CN111268639A - Multi-stimulus response actuating film and preparation and application thereof - Google Patents
Multi-stimulus response actuating film and preparation and application thereof Download PDFInfo
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- B81—MICROSTRUCTURAL TECHNOLOGY
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- 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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- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
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Abstract
The invention relates to a multi-stimulus response actuating film, and preparation and application thereof. The preparation method is simple and rapid, and can be used for large-scale production, and the prepared carbon nanotube-chitosan/cellulose acetate filter paper film has rapid, obvious and stable deformability under the conditions of electrification, water vapor and infrared light, and has important application value in the fields of flexible switches, artificial muscles, soft robots, environment monitoring and the like.
Description
Technical Field
The invention belongs to the field of actuating films and preparation and application thereof, and particularly relates to a multi-stimulus response actuating film and preparation and application thereof.
Background
A flexible actuator is an intelligent device that can respond to external environmental stimuli such as light, heat, electricity, humidity, magnetic field, pressure, etc., thereby being classified into a photo 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 response to more external environmental conditions, convenience and controllability, and high research value and application prospect in the fields of flexible control, artificial muscles, biomedicine, environmental monitoring and the like.
The carbon nano tube is a one-dimensional nano material, has light weight and excellent mechanical, electrical and chemical properties and the like. With the progress of research, the rich application value of the method is gradually shown. The chitosan is a product of natural polysaccharide chitin with partial acetyl removed, has the characteristics of biodegradability, biocompatibility and the like, and is widely applied to a plurality of fields of food additives, textiles, environmental protection, artificial tissue materials, medical materials and the like. The carbon nano tube can improve the dispersibility by surface modification, the carbon nano tube is ultrasonically dispersed in chitosan dispersion liquid, and water is removed by suction filtration and evaporation. The carbon nanotube and chitosan matrix have strong interface bonding force, and the tensile strength of the composite material is more than 90% higher than that of a pure chitosan material.
At present, most of optical, water vapor and electric actuating films based on carbon nano tubes have single response, most of the optical and electric actuating films attach the carbon nano tubes to the film with better thermal deformation performance, the carbon nano tubes expand by utilizing the excellent thermal performance and bend towards one direction, and the water vapor actuating film has lower strength and poorer cycle performance.
CN106058038A discloses an electrically actuated thin film material, and its preparation and application, but the mechanical strength of the carbon nanotube thin film layer and the graphene oxide layer is low, especially the graphene oxide blade coating process is easy to damage the carbon nanotube thin film, and can only respond to a voltage stimulus, so the applicable environmental limitation is large.
Disclosure of Invention
The invention aims to solve the technical problem of providing a multi-stimulus response actuating film and preparation and application thereof, and overcoming the defects of low film forming strength and single response stimulus condition of the carbon-based material actuating film. The invention is formed by compounding a carbon nanotube film taking chitosan as a matrix and acetate fiber water system filter paper.
The invention discloses an actuating film, which comprises a carbon nano tube-chitosan film layer and a microporous filter film layer.
In the carbon nanotube-chitosan film layer, the mass ratio of the carbon nanotubes 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 nano tube-chitosan network and the acetate fiber filter paper network are crosslinked by physical action, and can be bent in different directions due to different expansion rates, hygroscopicity and the like.
The actuating 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 actuating film is formed by compounding a carbon nanotube film taking chitosan as a matrix and cellulose acetate water system filter paper, and an asymmetric but tightly combined film is formed, wherein differences of hydrophilicity, conductivity, photo-thermal conversion efficiency and thermal expansion coefficient exist between two layers of different components. The multi-stimulus responsive actuation film can deform in response to photothermal, humidity and electrothermal stimuli.
The invention provides a preparation method of an actuating film, which comprises the following steps:
(1) adding the carbon nano tube into the chitosan dispersion liquid, and treating to obtain carbon nano tube-chitosan dispersion liquid;
(2) and carrying out suction filtration and drying on the carbon nanotube-chitosan dispersion liquid to obtain the actuating film.
The preferred mode of the above preparation method is as follows:
the carbon nano tube in the step (1) is an acidified carbon nano tube and has more carboxyl; the chitosan has a molecular weight of 161.16.
The solvent of the chitosan dispersion liquid in the step (1) is an acetic acid solution, and the acetic acid solution is as follows: dissolving acetic acid in deionized water to obtain an acetic acid solution with the volume percentage concentration of 3%; the chitosan dispersion liquid is: uniformly dispersing chitosan powder in acetic acid solution, heating and stirring at 50-70 ℃ and at the rotation speed of 400-.
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 tubes in the dispersion liquid is 2-5 mg/ml.
The treatment in the step (1) is specifically as follows: and (5) treating the cells by using an ultrasonic crusher for 1-2 h.
The vacuum filtration in the step (2) is vacuum filtration, and specifically comprises the following steps: pouring the carbon nanotube-chitosan dispersion liquid into a sand core funnel, and performing suction filtration by using an acetate fiber microporous filter membrane through a circulating water type vacuum pump; and drying in an oven at 50-70 ℃ for 1-2 h.
The water adopted in the steps (1) and (2) is deionized water.
The invention provides an actuating film prepared by the method.
The invention provides an application of the actuating membrane, such as the application in the fields of flexible control, artificial muscle, biomedicine, environmental monitoring and the like.
Advantageous effects
(1) The preparation method is simple and quick, and can be used for large-scale production;
(2) the carbon nano tube and the chitosan in the multi-stimulus response actuating film have strong binding force, and are also tightly bound with water system filter paper after being subjected to suction filtration and oven evaporation, so that the problem of interfaces among different components is greatly reduced;
(3) the flexible actuator prepared by utilizing the interfacial characteristics of the carbon nano tube and the chitosan and the network structure formed by the carbon nano tube and the chitosan and the filter paper has certain potential application value;
(4) the invention can realize the thickness control of the multi-stimulus response actuating film 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, thereby influencing the conductivity of the film, further influencing the response rate of voltage, and influencing the bending elasticity of the film by the thickness of the film; the carbon nanotube-chitosan layer and the acetate fiber filter paper layer have differences in a series of physical and chemical properties such as hydrophilicity, electrical conductivity, photo-thermal conversion efficiency, thermal expansion coefficient and the like, so that the carbon nanotube-chitosan layer and the acetate fiber filter paper layer are stimulated to different external environments to generate different stress gradients inside the carbon nanotube-chitosan layer, and deformation performance in different directions is generated macroscopically;
(5) the multi-stimulus response actuating film prepared by the invention can be driven under the conditions of low voltage, infrared illumination and water vapor, and has the advantages of high response speed, large deformation, obvious actuating behavior and good cycle stability. The method has important application value in the fields of flexible control, artificial muscle, biomedicine, environmental monitoring and the like.
Drawings
FIG. 1 is a surface SEM photograph of a carbon nanotube-chitosan layer in example 1;
FIG. 2 is an SEM image of the carbon nanotube-chitosan/cellulose acetate filter paper composite film interface in example 1; wherein, (a) is the cross section of the carbon nano tube-chitosan/acetate fiber filter paper composite film, (b) is a partial enlarged view of the interface joint of the carbon nano tube-chitosan/acetate fiber filter paper composite film;
FIG. 3 is a diagram showing the macroscopic actuation effect of the carbon nanotube-chitosan/cellulose acetate fiber filter paper composite film under the irradiation of 3V DC voltage, water vapor and infrared light, respectively, in example 1;
FIG. 4 is a graph of the mechanical property data of the carbon nanotube-chitosan/cellulose acetate filter paper composite film in example 1;
FIG. 5 is a graph showing the relationship between the time for the carbon nanotube-chitosan/cellulose acetate filter paper composite film to deform and recover when stimulated by a 3V DC voltage, water vapor and infrared light irradiation in example 1 and the bending angle.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Chitosan was purchased from shanghai tympanock technologies ltd with a molecular weight of 1526.46; the carbon nano tube is a carboxylated multi-wall carbon nano tube of Nanjing Xiancheng nano material science and technology Limited company, and is treated by sulfuric acid and nitric acid mixed acid, the purity is 95 percent, the length is 10-30nm, and the carboxyl content is 1.23wt percent; the cellulose acetate filter paper was purchased from Shanghai Xingya purification materials works, and had a diameter of 50mm and a pore size of 0.22 μm.
Example 1
(1) Measuring 0.3ml of acetic acid at room temperature, adding deionized water to dilute the acetic acid to 10ml to obtain an acetic acid solution with the volume concentration of 3%, weighing 250mg of chitosan to disperse the chitosan into the 3% acetic acid solution, heating and stirring the mixture at 60 ℃ to obtain a chitosan dispersion solution, weighing 25mg of carbon nanotubes to add the carbon nanotubes into the chitosan dispersion solution, and treating the mixture in an ice water bath for 2 hours by using a cell ultrasonic crusher to uniformly disperse the carbon nanotubes to obtain a carbon nanotube-chitosan dispersion solution;
(2) pouring the carbon nanotube-chitosan dispersion liquid obtained in the step (1) into a sand core funnel, and performing suction filtration by using acetate fiber filter paper as a filter membrane through a circulating water type vacuum pump. And after the carbon nanotube-chitosan/cellulose acetate filter paper film is formed by suction filtration, namely the carbon nanotube-chitosan dispersion liquid loses fluidity, the carbon nanotube-chitosan/cellulose acetate filter paper film is dried in a 50 ℃ oven for 2 hours to obtain the carbon nanotube-chitosan/cellulose acetate filter paper film, and the multi-stimulus response actuation film can respond to photo-thermal stimulus, humidity and electric-thermal stimulus to generate deformation.
As shown in fig. 1, the surface of the carbon nanotube-chitosan film has many pores.
As shown in FIG. 2, it is shown that the carbon nanotube-chitosan thin film and the acetate filter paper both have different network structures and are tightly combined, and the thickness of the carbon nanotube-chitosan/acetate filter paper thin film is 69 μm.
As shown in fig. 3, it is shown that the carbon nanotube-chitosan/cellulose acetate filter paper film can generate bending deformations of different degrees and directions, and each deformation can be automatically restored to its original shape.
As shown in fig. 4, it is shown that the carbon nanotube-chitosan/cellulose acetate filter paper film has a strong tensile stress. Test standards and methods: an electronic universal material tester is used, the sensor is 10kN, the clamp is 250N, and the stretching speed is 10 mm/min. Quantitative data: tensile breaking stress of 13.72MPa, elastic modulus of 277.48MPa, and tensile breaking displacement of 2.68 mm.
As shown in fig. 5, the relationship between the time for the carbon nanotube-chitosan/cellulose acetate filter paper film to be stimulated, deformed and recovered under the conditions of 3V direct current voltage, water vapor and infrared light irradiation and the bending angle is shown, and the bending angle of the film in the photo recorded by the digital camera is measured by using a ruler tool of Photoshop software.
Example 2
(1) Measuring 0.3ml of acetic acid at room temperature, adding deionized water to dilute the acetic acid to 10ml to obtain an acetic acid solution with the volume concentration of 3%, weighing 250mg of chitosan to disperse the chitosan into the 3% acetic acid solution, heating and stirring the mixture at 60 ℃ to obtain a chitosan dispersion solution, weighing 35mg of carbon nanotubes to add the carbon nanotubes into the chitosan dispersion solution, and treating the mixture in an ice water bath for 2 hours by using a cell ultrasonic crusher to uniformly disperse the carbon nanotubes to obtain a carbon nanotube-chitosan dispersion solution;
(2) pouring the carbon nanotube-chitosan dispersion liquid obtained in the step (1) into a sand core funnel, and performing suction filtration by using acetate fiber filter paper as a filter membrane through a circulating water type vacuum pump. And after the carbon nanotube-chitosan/cellulose acetate filter paper film is formed by suction filtration, namely the carbon nanotube-chitosan dispersion liquid loses fluidity, the carbon nanotube-chitosan/cellulose acetate filter paper film is dried in a 60 ℃ drying oven for 1.5 hours to obtain the carbon nanotube-chitosan/cellulose acetate filter paper film, and the multi-stimulus response actuation film can respond to photo-thermal stimulus, humidity and electric-thermal stimulus to generate deformation.
Example 3
(1) Measuring 0.3ml of acetic acid at room temperature, adding deionized water to dilute the acetic acid to 10ml to obtain an acetic acid solution with the volume concentration of 3%, weighing 250mg of chitosan to disperse the chitosan into the 3% acetic acid solution, heating and stirring the mixture at 60 ℃ to obtain a chitosan dispersion solution, weighing 45mg of carbon nanotubes to add the carbon nanotubes into the chitosan dispersion solution, and treating the mixture in an ice water bath for 2 hours by using a cell ultrasonic crusher to uniformly disperse the carbon nanotubes to obtain a carbon nanotube-chitosan dispersion solution;
(2) pouring the carbon nanotube-chitosan dispersion liquid obtained in the step (1) into a sand core funnel, and performing suction filtration by using acetate fiber filter paper as a filter membrane through a circulating water type vacuum pump. And after the carbon nanotube-chitosan/cellulose acetate filter paper film is formed by suction filtration, namely the carbon nanotube-chitosan dispersion liquid loses fluidity, the carbon nanotube-chitosan/cellulose acetate filter paper film is dried in a 70 ℃ drying oven for 1h to obtain the carbon nanotube-chitosan/cellulose acetate filter paper film, and the multi-stimulus response actuation film can respond to photo-thermal stimulus, humidity and electric-thermal stimulus to generate deformation.
Comparative example
CN106058038A adopts repeated blade coating and repeated drying to compound the double-layer film, but the invention directly compounds the double-layer film through suction filtration, 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 recovered in 40s, while the three response deformation processes of the invention are relatively fast, and the film is completely recovered in about 10s (figure 5), so that the reaction rate is greatly improved. CN106058038A can only respond to voltage stimulation, but the invention can respond to voltage, water vapor and infrared light respectively, and the applicable environment is more diversified.
Claims (10)
1. An actuating membrane, wherein the membrane comprises a carbon nanotube-chitosan membrane layer and a microporous filter membrane layer.
2. The film according to claim 1, wherein in the carbon nanotube-chitosan film layer, the mass ratio of the carbon nanotubes to the chitosan is 1:9-2: 8; the microporous filter membrane layer is an acetate fiber microporous filter membrane layer.
3. The membrane of claim 1, wherein the actuating membrane has a double-layer network structure and a thickness of 30-100 μm.
4. A method of making an actuation film, comprising:
(1) adding the carbon nano tube into the chitosan dispersion liquid, and treating to obtain carbon nano tube-chitosan dispersion liquid;
(2) and carrying out suction filtration and drying on the carbon nanotube-chitosan dispersion liquid to obtain the actuating film.
5. The method according to claim 4, wherein the carbon nanotubes in the step (1) are acidified carbon nanotubes.
6. The method according to claim 4, wherein the solvent of the chitosan dispersion of step (1) is acetic acid solution; the chitosan dispersion liquid is: uniformly dispersing chitosan powder in acetic acid solution, heating and stirring at 50-70 ℃ and at the rotation speed of 400-.
7. The preparation method according to claim 4, wherein the treatment in the step (1) is specifically: and (5) treating the cells by using an ultrasonic crusher for 1-2 h.
8. The preparation method according to claim 4, wherein the suction filtration in the step (2) is specifically: pouring the carbon nanotube-chitosan dispersion liquid into a sand core funnel, and performing suction filtration by using an acetate fiber microporous filter membrane through a circulating water type vacuum pump; the drying temperature is 50-70 ℃ and the drying time is 1-2 h.
9. An actuating membrane prepared by the method of claim 4.
10. Use of an actuating membrane according to claim 1.
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| CN112520685A (en) * | 2020-12-04 | 2021-03-19 | 青岛大学 | Double-layer thin film actuator and preparation method thereof |
| CN113603913A (en) * | 2021-08-24 | 2021-11-05 | 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 |
| CN117488480A (en) * | 2024-01-03 | 2024-02-02 | 东华大学 | Asymmetric functional fiber membrane and preparation method and application thereof |
| CN117488482A (en) * | 2023-12-29 | 2024-02-02 | 东华大学 | Asymmetric deformed fiber membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112520685A (en) * | 2020-12-04 | 2021-03-19 | 青岛大学 | Double-layer thin film actuator and preparation method thereof |
| CN112520685B (en) * | 2020-12-04 | 2024-03-01 | 青岛大学 | Double-layer film actuator and preparation method thereof |
| CN113603913A (en) * | 2021-08-24 | 2021-11-05 | 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 |
| 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 |
| CN117488482A (en) * | 2023-12-29 | 2024-02-02 | 东华大学 | Asymmetric deformed fiber membrane 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 |
| CN117488480A (en) * | 2024-01-03 | 2024-02-02 | 东华大学 | Asymmetric functional 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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