CN101870772B - Preparation method of polymer film with periodic nano-structure and template used by same - Google Patents
Preparation method of polymer film with periodic nano-structure and template used by same Download PDFInfo
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- CN101870772B CN101870772B CN2009100499593A CN200910049959A CN101870772B CN 101870772 B CN101870772 B CN 101870772B CN 2009100499593 A CN2009100499593 A CN 2009100499593A CN 200910049959 A CN200910049959 A CN 200910049959A CN 101870772 B CN101870772 B CN 101870772B
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Abstract
The invention discloses a preparation method of a polymer film with a periodic nano-structure, which comprises the following steps that: (1) a polymer material is dissolved in an organic solvent by heating to obtain a mold casting liquid; (2) the mold casting liquid is dripped on the template, and a wet polymer film is prepared on the template by a spin-coating method; (3) the organic solvent in the wet polymer film is removed until the weight of the polymer film is constant, and then a dry polymer film is obtained; and (4) the dry polymer film is removed from the template in deionized water by ultrasonic vibration, and then the product of the invention is obtained. The invention also provides a template used in the preparation method of the polymer film with the periodic nano-structure. The preparation method of the polymer film with the periodic nano-structure has good repetitiveness and fast preparation speed, and is easy and economical.
Description
Technical field
The present invention relates to a kind of preparation method of polymeric membrane and template used, relate in particular to a kind of preparation method of the polymeric membrane with periodic nano-structure and template used.
Background technology
Polymeric membrane with nanometer pattern structure is widely used in biology and the bionics Study as a research object.
For the chemical structure of investigating substrate and decorative pattern shape to the migration of some cell and the influence of disruptive behaviour; Document 1 has reported that (Wang Xuefeng etc.) adopt wavelength is that the polarization laser of 266nm comes the film of p-poly-phenyl ethene to handle, with method of the high-polymer membrane that had different nanometer floral designs and hydrophilic and hydrophobic simultaneously or the like.
The little exposal technology of document 2 applying electronic bundles utilizes electron beam to focus on the mode of directly writing, and etching precision is less than the floral designs of 200nm.
In addition; Use soft lithographic technique (document 3,4), photolithography (document 5), nano print lithographic technique (document 6), colloid lithographic technique (document 7), Langmuire Blodgett lithographic technique (document 8), polymkeric substance demixing technology (document 9) in addition, electric spining technology (document 10) or the like.
Document 1:Cell directional migration and oriented division on three-dimensionallaser-induced periodic surface structures on polystyrene; Biomaterials; 2008,29,2049-2059.
Document 2:The effects of continuous and discontinuous groove edges on cellshape and alignment.Experimental Cell Research 2003,288,177-188.
Document 3:Nanopattern-induced changes in morphology and motility of smoothmuscle cells.Biomaterials 2005,26:5405-5413.
Document 4:Cell interaction with three-dimensional sharp-tip nanotopography.Biomaterials, 2007,28:1672-1679.
Document 5:Epithelial contact guidance on well-defined micro-andnanostructured substrates.Journal of Cell Science, 2003,116,1881-1892.
Document 6:Nanopattern-induced changes in morphology and motility ofsmooth muscle cells.Biomaterials, 2005,26,5405-5413.
Document 7:The effects of continuous and discontinuous groove edges on cellshape and alignment.Experimental Cell Research, 2003,288,177-188.
Document 8:Osteoblast alignment, elongation and migration on groovedpolystyrene surfaces patterned by LangmuireBlodgett lithography.Biomaterials, 2005,26,563-570.
Document 9:In vitro reaction of endothelial cells to polymer demixednanotopography.Biomaterials, 2002,23,2945-2954.
Document 10:Electrospinning polyaniline-contained gelatin nanofibers for tissueengineering applications.Biomaterials, 2006,27,2705-2715.
But these document institute reported method all have cost height, time-consuming length and the low defective of repeatability.
Summary of the invention
The method repeatability that technical problem to be solved by this invention has been to overcome existing preparation periodic nano-structure polymeric membrane is low, cost is high, the defective of time-consuming length; Traditional solution injection molding is applied among the preparation method of periodic nano-structure polymeric membrane, the preparation method of fast, the simple and economic periodic nano-structure polymeric membrane of a kind of good reproducibility, preparation speed is provided.
The preparation method of periodic nano-structure polymeric membrane of the present invention comprises the steps: that (1) is dissolved in macromolecular material in the organic solvent, and heating for dissolving obtains mold liquid; (2) the mold drop is added on the template, (spin coating method) prepares the hygrometric state polymeric membrane on template through spin-coating method; (3) organic solvent in the hygrometric state polymeric membrane is removed, after polymeric membrane is constant weight, obtained the dry state polymeric membrane; (4) in deionized water, the dry state polymeric membrane is removed from template, obtain having the polymeric membrane of periodic nano-structure through ultrasonic concussion.
Wherein, the preparation method of step (1) mold liquid is conventional preparation method.That the concentration of macromolecular material is preferable in the mold liquid is mass percent 1%-10%.Described macromolecular material be in this area conventional that use, can be used for film forming and can be dissolved in the macromolecular material of solvent; Comprise that mainly surface after polymer homopolymer and the graft modification contains the graftomer of hydrophilic or hydrophobic grouping, preferably be selected from a kind of in polysulfones, polyethersulfone, PS, PVDF, polyacrylonitrile, polyetheretherketone, polyetherketone and the polycarbonate.What the molecular weight of described macromolecular material was preferable is weight-average molecular weight 200,000-2,000,000.What the form of described macromolecular material was preferable can be powder or particle.Macromolecular materials such as polyethersulfone, PVDF, polyacrylonitrile, PS are the general-purpose plastics of one type of excellent property; Have good physical properties and chemical property; Adopt the polymeric membrane of their preparations not only to have good separation performance; And have favorable mechanical performance, acid and alkali-resistance and the anti-microbial attack of other chemical burn into, be several kinds of mould materials commonly used.Choice of Solvent is relevant with want dissolved macromolecular material, is as the criterion so that macromolecular material is dissolved in the solvent fully, preferably is selected from N-Methyl pyrrolidone, N, one or more in dinethylformamide, DMAC N,N and the chloroform.Described heating for dissolving is preferably carried out in closed environment, and as in a conventional oven, carrying out, the temperature of heating for dissolving is so that the macromolecular material dissolving is as the criterion, and preferable is 55-95 ℃.
Step (2) adopts spin-coating method to prepare the hygrometric state polymeric membrane, specifically can operate by the spin-coating method normal condition.Wherein, it is excessive that the dripping quantity of mold liquid generally can be selected, can be so that unnecessary film-casting liquid throws away from substrate through rotating speed and the rotational time of adjusting the spin coating instrument.That dripping quantity is preferable is 5-1000 microlitre/mm
2, that better is 10-30 microlitre/mm
2That the rotating speed of spin coating is preferable is 100-20000rpm, and that better is 6000-8000rpm.What the time of spin coating was preferable is 5-600 second, and better is 15-60 second.
The purpose of step (3) is that the organic solvent in the hygrometric state polymeric membrane of step (2) is removed.Remove the method for desolvating and can adopt this area ordinary method, as drying naturally or drying, preferable dries in the baking oven to constant weight for the hygrometric state polymeric membrane is placed on together with template, and oven temperature is 60-80 ℃.
Adopting conventional ultrasonic concussion method in the step (4), is solution with the deionized water, and polymeric membrane is peeled off from template.The temperature of ultrasonic concussion is the conventional temperature in this area, and preferable is 30-100 ℃.That the power of ultrasonic concussion is preferable is 100-800W, and that better is 600-800W.
In the above-mentioned steps, but each optimum condition arbitrary combination promptly gets each preferred embodiment of the present invention.
The present invention also further relates to the template of using in the aforesaid method step (2), and it comprises that a substrate and one are attached to suprabasil surface.This surface has the periodicity decorative pattern of nanoscale, and it can form the complementary structure with the high score film, i.e. the recess of the corresponding polymeric membrane of the high spot of template, the high spot of the corresponding polymeric membrane of the recess of template.Described decorative pattern can be selected various structure for use according to the needs of biological study, and preferable is striated structure, cylindrical lattice structure or trapezoidal lattice structure.
The periodicity decorative pattern of template surface is that the soft X-ray through synchronous light source carries out etching to template and obtains.Spacing, the degree of depth or the width of the periodicity decorative pattern on surface selected according to the polymeric membrane that is used for biological platform research of required preparation, and the decorative pattern width all can from 20nm to 500nm.The material of template surface can be selected any etched material of X soft rays that can be synchronized light source for use, and preferable is gold or silicon chip.If select for use gold as mould material, the words thickness of deposition of gold is confirmed according to the gash depth of required preparation lamina membranacea.When surfacing is selected gold for use, the chemical Vapor deposition process through routine with deposition of gold to base material.The thickness of deposition back gold layer is greater than 200nm at least, be good with 2 times of pattern depth, as needs etching to obtain the template that pattern depth is 200nm, and then layer to get 400nm preferable for gold.
The substrate of template plays surface-supported effect, and the thickness of substrate is controlled according to the degree of depth of needed decorative pattern, generally gets final product greater than pattern depth, substrate thickness is preferable be pattern depth 1.5-420 doubly.If the degree of depth of required decorative pattern is 200nm, then the gauge control of substrate is preferable in the 400nm left and right sides.The template base material that the material selection of substrate is conventional, it does not dissolve, does not swell in organic solvent, does not react with organic solvent yet, and preferable is glass, quartz, pottery or silicon chip etc.Consider the etched efficient limitation of synchronous light source soft X-ray, and the needs of studying in the biology, that the size of template is preferable is 1mm * 1mm.
In the present invention's one preferred embodiment, the periodicity decorative pattern of template surface is a striated structure, and wherein the height of striped is 1200nm; Width of fringe is 20-500nm, and that better is 150nm; Fringe spacing is 20-500nm, and that better is 150nm.Use the width of fringe and the fringe spacing of the polymeric membrane that described template makes to be 5-500nm; Width of fringe and fringe spacing ratio are 1: 10-10: 1; Fringe depths is 50-800nm.
In another preferred embodiment of the present invention, the periodicity decorative pattern of template surface is the decorative pattern of cylindrical lattice structure, round platform lattice structure, terrace with edge lattice structure or straight quadrangular lattice structure; That the height of described lattice structure is preferable is 50nm-500nm; That columniform diameter is preferable is 20nm-200nm; Round platform in the described round platform lattice structure is the rounding platform of upper surface greater than lower surface, and that the diameter of upper surface is preferable is 20nm-200nm; Terrace with edge in the described terrace with edge lattice structure is the chamfered edge platform of upper surface greater than lower surface, and the length of upper surface equates that with width that preferable is 20nm-200nm; The upper surface of described straight quadrangular is a square or rectangular, and that the foursquare length of side and rectangular length are preferable is 20nm-200nm; That described dot matrix between centers is preferable is 20nm-100nm; Use the decorative pattern width of the polymeric membrane that described template makes to be 50nm-500nm as 40nm-400nm, pattern depth as 20nm-100nm, decorative pattern spacing.
Among the present invention,, can adjust and control the ratio of decorative pattern width, decorative pattern spacing, pattern depth and decorative pattern width and decorative pattern spacing, make polymeric membrane respectively with different scale nanometer pattern structure through changing the concentration of macromolecular material in the mold liquid.This is that solvent evaporates speed is also different under the same situation of other factors owing to after the concentration change, make the viscosity of solution change.Generally speaking, macromolecular material content is high more, and the viscosity of mold liquid is big more, and solvent evaporates is slow more, and the polymeric membrane of formation is finer and close.And when through ultrasonic with polymeric membrane when substrate takes off; Size deformation can take place in high-polymer membrane; Originally be limited in the inner polymer of template recess because there has not been the limitation of size of substrate, expanded, and made width of fringe, fringe spacing, fringe depths etc. change.The finer and close expansion of polymeric membrane is big more, and vice versa.Thus, in the method for the present invention, only use a template, just can obtain the different polymeric membrane of decorative pattern size, promptly use same template, the concentration of mold liquid changes at 10% o'clock from 1%, and the width of striped, the variation range of spacing are about 10nm.But as needing the bigger template used size characteristic of necessary change of preparation decorative pattern dimensional change, i.e. employing has the template of new characteristic dimension.
The polymeric membrane that uses method of the present invention to prepare is dense film; Can be used as the substrate of various cell culture experiments in the biological study, as study dissimilar cells migration and disruptive behaviour on substrate etc. with different hydrophilic and hydrophobics, different nanometer decorative patterns.
Raw material that the present invention is used or reagent except that specifying, all commercially available getting.
Positive progressive effect of the present invention is:
1, the preparation method of the polymeric membrane with periodic nano-structure of the present invention repeatable high, simple, quick, cost is low.
2, through the concentration of macromolecular material in the liquid that adjusts the mould, can prepare the different polymeric membrane of decorative pattern size only with a template.
3, when employing has the macromolecular material of hydrophilic or hydrophobic grouping, the film that makes can also have different close and distant WS character, in bioengineered tissue is learned, has the potential substantial economics as substituting biomaterial.
Description of drawings
Fig. 1 is the vertical view of the template among the embodiment 1-7.
Fig. 2 is the local amplification sectional view of the template among the embodiment 1-7.
Fig. 3 is the AFM figure of the polymeric membrane that obtains among the embodiment 1.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Per-cent among the following embodiment is all weight percent.
Embodiment 1
The preparation template:
1, with vapor deposition method with vaporific deposition of gold to the sheet glass of 1mm * 1mm, make that the thickness of metallographic is 1200nm; The height of sheet glass is 0.5mm;
2, the soft X-ray with synchronous light source carries out etching from the angle perpendicular to sheet glass to metallographic.Etching employing program is controlled, and launches the gold bar that 150 * 1200nm is removed in the first road ray etching, and gamma ray source moves 150nm, launches the second road ray, finally obtains the wide 150nm of being of striped by that analogy, and fringe spacing is the template of 150nm.The synchronous light source of soft X-ray China Science & Technology University of light source provides synchronously.
Embodiment 2
Choose the silicon chip of a 1mm * 1mm, from angle metallographic is carried out etching perpendicular to sheet glass with the soft X-ray of synchronous light source.Etching employing program is controlled, and launches the silicon chip that 20 * 1200nm is removed in the first road ray etching, and gamma ray source moves 20nm, launches the second road ray, finally obtains the wide 20nm of being of striped by that analogy, and fringe spacing is the template of 20nm.The synchronous light source of soft X-ray China Science & Technology University of light source provides synchronously.
The method that the template of using in following each enforcement is all with embodiment 1 makes.
Embodiment 3 has polyethersulfone (PES) polymeric membrane (film 1) of periodic nano-structure
Take by weighing (PES) powder of 1 gram polyethersulfone (weight-average molecular weight is 800,000) with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 150 milliliters of Erlenmeyer flasks, after adding N-Methyl pyrrolidone (NMP) to solution gross weight and being 100 grams, solution was placed in 60 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 1%).The mold liquid that obtains is drawn 1mL mold drop with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 100rpm at rotating speed on the sol evenning machine, with 100rpm rotating speed spin coating 600s film forming.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 60 degrees centigrade a conventional oven; (temperature of ultrasonic concussion is 60 ℃ in the deionized water for ultrasonic concussion with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 300W), polymeric membrane is removed from template, obtain having the polyethersulfone polymeric membrane 1 of periodic nano-structure.
Observe the surface elevation distribution (Fig. 1) of above-mentioned polyethersulfone polymeric membrane 1 with AFM (AFM).The figure of test adopts the depth of color to come the altitude distribution of presentation surface, and color is explained low highly more more deeply, and color is shallow more, and is high highly more.Visible from Fig. 1, obtained the periodic nano-structure polymeric membrane with method of the present invention.
The size characteristic of the polymeric membrane that makes does, fringe depths is 800nm, and width of fringe is 270nm, and fringe spacing is 30nm, and width of fringe and fringe spacing ratio are 9: 1.
Embodiment 4 has graft acrylic acid polyethersulfone (PES) polymeric membrane (film 2) of periodic nano-structure
Take by weighing 1 gram graft acrylic acid modified poly (ether-sulfone) (weight-average molecular weight is 800,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 50 milliliters of Erlenmeyer flasks, after adding DMAC N,N (DMAc) to solution gross weight and being 10 grams, solution was placed in 90 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 10%).The mold liquid that obtains is drawn 5 microlitre mold drops with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 20000rpm at rotating speed on the sol evenning machine, with rotating speed spin coating 5s film forming.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 60 degrees centigrade a conventional oven; (temperature of ultrasonic concussion is 80 ℃ in the deionized water for ultrasonic concussion with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 800W), polymeric membrane is removed from template, obtain having the graft acrylic acid polyethersulfone polymeric membrane 2 of periodic nano-structure.
The size characteristic of the polymeric membrane that makes does, fringe depths is 1000nm, and width of fringe is 210nm, and fringe spacing is 90nm, and width of fringe and fringe spacing ratio are 7: 3.
Embodiment 5 has graft acrylamide polyethersulfone (PES) polymeric membrane (film 3) of periodic nano-structure
Take by weighing 5 gram graft acrylamide modified poly (ether-sulfone) (weight-average molecular weight is 800,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 150 milliliters of Erlenmeyer flasks, add N, after dinethylformamide (DMF) to solution gross weight is 100 grams, solution was placed in 75 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 5%).The mold liquid that obtains is drawn 300 microlitre mold drops with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 5000rpm at rotating speed on the sol evenning machine, with rotating speed spin coating 200s film forming.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 60 degrees centigrade a conventional oven; (temperature of ultrasonic concussion is 70 ℃ in the deionized water for ultrasonic concussion with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 500W), polymeric membrane is removed from template, obtain having the grafting graft acrylamide polyethersulfone polymeric membrane 3 of periodic nano-structure.
The size characteristic of the polymeric membrane that makes does, fringe depths is 1100nm, and width of fringe is 240nm, and fringe spacing is 60nm, and width of fringe and fringe spacing ratio are 4: 1.
Embodiment 6 has graft phenylethene modified pvdf (PVDF) polymeric membrane (film 4) of periodic nano-structure
Take by weighing 1 gram graft phenylethene modified pvdf (weight-average molecular weight is 1,000,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 150 milliliters of Erlenmeyer flasks, after adding N-Methyl pyrrolidone (NMP) to solution gross weight and being 100 grams, solution was placed in 60 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 1%).The mold liquid that obtains is drawn 1mL mold drop with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Rotating speed is a 100rpm spin coating 600s film forming on sol evenning machine.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 60 degrees centigrade a conventional oven; (temperature of ultrasonic concussion is 50 ℃ in the deionized water for ultrasonic concussion with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 500W), polymeric membrane is removed from template, obtain having the graft phenylethene modified pvdf polymeric membrane 1 of periodic nano-structure.
The size characteristic of the polymeric membrane that makes does, fringe depths is 700nm, and width of fringe is 240nm, and fringe spacing is 60nm, and width of fringe and fringe spacing ratio are 4: 1.
Embodiment 7 has graft acrylic acid modified polyvinilidene fluoride (PVDF) polymeric membrane (film 5) of periodic nano-structure
Take by weighing 1 gram graft acrylic acid modified polyvinilidene fluoride (weight-average molecular weight is 1,000,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 50 milliliters of Erlenmeyer flasks, after adding DMAC N,N (DMAc) to solution gross weight and being 10 grams, solution was placed in 90 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 10%).The mold liquid that obtains is drawn 5 microlitre mold drops with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 20000rpm at rotating speed on the sol evenning machine, with rotating speed spin coating 5s film forming.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 60 degrees centigrade a conventional oven; (temperature of ultrasonic concussion is 60 ℃ in the deionized water for ultrasonic concussion with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 800W), polymeric membrane is removed from template, obtain having the graft acrylic acid pvdf polymeric membrane 2 of periodic nano-structure.
The size characteristic of the polymeric membrane that makes does, fringe depths is 900nm, and width of fringe is 240nm, and fringe spacing is 60nm, and width of fringe and fringe spacing ratio are 4: 1.
Embodiment 8 has graft acrylamide pvdf (PVDF) polymeric membrane (film 6) of periodic nano-structure
Take by weighing 5 gram graft acrylamide modified polyvinilidene fluoride (weight-average molecular weight is 100,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 150 milliliters of Erlenmeyer flasks, after adding N-N N (DMF) to solution gross weight and being 100 grams, solution was placed in 75 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 5%).The mold liquid that obtains is drawn 300 microlitre mold drops with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 5000rpm at rotating speed on the sol evenning machine, with rotating speed spin coating 200s film forming.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 60 degrees centigrade a conventional oven; In the deionized water for ultrasonic concussion, (temperature of ultrasonic concussion is 55 ℃ with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 300W) polymeric membrane is removed from template, obtain having the grafting graft acrylamide pvdf polymeric membrane 6 of periodic nano-structure.
The size characteristic of the polymeric membrane that makes does, fringe depths is 1000nm, and width of fringe is 180nm, and fringe spacing is 120nm, and width of fringe and fringe spacing ratio are 3: 2.
Embodiment 9 has PS (PS) polymeric membrane (film 7) of periodic nano-structure
Take by weighing 20 gram PS (weight-average molecular weight is 600,000) powder with electronic balance, particle diameter is 1 millimeter.The powder that weighs up is inserted 150 milliliters of Erlenmeyer flasks, after adding chloroform to solution gross weight and being 100 grams, solution was placed in 60 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 10%).The mold liquid that obtains is drawn 1mL mold drop with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Rotating speed is a 100rpm spin coating 600s film forming on sol evenning machine.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 60 degrees centigrade a conventional oven; (temperature of ultrasonic concussion is 75 ℃ in the deionized water for ultrasonic concussion with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 550W), polymeric membrane is removed from template, obtain having the PS polymeric membrane 7 of periodic nano-structure.
The size characteristic of the polymeric membrane that makes does, fringe depths is 900nm, and width of fringe is 240nm, and fringe spacing is 60nm, and width of fringe and fringe spacing ratio are 4: 1.
Embodiment 10 has the polyacrylonitrile polymeric membrane (film 8) of periodic nano-structure
Take by weighing 5 gram polyacrylonitrile (weight-average molecular weight is 100,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 150 milliliters of Erlenmeyer flasks, after adding N-N N (DMF) to solution gross weight and being 100 grams, solution was placed in 55 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 5%).The mold liquid that obtains is drawn 10 microlitre mold drops with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 6000rpm at rotating speed on the sol evenning machine, with rotating speed spin coating 15s film forming.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 80 degrees centigrade a conventional oven; In the deionized water for ultrasonic concussion, (temperature of ultrasonic concussion is 30 ℃ with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 800W) polymeric membrane is removed from template, obtain having the grafting graft acrylamide pvdf polymeric membrane 8 of periodic nano-structure.
The size characteristic of the polymeric membrane that makes does, fringe depths is 950nm, and width of fringe is 210nm, and fringe spacing is 90nm, and width of fringe and fringe spacing ratio are 7: 3.
Embodiment 11 has the polyetheretherketone polymeric membrane (film 9) of periodic nano-structure
Take by weighing 5 gram polyetheretherketone (weight-average molecular weight is 100,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 150 milliliters of Erlenmeyer flasks, after adding N-N N (DMF) to solution gross weight and being 100 grams, solution was placed in 95 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 5%).The mold liquid that obtains is drawn 30 microlitre mold drops with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 8000rpm at rotating speed on the sol evenning machine, with rotating speed spin coating 60s film forming.The film that spin coating is good (together with the silicon chip template) is placed on and dries the polymeric membrane (together with template) that obtains dry state to the constant weight in 60 degrees centigrade a conventional oven; In the deionized water for ultrasonic concussion, (temperature of ultrasonic concussion is 100 ℃ with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 100W) polymeric membrane is removed from template, obtain having the grafting graft acrylamide pvdf polymeric membrane 9 of periodic nano-structure.
The size characteristic of the polymeric membrane that makes does, fringe depths is 1050nm, and width of fringe is 200nm, and fringe spacing is 100nm, and width of fringe and fringe spacing ratio are 2: 1.
Embodiment 12 has the polyetherketone polymeric membrane (film 10) of periodic nano-structure
Take by weighing 1 gram polyetherketone (weight-average molecular weight is 1,000,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 50 milliliters of Erlenmeyer flasks, after adding DMAC N,N (DMAc) to solution gross weight and being 10 grams, solution was placed in 90 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 10%).The mold liquid that obtains is drawn 5 microlitre mold drops with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 20000rpm at rotating speed on the sol evenning machine, with rotating speed spin coating 5s film forming.The film that spin coating is good (together with the silicon chip template) dries the polymeric membrane (together with template) that obtains dry state to the constant weight naturally; (temperature of ultrasonic concussion is 50 ℃ in the deionized water for ultrasonic concussion with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 500W), polymeric membrane is removed from template, obtain having the graft acrylic acid pvdf polymeric membrane 10 of periodic nano-structure.
The size characteristic of polymeric membrane does, fringe depths is 1100nm, and width of fringe is 220nm, and fringe spacing is 80nm, and width of fringe and fringe spacing ratio are 11: 4.
Embodiment 13 has the polycarbonate polymeric membrane (film 11) of periodic nano-structure
Take by weighing 1 gram polycarbonate (weight-average molecular weight is 1,000,000) powder with electronic balance, particle diameter is 0.2 millimeter.The powder that weighs up is inserted 50 milliliters of Erlenmeyer flasks, after adding DMAC N,N (DMAc) to solution gross weight and being 10 grams, solution was placed in 90 degrees centigrade of a conventional ovens heating for dissolving 3 days, be prepared into mold liquid (concentration of mold liquid is 10%).The mold liquid that obtains is drawn 5 microlitre mold drops with liquid-transfering gun and is added on the silicon chip template after standing and defoaming.Being under the 20000rpm at rotating speed on the sol evenning machine, with rotating speed spin coating 5s film forming.The film that spin coating is good (together with the silicon chip template) dries the polymeric membrane (together with template) that obtains dry state to the constant weight naturally; (temperature of ultrasonic concussion is 50 ℃ in the deionized water for ultrasonic concussion with foregoing dry state polymeric membrane (together with template); The power of ultrasonic concussion is 500W), polymeric membrane is removed from template, obtain having the graft acrylic acid pvdf polymeric membrane 11 of periodic nano-structure.
The size characteristic of polymeric membrane does, fringe depths is 1060nm, and width of fringe is 210nm, and fringe spacing is 90nm, and width of fringe and fringe spacing ratio are 7: 3.
Claims (14)
1. template that is used for preparation cycle property nanostructure polymeric membrane, it comprises that a substrate and one are attached to suprabasil surface, it is characterized in that: described surface has the periodicity decorative pattern of nanoscale; Described periodicity decorative pattern is the decorative pattern of striated structure, cylindrical lattice structure, rounding platform lattice structure, chamfered edge platform lattice structure or straight quadrangular lattice structure; In the described striated structure, the height of striped is 1200nm, and width of fringe is 20-500nm, and fringe spacing is 20-500nm; The height of described lattice structure is 50nm-500nm; Described columniform diameter is 20nm-200nm; In the described rounding platform lattice structure, the diameter of the upper surface of round platform is 20nm-200nm; In the described chamfered edge platform lattice structure, the length of the upper surface of terrace with edge equates with width, is 20nm-200nm; The upper surface of described straight quadrangular is a square or rectangular, and the foursquare length of side and rectangular length are 20nm-200nm.
2. template as claimed in claim 1 is characterized in that: described periodicity decorative pattern is that the soft X-ray through synchronous light source carries out etching to template and obtains.
3. template as claimed in claim 1 is characterized in that: the material of described template surface is gold or silicon chip, and the material of substrate is glass, quartz, pottery or silicon chip; The thickness of substrate is 1.5-420 times of pattern depth.
4. template as claimed in claim 1 is characterized in that: in the described striated structure, the height of striped is 1200nm, and width is 150nm, and fringe spacing is 150nm.
5. the preparation method of a periodic nano-structure polymeric membrane, it comprises the steps: that (1) is dissolved in macromolecular material in the organic solvent, heating for dissolving obtains mold liquid; (2) the mold drop is added to as on each described template of claim 1～4, on template, prepares the hygrometric state polymeric membrane through spin-coating method; (3) organic solvent in the hygrometric state polymeric membrane is removed, after polymeric membrane is constant weight, obtained the dry state polymeric membrane; (4) in deionized water, the dry state polymeric membrane is removed from template, promptly get through ultrasonic concussion.
6. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 5 is characterized in that: the concentration of macromolecular material is mass percent 1%-10% in the mold liquid described in the step (1).
7. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 5 is characterized in that: the macromolecular material described in the step (1) is a kind of in polysulfones, polyethersulfone, PS, PVDF, polyacrylonitrile, polyetheretherketone, polyetherketone and the polycarbonate; The molecular weight of described macromolecular material is a weight-average molecular weight 200,000-2,000,000.
8. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 5 is characterized in that: the organic solvent in the step (1) is N-Methyl pyrrolidone, N, one or more in dinethylformamide, DMAC N,N and the chloroform; Described solvent temperature is 55-95 ℃.
9. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 5 is characterized in that: the dripping quantity of mold liquid is 5-1000 microlitre/mm in the step (2)
2
10. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 9 is characterized in that: the dripping quantity of mold liquid is 10-30 microlitre/mm in the step (2)
2
11. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 5 is characterized in that: the rotating speed of spin coating is 100-20000rpm in the step (2); The spin coating time is 5-600 second.
12. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 11 is characterized in that: the rotating speed of step (2) spin coating is 6000-8000rpm; The spin coating time is 15-60 second.
13. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 5 is characterized in that: the method for removing organic solvent in the step (3) is that nature dries or dries; The temperature of oven dry is 60-80 ℃.
14. the preparation method of periodic nano-structure polymeric membrane as claimed in claim 5 is characterized in that: the temperature of ultrasonic concussion is 30-100 ℃ in the step (4); The power of ultrasonic concussion is 100-800w.
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| CN104692321B (en) * | 2015-02-03 | 2016-08-24 | 天津大学 | A kind of method that mode utilizing orthogonal impressing induction prepares ordered porous membrane |
| CN108452689A (en) | 2017-03-06 | 2018-08-28 | 青岛致用新材料科技有限公司 | Highly selective full alicyclic polyamide NF membrane of one kind and preparation method thereof |
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| CN1453302A (en) * | 2002-04-25 | 2003-11-05 | 复旦大学 | Surface adsorption and spontaneous polymerization process of extra-thin polymer film |
| CN101225180A (en) * | 2008-01-28 | 2008-07-23 | 中国科学院化学研究所 | Method for preparing soakage polymer switch film based on polymer transformation temperature responsiveness |
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| CN1453302A (en) * | 2002-04-25 | 2003-11-05 | 复旦大学 | Surface adsorption and spontaneous polymerization process of extra-thin polymer film |
| CN101225180A (en) * | 2008-01-28 | 2008-07-23 | 中国科学院化学研究所 | Method for preparing soakage polymer switch film based on polymer transformation temperature responsiveness |
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