Double-layer thin film actuator and manufacturing method therefor

Abstract

The present invention relates to a double-layer thin film actuator and a manufacturing method therefor. The actuator is implemented as a double layer by applying, onto a sheet, a polymer composition prepared with the composition of agarose-PEDOT:PSS / PEG / methylene blue / MXene, and as a result of applying light to the double layer, the double layer reacts and is well driven, and thus can be effectively used as a thin film actuator.

Description

Double-layer thin-film actuator and method for manufacturing the same

[0001] The present invention was made under the support of the Ministry of Education under the project identification number 1345375525 and detailed project number 2016R1A6A1A03012845. The research management organization of the project is the National Research Foundation of Korea, the research project name is "Establishment of Academic Research Infrastructure for Science and Engineering", the research project name is "Development of Nano-Biochip with Brain Disease Drug Evaluation Function", the main organization is Sogang University, and the research period is from 2023-01-01 to 2023-12-31.

[0002] In addition, the present invention was made with the support of the Ministry of Science and ICT under the task identification number 1711180793 and the detailed task number 2022H1D3A2A02093530, and the research management specialized organization of the said task is the National Research Foundation of Korea, the research project name is "Support for Expansion of Talent Utilization", the research project name is "Ni-TiO2 / Photosystem II with Drug Screening Function and Muscle Bundle-Based Nano-Biohybrid Actuator", the main organization is Sogang University, and the research period is 2023-01-01 ~ 2023-12-31.

[0003] This patent application claims priority to Republic of Korea Patent Application No. 10-2023-0146918, filed with the Korean Intellectual Property Office on October 30, 2023, the disclosure of which is incorporated herein by reference.

[0004] The present invention relates to a double-layer thin-film actuator and a method for manufacturing the same, and more particularly, to a light-activated double-layer polymer / paper thin-film actuator manufactured with a composition of agarose-PEDOT:PSS / PEG / methylene blue / MXene and a method for manufacturing the same.

[0005] Nature has long been a source of inspiration for developing synthetic bio-hybrid devices that mimic the behavior of living organisms. Fascinated by the multidirectional movements achieved through flexibility and coordination between joints, researchers have conducted extensive research to integrate these capabilities into robotic systems. However, these efforts are limited, if not entirely based on simple methodologies and actuation driven solely by external stimuli.

[0006] When light is implemented as a free stimulus, it requires the fabrication of a variety of expensive light-driven actuators, such as liquid crystal polymer networks (LCNs), liquid crystal elastomers (LCEs), and liquid crystal polymers (LCPs). These types of polymers contain embedded photonic crystals, enabling the creation of smart materials and functions that aim to exhibit immediate responsiveness.

[0007] Synthetic robotic systems that operate by heat, light, chemicals, and humidity have always been a better choice because they do not require additional or external wiring, tubing for pressurized fluids, or other material connections, allowing soft robots to control autonomously and freely, enabling the creation of diverse and innovative systems.

[0008] However, applying low-energy signals to stimulate and control higher-level mechanical applications in various movements or automation is the key to these wireless stimulation signals. Other wireless stimuli, such as heat or chemicals, have demonstrated profound results in achieving actuation and reversible shape transitions. However, these modes have specific impacts on the overall environment.

[0009] For example, in the case of hydrogels, there is a tendency to affect the entire hydrogel system and its microstructure, and there are also limitations in precisely controlling specific, independent, and individual regions of actuators used in soft robots.

[0010] Accordingly, the inventors of the present invention fabricated a double-layer polymer / paper thin-film actuator based solely on light-triggered operation that does not affect the environment or microstructure of the system, and confirmed that it is effective not only for immediate responsiveness but also for precise operation or reversible shape transition of independent and individual parts of the system.

[0011] Accordingly, the purpose of the present invention is to provide a polymer comprising agarose and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate),

[0012] At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanine;

[0013] Mxene; and

[0014] One or more binder polymers selected from polyethylene glycol (PEG), polypropylene glycol (PPG), and polymethylmethacrylate;

[0015] It provides a polymer composition additionally comprising at least one selected from the group consisting of:

[0016] Another object of the present invention is to include agarose and PEDOT:PSS,

[0017] At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanin;

[0018] Mexico; and

[0019] One or more binder polymers selected from polyethylene glycol, polypropylene glycol and polymethyl methacrylate;

[0020] A polymer composition manufactured by polymerizing a polymer composition additionally comprising at least one selected from the group consisting of

[0021] A double-layer thin-film actuator comprising a polymer layer and a sheet layer is provided.

[0022] Another object of the present invention is to provide a method for manufacturing a thin film actuator comprising the following steps:

[0023] A first mixing step for preparing a polymer composition comprising agarose and PEDOT:PSS;

[0024] At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanin in the polymer composition;

[0025] Mexican; or

[0026] One or more binder polymers selected from polyethylene glycol, polypropylene glycol and polymethyl methacrylate;

[0027] A second mixing step of adding and mixing; and

[0028] A thin film forming step of forming a thin film by applying the above polymer composition onto a sheet.

[0029] The present invention relates to a double-layer thin-film actuator and a method for manufacturing the same. The actuator according to the present invention is not difficult to manufacture, and the polymer composition for manufacturing the actuator can maintain a stable liquid form for several months after manufacture. It was confirmed that the double-layer polymer / paper thin-film formed by applying the same reacts well to light and operates accordingly.

[0030] The present inventors prepared a polymer composition with the composition of agarose-PEDOT:PSS / PEG / methylene blue / MXene and applied it to a sheet layer to form a polymer layer, thereby fabricating a double-layer polymer / paper thin-film actuator.

[0031] Hereinafter, the present invention will be described in more detail.

[0032] One aspect of the present invention comprises agarose and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate),

[0033] At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanine;

[0034] Mxene; and

[0035] One or more binder polymers selected from polyethylene glycol (PEG), polypropylene glycol (PPG), and polymethylmethacrylate;

[0036] A polymer composition additionally comprising at least one selected from the group consisting of:

[0037] The term “mexene” in this specification refers to a two-dimensional nanomaterial formed by combining carbon (C) or nitrogen (N) with titanium (Ti), a transition metal.

[0038] In the present invention, the above-mentioned Mexine is Ti3C2, Ti2C, Ti3C2Tx, Ti3C2T x , Ti2CT x , Nb4C3T x , Ti3CNT x , Ta4C3T x , NB2CT x , V2CT x , NB4C3Tx It may be at least one selected from the group consisting of, for example, Ti3C2, but is not limited thereto.

[0039] Another aspect of the present invention comprises agarose and PEDOT:PSS,

[0040] At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanin;

[0041] Mexico; and

[0042] One or more binder polymers selected from polyethylene glycol, polypropylene glycol and polymethyl methacrylate;

[0043] A polymer composition manufactured by polymerizing a polymer composition additionally comprising at least one selected from the group consisting of

[0044] It is a double-layer thin-film actuator comprising a polymer layer and a sheet layer.

[0045] In the present invention, the above-mentioned Mexine is Ti3C2, Ti2C, Ti3C2Tx, Ti3C2T x , Ti2CT x , Nb4C3T x , Ti3CNT x , Ta4C3T x , NB2CT x , V2CT x , NB4C3T x It may be at least one selected from the group consisting of, for example, Ti3C2, but is not limited thereto.

[0046] The thickness of the polymer layer may be 0.1 to 50 mm, preferably 0.1 to 20 mm, 0.1 to 10 mm, 0.1 to 5 mm, 0.2 to 50 mm, 0.2 to 20 mm, 0.2 to 10 mm, 0.2 to 5 mm, 0.5 to 50 mm, 0.5 to 20 mm, 0.5 to 10 mm, 0.5 to 5 mm, 1 to 50 mm, 1 to 20 mm, 1 to 10 mm, 1 to 5 mm, 3 to 50 mm, 3 to 20 mm, 3 to 10 mm, or 3 to 5 mm, for example, but not limited thereto.

[0047] In the present invention, the sheet layer may be made of paper or polyimide, and may be made of paper, for example, but is not limited thereto.

[0048] Another aspect of the present invention is a method for manufacturing a thin film actuator comprising the following steps:

[0049] A first mixing step for preparing a polymer composition comprising agarose and PEDOT:PSS;

[0050] At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanin in the polymer composition;

[0051] Mexican; or

[0052] One or more binder polymers selected from polyethylene glycol, polypropylene glycol and polymethyl methacrylate;

[0053] A second mixing step of adding and mixing; and

[0054] A thin film forming step of forming a thin film by applying the above polymer composition onto a sheet.

[0055] In the present invention, the first mixing step may be performed by adding 0.1 to 4 g of agarose to 1 mL of PEDOT:PSS when preparing a polymer composition, and preferably, by adding 0.1 to 2 g, 0.1 to 1 g, 0.1 to 0.5 g, 0.2 to 4 g, 0.2 to 2 g, 0.2 to 1 g, 0.2 to 0.5 g, 0.4 to 4 g, 0.4 to 2 g, 0.4 to 1 g, or 0.4 to 0.5 g, and for example, by adding 0.4 g, but is not limited thereto.

[0056] The above first mixing step may be performed at 60 to 120°C, and preferably, at 60 to 110°C, 60 to 100°C, 60 to 90°C, 70 to 120°C, 70 to 110°C, 70 to 100°C, 70 to 90°C, 80 to 120°C, 80 to 110°C, 80 to 100°C, 80 to 90°C, 90 to 120°C, or 90 to 110°C, and for example, may be performed at 90 to 100°C, but is not limited thereto.

[0057] The first mixing step may be performed for 1 to 6 hours, preferably 1 to 5 hours, 1 to 4 hours, 1 to 3 hours, 2 to 6 hours, 2 to 5 hours, 2 to 4 hours, 2 to 3 hours, 3 to 6 hours, 3 to 5 hours, or 3 to 4 hours, for example, but not limited to, 3 hours.

[0058] In the present invention, the second mixing step may be to add and mix 0.1 to 15 mg of a photosensitizer, 5 to 500 mL of Mexene, and 5 to 500 mL of a binder polymer to 1 mL of PEDOT:PSS when preparing a polymer composition.

[0059] The photosensitizer may be preferably added in an amount of 0.1 to 10 mg, 0.1 to 5 mg, 0.1 to 2 mg, 0.2 to 15 mg, 0.2 to 10 mg, 0.2 to 5 mg, 0.2 to 2 mg, 0.5 to 15 mg, 0.5 to 10 mg, 0.5 to 5 mg, 0.5 to 2 mg, 1 to 15 mg, 1 to 10 mg, 1 to 5 mg, 1 to 2 mg, 1.5 to 15 mg, 1.5 to 10 mg, 1.5 to 5 mg, or 1.5 to 2 mg per 1 mL of PEDOT:PSS, and for example, it may be added in an amount of 1.5 mg, but is not limited thereto.

[0060] The above-described MXene may be preferably performed by adding 5 to 200 mL, 5 to 100 mL, 5 to 50 mL, 10 to 500 mL, 10 to 200 mL, 10 to 100 mL, 10 to 50 mL, 20 to 500 mL, 20 to 200 mL, 20 to 100 mL, 20 to 50 mL, 50 to 500 mL, 50 to 200 mL, or 50 to 100 mL to 1 mL of PEDOT:PSS, for example, by adding 50 mL.

[0061] The above-mentioned Mexine may be utilized under a concentration condition of 0.01 to 1 M, preferably 0.01 to 0.5 M, 0.01 to 0.2 M, 0.01 to 0.1 M, 0.1 to 1 M, 0.1 to 0.5 M, or 0.1 to 0.2 M, and for example, it may be performed by adding 0.1 M.

[0062] The binder polymer may be added preferably in an amount of 5 to 200 mL, 5 to 100 mL, 5 to 50 mL, 10 to 500 mL, 10 to 200 mL, 10 to 100 mL, 10 to 50 mL, 20 to 500 mL, 20 to 200 mL, 20 to 100 mL, 20 to 50 mL, 50 to 500 mL, 50 to 200 mL, or 50 to 100 mL per 1 mL of PEDOT:PSS, for example, it may be added in an amount of 50 mL.

[0063] The second mixing step may preferably be performed by adding a photosensitizer or a mexene, and for example, it may be performed by adding both a photosensitizer and a mexene, but is not limited thereto. More preferably, it may be performed by adding all of a photosensitizer, a mexene, and a binder polymer, but is not limited thereto.

[0064] In the present invention, the above-mentioned Mexine is Ti3C2, Ti2C, Ti3C2Tx, Ti3C2T x , Ti2CT x , Nb4C3T x , Ti3CNT x , Ta4C3T x , NB2CT x , V2CT x , NB4C3T xIt may be at least one selected from the group consisting of, for example, Ti3C2, but is not limited thereto.

[0065] In the present invention, the method may additionally include a polymerization step performed by adding a chlorine salt or a bromine salt to the polymer composition after the second mixing step.

[0066] The above chloride salt may be, for example, potassium chloride, and the above bromide salt may be, for example, N-bromosuccinimide, but is not limited thereto.

[0067] The potassium chloride may be added preferably in an amount of 0.1 to 10 mg per 1 mL of PEDOT:PSS, preferably 0.1 to 5 mg, 0.1 to 2 mg, 0.1 to 1 mg, 0.2 to 10 mg, 0.2 to 5 mg, 0.2 to 2 mg, 0.2 to 1 mg, 0.5 to 10 mg, 0.5 to 5 mg, 0.5 to 2 mg, 0.5 to 1 mg, 1 to 10 mg, or 1 to 5 mg, for example, 1 to 2 mg may be added, but is not limited thereto.

[0068] In the present invention, the sheet layer may be made of paper or polyimide, and may be made of paper, for example, but is not limited thereto.

[0069] In the present invention, the thin film forming step may be performed through a doctor blade or a painting method, and for example, may be performed through a doctor blade method, but is not limited thereto.

[0070] The present invention relates to a double-layer thin-film actuator and a method for manufacturing the same. The actuator is implemented as a double layer by applying a polymer composition manufactured with a composition of agarose-PEDOT:PSS / PEG / methylene blue / MXene onto a sheet layer, and when light is applied thereto, it reacts and is well actuated, so that it can be effectively used as a thin-film actuator.

[0071] FIG. 1a is a schematic diagram showing a process for fabricating a bilayer polymer / paper thin film actuator composed of agarose-PEDOT:PSS / PEG / methylene blue / MXene according to one embodiment of the present invention.

[0072] FIG. 1b is a photograph of a bilayer polymer / paper thin film actuator composed of agarose-PEDOT:PSS / PEG / methylene blue / MXene manufactured according to one embodiment of the present invention.

[0073] Figure 2a is a schematic diagram showing an agarose-PEDPT:PSS polymerization process manufactured according to one embodiment of the present invention.

[0074] FIG. 2b is a scanning electron microscope (SEM) photograph of a single layer of agarose-PEDOT:PSS manufactured according to one embodiment of the present invention.

[0075] FIG. 2c is a graph of Fourier-transform infrared spectroscopy (FT-IR) analysis data for agarose-PEDOT:PSS manufactured according to one embodiment of the present invention.

[0076] FIG. 3a is a photograph confirming the light-induced operation of an agarose-PEDOT:PSS-based actuator manufactured according to one embodiment of the present invention.

[0077] FIG. 3b is a photograph confirming the light-induced operation of an agarose-PEDOT:PSS / methylene blue-based actuator manufactured according to one embodiment of the present invention.

[0078] FIG. 3c is a photograph confirming the light-induced operation of an agarose-PEDOT:PSS / PEG / methylene blue-based actuator manufactured according to one embodiment of the present invention.

[0079] FIG. 3d is a photograph confirming the light-induced operation of an agarose-PEDOT:PSS / PEG / methylene blue / Mxene-based actuator manufactured according to one embodiment of the present invention.

[0080] Figure 4 is a graph comparing the degree of motion improvement according to the composition of an actuator manufactured according to one embodiment of the present invention.

[0081] FIG. 5A is a photograph comparing the 5 mg weight-lifting movement of a double-layer polymer / paper thin-film actuator manufactured according to one embodiment of the present invention.

[0082] FIG. 5b is a photograph comparing the 37 mg weight-lifting movement of a double-layer polymer / paper thin-film actuator manufactured according to one embodiment of the present invention.

[0083] FIG. 5c is a photograph comparing the movement of different types of light in a double-layer polymer / paper thin film actuator manufactured according to one embodiment of the present invention.

[0084] The present invention relates to a polymer composition comprising agarose and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), and further comprising at least one selected from the group consisting of at least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanine; Mxene; and at least one binder polymer selected from polyethylene glycol (PEG), polypropylene glycol (PPG), and polymethylmethacrylate.

[0085] Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are only intended to illustrate the present invention, and the scope of the present invention is not limited by these examples.

[0086] Throughout this specification, "%" used to indicate the concentration of a particular substance is (wt / wt)% for solid / solid, (wt / vol)% for solid / liquid, and (vol / vol)% for liquid / liquid, unless otherwise stated.

[0087]

[0088] Manufacturing Example 1: Synthesis of agarose-PEDOT: PSS / methylene blue polymer composition

[0089] As shown in Fig. 2a, 4 g of agarose was mixed with PEDOT:PSS (density 1.011 g / cm 3 ) was added to 10 mL and stirred at 90°C for 3 hours to completely dissolve the agarose in PEDOT:PSS. 15 mg of methylene blue was added to this polymer solution and stirred for another 12 hours, after which 10 mg of potassium chloride, which acts as a radical for efficient polymerization, was added.

[0090] The resulting polymer composition was cast onto a polystyrene substrate by a painting method using a paint brush and dried overnight.

[0091] As can be seen in Fig. 2b, the single layer thickness of the polymer thin film photographed with a scanning electron microscope (SEM) was measured to be approximately 3 to 4 mm.

[0092] As can be seen in Fig. 2c, the fabricated polymer was analyzed by Fourier-transform infrared spectroscopy (FT-IR), which confirmed the light responsiveness of the agarose-PEDOT:PSS / methylene blue thin film by showing a reversible shape transition in response to light in terms of operation.

[0093]

[0094] Manufacturing Example 2: Synthesis of agarose-PEDOT:PSS / PEG / methylene blue / MXene polymer composition

[0095] To increase the tensile strength and flexibility of the thin film synthesized in Manufacturing Example 1, 500 mL of polyethylene glycol (PEG) and 500 mL of a 0.1 M MXenes solution were added. Potassium chloride, which acts as a radical, was added at the end to ensure efficient polymerization, and a paper-thin agarose-PEDOT:PSS / PEG / methylene blue / MXene polymer mixture was attached in the form of a thin film using a painting method using a paint brush on paper to produce a double-layer polymer / paper thin film.

[0096] As shown in Figures 3a to 3d, the bilayer polymer / paper film fabricated with a simple paint brush exhibited stable operation even in light-induced activation. However, due to its lack of flexibility, it was not very effective in terms of movement.

[0097]

[0098] Test Example 1: Confirmation of the operation of a double-layer polymer / paper thin film by light.

[0099] A control experiment was conducted to study the operating speed of a double-layer polymer / paper thin film manufactured by changing the composition of the polymer as in Manufacturing Example 2 above.

[0100] Specifically, the upper end of the double-layer polymer / paper thin film was fixed with a clip, and the movement distance (mm) was measured based on the lower, unfixed edge by irradiating it with white light of 300-700 nm. The measurement was performed 10 times for approximately 5 to 15 seconds, and the average speed (mm / s) was calculated by dividing the movement distance by the measurement time.

[0101] Polymer compositionMoving distance (mm)Speed ​​(mm / s)Agarose-PEDOT:PSS20.6Agarose-PEDOT:PSS / Mxene41Agarose-PEDOT:PSS / Methylene blue71.7Agarose-PEDOT:PSS / Methylene blue / Mxene102.1Agarose-PEDOT:PSS / PEG / Methylene blue / Mxene203.3

[0102] As can be seen in Table 1 and Fig. 4, the bilayer polymer / paper thin films with added PEG and MXene showed a large difference in operating performance, which may be related to the increased flexibility and conductivity of the polymer thin films.

[0103]

[0104] Experimental Example 2: Confirmation of the role of dye-sensitized methylene blue and its application in weight-lifting of a double-layer polymer / paper thin film.

[0105] To verify the lifting function, one end of the double-layer polymer / paper thin film was fixed, and lightweight thermocol (polystyrene) weighing 5 mg and 37 mg was fixed to the other end, and then the operation of the double-layer polymer / paper thin film was verified by applying light stimulation of yellow light and white light.

[0106] As can be seen in Figures 5a and 5b, the activation of the double-layer polymer / paper thin film increased when white light was applied. This is not a result of the photothermal effect, but rather the role of methylene blue contained as a dye sensitizer in each double-layer polymer / paper thin film immobilized with 5 mg and 37 mg of lightweight thermocol.

[0107] Additionally, in order to observe the difference in movement of the double-layer polymer / paper thin film depending on the type of light, yellow light and white light were applied to the fabricated double-layer polymer / paper thin film, respectively.

[0108] As can be seen in Figure 5c, a 5.6-fold higher movement distance was measured when white light was applied compared to when yellow light was applied. This difference can be inferred to be due to the methylene blue contained within the double-layer polymer / paper thin film.

[0109] The present invention relates to a double-layer thin-film actuator and a method for manufacturing the same, and more particularly, to a light-activated double-layer polymer / paper thin-film actuator manufactured with a composition of agarose-PEDOT:PSS / PEG / methylene blue / MXene and a method for manufacturing the same.

Claims

1. Contains agarose and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanine; Mxene; and One or more binder polymers selected from polyethylene glycol (PEG), polypropylene glycol (PPG), and polymethylmethacrylate; A polymer composition further comprising at least one selected from the group consisting of:

2. A polymer composition according to claim 1, wherein the mexine is Ti3C2.

3. Contains agarose and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanine; Mxene; and One or more binder polymers selected from polyethylene glycol (PEG), polypropylene glycol (PPG), and polymethylmethacrylate; A polymer composition manufactured by polymerizing a polymer composition additionally comprising at least one selected from the group consisting of A double-layer thin-film actuator comprising a polymer layer and a sheet layer.

4. A double-layer thin-film actuator in the third paragraph, wherein the mexine is Ti3C2.

5. A double-layer thin-film actuator according to claim 3, wherein the sheet layer is made of paper or polyimide.

6. A method for manufacturing a double-layer thin-film actuator comprising the following steps: A first mixing step for preparing a polymer composition comprising agarose and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate); At least one photosensitizer selected from the group consisting of methylene blue, pheophorbide A, and cryptocyanine in the polymer composition; Mxene; or One or more binder polymers selected from polyethylene glycol (PEG), polypropylene glycol (PPG), and polymethylmethacrylate; A second mixing step of adding and mixing; and A thin film forming step of forming a thin film by applying the above polymer composition onto a sheet.

7. A method for manufacturing a double-layer thin-film actuator, wherein the mexine in the sixth paragraph is Ti3C2.

8. A method for manufacturing a double-layer thin-film actuator, wherein the method further comprises a polymerization step performed by adding a chlorine salt or a bromine salt to the polymer composition after the second mixing step.

9. A method for manufacturing a double-layer thin-film actuator, wherein the sheet is made of paper or polyimide in the sixth paragraph.

10. A method for manufacturing a double-layer thin-film actuator, wherein the thin-film forming step in paragraph 6 is performed using a doctor blade or a painting method.

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