CN107033377A - A kind of method and organo-mica film that macroscopical organo-mica film is prepared using the natural nano peeled off level mica sheet - Google Patents
A kind of method and organo-mica film that macroscopical organo-mica film is prepared using the natural nano peeled off level mica sheet Download PDFInfo
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Abstract
The invention discloses a kind of method and organo-mica film that macroscopical organo-mica film is prepared using the natural nano peeled off level mica sheet, natural mica powder peels off into the nanoscale mica sheet (eMica) of individual layer, and it is assembled into large area using spraying, the organo-mica film of soft soft clear, the size and size of film can regulate and control, as a result find in organo-mica film containing 60 wt%eMica not only with superior mechanical property, its tensile strength is far longer than mica powder and nano imvite hybrid films respectively much in proportion, and reach the 62% of natural mica splitting tensile stress, and with superior fatigue resistance, there is optimal visible ultraviolet selective simultaneously, effective back-fire relief and water stabilizing.
Description
Technical field
The method of macroscopical organo-mica film is prepared the present invention relates to a kind of natural nano level mica sheet using stripping and is had
Machine mica film, belongs to field of nano material preparation.
Background technology
Natural peral mother is the gradational micro-nano structure of tool, is design construction, light weight, strong, toughness bionical material
The model of material, the microstructure of mother-of-pearl is defined as the stratiform brick mud structure of superior interface reaction.So far, it is various
The hard two-dimensional material of various kinds and soft organic matter are assembled into biomimetic material.Possess high aspect ratio, the high boundary of the peacekeeping of nanometer two
The clay flake of face activity is a kind of structure material for most allowing people interested, some back-fire reliefs of main research material, it is seen that light is passed through, excellent
Mechanical property more.
The U.S.《It is natural》（Nature, volume 2, the 413-418 pages in 2003）Report and utilize montmorillonite-based nano piece
（MTM）And PDDA（PDDA）As construction unit, the PDDA- with natural seashell structure is assembled into
MTM nanocomposite films, its tensile strength is up to 106MPa, and Young's modulus is 13GPa, the reason for mechanics strengthens it is main by
Powerful positive and negative charge attracts each other and Van der Waals force between the design of imitative clam shell feature and MTM and polymer molecular chain interface
Interaction, the U.S.《Science》（Science, volume 318, the 80-93 pages in 2007）Report and utilize montmorillonite-based nano
Piece (MTM) and polyvinyl alcohol（PVA）For construction unit, obtain transparent by layer assembly, it is soft, and self-supporting MTM-
PVA composite membranes, his tensile stress can reach mechanicalness of the 400MPa Young's modulus up to 106GPa, significantly larger than natural seashell
Can, the U.S.《Science》（Nature Communications, 2015, volume 6, page 5697）Utilize different draw ratios
Synthesis of clay mineral (Synthetic clay) and PVA obtain a series of imitative shell composite membranes by evaporating self assembly
(Synthetic clay-PVA), discloses influence of the clay mineral of different draw ratios to imitative shell composite membrane mechanics, major diameter
Better than bigger mechanical property, the smaller translucency of draw ratio is better, and its optimum stretch stress is 200MPa.Contrast and other clays
Mineral, mica is a kind of unique clay mineral, with high aspect ratio, and atom level is smooth, electrical insulating property, fire-resistance, and ultraviolet suction
The performance such as receive, thus mica not only extensive utilization to industry with above agricultural, but also absorb the huge attention of scientific circles
So far, prepare olivet mother and mainly use peel montmorillonite and synthesis of clay piece or modified organisms, but day
Right nano mica piece is but not yet reported that.
The content of the invention
There is provided utilize the natural nano level mica sheet peeled off to solve the weak point present in prior art by the present invention
The method for preparing macroscopical organo-mica film, the technical problem of solution is successfully to be assembled into macroscopic view using natural nano mica sheet to have
Machine mica film.
To achieve the above object, the technical scheme that provides of the present invention is：It is a kind of to utilize the natural nano peeled off level mica sheet
The method for preparing macroscopical organo-mica film, it is characterised in that：Comprise the following steps：
The first step：0.2 ~ 1mL aq. polyethyleneimine and 1 ~ 5mL is added into 10 ~ 500mL nano mica piece suspension
Sodium-chloride water solution, stir 0.5 ~ 2h, be then centrifuged in centrifuge with 6000 ~ 10000r/min rotating speed,
It is redispersed in obtaining the amine-modified nano mica piece suspension of polyethyleneimine in water after obtained sediment washing；
Second step：Under conditions of stirring, chitosan is added into the amine-modified nano mica piece suspension of the polyethyleneimine
Solution, then obtains nano mica piece-chitosan dispersion by sustained oscillation；Wherein, the preparation side of the chitosan solution
Method includes：0.6 ~ 2mL acetic acid is added in 30 ~ 100mL water and obtains acetic acid aqueous solution, 0.5 ~ 2g chitosans are then added into institute
Stating stirring in acetic acid aqueous solution produces chitosan dissolving；
3rd step：Nano mica piece-the chitosan dispersion is sprayed on to the surface of 60 ~ 90 DEG C of substrate of glass, described
The surface of substrate of glass forms organo-mica film, then has the substrate of glass bubble of organo-mica film dense in mass percent on surface
Spend in the sodium hydroxide solution for 1 ~ 10%, organo-mica film is departed from substrate of glass and produce organo-mica film product.
It is preferred that technical scheme be：Nano mica tablet quality fraction in the nano mica piece-chitosan is 20 ~ 80%.
It is preferred that technical scheme be：Nano mica tablet quality fraction in the nano mica piece-chitosan is 60%.
It is preferred that technical scheme be：The aq. polyethyleneimine is the polyethyleneimine aqueous amine that concentration is 10 ~ 30mg/mL
Solution；The sodium-chloride water solution is the sodium-chloride water solution that concentration is 0.1 ~ 0.5mol/L；The nano mica piece suspension
Refer to 2-10mg nano mica piece being scattered in 1mL water and be made.
It is preferred that technical scheme be：The preparation method of the nano mica piece comprises the following steps：
The first step：Mica powder is warming up to 0.5 ~ 2h of insulation after 800 DEG C in heater with 2 ~ 10 DEG C/min programming rate,
Obtain calcining mica powder；
Second step：10 ~ 40g calcining mica powder is placed in one first reaction vessel, then adds 500mL 3 ~ 6mol/L's
Nitric acid, reacts 3 ~ 6 hours, then suction filtration obtains filter residue, after the residue washing to neutrality, then through drying under the conditions of 70 ~ 95 DEG C
Produce mica powder after pickling；
3rd step：Mica powder after 10 ~ 35g pickling is added into one second reaction vessel, 500mL mass percent is then added
Concentration is 20 ~ 40% sodium chloride solution, is reacted 3 ~ 6 hours under the conditions of 70 ~ 95 DEG C, then suction filtration obtains filter residue, and the filter residue is washed
Wash to no chlorion, then be dried and obtain salt and wash rear mica powder；
4th step：2 ~ 10g salt is washed into rear mica powder to add in one the 3rd reaction vessel, 500mL deionized water is then added,
6 ~ 30g cetane trimethyl ammonium bromide, reacts 3 ~ 6 hours, then suction filtration obtains filter residue, the filter residue under the conditions of 70 ~ 95 DEG C
Washing is to no chlorion, then is dried and obtains intercalation mica powder；
5th step：0.2 ~ 2g intercalation mica powder is scattered in 20 ~ 200mL ethanol, is then surpassed using ultrasonication machine
Sound is peeled off, and is centrifuged 10min using 3000r/min every 0.5h, is collected upper strata suspension, then remaining sample is dispersed in again
Continue ultrasound in the ethanol of volume to peel off, suspension is no longer produced after centrifugation, nano mica piece is produced after drying.
It is preferred that technical scheme be：The heater is resistance furnace.
It is preferred that technical scheme be：The mass percent concentration of the amine-modified nano mica piece suspension of the polyethyleneimine
For 2%.
To achieve the above object, the technical scheme that provides of the present invention is：A kind of organo-mica film, the organo-mica film
Tensile strength is that 259Mpa, Young's modulus are 16Gpa.
Because above-mentioned technical proposal is used, the present invention this have the advantage that compared with prior art：
1st, the method provided by the present invention for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet, preparation side
Method is simple, and nano mica piece-chitosan dispersion of uniform different proportion is obtained by concussion, using spraying self assembly first
Obtain nano mica piece-chitosan complex film.
2nd, nano mica piece-chitosan complex film that the present invention is obtained, optimal 60% nano mica piece-chitosan is multiple
Close the tensile stress of film（259MPa）It is far longer than mica powder chitosan complex film（26MPa）It is compound with nano imvite chitosan
Film（95MPa）, and reach mica splitting（420MPa）62%.
3rd, 60% nano mica piece-chitosan complex film provided by the present invention, with good fatigue resistance, passes through
1000 bend cycles, tensile stress is almost unchanged and size of composite membrane, the equal controllable of thickness.
Brief description of the drawings
Fig. 1 is the nano mica piece of example 1-chitosan film section surface sweeping electromicroscopic photograph（a）20%,（b）40%,（c）60%,（d）
80%。
Fig. 2 is 0%, 20%, 40%, 60%, 80% nano mica piece-chitosan film（a）Tensile strength and Young's modulus,（b）
60% nano mica piece-chitosan film, 60% nano mica powder-chitosan film, 60% nano imvite-chitosan film, mica splitting
Tensile strength data,（c）60% nano mica piece-chitosan film is that 2.0mm passes through 10,100,1000 times in maximum deflection radius
The tensile strength of circulation.
Fig. 3 (a) is the light transmittance of the organo-mica film of different nano mica piece contents；Fig. 3 (b) is 60% nano mica
Light transmittance of the piece-chitosan film under the conditions of wavelength is 275,555.Fig. 3 (c) sweeps for the section of several thickness organo-mica films
Retouch 5 μm of electron microscope, 10 μm, 20 μm, 40 μ do not have photo.60wt% organo-mica film of Fig. 3 (d) displayings with different-thickness
UV, visible light transmitance.
Fig. 4（a）One transparent and soft 8*8 60wt% organo-mica film optical photographs,（b）60wt% organo-micas film soaks
The optical photograph ducked in drink more than 30 days,（c）Change of the 60wt% organo-micas film in gas torch burning surface temperature over time
Change, illustration is infrared image of the 60wt% organo-micas film in gas torch burning.
Embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.
Embodiment one：It is a kind of to prepare the method for macroscopical organo-mica film and organic using the natural nano peeled off level mica sheet
Mica film
The present embodiment carries out preparing macroscopical organo-mica film using the natural nano level mica sheet peeled off as follows：
In a, configuration 10mg/mL polyethyleneimines, 0.1mol/L sodium chloride solutions, 200mL, 4mg/mL nano mica piece suspensions
4mL polyethyleneimines and sodium chloride solution are added, 1h is stirred while adding under 20mL, 0.1mol/L sodium chloride solutions, normal temperature,
8000r/min centrifuges 10min, washs 3 times, obtains the 2% amine-modified nano mica piece suspension of polyethyleneimine.
B, it is added in 50mL water in 1mL acetic acid, takes 1g chitosans to add in beaker stirring and dissolving at room temperature, by 2% nanometer
Mica sheet suspension is added in chitosan solution under conditions of the stirring, by sustained oscillation obtain uniform nano mica piece-
Chitosan dispersion, regulates and controls the content 60% of nano mica piece.
C, uniform nano mica piece-chitosan suspension are poured into inside spray gun, are then sprayed at 90 DEG C of substrate of glass
Above.Film, which is immersed in 2% sodium hydroxide solution, departs from substrate, so can be obtained by 60% organo-mica film.
60% organo-mica film prepared by the present embodiment（Fig. 1（c））Cross-sectional scans electron microscope can be seen that good layer
Shape structure and it is hardly visible organic matter.
Such as Fig. 2（a）Shown, 60% organo-mica film has the tensile stress and Young's modulus difference of optimal mechanical performance
For 259Mpa and 16.3GPa；Pure chistosan film enhances 6.7 and 36 times.The tensile strength of 60% organo-mica film is significantly larger than
60% mica powder-chitosan film（26MPa）With 60% nano imvite-chitosan film（95MPa）, reach the 62% of mica splitting（Fig. 2
（a））, and with good fatigue resistance（Fig. 3（c））.
Such as Fig. 3（A, b）It is shown by the way that there is optimal visible light permeability to 60% organo-mica film（38-65%）Almost
Complete uv-shielding capacity.
The regulation and control of 60% organo-mica dispersion liquid volume can be prepared into the composite membrane of different-thickness using self assembly is sprayed,
Fig. 3（c）For the cross-sectional scans electron microscope of several thickness organo-mica films prepared by the present embodiment, such as 5 μm, 10 μm, 20 μm,
40 μm, their optical photograph is correspond in illustration respectively.Fig. 3（d）60 wt% organo-mica films of the displaying with different-thickness
UV, visible light transmitance and the thinner transmitance of film thickness is higher, the transmitances of 5 μm of 60wt% organo-mica films is 57%-84%
Fig. 4（a）Shown, transparent and soft 8*8 60wt% organo-mica films are readily available, show we assemble have
Machine mica film is easy to be exaggerated preparation.In addition, the time that organo-mica film is placed in water more than 1 month can keep stable（Fig. 4
（b））.Superior Fire resistances are detected.From the picture of thermograph, when 60wt% organo-mica films are placed on flame, the table of film
Face mean temperature is quickly more than 700oC, prevents flame from not collapsing more than 90s（Fig. 4（c））
Embodiment two：A kind of method and organo-mica that macroscopical organo-mica film is prepared using the natural nano peeled off level mica sheet
Film
The present embodiment carries out preparing macroscopical organo-mica film using the natural nano level mica sheet peeled off as follows：
In a, configuration 20mg/mL polyethyleneimines, 0.2mol/L sodium chloride solutions, 100mL, 8mg/mL nano mica piece suspensions
8mL polyethyleneimines and sodium chloride solution are added, 1h is stirred while adding under 10mL, 0.1mol/L sodium chloride solutions, normal temperature,
8000r/min centrifuges 10min, washs 3 times, obtains the 2% amine-modified nano mica piece suspension of polyethyleneimine.
B, it is added in 100mL water in 2mL acetic acid, takes 2g chitosans to add in beaker stirring and dissolving at room temperature, 2% is received
Rice mica sheet suspension is added in chitosan solution under conditions of stirring, and uniform nano mica is obtained by sustained oscillation
Piece-chitosan dispersion, regulates and controls the content 60% of nano mica piece.
C, uniform nano mica piece-chitosan suspension are poured into inside spray gun, are then sprayed at 80oC substrate of glass
Above.Film, which is immersed in 1% sodium hydroxide solution, departs from substrate, so can be obtained by 60% organo-mica film.
Such as Fig. 3（A, b）It is shown by the way that there is optimal visible light permeability to 60% organo-mica film（38-65%）Almost
Complete uv-shielding capacity.The exemplary embodiment of the present invention is the foregoing is only, is not intended to limit the invention, it is all
Any modifications, equivalent substitutions and improvements made within the spirit and principles in the present invention etc., should be included in the guarantor of the present invention
Within the scope of shield.
The preparation method of nano mica piece is as follows：
A, 30g mica powders are weighed, 800 DEG C are warming up in resistance furnace, programming rate is 5 DEG C/min, is incubated 1h；
B, 20g calcined into the reaction vessel that later mica powder adds 1000mL, then add 500mL3mol/L nitric acid, 90 DEG C,
4h is reacted, reaction terminates rear filtering and washing, washing to neutrality, 60 DEG C of dryings；
C, the reaction vessel by mica powder addition 1000mL after 20g pickling, then add 500mL30% sodium chloride solutions, 87 DEG C
5h is reacted, reaction terminates rear filtering and washing, and no chlorion, 60 DEG C of dryings are arrived in washing；
D, the reaction vessel by mica powder addition 1000mL after 8g pickling, then add 500mL deionized waters, 20g hexadecanes
Base front three ammonium bromide, reaction temperature is 80 DEG C of reaction 6h, and reaction terminates rear filtering and washing, and no chlorion is arrived in washing, and 60 DEG C are done
It is dry to obtain mica powder after intercalation.
E, mica powder after 0.4g intercalations is taken to be dispersed in 40mL ethanol, using ultrasonication machine（40%×950W）Carry out
Ultrasound is peeled off；
After f, ultrasound 0.5h, 10min is centrifuged by 3000r/min, upper liquid is collected, the mica powder do not peeled off disperses again
In 40mL ethanol, continue ultrasound and peel off；
G, ten times the step of repeat the above, the scattered nano mica pieces in ethanol of obtained 400mL, nano mica piece be individual layer or
It is double-deck.
Embodiment three：It is a kind of to prepare the method for macroscopical organo-mica film and organic using the natural nano peeled off level mica sheet
Mica film
A kind of method for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet, comprises the following steps：
The first step：The chlorination of 0.3mL aq. polyethyleneimine and 4mL is added into 200mL nano mica piece suspension
Sodium water solution, is stirred 1h, is then centrifuged in centrifuge with 8000r/min rotating speed, obtained sediment washing
It is redispersed in obtaining the amine-modified nano mica piece suspension of polyethyleneimine in water afterwards；
Second step：Under conditions of stirring, chitosan is added into the amine-modified nano mica piece suspension of the polyethyleneimine
Solution, then obtains nano mica piece-chitosan dispersion by sustained oscillation；Wherein, the preparation side of the chitosan solution
Method includes：1mL acetic acid is added in 80mL water and obtains acetic acid aqueous solution, 1g chitosans are then added into the acetic acid aqueous solution
Middle stirring produces chitosan dissolving；
3rd step：Nano mica piece-the chitosan dispersion is sprayed on to the surface of 80 DEG C of substrate of glass, in the glass
The surface of substrate forms organo-mica film, then it is 9% that the substrate of glass that surface has organo-mica film, which is steeped in mass percent concentration,
Sodium hydroxide solution in, make organo-mica film depart from substrate of glass produce organo-mica film product.
It is preferred embodiment：Nano mica piece best in quality fraction in the nano mica piece-chitosan is
60%。
It is preferred embodiment：The aq. polyethyleneimine is that the polyethyleneimine that concentration is 20mg/mL is water-soluble
Liquid；The sodium-chloride water solution is the sodium-chloride water solution that concentration is 0.3mol/L；The nano mica piece suspension refer to by
8mg nano mica piece, which is scattered in 1mL water, to be made.
It is preferred embodiment：The preparation method of the nano mica piece comprises the following steps：
The first step：1h is incubated after mica powder is warming up into 800 DEG C with 5 DEG C/min programming rate in heater, is forged
Glowing cloud female powder；
Second step：20g calcining mica powder is placed in one first reaction vessel, 500mL 4mol/L nitric acid is then added,
Reacted 5 hours under the conditions of 95 DEG C, then suction filtration obtains filter residue, after the residue washing to neutrality, then after being drying to obtain pickling
Mica powder；
3rd step：Mica powder after 20g pickling is added into one second reaction vessel, the mass percent for then adding 500mL is dense
The sodium chloride solution for 30% is spent, is reacted 3 hours under the conditions of 95 DEG C, then suction filtration obtains filter residue, the residue washing to no chlorine
Ion, then be dried and obtain salt and wash rear mica powder；
4th step：8g salt is washed into rear mica powder to add in one the 3rd reaction vessel, 500mL deionized water, 20g is then added
Cetane trimethyl ammonium bromide, reacted 3 hours under the conditions of 95 DEG C, then suction filtration obtains filter residue, the residue washing is not to having
Chlorion, then be dried and obtain intercalation mica powder；
5th step：0.5g intercalation mica powder is scattered in 100mL ethanol, then carries out ultrasonic stripping using ultrasonication machine
From, every 0.5h using 3000r/min centrifuge 10min, collect upper strata suspension, then remaining sample be dispersed in again in equal volume
Ethanol in continue ultrasound and peel off, no longer produce suspension after centrifugation, nano mica piece produced after drying.
It is preferred embodiment：The heater is resistance furnace.
It is preferred embodiment：The mass percent concentration of the amine-modified nano mica piece suspension of the polyethyleneimine
For 2%.
The tensile strength of obtained organo-mica film is that 259Mpa, Young's modulus are 16Gpa.
Example IV：It is a kind of to prepare the method for macroscopical organo-mica film and organic using the natural nano peeled off level mica sheet
Mica film
A kind of method for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet, comprises the following steps：
The first step：1mL aq. polyethyleneimine and 5mL sodium chloride are added into 500mL nano mica piece suspension
The aqueous solution, is stirred 2h, is then centrifuged in centrifuge with 10000r/min rotating speed, after obtained sediment washing
It is redispersed in obtaining the amine-modified nano mica piece suspension of polyethyleneimine in water；
Second step：Under conditions of stirring, chitosan is added into the amine-modified nano mica piece suspension of the polyethyleneimine
Solution, then obtains nano mica piece-chitosan dispersion by sustained oscillation；Wherein, the preparation side of the chitosan solution
Method includes：2mL acetic acid is added in 100mL water and obtains acetic acid aqueous solution, it is water-soluble that 2g chitosans then are added into the acetic acid
Stirring produces chitosan dissolving in liquid；
3rd step：Nano mica piece-the chitosan dispersion is sprayed on to the surface of 90 DEG C of substrate of glass, in the glass
The surface of substrate forms organo-mica film, then the substrate of glass that surface has organo-mica film is steeped in mass percent concentration is
In 10% sodium hydroxide solution, organo-mica film is departed from substrate of glass and produce organo-mica film product.
Nano mica tablet quality fraction in the nano mica piece-chitosan is 80%.
The aq. polyethyleneimine is the aq. polyethyleneimine that concentration is 30mg/mL；The aqueous sodium chloride
Liquid is the sodium-chloride water solution that concentration is 0.5mol/L；The nano mica piece suspension refers to 10mg nano mica piece point
Dissipate and be made in 1mL water.
The preparation method of the nano mica piece comprises the following steps：
The first step：2h is incubated after mica powder is warming up into 800 DEG C with 10 DEG C/min programming rate in heater, is forged
Glowing cloud female powder；
Second step：40g calcining mica powder is placed in one first reaction vessel, 500mL 6mol/L nitric acid is then added,
Reacted 6 hours under the conditions of 95 DEG C, then suction filtration obtains filter residue, after the residue washing to neutrality, then after being drying to obtain pickling
Mica powder；
3rd step：Mica powder after 35g pickling is added into one second reaction vessel, the mass percent for then adding 500mL is dense
The sodium chloride solution for 40% is spent, is reacted 6 hours under the conditions of 95 DEG C, then suction filtration obtains filter residue, the residue washing to no chlorine
Ion, then be dried and obtain salt and wash rear mica powder；
4th step：10g salt is washed into rear mica powder to add in one the 3rd reaction vessel, 500mL deionized water is then added,
30g cetane trimethyl ammonium bromide, reacts 6 hours, then suction filtration obtains filter residue under the conditions of 95 DEG C, and the residue washing is not to having
There is chlorion, then be dried and obtain intercalation mica powder；
5th step：2g intercalation mica powder is scattered in 200mL ethanol, then carries out ultrasonic stripping using ultrasonication machine,
10min is centrifuged using 3000r/min every 0.5h, upper strata suspension is collected, then remaining sample is dispersed in isometric again
Continue ultrasound in ethanol to peel off, suspension is no longer produced after centrifugation, nano mica piece is produced after drying.
The heater is resistance furnace.
The mass percent concentration of the amine-modified nano mica piece suspension of the polyethyleneimine is 2%.
A kind of organo-mica film, the tensile strength of the organo-mica film is that 259Mpa, Young's modulus are 16Gpa.
Embodiment five：It is a kind of to prepare the method for macroscopical organo-mica film and organic using the natural nano peeled off level mica sheet
Mica film
1st, a kind of method for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet, it is characterised in that：Including
The following steps：
The first step：The aq. polyethyleneimine and 1 aqueous sodium chloride of addition 0.2 into 10 nano mica piece suspension
Liquid, stirring 0.5, is then centrifuged in centrifuge with 6000r/min rotating speed, is divided again after obtained sediment washing
Dissipate and the amine-modified nano mica piece suspension of polyethyleneimine is obtained in water；
Second step：Under conditions of stirring, chitosan is added into the amine-modified nano mica piece suspension of the polyethyleneimine
Solution, then obtains nano mica piece-chitosan dispersion by sustained oscillation；Wherein, the preparation side of the chitosan solution
Method includes：0.6 acetic acid is added in 30 water and obtains acetic acid aqueous solution, 0.5 chitosan is then added into the acetic acid aqueous solution
Middle stirring produces chitosan dissolving；
3rd step：Nano mica piece-the chitosan dispersion is sprayed on to the surface of 60 DEG C of substrate of glass, in the glass
The surface of substrate forms organo-mica film, then it is 1% that the substrate of glass that surface has organo-mica film, which is steeped in mass percent concentration,
Sodium hydroxide solution in, make organo-mica film depart from substrate of glass produce organo-mica film product.
Nano mica tablet quality fraction in the nano mica piece-chitosan is 20.
The aq. polyethyleneimine is the aq. polyethyleneimine that concentration is 10mg/mL；The aqueous sodium chloride
Liquid is the sodium-chloride water solution that concentration is 0.1mol/L；The nano mica piece suspension refers to 2mg nano mica piece point
Dissipate and be made in 1mL water.
A kind of organo-mica film, the tensile strength of the organo-mica film is that 259Mpa, Young's modulus are 16Gpa.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (8)
1. a kind of method for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet, it is characterised in that：Including
The following steps：
The first step：0.2 ~ 1mL aq. polyethyleneimine and 1 ~ 5mL is added into 10 ~ 500mL nano mica piece suspension
Sodium-chloride water solution, stir 0.5 ~ 2h, be then centrifuged in centrifuge with 6000 ~ 10000r/min rotating speed,
It is redispersed in obtaining the amine-modified nano mica piece suspension of polyethyleneimine in water after obtained sediment washing；
Second step：Under conditions of stirring, chitosan is added into the amine-modified nano mica piece suspension of the polyethyleneimine
Solution, then obtains nano mica piece-chitosan dispersion by sustained oscillation；Wherein, the preparation side of the chitosan solution
Method includes：0.6 ~ 2mL acetic acid is added in 30 ~ 100mL water and obtains acetic acid aqueous solution, 0.5 ~ 2g chitosans are then added into institute
Stating stirring in acetic acid aqueous solution produces chitosan dissolving；
3rd step：Nano mica piece-the chitosan dispersion is sprayed on to the surface of 60 ~ 90 DEG C of substrate of glass, described
The surface of substrate of glass forms organo-mica film, then the substrate of glass that surface has organo-mica film is steeped in mass percent concentration
Organo-mica film product is produced in 1 ~ 10% sodium hydroxide solution, to make organo-mica film depart from substrate of glass.
2. the method according to claim 1 for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet,
It is characterized in that：Nano mica tablet quality fraction in the nano mica piece-chitosan is 20 ~ 80%.
3. the method according to claim 1 for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet,
It is characterized in that：Nano mica piece best in quality fraction in the nano mica piece-chitosan is 60%.
4. the method according to claim 1 for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet,
It is characterized in that：The aq. polyethyleneimine is the aq. polyethyleneimine that concentration is 10 ~ 30mg/mL；The chlorination
Sodium water solution is the sodium-chloride water solution that concentration is 0.1 ~ 0.5mol/L；The nano mica piece suspension refers to 2-10mg's
Nano mica piece, which is scattered in 1mL water, to be made.
5. the method according to claim 4 for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet,
It is characterized in that：The preparation method of the nano mica piece comprises the following steps：
The first step：Mica powder is warming up to 0.5 ~ 2h of insulation after 800 DEG C in heater with 2 ~ 10 DEG C/min programming rate,
Obtain calcining mica powder；
Second step：10 ~ 40g calcining mica powder is placed in one first reaction vessel, then adds 500mL 3 ~ 6mol/L's
Nitric acid, reacts 3 ~ 6 hours, then suction filtration obtains filter residue, after the residue washing to neutrality, then through drying under the conditions of 70 ~ 95 DEG C
Produce mica powder after pickling；
3rd step：Mica powder after 10 ~ 35g pickling is added into one second reaction vessel, 500mL mass percent is then added
Concentration is 20 ~ 40% sodium chloride solution, is reacted 3 ~ 6 hours under the conditions of 70 ~ 95 DEG C, then suction filtration obtains filter residue, and the filter residue is washed
Wash to no chlorion, then be dried and obtain salt and wash rear mica powder；
4th step：2 ~ 10g salt is washed into rear mica powder to add in one the 3rd reaction vessel, 500mL deionized water is then added,
6 ~ 30g cetane trimethyl ammonium bromide, reacts 3 ~ 6 hours, then suction filtration obtains filter residue, the filter residue under the conditions of 70 ~ 95 DEG C
Washing is to no chlorion, then is dried and obtains intercalation mica powder；
5th step：0.2 ~ 2g intercalation mica powder is scattered in 20 ~ 200mL ethanol, is then surpassed using ultrasonication machine
Sound is peeled off, and is centrifuged 10min using 3000r/min every 0.5h, is collected upper strata suspension, then remaining sample is dispersed in again
Continue ultrasound in the ethanol of volume to peel off, suspension is no longer produced after centrifugation, nano mica piece is produced after drying.
6. the method according to claim 5 for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet,
It is characterized in that：The heater is resistance furnace.
7. the method according to claim 1 for preparing macroscopical organo-mica film using the natural nano peeled off level mica sheet,
It is characterized in that：The mass percent concentration of the amine-modified nano mica piece suspension of the polyethyleneimine is 2%.
8. a kind of organo-mica film, it is characterised in that：The tensile strength of the organo-mica film is that 259Mpa, Young's modulus are
16Gpa。
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