CN113684035B - Electric control soft actuator and preparation method and application thereof - Google Patents

Electric control soft actuator and preparation method and application thereof Download PDF

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CN113684035B
CN113684035B CN202110954615.8A CN202110954615A CN113684035B CN 113684035 B CN113684035 B CN 113684035B CN 202110954615 A CN202110954615 A CN 202110954615A CN 113684035 B CN113684035 B CN 113684035B
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liquid crystal
conductive layer
soft actuator
hcm
layer
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CN113684035A (en
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袁冬
赵可
王凯宇
杨婷姣
刘丹青
周国富
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South China Normal University
Shenzhen Guohua Optoelectronics Co Ltd
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South China Normal University
Shenzhen Guohua Optoelectronics Co Ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C09K19/0233—Electroclinic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3833—Polymers with mesogenic groups in the side chain
    • C09K19/3842—Polyvinyl derivatives
    • C09K19/3852—Poly(meth)acrylate derivatives
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation

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Abstract

The invention discloses an electric control soft actuator and a preparation method and application thereof. The electric control soft actuator can deform the electric response liquid crystal polymer layer only by applying voltage to change the directors of the liquid crystal molecules, and the bending and flat state conversion is achieved by switching the voltage.

Description

Electric control soft actuator and preparation method and application thereof
Technical Field
The invention relates to the technical field of software executors, in particular to an electric control soft executor and a preparation method and application thereof.
Background
In recent years, soft robots have been developed very rapidly, and unlike conventional rigid robots, soft robots using stimulus-responsive elastic materials can be deformed in a continuous shape, have high structural softness, and have wide research and application prospects in the fields of soft actuators, mechanical arms, artificial muscles, and the like. Nowadays, among polymer actuators, thermal driving type and optical driving type are included. However, typical thermal drives generate a large amount of heat, greatly limiting the application of soft actuators; most of the light driving requires light of a specific wavelength, and the application range is small.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides an electric control soft actuator which has the characteristics of convenient use and wide application range.
The invention also provides a preparation method of the electric control soft actuator.
The invention also provides application of the electric control soft actuator.
In a first aspect of the present invention, an electrically controlled soft actuator is provided, including a conductive layer, where the conductive layer includes at least a first conductive layer and a second conductive layer, an electrically responsive liquid crystal polymer layer is disposed between the first conductive layer and the second conductive layer, and when no voltage is applied between adjacent conductive layers, an alignment mode of directors of liquid crystal molecules inside the electrically responsive liquid crystal polymer layer is a domain alignment.
The electric control soft actuator provided by the embodiment of the invention has at least the following beneficial effects: the electric control soft actuator can deform the electric response liquid crystal polymer layer only by applying voltage to change the directors of the liquid crystal molecules under the condition that no heat is generated, and the conversion between the bending state and the flat state is achieved by switching the voltage.
The method comprises the following steps: and voltage is applied between the first conductive layer and the second conductive layer (namely, the first conductive layer and the second conductive layer are respectively connected with two poles of a power supply and are electrified), liquid crystal molecules in the electric response liquid crystal polymer layer are arranged parallel to the electric field under the action of the electric field, and the liquid crystal molecules are initially arranged in a display area, so that directors of the liquid crystal molecules are different, and the rotation angles of the molecules are different. The liquid crystal molecules which are arranged in parallel are large in rotation angle, large in deformation, small in rotation angle and small in deformation, and the electric response liquid crystal polymer layers are bent due to different bending degrees of the surfaces of the two sides of the electric response liquid crystal polymer layers, so that the electric control soft actuator is in a curled state. After the electric field is closed, no external acting force and energy exist, the liquid crystal molecules can restore to an initial state, and the electric control soft actuator restores to an initial flat state.
The electric control soft actuator disclosed by the invention is free from thermal driving or optical driving, is directly controlled by electricity and is free from heat generation, and under the condition of thermal insulation, the director of liquid crystal molecules is changed only by applying lower voltage, so that the electric response liquid crystal polymer layer generates larger bending deformation, the conversion between bending and flat states is achieved, the driving is controlled according to the human needs, and the electric control soft actuator is more convenient, and is especially applied to portable equipment, therefore, the electric control soft actuator is convenient to use and wide in application range, and has wide research and application prospects in the fields of soft actuators, mechanical arms, artificial muscles and the like.
In some embodiments of the present invention, the electrically controlled soft actuator further includes a power component, and the first conductive layer and the second conductive layer are electrically connected to the power component, respectively.
In some preferred embodiments of the present invention, the power supply assembly includes an ac power source and a voltage controller connected in series with the ac power source.
In some embodiments of the invention, the electrically responsive liquid crystal polymer layer is a liquid crystal polymer network layer.
In some embodiments of the invention, the starting materials for the electrically responsive liquid crystal polymer layer include a liquid crystal monomer mixture, a photoinducer, and a polymerization inhibitor.
In some preferred embodiments of the invention, the ratio of the liquid crystal monomer mixture to the photo-initiator is (85-98): 1-2 by mass.
In some preferred embodiments of the present invention, the ratio of the parts by mass of the photoinduced agent to the polymerization inhibitor is (1-2): 0.01-0.03.
In some more preferred embodiments of the present invention, the liquid crystal monomer mixture includes a diacrylate liquid crystal monomer and a monoacrylate liquid crystal monomer.
In some more preferred embodiments of the present invention, the diacrylate liquid crystal monomer includes; at least one of HCM-008 or HCM-009.
In some more preferred embodiments of the present invention, the monoacrylate liquid crystal monomer is included; at least one of HCM-020 or HCM-021.
In some more preferred embodiments of the present invention, the ratio of the parts by mass of the diacrylate liquid crystal monomer to the monoacrylate liquid crystal monomer is (20-50): (45-83).
In some more preferred embodiments of the present invention, the ratio of the parts by mass of the diacrylate liquid crystal monomer to the monoacrylate liquid crystal monomer is (40-50): (45-48).
In some more preferred embodiments of the present invention, the ratio of the parts by mass of the diacrylate liquid crystal monomer to the monoacrylate liquid crystal monomer is (20-25): (65-83).
In some more preferred embodiments of the present invention, the liquid crystal monomer mixture includes: HCM-008, HCM-009 and HCM-020.
The reagent can be purchased from the market, and manufacturers comprise Jiangsu and new material forming limited companies and the like.
In some more preferred embodiments of the invention, the ratio of parts by weight of HCM-008, HCM-009, and HCM-020 is (20-25): 45-48.
Through the embodiment, the raw material proportion can be adopted to achieve complete polymerization, the electric control soft actuator has good electric response effect, the deformation is completely recovered after power failure, the viscosity and the flexibility of the electric response liquid crystal polymer layer are good, and the electric response soft actuator is convenient to desorb from the substrate during preparation.
In some more preferred embodiments of the present invention, the liquid crystal monomer mixture includes: HCM-009, HCM-020 and HCM-021.
The reagent can be purchased from the market, and manufacturers comprise Jiangsu and new material forming limited companies and the like.
In some more preferred embodiments of the invention, the ratio of parts by weight of HCM-009, HCM-021 and HCM-020 is (20-25): 45-48.
In some embodiments of the invention, the electrically responsive liquid crystal polymer layer is polymerized from a liquid crystal monomer mixture, a photoinducer, and a polymerization inhibitor by ultraviolet light.
In some embodiments of the invention, the thickness of the electro-responsive liquid crystal polymer layer is 10-50nm.
In some embodiments of the invention, the electrically controlled soft actuator further comprises an insulating substrate disposed on a side of the first conductive layer facing away from the electrically responsive liquid crystal polymer layer.
In some preferred embodiments of the invention, the insulating substrate is adjacent to a side of the electrically responsive liquid crystal polymer layer where liquid crystal molecules are arranged in parallel.
In some preferred embodiments of the invention, the conductive layer is adjacent to a side of the electrically responsive liquid crystal polymer layer where liquid crystal molecules are arranged in parallel.
In some more preferred embodiments of the invention, the insulating substrate is an elastomer.
By the embodiment, the insulating plastic substrate is applied on the first conductive layer, so that the elasticity and toughness of the soft actuator are enhanced, and deformation, which is caused by contact short circuit of the conductive layer after the soft actuator is curled, can be avoided from being recovered.
In some more preferred embodiments of the invention, the insulating substrate comprises a PDMS elastomer.
The polydimethylsiloxane is PDMS.
In some preferred embodiments of the invention, the insulating substrate has a thickness of 20-50nm.
In some more preferred embodiments of the invention, the starting material of the insulating substrate comprises a precursor comprising PDMS and a cross-linking agent.
Such reagents are commercially available, wherein the manufacturer of the PDMS precursor and the cross-linking agent includes the company dakaning.
In some more preferred embodiments of the invention, the ratio of the parts by weight of the precursor of PDMS and the crosslinking agent is about 9:1.
in some embodiments of the invention, the first conductive layer comprises a material comprising at least one of gold or silver.
In some preferred embodiments of the present invention, the first conductive layer has a thickness of 30-100nm.
In some more preferred embodiments of the present invention, the first conductive layer has a thickness of about 50nm.
In some embodiments of the present invention, the second conductive layer comprises a material including at least one of gold or silver.
In some preferred embodiments of the present invention, the second conductive layer has a thickness of 30-100nm.
In some more preferred embodiments of the invention, the second conductive layer has a thickness of about 50nm.
In a second aspect of the present invention, a method for manufacturing an electronically controlled soft actuator is provided, comprising the steps of:
s1, an electric response liquid crystal polymer layer raw material mixture I induces liquid crystal molecules in the mixture I to form exhibition area arrangement, and a mixture II is obtained;
s2, performing photopolymerization and thermal polymerization on the mixture II in the exhibition area arrangement obtained in the step S1 to obtain an electric response liquid crystal polymer layer;
s3, assembling the electric response liquid crystal polymer layer obtained in the step S2 with the first conductive layer and the second conductive layer to obtain the electric control soft actuator.
In some embodiments of the invention, the mixture ii is a nematic liquid crystal.
In some preferred embodiments of the present invention, the method further comprises step S1-1, wherein the materials of the electro-responsive liquid crystal polymer layer are mixed and dissolved in a solvent, heated and stirred to remove the solvent, and cooled to room temperature to obtain a mixture I.
In some more preferred embodiments of the present invention, in step S1-1, the solvent comprises methylene chloride.
In some more preferred embodiments of the present invention, the heating temperature is about 60℃in step S1-1.
In some embodiments of the invention, in step S1, the liquid crystal molecules in mixture i are induced by the alignment layer to form a domain arrangement.
In some preferred embodiments of the present invention, the alignment layer includes a vertical alignment layer and a parallel alignment layer.
In some preferred embodiments of the invention, the alignment layers are vertical alignment layers and parallel alignment layers.
In some more preferred embodiments of the present invention, the method further comprises the step S1-2, wherein one side of the first transparent substrate is provided with a parallel alignment layer, the friction orientation forms parallel ravines, and one side of the second transparent substrate is provided with a vertical alignment layer; and (3) oppositely arranging one side of the first transparent substrate provided with the parallel alignment layer and one side of the second transparent substrate provided with the vertical alignment layer, pressing the first transparent substrate and the second transparent substrate by using acrylic pressure-sensitive adhesives, forming a closed space to obtain a liquid crystal box, and filling the mixture I into the liquid crystal box to obtain a mixture II.
In some more preferred embodiments of the invention, in step S1-2, mixture I is filled into a liquid crystal cell at 70-75deg.C, and the temperature is adjusted to about 40deg.C to obtain mixture II.
In some embodiments of the invention, in step S2, the photopolymerization is: polymerization is carried out for about 30min under 365nm ultraviolet light.
In some embodiments of the invention, in step S2, the thermal polymerization is: thermal polymerization was carried out at 120℃for about 15min.
In some embodiments of the present invention, in step S3, the first conductive layer and the second conductive layer are disposed on both sides of the electro-responsive liquid crystal polymer layer by vapor deposition.
In some embodiments of the present invention, in step S3, the evaporation is a vacuum evaporation method.
In some embodiments of the present invention, the method further comprises step S4 of preparing an insulating substrate on a side of the conductive layer facing away from the electro-responsive liquid crystal polymer layer, wherein the conductive layer is adjacent to a side of the electro-responsive liquid crystal polymer layer where liquid crystal molecules are arranged in parallel.
In some preferred embodiments of the present invention, the insulating substrate is formed by spin-coating a raw material mixture of the insulating substrate on a side of the first conductive layer, and thermally curing the raw material mixture.
In some more preferred embodiments of the present invention, the raw material mixture of the insulating substrate includes a PDMS mixed solution obtained by mixing a precursor of PDMS and a crosslinking agent.
In some preferred embodiments of the present invention, the PDMS mixed solution is spin-coated on the side of the first conductive layer, and the insulating substrate is formed after thermal curing.
In some more preferred embodiments of the invention, the spin-coating of the PDMS mixture solution is performed at a speed of about 1000rpm for a period of about 20 seconds.
In some more preferred embodiments of the present invention, the conditions for thermally curing the PDMS mixed solution are: the temperature was about 60℃and the curing was about 2 hours.
In some more preferred embodiments of the present invention, certain areas of the first conductive layer remain exposed for connection to a power source when the PDMS mixed solution is spin-coated.
In a third aspect of the present invention, the application of the electrically controlled soft actuator in the fields of soft actuators, mechanical arms or artificial muscles is provided.
The electric control soft actuator disclosed by the invention is free from thermal driving or optical driving, is directly controlled by electricity and is free from heat generation, and under the condition of thermal insulation, the liquid crystal molecular directors are changed only by applying lower voltage, so that the electric response liquid crystal polymer layer generates larger bending deformation (curling), the conversion between bending and flat states is achieved, the driving is controlled according to the artificial requirement, and the electric control soft actuator is more convenient, particularly applied to portable equipment, therefore, the electric control soft actuator is convenient to use and wide in application range, and has wide research and application prospects in the fields of soft actuators, mechanical arms, artificial muscles and the like.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a schematic diagram of an electrically controlled soft actuator in an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of a liquid crystal molecular director arrangement without applying a driving voltage and with applying a driving voltage according to an embodiment of the present invention;
FIG. 3 is an external schematic view of an electrically controlled soft actuator without and with a driving voltage applied in an embodiment of the present invention;
FIG. 4 is a diagram of a deformed embodiment of the electrically controlled soft actuator without applying a driving voltage and with applying a driving voltage in accordance with an embodiment of the present invention.
Reference numerals: 1. an electrically responsive liquid crystal polymer layer; 2. a second conductive layer; 3. a first conductive layer; 4. an insulating substrate.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention. In the description of the present invention, it should be understood that references to orientation descriptions such as upper, lower, front, rear, left, right, etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description of the present invention and to simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, the meaning of a number is one or more, the meaning of a number is two or more, and greater than, less than, exceeding, etc. are understood to exclude the present number, and the meaning of a number is understood to include the present number. If one or two are described for the purpose of distinguishing technical features, that is, they are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, unless explicitly defined otherwise, terms such as arrangement, installation, connection, etc. should be construed broadly and the specific meaning of the terms in the present invention can be reasonably determined by a person skilled in the art in combination with the specific contents of the technical scheme.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The details of the chemical reagents used in the examples of the present invention are as follows:
diacrylate liquid crystal monomer-HCM-009 (Jiangsu Hecheng New Material Co., ltd.)
Diacrylate liquid crystal monomer-HCM-008 (Jiangsu Hecheng New Material Co., ltd.)
Monoacrylate liquid crystal monomer-HCM-020 (Jiangsu Hecheng New Material Co., ltd.)
Monoacrylate liquid crystal monomer-HCM-021 (Jiangsu Hecheng New Material Co., ltd.)
photo-inducer-Irg-819 (Kunshan century dragon chemical Co., ltd.)
Polymerization inhibitor-4-methoxyphenol (Hubei neutralization chemical Co., ltd.)
The precursor of PDMS and the crosslinking agent-DC 184 (DOW CORNING/DOCorning Co.), wherein DC184 specifically comprises the precursor of PDMS, the crosslinking agent and the precursor of PDMS are purchased in a kit
Dichloromethane (Tianjin city far chemical agent Co., ltd.)
Example 1
An electric control soft actuator is shown in fig. 1, and comprises a power supply assembly (not shown in the figure), a first conductive layer 3 and a second conductive layer 2 which are oppositely arranged, wherein an electric response liquid crystal polymer layer 1 is arranged between the first conductive layer 3 and the second conductive layer 2, an insulating substrate 4 is arranged on one side of the first conductive layer 3, which is away from the electric response liquid crystal polymer layer 1, the insulating substrate 4 is an elastomer (PDMS elastomer), and one side of the first conductive layer 3, which is close to the parallel arrangement of liquid crystal molecules in the electric response liquid crystal polymer layer 1. The first conductive layer 3 and the second conductive layer 2 are silver layers, and the thicknesses of the silver layers are about 50nm. The power supply assembly comprises an alternating current power supply and a voltage controller connected in series on the alternating current power supply, the first conductive layer 3 and the second conductive layer 2 are respectively and electrically connected with the power supply assembly, and when no voltage is applied, the arrangement mode of directors of liquid crystal molecules in the electric response liquid crystal polymer layer 1 is exhibition area arrangement. The thickness of the electro-responsive liquid crystal polymer layer 1 is about 20nm; the thickness of the insulating substrate 4 is about 50nm.
Wherein the electric response liquid crystal polymer layer 1 is a liquid crystal polymer network obtained by ultraviolet polymerization and thermal polymerization of a liquid crystal monomer mixture, a photoinducer and a polymerization inhibitor. The liquid crystal monomer mixture comprises a diacrylate liquid crystal monomer and a monoacrylate liquid crystal monomer.
The preparation method of the electric control soft actuator comprises the following steps:
preparing liquid crystal monomer mixture
1.0g of raw materials are taken according to the following proportion: specifically, the weight percentages of HCM-009, HCM-008, HCM-020, photo-inducer and polymerization inhibitor are 24.5wt%, 49wt%, 1.98wt% and 0.02 wt%. The above raw materials are dissolved in 2ml of solvent dichloromethane (or other volumes of dichloromethane can be used, so that the above raw materials can be dissolved in dichloromethane), and stirred at 60 ℃ for 300r/min until the solvent in the raw materials is completely volatilized, and the raw materials are slowly cooled to room temperature to obtain a mixture I. The raw material ratio can achieve complete polymerization, the electric response effect is good, the deformation is completely recovered after power failure, the viscosity and the flexibility of the liquid crystal film are good, and the liquid crystal film is convenient to desorb from the glass substrate.
(II) preparation of liquid Crystal Polymer film
The single-side surface of the first light-transmitting substrate is coated with a parallel alignment layer, parallel ravines are formed on the swan flannelette through multiple rubbing orientations, and the single-side surface of the second light-transmitting substrate is coated with a vertical alignment layer. The side, provided with the parallel alignment layer, of the first light-transmitting substrate and the side, provided with the vertical alignment layer, of the second light-transmitting substrate are oppositely arranged, acrylate pressure-sensitive adhesives with the thickness of 20 mu m are used for pressing, and a closed space is formed, so that a liquid crystal box with the thickness of 20 mu m is obtained. Filling the mixture I obtained in the step (I) into a liquid crystal box at 75 ℃, adjusting the temperature to 40 ℃, and inducing the liquid crystal molecules to form a domain arrangement under the action of the vertical alignment layer and the parallel alignment layer to obtain a mixture II. Polymerizing for 30min under 365nm ultraviolet light, finally thermally polymerizing for 15min at 120 ℃, and naturally cooling to room temperature to obtain the transparent liquid crystal polymer film, namely the electric response liquid crystal polymer layer.
(III) deposition of conductive layer
And removing the upper and lower glass substrates, respectively evaporating a first conductive layer and a second conductive layer on the upper and lower surfaces of the electric response liquid crystal polymer layer, wherein the first conductive layer and the second conductive layer are obtained through a vacuum evaporation method, and the conductive layer is made of silver and has a thickness of about 50nm.
(IV) applying an insulating substrate
And spin-coating the PDMS mixed solution on the first conductive layer, and leaving a certain area of the first conductive layer exposed for accessing a circuit. The PDMS mixed solution is prepared from a precursor of PDMS and a crosslinking agent in a mass ratio of 9:1, placing the mixture into a vacuum pump, and vacuumizing for 10min to remove bubbles (the vacuum degree is-0.085 Mpa or other vacuum degrees which can meet the requirement of removing bubbles). And spin-coating the PDMS mixed solution on the first conductive layer at 1000rpm for 20s, and finally curing for 2h on a 60 ℃ hot table.
Example 2
The difference from example 1 is that in the preparation method:
preparing liquid crystal monomer mixture
1.0g of raw materials are taken according to the following proportion: specifically, the weight percentages of HCM-009, HCM-021, HCM-020, photo-inducer and polymerization inhibitor are 24.5wt%, 49wt%, 1.98wt% and 0.02 wt%. The above raw materials are dissolved in 2ml of solvent dichloromethane (or other volumes of dichloromethane can be used, so that the above raw materials can be dissolved in dichloromethane), and stirred at 60 ℃ for 300r/min until the solvent in the raw materials is completely volatilized, and the raw materials are slowly cooled to room temperature to obtain a mixture I.
(II) preparation of liquid Crystal Polymer film
Filling the mixture I obtained in the step (I) into a liquid crystal box at 70 ℃, regulating the temperature to 40 ℃ to obtain a mixture II, polymerizing for 30min under 365nm ultraviolet light, finally thermally polymerizing for 15min at 120 ℃, and naturally cooling to room temperature to obtain a transparent liquid crystal polymer film, namely an electric response liquid crystal polymer layer.
Namely: this embodiment differs from embodiment 1 in that: the materials from which the liquid crystal monomer mixture is formulated in step (I) and the temperature parameters from which the electrically responsive liquid crystal polymer layer is prepared in step (II).
The experimental effect of example 2 is equivalent to that of example 1, and the prepared electronically controlled soft actuator can achieve the same deformation effect as that of example 1.
In addition, except for the silver layer as the first conductive layer and the silver layer as disclosed in embodiments 1-2, the first conductive layer and the second conductive layer may be gold layers, silver layers, or other conductive materials, that is, the first conductive layer and the second conductive layer may be conductive.
Test examples
This test example tested the performance of the electronically controlled soft actuator prepared in example 1. Wherein, the deformation performance of the electric control soft actuator without and when the driving voltage is applied is tested, and the test result is shown in fig. 4. The test conditions were: the upper and lower conductive layers in the electric control soft actuator are respectively and electrically connected with two poles of an alternating current power supply assembly, the access voltage is 60V, and the frequency is 900kHz.
As can be seen from fig. 4, the upper and lower conductive layers in the electrically controlled soft actuator are electrically connected with the two poles of the power supply assembly respectively, and after the voltage is applied, the molecular arrangement of the electrically responsive liquid crystal polymer layer can be controlled from the display area to the arrangement parallel to the electric field, so that the soft actuator is curled upwards, and the initial arrangement state is quickly restored after the electric field is removed. The soft actuator can be switched between a curled state and a flat state by energizing and de-energizing. Has wide research and application prospect in the fields of software executors, mechanical arms, artificial muscles and the like.
Meanwhile, the electric response liquid crystal polymer layer is prepared from a liquid crystal monomer mixture, a photo-initiator and a polymerization inhibitor through ultraviolet polymerization and thermal polymerization, two groups of liquid crystal diacrylate (HCM-009 and HCM-008) or (HCM-009 and HCM-021) are selected to form a polymer network, and a section of monoacrylate (HCM-020) containing cyano is connected into the polymer network to initially form a side chain type liquid crystal polymer network containing electric response groups. The films were completely polymerized under ultraviolet light using an ultraviolet light-activated photoinitiator (Irg-819) to form LCNs (liquid crystal polymers).
In addition, the invention adopts proper raw material proportion to achieve complete polymerization, has better electric response effect, completely recovers deformation after power failure, has better viscosity and flexibility of the electric response liquid crystal polymer layer and is convenient for desorption from the glass substrate. The raw materials are specifically as follows: the ratio of the parts by mass of HCM-008, HCM-009, HCM-020, photo-initiator and polymerization inhibitor is (20-25), the ratio of the parts by mass of HCM-009, HCM-021, HCM-020, photo-initiator and polymerization inhibitor is (20-25), the ratio of the parts by mass of HCM-009, HCM-020, photo-initiator and polymerization inhibitor is (20-25), the ratio of the parts by mass of HCM-48, the ratio of the parts by mass of HCM-9, HCM-020, photo-initiator and polymerization inhibitor is (20-25), the ratio of the parts by mass of HCM-48, the ratio of the parts by mass of the photo-initiator and the weight of the polymerization inhibitor is (45-48), the ratio of the parts by mass of the photo-initiator is (1-2), and the ratio of the mass of the photo-initiator is (0.01-0.03.
The invention can control the curling degree of the electric control soft actuator by controlling the magnitude of the access voltage. Specifically, the larger the access voltage is, the larger the curl degree of the electric control soft actuator is. The invention can also control the curling degree of the electric control soft actuator by controlling the frequency of the accessed alternating voltage. The frequency of the alternating voltage is specifically: the range of the access voltage includes 10-80V. Preferably, the range of access voltages includes 20-80V. The frequency of the alternating voltage comprises 700kHz-1MHz. Preferably, the frequency of the alternating voltage comprises 700kHz-900 kHz. Meanwhile, the electric control soft actuator disclosed by the invention has higher electric response sensitivity, and the bending response of the electric control soft actuator can be realized even if the access voltage is 10V. The invention adopts an alternating current power supply, has wide application range, and is beneficial to the application of the electric control soft actuator in the fields of soft actuators, mechanical arms, artificial muscles and the like.
It should be noted that the meaning of "about" with respect to a numerical value herein is an error of 2%.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (24)

1. The electric control soft actuator is characterized by comprising a conductive layer, wherein the conductive layer at least comprises a first conductive layer and a second conductive layer, an electric response liquid crystal polymer layer is arranged between the first conductive layer and the second conductive layer, and when no voltage is applied between adjacent conductive layers, the arrangement mode of liquid crystal molecule directors in the electric response liquid crystal polymer layer is exhibition area arrangement; namely, the alignment layer induces liquid crystal molecules of the raw material mixture inside the electric response liquid crystal polymer layer to form a domain arrangement; the alignment layer comprises a vertical alignment layer and a parallel alignment layer; the electric response liquid crystal polymer layer is a liquid crystal polymer network layer; the conductive layer is close to one side of the electrically-responsive liquid crystal polymer layer, in which liquid crystal molecules are arranged in parallel;
the frequency of the alternating voltage driving the electric control soft actuator comprises 700kHz-1MHz;
the raw materials of the electric response liquid crystal polymer layer comprise a liquid crystal monomer mixture, a photoinducer and a polymerization inhibitor; the liquid crystal monomer mixture comprises a diacrylate liquid crystal monomer and a monoacrylate liquid crystal monomer; the diacrylate liquid crystal monomer comprises at least one of HCM-008 or HCM-009, and the monoacrylate liquid crystal monomer comprises at least one of HCM-020 or HCM-021; the mass part ratio of the liquid crystal monomer mixture to the photoinduced agent is (85-98) (1-2); the weight portion ratio of the photoinduced agent to the polymerization inhibitor is (1-2) (0.01-0.03).
2. The electrically controlled soft actuator of claim 1, further comprising a power component, wherein the first conductive layer and the second conductive layer are electrically connected to the power component, respectively.
3. The electrically controlled soft actuator of claim 2, wherein the power supply assembly comprises an ac power source and a voltage controller coupled in series with the ac power source.
4. The electrically controlled soft actuator of claim 1, wherein the liquid crystal monomer mixture comprises: HCM-008, HCM-009 and HCM-020.
5. The electrically controlled soft actuator of claim 4, wherein the ratio of parts by mass of HCM-008, HCM-009, and HCM-020 is (20-25): (20-25): (45-48).
6. The electrically controlled soft actuator of claim 1, wherein the liquid crystal monomer mixture comprises: HCM-009, HCM-020 and HCM-021.
7. The electrically controlled soft actuator of claim 6, wherein the ratio of parts by mass of HCM-009, HCM-021 and HCM-020 is (20-25): (20-25): (45-48).
8. The electrically controlled soft actuator of claim 1, wherein the thickness of the electrically responsive liquid crystal polymer layer is 10-50 a nm a.
9. The electrically controlled soft actuator of claim 1, further comprising an insulating substrate disposed on a side of the first conductive layer facing away from the electrically responsive liquid crystal polymer layer.
10. The electrically controlled soft actuator of claim 9, wherein the insulating substrate is an elastomer.
11. The electrically controlled soft actuator of claim 9, wherein the insulating substrate comprises a PDMS elastomer.
12. The electrically controlled soft actuator of claim 9, wherein the insulating substrate comprises a precursor comprising PDMS and a cross-linking agent.
13. The electrically controlled soft actuator of claim 9, wherein the insulating substrate has a thickness of 20-50 a nm a.
14. The electrically controlled soft actuator of claim 1, wherein the first conductive layer comprises at least one of gold or silver.
15. The electrically controlled soft actuator of claim 1, wherein the second conductive layer comprises at least one of gold or silver.
16. The electrically controlled soft actuator of claim 1, wherein the first conductive layer has a thickness of 30-100 a nm a.
17. The electrically controlled soft actuator of claim 1, wherein the first conductive layer has a thickness of about 50 a nm a, and wherein "about" means 2% error.
18. The electrically controlled soft actuator of claim 1, wherein the second conductive layer has a thickness of 30-100nm.
19. The electrically controlled soft actuator of claim 1, wherein the second conductive layer has a thickness of about 50 a nm a, wherein the meaning of "about" is an error of 2%.
20. A method of making an electronically controlled soft actuator as claimed in claim 1, comprising the steps of:
s1, an electric response liquid crystal polymer layer raw material mixture I, and inducing liquid crystal molecules in the mixture I to form a domain arrangement through an alignment layer to obtain a mixture II; the alignment layer comprises a vertical alignment layer and a parallel alignment layer;
s2, performing photopolymerization and thermal polymerization on the mixture II in the exhibition area arrangement obtained in the step S1 to obtain an electric response liquid crystal polymer layer;
s3, assembling the electric response liquid crystal polymer layer obtained in the step S2 with the first conductive layer and the second conductive layer to obtain the electric control soft actuator.
21. The method according to claim 20, wherein in step S3, the first conductive layer and the second conductive layer are disposed on both sides of the electrically-responsive liquid crystal polymer layer by vapor deposition.
22. The method of claim 20, further comprising the step of S4, preparing an insulating substrate on a side of the conductive layer facing away from the electrically-responsive liquid crystal polymer layer, wherein the conductive layer is adjacent to a side of the electrically-responsive liquid crystal polymer layer where liquid crystal molecules are arranged in parallel.
23. The method of claim 22, wherein the electrically-controlled soft actuator is formed by spin-coating a polydimethyl siloxane mixture on a side of the first conductive layer, and thermally curing the polydimethyl siloxane mixture.
24. Use of an electronically controlled soft actuator according to any one of claims 1 to 19 or prepared by a method according to any one of claims 20 to 23 in the field of soft actuators, robotic arms or artificial muscles.
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JP2009191117A (en) * 2008-02-13 2009-08-27 Tokai Rubber Ind Ltd Liquid crystal elastomer and actuator using the same
CN104375336A (en) * 2013-08-13 2015-02-25 天马微电子股份有限公司 Stereoscopic display
CN109756147A (en) * 2018-12-13 2019-05-14 西安交通大学 A kind of looper biomimetic features and manufacturing process based on liquid crystal elastomeric polymer
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