CN106700110B - Graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol preparation method - Google Patents
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Abstract
Graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol preparation method, the present invention is to solve the problems of existing degradable polyethylene alcohol packaging film dynamic performance and barrier property difference.Method: one, nano-cellulose is prepared；Two, graphene oxide is prepared；Three, nano-cellulose/polyvinyl alcohol solution preparation；Four, graphene oxide solution is equipped with；Five, composite membrane is prepared.Laminated film mechanical property prepared by the present invention, tensile strength improve 42.4% up to 101.49MPa, than PVA film, and oxygen-barrier property improves 2.08 times than pure PVA film, and thermal decomposition temperature improves 10~20 DEG C, while translucency with higher.The invention belongs to the preparation fields of composite package film.
Description
Technical field
The present invention relates to a kind of preparation methods of composite packing film.
Background technique
Polyvinyl alcohol (PVA) has good biological degradability, film forming, impressionability, environmental-friendly and soluble, is
One of huge packaging material of application potential, is widely used in the industries such as packaging, biologic medical.But the molecule of polyvinyl alcohol
Contain great amount of hydroxy group in chain, there are a large amount of hydrogen bonds for intramolecular, using it as the mechanical property of the biodegradable material of raw material preparation
And barrier property tends not to meet higher requirement.Therefore, it improves the mechanical property of polyvinyl alcohol and improves its barrier
Performance becomes main problem anxious to be resolved.
The size of nano-cellulose (NCC) reaches nanoscale, light high-strength, thus with some polymer material compound tenses,
The Nanofiber Network structure of height winding can be formed, a series of this excellent property of nano-cellulose make it as a kind of property
The excellent packing material of energy, is widely used in high-performance composite materials.People enhance polylactic acid, shell using nano-cellulose
Significant progress is achieved in terms of the polymer such as glycan, epoxy resin, polyvinyl alcohol, the addition of nano-cellulose is so that polymer
Intensity, mechanical property, thermal stability etc. all obtained apparent improvement, widened the application field of polymer.
Graphene oxide has two-dimensional nano lamella structure, this makes graphene oxide have fine barrier property, aoxidizes stone
Black alkene contains a large amount of oxygen-containing group (- OH, C=O, C=O and other oxygen-containing groups) on the surface of carbon atom layered framework ,-
OH, C=O are distributed in the edge of graphene oxide sheet, and C=O and other oxygen-containing groups are distributed between graphene oxide layer, this
The presence of a little functional groups, increases distance between graphene oxide layer, and solvent is preferably entered inside lamella, is improved
Graphene oxide dispersibility.
But the NCC/PVA laminated film of existing method preparation and the mechanical property and barrier property of GO/PVA laminated film
It is poor.
Summary of the invention
The present invention is to solve the problems of existing degradable polyethylene alcohol packaging film dynamic performance and barrier property difference, mention
A kind of graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol preparation method is supplied.
Graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol preparation method follows the steps below:
One, nano-cellulose is prepared；
Two, graphene oxide is prepared；
Three, nano-cellulose/polyvinyl alcohol solution preparation:
Nano-cellulose suspension, 3.919g polyvinyl alcohol and the 86.44ml distillation for being 5.9g/L by 13.56ml concentration
Water obtains nano-cellulose/polyvinyl alcohol solution with 500r/min revolving speed high-speed stirred 2h in 90 DEG C of water-baths；
Four, graphene oxide solution is equipped with:
The graphene oxide solution that weight percent is 0.1wt%-0.3wt%, and ultrasonication 30min are prepared, is obtained
To graphene oxide solution；
Five, it prepares composite membrane: graphene oxide solution being poured into nano-cellulose/polyvinyl alcohol solution, is stirred
It mixes ultrasound 30min after mixing and removes bubble, obtain into film liquid, it will be at film liquid plastic film mulch on a flat glass plate, at room temperature
It dries, obtains graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol.
In step 1 nano-cellulose the preparation method is as follows:
7g microcrystalline cellulose is weighed, is added in the sulfuric acid solution that 100mL mass fraction is 64%, is stirred with magnetic stirring apparatus
Mixing is uniformly mixed it, is then placed in 40 DEG C of water-baths and stirs 2h with 500r/min revolving speed, then ultrasound 15min, uses
The dilution of 1000ml deionized water, reaction was completed, stands for 24 hours, is poured off supernatant liquor, collects lower layer's solution and is placed in revolving speed 8000r/
Centrifuge washing under min, until not stratified water soluble colloid shape, collects colloid and be placed in bag filter, be dialyzate with deionized water, thoroughly
Analysing to the pH value of suspension liquogel is 7, obtains nano-cellulose.
In step 2 graphene oxide the preparation method is as follows:
(1) by the natural flaky graphite of 1.0g, 1.0g NaNO3It is that the mixing of 98% concentrated sulfuric acid is placed in 46mL mass fraction
In ice bath under conditions of 5 DEG C, 1h is stirred, is uniformly mixed, obtains mixed liquor；
(2) 6g KMnO is added into mixed liquor4, 1h is stirred, is then moved to solution in 50 DEG C of water-baths, with 500r/min
Revolving speed stir 4h, solution becomes taupe by black；
(3) temperature in water-bath is raised to 85 DEG C, 1h is stirred with 500r/min revolving speed, obtains russet aaerosol solution；
(4) gained russet aaerosol solution is poured into 200mL H2O2In deionized water solution, ice bath processing, suspension becomes
At brown color, suspension is stood for 24 hours at room temperature；
Wherein 200mL H2O2The H that mass concentration in deionized water solution containing 6mL is 30%2O2；
(5) upper layer acid solution is poured out, washing, centrifuge speed 8000r/min is centrifuged repeatedly with deionized water, until suspending
Until liquid pH value is in neutrality, graphite oxide colloid is obtained；
(6) graphene oxide colloid is put into desk-top air blast thermostatic drying chamber dry under conditions of temperature is 75 DEG C
For 24 hours, graphene oxide is obtained.
Laminated film mechanical property prepared by the present invention, tensile strength are improved up to 101.49MPa than PVA film
42.4%, oxygen-barrier property improves 2.08 times than pure PVA film, and thermal decomposition temperature improves 10~20 DEG C, while having higher
Translucency.
Detailed description of the invention
Fig. 1 is PVA laminated film surface SEM photograph in experiment one；Fig. 2 is PVA-N1 laminated film surface in experiment one
SEM photograph；Fig. 3 is PVA-N6 laminated film surface SEM photograph in experiment one；Fig. 4 is PVA laminated film section in experiment one
SEM photograph；Fig. 5 is PVA-N1 laminated film section SEM photograph in experiment one；Fig. 6 is that PVA-N6 laminated film is disconnected in experiment one
Face SEM photograph；Fig. 7 is the infrared spectrum for testing laminated film in one；Fig. 8 is the X-ray diffraction spectrum for testing laminated film in one
Figure；Fig. 9 is the TG curve for testing laminated film in one；Figure 10 is the TG curve for testing laminated film in one；Figure 11 is experiment one
The tensile strength curve of middle laminated film；Figure 12 is the elongation at break curve for testing laminated film in one；Figure 13 is experiment one
The oxygen transmission coefficient curve of middle laminated film；Figure 14 is the light transmittance curve for testing laminated film in one；Figure 15 is experiment one
The mist degree curve of middle laminated film；Figure 16 is the water absorption rate curve for testing laminated film in one；Figure 17 is the table for testing PVA in two
Face SEM figure；Figure 18 is the surface SEM figure for testing laminated film PVA-G3 in two；Figure 19 is laminated film PVA-G5 in experiment two
Surface SEM figure；Figure 20 is the section SEM figure for testing PVA in two；Figure 21 is the section for testing laminated film PVA-G3 in two
SEM figure；Figure 22 is the section SEM figure for testing laminated film PVA-G5 in two；Figure 23 is the INFRARED SPECTRUM for testing laminated film in two
Figure；Figure 24 is the XRD diagram for testing laminated film in two；Figure 25 is the TG curve graph for testing laminated film in two；Figure 26 is experiment
The DTG curve graph of laminated film in two；Figure 27 is the tensile strength curve figure for testing laminated film in two；Figure 28 is in experiment two
The elongation at break curve graph of laminated film；Figure 29 is the oxygen transmission coefficient curve for testing laminated film in two；Figure 30 is real
Test the light transmittance curve of laminated film in two；Figure 31 is the mist degree curve for testing laminated film in two；Figure 32 is multiple in experiment two
Close the water absorption rate curve of film；Figure 33 is SEM figure in PVA film surface in experiment three；Figure 34 is laminated film PN-G1 in experiment three
SEM figure；Figure 35 is the SEM figure for testing laminated film PN-G3 in three；Figure 36 is the cross-section morphology figure for testing PVA film in three；
Figure 37 is the cross-section morphology figure for testing laminated film PN-G1 in three；Figure 38 is the section for testing laminated film PN-G3 in three
Shape appearance figure；Figure 39 is the infrared spectrogram for testing NCC/GO/PVA laminated film in three；Figure 40 is NCC/GO/PVA in experiment three
X-ray diffraction comparison diagram Figure 41 of laminated film is the TG curve for testing NCC/GO/PVA laminated film in three；Figure 42 is experiment
The DTG curve of NCC/GO/PVA laminated film in three；Figure 43 is the tensile strength song for testing NCC/GO/PVA laminated film in three
Line；Figure 44 is the elongation at break curve for testing NCC/GO/PVA laminated film in three；Figure 45 is NCC/GO/PVA in experiment three
The oxygen transmission coefficient curve of laminated film；Figure 46 is the light transmittance curve for testing NCC/GO/PVA laminated film in three；Figure 47
It is the mist degree curve for testing NCC/GO/PVA laminated film in three；Figure 48 is the water suction for testing NCC/GO/PVA laminated film in three
Rate curve.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol preparation in present embodiment
Method follows the steps below:
One, nano-cellulose is prepared；
Two, graphene oxide is prepared；
Three, nano-cellulose/polyvinyl alcohol solution preparation:
Nano-cellulose suspension, 3.919g polyvinyl alcohol and the 86.44ml distillation for being 5.9g/L by 13.56ml concentration
Water obtains nano-cellulose/polyvinyl alcohol solution with 500r/min revolving speed high-speed stirred 2h in 90 DEG C of water-baths；
Four, graphene oxide solution is equipped with:
The graphene oxide solution that weight percent is 0.1wt%-0.3wt%, and ultrasonication 30min are prepared, is obtained
To graphene oxide solution；
Five, it prepares composite membrane: graphene oxide solution being poured into nano-cellulose/polyvinyl alcohol solution, is stirred
It mixes ultrasound 30min after mixing and removes bubble, obtain into film liquid, it will be at film liquid plastic film mulch on a flat glass plate, at room temperature
It dries, obtains graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol.
Present embodiment is raw materials used such as table 1:
Table 1
| Experimental raw and title | Specification | Manufacturer |
| Microcrystalline cellulose | Column chromatography | Sinopharm Chemical Reagent Co., Ltd. |
| The concentrated sulfuric acid (98%) | It analyzes pure | Sinopharm Chemical Reagent Co., Ltd. |
| Phosphotungstic acid | It analyzes pure | Tianjin Ke Miou chemical reagent Co., Ltd |
| Polyvinyl alcohol (alcoholysis degree 99.8%~100%) | Chemistry is pure | Tianjin Ke Miou chemical reagent Co., Ltd |
| Bag filter | Molecular cut off 8000 | Beijing Suo Laibao Science and Technology Ltd |
Present embodiment instrument and equipment such as table 2:
Table 2
| Instrument title | Model | Manufacturer |
| Digital display temperature control magnetic stirring apparatus | 90-4 | Shanghai Zhen Re experimental facilities Co., Ltd |
| Electronic balance | JA5003 | Shanghai Sunny Hengping Scientific Instrument Co., Ltd. |
| Electric-heated thermostatic water bath | DK-98-ⅡA | Tianjin Stettlen Instrument Ltd. |
| Centrifuge | TGL-20B | Anting Scientific Instrument Factory, Shanghai |
Specific embodiment 2: the present embodiment is different from the first embodiment in that nano-cellulose in step 1
The preparation method is as follows:
7g microcrystalline cellulose is weighed, is added in the sulfuric acid solution that 100mL mass fraction is 64%, is stirred with magnetic stirring apparatus
Mixing is uniformly mixed it, is then placed in 40 DEG C of water-baths and stirs 2h with 500r/min revolving speed, then ultrasound 15min, uses
The dilution of 1000ml deionized water, reaction was completed, stands for 24 hours, is poured off supernatant liquor, collects lower layer's solution and is placed in revolving speed 8000r/
Centrifuge washing under min, until not stratified water soluble colloid shape, collects colloid and be placed in bag filter, be dialyzate with deionized water, thoroughly
Analysing to the pH value of suspension liquogel is 7, obtains nano-cellulose.It is other same as the specific embodiment one.
Specific embodiment 3: being aoxidized in step 2 unlike one of present embodiment and specific embodiment one or two
Graphene the preparation method is as follows:
(1) by the natural flaky graphite of 1.0g, 1.0g NaNO3It is that the mixing of 98% concentrated sulfuric acid is placed in 46mL mass fraction
In ice bath under conditions of 5 DEG C, 1h is stirred, is uniformly mixed, obtains mixed liquor；
(2) 6g KMnO is added into mixed liquor4, 1h is stirred, is then moved to solution in 50 DEG C of water-baths, with 500r/min
Revolving speed stir 4h, solution becomes taupe by black；
(3) temperature in water-bath is raised to 85 DEG C, 1h is stirred with 500r/min revolving speed, obtains russet aaerosol solution；
(4) gained russet aaerosol solution is poured into 200mL H2O2In deionized water solution, ice bath processing, suspension becomes
At brown color, suspension is stood for 24 hours at room temperature；
Wherein 200mL H2O2The H that mass concentration in deionized water solution containing 6mL is 30%2O2；
(5) upper layer acid solution is poured out, washing, centrifuge speed 8000r/min is centrifuged repeatedly with deionized water, until suspending
Until liquid pH value is in neutrality, graphite oxide colloid is obtained；
(6) graphene oxide colloid is put into desk-top air blast thermostatic drying chamber dry under conditions of temperature is 75 DEG C
For 24 hours, graphene oxide is obtained.It is other identical as one of specific embodiment one or two.
Specific embodiment 4: being prepared in step 4 unlike one of present embodiment and specific embodiment one to three
Weight percent is the graphene oxide solution of 0.2wt%.It is other identical as one of specific embodiment one to three.
Using following experimental verifications effect of the present invention:
Experiment one:
The preparation method of laminated film:
One, nano-cellulose (NCC) Preparation Method is as follows:
7g microcrystalline cellulose is weighed, is added in the sulfuric acid solution that 100mL mass fraction is 64%, is stirred with magnetic stirring apparatus
Mixing is uniformly mixed it, is then placed in 40 DEG C of water-baths and stirs 2h with 500r/min revolving speed, then ultrasound 15min, uses
The dilution of 1000ml deionized water, reaction was completed, stands for 24 hours, is poured off supernatant liquor, collects lower layer's solution and is placed in revolving speed 8000r/
Centrifuge washing under min, until not stratified water soluble colloid shape, collects colloid and be placed in bag filter, be dialyzate with deionized water, thoroughly
Analysing to the pH value of suspension liquogel is 7, obtains nano-cellulose.
Two, nano-cellulose/polyvinyl alcohol solution preparation:
It is high with 500r/min revolving speed in 90 DEG C of water-baths by nano-cellulose suspension, polyvinyl alcohol (PVA) distilled water
Speed stirring 2h, obtains nano-cellulose/polyvinyl alcohol solution；
Three, by nano-cellulose/polyvinyl alcohol solution, ultrasound 30min removes the bubble in solution again, will be appropriate molten
Liquid is poured on plastic film mulch on smooth glass plate, dries at room temperature, obtains laminated film.
Raw material such as table 3:
Table 3
Experimental result is indicated with the arithmetic mean of instantaneous value of three results of same component obtained under identical exposure condition.
Smooth by Fig. 1-Fig. 3 it is found that the surface uniformity of pure PVA film and laminated film is good, nothing is obviously split
Trace illustrates that compatibility is preferable between PVA and NCC, phenomenon of phase separation does not occur.NCC particle size is smaller, works as additive amount
When 0.5wt%, it can be uniformly distributed in PVA matrix；But when additive amount is 6wt%, there is part and reunites in NCC, performance
For white bulky grain, while surface smoothness declines.
Fig. 3-Fig. 6 show pure PVA film and the section SEM of 0.5wt% and 6wt%PVA/NCC laminated film schemes, pure PVA
Film section has lamination, and mark of break is unevenly distributed, and illustrates that pure PVA molecular binding affinities are weaker, discontinuity.And NCC adds
Dosage is the mark of break distribution uniform of 0.5wt% laminated film, illustrates that suitable NCC can be evenly dispersed in PVA matrix,
It is acted on by the binding force of hydrogen bond so that laminated film is more uniformly stressed by the evenly dispersed of NCC and with matrix.As NCC plus
Enter amount be 6wt% when, the section mark of break of laminated film is more, without rule.This may be to reunite because of excessive NCC,
Make its compatibility poor between PVA, lead to film unbalance stress, influences the mechanical property of laminated film.
Fig. 7 show the infrared spectrum of PVA film Yu NCC/PVA laminated film, and as seen from the figure, wave number is in 3346cm-1Place
Characteristic peak is the characteristic peak of-OH group, 2939cm-1It is flexible that the c h bond that a stronger absorption peak is PVA methylene occurs in place
Vibration absorption peak.As NCC content increases laminated film in 1050cm-1Characteristic peak at left and right is further obvious, this is by NCC
Caused by C-O (C-3) stretching vibration of alcohol.The not new characteristic peak of laminated film after adding NCC generates, and illustrates NCC and PVA
Association physical reactions only occur, be not the variation of chemical property[21]。
Fig. 8 is the XRD spectra of pure PVA film and NCC/PVA laminated film, and PVA has strong diffraction maximum at 2 θ=19.6 °,
Also there is strong diffraction maximum at 2 θ=19.6 ° in the XRD diagram of laminated film, and no change has taken place for position, illustrates that the addition of NCC does not have
Have and change PVA crystal structure, but intensity slightly improves, illustrates that the crystallinity of PVA increases, NCC plays the role of nucleating agent.
Fig. 9 and Figure 10 is influence curve of the NCC to the thermal stability of PVA laminated film of different content.In conjunction with Fig. 2-
As can be seen that the thermal weight loss of pure PVA film and NCC/PVA laminated film is divided into three phases in the DTG curve of 10 films, 79 DEG C~
165 DEG C weightless for absorption water, and the weight-loss ratio that combination film TG weight-loss curve can be seen that this stage of laminated film is omited than PVA film
It is small, it is seen that the reduced capability of laminated film absorption water；193 DEG C~332 DEG C of second stage are the dehydration on PVA side chain, PVA
Film initial decomposition temperature is 193 DEG C, and hereafter as the temperature rises, decomposition rate is accelerated, and is schemed in conjunction with DTG it can be seen that 235
DEG C when decomposition rate it is most fast, the weight-loss ratio in the region is 56.44%；Phase III weightlessness is at 390 DEG C or more, this elementary reaction master
If the burning of carbon skeleton is lost, after the thermal decomposition of second stage, the polyene of the macromolecular of residue can be in thermal weight loss
Three stage further occurrence chain-breaking reactions, form the polyene of small molecule.The thermal weight loss result for comparing pure PVA film and composite membrane can
Know, the addition of NCC increases the initial decomposition temperature of PVA laminated film second stage, and the initial decomposition temperature of PVA-N6 omits
Higher than PVA-N4, this is because the hot initial decomposition temperature of NCC is higher (330 DEG C start to decompose), NCC and the intermolecular generation of PVA
Strong effect power, so that laminated film thermal stability increases.The addition of NCC can be improved the main of the laminated film prepared by it
The incipient degradation temperature of degradation process.As it can be seen that NCC be added can enhanced film to a certain extent thermal stability.
Mechanical performance mainly includes plasticity, flexibility, elasticity and hardness of material etc., is the base that packaging material needs to have
The packaging material of this index, different applications and purposes, the requirement to mechanical performance are also not quite similar.Different quality containing
Influence of the NCC to PVA laminated film tensile strength is as shown in figure 11.The tensile strength of laminated film is in the increase of NCC content
Existing ascendant trend, when NCC mass fraction is 2wt%, there is maximum 88.48MPa in the tensile strength of laminated film, than pure
PVA film increases 24.17%.But with continuing growing for NCC content, tensile strength is gradually reduced, when additional amount is 6wt%
When, tensile strength drops to 75.71MPa.This is primarily due to the hydroxyl in NCC structure and the hydroxyl on PVA strand associates,
There is strong adhesive effect between molecule both under hydrogen bond action, this leads to occur during stretching stress by PVA and NCC
The two is shared, and NCC itself mechanical strength with higher, and nano composite membrane is made to show good mechanical performance.When NCC contains
When amount is higher than 2wt%, the mechanical performance of composite membrane is again on a declining curve, and it is related that this reunion may occur with NCC in composite membrane.
Elongation at break is the index parameter for characterizing material stretch percentage elongation and toughness.Figure 12 is the elongation at break knot of laminated film
Fruit, with increasing for NCC content, downward trend is presented in the elongation at break of laminated film, and reason with NCC first is that due to being added
The increase of amount, the compatibility poor with matrix, and NCC whisker will limit the movement of PVA strand, cause laminated film flexible
Property reduce, brittleness increase；Cause stress to be concentrated in addition, the increase of NCC content will appear reunion to a certain extent, is easy to happen crisp
It is disconnected.
Table 4 is the oxygen transit dose of laminated film.The oxygen transit dose of pure PVA film is 2141.17cm3/m2·24h·
0.1Mpa is low barrier film.After adding a small amount of NCC, the oxygen transit dose of laminated film is reduced therewith, the barrier property of film
It becomes better and better.Since sample thickness has differences, therefore OTR oxygen transmission rate is scaled oxygen transmission coefficient to characterize the oxygen of film
Gas barrier property, to remove the difference as caused by thickness.Figure 13 is the oxygen transmission coefficient of laminated film.The oxygen of pure PVA film
Transmission coefficient is 85.65cm3·cm/m2·24h·0.1Mpa.With the raising of NCC content, the oxygen transmission coefficient of film by
Decrescence few, when NCC content is 0.5wt%, 1wt%, 1.5wt%, 2wt%, 4 wt%, 6wt%, oxygen transmission coefficient is respectively
60.22%, 55.67%, 57.25%, 51.25%, 39.67% and the 51.21% of pure PVA film oxygen transmission coefficient hinders oxygen
Performance significantly improves, and reason may be due to NCC molecule very little, and after mixing with PVA, PVA is reduced in intermolecular gap, i.e., freely
Volume reduces, and when gas passes through film, obstruction increases, and increases through the distance of film, while crosslinked action, small molecule NCC
It is added, polymer molecule segment activity reduces, and bulk density increase causes transmission coefficient to reduce.But when NCC content is more than
When 4wt%, only increasing NCC content not can effectively improve laminated film to the barrier property of oxygen.
Table 4
| Number | Film thickness (μm) | Air permenbility (cm3/m2·24h·0.1Mpa) |
| PVA | 40 | 2141.165 |
| PVA-N1 | 31 | 1663.776 |
| PVA-N2 | 29 | 1644.341 |
| PVA-N3 | 38 | 1290.400 |
| PVA-N4 | 37 | 1186.414 |
| PVA-N5 | 28 | 1213.368 |
| PVA-N6 | 22 | 1993.494 |
Translucency is the ability of material transmitted light, related to the absorption of light and reflectivity properties with material, general with saturating
Light rate and mist degree characterization[45].The translucency of laminated film depends greatly on dispersion situation of the NCC in PVA.Figure 14
With shown in Figure 15 be respectively laminated film light transmittance and mist degree with NCC content situation of change.Although with the increasing of NCC content
Add, the light transmittance of NCC/PVA laminated film is gradually reduced, and mist degree gradually increases.There is result it is found that even if NCC content reaches most
When big 6wt%, the light transmittance of laminated film is still 90% or more, and mist degree is below 2.5%, it is seen that within this range NCC plus
Enter not cause the light transmittance of laminated film to be decreased obviously, addition NCC influences very little to the light transmittance of film and mist degree.
Water absorption rate is the important indicator for measuring materials water-resistant energy, and table 5 gives different thin-film materials in humidity 50%RH
The weight amount of changing over time in humidity environment, the quality of film is increasing always as can be seen from Table 5, in order to eliminate film starting
Difference in weight, and quantify water absorption rate, the water absorption rate change curve that film changes over time is calculated, as shown in figure 16.From
It can intuitively find out very much that PVA is to be very easy to water suction in Figure 16, pure PVA film water absorption rate linearly increases always, passes through
After being blended with NCC, the water imbibition decrease to some degree of laminated film, and with the increase of NCC content, NCC/PVA is multiple
The water absorption rate for closing film is obviously lower than pure PVA.Laminated film rate of water absorption of 10h or so, the NCC content greater than 1wt% reduces, and
The growth pattern of pure PVA and PVA-N1 laminated film rate of water absorption does not have significant change.
Table 5
From the above experimental results, we know that:
(1) there is no the reactions of chemical property by NCC and PVA, and NCC, which is added, improves the crystallinity of PVA.PVA film and
The surface finishing of NCC/PVA laminated film is smooth, and section is uniform, mutually separates there is no apparent, NCC and PVA compatibility compared with
It is good.
(2) thermogravimetric analysis shows that the addition of NCC enables in laminated film thermal decomposition temperature to be higher than PVA film, can one
Determine the thermal stability of enhanced film in degree.
(3) addition NCC can improve the tensile strength of PVA film, but can reduce the elongation at break of film, NCC matter simultaneously
The tensile property for measuring laminated film when score is 2wt% is best, and tensile strength is up to 88.48MPa.
(4) addition NCC can improve the oxygen barrier property of laminated film.When NCC content is 4wt%, laminated film oxygen
Transmission coefficient is the 39.67% of pure PVA film oxygen transmission coefficient.
(5) as the increase of NCC content, the light transmittance of laminated film gradually decrease, mist degree is gradually risen, but in 6wt%
The addition of NCC influences very little to the light transmittance of film and mist degree in range, and the translucency of laminated film is not decreased obviously.
(6) water resistance of NCC/PVA laminated film is slightly improved compared with PVA film, and with the increase of NCC content, compound
The water absorption rate of film is lower than pure PVA film.
Experiment two:
The preparation method of laminated film:
One, graphene oxide the preparation method is as follows:
(1) by the natural flaky graphite of 1.0g, 1.0g NaNO3It is that the mixing of 98% concentrated sulfuric acid is placed in 46mL mass fraction
In ice bath under conditions of 5 DEG C, 1h is stirred, is uniformly mixed, obtains mixed liquor；
(2) 6g KMnO is added into mixed liquor4, 1h is stirred, is then moved to solution in 50 DEG C of water-baths, with 500r/min
Revolving speed stir 4h, solution becomes taupe by black；
(3) temperature in water-bath is raised to 85 DEG C, 1h is stirred with 500r/min revolving speed, obtains russet aaerosol solution；
(4) gained russet aaerosol solution is poured into 200mL H2O2In deionized water solution, ice bath processing, suspension becomes
At brown color, suspension is stood for 24 hours at room temperature；
Wherein 200mL H2O2The H that mass concentration in deionized water solution containing 6mL is 30%2O2；
(5) upper layer acid solution is poured out, washing, centrifuge speed 8000r/min is centrifuged repeatedly with deionized water, until suspending
Until liquid pH value is in neutrality, graphite oxide colloid is obtained；
(6) graphene oxide colloid is put into desk-top air blast thermostatic drying chamber dry under conditions of temperature is 75 DEG C
For 24 hours, graphene oxide (GO) is obtained.
Two, PVA is put into the conical flask for filling 60mL distilled water, reinforcement electric mixing is used under the conditions of 90 DEG C of water-baths
Device high-speed stirred 2h is mixed, revolving speed 500r/min is completely dissolved PVA, obtains PVA aqueous solution；
Three, configuration concentration is 0.05wt% (laminated film obtained under this concentration is PVA-G1), 0.1wt% (this concentration
Under obtained laminated film be PVA-G2), 0.15wt% (laminated film obtained under this concentration is PVA-G3), 0.2wt% (this
The laminated film obtained under concentration is PVA-G4), the GO solution of 0.3wt% (laminated film obtained under this concentration is PVA-G5)
And it is ultrasonically treated 30min, it is dispersed in it in distilled water, then GO solution is poured into PVA aqueous solution, reinforcement stirs
Device strong stirring 1h is mixed, ultrasound 30min removes bubble again after mixing, then on a flat glass plate by mixed solution
Plastic film mulch is dried at room temperature, obtains laminated film.
Figure 17-Figure 22 is laminated film surface and the section SEM photograph of PVA-G3, PVA-G5, and laminated film surface is smooth
Corrugationless illustrates that GO is dispersed in PVA matrix.Thin-membrane section is more regular, compares pure PVA film cross-section image, can be with
Find out the increase with GO content, the flatness of section is gradually reduced.
Figure 23 show PVA and laminated film infrared spectrum, and wave number is in 2939cm-1There is a stronger absorption peak in place
The c h bond stretching vibration absworption peak of PVA methylene.Wave number is 1731cm in former graphite oxide-1Locate the C=in corresponding carboxyl
O key stretching vibration peak disappears, and illustrates that GO and PVA there is no chemical reaction, belong to physical bond.
Figure 24 is X-ray diffracting spectrum, and laminated film diffraction maximum nearby occurs in 2 θ=19.6 ° as seen from the figure.With it is pure
PVA film is compared, and diffraction maximum does not have appearance position mobile, so the addition of GO does not change PVA crystal structure, diffraction peak intensity
Increase, it may be possible to be influenced by hydroxyl hydrogen bond action in PVA and GO.2 θ are 26 ° and do not occur the characteristic peak of GO, explanation nearby
GO is well dispersed in PVA, does not reunite.
The GO of different content to laminated film thermal stability influence curve as illustrated in figs. 25 and 26.PVA,PVA-G2,
PVA-G5 first stage weight-loss ratio is respectively 6.84%, 5.26%, 5.01%, and outlet capacity is adsorbed under laminated film room temperature and is slightly less than
PVA film；Second stage is the film main weightless stage, PVA, PVA-G2, PVA-G5 weightlessness is about 54.41%, 54.38%,
53.88%, compared with PVA, PVA/GO film is in this 10 DEG C of PVA high of stage initial decomposition temperature ratio；Phase III, weightlessness was 396
DEG C or more, this elementary reaction is mainly that the burning of carbon skeleton is lost, after the thermal decomposition of second stage, the macromolecular of residue
Polyene can form the polyene of small molecule in thermal weight loss phase III further occurrence chain-breaking reaction, and compound continues to decompose,
Sample carbon yield is about 15.74%.
Figure 27 and Figure 28 is respectively that influence of the GO of different quality containing to composite membrane tensile strength and elongation at break is bent
Line chart.The tensile strength of laminated film first rises with the increase of GO content to be reduced afterwards, compound when GO mass fraction is 0.1wt%
There is maximum value 90.96MPa in the tensile strength of film, increases 27.66% compared to pure PVA film.But with GO content
Increase, tensile strength is decreased obviously, and when additional amount is 0.3wt%, tensile strength drops to 49.95MPa.This is mainly due to
The oxygen-containing group and the hydroxyl on PVA strand of GO forms intermolecular force and composite membrane is made to show good draftability
Can, GO monolithic multi-slice nanoscale is evenly dispersed, large specific surface area, has good compatibility with PVA matrix, increases composite wood
The mechanical property of material.When GO content is higher, the tensile property of composite membrane is again on a declining curve, this may be related with GO reunion.
The elongation at break of Figure 28 laminated film shows, the elongation at break of laminated film is under the increasing gradually of GO content
Drop leads to laminated film reduction of pliability the reason is that GO lamella will limit the movement of PVA strand, and brittleness increases；In addition, GO
Content increase will appear reunion to a certain extent, and dispersion is uneven, causes stress to be concentrated, is easy to happen brittle fracture.
Table 6 is the oxygen transit dose of the composite membrane of different GO contents.After GO is added, the oxygen transit dose of laminated film is in subtract
Few trend, the oxygen barrier for increasing laminated film with GO content are better.OTR oxygen transmission rate is scaled oxygen transmission coefficient to characterize
The oxygen barrier of film, to remove the difference as caused by thickness.
Figure 29 is the oxygen transmission coefficient of the laminated film after conversion.GO content be 0.05wt%, 0.1wt%,
When 0.15wt%, 0.2wt%, 0.3wt%, oxygen transmission coefficient be respectively PVA film oxygen transmission coefficient 94.97%,
78.03%, 61.77%, 60.41% and 54.77%, the oxygen resistance of PVA film can be enhanced with a small amount of GO, this may be
The GO lamella good dispersion of ultrasound removing is easy intercalation in PVA matrix, and this intercalation configuration is provided to the diffusion of oxygen molecule
Curved channel, small molecule must be spread around GO, cannot directly pass perpendicularly through film surface, oxygen molecule is caused to contain
There is increasing in the PVA film of GO through path, to improve composite membrane to the barrier property of oxygen.
Table 6
| Number | Film thickness (μm) | Air permenbility (cm3/m2·24h·0.1Mpa) |
| PVA | 40 | 2141.165 |
| PVA-G1 | 36 | 2259.520 |
| PVA-G2 | 48 | 1392.352 |
| PVA-G3 | 39 | 1356.667 |
| PVA-G4 | 40 | 1293.450 |
| PVA-G5 | 31 | 1513.201 |
The light transmittance and mist degree for being respectively composite membrane shown in film light transmittance and mist degree figure, Figure 30 and Figure 31 are with GO content
Situation of change.Although the light transmittance of GO/PVA laminated film is gradually reduced, and mist degree gradually increases with the increase of GO content,
When GO content is lower than 0.15wt%, the light transmittance of laminated film is still 85.26% or more, and mist degree is 3% hereinafter, in this range
The addition of interior GO influences the light transmittance of film and mist degree smaller.When GO content is more than 0.20wt%, the light transmittance of laminated film
Further decline, mist degree further increase.This is because substance increases in film, the obstruction and reflection to transmitted ray are reinforced,
Light transmittance is reduced, GO content is that 0.3wt% is that laminated film light transmittance is minimum, because GO is scattered in film, is more weakened
Transmitted light, hinders it and reflex is larger.
Table 7 gives PVA and different GO content the laminated films weight in humidity 50%RH humidity environment and changes over time
Amount, the quality of film is increasing always as can be seen from Table 7, eliminates the difference in film starting weight, and quantify water absorption rate, counts
The water absorption rate change curve that film changes over time is calculated, as shown in figure 32.As seen from the figure, with the increase of GO content, GO/
The water absorption rate of PVA laminated film is slightly reduced than pure PVA, but after 10h, the water absorption rate of pure PVA film and laminated film is not
There is tendency, illustrate after being blended with GO, composite membrane water imbibition decreases, and water resistance is enhanced, this may be total with PVA
Mixed GO content is less, can be limited with the oxygen-containing functional group content of PVA intramolecular hydroxy combining.
Table 7
| Number | Dry weight | 2h | 4h | 6h | 8h | 10h |
| PVA | 0.621 | 0.6499 | 0.6643 | 0.6759 | 0.6905 | 0.7011 |
| PVA-G1 | 0.5103 | 0.5382 | 0.5507 | 0.5614 | 0.5758 | 0.5848 |
| PVA-G2 | 0.4662 | 0.4892 | 0.5025 | 0.5116 | 0.5241 | 0.5292 |
| PVA-G3 | 0.5259 | 0.5535 | 0.5562 | 0.5607 | 0.5738 | 0.582 |
| PVA-G4 | 0.63 | 0.6515 | 0.6562 | 0.6678 | 0.6731 | 0.6808 |
| PVA-G5 | 0.4335 | 0.454 | 0.4591 | 0.4668 | 0.4766 | 0.4816 |
The above experimental result is concluded that
(1) GO obtained after graphite oxidation has oxygen-containing functional group, and the GO number of plies after ultrasonic treatment is less, after adding GO
By in conjunction with intermolecular force chemical change does not occur for both PVA and GO；PVA/GO film originates in second stage and decomposes temperature
Degree improves 10 DEG C than PVA.
(2) tensile strength of laminated film first rises with the increase of GO content and reduces afterwards, and GO mass fraction is 0.1wt%
When, there is maximum value 90.96MPa in the tensile strength of laminated film, increases 27.66% than pure PVA film.But with GO content
Increase, tensile strength is decreased obviously, and when additional amount is 0.3wt%, tensile strength drops to 49.95MPa.Laminated film
Elongation at break gradually declines with increasing for GO content.
(3) oxygen resistance of PVA film can be enhanced by adding a small amount of GO, under OTR oxygen transmission rate is with the increase of GO content
Drop.
(4) as the increase of GO content, the light transmittance of laminated film are gradually reduced, mist degree is gradually increased, when GO content is
When 0.30wt%, the light transmittance of GO/PVA laminated film drops to 77.68%, and mist degree is increased to 5.36, and translucency reduces.
(5) addition of GO reduces the water absorption rate of PVA laminated film slightly.
Experiment three:
Graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol preparation method follows the steps below:
One, nano-cellulose is prepared:
7g microcrystalline cellulose is weighed, is added in the sulfuric acid solution that 100mL mass fraction is 64%, is stirred with magnetic stirring apparatus
Mixing is uniformly mixed it, is then placed in 40 DEG C of water-baths and stirs 2h with 500r/min revolving speed, then ultrasound 15min, uses
The dilution of 1000ml deionized water, reaction was completed, stands for 24 hours, is poured off supernatant liquor, collects lower layer's solution and is placed in revolving speed 8000r/
Centrifuge washing under min, until not stratified water soluble colloid shape, collects colloid and be placed in bag filter, be dialyzate with deionized water, thoroughly
Analysing to the pH value of suspension liquogel is 7, obtains nano-cellulose.
Two, graphene oxide is prepared:
(1) by the natural flaky graphite of 1.0g, 1.0g NaNO3It is that the mixing of 98% concentrated sulfuric acid is placed in 46mL mass fraction
In ice bath under conditions of 5 DEG C, 1h is stirred, is uniformly mixed, obtains mixed liquor；
(2) 6g KMnO is added into mixed liquor4, 1h is stirred, is then moved to solution in 50 DEG C of water-baths, with 500r/min
Revolving speed stir 4h, solution becomes taupe by black；
(3) temperature in water-bath is raised to 85 DEG C, 1h is stirred with 500r/min revolving speed, obtains russet aaerosol solution；
(4) gained russet aaerosol solution is poured into 200mL H2O2In deionized water solution, ice bath processing, suspension becomes
At brown color, suspension is stood for 24 hours at room temperature；
Wherein 200mL H2O2The H that mass concentration in deionized water solution containing 6mL is 30%2O2；
(5) upper layer acid solution is poured out, washing, centrifuge speed 8000r/min is centrifuged repeatedly with deionized water, until suspending
Until liquid pH value is in neutrality, graphite oxide colloid is obtained；
(6) graphene oxide colloid is put into desk-top air blast thermostatic drying chamber dry under conditions of temperature is 75 DEG C
For 24 hours, graphene oxide is obtained.
Three, nano-cellulose/polyvinyl alcohol solution preparation:
Nano-cellulose suspension, 3.919g polyvinyl alcohol and the 86.44ml distillation for being 5.9g/L by 13.56ml concentration
Water obtains nano-cellulose/polyvinyl alcohol solution with 500r/min revolving speed high-speed stirred 2h in 90 DEG C of water-baths；
Four, graphene oxide solution is equipped with:
Preparation weight percent is 0.1wt% (laminated film obtained under this concentration is PN-G1), 0.2wt% (this concentration
Under obtained laminated film be PN-G2), the graphene oxide of 0.3wt% (laminated film obtained under this concentration is PN-G3) it is molten
Liquid, and ultrasonication 30min, obtain graphene oxide solution；
Five, it prepares composite membrane: graphene oxide solution being poured into nano-cellulose/polyvinyl alcohol solution, is stirred
It mixes ultrasound 30min after mixing and removes bubble, obtain into film liquid, it will be at film liquid plastic film mulch on a flat glass plate, at room temperature
It dries, obtains graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol (NCC/GO/PVA laminated film).
The surface topography of laminated film is as shown in Figure 33-35, the defects of laminated film smooth surface, flawless, says
Tri- kinds of COMPONENTS COMPATIBILITYs of bright GO, NCC and PVA are good.The mark of break of PN-G3 composite membrane section increases, and reason may be excessive GO
Reunite, makes its compatibility poor between PVA, lead to film unbalance stress, reduce the mechanical property of composite membrane.
Nearby there is stronger spread out in 2 θ=19.6 ° in the NCC/PVA nano compound film for being added to GO as shown in Figure 40
Peak is penetrated, illustrates that the addition of GO in scope of experiment has not been changed PVA crystal structure, diffraction peak intensity increases, it may be possible to by GO, PVA
With hydroxyl hydrogen bond collective effect in NCC PVA crystallinity is increased.
Figure 41 and 42 is laminated film thermogravimetric change curve, and the thermal decomposition of laminated film is divided into three phases, and absorption water loses
Weight stage PN-G1 and PN-G3 film weight-loss ratio is respectively 4.79% and 5.13%；After adding GO, laminated film is in second stage
Initial decomposition temperature ratio PVA-N4 film it is 5~10 DEG C high, this is because blending structure and PVA point that GO and NCC are formed together
The active force of interchain is stronger between son, so that laminated film thermal decomposition is made between must first consuming this moieties of more energy damages
Firmly, so that the thermal stability of laminated film be made to increase；The addition of GO influences less, after 600 DEG C phase III thermal decomposition
Film carbon left tends towards stability.
Find out that the tensile strength of the NCC/PVA laminated film of addition GO first increases by Figure 43 reduces afterwards, and a small amount of GO is helped
In the tensile property for improving NCC/PVA laminated film, the film tensile strength of 0.1wt%GO is added up to 101.49MPa, than
The tensile strength of PVA-N4 film improves 12.39%, and elongation at break is gradually reduced with the increase of GO content.
Table 8 is after GO is added, and the addition of the oxygen transit dose situation of change of laminated film, GO can increase laminated film
Oxygen barrier.
Table 8
| GO content wt% | Film thickness (μm) | Air permenbility (cm3/m2·24h·0.1Mpa) |
| 0 | 37 | 1186.414 |
| 0.1 | 29 | 1518.043 |
| 0.2 | 25 | 1306.358 |
| 0.3 | 37 | 1510.229 |
Figure 45 is the oxygen transmission coefficient of the laminated film after conversion.GO content is 0.1wt%, 0.2wt%, 0.3wt%
When, oxygen transmission coefficient is 93.68%, 74.40%, the 127.30% of PVA-N4 film oxygen transmission coefficient, oxygen blocking respectively
It first increases every property and declines afterwards, oxygen resistance increases, this is the screen of the three-dimensional structure that is formed after GO, NCC hydridization to small molecule
The effect of covering becomes apparent from.
Figure 46 and 47 show this experiment preparation composite membrane light transmittance and mist degree with GO content situation of change.Although
With the increase of GO content, the light transmittance of GO/NCC/PVA laminated film is gradually reduced, and mist degree gradually increases.But work as GO content most
When big 0.3wt%, the light transmittance of laminated film falls below 76.88%, and mist degree has risen to 5.54, it is seen that the addition of GO can weaken
The light transmittance of laminated film, but influence limited.
Table 9 gives the modified NCC/PVA laminated film of different quality containing GO weight in humidity 50%RH humidity environment
The amount of changing over time is measured, as can be seen from Table 9 the mass change of film, elimination film starting weight calculates film and becomes at any time
The water absorption rate change curve of change, as shown in figure 48.As shown in Figure 48, it is compound can to significantly reduce NCC/PVA for the addition of GO content
The water absorption rate of film, for GO/NCC/PVA laminated film after testing 2h, rate of water absorption is significantly smaller than pure PVA film and NCC/PVA
Laminated film, when 10h, water suction tends to be saturated, and water resistance has and enhances to a certain degree, although main cause may be GO content content
It is less, but after being mixed with NCC, three-dimensional structure can be formed with NCC, after PVA strand intercalation is come in, PVA strand is subject to
Intermolecular force is stronger than single two-dimensional structure, makes it can not be with water molecules.
Table 9
| Number | Dry weight | 2h | 4h | 6h | 8h | 10h |
| PVA-N4 | 0.4878 | 0.5085 | 0.51277 | 0.5227 | 0.5294 | 0.5367 |
| PN-G1 | 0.3882 | 0.4077 | 0.407 | 0.4112 | 0.4165 | 0.4161 |
| PN-G2 | 0.5061 | 0.5225 | 0.5242 | 0.5269 | 0.5298 | 0.5323 |
| PN-G3 | 0.396 | 0.4112 | 0.4139 | 0.4168 | 0.4196 | 0.4213 |
From the above experimental results, we know that:
(1) three kinds of components are well dispersed in NCC, GO and PVA film, surfacing, without being clearly separated, as GO content increases
It is more, section roughness descent；
(2) three's mixing does not generate new absorption peak, and NCC, GO and PVA are combined together by intermolecular force；
(3) GO can improve the initial decomposition temperature of NCC/PVA laminated film；Add the stretching of 0.1wt%GO laminated film
The tensile strength of intensity ratio PVA-N4 film improves 12.39%, but adding GO causes elongation at break to reduce；GO and NCC association
Same-action can significantly improve the water resistance of PVA film；A small amount of GO can enhance the oxygen barrier property of PVA-N4 film；GO's adds
Membership weakens the light transmittance of PVA-N4 film, increases the mist degree of film, declines the light transmittance of film.
(4) in GO, NCC, PVA co-mixing system, in scope of experiment the optimal component of comprehensive performance be 4wt%NCC and
The laminated film of 0.1wt%GO collaboration enhancing PVA, the laminated film mechanical property that this component obtains is best, and tensile strength is reachable
101.49MPa improves 42.4% than PVA film, and oxygen-barrier property improves 2.08 times than pure PVA film, and thermal decomposition temperature mentions
It is 10~20 DEG C high, while translucency with higher.
Gained Main Conclusions is as follows:
(1) acidolysis processing is aided with the ultrasonic NCC length prepared between 137~258nm, and diameter is 9~20nm, draw ratio
It is 13；The GO of improved Hummers method preparation transparent flake, there are folds in number of plies fewer parts region.
(2) the tape casting is prepared for the laminated film of the NCC and PVA of different quality ratio, and NCC and PVA compatibility are good, compound
The surface finishing of film is smooth, and section is uniform, mutually separates there is no apparent.The addition of NCC can improve the mechanics of composite membrane
Performance, thermal stability and water resistance, the addition of NCC enables to laminated film thermal decomposition temperature to be higher than PVA in scope of experiment
The addition of film, NCC influences very little to the light transmittance of film and mist degree, adds the NCC/PVA laminated film performance of 2wt%NCC
Most preferably, the laminated film tensile strength of this ratio is 88.48MPa, improves 24% than PVA film tensile strength；Oxygen is through system
Number is 51.25cm3·cm/cm2SPa, is the 51.25% of pure PVA film oxygen transmission coefficient, light transmittance 91.42%,
Mist degree is 1.60, and translucency is good.
(3) graphite oxidation is handled and the GO obtained after ultrasonic disperse has oxygen-containing functional group, and GO is dispersed good in water
Both good, the GO/PVA laminated film surface for being cast the different quality containing of preparation is smooth, and SEM shows compatibility is good, GO/
10 DEG C of PVA high of PVA film decomposition temperature ratio；When GO mass fraction is 0.1wt%, the tensile strength maximum of laminated film is reachable
90.96MPa increases 27.66% than pure PVA film.The oxygen resistance of PVA film, oxygen blocking can be enhanced with a small amount of GO
1.56 times are at most improved than pure PVA film every property；The addition of GO can reduce the translucency of laminated film, but influence limited；GO
Addition make the water absorption rate of laminated film lower than PVA film.
(4) by NCC/GO/PVA ternary film research shows that three kinds of components are well dispersed in composite membrane, compatibility
Preferably, it is mutually separated without obvious, combines between three by intermolecular force, combined for physical property.The addition of GO makes PVA-
N4 film initial decomposition temperature improves 5~10 DEG C；Adding a small amount of GO can be improved laminated film tensile strength, water resistance, oxygen
Barrier property.
(5) the optimal component of GO/NCC/PVA ternary film comprehensive performance is 2wt%NCC and 0.1wt% in scope of experiment
The laminated film of GO collaboration enhancing PVA, the laminated film mechanical property that this component obtains is best, and tensile strength is reachable
101.49MPa improves 42.4% than PVA film, and oxygen-barrier property improves 2.08 times than pure PVA film, and thermal decomposition temperature mentions
It is 10~20 DEG C high, while translucency with higher.
Claims (2)
1. graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol preparation method, it is characterised in that graphene oxide/receive
The preparation method of rice cellulose/polyvinyl alcohol composite membrane follows the steps below:
One, nano-cellulose is prepared:
7g microcrystalline cellulose is weighed, is added in the sulfuric acid solution that 100mL mass fraction is 64%, is made with magnetic stirrer
It is uniformly mixed, and is then placed in 40 DEG C of water-baths and stirs 2h with 500r/min revolving speed, then ultrasound 15min, is gone with 1000ml
Ionized water dilution, reaction was completed, stands for 24 hours, is poured off supernatant liquor, collect lower layer's solution be placed under revolving speed 8000r/min from
Heart washing is dialysed until not stratified water soluble colloid shape, collects colloid and be placed in bag filter, be dialyzate with deionized water to outstanding
The pH value of supernatant liquid colloid is 7, obtains nano-cellulose；
Two, graphene oxide is prepared:
(1) by the natural flaky graphite of 1.0g, 1.0g NaNO3It is that the mixing of 98% concentrated sulfuric acid is placed in ice bath with 46mL mass fraction
Under conditions of 5 DEG C, 1h is stirred, is uniformly mixed, obtains mixed liquor；
(2) 6g KMnO is added into mixed liquor4, 1h is stirred, is then moved to solution in 50 DEG C of water-baths, with the revolving speed of 500r/min
4h is stirred, solution becomes taupe by black；
(3) temperature in water-bath is raised to 85 DEG C, 1h is stirred with 500r/min revolving speed, obtains russet aaerosol solution；
(4) gained russet aaerosol solution is poured into 200mL H2O2In deionized water solution, ice bath processing, suspension becomes palm fibre
Yellow stands suspension for 24 hours at room temperature；
Wherein 200mL H2O2The H that mass concentration in deionized water solution containing 6mL is 30%2O2；
(5) upper layer acid solution is poured out, is centrifuged repeatedly washing, centrifuge speed 8000r/min, until pH of suspension with deionized water
Until value is in neutrality, graphite oxide colloid is obtained；
(6) graphene oxide colloid drying under conditions of temperature is 75 DEG C is put into desk-top air blast thermostatic drying chamber for 24 hours, to obtain
To graphene oxide；
Three, nano-cellulose/polyvinyl alcohol solution preparation:
Nano-cellulose suspension, 3.919g polyvinyl alcohol and the 86.44ml distilled water for being 5.9g/L by 13.56ml concentration,
With 500r/min revolving speed high-speed stirred 2h in 90 DEG C of water-baths, nano-cellulose/polyvinyl alcohol solution is obtained；
Four, graphene oxide solution is equipped with:
The graphene oxide solution that weight percent is 0.1wt%-0.3wt%, and ultrasonication 30min are prepared, oxygen is obtained
Graphite alkene solution；
Five, it prepares composite membrane: graphene oxide solution is poured into nano-cellulose/polyvinyl alcohol solution, stirring is mixed
Ultrasound 30min removing bubble, obtains into film liquid after closing uniformly, will dry at room temperature at film liquid plastic film mulch on a flat glass plate,
Obtain graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol.
2. graphene oxide/nano-cellulose/composite membrane of polyvinyl alcohol preparation method according to claim 1, feature
It is to prepare the graphene oxide solution that weight percent is 0.2wt% in step 4.
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| CN113929958A (en) * | 2021-11-25 | 2022-01-14 | 南京林业大学 | Preparation method of composite cellulose hydrogel |
| CN114805900B (en) * | 2022-04-16 | 2023-05-30 | 大连工业大学 | Method for improving gas barrier property of film substrate, film and application |
| CN117143378B (en) * | 2023-09-21 | 2024-03-12 | 东北林业大学 | Preparation method of high-barrier antibacterial flame-retardant food packaging film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492247A (en) * | 2011-12-21 | 2012-06-13 | 西北师范大学 | Water-resistant polyvinyl alcohol (PVA)-based composite film and preparation method thereof |
| CN103265714A (en) * | 2013-05-20 | 2013-08-28 | 西安理工大学 | Polyvinyl alcohol/graphene oxide composite film preparation method |
| CN103319827A (en) * | 2013-07-02 | 2013-09-25 | 中国科学技术大学 | Method for preparing organic-inorganic nano composite film |
-
2017
- 2017-01-09 CN CN201710013037.1A patent/CN106700110B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492247A (en) * | 2011-12-21 | 2012-06-13 | 西北师范大学 | Water-resistant polyvinyl alcohol (PVA)-based composite film and preparation method thereof |
| CN103265714A (en) * | 2013-05-20 | 2013-08-28 | 西安理工大学 | Polyvinyl alcohol/graphene oxide composite film preparation method |
| CN103319827A (en) * | 2013-07-02 | 2013-09-25 | 中国科学技术大学 | Method for preparing organic-inorganic nano composite film |
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