CN109135286B - Electric heating phase change actuator based on graphene/nano silver-latex film and manufacturing method thereof - Google Patents

Electric heating phase change actuator based on graphene/nano silver-latex film and manufacturing method thereof Download PDF

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CN109135286B
CN109135286B CN201810744365.3A CN201810744365A CN109135286B CN 109135286 B CN109135286 B CN 109135286B CN 201810744365 A CN201810744365 A CN 201810744365A CN 109135286 B CN109135286 B CN 109135286B
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phase change
graphene
thermal feedback
latex film
change actuator
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黄英
胡伟
刘平
郭小辉
郝超
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Hefei University of Technology
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/08Metals
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    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0806Silver
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Abstract

The invention discloses an electrothermal phase change actuator based on a graphene/nano silver-latex film and a manufacturing method thereof. Compared with the existing actuator, the actuator has the characteristics of simple manufacture, large feedback force range, low driving voltage and controllable feedback force, and can be used for medicine, underwater detection, manipulators and wearable devices.

Description

Electric heating phase change actuator based on graphene/nano silver-latex film and manufacturing method thereof
Technical Field
The invention belongs to the field of electrothermal phase change actuators, and particularly relates to a feedback force controllable electrothermal phase change actuator based on a graphene/nano silver-latex film and a manufacturing method thereof.
Background
An actuator is a device that converts other forms of energy (including chemical, light, electrical, and thermal) into mechanical energy via a control signal. The feedback is widely applied to the fields of man-machine interaction, artificial limbs, medical equipment, bionic application, touch display, cargo transportation and the like.
The programmable soft chemical mechanical actuator studied by p.yuan et al uses a chemical reaction to convert chemical energy into mechanical energy. However, such actuators have the obvious disadvantages of long response time and poor repeatability. It is therefore necessary to replace the chemical solution to maintain the performance of the actuator. Most of the current research is based on electroactive polymer actuators. Such actuators are largely divided into two main categories: electronic and ionic, and mostly sheet-like structures. The electronic actuator is deformed by using the principle of expansion with heat and contraction with cold of materials. By bonding two or more materials having different coefficients of thermal expansion together, temperature changes can cause the materials to contract or expand, eventually bending and creating a feedback force. In earlier studies, the materials used were typically metals, graphene or graphene oxide. In recent studies, researchers have found that super-aligned carbon nanotubes have better performance. Single-walled carbon nanotube/polymer-based drives have transparent features and are expected to be developed in stealth robots. Liqingwei et al studied low voltage (20-200V) anisotropic carbon nanotube sheet actuators that could simulate human hand bending movements. Researchers developing such actuators strive to lower the drive voltage, shorten the response time, and increase the feedback force. The key scientific problems to be solved show an opposite relationship, and are difficult to be realized in a research. After long-term research, the driving voltage generally drops below 50V, and the driving voltage is lower than 20V in recent research results. The feedback force of the electroactive polymer actuator is difficult to further increase. Since the thickness requirement is very high (typically not more than 1mm) to ensure flexibility and rapidity, this greatly limits the amount of feedback force that can be applied, typically by holding up only a light sponge. Researchers are not limited to the study of electrical stimulation actuators. They also investigated actuators sensitive to light, humidity and temperature. Some actuators may respond to multiple stimuli simultaneously, which may increase response speed and may bend to both sides to meet more complex requirements. Graphene oxide and graphene are often used as moisture sensitive materials due to their swelling properties. The research of Mingcen Weng et al is that a bidirectional bending response actuator is made by depositing a pencil on paper, which can respond to humidity and illumination at the same time, so that the sensor is in different humidity environments, and bidirectional bending of the actuator can be realized through the sensitivity of the paper to humidity.
The high feedback force provided by pneumatic actuators is preferred by researchers because conventional actuators provide only a small feedback force. Existing pneumatic actuators achieve expansion by inflating a flexible bladder. However, this method requires an external inflation device, so it is inflexible and not easily controllable.
Therefore, solving the problems of large feedback force, flexibility and controllability is a trend in the development of actuators at present.
Disclosure of Invention
The invention provides an electrothermal phase change actuator based on a graphene/nano silver-latex film and a manufacturing method thereof based on a reverse mold-adhesion-injection method, and aims to solve the problems of large driving voltage, small feedback force and uncontrollable feedback force of the conventional actuator, so that the actuator is suitable for occasions needing to accurately control the feedback state.
The invention solves the technical problem and adopts the following technical scheme:
the invention relates to an electrothermal phase change actuator based on a graphene/nano silver-latex film, which is characterized in that:
the electrothermal phase change actuator comprises a thermal feedback substrate; the thermal feedback substrate is obtained by mixing graphene and nano silver serving as conductive fillers with silicon rubber and forming;
a groove is formed in the thermal feedback substrate, and an emulsion film cover plate is packaged on the upper surface of the thermal feedback substrate, so that the groove becomes a closed cavity in which phase change material alcohol is stored;
the latex film cover sheet is formed by wrapping a stretchable flexible latex film on a copper sheet which is as large as the upper surface of the thermal feedback substrate; the latex film cover plate is exposed on the copper sheet in the area right above the groove of the thermal feedback substrate and is provided with a plurality of through holes, so that the latex film on the upper surface of the copper sheet is communicated with the groove of the thermal feedback substrate.
The feedback force controllable electrothermal phase change actuator takes graphene/nano silver/silicon rubber as a thermal feedback substrate, takes alcohol as a phase change material of the actuator, and takes a stretchable elastic latex film as an actuating film of the actuator.
Further, in the conductive filler, the mass ratio of graphene to nano silver is 1: 4.5; the mass of the conductive filler accounts for 45-55% of the total mass of the conductive filler and the silicon rubber.
Furthermore, the electric heating phase change actuator is powered by the square wave signal with the adjustable duty ratio, so that the electric heating phase change actuator can reach different stable states of heat absorption and heat dissipation balance under different duty ratios, and different feedback forces are obtained. Furthermore, the electric heating phase change actuator realizes the controllability of the displacement and the feedback force of the latex film and the step difference control of the feedback force of 0.02N, and the maximum feedback force exceeds 1N. The actuator is driven by a square wave signal with adjustable duty ratio, and the actuator achieves the balance of heat absorption and heat dissipation through the expansion and contraction of the latex film so as to realize the function of controllable feedback state or feedback force. The larger the duty cycle, the faster the rate of evaporation of the alcohol, the higher the latex film expansion, the greater the feedback force, and vice versa.
Furthermore, the thermal feedback substrate is cuboid, alcohol is convenient to store, multi-surface heating is achieved, and the speed is high.
The manufacturing method of the electrothermal phase change actuator based on the graphene/nano silver-latex film comprises the following steps:
step 1, weighing graphene and nano silver, dissolving the graphene and the nano silver into solvent naphtha, stirring uniformly, sequentially performing 30-minute ultrasonic dispersion and 2-hour magnetic stirring, adding silicon rubber, and continuing magnetic stirring until the mixed solution is in a semi-solid state to obtain a composite conductive colloid;
pouring the composite conductive colloid into a mold, and air-drying at room temperature to obtain a thermal feedback substrate with a groove;
step 2, taking a copper sheet with the same size as the upper surface of the thermal feedback substrate, and forming a plurality of through holes in an area corresponding to the grooves of the copper sheet and the thermal feedback substrate; wrapping all areas of the copper sheet except the position corresponding to the groove of the thermal feedback substrate with a latex film, and adhering the areas through epoxy resin AB glue to obtain a latex film cover plate;
step 3, adhering the latex film cover plate and the thermal feedback substrate through epoxy resin AB glue to enable the groove to be a closed cavity;
and 4, injecting alcohol into the closed cavity from one side of the thermal feedback substrate by using an injector to fill the closed cavity with the alcohol, connecting electrodes on two sides of the thermal feedback substrate through conductive silver paste, and curing at room temperature to obtain the feedback force controllable electric heating phase change actuator based on the graphene/nano silver-emulsion film.
In order to enable the latex film and the thermal feedback substrate to be firmly adhered, the latex film is firstly used for covering the copper sheet with the through hole to form the square top cover, and then the square top cover is adhered to the thermal feedback substrate, so that the latex film on the adhered part is horizontally pulled instead of longitudinally pulled after the latex film expands, and the adhesion is more firmly ensured.
According to a power calculation formula: p is U2the/R is obtained that the power and the resistance are in inverse proportion under the condition that the driving voltage is not changed, so that the resistivity of the thermal feedback substrate needs to be lower in order to increase the heating rate of the thermal feedback substrate. The nano silver particles are adsorbed on the surface of the graphene, and the resistivity can be effectively reduced through the synergistic effect of the nano silver particles and the graphene. The mass ratio of the graphene to the nano silver is 1:4.5, accounting for 45-55% of the total mass of the prepared thermal feedback substrate. When the mass ratio of the graphene to the nano silver is too large, only a few nano silver particles are distributed on the surface of the graphene, the synergistic effect is poor, and the resistivity is high; when the mass of the graphene and the nano silver is smaller, the nano silver is agglomerated, the conductivity of the graphene is affected, and the resistivity is higher.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the existing actuator, the actuator has the characteristics of simple manufacture, large feedback force range, low driving voltage and controllable feedback force, and can be used for medicine, underwater detection, manipulators and wearable devices.
2. According to the invention, graphene and nano-silver are selected as the composite conductive filler, and the normal conductivity of the graphene nanosheet is two orders of magnitude smaller than the in-plane conductivity. The filled nano silver is attached to the surface of the graphene, so that the electronic exchange of the surface of the graphene can be promoted, the resistivity of the composite material can be obviously reduced, the thermal response rate of the thermal feedback substrate can be improved, and the thermal response rate of the thermal feedback substrate can be further improved by taking the nano silver as a metal material.
3. The invention selects alcohol as the filler of the cavity of the electrothermal phase change actuator, and the alcohol is low in boiling point and easy to volatilize, so that the electrothermal phase change actuator is easier to start, namely the driving voltage is greatly reduced.
4. When the actuator works, the alcohol evaporates to increase the air pressure in the cavity of the electrothermal phase change actuator, so that the latex film expands, the latex film moves upwards to provide a feedback force, and the feedback force provided by the air pressure is obviously higher than the feedback force provided by other existing actuators.
5. The invention realizes the control of the electrothermal phase change actuator by controlling the balance of heat absorption and heat dissipation of the electrothermal phase change actuator. The square wave signal with the adjustable duty ratio is used for supplying power to the actuator, so that the actuator achieves different stable states of heat absorption and heat dissipation balance, different feedback forces are obtained, and accurate and stable control over the feedback states is achieved.
Drawings
Fig. 1 is a schematic cross-sectional structure diagram of the electrothermal phase change actuator based on graphene/nano silver-latex film, wherein the reference numbers in the diagram are as follows: 1 is a thermal feedback substrate, 2 is a latex film, 3 is a copper sheet, 3a is a through hole, and 4 is alcohol.
Fig. 2 is an electronic photograph of the electrothermal phase change actuator according to embodiment 1 of the present invention (the left and right two are taken at different angles of the same device).
Fig. 3 is a Scanning Electron Microscope (SEM) image at different magnifications of the composite conductive colloid prepared in example 1 of the present invention.
Fig. 4 is an electric heating response diagram of an electric heating film obtained by graphene and nano silver in different mass ratios in embodiment 1 of the present invention, wherein: fig. 4(a) and 4(b) are the sheet resistance and the electrothermal response of the electrothermal film obtained by graphene and nano silver under different mass ratios, respectively; fig. 4(c) is an electrothermal response diagram of an electrothermal film (GR/Ag ═ 1:4.5) to different voltages; fig. 4(d) is a schematic diagram showing a relationship between a duty ratio and a stable temperature of an electrothermal film (GR/Ag ═ 1:4.5) under a driving voltage having an amplitude of 10V and a frequency of 1 Hz.
Fig. 5 is a state change diagram (fig. 5(a)) of the electrothermal phase change actuator manufactured in example 1 of the present invention under a constant voltage of 6V, a height change of the emulsion film (fig. 5(b)), and a measured feedback force (fig. 5 (c)).
Fig. 6 is a corresponding relationship between the duty ratio and the expansion height of the latex film of the electrothermal phase change actuator manufactured in embodiment 1 of the present invention under a driving voltage with an amplitude of 6V and a frequency of 1 Hz.
Fig. 7 is a corresponding relationship between the duty ratio and the feedback force of the electrothermal phase change actuator under the driving voltage with the amplitude of 6V and the frequency of 1 Hz.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
As shown in fig. 1, the electrothermal phase change actuator of the present embodiment includes a thermal feedback substrate 1; the thermal feedback substrate is obtained by mixing graphene and nano silver serving as conductive fillers with silicon rubber and forming;
a groove is arranged on the thermal feedback substrate 1, and an emulsion film cover plate is packaged on the upper surface of the thermal feedback substrate, so that the groove becomes a closed cavity in which phase change material alcohol 4 is stored;
the latex film cover sheet is formed by wrapping a stretchable flexible latex film 2 outside a copper sheet 3 with the same size as the upper surface of the thermal feedback substrate; the copper sheet of the latex film cover plate in the area right above the groove of the thermal feedback substrate is exposed (namely the latex film only covers the whole upper surface and part of the lower surface of the copper sheet, and the area of the lower surface corresponding to the groove is not covered), and a plurality of through holes 3a are arranged, so that the latex film on the upper surface of the copper sheet is communicated with the groove of the thermal feedback substrate.
Fig. 2 is an electron photograph of the electrothermal phase change actuator of this example, the size of the entire actuator is 10mm x 4mm (length x width x height, wherein the height of the thermal feedback substrate is about 3.5mm), the size of the grooves is about 7mm x 2.5mm (length x width x height), and the copper sheet has a total of four through holes with a diameter of about 0.5 mm.
The manufacturing method of the electrothermal phase change actuator comprises the following steps:
step 1, weighing 0.4g of graphene and 1.8g of nano silver (the mass ratio of the graphene to the nano silver is 1:4.5), dissolving in 15mL of solvent naphtha, stirring uniformly, then sequentially performing ultrasonic dispersion for 30 minutes and magnetic stirring for 2 hours (at room temperature), then adding a proper amount of silicon rubber (the mass of the conductive filler accounts for 50% of the total mass of the conductive filler and the silicon rubber), and continuing the magnetic stirring until the mixed solution is in a semi-solid state, thereby obtaining the composite conductive colloid. Scanning Electron Micrographs (SEM) at different magnifications are shown in fig. 3, and it can be seen that Ag particles are uniformly distributed in the graphene sheet. From this observation, it can be concluded that Ag particles are uniformly distributed without significant agglomeration in the planar direction and that particles exist between graphene layers in the perpendicular direction, which ensures uniform distribution of temperature in electrothermal measurements.
And pouring the composite conductive colloid into a mold, and air-drying at room temperature to obtain the grooved thermal feedback substrate.
Step 2, taking a copper sheet with the same size as the upper surface of the thermal feedback substrate, and forming a through hole in an area corresponding to the groove of the copper sheet and the thermal feedback substrate; wrapping all areas of the copper sheet except the position corresponding to the groove of the thermal feedback substrate with a latex film, and adhering the areas through epoxy resin AB glue to obtain a latex film cover plate;
step 3, adhering the latex film cover plate and the thermal feedback substrate through epoxy resin AB glue to enable the groove to be a closed cavity;
and 4, injecting alcohol into the closed cavity from one side of the thermal feedback substrate by using an injector to enable the closed cavity to be filled with the alcohol, connecting electrodes on two sides of the thermal feedback substrate through conductive silver paste, and curing at room temperature to obtain the feedback force controllable electrothermal phase change actuator based on the graphene/nano silver-emulsion film.
In order to test the influence of graphene and nano-silver with different mass ratios on the electrothermal response of the thermal feedback substrate, the composite conductive colloid is prepared according to the same method, and is manufactured into an electrothermal film (the length is 30mm, the width is 30mm, and the thickness is 660 μm), wherein the mass ratios of the graphene and the nano-silver are respectively 1:1.8, 1:4.5 and 1:9, and the mass of the conductive filler accounts for 50% of the total mass of the conductive filler and the silicon rubber, and the obtained electrothermal film is respectively marked as an electrothermal film (GR/Ag is 1:1.8), an electrothermal film (GR/Ag is 1:4.5) and an electrothermal film (GR/Ag is 1: 9). Fig. 4 shows the sheet resistance (fig. 4(a)) and the electrothermal response (fig. 4(b)) of the electrothermal film obtained by graphene and nano silver under different mass ratios. It can be seen that the performance is optimal when the mass ratio of graphene to nano silver is 1: 4.5.
Fig. 4(c) is an electrothermal response diagram of an electrothermal film (GR/Ag ═ 1:4.5) to different voltages; fig. 4(d) is a schematic diagram showing a relationship between a duty ratio and a stable temperature of an electrothermal film (GR/Ag ═ 1:4.5) under a driving voltage having an amplitude of 10V and a frequency of 1 Hz.
Fig. 5 is a state change diagram (fig. 5(a)) of the electrothermal phase change actuator manufactured in this example under the constant voltage of 6V, a corresponding height change of the latex film (fig. 5(b)) and a measured feedback force (fig. 5(c)), and it can be seen that the feedback force reaches a maximum value of 0.54N when the power supply time is 20 s. In addition, the feedback force is further increased by continuously increasing the power supply time, and reaches 1.2N when the time is 30 s.
Fig. 6 is a corresponding relationship between the duty ratio and the expansion height of the emulsion film of the electrothermal phase change actuator manufactured in this embodiment under the driving voltage with the amplitude of 6V and the frequency of 1 Hz. Fig. 7 shows a corresponding relationship between a duty ratio and a feedback force of the electrothermal phase change actuator, under a driving voltage with an amplitude of 6V and a frequency of 1Hz, which can achieve a minimum force difference control of 0.02N.
The present invention is not limited to the above exemplary embodiments, and any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. Electric heat phase transition executor based on graphite alkene/nanometer silver-emulsion membrane, its characterized in that:
the electrothermal phase change actuator comprises a thermal feedback substrate; the thermal feedback substrate is obtained by mixing graphene and nano silver serving as conductive fillers with silicon rubber and then forming;
a groove is formed in the thermal feedback substrate, and an emulsion film cover plate is packaged on the upper surface of the thermal feedback substrate, so that the groove becomes a closed cavity in which phase change material alcohol is stored;
the latex film cover sheet is formed by wrapping a stretchable flexible latex film on a copper sheet which is as large as the upper surface of the thermal feedback substrate; the latex film cover plate is exposed on the copper sheet in the area right above the groove of the thermal feedback substrate and is provided with a plurality of through holes, so that the latex film on the upper surface of the copper sheet is communicated with the groove of the thermal feedback substrate.
2. The electro-thermal phase change actuator of claim 1, wherein: in the conductive filler, the mass ratio of graphene to nano silver is 1: 4.5; the mass of the conductive filler accounts for 45-55% of the total mass of the conductive filler and the silicon rubber.
3. The electro-thermal phase change actuator of claim 1, wherein: the electric heating phase change actuator is powered by the square wave signal with the adjustable duty ratio, so that the electric heating phase change actuator can reach different stable states of heat absorption and heat dissipation balance under different duty ratios, and different feedback forces are obtained.
4. The electro-thermal phase change actuator of claim 3, wherein: the electrothermal phase change actuator realizes the controllability of the displacement and the feedback force of the latex film and the step difference control of the feedback force of 0.02N, and the maximum feedback force exceeds 1N.
5. The electro-thermal phase change actuator of claim 1, wherein: the thermal feedback substrate is cuboid.
6. The method for manufacturing the electrothermal phase change actuator based on the graphene/nano silver-latex film according to any one of claims 1 to 5, which is characterized by comprising the following steps:
step 1, weighing graphene and nano silver, dissolving the graphene and the nano silver into solvent naphtha, stirring uniformly, sequentially performing 30-minute ultrasonic dispersion and 2-hour magnetic stirring, adding silicon rubber, and continuing magnetic stirring until the mixed solution is in a semi-solid state to obtain a composite conductive colloid;
pouring the composite conductive colloid into a mold, and air-drying at room temperature to obtain a thermal feedback substrate with a groove;
step 2, taking a copper sheet with the same size as the upper surface of the thermal feedback substrate, and forming a plurality of through holes in an area corresponding to the grooves of the copper sheet and the thermal feedback substrate; wrapping all areas of the copper sheet except the position corresponding to the groove of the thermal feedback substrate with a latex film, and adhering the areas through epoxy resin AB glue to obtain a latex film cover plate;
step 3, adhering the latex film cover plate and the thermal feedback substrate through epoxy resin AB glue to enable the groove to be a closed cavity;
and 4, injecting alcohol into the closed cavity from one side of the thermal feedback substrate by using an injector to fill the closed cavity with the alcohol, connecting electrodes on two sides of the thermal feedback substrate through conductive silver paste, and curing at room temperature to obtain the electrothermal phase change actuator based on the graphene/nano silver-emulsion film.
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