CN103923329A - Super-strength transparent imitated shell composite thin film and preparation method thereof - Google Patents
Super-strength transparent imitated shell composite thin film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super-strength transparent imitated shell composite thin film and a preparation method thereof, and belongs to the technical field of bionics. The preparation method comprises the steps of mixing MMT colloid and ALG aqueous solution, and adding calcium chloride into the mixed solution to form an egg tray structure; and then performing vacuum filtration to obtain the super-strength transparent imitated shell composite thin film. The imitated shell thin film with a 'brick-mud' structure, an inorganic phase surface micro-protrusion interlocking structure and an organic matter bridging structure are prepared by using the sodium alginate and the montmorillonite as raw materials, the thin film has excellent mechanical property, the tensile strength is up to 243MPa, the average deformation is 5.38%, the thin film has excellent transparency, and the transmittance of visible light is up to over 88%.
Description
Technical field
The invention belongs to bionics techniques field, refer to specifically a kind of super-strength transparent artificial shell laminated film and preparation method thereof, there is broad prospect of application in fields such as aerospace, military affairs, civil engineering and machineries.
Background technology
The Nature creates perfect structure in the process of evolving, and has attracted concern and the research interest of Many researchers, encourages them to remove to imitate the Nature.Wherein shell is a kind of natural organic/inorganic stratified composite, and its unique multilevel " brick-mud " packaging assembly is given it and had that quality is light, intensity is high, the excellent mechanical property of good toughness.But nearly all investigator is only in " brick-mud " structure of imitating shell, has ignored the micro-protuberance interlocking of inorganic phase surface, the raising of the mineral bridge joint between organic bridge joint and aragonite sheet to shell mechanical property.Therefore the matrix material preparing in prior art can't better imitate preparation class shellfish material.Mechanical property is not that intensity is not high, is exactly that intensity has got on, and it is very crisp that sample just becomes, and tensile deformation is very low, and toughness sharply declines.
Shell pearl layer is made up of aragonite sheet calcium carbonate (mass percent approximately 95%) and organic (about 5wt%), its toughness is more than 3000 times of aragonite sheet, and this thundering mechanical property is owing to multiple dimensioned, multilevel " brick-mud " packaging assembly of nacreous layer uniqueness.Inspired by this, domestic and international many seminars have utilized that different methods is synthetic has prepared a series of bionical high-strength ultra-tough stratified composites.For example, the bionical shell nano-multilayered structures of self-supporting PDDA/MMT nano composite film is successfully prepared by LBL (Layer-by-Layer) method by Kotov group [Nano Lett., Vol.7, No.5,2007].Tensile strength and deformation are respectively σ
u=100 ± 10MPa, ε=0.1%.MMT/PVA class shell laminated film has been prepared with LBL equally by Kotov group [Science2007,80,318], carries out covalent cross-linking back draft intensity and deformation is respectively σ introducing glutaraldehyde
u=400 ± 40, ε=0.33 ± 0.04%.Yu Shuhong group [.Angew.Chem., Int.Ed., 2010,49,10127-10131.] utilizes the method for vacuum filtration to prepare Chitosan/MMT (chitosan-polynite) class shell composite film material, and tensile strength and deformation are respectively σ
u=76 ± 10MPa, ε=0.97 ± 0.14%.[the Angew.Chem. of Yu Shuhong group in addition, Int.Ed., 2010,49,2140-2145.] utilize and there is functional inorganic phase LDH (the layered double hydroxide is commonly called as hydrotalcite) and surperficially carry out amination processing at it, between organic layer and inorganic layer, introduce hydrogen bond action and prepare obdurability layered composite film.Utilize dip coating that the LDH colloid after modifying is assembled into height-oriented Two-dimensional Inorganic layer, then chitosan solution is spun on to mineral membrane surface, repeats so continuously to obtain the stratiform Chitosan/LDH hybrid film that thickness is tens microns after dip-coating-spin coating step.Tensile strength and deformation are respectively σ
u=160MPa, ε=5%.The people [Nano Lett., 2010,10:2742-2748.] such as same Walther also use the method for vacuum filtration, use for reference the technique of paper process, have prepared multi-layer compound film.
Existing technology is many prepares stratiform " brick-mud " structural models of shell in imitation, and has studied the laminated film of several different methods and the different imitative shell of the compound preparation of organic-inorganic.But simple " brick-mud " structural models can not be explained the energy expenditure that experiment records completely.Marc etc. [Journal of the mech anical behavior of biomedical materials, 2008,1,76-85.] have proved respectively and on three kinds of Nano grades, have resisted lamella and see sliding model by the method for experiment.They are respectively the mineral bridge model between organic bridge model, inorganic phase surface micro-protuberance interlocking model, aragonite sheet, and C figure in Fig. 4 is shown in by its schematic diagram.
Meanwhile, the organism of selecting in existing technical scheme is mostly the material of chemical organic synthesis, has hazardous and noxious substances more, and non-green natural biopolymer is short of to some extent in environmental protection.
Summary of the invention
The object of the invention is for solve of the prior art can not micro-prominent and " brick-mud " structure problem in organic bridge joint, inorganic phase surface green, that imitate fast shell, propose a kind of fast, the green method of preparing super-strength transparent artificial shell laminated film.
For nontoxic, the free of contamination multilevel hierarchy that imitates fast and effectively shell, the invention provides one prepares and has by organic bridge joint, the micro-prominent method of imitating the nano compound film of shell high-strength and high-transparent with " brick-mud " structure in inorganic phase surface, in described preparation method, utilize the polynite (MMT) of churned mechanically method stripped laminar, after centrifugal, obtain the aqueous solution of individual layer MMT sheet, then with the abundant mix and blend of isocyatic sodium alginate (ALG) aqueous solution after, add a certain amount of calcium chloride, allow ALG form reticulated structure under the effect of calcium ion, finally imitate the laminated film of shell multilevel hierarchy with the method preparation of vacuum filtration.Concrete steps are as follows:
The first step, preparation MMT colloid;
Second step, preparation ALG solution, and by MMT colloid and ALG aqueous solution.
The 3rd step adds calcium chloride in the mixing solutions of second step.
The 4th step, carries out vacuum filtration to the solution of the 3rd step, obtains super-strength transparent artificial shell laminated film.
Described super-strength transparent artificial shell film has " brick-mud " structure, the micro-protuberance interlocking of inorganic phase surface, three kinds of structures of organic bridge joint, there is excellent mechanical property, tensile strength is up to 243MPa, averaged deformation is 5.38%, and this film has the excellent transparency, visible light transmissivity is up to more than 88%.
The invention has the advantages that:
(1) in the present invention, starting material used are all a large amount of materials that exist of occurring in nature, do not need to carry out chemical industry and synthesize, and have green, nontoxic, free of contamination characteristic, and raw materials cost is very low, has economically very large advantage;
(2) method steps of using in the present invention is simple to operation, possesses equally green, economy, feature fast;
(3) the present invention prepares a kind of material of the new multistage imitative shell with the micro-prominent and three kinds of structures of " brick-mud " structure of organic bridge joint, inorganic phase surface;
(4) film that prepared by the present invention has high strength, and tensile strength is up to being 243MPa, and its stress is all much larger than the stress of shell (130MPa).The visible light transmissivity of film exceedes 88%, and this is also the rarely found so high transmitance that has in other imitative shell films.
(5) the superstrength transparent artificial shell laminated film that prepared by the present invention shows broad prospect of application in fields such as aerospace, military affairs, civil engineering and machineries.Simultaneously also for other scientific research personnel provide a kind of new thinking.
Brief description of the drawings
Fig. 1 is the Egg tray structure schematic diagram that calcium ion crosslinking sodium alginate forms.
Fig. 2 A is for peeling off MMT sample TEM Electronic Speculum figure, and scale is 100nm; Fig. 2 B is the AFM figure of peel sample; Fig. 2 C is ALG/MMT laminated film cross section low power SEM figure, and scale is 10um; Fig. 2 D is ALG/MMT laminated film cross section high power SEM figure, and scale is 500nm.
Fig. 3 A and 3B are respectively the AFM figure of the different surface sweeping scopes of film surface that pure sodium alginate is mixed to get with calcium ion; Fig. 3 C schemes with the AFM that 3D is respectively the different surface sweeping scopes of ALG/MMT film surface;
Fig. 4 A is ALG/MMT laminated film stress-strain curve, wherein the sample in the corresponding embodiment 1～3 of curve 1～3 difference;
Fig. 4 B is mechanical property contrast between the film sample prepared of the present invention and shell and bionic thin film of the prior art thereof;
Fig. 4 C resists sheet interlayer sliding model on three kinds of Nano grades.The organic bridge model of figure (a) wherein; (b) inorganic phase surface micro-protuberance interlocking model; (c) the mineral bridge model between aragonite sheet;
Fig. 4 D is the ALG/MMT laminated film UV, visible light transmitance prepared of the present invention and the photo of sample, curve 1～3 corresponding embodiment 1～3 respectively wherein.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The invention provides a kind of super-strength transparent artificial shell laminated film and preparation method thereof, described preparation method specifically comprises the steps:
The first step, preparation MMT colloid;
MMT is dissolved in distilled water and forms 0.2～2wt%MMT aqueous solution, and then, with after magnetic stirrer at least 1 time-of-week, the centrifugal supernatant liquor obtaining is the MMT colloid of peeling off into monolithic;
Second step, by the MMT colloid obtaining and ALG aqueous solution, is stirred to and is fully mixed to get mixing solutions; The mass percent concentration of the described ALG aqueous solution is 0.1～1wt%; In mixing solutions, MMT and ALG mass ratio are that 1:9 is to 1:1.
The 3rd step adds CaCl in the mixing solutions of second step
2, stir and make it abundant mixing, due to Ca
2+there is coupling with ALG, form Egg tray structure as shown in Figure 1; Described CaCl
2quality be 10～200% of ALG quality.
The 4th step, finally carries out vacuum filtration by solution, obtains super-strength transparent artificial shell laminated film of the present invention.
Under the effect of vacuum, the Egg tray structure that MMT sheet and coupling form forms class shell " brick-mud " structure replacing layer by layer, simultaneously Egg tray structure sticks to the pimple structure that MMT sheet surface forms, and ALG organic chain sticks to and between MMT sheet, is formed with chain bridge construction.
embodiment 1:
The first step, is dissolved in 0.2g MMT in 100g distilled water and forms the 0.2wt%MMT aqueous solution, then uses magnetic stirrer after 1 week, and the centrifugal supernatant liquor obtaining is the MMT colloid of peeling off into monolithic;
Second step, by the MMT supernatant liquor obtaining and 1wt%ALG aqueous solution, is stirred to and is fully mixed to get mixing solutions; In mixing solutions, the mass ratio of MMT and ALG is 1:9.
The 3rd step adds appropriate CaCl in the mixing solutions of second step
2, stir and make it abundant mixing, due to Ca
2+there is coupling with ALG, form Egg tray structure as shown in Figure 1; The described CaCl adding
2quality be 200% of ALG quality.
The 4th step, finally carries out vacuum filtration by solution, obtains super-strength transparent artificial shell laminated film of the present invention.
Under the effect of vacuum, the Egg tray structure that MMT sheet and coupling form forms class shell " brick-mud " structure replacing layer by layer, simultaneously Egg tray structure sticks to the pimple structure that MMT sheet surface forms, and ALG organic chain sticks to and between MMT sheet, is formed with chain bridge construction.
embodiment 2:
The first step, is dissolved in 1g MMT in 100g distilled water and forms the 1wt%MMT aqueous solution, then uses magnetic stirrer after 1 week, and the centrifugal supernatant liquor obtaining is the MMT colloid of peeling off into monolithic;
Second step, by the MMT supernatant liquor obtaining and 1wt%ALG aqueous solution, is stirred to and is fully mixed to get mixing solutions; In mixing solutions, the mass ratio of MMT and ALG is 1:1.
The 3rd step adds appropriate CaCl in the mixing solutions of second step
2, stir and make it abundant mixing, due to Ca
2+there is coupling with ALG, form Egg tray structure; The described CaCl adding
2quality be 100% of ALG quality.
The 4th step, finally carries out vacuum filtration by solution, obtains super-strength transparent artificial shell laminated film of the present invention.
Under the effect of vacuum, the Egg tray structure that MMT sheet and coupling form forms class shell " brick-mud " structure replacing layer by layer, simultaneously Egg tray structure sticks to the pimple structure that MMT sheet surface forms, and ALG organic chain sticks to and between MMT sheet, is formed with chain bridge construction.
embodiment 3:
The first step, is dissolved in 2g MMT in 100g distilled water and forms the 2wt%MMT aqueous solution, then uses magnetic stirrer after 1 week, and the centrifugal supernatant liquor obtaining is the MMT colloid of peeling off into monolithic;
Second step, by the MMT supernatant liquor obtaining and 0.1wt%ALG aqueous solution, is stirred to and is fully mixed to get mixing solutions; In mixing solutions, the mass ratio of MMT and ALG is 1:9.
The 3rd step adds appropriate CaCl in the mixing solutions of second step
2, stir and make it abundant mixing, due to Ca
2+there is coupling with ALG, form Egg tray structure; The described CaCl adding
2quality be 10% of ALG quality.
The 4th step, finally carries out vacuum filtration by solution, obtains super-strength transparent artificial shell laminated film of the present invention.
Under the effect of vacuum, the Egg tray structure that MMT sheet and coupling form forms class shell " brick-mud " structure replacing layer by layer, simultaneously Egg tray structure sticks to the pimple structure that MMT sheet surface forms, and ALG organic chain sticks to and between MMT sheet, is formed with chain bridge construction.
In Fig. 2, C figure, D figure are respectively ALG/MMT laminated film cross section low power SEM figure and high power SEM figure, in Fig. 2 C figure, illustrate that film thickness prepared by the present invention is evenly regular, Fig. 2 D is to Fig. 2 C partial enlarged drawing, can find out, the ALG/MMT laminated film that the present invention prepares has " brick-mud " structure layer by layer of class shell.In square frame in Fig. 2 D, small embossment is that sodium alginate is at Ca
2+effect under coupling form " Egg tray structure ", the present invention utilizes sodium alginate at Ca first
2+effect under coupling form " Egg tray structure " and stick to MMT sheet surface MMT surface is formed to coarse small embossment, in conjunction with atomic power sign is carried out to as shown in Fig. 3 A～3D in the surface of containing MMT and not containing two kinds of films of MMT, the surface topography of two kinds of films is about the same.The bead that surface is 20-30nm for diameter is piled up and is formed, and is not adding CaCl in addition
2situation under, the result of pure ALG aqueous solution suction filtration can not get film, and Ca is described
2+to add be the key of this experiment, further illustrate small embossment is exactly that sodium alginate is at Ca simultaneously
2+effect under coupling form " Egg tray structure ".The small embossment here improves and has very large effect the mechanical property of film, and this can be described further by mechanics property analysis below.The place of the arrow instruction in Fig. 2 D figure is the organism chain bridge that sodium alginate forms, and connects levels MMT lamella.Can the mechanical property of film be improved and is very helpful equally.
The tension test stress-strain curve of the ALG/MMT laminated film in Fig. 4 A in three corresponding embodiment 1～3 of curve difference.From accompanying drawing, the stable performance of the prepared ALG/MMT laminated film of the present invention sample,, the highest tensile stress can reach 243MPa.What strain was passable is reached for 5.38%, has super-strength characteristic.In Fig. 4 B, No. 8 samples are ALG/MMT laminated film sample prepared by the present invention, and with shelly facies ratio, its stress-strain is all much larger than the stress-strain of shell (130MPa).Simultaneously in Fig. 4 B in listed sample 2～7, the tensile strength of ALG/MMT laminated film sample prepared by the present invention is not except there is no sample (No. 7 samples of PVA/MMT through glutaraldehyde cross-linking, tensile strength is 420MPa) outside intensity height, all will be higher than the tensile strength of other samples, and ALG/MMT laminated film prepared by the present invention has good stress-strain over-all properties.The tension strain of ALG/MMT laminated film prepared by simultaneously the present invention is all greater than the tension strain of other samples, can find out that the tension strain of film prepared by the present invention is greater than the tension strain 0.35% of PVA/MMT through the sample of glutaraldehyde cross-linking.The toughness of film sample prepared by large deformation explanation the present invention is fine, has good comprehensive mechanical property.
From Fig. 4 D, we can find out, the film sample that the present invention prepares is greater than 88% in the transmitance of visible region, its transmitance is greater than sample prepared by other researchers, it is regular that the method that vacuum filtration is described is prepared ALG/MMT laminated film, coincide with the layer structure of SEM image regulation, because MMT sheet stacked in parallel layer by layer, is conducive to seeing through of visible ray.Simultaneously can find out that from the photo in Fig. 4 D lower right corner ALG/MMT laminated film sample prepared by the present invention is the round film that the diameter of almost all-transparent is about 4cm.
In Fig. 4 C, be on three kinds of Nano grades, to resist lamella to see sliding model.(a) organic bridge model; (b) inorganic phase surface micro-protuberance interlocking model; (c) the mineral bridge model between aragonite sheet.In the present invention, possesses (a) organic bridge model; (b) inorganic phase surface micro-protuberance interlocking model.If there is method to make to form mineral bridge between inorganic MMT nanoscale twins, the mechanical property of sample will further improve greatly, the direction that this makes great efforts after being also.
Claims (6)
1. a preparation method for super-strength transparent artificial shell laminated film, is characterized in that: comprises the steps,
The first step, preparation MMT colloid;
Second step, preparation ALG solution, and by MMT colloid and ALG aqueous solution, in mixing solutions, MMT and ALG mass ratio are that 1:9 is to 1:1;
The 3rd step adds calcium chloride in the mixing solutions of second step, forms Egg tray structure;
The 4th step, carries out vacuum filtration to the solution of the 3rd step, obtains super-strength transparent artificial shell laminated film.
2. the preparation method of a kind of super-strength transparent artificial shell laminated film according to claim 1, it is characterized in that: the first step is specially: MMT is dissolved in and in distilled water, forms 0.2～2wt%MMT aqueous solution, then with after magnetic stirrer at least 1 time-of-week, the centrifugal supernatant liquor obtaining is the MMT colloid of peeling off into monolithic.
3. the preparation method of a kind of super-strength transparent artificial shell laminated film according to claim 1, is characterized in that: the mass percent concentration of the described ALG aqueous solution is 0.1～1wt%.
4. the preparation method of a kind of super-strength transparent artificial shell laminated film according to claim 1, is characterized in that: CaCl described in the 3rd step
2the quality that adds be 10～200% of ALG quality.
5. the preparation method of a kind of super-strength transparent artificial shell laminated film according to claim 1, is characterized in that:
The first step, is dissolved in 1g MMT in 100g distilled water and forms the 1wt%MMT aqueous solution, then uses magnetic stirrer after 1 week, and the centrifugal supernatant liquor obtaining is the MMT colloid of peeling off into monolithic;
Second step, by the MMT supernatant liquor obtaining and 1wt%ALG aqueous solution, is stirred to and is fully mixed to get mixing solutions; In mixing solutions, the mass ratio of MMT and ALG is 1:1;
The 3rd step adds CaCl in the mixing solutions of second step
2, stir and make it abundant mixing, due to Ca
2+there is coupling with ALG, form Egg tray structure; The described CaCl adding
2quality be 10% of ALG quality;
The 4th step, finally carries out vacuum filtration by solution, obtains super-strength transparent artificial shell laminated film of the present invention;
Under the effect of vacuum, the Egg tray structure that MMT sheet and coupling form forms class shell " brick-mud " structure replacing layer by layer, simultaneously Egg tray structure sticks to the pimple structure that MMT sheet surface forms, and ALG organic chain sticks to and between MMT sheet, is formed with chain bridge construction.
6. a super-strength transparent artificial shell laminated film, it is characterized in that: there are " brick-mud " structure, the micro-protuberance interlocking of inorganic phase surface and three kinds of structures of organic bridge joint, tensile strength is up to 243MPa, deformation reaches 5.38%, and this film has the excellent transparency, visible light transmissivity is up to more than 88%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104928741A (en) * | 2015-05-21 | 2015-09-23 | 武汉大学 | Multi-sensitive chitosan gel with brick-mud structure and preparation method and application thereof |
| CN106167555A (en) * | 2016-04-28 | 2016-11-30 | 华南理工大学 | A kind of imitative shell environmental protection composite membrane of interpenetrating type petal design and preparation method thereof |
| CN106750570A (en) * | 2016-11-24 | 2017-05-31 | 山东赛航新材料有限公司 | A kind of high intensity blush transparent artificial shell laminated film and preparation method thereof |
| CN108912602A (en) * | 2018-05-30 | 2018-11-30 | 中国科学技术大学 | A kind of three-dimensional imitative clam shell feature material and preparation method thereof |
| CN109433016A (en) * | 2018-10-04 | 2019-03-08 | 南京航空航天大学溧水仿生产业研究院有限公司 | The preparation method of bionical water-oil separationg film |
| CN110284358A (en) * | 2019-06-26 | 2019-09-27 | 陕西科技大学 | A kind of preparation method of aramid nano-fiber/montmorillonite insulating materials |
| CN110643919A (en) * | 2019-10-22 | 2020-01-03 | 兰州理工大学 | Method for preparing steel-based coating with shell-like structure on aluminum substrate |
| US10570304B2 (en) * | 2013-10-03 | 2020-02-25 | Technische Universiteit Delft | Biobased membrane |
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-
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- 2014-04-25 CN CN201410171248.4A patent/CN103923329B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 孙娜等: ""贝壳珍珠层及其仿生材料的研究进展"", 《高等学校化学学报》 * |
| 龙斌等: "聚丙烯酰胺/蒙脱土仿贝壳纳米复合材料的制备", 《稀有金属材料与工程》 * |
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| US10570304B2 (en) * | 2013-10-03 | 2020-02-25 | Technische Universiteit Delft | Biobased membrane |
| CN104928741A (en) * | 2015-05-21 | 2015-09-23 | 武汉大学 | Multi-sensitive chitosan gel with brick-mud structure and preparation method and application thereof |
| CN106167555A (en) * | 2016-04-28 | 2016-11-30 | 华南理工大学 | A kind of imitative shell environmental protection composite membrane of interpenetrating type petal design and preparation method thereof |
| CN106750570A (en) * | 2016-11-24 | 2017-05-31 | 山东赛航新材料有限公司 | A kind of high intensity blush transparent artificial shell laminated film and preparation method thereof |
| CN108912602A (en) * | 2018-05-30 | 2018-11-30 | 中国科学技术大学 | A kind of three-dimensional imitative clam shell feature material and preparation method thereof |
| CN109433016A (en) * | 2018-10-04 | 2019-03-08 | 南京航空航天大学溧水仿生产业研究院有限公司 | The preparation method of bionical water-oil separationg film |
| CN110284358A (en) * | 2019-06-26 | 2019-09-27 | 陕西科技大学 | A kind of preparation method of aramid nano-fiber/montmorillonite insulating materials |
| CN110643919A (en) * | 2019-10-22 | 2020-01-03 | 兰州理工大学 | Method for preparing steel-based coating with shell-like structure on aluminum substrate |
| CN113401892A (en) * | 2021-07-06 | 2021-09-17 | 中国科学院山西煤炭化学研究所 | Preparation method of ultra-thick heat-conducting graphene film |
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