CN103100308A - Preparation method of gelatin thin film and composite thin film for single-walled gelatin carbon nanometer tube - Google Patents
Preparation method of gelatin thin film and composite thin film for single-walled gelatin carbon nanometer tube Download PDFInfo
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- CN103100308A CN103100308A CN2013100165989A CN201310016598A CN103100308A CN 103100308 A CN103100308 A CN 103100308A CN 2013100165989 A CN2013100165989 A CN 2013100165989A CN 201310016598 A CN201310016598 A CN 201310016598A CN 103100308 A CN103100308 A CN 103100308A
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Abstract
The invention discloses a preparation method of a gelatin thin film and a composite thin film for a single-walled gelatin carbon nanometer tube. The gelatin thin film is prepared by using Cu(OH)2 nanometer wires as a sacrificial layer, depositing gelatin on the Cu(OH)2 nanometer wires by using a filtering method, and carrying out glue combination. The composite thin film for the single-walled gelatin carbon nanometer tube is prepared by using the single-walled carbon nanometer tube as a filter substrate, depositing the gelatin on the single-walled carbon nanometer tube by using the filtering method, and carrying out the glue combination. The gelatin thin film and the composite thin film for the single-walled gelatin carbon nanometer tube, provided by the invention, can be used for quickly separating micro-molecules in an aqueous solution. Under the same rejection rate, water fluxes of the gelatin thin film and the composite thin film for the single-walled gelatin carbon nanometer tube are higher than that of the common thin film in the existing market by 1-2 magnitude orders, so that the gelatin thin film and the composite thin film for the single-walled gelatin carbon nanometer tube are relatively stable, and the separation property of the aqueous solution of the thin film basically keeps unchanged after being stored for 1 year.
Description
Technical field
The present invention relates to the preparation method of film, relate in particular to the preparation method of a kind of gelatin film and gelatin SWCN laminated film.
Technical background
Along with in recent years, in the raising aspect the large-scale production nanofiber, nano fibrous membrane is widely used in filtering, medical domain, the aspects such as chemical-biological protection.For example, the brave seminar of Zhu Huai has prepared high-throughout TiO by casting technique
2and Al
2o
3nano-fiber film, this film can be held back the nano particle that is less than the 12nm size.Analyse prosperous and partner by filtering and the method for hot pressing has prepared multi-functional superfine Ti O
2the nano wire filter membrane, this membrane aperture size is about the 20nm left and right.At present, it is 10nm that the metal hydroxides nano wire that we are tens microns by the vacuum filtration process Filter length has obtained pore size, and thickness is approximately the superfine nano tunica fibrosa of 2-3nm.On the surface of above-mentioned nano fibrous membrane, the extra last layer polymer barrier layer that covers can further reduce the size in aperture.For example, the polyvinyl alcohol hydrogel that has the people by casting or interfacial polymerization, glue to be joined or polyamide ethylene glycol copolymer barrier layer cover on the electrostatic spinning polymer support and have obtained complex thin film.This complex thin film has the flux higher than traditional film.Gelatin, as a kind of fibrin of cheap, rich content, is widely used in medicine transmission, electrochromic device and novel diffusion barrier.And, because the glutin molecule has the radius of gyration of 20nm, thus it can be deposited on equably on the nanofiber layer that pore size is 20 nm, thereby obtain gelatin film.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the preparation method of a kind of gelatin film and gelatin SWCN laminated film is provided.
The preparation method's of gelatin film and gelatin SWCN laminated film step is as follows:
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 2-3 days, generates Cu (OH)
2nano wire solution, by 10mlCu (OH)
2form the thick hydrophilic mesoporous film of 120nm in the polycarbonate film substrate that the nano wire solution filter is 200nm to pore size;
2) getting 25-100 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the hydrophilic mesoporous film that 120nm is thick, use 3ml, the glutaraldehyde solution glue connection 2-3 hour that mass fraction is 2.5%, obtain gelatin Cu (OH)
2the nano wire laminated film, and remove Cu (OH) with the watery hydrochloric acid of pH=2
2nano wire obtains gelatin film;
3) under 80 ℃, add thermal response 20-24 hour in the salpeter solution that is 6M in concentration by SWCN, wash 2-3 time until the pH value reaches 6.5 by deionized water, obtain water miscible SWCN, and be diluted with water to the solution that concentration is 0.1 mg/mL, get in the polycarbonate film substrate that the solution filter after 3ml dilutes is 200nm to pore size and form the SWCN mesoporous film;
4) getting 25-100 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the SWCN mesoporous film, use 3ml, the glutaraldehyde solution glue connection 2-3 hour that mass fraction is 2.5%, obtain gelatin SWCN laminated film.
The film of two types that the present invention obtains can be used for the little molecule in quick fractionate aqueous solutions.Under identical rejection, the water flux of gelatin film and gelatin SWCN laminated film has than the water flux of the film sold on the market and exceeds more than 1 to 2 order of magnitude, and the gelatin single wall carbon nano-tube film also has excellent separating property in the situation that pressure reaches 18bar, gelatin film and gelatin SWCN laminated film are quite stables, and preserving separating property after 1 year more than in the aqueous solution does not have too large variation.
The accompanying drawing explanation
Fig. 1 is a) the surperficial SEM figure of Kocide SD nano wire;
Fig. 1 b) be the surperficial SEM figure of SWCN;
Fig. 2 is a) the section SEM figure of gelatin film;
Fig. 2 b) be the surperficial SEM figure of gelatin film;
Fig. 3 is a) the section SEM figure of gelatin SWCN laminated film;
Fig. 3 b) be the surperficial SEM figure of gelatin SWCN laminated film.
The specific embodiment
Further illustrate the present invention below in conjunction with example.
Embodiment 1
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 2 days, generates Cu (OH)
2nano wire solution, by 10mlCu (OH)
2form the thick hydrophilic mesoporous film of 120nm in the polycarbonate film substrate that the nano wire solution filter is 200nm to pore size;
2) getting 25 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the hydrophilic mesoporous film that 120nm is thick, use 3ml, the glutaraldehyde solution glue connection that mass fraction is 2.5% 2 hours, obtain gelatin Cu (OH)
2the nano wire laminated film, and remove Cu (OH) with the watery hydrochloric acid of pH=2
2nano wire obtains gelatin film, the gelatin film thickness obtained is 105 ± 10nm, water contact angle is 32 ± 2 °, Young's modulus is 2.04Mpa, tensile stress is 50.12Mpa, the gelatin film obtained has good separating property, to the rejection of 5 nm gold nano grains, is wherein 35%, and water flux is 2694L/m
2hbar, be 20% to the rejection of Cytochrome c, and water flux is 1224L/m
2hbar, be 25% to the rejection of Direct Yellow50, and water flux is 1342 L/m
2hbar;
3) under 80 ℃, add thermal response in the salpeter solution that is 6M in concentration by SWCN 20 hours, wash 2 times until the pH value reaches 6.5 by deionized water, obtain water miscible SWCN, and be diluted with water to the solution that concentration is 0.1 mg/mL, get in the polycarbonate film substrate that the solution filter after 3ml dilutes is 200nm to pore size and form the SWCN mesoporous film;
4) getting 25 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the SWCN mesoporous film, use 3ml, the glutaraldehyde solution glue connection that mass fraction is 2.5% 2 hours, obtain gelatin SWCN laminated film, the thickness of the gelatin SWCN laminated film obtained is 62 ± 10nm, water contact angle is 33 ± 2 °, Young's modulus is 9.5Mpa, tensile stress is 126.2Mpa, gelatin SWCN laminated film has good separating property, to the rejection of 5 nm gold nano grains, be wherein 90%, water flux is 1590L/m
2hbar, be 78% to the rejection of Cytochrome c, and water flux is 1610 L/m
2hbar, be 30% to the rejection of Direct Yellow50, and water flux is 1606 L/m
2hbar.
Embodiment 2
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 3 days, generates Cu (OH)
2nano wire solution, by 10mlCu (OH)
2form the thick hydrophilic mesoporous film of 120nm in the polycarbonate film substrate that the nano wire solution filter is 200nm to pore size;
2) getting 100 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the hydrophilic mesoporous film that 120nm is thick, use 3ml, the glutaraldehyde solution glue connection that mass fraction is 2.5% 3 hours, obtain gelatin Cu (OH)
2the nano wire laminated film, and remove Cu (OH) with the watery hydrochloric acid of pH=2
2nano wire obtains gelatin film, the gelatin film thickness obtained is 175 ± 10nm, water contact angle is 31 ± 2 °, Young's modulus is 2.05Mpa, tensile stress is 50.53Mpa, the gelatin film obtained has good separating property, to the rejection of 5 nm gold nano grains, is wherein 97%, and water flux is 610L/m
2hbar, be 93% to the rejection of Cytochrome c, and water flux is 612 L/m
2hbar, be 69% to the rejection of Direct Yellow50, and water flux is 618 L/m
2hbar;
3) under 80 ℃, add thermal response 20-24 hour in the salpeter solution that is 6M in concentration by SWCN, wash 3 times until the pH value reaches 6.5 by deionized water, obtain water miscible SWCN, and be diluted with water to the solution that concentration is 0.1 mg/mL, get in the polycarbonate film substrate that the solution filter after 3ml dilutes is 200nm to pore size and form the SWCN mesoporous film;
4) getting 100 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the SWCN mesoporous film, use 3ml, the glutaraldehyde solution glue connection that mass fraction is 2.5% 3 hours, obtain gelatin SWCN laminated film, the thickness of the gelatin SWCN laminated film obtained is 165 ± 15nm, water contact angle is 34 ± 2 °, Young's modulus is 9.4Mpa, tensile stress is 127.3Mpa, gelatin SWCN laminated film has good separating property, to the rejection of 5 nm gold nano grains, be wherein 99%, water flux is 663L/m
2hbar, be 99% to the rejection of Cytochrome c, and water flux is 670 L/m
2hbar, be 73% to the rejection of Direct Yellow50, and water flux is 667 L/m
2hbar.
Embodiment 3
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 2 days, generates Cu (OH)
2nano wire solution, by 10mlCu (OH)
2form the thick hydrophilic mesoporous film of 120nm in the polycarbonate film substrate that the nano wire solution filter is 200nm to pore size;
2) getting 75 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the hydrophilic mesoporous film that 120nm is thick, use 3ml, the glutaraldehyde solution glue connection that mass fraction is 2.5% 2 hours, obtain gelatin Cu (OH)
2the nano wire laminated film, and remove Cu (OH) with the watery hydrochloric acid of pH=2
2nano wire obtains gelatin film, the gelatin film thickness obtained is 250 ± 12nm, water contact angle is 34 ± 2 °, Young's modulus is 2.01Mpa, tensile stress is 49.23Mpa, the gelatin film obtained has good separating property, to the rejection of 5 nm gold nano grains, is wherein 90%, and water flux is 250L/m
2hbar, be 65% to the rejection of Cytochrome c, and water flux is 260L/m
2hbar, be 30% to the rejection of Direct Yellow50, and water flux is 256 L/m
2hbar;
3) under 80 ℃, add thermal response 20-24 hour in the salpeter solution that is 6M in concentration by SWCN, wash 2 times until the pH value reaches 6.5 by deionized water, obtain water miscible SWCN, and be diluted with water to the solution that concentration is 0.1 mg/mL, get in the polycarbonate film substrate that the solution filter after 3ml dilutes is 200nm to pore size and form the SWCN mesoporous film;
4) getting 50 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the SWCN mesoporous film, use 3ml, the glutaraldehyde solution glue connection that mass fraction is 2.5% 2 hours, obtain gelatin SWCN laminated film, the thickness of the gelatin SWCN laminated film obtained is 108 ± 10nm, water contact angle is 32 ± 2 °, Young's modulus is 9.6Mpa, tensile stress is 128.1Mpa, gelatin SWCN laminated film has good separating property, to the rejection of 5 nm gold nano grains, be wherein 97%, water flux is 922L/m
2hbar, be 85% to the rejection of Cytochrome c, and water flux is 930 L/m
2hbar, be 61% to the rejection of Direct Yellow50, and water flux is 928 L/m
2hbar.
Claims (1)
1. the preparation method of a gelatin film and gelatin SWCN laminated film is characterized in that its step is as follows:
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 2-3 days, generates Cu (OH)
2nano wire solution, by 10mlCu (OH)
2form the thick hydrophilic mesoporous film of 120nm in the polycarbonate film substrate that the nano wire solution filter is 200nm to pore size;
2) getting 25-100 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the hydrophilic mesoporous film that 120nm is thick, use 3ml, the glutaraldehyde solution glue connection 2-3 hour that mass fraction is 2.5%, obtain gelatin Cu (OH)
2the nano wire laminated film, and remove Cu (OH) with the watery hydrochloric acid of pH=2
2nano wire obtains gelatin film;
3) under 80 ℃, add thermal response 20-24 hour in the salpeter solution that is 6M in concentration by SWCN, wash 2-3 time until the pH value reaches 6.5 by deionized water, obtain water miscible SWCN, and be diluted with water to the solution that concentration is 0.1 mg/mL, get in the polycarbonate film substrate that the solution filter after 3ml dilutes is 200nm to pore size and form the SWCN mesoporous film;
4) getting 25-100 μ l the gelatin solution that is 0.1% from mass fraction is diluted in the 3ml deionized water, gelatin solution after dilution is filled on the SWCN mesoporous film, use 3ml, the glutaraldehyde solution glue connection 2-3 hour that mass fraction is 2.5%, obtain gelatin SWCN laminated film.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103570755A (en) * | 2013-10-25 | 2014-02-12 | 浙江大学 | Method of assisted-synthesizing metallic aluminum organic framework object nanorod array on aluminum oxide macroporous substrate through hydroxide nanowire |
| CN107137772A (en) * | 2017-05-18 | 2017-09-08 | 河北工业大学 | The preparation method of carbon nano-tube reinforced hydroxylapatite composite material |
| CN108261929A (en) * | 2016-12-29 | 2018-07-10 | 湖南尔康明胶有限公司 | A kind of preparation method of gelatin film |
| CN110354693A (en) * | 2019-07-10 | 2019-10-22 | 浙江海印数码科技有限公司 | A kind of bacteria cellulose filter membrane and its preparation method and application |
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| CN102585282A (en) * | 2012-03-13 | 2012-07-18 | 浙江大学 | Method for preparing organic/inorganic composite nanowire filtering membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20120050195A (en) * | 2010-11-10 | 2012-05-18 | 국립대학법인 울산과학기술대학교 산학협력단 | Hybrid graphene film, method for producing it, and display panel comprising it |
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| LI SHI，ET AL: "Superior separation performance of ultrathin gelatin films", 《J.MATER.CHEM.A》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570755A (en) * | 2013-10-25 | 2014-02-12 | 浙江大学 | Method of assisted-synthesizing metallic aluminum organic framework object nanorod array on aluminum oxide macroporous substrate through hydroxide nanowire |
| CN108261929A (en) * | 2016-12-29 | 2018-07-10 | 湖南尔康明胶有限公司 | A kind of preparation method of gelatin film |
| CN107137772A (en) * | 2017-05-18 | 2017-09-08 | 河北工业大学 | The preparation method of carbon nano-tube reinforced hydroxylapatite composite material |
| CN107137772B (en) * | 2017-05-18 | 2020-03-27 | 河北工业大学 | Preparation method of carbon nano tube reinforced hydroxyapatite composite material |
| CN110354693A (en) * | 2019-07-10 | 2019-10-22 | 浙江海印数码科技有限公司 | A kind of bacteria cellulose filter membrane and its preparation method and application |
| CN110354693B (en) * | 2019-07-10 | 2021-10-12 | 浙江海印数码科技有限公司 | Bacterial cellulose filter membrane and preparation method and application thereof |
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Application publication date: 20130515 |