CN103923329B - A kind of super-strength transparent artificial shell laminated film and preparation method thereof - Google Patents
A kind of super-strength transparent artificial shell laminated film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of super-strength transparent artificial shell laminated film and preparation method thereof, belong to bionics techniques field.Described preparation method is by MMT colloid and ALG aqueous solution, and adds calcium chloride in mixed solution, forms Egg tray structure；Then carry out vacuum filtration, obtain super-strength transparent artificial shell laminated film.The present invention utilizes sodium alginate and montmorillonite to prepare for raw material to have " brick mud " structure, the interlocking of inorganic phase surface micro-protuberance, the class shell thin film of three kinds of structures of organic bridge joint, described thin film has the mechanical property of excellence, hot strength is up to for 243MPa, averaged deformation is 5.38%, and described thin film has the transparency of excellence, it is seen that light transmission rate is up to more than 88%.
Description
Technical field
The invention belongs to bionics techniques field, refer to a kind of super-strength transparent artificial shell laminated film and system thereof specifically
Preparation Method, has broad prospect of application in fields such as Aero-Space, military affairs, civil engineering and machineries.
Background technology
The Nature creates perfect structure during evolving, and has attracted the concern of Many researchers and has studied emerging
Interest, encourages them to go to imitate the Nature.Wherein shell is a kind of natural organic/inorganic laminar composite, and its uniqueness is many
Level time " brick-mud " package assembly gives it and has light weight, intensity height, the excellent mechanical performance of good toughness.But it is nearly all
Researcher the most only imitating " brick-mud " structure of shell, have ignored the interlocking of inorganic phase surface micro-protuberance, organic bridge joint and
The raising to shell mechanical property of the mineral bridge joint between aragonite sheet.Therefore the composite prepared in prior art is the most not
Can preferably imitate preparation class shellfish material.Mechanical performance is not that intensity is the highest, it is simply that up, sample just becomes very intensity
Crisp, tensile deformation is the lowest, and toughness drastically declines.
Shell pearl layer is made up of aragonite sheet calcium carbonate (mass percent about 95%) and organic (about 5wt%), and it is tough
Property be more than 3000 times of aragonite sheet, this thundering mechanical property is owing to unique multiple dimensioned, the multilevel of nacreous layer
" brick-mud " package assembly.Inspired by this, both at home and abroad many seminars a series of bionical height that utilized distinct methods synthetically prepared
Strong ultra-tough laminar composite.Such as, Kotov group [Nano Lett., Vol.7, No.5,2007] LBL (Layer-
By-Layer) method successfully prepares self-supporting bionical shell nano-multilayered structures PDDA/MMT nano composite film.Stretching
Intensity and deformation are σ respectivelyu=100 ± 10MPa, ε=0.1%.Kotov group [Science2007,80,318] uses equally
LBL is prepared for MMT/PVA class shell laminated film, carries out covalent cross-linking after-drawing intensity and deformation is respectively introducing glutaraldehyde
σu=400 ± 40, ε=0.33 ± 0.04%.Yu Shuhong group [.Angew.Chem., Int.Ed., 2010,49,10127-
10131.] method utilizing vacuum filtration is prepared for Chitosan/MMT (chitosan-montmorillonite) class shell composite film material,
Hot strength and deformation are σ respectivelyu=76 ± 10MPa, ε=0.97 ± 0.14%.Additionally Yu Shuhong group [Angew.Chem.,
Int.Ed., 2010,49,2140-2145.] utilize there is functional inorganic phase LDH (the layered double
Hydroxide is commonly called as brucite) carry out amination process at its surface, introduce hydrogen bond action at organic layer with inorganic interlayer
Prepare obdurability layered composite film.LDH colloid after utilizing dip coating to modify is assembled into height-oriented Two-dimensional Inorganic
Layer, is then spun on inoranic membrane surface by chitosan solution, and obtaining thickness after so continuously repeating dip-coating-spin-coating step is tens
The stratiform Chitosan/LDH hybrid film of individual micron.Hot strength and deformation are σ respectivelyu=160MPa, ε=5%.Equally
Walther et al. [Nano Lett., 2010,10:2742-2748.] also by the method for vacuum filtration, uses for reference the work of paper process
Skill, is prepared for multi-layer compound film.
Many stratiform " brick-mud " structural models preparing shell in imitation of existing technology, and have studied multiple method and
The laminated film of the different imitative shells of organo-mineral complexing preparation.But simple " brick-mud " structural model can not solve completely
Release the energy expenditure that experiment records.[the Journal of the mech anical behavior of biomedical such as Marc
Materials, 2008,1,76-85.] demonstrate the most respectively on three kinds of Nano grades resist lamella see sliding mould
Type.They are respectively the organic bridge joint mould of mineral between bridge model, inorganic phase surface micro-protuberance interlocking model, aragonite sheet
Type, C figure in Fig. 4 is shown in by its schematic diagram.
Meanwhile, the Organic substance selected in existing technical scheme is mostly the material of chemistry organic synthesis, has poisonous more
Harmful substance, non-green native biopolymer, has been short of in environmental protection.
Summary of the invention
The invention aims to solve of the prior art can not green, quickly imitate the organic bridge of shell
Connect, inorganic phase surface is micro-prominent and " brick-mud " structure problem, propose a kind of quickly, green preparation super-strength transparent artificial shell is combined
The method of thin film.
For the multilevel hierarchy imitating shell fast and effectively nontoxic, free of contamination, the present invention provides one to prepare to have
By organic matter bridge joint, inorganic phase surface is micro-prominent and " brick-mud " structure imitates the nano compound film of shell high-strength and high-transparent
Method, in described preparation method, utilizes the montmorillonite (MMT) of churned mechanically method stripped laminar, obtains monolayer MMT after being centrifuged
The aqueous solution of sheet, after being then sufficiently mixed stirring with isocyatic sodium alginate (ALG) aqueous solution, adds a certain amount of chlorination
Calcium, allows ALG form network structure under the effect of calcium ion, finally prepares imitative shell multilevel hierarchy by the method for vacuum filtration
Laminated film.Specifically comprise the following steps that
The first step, prepares MMT colloid；
Second step, prepares ALG solution, and by MMT colloid and ALG aqueous solution.
3rd step, adds calcium chloride in the mixed solution of second step.
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 thin film has " brick-mud " structure, the interlocking of inorganic phase surface micro-protuberance, organic bridge
Connecing three kinds of structures, have the mechanical property of excellence, hot strength is up to 243MPa, and averaged deformation is 5.38%, and this thin film
There is the transparency of excellence, it is seen that light transmission rate is up to more than 88%.
It is an advantage of the current invention that:
(1) raw material used in the present invention is all a large amount of materials existed in nature, it is not necessary to carry out chemical industry synthesis,
Having characteristic green, nontoxic, free of contamination, cost of material is the lowest, economically has the biggest advantage；
(2) method step used in the present invention is simple to operation, is likewise supplied with green, economy, quick feature；
(3) present invention prepares and a kind of new has that organic bridge joint, inorganic phase surface be micro-prominent and three kinds of " brick-mud " structure
The material of the multistage imitative shell of structure；
(4) thin film prepared by the present invention has high intensity, and hot strength is up to 243MPa, and its stress is all much larger than shell
(130MPa) stress.The visible light transmissivity of thin film is more than 88%, and this is also rarely found to have this in other imitative shell thin film
High transmitance.
(5) the superhigh intensity transparent artificial shell laminated film that prepared by the present invention is at Aero-Space, military affairs, civil engineering and machine
The fields such as tool show broad prospect of application.Also provide a kind of new thinking for other scientific research personnel simultaneously.
Accompanying drawing explanation
Fig. 1 is the Egg tray structure schematic diagram that calcium ion crosslinking sodium alginate is formed.
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, scale is 10um；Fig. 2 D is ALG/MMT laminated film cross section high power SEM figure, mark
Chi is 500nm.
The AFM of the film surface different surface sweeping scope that Fig. 3 A with 3B respectively pure sodium alginate is mixed to get with calcium ion
Figure；Fig. 3 C with 3D is respectively the AFM figure of ALG/MMT film surface different surface sweeping scope；
Fig. 4 A is ALG/MMT laminated film load-deformation curve, wherein in the most corresponding embodiment 1～3 of curve 1～3
Sample；
Fig. 4 B is mechanical property between film sample and shell and bionic thin film of the prior art thereof prepared by the present invention
Contrast；
Fig. 4 C is opposing sheet interlayer sliding model on three kinds of Nano grades.The organic bridge model of figure (a) therein；(b)
Inorganic phase surface micro-protuberance interlocking model；Mineral bridge model between (c) 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, wherein
Curve 1～3 respectively corresponding embodiment 1～3.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The present invention provides a kind of super-strength transparent artificial shell laminated film and preparation method thereof, and described preparation method is concrete
Comprise the steps:
The first step, prepares MMT colloid；
MMT is dissolved in distilled water formation 0.2～2wt%MMT aqueous solution, then by magnetic stirrer at least 1
After time-of-week, the centrifugal supernatant obtained is the MMT colloid peeling off into monolithic；
Second step, by the MMT colloid obtained and ALG aqueous solution, stirs to being sufficiently mixed and obtains mixed solution；Described
The mass percent concentration of ALG aqueous solution is 0.1～1wt%；In mixed solution, MMT and ALG mass ratio is 1:9 to 1:1.
3rd step, adds CaCl in the mixed solution of second step2, stirring is allowed to be sufficiently mixed, due to Ca2+Send out with ALG
Raw coupling, forms Egg tray structure as shown in Figure 1；Described CaCl2Quality is ALG mass 10～200%.
4th step, finally carries out vacuum filtration by solution, obtains the 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 are formed forms the class shell " brick-mud " replaced layer by layer
Structure, Egg tray structure sticks to the kick structure that MMT sheet surface is formed simultaneously, and ALG organic chain sticks to be formed between MMT sheet
Organic chain bridge construction.
Embodiment 1:
The first step, is dissolved in 0.2g MMT in 100g distilled water formation 0.2wt%MMT aqueous solution, then stirs with magnetic force
Mixing after device stirs 1 week, the centrifugal supernatant obtained is the MMT colloid peeling off into monolithic；
Second step, by the MMT supernatant obtained and 1wt%ALG aqueous solution, stir to be sufficiently mixed obtain mixing molten
Liquid；In mixed solution, the mass ratio of MMT and ALG is 1:9.
3rd step, adds appropriate CaCl in the mixed solution of second step2, stirring is allowed to be sufficiently mixed, due to Ca2+With
There is coupling in ALG, forms Egg tray structure as shown in Figure 1；The CaCl of described addition2Quality be ALG mass
200%.
4th step, finally carries out vacuum filtration by solution, obtains the 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 are formed forms the class shell " brick-mud " replaced layer by layer
Structure, Egg tray structure sticks to the kick structure that MMT sheet surface is formed simultaneously, and ALG organic chain sticks to be formed between MMT sheet
Organic chain bridge construction.
Embodiment 2:
The first step, is dissolved in 1g MMT in 100g distilled water formation 1wt%MMT aqueous solution, then uses magnetic stirring apparatus
After stirring 1 week, the centrifugal supernatant obtained is the MMT colloid peeling off into monolithic；
Second step, by the MMT supernatant obtained and 1wt%ALG aqueous solution, stir to be sufficiently mixed obtain mixing molten
Liquid；In mixed solution, the mass ratio of MMT and ALG is 1:1.
3rd step, adds appropriate CaCl in the mixed solution of second step2, stirring is allowed to be sufficiently mixed, due to Ca2+With
There is coupling in ALG, forms Egg tray structure；The CaCl of described addition2Quality is ALG mass 100%.
4th step, finally carries out vacuum filtration by solution, obtains the 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 are formed forms the class shell " brick-mud " replaced layer by layer
Structure, Egg tray structure sticks to the kick structure that MMT sheet surface is formed simultaneously, and ALG organic chain sticks to be formed between MMT sheet
Organic chain bridge construction.
Embodiment 3:
The first step, is dissolved in 2g MMT in 100g distilled water formation 2wt%MMT aqueous solution, then uses magnetic stirring apparatus
After stirring 1 week, the centrifugal supernatant obtained is the MMT colloid peeling off into monolithic；
Second step, by the MMT supernatant obtained and 0.1wt%ALG aqueous solution, stirs to being sufficiently mixed and is mixed
Solution；In mixed solution, the mass ratio of MMT and ALG is 1:9.
3rd step, adds appropriate CaCl in the mixed solution of second step2, stirring is allowed to be sufficiently mixed, due to Ca2+With
There is coupling in ALG, forms Egg tray structure；The CaCl of described addition2Quality is ALG mass 10%.
4th step, finally carries out vacuum filtration by solution, obtains the 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 are formed forms the class shell " brick-mud " replaced layer by layer
Structure, Egg tray structure sticks to the kick structure that MMT sheet surface is formed simultaneously, and ALG organic chain sticks to be formed between MMT sheet
Organic 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
Illustrating that film thickness prepared by the present invention is the most regular, Fig. 2 D is to Fig. 2 C partial enlarged drawing, it can be seen that the present invention prepares
ALG/MMT laminated film there is " brick-mud " structure layer by layer of class shell.The medium and small projection of square frame in Fig. 2 D is alginic acid
Sodium is at Ca2+Effect under couple formation " Egg tray structure ", the present invention is to utilize sodium alginate at Ca first2+Effect under couple
Form " Egg tray structure " to stick to MMT sheet surface MMT surface is formed coarse little projection, combine to containing MMT with do not contain
The surface of two kinds of thin film of MMT carries out atomic force and characterizes as shown in Fig. 3 A～3D, and the surface topography of two kinds of thin film is about the same.Table
Face is that the bead accumulation of a diameter of 20-30nm forms, and is not additionally adding CaCl2In the case of, pure ALG aqueous solution sucking filtration
Result can not get thin film, and Ca is described2+Addition be the key of this experiment, further illustrate little projection is exactly that sodium alginate exists simultaneously
Ca2+Effect under couple formation " Egg tray structure ".The mechanical property of thin film is improved by little projection here the biggest effect, this
Can be described further at following mechanics property analysis.The place of the arrow instruction in Fig. 2 D figure is having of sodium alginate formation
Machine thing chain bridge, connects levels MMT lamella.The mechanical property of thin film can be improved equally and be very helpful.
The tension test stress of the ALG/MMT laminated film in the most corresponding embodiments 1～3 of three curves in Fig. 4 A-should
Varied curve.Knowable to accompanying drawing, the stable performance of ALG/MMT laminated film sample prepared by the present invention, the highest tensile stress is permissible
Reach 243MPa,.Strain and permissible be reached for 5.38%, there is super-strength characteristic.In Fig. 4 B, No. 8 samples are prepared by the present invention
ALG/MMT laminated film sample, with shelly facies ratio, its ess-strain is all much larger than the ess-strain of shell (130MPa).Simultaneously
In sample 2～7 listed in Fig. 4 B, the hot strength of ALG/MMT laminated film sample prepared by the present invention is not except having
PVA/MMT, outside sample (No. 7 samples, hot strength is 420MPa) the intensity height of glutaraldehyde cross-linking, will be higher than other samples
The hot strength of product, and ALG/MMT laminated film prepared by the present invention has excellent ess-strain combination property.The most originally
The elongation strain of the ALG/MMT laminated film of invention preparation is both greater than the elongation strain of other samples, it can be seen that system of the present invention
The elongation strain of standby thin film is greater than the PVA/MMT elongation strain 0.35% through the sample of glutaraldehyde cross-linking.Big deformation
Illustrate that the toughness of film sample prepared by the present invention is fine, there is good comprehensive mechanical property.
It will be seen that the film sample for preparing of the present invention transmitance in visible region is more than from Fig. 4 D
88%, the sample that its transmitance is prepared more than other researchers, illustrate that the method for vacuum filtration prepares ALG/MMT THIN COMPOSITE
Film is regular, and the regular Rotating fields of SEM image coincide, because the passing through of MMT sheet stacked in parallel layer by layer, beneficially visible ray.With
Time photo from Fig. 4 D lower right corner can be seen that the diameter that ALG/MMT laminated film sample is almost all-transparent prepared by the present invention
It is about the round thin film of 4cm.
Fig. 4 C is resist lamella on three kinds of Nano grades to see sliding model.(a) organic bridge model；(b) inorganic phase
Surface micro-protuberance interlocking model；Mineral bridge model between (c) aragonite sheet.The present invention has possessed (a) organic bridge joint mould
Type；(b) inorganic phase surface micro-protuberance interlocking model.Mineralogical Digital Museum is formed if there being method to make between inorganic MMT nanoscale twins, sample
Mechanical property will be greatly improved further, this direction made great efforts after being also.
Claims (6)
1. the preparation method of a super-strength transparent artificial shell laminated film, it is characterised in that: comprise the steps,
The first step, prepares MMT colloid；
Second step, prepares ALG solution, and by MMT colloid and ALG aqueous solution, in mixed solution, MMT and ALG mass ratio is
1:9 to 1:1；
3rd step, adds calcium chloride in the mixed solution of second step, forms Egg tray structure；
4th step, carries out vacuum filtration to the solution of the 3rd step, obtains super-strength transparent artificial shell laminated film.
The preparation method of a kind of super-strength transparent artificial shell laminated film the most according to claim 1, it is characterised in that: the
One step particularly as follows: be dissolved in distilled water formation 0.2～2wt%MMT aqueous solution, then by magnetic stirrer extremely by MMT
After few 1 time-of-week, the centrifugal supernatant obtained is the MMT colloid peeling off into monolithic.
The preparation method of a kind of super-strength transparent artificial shell laminated film the most according to claim 1, it is characterised in that: institute
The mass percent concentration stating ALG aqueous solution is 0.1～1wt%.
The preparation method of a kind of super-strength transparent artificial shell laminated film the most according to claim 1, it is characterised in that: the
CaCl described in three steps2Addition quality is ALG mass 10～200%.
The preparation method of a kind of super-strength transparent artificial shell laminated film the most according to claim 1, it is characterised in that:
The first step, is dissolved in 100g distilled water formation 1wt%MMT aqueous solution, then by magnetic stirrer 1 by 1g MMT
Zhou Hou, the centrifugal supernatant obtained is the MMT colloid peeling off into monolithic；
Second step, by the MMT supernatant obtained and 1wt%ALG aqueous solution, stirs to being sufficiently mixed and obtains mixed solution；
In mixed solution, the mass ratio of MMT and ALG is 1:1；
3rd step, adds CaCl in the mixed solution of second step2, stirring is allowed to be sufficiently mixed, due to Ca2+Coupling is there is with ALG
Cooperation use, forms Egg tray structure；The CaCl of described addition2Quality is ALG mass 10%；
4th step, finally carries out vacuum filtration by solution, obtains the 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 are formed forms class shell " brick-mud " structure replaced layer by layer,
Egg tray structure sticks to the kick structure that MMT sheet surface is formed simultaneously, and ALG organic chain sticks to be formed between MMT sheet organic
Chain bridge construction.
6. a super-strength transparent artificial shell laminated film, it is characterised in that: use claim 1 preparation method prepare one
Plant super-strength transparent artificial shell laminated film, there is " brick-mud " structure, the interlocking of inorganic phase surface micro-protuberance and organic bridge joint three
Planting structure, hot strength is up to 243MPa, and deformation reaches 5.38%, and this thin film has the transparency of excellence, it is seen that light transmission
Rate is up to more than 88%.
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| NL2011542B3 (en) * | 2013-10-03 | 2024-02-28 | Univ Delft Tech | Biobased membrane. |
| CN104928741B (en) * | 2015-05-21 | 2017-07-11 | 武汉大学 | How sensitive chitosan gel rubber of brick mud structure and its preparation method and application |
| CN106167555B (en) * | 2016-04-28 | 2019-03-05 | 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 |
| CN108912602B (en) * | 2018-05-30 | 2019-11-22 | 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 |
| CN110643919B (en) * | 2019-10-22 | 2020-06-23 | 兰州理工大学 | Method for preparing steel-based coating with shell-like structure on aluminum substrate |
| CN113401892B (en) * | 2021-07-06 | 2022-08-30 | 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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