CN103612423A - Polyimide film-alumina template compound asymmetric porous composite material and preparation method thereof - Google Patents
Polyimide film-alumina template compound asymmetric porous composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyimide film-alumina template compound asymmetric porous composite material and a preparation method thereof. The preparation method of the polyimide film-alumina template compound asymmetric porous composite material comprises the steps of: coating a porous alumina template having a honeycomb nanopore structure in a reaction chamber with a film-forming solution which is formed by mixing polyimide and trichloromethane, blowing in an inert gas with water vapor, condensating the water vapor on the surface of the film-forming solution to form water drips which enter the film-forming solution, thus obtaining a porous polyimide film having a honeycomb micropore structure after the trichloromethane and water volatilize completely, and forming an asymmetric penetrating-pore structure in which micro-diameter pores are communicated with nano-diameter pores because the pores at the joint of the micropores in the porous polyimide film and the nanopores in the porous alumina template are communicated with each other, thus obtaining the polyimide film-alumina template compound asymmetric porous-structure composite material, wherein the asymmetric penetrating pores have excellent ion rectification property in transporting electrolyte ions.
Description
Technical field
The present invention relates to bionical ion channel composite, composite of the asymmetric porous micro nano structure with good ion rectification that particularly polyimides polymer material film and alumina formwork are compounded to form and preparation method thereof.
Background technology
Miscellaneous biology, through long-term evolution in 4,500,000,000 years, makes its structure and function reach the degree of almost Perfect, has realized the unification of structure and function, local and whole coordination and unification.Bionic Design principle provides new method and approach for creating new structure and functional material, to naturally learning, is the important source of new material development.In recent years, biomimetic features and functional material thereof have been subject to people and have more and more paid close attention to, as bionical photon crystal material, bionical hollow structure material, bionical ion channel, the imitative super tough fiber of spider silk, bionical special wellability surface, bionical high-strength ultra-tough laminar composite, bionical high pasting material etc.
Ion channel is to be extensively present in the important channel of controlling cell and surrounding material exchange on various cell membranes, it is all by ion channel that the various ions of large multipair life important in inhibiting, carbohydrate etc. enter the water-soluble refuse producing in cell and vital movement when leaving cell, wherein has the ion channel of rectification as K
+postpone outward rectification passage and inward rectification passage to maintain cell resting potential, regulate relax contracting etc. of vascular smooth muscle to there is most important effect, therefore the research of the bionical ion channel of rectification is had to very important scientific meaning.At present rectification ion channel biomimetic material synthetic focus on build channel design or chemical composition asymmetric, thereby reach good rectification or ion is selected gate effect.When building nano-scale passage, by etched ion track technology, electrochemical etching modification or chemical etching, modifying aperture or the asymmetric duct of chemical composition at the two ends that obtain can give passage good ion rectification when as ion channel, but the formation in these ducts needs comparatively exacting terms and control accuracy, energy consumption high and during for the preparation of nano-device size limited, application is restricted.The hole with the film of cellular loose structure is the perforation duct of micron-scale array, this film with cellular loose structure combines with the alumina formwork with nano-scale array perforation duct, different with the aperture in perforation duct of alumina formwork with cellular perforation duct owing to thering is the aperture in perforation duct of film of cellular loose structure, can obtain thus the asymmetric perforation pore passage structure of large area array, this asymmetric perforation pore passage structure will be to bio-sensing, receiving flow control device and bionical ion channel systematic research produces important meaning.
Summary of the invention
One of object of the present invention be to provide the porous alumina formwork that there is the porous polyimide film of cellular micron pore passage structure and there is cellular nano pore passage structure carry out compound obtain there is the asymmetric composite porous of good ion rectification and high stability.
Two of object of the present invention is in order to overcome the harsh wayward and problem that application is difficult of loaded down with trivial details time-consuming, the condition of current bionical ion channel material preparation method, thereby provides a kind of preparation method simply to have the porous polyimide film of the cellular micron of having of good ion rectification and high stability pore passage structure and have the compound asymmetric composite porous preparation method of porous alumina formwork of cellular nano pore passage structure.
The present invention is the porous polyimide film that utilizes polyimides to form to have cellular micron pore passage structure on the porous alumina formwork with array cellular nano pore passage structure, the duct of the junction of described porous polyimide rete and described porous alumina formwork is connected, and forms aperture for micron perforation duct that the duct that is nanometer with aperture is connected.By pattern, observe and electrical performance testing, confirmed the existence of this asymmetric composite porous interior composite via structures, and this composite has good ion rectification.
Compound asymmetric composite porous of polyimide film of the present invention and alumina formwork is to be composited by the porous alumina formwork that has the porous polyimide film of cellular micron pore passage structure and have a cellular nano pore passage structure, micron duct in the described porous polyimide film with cellular micron pore passage structure and the duct with the junction of the nano pore in the porous alumina formwork of cellular nano pore passage structure are connected, and the asymmetric perforation pore passage structure being connected is docked in the duct that to form aperture be nanometer for micron with aperture.
Asymmetric micron and nanometer composite structure through hole road in composite porous of the present invention has good ion rectification, and when as bionical ion channel, utilizing picoammeter to record its best ion rectified value is 20.8.By adopting the KCl solution of concentration difference 0.01M, 0.1M, 1M as electrolyte solution in embodiment 2, the compound asymmetric composite porous I-V curve (see figure 3) of measured above-mentioned polyimide film and alumina formwork can be found out, when other condition is identical, the ion rectification in the perforation duct in compound asymmetric composite porous of polyimide film and alumina formwork increases and reduces with the concentration of test KCl electrolyte solution used.By adopting concentration in embodiment 1,2,3,4, be that the KCl solution of 0.01M is during as electrolyte solution, the corresponding relation figure (Fig. 4) in the aperture in the ion rectified value in the perforation duct in compound asymmetric composite porous of measured polyimide film and alumina formwork and alumina formwork used can find out, use the prepared asymmetric composite porous rectification of alumina formwork in 20～30nm aperture best, use the prepared asymmetric composite porous rectification of alumina formwork in other aperture relatively less than normal.
Compound asymmetric composite porous of polyimide film of the present invention and alumina formwork is that the chloroform soln by polyimides utilizes water template to be prepared under high humidity environment on alumina formwork, specifically comprises the following steps:
(1) polyimide powder is fully dissolved in in chloroform, to be made into mass concentration be 1% polyimides film forming solution;
(2) polyimides film forming solution step (1) being obtained is evenly coated on the porous alumina formwork with cellular nano pore passage structure in reative cell, then in reative cell, be blown into the inert gas (as nitrogen) that carries steam, make reative cell form high humidity environment, in chloroform solvent evaporates in polyimides film forming solution, the volatilization that steam is accompanied by chloroform solvent is condensate in the surface of polyimides film forming solution and forms water droplet and enters into polyimides film forming solution, after chloroform solvent is evaporated completely completely, the polyimides solid that contains water droplet obtaining is positioned under room temperature, after the water in the polyimides solid that contains water droplet is evaporated completely completely, on the porous alumina formwork with cellular nano pore passage structure, obtain having the porous polyimide film of cellular micron pore passage structure, and the micron duct in the described porous polyimide film with cellular micron pore passage structure and the duct with the junction of the nano pore in the porous alumina formwork of cellular nano pore passage structure are connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected, make thus the compound asymmetric composite material having porous structure of polyimide film and alumina formwork.
The volatilization of the chloroform solvent in preparation method of the present invention can make the surface temperature of polyimides film forming solution reduce, steam can condense into little water droplet (template) on the surface of polyimides film forming solution, and hole in porous polyimide film is evaporated completely rear formation by water.
The thickness of the described porous polyimide film with cellular micron pore passage structure is 2.8～5.5 μ m.
The aperture in the micron duct in the described porous polyimide film with cellular micron pore passage structure is 0.9～1.5 μ m.
The thickness of the described porous alumina formwork with cellular nano pore passage structure is 57～60 μ m.
The aperture of the nano pore in the described porous alumina formwork with cellular nano pore passage structure is preferably 10nm～100nm.
The flow velocity of described inert gas (as nitrogen) is 2L/min.
The ambient humidity of described high humidity environment is 70%～90%.
The compound asymmetric composite porous preparation method's advantage of polyimide film of the present invention and alumina formwork is that it can operate at normal temperatures, and simple and easy to do, preparation technology is controlled, low for equipment requirements, with low cost, application is strong, has stronger promotion and application and is worth.The thickness of this asymmetric polyimides rete in composite porous is 2.8～5.5 μ m, aperture approximately 0.9～1.5 μ m in micron duct.Between this asymmetric duct in composite porous, form micro-nano asymmetric perforation pore passage structure, this asymmetric perforation duct has ion rectification characteristic when electrolyte ion is transported, experiment records its ion rectified value and reaches as high as 20.8, and the compound composite of the polyimide film of level and smooth atresia and alumina formwork, single alumina formwork are all without ion rectification.Experiment shows, compound asymmetric composite porous of polyimide film of the present invention and alumina formwork having potential application prospect aspect bionical ion channel material.
Compound asymmetric composite porous of polyimide film of the present invention and alumina formwork, without complicated exacting terms and chemical method, easy and simple to handle being easy to controlled, less energy consumption, has improved the defect that the techniques such as chemical modification in the past, electrochemical etching, ion sputtering exist aspect cost and application.While, preparation method of the present invention was than traditional new technology, the prepared asymmetric composite porous fields such as bio-sensing, bionical ion channel, bionical energy conversion system that are widely used in.
Accompanying drawing explanation
Fig. 1 (a). the front scan Electronic Speculum figure (SEM) of the polyimides rete in compound asymmetric composite porous of the prepared polyimide film of the embodiment of the present invention 1 and alumina formwork.
Fig. 1 (b). the back scan Electronic Speculum figure (SEM) of the polyimides rete in compound asymmetric composite porous of the prepared polyimide film of the embodiment of the present invention 1 and alumina formwork.
Fig. 2 (a). compound asymmetric composite porous of the prepared polyimide film of the embodiment of the present invention 1 and alumina formwork, measured I-V curve when adopting KCl solution that concentration is 0.01M as electrolyte solution.
Fig. 2 (b). in comparative example 1, adopting concentration is the KCl solution of 0.01M during as electrolyte solution, the I-V curve of measured single alumina formwork.
Fig. 3. compound asymmetric composite porous of the prepared polyimide film of the embodiment of the present invention 2 and alumina formwork, at the KCl solution that adopts concentration to be respectively 0.01M, 0.1M, 1M measured I-V curve during as electrolyte solution.
Fig. 4. in the embodiment of the present invention 1,2,3,4, adopting concentration is the KCl solution of 0.01M during as electrolyte solution, the corresponding relation figure in the aperture in the ion rectified value in the duct in compound asymmetric composite porous of measured polyimide film and alumina formwork and alumina formwork used.
The specific embodiment
(1) polyimide powder is fully dissolved in in chloroform, to be made into mass percent be 1% polyimides film forming solution;
(2) (25 ± 1 ℃) under room temperature, it is on the diameter of the 10～20nm pore passage structure circular porous alumina formwork (thickness is 57～60 μ m) that is 12mm that the polyimides film forming solution that step (1) is obtained is evenly coated to the cellular aperture that has cleaning up in reative cell, then in reative cell, be blown into the nitrogen (flow velocity of nitrogen is 2L/min) that carries steam, making reative cell form ambient humidity is 70%～90%, in chloroform solvent evaporates in polyimides film forming solution, the volatilization that steam is accompanied by chloroform solvent is condensate in the surface of polyimides film forming solution and forms water droplet and enters into polyimides film forming solution, after chloroform solvent is evaporated completely completely, the polyimides solid that contains water droplet obtaining is positioned under room temperature, after the water in the polyimides solid that contains water droplet is evaporated completely completely, on above-mentioned porous alumina formwork, obtain thering is the porous polyimide film that cellular aperture is 0.9～1.5 μ m pore passage structure (thickness is 2.8～5.5 μ m), and the aperture in described porous polyimide film is that the duct of the duct of 0.9～1.5 μ m and the junction in the duct that the aperture in described porous alumina formwork is 10～20nm is connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected, make thus the compound asymmetric composite material having porous structure of polyimide film and alumina formwork.
Adopt cold field emission scanning electron microscope (JEOL, JSM-7500F) observe the surface topography of surface, polyimides rete and the alumina formwork junction of the compound asymmetric composite porous middle polyimides rete of polyimide film prepared by the present embodiment and alumina formwork, the front scan Electronic Speculum figure (SEM) of the polyimides rete in compound asymmetric composite porous of prepared polyimide film and alumina formwork is shown in Fig. 1 (a); Back scan Electronic Speculum figure (SEM) is shown in Fig. 1 (b).From Fig. 1 (a), can find out, the surface of described polyimides rete in asymmetric composite porous is to be ordered porous structural cellular, array; From Fig. 1 (b), can find out, the surface of polyimides rete and alumina formwork junction is to be also ordered porous structural cellular, array, show to have formed in this polyimide film cellular duct structure, micron duct in this porous polyimide film with cellular micron pore passage structure and the duct with the junction of the nano pore in the porous alumina formwork of cellular nano pore passage structure are connected, and the asymmetric perforation pore passage structure being connected is docked in the duct that to form aperture be nanometer for micron with aperture.
Utilize Keithley (keithley) 6487 type picoammeters to measure compound asymmetric composite porous when as bionical ion channel material of polyimide film prepared by the present embodiment and alumina formwork, the electric current in electrolyte solution when passing through this asymmetric perforation duct in composite porous with the variation relation (I-V curve) of voltage.Concrete test process is for by the prepared polyimide film of the present embodiment and compound asymmetric composite porous being fixed in electrolytic cell to be divided into two chambers of alumina formwork, to implantation concentration is 0.01M respectively in two chambers of electrolytic cell KCl solution as electrolyte solution, or to implantation concentration is 0.1M respectively in two chambers of electrolytic cell KCl solution as electrolyte solution, or to implantation concentration is 1M respectively in two chambers of electrolytic cell KCl solution as electrolyte solution; And in two chambers, Ag/AgCl test electrode is installed respectively, when the test voltage of Keithley (keithley) 6487 type picoammeters is from the process of-be increased to+2V of 2V, the electric current of test by this asymmetric perforation duct in composite porous is with voltage change relation (I-V curve).
When adopting KCl solution that concentration is 0.01M as electrolyte solution, I-V curve is as shown in Fig. 2 (a).From Fig. 2 (a), can find out that the through hole road in compound asymmetric composite porous of polyimide film that the present embodiment is prepared and alumina formwork has good ion rectification, according to test result calculations go out its ion rectified value (test voltage for+2V and-ratio of electric current absolute value by this asymmetric perforation duct in composite porous during 2V) be 16.5.
While adopting KCl solution that concentration is 0.01M as electrolyte solution, the corresponding relation figure in the aperture in the ion rectified value in the perforation duct in compound asymmetric composite porous of measured polyimide film and alumina formwork and alumina formwork used as shown in Figure 4.Prepared asymmetric composite porous of the present embodiment is numbered 1.
When adopting KCl solution that concentration is 0.1M as electrolyte solution, test result shows that the through hole road in polyimide film that the present embodiment is prepared and compound asymmetric composite porous of alumina formwork has good ion rectification, and according to test result calculations, going out its ion rectified value is 5.5.
When adopting KCl solution that concentration is 1M as electrolyte solution, test result shows that the through hole road in polyimide film that the present embodiment is prepared and compound asymmetric composite porous of alumina formwork has good ion rectification, and according to test result calculations, going out its ion rectified value is 4.3.
Preparation process is substantially identical with embodiment 1, and the aperture that is the nano pore in the used porous alumina formwork with cellular nano pore passage structure is 20～30nm, and the ambient humidity that reative cell forms is 80%.
Obtain under these conditions thering is the porous polyimide film that cellular aperture is 1.2 μ m pore passage structures (thickness is 3.8 μ m), and the aperture in described porous polyimide film is that the duct of the duct of 1.2 μ m and the junction in the duct that the aperture in described porous alumina formwork is 20～30nm is connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected, make thus the compound asymmetric composite material having porous structure of polyimide film and alumina formwork.
Utilize the surface of the compound asymmetric composite porous middle polyimides rete of scanning electron microscopic observation polyimide film obtained above and alumina formwork, the condition of the surface topography of polyimides rete and alumina formwork junction is identical with embodiment 1, the duct that observed result shows to have in asymmetric composite porous compound with alumina formwork of the prepared polyimide film of the present embodiment the micron duct in the porous polyimide film of cellular micron pore passage structure and has a junction of the nano pore in the porous alumina formwork of cellular nano pore passage structure is connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected.
Identical with embodiment 1 with variation relation (I-V curve) method therefor of voltage while utilizing Keithley (keithley) 6487 type picoammeters to measure perforation duct in asymmetric composite porous compound with alumina formwork of the polyimide film of preparing by the present embodiment of electric current in electrolyte solutions, when adopting KCl solution that concentration is 0.01M as electrolyte solution, I-V curve as shown in Figure 3.As can be seen from Figure 3, the through hole road in compound asymmetric composite porous of the polyimide film that the present embodiment is prepared and alumina formwork has good ion rectification, and according to test result calculations, going out its ion rectified value is 20.8.
When adopting KCl solution that concentration is 0.1M as electrolyte solution, I-V curve as shown in Figure 3.As can be seen from Figure 3, the through hole road in compound asymmetric composite porous of the polyimide film that the present embodiment is prepared and alumina formwork has good ion rectification, and according to test result calculations, going out its ion rectified value is 8.9.
When adopting KCl solution that concentration is 1M as electrolyte solution, I-V curve as shown in Figure 3.As can be seen from Figure 3, the through hole road in compound asymmetric composite porous of the polyimide film that the present embodiment is prepared and alumina formwork has good ion rectification, and according to test result calculations, going out its ion rectified value is 4.1.
The KCl solution that is respectively 0.01M, 0.1M, 1M by embodiment 2 employing concentration is as electrolyte solution, the compound asymmetric composite porous I-V curve (see figure 3) of measured above-mentioned polyimide film and alumina formwork can be found out, when other condition is identical, the ion rectification in the perforation duct in compound asymmetric composite porous of polyimide film and alumina formwork increases and reduces with the concentration of test KCl electrolyte solution used.
While adopting KCl solution that concentration is 0.01M as electrolyte solution, the corresponding relation figure in the aperture in the ion rectified value in the perforation duct in compound asymmetric composite porous of measured polyimide film and alumina formwork and alumina formwork used as shown in Figure 4.The prepared composite of the present embodiment is numbered 2.
Preparation process is substantially identical with embodiment 1, and the aperture that is the nano pore in the used porous alumina formwork with cellular nano pore passage structure is 40～70nm, and the ambient humidity that reative cell forms is 85%.
Obtain under these conditions thering is the porous polyimide film that cellular aperture is 1.3 μ m pore passage structures (thickness is 3.9 μ m), and the aperture in described porous polyimide film is that the duct of the duct of 1.3 μ m and the junction in the duct that the aperture in described porous alumina formwork is 40～70nm is connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected, make thus the compound asymmetric composite material having porous structure of polyimide film and alumina formwork.
Utilize the surface of the compound asymmetric composite porous middle polyimides rete of scanning electron microscopic observation polyimide film obtained above and alumina formwork, the condition of the surface topography of polyimides rete and alumina formwork junction is identical with embodiment 1, the duct that observed result shows to have in asymmetric composite porous compound with alumina formwork of the prepared polyimide film of the present embodiment the micron duct in the porous polyimide film of cellular micron pore passage structure and has a junction of the nano pore in the porous alumina formwork of cellular nano pore passage structure is connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected.
Identical with embodiment 1 with variation relation (I-V curve) method therefor of voltage while utilizing Keithley (keithley) 6487 type picoammeters to measure perforation duct in asymmetric composite porous compound with alumina formwork of the polyimide film of preparing by the present embodiment of electric current in electrolyte solutions, when adopting KCl solution that concentration is 0.01M as electrolyte solution, test result shows that the through hole road in polyimide film that the present embodiment is prepared and compound asymmetric composite porous of alumina formwork has good ion rectification, according to test result calculations, going out its ion rectified value is 9.8.
When adopting KCl solution that concentration is 0.1M as electrolyte solution, test result shows that the through hole road in polyimide film that the present embodiment is prepared and compound asymmetric composite porous of alumina formwork has good ion rectification, and according to test result calculations, going out its ion rectified value is 4.9.
When adopting KCl solution that concentration is 1M as electrolyte solution, test result shows that the perforation duct ion rectification in polyimide film that the present embodiment is prepared and compound asymmetric composite porous of alumina formwork is poor, and according to test result calculations, going out its ion rectified value is 2.7.
While adopting KCl solution that concentration is 0.01M as electrolyte solution, the corresponding relation figure in the aperture in the ion rectified value in the perforation duct in compound asymmetric composite porous of measured polyimide film and alumina formwork and alumina formwork used as shown in Figure 4.Prepared asymmetric composite porous of the present embodiment is numbered 3.
Preparation process is substantially identical with embodiment 1, and the aperture that is the nano pore in the used porous alumina formwork with cellular nano pore passage structure is 80～100nm, and the ambient humidity that reative cell forms is 82%.
Obtain under these conditions thering is the porous polyimide film that cellular aperture is 1.4 μ m pore passage structures (thickness is 3.7 μ m), and the aperture in described porous polyimide film is that the duct of the duct of 1.4 μ m and the junction in the duct that the aperture in described porous alumina formwork is 80～100nm is connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected, make thus the compound asymmetric composite material having porous structure of polyimide film and alumina formwork.
Utilize the surface of the compound asymmetric composite porous middle polyimides rete of scanning electron microscopic observation polyimide film obtained above and alumina formwork, the condition of the surface topography of polyimides rete and alumina formwork junction is identical with embodiment 1, the duct that observed result shows to have in asymmetric composite porous compound with alumina formwork of the prepared polyimide film of the present embodiment the micron duct in the porous polyimide film of cellular micron pore passage structure and has a junction of the nano pore in the porous alumina formwork of cellular nano pore passage structure is connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected.
Identical with embodiment 1 with variation relation (I-V curve) method therefor of voltage while utilizing Keithley (keithley) 6487 type picoammeters to measure perforation duct in asymmetric composite porous compound with alumina formwork of the polyimide film of preparing by the present embodiment of electric current in electrolyte solutions, when adopting KCl solution that concentration is 0.01M as electrolyte solution, test result shows that the through hole road in polyimide film that the present embodiment is prepared and compound asymmetric composite porous of alumina formwork has good ion rectification, according to test result calculations, going out its ion rectified value is 7.1.
When adopting KCl solution that concentration is 0.1M as electrolyte solution, test result shows that the through hole road in polyimide film that the present embodiment is prepared and compound asymmetric composite porous of alumina formwork has good ion rectification, and according to test result calculations, going out its ion rectified value is 4.2.
When adopting KCl solution that concentration is 1M as electrolyte solution, test result shows that the ion rectification in the perforation duct in polyimide film that the present embodiment is prepared and compound asymmetric composite porous of alumina formwork is poor, and according to test result calculations, going out its ion rectified value is 2.2.
While adopting KCl solution that concentration is 0.01M as electrolyte solution, the corresponding relation figure in the aperture in the ion rectified value in the perforation duct in compound asymmetric composite porous of measured polyimide film and alumina formwork and alumina formwork used as shown in Figure 4.Prepared asymmetric composite porous of the present embodiment is numbered 4.
By adopting concentration in embodiment 1,2,3,4, be that the KCl solution of 0.01M is during as electrolyte solution, the corresponding relation figure (Fig. 4) in the aperture in the ion rectified value in the perforation duct in compound asymmetric composite porous of measured polyimide film and alumina formwork and alumina formwork used can find out, use the prepared asymmetric composite porous rectification of alumina formwork in 20～30nm aperture best, use the prepared asymmetric composite porous rectification of alumina formwork in other aperture relatively less than normal.
Comparative example 1
As a comparison, use that used in embodiment 1 to have cellular aperture be that the porous alumina formwork of 10～20nm pore passage structure measures as bionical ion channel material the ion rectification that this single alumina formwork mesoporous is 10～20nm duct, utilize Keithley (keithley) 6487 type picoammeters to measure the method for ion rectification in duct in this alumina formwork identical with embodiment 1, while adopting KCl solution that concentration is 0.01M as electrolyte solution, test result is as shown in Fig. 2 (b), the test result of the ion rectification of the KCl solution that is 0.01M in employing concentration using compound asymmetric composite porous of polyimide film prepared in itself and embodiment 1 and alumina formwork during as electrolyte solution contrasts known, duct in this single alumina formwork when On current without ion rectification effect, perforation duct in embodiment 1 in compound asymmetric composite porous of prepared polyimide film and alumina formwork has good ion rectification.
Comparative example 2
As a comparison, use that used in embodiment 2 to have cellular aperture be that the porous alumina formwork of 20～30nm pore passage structure measures as bionical ion channel material the ion rectification that this single alumina formwork mesoporous is 20～30nm duct, utilize Keithley (keithley) 6487 type picoammeters to measure the method for ion rectification in duct in this alumina formwork identical with embodiment 2, adopt the KCl solution that concentration is 0.01M to test as electrolyte solution, the test result of polyimide film prepared in test result and embodiment 2 and the compound asymmetric composite porous ion rectification when adopting KCl solution that concentration is 0.01M as electrolyte solution of alumina formwork is contrasted known, the duct of this single alumina formwork when On current without ion rectification effect, perforation duct in embodiment 2 in compound asymmetric composite porous of prepared polyimide film and alumina formwork has good ion rectification.
Comparative example 3
As a comparison, use that used in embodiment 3 to have cellular aperture be that the porous alumina formwork of 40～70nm pore passage structure measures as bionical ion channel material the ion rectification that this single alumina formwork mesoporous is 40～70nm duct, utilize Keithley (keithley) 6487 type picoammeters to measure the method for ion rectification in duct in this alumina formwork identical with embodiment 3, adopt the KCl solution that concentration is 0.01M to test as electrolyte solution, the test result of polyimide film prepared in test result and embodiment 3 and the compound asymmetric composite porous ion rectification when adopting KCl solution that concentration is 0.01M as electrolyte solution of alumina formwork is contrasted known, the duct of this single alumina formwork when On current without ion rectification effect, perforation duct in embodiment 3 in compound asymmetric composite porous of prepared polyimide film and alumina formwork has good ion rectification.
Comparative example 4
As a comparison, use that used in embodiment 4 to have cellular aperture be that the porous alumina formwork of 80～100nm pore passage structure measures as bionical ion channel material the ion rectification that this single alumina formwork mesoporous is 80～100nm duct, utilize Keithley (keithley) 6487 type picoammeters to measure the method for ion rectification in duct in this alumina formwork identical with embodiment 4, adopt the KCl solution that concentration is 0.01M to test as electrolyte solution, the test result of polyimide film prepared in test result and embodiment 4 and the compound asymmetric composite porous ion rectification when adopting KCl solution that concentration is 0.01M as electrolyte solution of alumina formwork is contrasted known, the duct of this single alumina formwork when On current without ion rectification effect, perforation duct in embodiment 4 in compound asymmetric composite porous of prepared polyimide film and alumina formwork has good ion rectification.
Claims (8)
1. compound asymmetric composite porous of a polyimide film and alumina formwork, it is characterized in that: compound asymmetric composite porous of described polyimide film and alumina formwork is to be composited by the porous alumina formwork that has the porous polyimide film of cellular micron pore passage structure and have a cellular nano pore passage structure, micron duct in the described porous polyimide film with cellular micron pore passage structure and the duct with the junction of the nano pore in the porous alumina formwork of cellular nano pore passage structure are connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected.
2. compound asymmetric composite porous of polyimide film according to claim 1 and alumina formwork, is characterized in that: the thickness of the described porous polyimide film with cellular micron pore passage structure is 2.8～5.5 μ m.
3. compound asymmetric composite porous of polyimide film according to claim 1 and 2 and alumina formwork, is characterized in that: the aperture in the micron duct in the described porous polyimide film with cellular micron pore passage structure is 0.9～1.5 μ m.
4. compound asymmetric composite porous of polyimide film according to claim 1 and alumina formwork, is characterized in that: the thickness of the described porous alumina formwork with cellular nano pore passage structure is 57～60 μ m.
5. according to the polyimide film described in claim 1 or 4 and compound asymmetric composite porous of alumina formwork, it is characterized in that: the aperture of the nano pore in the described porous alumina formwork with cellular nano pore passage structure is 10nm～100nm.
6. the compound asymmetric composite porous preparation method of the polyimide film described in claim 1～5 any one and alumina formwork, is characterized in that, described preparation method comprises the following steps:
(1) polyimide powder is dissolved in in chloroform, to be made into mass concentration be 1% polyimides film forming solution;
(2) polyimides film forming solution step (1) being obtained is evenly coated on the porous alumina formwork with cellular nano pore passage structure in reative cell, then in reative cell, be blown into the inert gas that carries steam, make reative cell form high humidity environment, the volatilization that steam is accompanied by chloroform solvent is condensate in the surface of polyimides film forming solution and forms water droplet and enters into polyimides film forming solution, after chloroform solvent is evaporated completely completely, the polyimides solid that contains water droplet obtaining is positioned under room temperature, after the water in the polyimides solid that contains water droplet is evaporated completely completely, on the porous alumina formwork with cellular nano pore passage structure, obtain having the porous polyimide film of cellular micron pore passage structure, and the micron duct in the described porous polyimide film with cellular micron pore passage structure and the duct with the junction of the nano pore in the porous alumina formwork of cellular nano pore passage structure are connected, form aperture for micron asymmetric perforation pore passage structure that the duct that is nanometer with aperture docking is connected, make thus the compound asymmetric composite material having porous structure of polyimide film and alumina formwork.
7. preparation method according to claim 6, is characterized in that: the flow velocity of described inert gas is 2L/min.
8. preparation method according to claim 6, is characterized in that: the ambient humidity of described high humidity environment is 70%～90%.
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| CN104959045B (en) * | 2015-06-16 | 2017-03-29 | 陕西科技大学 | A kind of method for preparing polyvinylidene fluoride nanometer array pore membrane |
| CN106540758A (en) * | 2016-10-21 | 2017-03-29 | 北京保利星数据光盘有限公司 | Micro-fluidic chip |
| CN106540758B (en) * | 2016-10-21 | 2019-07-23 | 北京保利星数据光盘有限公司 | Micro-fluidic chip |
| CN107188114A (en) * | 2017-05-18 | 2017-09-22 | 南昌大学 | A kind of surface micro-structure preparation method based on active refrigeration droplets agglomerate |
| CN109179310A (en) * | 2018-09-30 | 2019-01-11 | 江南大学 | A kind of bionic nano channel and preparation method thereof with short distance ion selectivity |
| CN109179310B (en) * | 2018-09-30 | 2021-03-02 | 江南大学 | Bionic nano-channel with short-distance ion selectivity and preparation method thereof |
| CN113416342A (en) * | 2021-06-18 | 2021-09-21 | 四川大学 | Polymer membrane with hierarchical porous structure and preparation method and application thereof |
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