CN113278195B - Preparation method and application of electric field induction driven ionic electroactive polymer - Google Patents
Preparation method and application of electric field induction driven ionic electroactive polymer Download PDFInfo
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- CN113278195B CN113278195B CN202110549553.2A CN202110549553A CN113278195B CN 113278195 B CN113278195 B CN 113278195B CN 202110549553 A CN202110549553 A CN 202110549553A CN 113278195 B CN113278195 B CN 113278195B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
Abstract
The invention discloses a preparation method and application of an electric field induction driven ionic type electroactive polymer. The ionic electroactive polymer driven by electric field induction does not need electrodes and has no electrode fatigue problem, the ionic electroactive polymer is driven to actuate by the dual action of ion concentration gradient and electric field force in the electric field, and deflection of 1 to 60 degrees can be rapidly generated in the electric field with the voltage of 1 to 10 kV and the frequency of 0.1 to 10 Hz. The electric field induction-driven ionic electroactive polymer is used for controlling the actions of grabbing, holding, releasing and the like of the VR glove, so that the force feedback of the polymer to hands is realized, and the visual and auditory feedback of VR is combined, so that the multi-sense effect of man-machine touch interaction is perfected.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method and application of an electric field induction driven ionic electroactive polymer.
Background
The intelligent material integrates sensing (a sensor), judging (a controller) and executing (a driver) into a whole, and is widely applied to the technical fields of aerospace, national defense safety, rehabilitation and health care and the like. Compared with the traditional intelligent driving materials such as Shape Memory Alloy (SMA), piezoelectric ceramic (PZ) and magnetic actuating material (EM), the electroactive polymer (EAP) has the advantages of light weight, corrosion resistance, high flexibility, simplicity and easiness in control, low energy consumption and the like, and becomes a novel intelligent driving material with wide application prospect. The united states Defense Advanced Research Program Agency (DARPA) research shows that: the energy density of EAP is much higher than that of the traditional intelligent material, and the EAP can be used as a high-efficiency, energy-saving, light and flexible driving source. At present, EAP has become a research hotspot in interdisciplinary fields of material chemistry, biomimetic mechanics, information technology, and the like.
As an ionic EAP, an ion exchange polymer-metal composite (IPMC) is composed of an ion exchange resin (e.g., perfluorosulfonic acid (Nafion), perfluorocarboxylic acid, polyetheretherketone, etc.) and an inert metal nanoelectrode (e.g., ag, au, pt, etc.) adsorbed on the surface of the resin. The structural characteristics of the ion exchange resin are as follows: the main chain is hydrophobic fluorocarbon skeleton; the side chain is hydrophilic acid radical and has ion exchange function. After crystallization and film formation, the hydrophilic groups in the polymer are subjected to microphase separation, and a plurality of water molecule migration channels are formed in the film. Under an electric field, hydrated cations carry certain solvent molecules to move to a cathode through a micro inner pipeline and are bound by a 'damming effect' of an electrode/polymer interface, a concentration gradient of the hydrated cations is formed between two electrodes, and macroscopically, anode contraction and cathode expansion are initiated, so that displacement and force output are shown to the outside, and the device can be used as an electric driver; on the contrary, the IPMC deforms to induce the unbalanced distribution of the surface charges thereof, resulting in the change of the surface electric field, thereby being used as a flexible displacement, strain and resonance sensor.
In conventional IPMC, metal nano-electrodes are fixed on the surface of a polymer matrix film by physical adsorption. Due to poor chemical compatibility of the electrode and the polymer, after long-time work, the metal nano block is gradually peeled off from the surface of the polymer, so that the conductivity of the electrode is lost, or the electric field on the surface of the electrode is unevenly distributed, the former attenuates the mechanical output performance of the IPMC, and the latter distorts the IPMC. When the peeling is severe, the IPMC stops working. The surface electrode of IPMC always has a large number of cracks, which are generated during the fabrication and driving processes. In addition, when the bending amplitude of the IPMC exceeds the yield limit of the metal nanoparticle electrode, the electrode crack is inevitably enlarged (deepened). The presence of these cracks causes the loss of electrolyte solution (including water, ionic liquids, organic solvents) and, particularly under pulsed electric fields, the loss of solvent is more severe. Loss of electrolyte solution necessarily causes a decrease in ionic conductivity within the parent membrane until finally conductivity is 0, and macroscopically IPMC stops working.
Existing IPMCs typically employ a three-layer sandwich structure, i.e., electrode/electrolyte membrane/electrode. The electrodes on both sides are prone to electrode fatigue during operation, which is manifested as electrode peeling or deep cracking, resulting in unstable actuation performance of IPMC and short operating life in air, and thus electrode fatigue is a main cause of the above defects. The electrolyte membrane has low ion exchange equivalent, large viscous resistance of solvated ion movement, and can not support rapid migration of a large number of ions at the same time, so that the low charge transfer capacity is another reason for the defects. Therefore, the improvement of the composition and structure of the IPMC is an effective method for improving the driving performance of the IPMC. In addition, the kinetics of IPMC motion are derived from ion concentration gradients within the electrolyte membrane, but this driving mechanism has not fully satisfied the power requirements of practical IPMC mechanisms.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of an electric field induction driven ionic electroactive polymer. From the preparation of the polymer, a gas-liquid two-phase exchange method is utilized to prepare a highly porous PVDF membrane, and then the porous PVDF membrane is soaked in an electrolyte solution to adsorb anions and cations for serving as an ionic electroactive polymer driven by electric field induction. The ionic electroactive polymer driven by electric field induction does not need electrodes and has no problems, and the ionic electroactive polymer is driven to actuate by using the dual functions of ion concentration gradient and electric field force in an electric field, so that the ionic electroactive polymer can deflect by 1 to 60 degrees in the electric field with the voltage of 1 to 10 kV and the frequency of 0.1 to 10 Hz.
The invention also provides application of the electric field induction driven ionic type electroactive polymer in VR gloves, and the electric field induction driven ionic type electroactive polymer is used for controlling the actions of grabbing, holding, releasing and the like of the VR gloves, so that force feedback of the polymer to human hands is realized, visual and auditory feedback of VR is combined, and the multi-sense effect of man-machine touch interaction is perfected.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation method of an electric field induction driven ionic electroactive polymer comprises the following steps:
(1) Completely dissolving polyvinylidene fluoride (PVDF) in N, N-Dimethylformamide (DMF), placing the solution in a vacuum box to remove bubbles, pouring the membrane solution into a 30 x 50 x 2 mm glass mold, placing the glass mold in a vacuum drying box filled with 300mL of deionized water, and preparing a porous PVDF membrane by a gas-phase exchange method;
(2) And (2) soaking the porous PVDF membrane prepared in the step (1) in a solution taking water, ionic liquid or inorganic salt as electrolyte for 24 hours, taking out the porous PVDF membrane, and wiping off redundant liquid on the surface to obtain the ionic electroactive polymer driven by electric field induction.
Further, the porous PVDF film prepared in the step (1) has the aperture of 70-100 nm and the thickness of 500 μm.
Further, when the porous PVDF membrane is prepared by the gas-phase exchange method in the step (1), the temperature of vacuum drying is 70-75 ℃ and the time is 12 hours.
Further, the ionic liquid in the step (2) is 1-ethyl-3-methylimidazolium tetrafluoroborate, and the inorganic salt is at least one of lithium chloride, sodium chloride or potassium chloride.
Further, the concentration of the solution using the inorganic salt as the electrolyte in the step (2) is 1 mol/L.
Further, the electric field induction driven ionic electroactive polymer is capable of rapidly responding to an electric field without electrodes and generating high frequency and large angle deflection, compared to conventional electroactive polymers (IPMC, DE, CP, etc.), which is a synergistic effect of electric field force and ion concentration gradient.
Furthermore, the electric field induction driven ionic electroactive polymer (the PVDF film after adsorbing the electrolyte) can generate deflection of 1 to 60 degrees in an electric field with the voltage of 1 to 10 kV and the frequency of 0.1 to 10 Hz.
The electric field induction driven ionic type electroactive polymer is applied to VR gloves, and human-machine touch interaction is realized by establishing mutual force feedback between the electric field induction driven ionic type electroactive polymer and human hands.
The invention has the beneficial effects that:
1) The PVDF porous membrane prepared by the invention has a large number of pipelines with the pore diameter of 70-100 nm inside, and provides a channel for the rapid transmission of anions and cations in the PVDF porous membrane, so that the membrane can deflect due to an ion concentration gradient generated by ion motion under an electric field.
2) Conventional IPMC uses metal nano-electrodes, there is electrode fatigue, so that actuation performance is degraded, or distortion occurs. The ionic electroactive polymer driven by electric field induction developed by the project induces the migration of anions and cations in an electrolyte membrane by using a pulse electric field, so as to generate an ion concentration gradient and drive the ion concentration gradient to move. The driver does not directly use electrodes, does not have electrode fatigue, does not generate heat, has long stable working life, and thoroughly solves the bottleneck of unstable actuating performance which puzzles IPMC commercialization for a long time.
3) The conventional IPMC is a flexible electric driver, the motive force of the movement is derived from the concentration gradient of solvated ions in an electrolyte membrane, and the defect of small force output exists. In the invention, the ionic electroactive polymer driven by electric field induction moves by utilizing the dual action of the ion concentration gradient and the electric field force, and the force and power output are greatly increased.
Drawings
FIG. 1 shows an actuation mechanism (a-c) and VR glove schematic (d, e) for electric field induced driving of ionic electroactive polymers.
FIG. 2 is an electron micrograph of a PVDF porous membrane.
FIG. 3 shows a driving device for driving an ionic electroactive polymer by electric field induction.
FIG. 4 is a photograph of an electric field induced deflection of an ionic electroactive polymer under an electric field based on a PVDF porous membrane.
FIG. 5 an electric field induced driven ionomeric electroactive polymer based on PVDF porous membrane applied to VR gloves.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
Preparation of PVDF porous film
PVDF (2.196 g) was weighed into a beaker containing N, N-dimethylformamide (15 mL), and after 2 hours of magnetic stirring, the PVDF was completely dissolved and placed in a vacuum chamber to remove air bubbles from the solution by vacuum. The solution was then poured into a 30 x 50 x 2 mm glass mold into a vacuum drying oven and a glass (300 mL) of deionized water was placed in the oven and heated at 75 ℃ for 12 hours to produce a porous PVDF membrane by gas phase exchange.
Example 2
Adsorption of PVDF porous membrane to water or ionic liquid as electrolyte
Adding two thirds of deionized water or ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) into a glass culture dish, completely soaking the PVDF porous membrane dried in an oven at 70 ℃ for 12 hours in the deionized water and the ionic liquid, and wiping off the redundant deionized water or the ionic liquid on the surface after 24 hours of soaking.
Example 3
Adsorption of inorganic salts as electrolytes for PVDF porous membranes
Lithium chloride, sodium chloride, potassium chloride and deionized water are respectively adopted to prepare lithium chloride, sodium chloride and potassium chloride solutions with the concentration of 1 mol/L. Adding two-thirds of the volume of lithium chloride or sodium chloride or potassium chloride solution into a glass culture dish, completely soaking the PVDF porous membrane dried for 12 hours in an oven at 70 ℃ in deionized water and ionic liquid, and wiping off the redundant inorganic salt solution on the surface after 24 hours of soaking.
Example 4
The microstructure of the PVDF porous membrane was observed by a field emission scanning electron microscope. The PVDF porous membrane is subjected to cold fracture by using liquid nitrogen, and then a layer of Pt nano particles is sputtered on the section of the PVDF membrane, so that the conductivity of the membrane is improved and the membrane is convenient to observe. As is apparent from FIG. 2, the PVDF porous membrane had a pore diameter of 70 to 100 nm and a thickness of 500 μm.
Example 5
Driving device for driving ionic electroactive polymer by electric field induction
Fig. 3 is a driving device for driving an ionic electroactive polymer by electric field induction, which comprises a clamp 1, an ionic electroactive polymer 2 driven by electric field induction, a measuring hole 3 of a laser displacement sensor and a copper sheet 4 with an area of 5 x 8 cm. The electric field induction driving ionic type electroactive polymer fixed by the clamp is arranged between the two copper sheets, and in an electric field formed between the copper sheets after the voltage is switched on, the electric field induction driving ionic type electroactive polymer can respond to the deflection of the electric field and is measured by the laser displacement sensor to deflect.
Example 6
Electric field induction driven high-frequency actuation of ionic electroactive polymers under electric field
And (3) placing the PVDF porous membrane adsorbing water in an electric field, wherein flexible electrodes are not fixed on two sides of the PVDF porous membrane. After the electric field is initiated, the PVDF membrane vibrates in high frequency towards both sides as shown in FIGS. 1 and 4. The positive and negative ions in the ionic liquid move towards two sides respectively under the drive of surface induced charges, and the PVDF membrane bends towards the anode because the volume of the positive ion group is larger than that of the negative ion group. In addition, the ability to dither is due to the combined action of ion concentration gradients and electric field forces.
Example 7
Electric field induction driven ionic electroactive polymer displacement after adsorbing different electrolytes
The PVDF porous membrane, which absorbed water, ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate), lithium chloride, sodium chloride, and potassium chloride solutions, was placed in a driving device, and the displacements at different voltages were recorded in table 1. Pure PVDF porous membranes exhibit minimal displacement because they do not adsorb electrolyte and do not contain any anions or cations, and do not have the effect of an ion concentration gradient. After absorbing water, ionic liquid or inorganic salt electrolyte, the displacement is obviously increased. Particularly, after the lithium chloride solution is adsorbed, the displacement is 2.99 mm under an electric field of 8kV, which is caused by the combined action of the ion concentration gradient and the electric field force.
TABLE 1 Displacement of PVDF porous membranes having different electrolytes adsorbed thereon
Example 8
Electric field induction driven ionic type electroactive polymer for VR gloves
The prepared electric field induction driven ionic type electroactive polymer is used in the field of human-computer touch interaction by combining a virtual reality technology. As shown in figure 5, electric field induction driven ionic electroactive polymer is used for replacing a micro-motor driven VR glove, so that force feedback of the polymer to a human hand is realized, visual and auditory feedback of VR is combined, and the multi-sense effect of human-computer touch interaction is perfected. The human-computer touch control device has the advantages that a more vivid movement effect can be generated, human-computer touch interaction is realized to a high degree, the size of a driving source can be greatly reduced, and the heating problem is avoided.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. An electric field induction driven ionic electroactive polymer, comprising: compared with the conventional electroactive polymer, the ionic electroactive polymer driven by electric field induction can rapidly respond to an electric field under the condition of no electrode and generate high frequency and large-angle deflection, and the response of the ionic electroactive polymer to the electric field is the synergistic effect of electric field force and ion concentration gradient;
the ionic electroactive polymer driven by electric field induction can deflect 1 to 60 degrees in an electric field with the voltage of 1 to 10 kV and the frequency of 0.1 to 10 Hz;
the preparation method of the electric field induction driven ionic electroactive polymer comprises the following steps:
(1) Completely dissolving polyvinylidene fluoride (PVDF) in N, N-Dimethylformamide (DMF), placing the solution in a vacuum box to remove bubbles, pouring the membrane solution into a glass mold, placing the glass mold in a vacuum drying box filled with deionized water, and preparing a porous PVDF membrane by a gas phase exchange method;
(2) Soaking the porous PVDF membrane prepared in the step (1) in a solution taking water, ionic liquid or inorganic salt as electrolyte for 24 hours, taking out the porous PVDF membrane, and wiping off redundant liquid on the surface to obtain an electric field induction driven ionic electroactive polymer;
the ionic liquid in the step (2) is 1-ethyl-3-methylimidazole tetrafluoroborate, and the inorganic salt is at least one of lithium chloride, sodium chloride or potassium chloride.
2. The method for preparing the electric field induction driven ionic electroactive polymer according to claim 1, comprising the following steps:
(1) Completely dissolving polyvinylidene fluoride (PVDF) in N, N-Dimethylformamide (DMF), placing the solution in a vacuum box to remove bubbles, pouring the membrane solution into a glass mold, placing the glass mold in a vacuum drying box filled with deionized water, and preparing a porous PVDF membrane by a gas phase exchange method;
(2) Soaking the porous PVDF membrane prepared in the step (1) in a solution taking water, ionic liquid or inorganic salt as electrolyte for 24 hours, taking out the porous PVDF membrane, and wiping off redundant liquid on the surface to obtain an electric field induction driven ionic electroactive polymer;
the pore diameter of the porous PVDF membrane prepared in the step (1) is 70 to 100 nm, and the thickness is 500 mu m;
the ionic liquid in the step (2) is 1-ethyl-3-methylimidazole tetrafluoroborate, and the inorganic salt is at least one of lithium chloride, sodium chloride or potassium chloride.
3. The method for preparing the electric field induction driven ionic electroactive polymer according to claim 2, wherein the method comprises the following steps: when the porous PVDF film is prepared by the gas-phase exchange method in the step (1), the temperature of vacuum drying is 70 to 75 ℃, and the time is 12 hours.
4. The method for preparing the electric field induction driven ionic electroactive polymer according to claim 2, wherein the method comprises the following steps: the concentration of the solution taking the inorganic salt as the electrolyte in the step (2) is 1 mol/L.
5. The electric field induction driven ionic electroactive polymer of claim 1, applied to VR gloves, wherein human-machine touch interaction is achieved by establishing force feedback between the electric field induction driven ionic electroactive polymer and human hands.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603567A (en) * | 2018-12-24 | 2019-04-12 | 郑州轻工业学院 | The preparation method and applications of the highly porous film of PVDF-PVP |
| CN110510570A (en) * | 2019-08-31 | 2019-11-29 | 三体次元信息科技（宁波）有限公司 | Sulfonation PVDF base IPMC electric actuator and preparation method thereof and the application in VR sense of touch gloves |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109603567A (en) * | 2018-12-24 | 2019-04-12 | 郑州轻工业学院 | The preparation method and applications of the highly porous film of PVDF-PVP |
| CN110510570A (en) * | 2019-08-31 | 2019-11-29 | 三体次元信息科技（宁波）有限公司 | Sulfonation PVDF base IPMC electric actuator and preparation method thereof and the application in VR sense of touch gloves |
Non-Patent Citations (1)
| Title |
|---|
| Hydrophilic Poly(vinylidene Fluoride) Film with Enhanced Inner Channels for Both Water- and Ionic Liquid-Driven Ion-Exchange Polymer Metal Composite Actuators;Dongjie Guo等;《ACS APPLIED MATERIALS & INTERFACES》;20190103;第11卷(第2期);第2386-2397页 * |
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