favorable for forming a corrugated polymer coating and low transmission resistance.
TABLE 1 Properties of substrates prepared under different hot pressing conditions
2. Effect of average diameter of substrate recess region on PDMS nanofiber composite film characteristics
The pervaporation performance of the PDMS composite membranes prepared under the substrate using the depressed regions with different average diameters is detected, and the detection result is shown in FIG. 2, and it can be observed that when 5wt% ethanol/water mixture is separated at the feeding temperature of 40 ℃, the total flux of the corrugated PDMS composite membranes is 1.9-3.9 kg m-2 h-1The separation factor exceeds 7.
A PDMS film was prepared on the substrate (average diameter of the depressed regions is 259 nm) of S3 in experiment 1, and as shown in fig. 3a-c, a defect-free PDMS film layer was formed on the substrate, which was extremely rough and corrugated in structure from the surface morphology of the composite film. Further increasing the average diameter of the depressed regions of the substrate beyond 300 nm, the PDMS membrane layer became defective (see fig. 3 d-e), resulting in a large drop in the separation ethanol/water solution separation factor to 5.83 (see fig. 2), which is lower than the intrinsic selectivity of the PDMS membrane material, as evidenced by EDX diffraction of the Si element (from PDMS) along a cross-sectional view of the PDMS/PVDF nanofiber composite membrane (fig. 3c, f), the intrusion of the PDMS coating into the substrate with an average depressed region diameter of about 307 nm was more pronounced than on the substrate with an average depressed region diameter of about 259 nm.
Influence of PDMS film thickness on PDMS nanofiber composite film characteristics
Defect-free PDMS film layers with different thicknesses of 2.5 [ mu ] m, 1.5 [ mu ] m and 0.5 [ mu ] m are successfully prepared on the S3 substrate in the test 1, at least three film samples are observed through a graph shown in FIG. 4, if the film thickness is less than 0.5 [ mu ] m, defects are more easily formed, and in addition, the repeatability of film manufacturing is low and the mechanical stability is reduced. According to fig. 4a-c, it can be seen that the ripple morphology of the PDMS film layer gradually appears as the thickness of the PDMS film layer gradually decreases, and further AFM is used to monitor the surface morphology of the PDMS composite films, and referring to fig. 5, it can be confirmed that the strip-shaped protrusion mechanism and the recessed area of the substrate generate a ripple film surface, and as the thickness of the PDMS film layer decreases, the height of the composite film increases by 2-3 times, and the ripple morphology effectively increases the surface area of the film.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (10)
1. The high-flux corrugated PDMS nanofiber composite membrane comprises a substrate and a surface layer, and is characterized in that the surface layer is a corrugated PDMS membrane, the substrate is a porous nanofiber material with a plurality of randomly distributed strip-shaped protruding structures, and the protruding structures are mutually crossed to form a plurality of concave regions.
2. The high-flux corrugated PDMS nanofiber composite membrane according to claim 1, wherein the height of the protruding structures is 230 to 260nm, and the average diameter of the recessed regions is 160 to 280 nm.
3. The high-flux corrugated PDMS nanofiber composite membrane according to claim 1, wherein the thickness of the surface layer is 0.5-2.5 μm.
4. The preparation method of the high-flux corrugated PDMS nanofiber composite membrane as claimed in claim 1, comprising the following steps:
s1, obtaining a substrate;
and S2, dissolving PDMS, a catalyst and a cross-linking agent in a solvent, applying the solution on the surface of a substrate, and performing film forming treatment to obtain the composite film.
5. The method for preparing the high-throughput corrugated PDMS nanofiber composite membrane according to claim 4, wherein the substrate is prepared by the following method: dissolving a polymer in an organic solvent to obtain a spinning solution; and preparing the electrospinning nanofiber substrate from the spinning solution by an electrostatic spinning method, and carrying out hot pressing treatment to obtain the substrate.
6. The preparation method of the high-flux corrugated PDMS nanofiber composite membrane according to claim 5, wherein the polymer is one of polyvinylidene fluoride, polyethersulfone, polysulfone or polyacrylonitrile, and the organic solvent is one or a mixture of acetone, dichloromethane, N-dimethylformamide or tetrahydrofuran.
7. The preparation method of the high-flux corrugated PDMS nanofiber composite membrane according to claim 6, wherein the organic solvent is N, N-dimethylformamide and acetone according to a volume ratio of (4-6): (1-2).
8. The preparation method of the high-flux corrugated PDMS nanofiber composite membrane according to claim 5, wherein the mass fraction of the polymer in the spinning solution is 8-15 wt%; the injection speed of the injector is kept at 0.1-1 mL/min; the speed of the rotary collector is 300 rpm, the voltage is set to be 5-20 kV, the distance between the collector and the metal needle is 10-20 cm, the temperature of the electrostatic spinning process is 25-50 ℃, and the relative humidity is 40-50%; the hot pressing temperature is 25-80 ℃, and the hot pressing pressure is 1-9 Mpa.
9. The method as claimed in claim 4, wherein the catalyst is one of dibutyltin dilaurate and dimethyl phthalate, the cross-linking agent is one of ethyl orthosilicate, vinyltrimethoxysilane and phenyltriethoxysilane, and the solvent is one or a mixture of n-heptane, n-hexane, n-octane, acetone and triethanolamine.
10. The preparation method of the high-flux corrugated PDMS nanofiber composite membrane according to claim 4, wherein the mass ratio of the catalyst to the crosslinking agent to the PDMS is (1-3): (10-16): (100-120).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1655927A (en) * | 2002-05-27 | 2005-08-17 | 帝人杜邦菲林日本株式会社 | Releasing film |
| CN101530010A (en) * | 2006-10-18 | 2009-09-09 | 3M创新有限公司 | Methods of patterning a material on polymeric substrates |
| CN105731364A (en) * | 2016-02-29 | 2016-07-06 | 天津大学 | PDMS elastomer micro-nano processing method based on surface oxidation control transfer printing |
| US20170341017A1 (en) * | 2014-11-13 | 2017-11-30 | Ohio State Innovation Foundation | Membranes for fluid separation |
| CN110033900A (en) * | 2019-04-09 | 2019-07-19 | 深圳市华星光电技术有限公司 | Flexible conductive film and preparation method thereof, display panel |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1655927A (en) * | 2002-05-27 | 2005-08-17 | 帝人杜邦菲林日本株式会社 | Releasing film |
| CN101530010A (en) * | 2006-10-18 | 2009-09-09 | 3M创新有限公司 | Methods of patterning a material on polymeric substrates |
| US20170341017A1 (en) * | 2014-11-13 | 2017-11-30 | Ohio State Innovation Foundation | Membranes for fluid separation |
| CN105731364A (en) * | 2016-02-29 | 2016-07-06 | 天津大学 | PDMS elastomer micro-nano processing method based on surface oxidation control transfer printing |
| CN110033900A (en) * | 2019-04-09 | 2019-07-19 | 深圳市华星光电技术有限公司 | Flexible conductive film and preparation method thereof, display panel |
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