CN111268639B - Multi-stimulus response actuation film and preparation and application thereof - Google Patents
Multi-stimulus response actuation film and preparation and application thereof Download PDFInfo
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- CN111268639B CN111268639B CN202010101016.7A CN202010101016A CN111268639B CN 111268639 B CN111268639 B CN 111268639B CN 202010101016 A CN202010101016 A CN 202010101016A CN 111268639 B CN111268639 B CN 111268639B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B3/00—Devices comprising flexible or deformable elements, e.g. comprising elastic tongues or membranes
- B81B3/0018—Structures acting upon the moving or flexible element for transforming energy into mechanical movement or vice versa, i.e. actuators, sensors, generators
- B81B3/0021—Transducers for transforming electrical into mechanical energy or vice versa
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B3/00—Devices comprising flexible or deformable elements, e.g. comprising elastic tongues or membranes
- B81B3/0018—Structures acting upon the moving or flexible element for transforming energy into mechanical movement or vice versa, i.e. actuators, sensors, generators
- B81B3/0024—Transducers for transforming thermal into mechanical energy or vice versa, e.g. thermal or bimorph actuators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B3/00—Devices comprising flexible or deformable elements, e.g. comprising elastic tongues or membranes
- B81B3/0018—Structures acting upon the moving or flexible element for transforming energy into mechanical movement or vice versa, i.e. actuators, sensors, generators
- B81B3/0029—Transducers for transforming light into mechanical energy or viceversa
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B3/00—Devices comprising flexible or deformable elements, e.g. comprising elastic tongues or membranes
- B81B3/0018—Structures acting upon the moving or flexible element for transforming energy into mechanical movement or vice versa, i.e. actuators, sensors, generators
- B81B3/0032—Structures for transforming energy not provided for in groups B81B3/0021 - B81B3/0029
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- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00134—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems comprising flexible or deformable structures
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Abstract
The application relates to a multi-stimulus response actuation film, and preparation and application thereof. The preparation method is simple and quick, can realize large-scale production, and the prepared carbon nano tube-chitosan/acetate fiber filter paper film can have rapid, obvious and stable deformability under the conditions of electrifying, water vapor and infrared light, and has important application value in the fields of flexible switches, artificial muscles, soft robots, environmental monitoring and the like.
Description
Technical Field
The application belongs to the field of actuation films and preparation and application thereof, and particularly relates to a multi-stimulus response actuation film and preparation and application thereof.
Background
A flexible actuator is an intelligent device that is responsive to external environmental stimuli such as light, heat, electricity, humidity, magnetic fields, pressure, etc., whereby the flexible actuator can be classified into an optical actuator, a thermal actuator, an electric actuator, a magnetic actuator, a pressure type actuator, etc. The flexible actuator capable of responding to various stimuli has the advantages of responding to more external environmental conditions, being convenient and controllable, and having high research value and application prospect in the fields of flexible control, artificial muscles, biomedical use, environmental monitoring and the like.
The carbon nano tube is a one-dimensional nano material, has light weight and excellent mechanical, electrical, chemical and other properties. With the deep research, the abundant application value of the compound is gradually revealed. The chitosan is a product of removing partial acetyl of natural polysaccharide chitin, has the characteristics of biodegradability, biocompatibility and the like, and is widely applied to various fields of food additives, textiles, environmental protection, artificial tissue materials, medical materials and the like. The dispersibility of the carbon nano tube can be improved by modifying the surface, the carbon nano tube is ultrasonically dispersed in the chitosan dispersion liquid, and the water is removed by suction filtration and evaporation. The carbon nanotube and the chitosan matrix have strong interfacial binding force, and the tensile strength of the composite material is higher than that of the pure chitosan material by more than 90 percent.
At present, the light, vapor and electric actuating films based on carbon nano tubes are mostly single in response, most of the light and electric actuating films are formed by attaching the carbon nano tubes to films with good thermal deformation performance, and the excellent thermal performance of the carbon nano tubes is utilized to generate expansion and bend towards one direction, and the vapor actuating films are low in strength and poor in circularity.
CN106058038A discloses an electrically actuated thin film material, and preparation and application thereof, but the mechanical strength of the carbon nanotube thin film layer and the graphene oxide layer is low, particularly the doctor-blading process of graphene oxide, which is easy to damage the carbon nanotube thin film, and can only respond to voltage stimulus, so that the applicable environmental limitation is large.
Disclosure of Invention
The application aims to solve the technical problem of providing a multi-stimulus-response actuation film, and preparation and application thereof, and overcomes the defects of low film forming strength and single stimulus-response condition of a carbon-based actuation film. The application is formed by compounding a carbon nano tube film taking chitosan as a matrix with acetate fiber water-based filter paper.
An actuation film of the present application includes a carbon nanotube-chitosan film layer and a microporous filter membrane layer.
In the carbon nano tube-chitosan film layer, the mass ratio of the carbon nano tube to the chitosan is 1:9-2:8; the microporous filter membrane layer is acetate fiber filter paper.
The actuating film is of a double-layer network structure, and the thickness of the actuating film is 30-100 mu m.
The double-layer network structure is as follows: the carbon nanotube-chitosan network and the acetate fiber filter paper network are crosslinked by physical action, and bending in different directions can be generated due to the difference of expansion rate, hygroscopicity and the like.
The actuation film has a double-layer structure, and is formed by compounding a carbon nano tube-chitosan film and an acetate fiber microporous filter film by utilizing a physical crosslinking effect.
The actuation film is formed by compounding a carbon nano tube film taking chitosan as a matrix and acetate fiber water-based filter paper, and the formed asymmetric film which is tightly combined is different in hydrophilicity, conductivity, photo-thermal conversion efficiency and thermal expansion coefficient between two layers of different components. The multi-stimulus responsive actuation film is deformable in response to photothermal, humidity, and electrothermal stimuli.
The application provides a preparation method of an actuation film, which comprises the following steps:
(1) Adding the carbon nano tube into the chitosan dispersion liquid, and processing to obtain a carbon nano tube-chitosan dispersion liquid;
(2) And (3) carrying out suction filtration and drying on the carbon nano tube-chitosan dispersion liquid to obtain the actuation film.
The preferred mode of the preparation method is as follows:
the carbon nanotubes in the step (1) are acidified carbon nanotubes, and have more carboxyl groups; the molecular weight of the chitosan is 161.16.
The solvent of the chitosan dispersion liquid in the step (1) is acetic acid solution, and the acetic acid solution is: dissolving acetic acid in deionized water to obtain acetic acid solution with the volume percentage concentration of 3%; the chitosan dispersion liquid comprises the following components: uniformly dispersing chitosan powder in acetic acid solution, heating and stirring at 50-70deg.C at 400-600r/min for 40-60min.
The carbon nano tube-chitosan dispersion liquid in the step (1), wherein the concentration of chitosan in the dispersion liquid is 10-50mg/ml, and the concentration of carbon nano tube in the dispersion liquid is 2-5mg/ml.
The treatment in the step (1) specifically comprises the following steps: and (3) treating the cells by using an ultrasonic pulverizer for 1-2 hours.
The step (2) of vacuum filtration is carried out, and the specific steps are as follows: pouring the carbon nano tube-chitosan dispersion liquid into a sand core funnel, and carrying out suction filtration by using a cellulose acetate microporous filter membrane through a circulating water type vacuum pump; and the drying is carried out in a drying oven at the temperature of 50-70 ℃ for 1-2h.
The water adopted in the steps (1) and (2) is deionized water.
The application provides an actuating film prepared by the method.
The application provides an application of the actuation film, such as application in the fields of flexible control, artificial muscle, biomedical use, environmental monitoring and the like.
Advantageous effects
(1) The preparation method is simple and rapid, and can be used for large-scale production;
(2) The carbon nano tube in the multi-stimulus response actuation film has strong binding force with chitosan, and is tightly combined with water-based filter paper after being filtered by suction and evaporated by an oven, so that the interface problem existing between different components is greatly reduced;
(3) The application utilizes the interface characteristic of the carbon nano tube and the chitosan, and forms a flexible actuator prepared by a network structure of filter paper, thereby having certain potential application value;
(4) According to the application, the thickness control of the multi-stimulus response actuation film can be realized by changing the concentration of the carbon nano tube and the chitosan in the dispersion liquid, the volume of the suction filtration carbon nano tube-chitosan dispersion liquid and the thickness of the acetate fiber filter paper, so that the conductivity of the film is influenced, the response speed of voltage is further influenced, and the bending elasticity of the film is influenced by the thickness of the film; the carbon nano tube-chitosan layer and the acetate fiber filter paper layer have a series of physical and chemical property differences such as hydrophilicity, conductivity, photo-thermal conversion efficiency, thermal expansion coefficient and the like, so that the carbon nano tube-chitosan layer and the acetate fiber filter paper layer have different external stimuli, different stress gradients are generated in the carbon nano tube-chitosan layer, and deformation performances in different directions are macroscopically generated;
(5) The multi-stimulus response actuation film prepared by the application can be driven under low voltage, infrared illumination and vapor conditions, and has the advantages of high response speed, large deformation, obvious actuation behavior and good cycling stability. The method has important application value in the fields of flexible control, artificial muscle, biomedical and environmental monitoring and the like.
Drawings
FIG. 1 is a surface SEM image of a carbon nanotube-chitosan layer of example 1;
FIG. 2 is an SEM image of the interface of the carbon nanotube-chitosan/acetate filter paper composite film in example 1; wherein (a) is the cross section of the (carbon nano tube-chitosan/acetate fiber filter paper composite film, and (b) is a partial enlarged view of the interface joint of the (a) carbon nano tube-chitosan/acetate fiber filter paper composite film;
FIG. 3 is a graph showing macroscopic actuation effects of the carbon nanotube-chitosan/acetate filter paper composite film of example 1 under 3V DC voltage, moisture and IR irradiation, respectively;
FIG. 4 is a graph showing the mechanical properties of the composite membrane of carbon nanotube-chitosan/acetate filter paper of example 1;
FIG. 5 is a graph showing the relationship between the time for deformation and recovery and the bending angle of the carbon nanotube-chitosan/acetate filter paper composite film of example 1 when the film was stimulated under the conditions of 3V DC voltage, water vapor and infrared light irradiation.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Chitosan is purchased from Shanghai Taitan technologies Co., ltd and has a molecular weight of 1526.46; the carbon nano tube is carboxylated multi-wall carbon nano tube of Nanjing Xianfeng nano material science and technology Co., ltd, and is treated by sulfuric acid and nitric acid mixed acid, the purity is 95%, the length is 10-30nm, and the carboxyl content is 1.23wt%; acetate filter paper was purchased from Shanghai sub-purification materials factory with a diameter of 50mm and a pore size of 0.22 μm.
Example 1
(1) At room temperature, 0.3ml of acetic acid is measured, deionized water is added for dilution to 10ml, so as to obtain acetic acid solution with volume concentration of 3%, 250mg of chitosan is weighed for dispersion into the acetic acid solution with volume concentration of 3%, chitosan dispersion liquid is obtained by heating and stirring at 60 ℃, then 25mg of carbon nano tube is weighed and added into the chitosan dispersion liquid, and the carbon nano tube is treated in ice water bath by a cell ultrasonic pulverizer for 2 hours so as to uniformly disperse the carbon nano tube, so as to obtain carbon nano tube-chitosan dispersion liquid;
(2) Pouring the carbon nano tube-chitosan dispersion liquid obtained in the step (1) into a sand core funnel, and carrying out suction filtration by using acetate fiber filter paper as a filter membrane through a circulating water type vacuum pump. And after the carbon nano tube-chitosan/acetate fiber filter paper film is formed by suction filtration, namely the carbon nano tube-chitosan dispersion liquid loses fluidity, the carbon nano tube-chitosan/acetate fiber filter paper film is dried in a baking oven at 50 ℃ for 2 hours, and the multi-stimulus response actuating film can respond to photo-thermal, humidity and electric heating stimulus to generate deformation.
As shown in fig. 1, the surface of the carbon nanotube-chitosan film was shown to have many pores.
As shown in FIG. 2, it was revealed that the carbon nanotube-chitosan film and the acetate filter paper both have different degrees of network structure and are tightly combined, and the thickness of the carbon nanotube-chitosan/acetate filter paper film is 69 μm.
As shown in fig. 3, it is shown that the carbon nanotube-chitosan/acetate filter paper film can be bent and deformed to different degrees and directions, and each deformation can be restored to its original shape independently.
As shown in fig. 4, it is shown that the carbon nanotube-chitosan/acetate filter paper film has a strong tensile stress. Test criteria and methods: using an electronic all-purpose material tester, sensor 10kN, jig 250N, stretching rate 10mm/min. Quantitative data: the tensile breaking stress is 13.72MPa, the elastic modulus is 277.48MPa, and the tensile breaking displacement is 2.68mm.
As shown in fig. 5, it was demonstrated that the carbon nanotube-chitosan/acetate filter paper film was stimulated under conditions of 3V dc voltage, water vapor and infrared light irradiation, and the relationship between the time of deformation and recovery and the bending angle was measured using the ruler tool of Photoshop software, and the bending angle of the film in the digital camera record photograph.
Example 2
(1) At room temperature, 0.3ml of acetic acid is measured, deionized water is added for dilution to 10ml, so as to obtain acetic acid solution with volume concentration of 3%, 250mg of chitosan is weighed for dispersion into the 3% acetic acid solution, chitosan dispersion is obtained by heating and stirring at 60 ℃, then 35mg of carbon nano tube is weighed and added into the chitosan dispersion, and the carbon nano tube is treated in ice water bath by a cell ultrasonic pulverizer for 2 hours so as to uniformly disperse the carbon nano tube, so as to obtain carbon nano tube-chitosan dispersion;
(2) Pouring the carbon nano tube-chitosan dispersion liquid obtained in the step (1) into a sand core funnel, and carrying out suction filtration by using acetate fiber filter paper as a filter membrane through a circulating water type vacuum pump. And after the carbon nano tube-chitosan/acetate fiber filter paper film is formed by suction filtration, namely the carbon nano tube-chitosan dispersion liquid loses fluidity, the carbon nano tube-chitosan/acetate fiber filter paper film is dried in a baking oven at 60 ℃ for 1.5 hours, and the multi-stimulus response actuating film can respond to photo-thermal, humidity and electric heating stimulus to generate deformation.
Example 3
(1) At room temperature, 0.3ml of acetic acid is measured, deionized water is added for dilution to 10ml, so as to obtain acetic acid solution with volume concentration of 3%, 250mg of chitosan is weighed for dispersion into the acetic acid solution with volume concentration of 3%, chitosan dispersion liquid is obtained by heating and stirring at 60 ℃, 45mg of carbon nano tube is weighed and added into the chitosan dispersion liquid, and the carbon nano tube is treated in ice water bath by a cell ultrasonic pulverizer for 2 hours so as to uniformly disperse the carbon nano tube, so as to obtain carbon nano tube-chitosan dispersion liquid;
(2) Pouring the carbon nano tube-chitosan dispersion liquid obtained in the step (1) into a sand core funnel, and carrying out suction filtration by using acetate fiber filter paper as a filter membrane through a circulating water type vacuum pump. And after the carbon nano tube-chitosan/acetate fiber filter paper film is formed by suction filtration, namely the carbon nano tube-chitosan dispersion liquid loses fluidity, the carbon nano tube-chitosan/acetate fiber filter paper film is dried in a baking oven at 70 ℃ for 1h, so that the carbon nano tube-chitosan/acetate fiber filter paper film is obtained, and the multi-stimulus response actuating film can respond to photo-thermal, humidity and electric heating stimulus to generate deformation.
Comparative example
CN106058038A is compounded with the double-layer film by adopting a repeated doctor-blading and repeated drying mode, and the application directly filters the double-layer film by suction, so that the preparation process is simpler and more convenient, and the safety of product preparation is improved. In CN106058038A, 0-8 s is the deformation process of the film, and the film is completely restored at 40s, while the three response deformation processes of the application are relatively quick, and the reaction rate is greatly improved about 10 s. CN106058038A can only respond to voltage stimulus, but the present application can respond to voltage, water vapor and infrared light, respectively, and the applicable environments are more diversified.
Claims (7)
1. An actuation membrane, characterized in that the membrane comprises a carbon nanotube-chitosan membrane layer and a microporous filter membrane layer; wherein the microporous filter membrane layer is an acetate fiber microporous filter membrane layer; in the carbon nano tube-chitosan film layer, the mass ratio of the carbon nano tube to the chitosan is 1:9-2:8; the actuating film is of a double-layer network structure and has the thickness of 30-100 mu m.
2. A method of making the actuation film of claim 1, comprising:
step 1, adding carbon nanotubes into chitosan dispersion liquid, and processing to obtain carbon nanotube-chitosan dispersion liquid; wherein the concentration of chitosan in the dispersion liquid is 10-50mg/ml, and the concentration of the carbon nano tube in the dispersion liquid is 2-5mg/ml;
step 2, performing suction filtration and drying on the carbon nanotube-chitosan dispersion liquid by using a cellulose acetate microporous filter membrane to obtain an actuation film; the suction filtration specifically comprises the following steps: pouring the carbon nano tube-chitosan dispersion liquid into a sand core funnel, and carrying out suction filtration by using a cellulose acetate microporous filter membrane through a circulating water type vacuum pump.
3. The method according to claim 2, wherein the carbon nanotubes in step 1 are acidified carbon nanotubes.
4. The method according to claim 2, wherein the solvent of the chitosan dispersion of step 1 is an acetic acid solution; the chitosan dispersion liquid comprises the following components: uniformly dispersing chitosan powder in acetic acid solution, heating and stirring at 50-70deg.C at 400-600r/min for 40-60min.
5. The preparation method according to claim 2, wherein the treatment in step 1 is specifically: and (3) treating the cells by using an ultrasonic pulverizer for 1-2 hours.
6. The preparation method according to claim 2, wherein the drying temperature in the step 2 is 50-70 ℃ and the time is 1-2h.
7. Use of the actuation film of claim 1 in the fields of flexible control, artificial muscle, biomedical or environmental monitoring.
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| CN112520685B (en) * | 2020-12-04 | 2024-03-01 | 青岛大学 | Double-layer film actuator and preparation method thereof |
| CN113603913B (en) * | 2021-08-24 | 2023-10-20 | 深圳市水务规划设计院股份有限公司 | Photo-thermal film and preparation method and application thereof |
| CN117488482B (en) * | 2023-12-29 | 2024-05-14 | 东华大学 | Asymmetric deformed fiber membrane and preparation method and application thereof |
| CN117488480B (en) * | 2024-01-03 | 2024-05-14 | 东华大学 | Asymmetric functional fiber membrane and preparation method and application thereof |
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