CN114133469A - Manufacturing method of 3D printing hydrogel electronic device and conductive material - Google Patents
Manufacturing method of 3D printing hydrogel electronic device and conductive material Download PDFInfo
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Images
Classifications
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/14—Printing inks based on carbohydrates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Abstract
The invention provides a manufacturing method of a 3D printing hydrogel electronic device and a conductive material. The method adopts calcium alginate-polyacrylamide double-crosslinked network hydrogel as a base material and utilizes a coordinate bond-covalent bond orthogonal curing mechanism. Alginate is cross-linked with calcium ions to form a gel, which is mechanically broken into a micellar matrix that can be used for embedded 3D printing. The substrate has the potential of subsequent covalent crosslinking and curing due to the acrylamide monomer, the crosslinking agent and the initiator contained in the substrate, and can be used as conductive ink for printing after being blended with the micron silver sheets. The method has the advantages of simple process, low price, high designability, high manufacturing freedom degree and the like. The prepared hydrogel electronic device has excellent conductivity, stretchability and strain responsiveness, and is expected to be applied to the fields of wearable equipment, flexible robots, electronic skins, medical care and the like.
Description
Technical Field
The invention relates to the field of flexible electronic device processing, in particular to a manufacturing method of a 3D printing hydrogel electronic device and a conductive material.
Background
Due to attractive prospects in biological detection and treatment, neuroscience research, wearable electronic equipment and the like, flexible electronic devices are paid more and more attention and researched, and are expected to replace traditional rigid electronic devices through technical breakthrough in the future to realize industrial innovation. As a novel material appearing recently, the hydrogel electronic device has the characteristics of natural biocompatibility, low toxicity, high water content, easiness in chemical modification, permission of ion diffusion, close to the mechanical property of biological tissues and the like, so that the hydrogel electronic device shows a good development prospect.
At the early stage of development of hydrogel electronic devices, methods for preparing hydrogel electronic devices, such as a die filling method, a laser etching method, a flow channel method and the like, reported in documents at present generally have the defects of complicated preparation process, excessive manual operation, low precision, low designability, low three-dimensional space freedom and the like, and cannot be popularized to be standardized methods. In addition, the conductive materials mainly used in the current hydrogel electronic devices, including (snakelike arrangement) metal wires, liquid metal and the like, also have the problems of limited stretching degree, leakage risk and the like.
CN110970232A discloses a stretchable microelectronic device with hydrogel as a substrate and a preparation method thereof, the device is composed of a hydrogel substrate with ionic conductivity and a stretchable patterned microelectrode on the surface, the preparation process comprises obtaining an intermediate product with a preset electrode pattern, pre-stretching a tough hydrogel, then attaching the hydrogel to the intermediate product to realize electrode pattern transfer, and slowly releasing the hydrogel to recover to an unstretched state, thereby obtaining the hydrogel electronic device with good stretchability and certain precision (the line width is 400 μm); the invention patent is prepared by a transfer printing method, but because the transfer printing method can only attach a circuit on the surface of hydrogel, hydrogel electronic devices with more complex functions, such as hydrogel-based solenoid antennas and the like, with a 3D structure are difficult to obtain, and the electrode materials available are limited. Moreover, the transfer printing method requires the manufacture of a corresponding mask plate in advance, and the transfer printing is performed after the electrode pattern is printed on the intermediate material, so that the process is complicated, and the number of manual operation processes is large.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for manufacturing a 3D printed hydrogel electronic device and a conductive material, which provides feasibility for more simply manufacturing a hydrogel electronic device with high precision, design and freedom.
In order to achieve the object of the present invention, in a first aspect, the present invention provides a hydrogel matrix material obtained by dissolving an ionically crosslinkable polymer compound (an ionically crosslinked polymer conforming to an orthogonal curing mechanism), a radically polymerizable monomer, a crosslinking agent, and an initiator in deionized water, then introducing metal ions (preferably calcium ions) to ionically crosslink the polymer compound through coordination bonds, and crushing the resulting gel into micro gel particles;
wherein the initiator is a thermal initiator or a photoinitiator.
Further, the ion-crosslinkable polymer compound may be selected from sodium alginate, chitosan, hyaluronic acid, etc., preferably sodium alginate.
Further, the radical polymerizable monomer may be selected from acrylamide, polyethylene glycol diacrylate (PEGDA), and the like, preferably acrylamide.
Further, the crosslinking agent may be selected from water-soluble small molecules containing 2C ═ C bonds, preferably N, N-methylene acrylamide.
Preferably, the initiator is Ammonium Persulfate (APS), other water soluble thermal initiators may also be used in the present invention.
Preferably, the photoinitiator is Igracure 2959, other water-soluble photoinitiators can also be used in the present invention. .
In a second aspect, the present invention provides a method for preparing the hydrogel matrix material, comprising the steps of:
(1) dissolving an ionic crosslinking polymer compound and a free radical polymerization monomer in deionized water under the heating condition by magnetic stirring to obtain a transparent viscous solution;
(2) cooling the viscous solution obtained in the step (1) to below 25 ℃, adding a cross-linking agent, an initiator and an Ethylene Diamine Tetraacetic Acid (EDTA) chelate of metal ions, and stirring to dissolve the mixture;
(3) adding D-gluconolactone into the solution obtained in the step (2), stirring to dissolve the D-gluconolactone, and refrigerating the obtained solution overnight to form an ionic crosslinked gel;
(4) and (3) mechanically crushing the ionic crosslinked gel obtained in the step (3) into coarse gel particles, filtering the coarse gel particles into fine gel particles by using an injector and a filter, and defoaming the fine gel particles by using a planetary stirrer to obtain the hydrogel matrix material for embedded 3D printing.
In one embodiment of the present invention, the hydrogel matrix material is prepared as follows:
(1) under the heating condition, dissolving acrylamide and sodium alginate in deionized water by magnetic stirring to obtain a transparent viscous solution;
(2) cooling the viscous solution obtained in the step (1) to below 25 ℃, adding an N, N-methylene acrylamide aqueous solution and ammonium persulfate, and then adding EDTA-CaCl2(ethylenediaminetetraacetic acid-calcium chloride) aqueous solution, stirring to dissolve it;
(3) adding D-gluconolactone into the solution obtained in the step (2), stirring to dissolve the D-gluconolactone, and refrigerating the solution overnight to form calcium alginate gel;
(4) and (3) mechanically crushing the calcium alginate gel obtained in the step (3) into coarse gel particles by using a pulverizer, filtering the coarse gel particles into fine gel particles by using an injector and a filter, and defoaming the fine gel particles by using a planetary stirrer (Thinky planetary stirrer) to obtain the hydrogel matrix material for embedded 3D printing.
The mass ratio of the sodium alginate to the acrylamide to the deionized water in the step (1) of the method is (0.6-1.4): (6-10): 55, wherein the proportion of sodium alginate influences the final rheological properties of the matrix gel obtained in step (4).
In the step (2), the mass ratio of acrylamide to N, N-methylene acrylamide (cross-linking agent) to ammonium persulfate (thermal initiator) is 1: (0.00082-0.04): (0.01-0.05). The proportion of the cross-linking agent can affect the mechanical properties of the matrix gel after the matrix gel is cured into the hydrogel.
Sodium alginate, 0.25M EDTA-CaCl at pH8-92The mass ratio of the aqueous solution to the D-gluconolactone is 1: (1.3-3.0): (0.48-1.12).
Preferably, the pore size of the syringe and filter used in step (4) is 20-50 μm.
In a third aspect, the invention provides a conductive material for 3D printing, wherein the hydrogel matrix material, the polyvinylpyrrolidone aqueous solution, glycerol and the micron silver flakes are uniformly mixed by a planetary mixer, and then transferred to a cylinder for centrifugal deaeration, so as to obtain the conductive material (conductive ink capable of being extruded and printed) for 3D printing.
Preferably, the mass ratio of the hydrogel matrix material, the 40% wt polyvinylpyrrolidone aqueous solution, the glycerol and the micron silver sheets is 1: (0.02-0.1): (0.05-0.1): (0.5-1.5). The molecular weight of polyvinylpyrrolidone is 44000-54000 Da.
Preferably, the micron silver flake size is 2-10 μm. The proportion of micron silver flakes can affect the conductivity of the slurry after curing.
Preferably, the centrifugation conditions are: centrifugation at 2000 and 2500g (more preferably 2500g) at 18 ℃ for 10 min.
In a fourth aspect, the invention provides a method for manufacturing a 3D printed hydrogel electronic device, the hydrogel matrix material is loaded into a mold with a certain shape, the conductive material for 3D printing is printed in the hydrogel matrix material by a 3D printer according to a preset program, and then curing is performed under ultraviolet light or heating conditions, so as to obtain the hydrogel electronic device with good stretchability and elasticity.
Preferably, the printing needle nozzle of the 3D printer can select the inner diameter size of 100 μm, 150 μm, 250 μm or 400 μm according to the requirement.
Preferably, the thermal initiator is Ammonium Persulfate (APS), the heating temperature is 60 ℃, and the heating time is 1 h. Curing should be carried out as much as possible in a high humidity, oxygen-free environment; the photoinitiator can be Igracure 2959 with good water solubility and low toxicity, and the light intensity of the ultraviolet light is 50mW/cm2The time is 1 h.
The invention provides a 3D printing manufacturing method of a hydrogel electronic device and a matched conductive material system. The method adopts calcium alginate-polyacrylamide double cross-linked network hydrogel as a base material and utilizes a specific coordinate bond-covalent bond orthogonal curing mechanism. Alginate is cross-linked with calcium ions to form a gel, which is mechanically broken into a micellar matrix that can be used for embedded 3D printing. The matrix has the potential of subsequent covalent crosslinking and curing due to the acrylamide monomer, the crosslinking agent and the initiator contained in the matrix, and can be used as conductive ink for printing after being blended with micron-sized silver sheets. The material system allows the three-dimensional conductive structure with certain functions (such as inductance and the like) to be freely printed in space, and can be conveniently cured and packaged by stimulation of light, heat and the like after printing. Compared with the currently reported hydrogel electronic device manufacturing methods such as a perfusion method, a laser etching method and the like, the method has the advantages of simple process, low price, high designability, high manufacturing freedom and the like. The prepared hydrogel electronic device has excellent conductivity, stretchability and strain responsiveness, and is expected to be applied to the fields of wearable equipment, flexible robots, electronic skins, medical care and the like.
The method solves the problems of complicated process, excessive manual operation, low precision, low spatial degree of freedom and the like in the conventional preparation method of the hydrogel electronic device, effectively solves the problems of stretching limitation, seepage and the like which can exist when a metal lead or liquid metal is used as a lead, has the advantages of simple and rapid process, low cost, high degree of freedom, strong designability and the like, and provides a new method for efficiently preparing the hydrogel electronic device.
Drawings
Figure 1 is a schematic illustration of an embedded 3D process for making hydrogel electronics in a preferred embodiment of the invention (a) and a cured hydrogel electronics photomicrograph (b).
FIG. 2 is a schematic diagram of the materials involved in the preferred embodiment of the present invention: (a) i schematic representation of the matrix gel (microgel particles); ii schematic of the matrix gel chemistry; (b) a conductive paste schematic diagram; (c) schematic diagram of the chemical composition of the cured hydrogel.
Fig. 3 is a graph (a) of viscosity-strain rate of matrix gel and a stress-strain curve (b) of hydrogel after curing under different mass ratios of sodium alginate in the preferred embodiment of the present invention, which respectively reflect the rheological characteristics of matrix gel before curing and the mechanical characteristics of matrix gel after curing (the figures indicate the mass ratio of sodium alginate).
FIG. 4 illustrates the fabrication and testing of a hydrogel electronic strain sensor in accordance with a preferred embodiment of the present invention; wherein, (a) the design G code of the hydrogel strain sensor simulates (upper) and the physical photograph (lower); (b) testing the hydrogel strain sensor by using a stretching instrument; (c) a graph of the rate of change of resistance versus strain for a hydrogel strain sensor; (d) hydrogel strain sensor resistance change rate versus strain at 300% strain cycle.
FIG. 5 is a diagram illustrating the fabrication and testing of hydrogel inductors and antennas in accordance with a preferred embodiment of the present invention; wherein, (a) a G-code simulation of a 5-turn spiral inductor; (b)2-5 circles of a real image of the spiral line hydrogel inductor; (c) experimental inductance and resistance of the spiral line hydrogel inductor of 2-5 circles and a simulated inductance and resistance comparison graph obtained by simulation of Comsol software; (d) g code simulation of a 3-turn solenoid antenna; (e) physical representation of solenoid antenna-led hydrogel electronics; (f) the solenoid antenna illuminates the light emitting diode under the energizing of the transmitting coil.
Detailed Description
The invention aims to provide a more efficient, more free and designable 3D printing manufacturing method of a hydrogel electronic device aiming at the defects of the prior art, wherein the hydrogel electronic device comprises a hydrogel matrix material suitable for embedded 3D printing and printable conductive ink; the manufacturing method comprises embedded 3D printing, a device curing and packaging process after printing and the like.
The invention adopts the following technical scheme:
A. preparation of embedded 3D printing hydrogel matrix
Sodium alginate, acrylamide, a cross-linking agent (N, N-methylene acrylamide, MBAA) and a thermal initiator (ammonium persulfate, APS) are dissolved in deionized water, and then calcium ions are introduced to enable alginate radical-calcium ions to carry out ionic cross-linking through coordination bonds. And mechanically crushing the crosslinked gel and passing the gel through an injection filter to obtain the embedded 3D printing gel matrix with certain rheological properties. Because the matrix still contains unreacted monomers, a cross-linking agent and an initiator, the matrix can be subjected to covalent cross-linking through heating, and the cured encapsulation of the printed electronic device is realized (fig. 2, a-c).
Preferably, sodium alginate: acrylamide: the mass ratio of the deionized water is 1: 8: 55. wherein, changing the mass ratio of sodium alginate can regulate the rheological property of the matrix gel and the mechanical property after the matrix gel is solidified (figure 3, a and b).
Preferably, the ratio of acrylamide: MBAA: the mass ratio of APS is 1: 0.0082: 0.03. the proportion of the cross-linking agent can affect the mechanical properties of the matrix gel after the matrix gel is cured into the hydrogel.
Preferably, the calcium source is introduced in a manner different from the conventional method (such as adding calcium sulfate, calcium chloride, etc.), but EDTA-CaCl is added2The method of the solution and the D-Gluconolactone (GDL) solution can slowly and uniformly release calcium ions in the gel, thereby being beneficial to forming uniform and transparent calcium alginate gel. Wherein, sodium alginate: EDTA-CaCl2(0.25M aqueous solution, pH 8.6): the mass ratio of GDL is 1: 2.16: 0.8.
preferably, a photoinitiator (e.g., Igracure 2959) can be used in place of the thermal initiator APS to impart photocurable properties to the matrix gel.
B. Preparation of printable conductive ink
And (3) uniformly mixing the matrix gel obtained in the step (A) with polyvinylpyrrolidone (PVP), glycerol and a micron silver sheet by using a planetary stirring instrument, and transferring the mixture into a 3mL charging barrel for centrifugation to obtain the conductive ink capable of being extruded and printed.
Preferably, the 3D printed hydrogel matrix: PVP (molecular weight 44000-54000Da, 40% wt aqueous solution): glycerol: the mass ratio of the micron silver sheets is 1: 0.05: 0.05: 0.5-1.5, wherein the mass ratio of the silver flakes can influence the rheological property of the ink and the conductivity of the cured ink, and the size of the micron silver flakes is 5 μm.
Preferably, the centrifugation conditions are: centrifugation is carried out at 2000 and 2500g for 10min at 18 ℃.
C. Printing of hydrogel electronics
And (2) defoaming the embedded 3D printing substrate of the ink B, filling the defoamed substrate into a mold with a proper shape, and printing the conductive ink of the ink B in the substrate according to a program by using a direct-writing 3D printer (mainly comprising three degrees of freedom in the directions of x, y and z and a dispenser with controllable air pressure). Due to the special rheological properties, the matrix can support the free printing of the conductive paste in three dimensions (fig. 1).
Preferably, the printing needle nozzle in C can select the inner diameter size of 100 μm, 150 μm, 250 μm or 400 μm according to the requirement.
D. Cured encapsulation of hydrogel electronic devices
And C, curing and packaging the printed hydrogel electronic device under the conditions of ultraviolet light, heating and the like according to the type of the initiator to form the hydrogel electronic device with good stretchability and elasticity.
Preferably, the thermal initiator is Ammonium Persulfate (APS), the heating temperature is 60 ℃, and the heating time is 1 h. Curing should be carried out as much as possible in a high humidity, oxygen-free environment; the photoinitiator can be Igracure 2959 with good water solubility and low toxicity, and the light intensity of the ultraviolet light is 50mW/cm2The time is 1 h.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available products.
The planetary stirrer (model ARE-310) used in the following examples was purchased from Thinky (Japan).
The 3D printer was a 3-axis high precision direct write printer built by the laboratory with a dispenser (model Performus V, available from nuxin EFD inc.
EXAMPLE 1 fabrication of hydrogel electronic Strain Sensors
The method comprises the following steps:
A. acrylamide (6.06g) and sodium alginate (0.75g) were dissolved in deionized water (41.2g) at 45 ℃ with magnetic stirring to give a clear viscous solution. After the solution had cooled to 25 ℃ room temperature, crosslinker MBAA (2.496mL, 2mg/mL aqueous solution), initiator APS (181.8mg), EDTA-CaCl were added2An aqueous solution (0.25M, pH 8-9). After the solution was completely dissolved, GDL (0.6g) was added, and after the solution was dissolved, the resulting viscous solution was sealed and stored in a refrigerator at 4 ℃ for 12 hours to form calcium alginate gel.
B. The gel obtained in step a was broken into coarse gel particles using a mill, and the coarse gel particles were filtered into fine gel particles using a 10mL syringe and a syringe filter having a pore size of 20 μm and defoamed using a Thinky planetary mixer (2200rpm until no bubbles were present) to obtain a uniform embedded 3D printing matrix gel, which was stored in a refrigerator at 4 ℃.
C. PVP (specification K30, 44000-54000Da, 50mg, 40% wt in water), glycerol (50mg) and silver flakes (0.5g, 1.0g and 1.5g) of size 5 μm were added to the matrix gel obtained in step B (1g) and mixed using a Thinky planetary mixer (2000rpm,1.5min,3 times, temperature not higher than 25 ℃). The resulting material was loaded into a 3mL cartridge and centrifuged at 2500g for 10min to give a printable conductive paste. The temperature of the whole process is required to be kept not to exceed 25 ℃ of room temperature. The conductivity of the cured conductive paste was measured by a Hall effect meter and Van der Paurg method, and the results were 2.1X 10 for pastes containing 0.5g, 1.0g and 1.5g of silver flakes, respectively1S/cm、4.0×102S/cm and 1.4X 103S/cm. And selecting the paste with the silver flake mass of 1.5g for subsequent printing.
D. And D, filling the matrix gel obtained in the step B into a die with the size of 30mm multiplied by 10mm multiplied by 2.5mm, extruding and printing the conductive paste selected in the step C into the matrix gel by using a direct-writing 3D printer, covering the die with the matrix by using a cover glass, and heating the die in a high-humidity environment for 1h to cure the die to obtain the hydrogel strain sensor. In this embodiment, the printed device is a linear strain sensor with exposed conductive interfaces at two ends, the line width is 250 μm, the needle is tightly attached to the bottom surface of the mold to extrude conductive paste when the exposed conductive interfaces are printed, and a G code simulation diagram and a physical diagram are shown in fig. 4 (a).
E. And D, performing resistance-strain test and cyclic tensile test on the hydrogel strain sensor obtained in the step D by using a desktop-level tensile tester, as shown in FIG. 4 (b). The result shows that the sensor can bear 1000% of strain before being damaged, and the resistance rise proportion of the sensor is approximately linearly related to the strain; in addition, the sensor showed better stability at 300% cyclic strain. Test results show that the hydrogel strain sensor prepared by the method and the matched material has the potential of being used as a biological strain sensor and flexible electronics.
FIG. 4(c) is a graph of the rate of change of resistance versus strain for a hydrogel strain sensor.
FIG. 4(d) is a graph of the rate of change of resistance versus strain for a hydrogel strain sensor at 300% strain cycle.
EXAMPLE 2 hydrogel inductor/antenna fabrication
The method comprises the following steps:
A. materials were prepared as in example 1.
B. And B, filling the matrix gel obtained in the step A into a mold with a proper size, extruding and printing the conductive paste into the matrix gel by using a direct-writing 3D printer, covering the mold filled with the matrix with a cover glass, and heating the mold at 60 ℃ for 1h to cure the mold in a high-humidity environment to obtain the hydrogel strain sensor. The printed device in this embodiment is a series of spiral inductors with exposed conductive interfaces at both ends and a solenoid wireless energy supply antenna connected with a Light Emitting Diode (LED), and G code simulation diagrams and physical diagrams thereof are shown in fig. 5(a, b, d, e).
C. Measuring the manufactured inductance value by using an LCR bridge under the measuring conditions of 1V and 200 kHz; and compared with the inductance value simulated by the Comsol software, the result proves that the two are close to fit, as shown in fig. 5 (c).
D. The result of using the rf transmitting coil to function as an antenna-LED device shows that the printed antenna can make a 1206 model red LED work normally to emit light, as shown in fig. 5 (f).
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (5)
1. A hydrogel matrix material is characterized in that the hydrogel matrix material is obtained by dissolving an ionic cross-linkable high molecular compound, a free radical polymerizable monomer, a cross-linking agent and an initiator in deionized water, then introducing metal ions to make the high molecular compound undergo ionic cross-linking through coordination bonds, and crushing the obtained gel into micron gel particles;
wherein the initiator is a thermal initiator or a photoinitiator.
2. The hydrogel matrix material of claim 1, wherein the hydrogel matrix material is prepared by a process comprising:
(1) dissolving an ionic crosslinking polymer compound and a free radical polymerization monomer in deionized water under the heating condition by magnetic stirring to obtain a transparent viscous solution;
(2) cooling the viscous solution obtained in the step (1) to below 25 ℃, adding a cross-linking agent, an initiator and an ethylene diamine tetraacetic acid chelate of metal ions, and stirring to dissolve the mixture;
(3) adding D-gluconolactone into the solution obtained in the step (2), stirring to dissolve the D-gluconolactone, and refrigerating the obtained solution overnight to form an ionic crosslinked gel;
(4) and (3) mechanically crushing the ionic crosslinked gel obtained in the step (3) into coarse gel particles, filtering the coarse gel particles into fine gel particles by using an injector and a filter, and defoaming the fine gel particles by using a planetary stirrer to obtain the hydrogel matrix material for embedded 3D printing.
3. The hydrogel matrix material of claim 2, wherein the pore size of the syringe and filter used in step (4) is 20-50 μm.
4. The conductive material for 3D printing is characterized in that the hydrogel matrix material of claim 2 or 3, an aqueous solution of polyvinylpyrrolidone, glycerol and a micron silver sheet are uniformly mixed by a planetary mixer, and then the mixture is transferred into a cylinder for centrifugal deaeration to obtain the conductive material for 3D printing;
preferably, the micron silver flake size is 2-10 μm;
the centrifugation conditions were: centrifugation is carried out at 2000 and 2500g for 10min at 18 ℃.
A method for manufacturing a 3D printed hydrogel electronic device, which is characterized in that the hydrogel matrix material of claim 2 or 3 is filled into a mold with a certain shape, the conductive material of claim 4 is printed in the hydrogel matrix material by a 3D printer according to a preset program, and then the hydrogel electronic device with good stretchability and elasticity is obtained by curing under ultraviolet light or heating.
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