CN113861480B - Multilayer composite barrier film based on reduced graphene oxide, and preparation method and application thereof - Google Patents
Multilayer composite barrier film based on reduced graphene oxide, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a multilayer composite barrier film based on reduced graphene oxide, a preparation method and application thereof, wherein a PEI/GO mixed solution is prepared; controlling conditions to reduce GO to RGO by PEI; filtering to remove redundant PEI; re-dissolving the PEI/RGO mixture in a solvent; preparing a layer of RGO/PEI composite film with a multilayer brick wall structure on a substrate by using a layer-by-layer sol-gel method. In the preparation process of the film, PEI simultaneously serves as a reducing agent and a matrix: the reduced graphene oxide is used as a matrix of the composite membrane, and redundant PEI is removed through suction filtration in the preparation process, so that the content of hydrophilic PEI in the composite membrane is effectively reduced, and the multilayer composite barrier membrane based on the reduced graphene oxide, low in PEI content and high in performance is prepared.
Description
Technical Field
The invention belongs to the technical field of packaging films, and particularly relates to a multilayer composite barrier film based on reduced graphene oxide, and a preparation method and application thereof.
Background
Active gases (such as oxygen) and moisture in nature are detrimental to long-term storage of goods, such as: can lead to spoilage of food, damage to microelectronic devices, reduced life and stability of metal devices, and the like. Therefore, the design of new high performance packaging films has been a focus of research for many years. For general inorganic barrier films, most of them have excellent intrinsic barrier properties, but are prone to penetrating pinholes or internal defects after bending or stretching. For most polymer barrier films, the polymer barrier film has stronger flexibility, better mechanical property and excellent intrinsic barrier property, but the microstructure and the barrier property of the polymer barrier film are sensitive to the external environment, and the change of the structure and the reduction of the property are easy to occur along with the lapse of time. In recent years, two-dimensional inorganic nanosheet/polymer composite films have attracted considerable attention, most of which have a thickness in the range of several tens of nanometers to several tens of micrometers, and provide extremely high gas barrier properties after coating on a substrate (such as PET). Through the layer-by-layer assembly preparation method, the nano sheets tend to be tiled and deposited in the film under the action of static electricity, so that a compact multilayer brick wall structure (brick-wall structure) is formed: the nano-sheets are used as bricks, and the polymer matrix is mortar. When gas molecules migrate inside the film, the gas molecules tend to avoid nanosheets with extremely strong barrier properties and permeate through the nanosheets in a more tortuous path, so that the gas barrier properties of the film are greatly enhanced. Among the various nanoplatelets, graphene (or reduced graphene oxide) is one of the most preferred choices because it has a very high specific surface area and excellent mechanical properties, is highly hydrophobic and can completely block most gas molecules. To date, scientists have discovered a series of graphene/polymer composite barrier films with superior air barrier properties.
Among them, the reduced graphene oxide/polyethyleneimine (RGO/PEI) composite membrane is one of the most sharp-pointed performances. The RGO/PEI composite membrane prepared by the layer-by-layer self-assembly technology has a multilayer structure, PEI molecular chains play a strong binding role on RGO sheets, and the composite membrane has extremely high gas barrier rate within the range of hundreds of nanometers to dozens of micrometers in thickness, and is a popular research object at present. However, due to the hydrophilicity of the polymer material, the film absorbs water when exposed to air, which causes plasticization of the film and rearrangement of the internal microstructure, thereby increasing the air permeability and reducing the service life of the film. Therefore, in the preparation of the thin film, the content of the hydrophobic RGO should be increased and the content of the hydrophilic polymer material should be decreased. However, the components of the composite material have great influence on the performance, and strong interaction exists between the components, which is a complicated research content.
In the technical scheme of the first prior art, layer-by-layer deposition (layer-by-layer deposition) of the czochralski method, for example, in the preparation of an a/B composite multilayer barrier film, one of a and B is graphene oxide, and the other is a polymer matrix material: the substrate is first selected (e.g., polyethylene terephthalate (PET)), subjected to conventional chemical treatment, corona treatment, and cleaning to render the substrate highly compatible with the deposited material. Preparing the solution A and the solution B, and adjusting the pH value to ensure that the solution A and the solution B have different acid-base properties. The different pH values are used for the purpose of stronger interaction between the materials A and B during layer-by-layer deposition and can be tightly combined.
The specific film forming steps are as follows: immersing the substrate in the solution A for a period of time, taking out the substrate, cleaning and drying (part of solute needs to be annealed to stabilize the structure), and depositing a layer of film A on the substrate; immersing the substrate in the solution B for a period of time, taking out the substrate, cleaning and drying (part of solute needs to be annealed to stabilize the structure), and depositing a layer of film A and a layer of film B on the substrate; and repeating the two steps until the preset number of the thin film layers is reached. Finally, the A/B composite multilayer film is deposited on the substrate, and the film usually has a brick wall structure under the condition that the single-layer thickness is preset reasonably.
The disadvantages of this technique:
1. since the solute must be stably dispersed in the solvent, graphene oxide having high surface activity is used. However, graphene oxide is not good for gas barrier due to its hydrophilic property, contains defects, a large number of oxygen-containing groups, and is not good in structural stability as graphene or reduced graphene oxide.
2. The single preparation process of the film comprises the steps of soaking in solution A, cleaning, soaking in solution B and cleaning. The steps are complex, the preparation time is long, and the preparation cost is high.
3. The film formation is influenced by various factors, such as: PH, soaking time, solution concentration, solute activity, etc. The control condition is complex, and the research difficulty is large.
In the prior art, layer-by-layer deposition of a doctor blade method, that is, a layer-by-layer sol-gel method, for example, in the preparation of an a/B composite multilayer barrier film, one of a and B is graphene oxide, and the other is a polymer matrix material: the substrate is first selected (e.g., polyethylene terephthalate (PET)), subjected to conventional chemical treatment, corona treatment, and cleaning to render the substrate highly compatible with the deposited material. A solution and B solution were prepared.
The specific film forming steps are as follows: uniformly coating a layer of solution A on a substrate by using a scraper, waiting for the solution to volatilize and self-assemble to form a film (part of solute needs to be annealed to stabilize the structure), and depositing a layer of film A on the substrate; uniformly coating a layer of solution B on a substrate by using a scraper, waiting for the solution to volatilize and forming a film by self-assembly (part of solute needs to be annealed to stabilize the structure), and depositing a layer of film A and a layer of film B on the substrate; repeating the two steps until reaching the preset film layer number. Finally, the A/B composite multilayer film is deposited on the substrate, and the film usually has a brick wall structure under the condition that the single-layer thickness is preset reasonably.
Or directly preparing AB mixed solution, and then preparing the A/B composite multilayer film by adopting a layer-by-layer sol-gel method. Namely: uniformly coating a layer of AB mixed solution on a substrate by using a scraper, waiting for the solution to volatilize and self-assemble to form a film (part of solute needs to be annealed to stabilize the structure), and depositing an A/B composite film on the substrate; and repeating the steps until the preset number of the thin film layers is reached. Finally, the A/B composite multilayer film is deposited on the substrate, and the film usually has a brick wall structure under the condition that the single-layer thickness is preset reasonably.
The disadvantages of this technique are: since the solute must be stably dispersed in the solvent, graphene oxide having a high surface activity is used. However, graphene oxide is not good for gas barrier due to its hydrophilic property, contains defects, a large number of oxygen-containing groups, and is not good in structural stability as graphene or reduced graphene oxide.
In the prior art, a suction filtration membrane forming method comprises the steps of firstly preparing a solution A and a solution B, wherein one of the solution A and the solution B is graphene oxide, and the other is a high-molecular matrix material. Mixing the solution A and the solution B as required, and filtering the AB mixed solution with a filter membrane (such as cellulose acetate filter cloth) made of material with small pores. The A/B composite film is deposited on the filter membrane.
The substrate is selected, such as polyethylene terephthalate (PET), and subjected to conventional chemical treatment, corona treatment and cleaning to render the substrate highly compatible with the deposited material. Transferring the A/B composite film left on the filter membrane to a substrate to prepare the A/B composite multilayer film coated on the substrate.
The disadvantages of this technique are: after the membrane is formed by suction filtration, the membrane is deposited on the filter cloth. The film needs to be transferred from the filter cloth to the substrate at the later stage, the film is very thin, the transfer difficulty is high, and defects are easy to generate in the transfer process.
Disclosure of Invention
The invention provides a multilayer composite barrier film based on reduced graphene oxide, a preparation method and application thereof.
The specific technical scheme is as follows:
the preparation method of the multilayer composite barrier film based on the reduced graphene oxide comprises the following steps:
preparing a PEI/GO mixed solution;
controlling conditions to reduce GO to RGO by PEI;
filtering to remove redundant PEI;
re-dissolving the PEI/RGO mixture in a solvent;
preparing a layer of RGO/PEI composite film with a multilayer brick wall structure on a substrate by using a layer-by-layer sol-gel method.
Specifically, the method comprises the following steps:
s1, selecting and carrying out conventional chemical treatment, corona treatment and cleaning on a thin film substrate to ensure that the substrate has high affinity to a deposition material;
s2, adding a certain amount of graphene oxide powder into deionized water, and carrying out ultrasonic stirring to disperse the graphene oxide powder and convert the graphene oxide powder into a single-layer structure; namely, preparing a single-layer graphene oxide GO solution;
s3, adding a polyethyleneimine PEI solution with a certain concentration into the GO solution, and stirring to uniformly mix;
s4, placing the mixed solution at 80 ℃ and stirring for a plurality of hours; PEI is used as a reducing agent to reduce or partially reduce GO into reduced graphene oxide RGO; meanwhile, part of PEI molecules are adsorbed on the RGO surface in a chemical modification or physical adsorption mode;
s5, filtering the reacted mixed solution by using filter cloth with small holes; leaving a mixture of RGO and PEI on the filter cloth;
s6, continuously performing suction filtration by using warm water, cleaning the mixture of RGO and PEI on the filter cloth, and removing redundant PEI molecules;
s7, scraping the mixture of RGO and PEI on the filter cloth, ultrasonically treating, stirring, dissolving again in deionized water, and dispersing in deionized water to prepare a new RGO/PEI mixed solution;
s8, horizontally placing and fixing the film substrate which is processed in advance;
s9, taking out a certain amount of mixed solution according to the concentration of the RGO/PEI mixed solution; the mixed solution taken out can form a composite film with the thickness smaller than the maximum diameter of the RGO on the substrate;
s10, uniformly coating the taken mixed solution on a substrate by using a coater or a scraper, and standing to form a film; the conditions of temperature, humidity, air blast and the like are controlled according to requirements in the film forming process;
s11, obtaining an RGO/PEI composite film coated on a substrate;
s12, repeating the steps S9-11, wherein the taking amount of the mixed solution is equal every time;
s13, repeating for a certain number of times to obtain an RGO/PEI composite film with a multilayer structure (brick wall structure) deposited on a substrate.
The multilayer composite barrier film based on the reduced graphene oxide can be used as a packaging material, and particularly can be used as a packaging material for food.
In the preparation process of the film, PEI is simultaneously used as a reducing agent and a matrix: reduced graphene oxide is used as a matrix (mortar structure) of the composite membrane. And redundant PEI is removed through suction filtration in the preparation process, so that the content of hydrophilic PEI in the composite film is effectively reduced (PEI is required and important, but excessive PEI causes the film to absorb water and is not beneficial to the barrier property of the film), and the multilayer composite barrier film based on reduced graphene oxide, low in PEI content and high in performance is prepared.
Drawings
FIG. 1 is an RGO/PEI-0.05 composite film prepared in example 1;
FIG. 2 is an RGO/PEI-0.1 composite film prepared in example 2;
FIG. 3 is an RGO/PEI-0.3 composite film prepared in example 3.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
Example 1
A10 cm X10 cm piece of PET having a thickness of 35 μm was taken as a substrate, washed with deionized water and methanol, and subjected to corona treatment to increase the affinity thereof. A certain amount of graphene oxide powder (outer diameter 0.5-3 μm,<3 layers) was mixed with deionized water and sonicated for 10 minutes at 10w with stirring to a concentration of 100mL and 0.1mg mL-1The single layer Graphene Oxide (GO) aqueous solution of (a). Add 100mL of 0.05mg mL to GO aqueous solution-1The Polyethyleneimine (PEI) solution was stirred to mix well. The mixed solution is placed at 80 ℃ and stirred for 3 hours, the color of the solution is changed from brown to black, and the reduction of the graphene oxide is realized. The mixed solution after the reaction was filtered using a cellulose acetate filter paper having a pore size of 0.2 μm, and washed with warm water several times. Scraping the mixture of RGO and PEI on the filter cloth, ultrasonically treating, stirring, dissolving again in deionized water, and dispersing to obtain RGO/PEI mixed solution with solute total content of 0.5 wt%. And horizontally placing and fixing the film substrate which is processed in advance. Taking out 1mL of the mixed solution, uniformly coating the taken-out mixed solution on a substrate by using a coater or a scraper, and standing at 60 ℃ to form a film. And (3) coating the mixed solution and standing for 20 times to form a film, and finally coating a RGO/PEI-0.05 composite film with a multilayer brick wall structure on the substrate, as shown in figure 1.
According to the analysis test, the gas permeability of the PET substrate coated with the RGO/PEI-0.05 composite film was from 54.86cm3m-2 day-1 atm-1Reduced to 0.94cm3 m-2 day-1 atm-1. The coating layer exhibits a very efficient gas barrier property.
Example 2
A10 cm X10 cm piece of PET having a thickness of 35 μm was taken as a substrate, washed with deionized water and methanol, and subjected to corona treatment to increase the affinity thereof. A certain amount of graphene oxide powder (outer diameter 0.5-3 μm,<3 layers) was mixed with deionized water and sonicated for 10 minutes at 10w with stirring to a concentration of 100mL and 0.1mg mL-1The monolayer Graphene Oxide (GO) aqueous solution of (a). Adding 100mL of GO into the aqueous solution with the concentration of 0.1mg mL-1The Polyethyleneimine (PEI) solution of (1) was stirred to mix well. The mixed solution is placed at 80 ℃ and stirred for 3 hours, the color of the solution is changed from brown to black, and the reduction of the graphene oxide is realized. The mixed solution after the reaction was filtered using a cellulose acetate filter paper having a pore size of 0.2 μm, and washed with warm water several times. Scraping the mixture of RGO and PEI on the filter cloth, ultrasonically treating, stirring, dissolving again in deionized water, and dispersing to obtain RGO/PEI mixed solution with solute total content of 0.5 wt%. And horizontally placing and fixing the film substrate which is processed in advance. Taking out 1mL of the mixed solution, uniformly coating the taken-out mixed solution on a substrate by using a coater or a scraper, and standing at 60 ℃ to form a film. And (3) coating the mixed solution and standing for 20 times to form a film, and finally coating a layer of RGO/PEI-0.1 composite film with a multilayer brick wall structure on the substrate, as shown in figure 2.
According to the analytical test, the gas permeability of the PET substrate coated with the RGO/PEI-0.1 composite film was from 54.86cm3m-2 day-1 atm-1Reduced to 0.25cm3 m-2 day-1 atm-1. The coating layer exhibits a very efficient gas barrier property.
Example 3
A10 cm X10 cm piece of PET having a thickness of 35 μm was taken as a substrate, washed with deionized water and methanol, and subjected to corona treatment to increase the affinity thereof. Mixing a certain amount of graphite oxideAn olefin powder (outer diameter 0.5-3 μm,<3 layers) was mixed with deionized water and sonicated for 10 minutes at 10w with stirring to a concentration of 100mL and 0.1mg mL-1The single layer Graphene Oxide (GO) aqueous solution of (a). Adding 100mL of GO into the aqueous solution with the concentration of 0.3mg mL-1The Polyethyleneimine (PEI) solution was stirred to mix well. The mixed solution is placed at 80 ℃ and stirred for 3 hours, the color of the solution is changed from brown to black, and the reduction of the graphene oxide is realized. The mixed solution after the reaction was filtered using a cellulose acetate filter paper having a pore size of 0.2 μm, and washed with warm water several times. Scraping the mixture of RGO and PEI on the filter cloth, ultrasonically treating, stirring, dissolving again in deionized water, and dispersing to obtain RGO/PEI mixed solution with solute total content of 0.5 wt%. And horizontally placing and fixing the film substrate which is processed in advance. Taking out 1mL of the mixed solution, uniformly coating the taken-out mixed solution on a substrate by using a coater or a scraper, and standing at 60 ℃ to form a film. And (3) coating the mixed solution and standing for 20 times to form a film, and finally coating a layer of RGO/PEI-0.3 composite film with a multilayer brick wall structure on the substrate, as shown in figure 3.
According to the analytical test, the gas permeability of the PET substrate coated with the RGO/PEI-0.3 composite film was from 54.86cm3m-2 day-1 atm-1Reduced to 0.17cm3 m-2 day-1 atm-1. The coating layer exhibits a very efficient gas barrier property.
Claims (6)
1. The preparation method of the multilayer composite barrier film based on the reduced graphene oxide is characterized by comprising the following steps:
preparing a PEI/GO mixed solution;
controlling conditions to reduce GO to RGO by PEI;
filtering to remove redundant PEI;
re-dissolving the PEI/RGO mixture in a solvent;
preparing a layer of RGO/PEI composite film with a multilayer brick wall structure on a substrate by using a layer-by-layer sol-gel method.
2. The method of preparing a reduced graphene oxide based multilayer composite barrier film according to claim 1, comprising the steps of:
s1, selecting and carrying out conventional chemical treatment, corona treatment and cleaning on a thin film substrate to ensure that the substrate has high affinity to a deposition material;
s2, adding a certain amount of graphene oxide powder into deionized water, and performing ultrasonic stirring to disperse the graphene oxide powder and convert the graphene oxide powder into a single-layer structure, namely preparing a single-layer graphene oxide GO solution;
s3, adding a polyethyleneimine PEI solution with a certain concentration into the GO solution, and stirring to uniformly mix;
s4, stirring the mixed solution at 80 ℃; PEI is used as a reducing agent to reduce or partially reduce GO into reduced graphene oxide RGO; meanwhile, part of PEI molecules are adsorbed on the RGO surface in a chemical modification or physical adsorption mode;
s5, filtering the reacted mixed solution by using filter cloth, and leaving a mixture of RGO and PEI on the filter cloth;
s6, continuously performing suction filtration by using warm water, cleaning the mixture of RGO and PEI on the filter cloth, and removing redundant PEI molecules;
s7, scraping the mixture of RGO and PEI on the filter cloth, ultrasonically treating, stirring, dissolving again in deionized water, and dispersing in deionized water to prepare a new RGO/PEI mixed solution;
s8, horizontally placing and fixing the film substrate which is well pretreated;
s9, taking out a certain amount of mixed solution according to the concentration of the RGO/PEI mixed solution; the mixed solution taken out is enough to form a composite film with the thickness smaller than the maximum diameter of the RGO on the substrate;
s10, uniformly coating the taken mixed solution on a substrate by using a coater or a scraper, and standing to form a film; controlling conditions according to requirements in the film forming process;
s11, obtaining an RGO/PEI composite film coated on a substrate;
s12, repeating the steps S9-11;
and S13, repeating for a certain number of times to obtain an RGO/PEI composite film which has a multilayer brick wall structure and is deposited on the substrate.
3. The method for preparing the multilayer composite barrier film based on the reduced graphene oxide according to claim 2, wherein the film forming process of S10 is carried out under the conditions of temperature, humidity and air blowing as required.
4. The method for preparing the multilayer composite barrier film based on the reduced graphene oxide according to claim 2, wherein in the step S12, the film forming process of S10 is carried out in such a manner that the taking amount of each mixed solution is equal when the steps S9-11 are repeated.
5. Multilayer composite barrier film based on reduced graphene oxide, characterized in that it is obtained according to the preparation process of any one of claims 1 to 4.
6. Use of a multilayer composite barrier film based on reduced graphene oxide according to claim 5 as a packaging material.
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| CN103937016A (en) * | 2014-03-28 | 2014-07-23 | 同济大学 | Spraying method for preparing graphene/polymer emulsion composite thin film material |
| CN105038222A (en) * | 2015-08-11 | 2015-11-11 | 河南科技大学 | Graphene/PEI (polyethyleneimine) gas barrier composite membrane and preparing method of graphene/PEI gas barrier composite membrane |
| CN105860117A (en) * | 2016-04-12 | 2016-08-17 | 河南科技大学 | Self-assembled graphene composite material, and preparation method and application thereof |
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| US10583407B2 (en) * | 2014-03-28 | 2020-03-10 | The University Of Manchester | Reduced graphene oxide barrier materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103937016A (en) * | 2014-03-28 | 2014-07-23 | 同济大学 | Spraying method for preparing graphene/polymer emulsion composite thin film material |
| CN105038222A (en) * | 2015-08-11 | 2015-11-11 | 河南科技大学 | Graphene/PEI (polyethyleneimine) gas barrier composite membrane and preparing method of graphene/PEI gas barrier composite membrane |
| CN105860117A (en) * | 2016-04-12 | 2016-08-17 | 河南科技大学 | Self-assembled graphene composite material, and preparation method and application thereof |
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