CN112647156B - Method for electrochemically assisting preparation of liquid metal hydrogel fiber - Google Patents
Method for electrochemically assisting preparation of liquid metal hydrogel fiber Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 87
- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title description 4
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 238000007711 solidification Methods 0.000 claims abstract description 30
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- 239000008384 inner phase Substances 0.000 claims description 39
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 17
- 235000010413 sodium alginate Nutrition 0.000 claims description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
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- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
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- 238000001000 micrograph Methods 0.000 description 4
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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Abstract
The invention discloses a method for electrochemically assisting in preparing liquid metal hydrogel fibers, which comprises the following steps: and respectively injecting liquid metal and hydrogel precursor liquid from an injection port of a microfluidic chip device by adopting a microfluidic spinning method, allowing the liquid metal and the hydrogel precursor liquid to flow into solidification liquid through an outlet of the microfluidic chip device to solidify the hydrogel, and applying a potential between the liquid metal and the solidification liquid to reduce the surface tension of the liquid metal so as to prepare the hydrogel fiber continuously filled with the liquid metal. The invention obviously reduces the surface tension of the liquid metal by using an electrochemical method, realizes the continuous filling of the liquid metal in the hydrogel fiber, and provides a new idea for preparing a high-conductivity multifunctional hydrogel flexible sensor.
Description
Technical Field
The invention relates to the technical field of functional hydrogel fiber preparation, in particular to a method for electrochemically assisting in preparing liquid metal hydrogel fiber.
Background
The hydrogel has excellent biocompatibility and mechanical properties similar to those of biological tissues, and is an ideal carrier for preparing flexible electronic devices. The hydrogel flexible electronic device has great application potential in the advanced scientific and technological fields of wearable sensors, implantable sensors, drug release, tissue engineering, organ chips and the like. When a hydrogel flexible electronic device is prepared, conductive materials are often required to be doped into the hydrogel to improve the electrical properties of the hydrogel, the conductive materials comprise ionic conductors, low-dimensional nano materials, conductive polymers and other materials, and the conductive materials have the problems of poor biocompatibility, low conductivity, mismatch with the mechanical properties of the hydrogel and the like.
Room temperature liquid metals such as gallium and its alloys, which have both high electrical conductivity and fluidity, are ideal materials for making flexible conductors. In addition, the liquid metal has the advantages of good biocompatibility, self-repairing property, stretchability and the like, so that the liquid metal is widely applied to the fields of flexible sensors, stretchable electronics, soft robots and the like. The liquid metal is introduced into the hydrogel matrix, so that the electrical property of hydrogel electrons can be obviously enhanced, and the application range and depth of the hydrogel flexible functional device can be expanded.
Microfluidic technology is a technology for manipulating fluids in channels on the micrometer scale. Within a microchannel, a fluid tends to exhibit some unique characteristics, such as laminar flow, fluid shear, and the like. The microstructure which is difficult to realize by the conventional technology can be prepared by utilizing the fluid characteristics presented under the microscopic scale, for example, the conductive hydrogel fiber with controllable structure can be prepared by utilizing the microfluidic spinning technology. However, these conductive hydrogel fibers have problems such as poor conductivity and biocompatibility. The problem can be well solved by filling high-conductivity liquid metal into the hydrogel fiber by using a microfluidic spinning technology, but the process is very challenging because the liquid metal has high surface tension and the continuous and uniform filling of the liquid metal in the hydrogel fiber is difficult to realize by using the traditional microfluidic spinning technology, so that it is very necessary to develop a novel microfluidic spinning technology to prepare the liquid metal hydrogel fiber.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for electrochemically assisting in preparing liquid metal hydrogel fibers, which can enable liquid metal to be continuously and uniformly filled in the hydrogel fibers.
The technical scheme is as follows: the invention discloses a method for electrochemically assisting in preparing liquid metal hydrogel fibers, which comprises the following steps: respectively injecting liquid metal and hydrogel precursor liquid from an injection port of a microfluidic chip device, flowing into a solidification liquid through an outlet of the microfluidic chip device, solidifying the hydrogel, applying a potential between the liquid metal and the solidification liquid, and reducing the surface tension of the liquid metal to prepare the liquid metal filled hydrogel fiber.
Furthermore, the microfluidic chip device comprises an inner phase channel and an outer phase channel which are communicated with each other through fluid, the inner phase channel is used for containing liquid metal, the outer phase channel is used for containing hydrogel precursor liquid, and the inner phase channel and the outer phase channel are respectively connected with the injection port.
Furthermore, the inner phase channel is provided with an inner phase channel outlet, the outlet of the inner phase channel is positioned inside the outer phase channel, the outer phase channel is provided with an outer phase channel outlet, and the liquid metal flows into the outer phase channel from the inner phase channel outlet, is coated by the hydrogel precursor liquid in the outer phase channel and then flows into the solidification liquid from the outlet of the outer phase channel.
Further, the ratio of the inner diameter of the inner phase channel to the outer phase channel is 1.
Further, the liquid metal is a simple metal substance which is liquid at normal temperature and an alloy thereof, such as gallium and an alloy thereof.
Further, the hydrogel precursor is a hydrogel monomer capable of rapidly polymerizing, such as an aqueous sodium alginate solution or an aqueous polyethylene glycol diacrylate (PEGDA) solution; when the concentration of the precursor solution of the hydrogel is sodium alginate aqueous solution, the concentration of the sodium alginate is 1-5wt%, the coagulating liquid is calcium chloride aqueous solution, and the concentration of the calcium chloride is 1-5wt%. When the PEGDA aqueous solution is used, its concentration is 1-4wt%, and a photoinitiator is mixed with the PEGDA aqueous solution, and uv light irradiation is provided at the outlet of the external phase channel to achieve rapid photocuring.
Furthermore, the ionic strength of the hydrogel precursor liquid and the solidification liquid is improved to realize electrochemical regulation and control of the surface tension of the liquid metal, and supporting electrolytes which do not react with the hydrogel precursor liquid and the solidification liquid, such as sodium chloride and potassium chloride, can be added into the hydrogel precursor liquid and the solidification liquid.
Further, the flow rate of the liquid metal is 6-12mL/h; the flow rate of the hydrogel precursor solution is 12-20mL/h.
Further, a specific method for applying a potential between the liquid metal and the solidification liquid is as follows: placing an inert electrode such as gold, platinum or carbon electrode in the coagulating liquid, connecting the inert electrode with the cathode of a direct current power supply, and connecting the liquid metal with the anode of the direct current power supply.
Further, the applied potential is 1 to 6V, preferably 2.5 to 3.5V.
The principle of the method for preparing the liquid metal hydrogel fiber by electrochemical assistance is that after an electric field is formed between liquid metal and solidification liquid, the surface tension of the liquid metal can be reduced, the generation of spherical liquid metal liquid drops is avoided, the liquid metal is still in a filament shape after being extruded, and when the liquid metal and the external-phase hydrogel precursor liquid contact the solidification liquid, hydrogel is solidified to form the hydrogel fiber uniformly filled with the liquid metal.
Further, in order to avoid the continuous electrochemical oxidation of the liquid metal in the coagulation liquid, an organic reagent which is insoluble in water and has a density greater than that of water may be added to the coagulation liquid, so that the solidified liquid metal hydrogel fibers are collected in the organic reagent, such as dichloromethane, chloroform, fluorosilicone oil, and the like.
Further, in view of the higher density of the liquid metal, the axial direction of the fluid channel should be kept vertical during the microfluidic spinning process.
Further, in order to improve the mechanical properties of the hydrogel, other hydrogel monomers can be added into sodium alginate or PEDGA hydrogel precursor solution, and secondary crosslinking is performed after spinning is finished.
Further, a plurality of internal phase channels may be provided for receiving the liquid metal in order to prepare a hydrogel fiber containing multiple cores of the liquid metal.
Has the advantages that: according to the invention, the surface tension of the liquid metal is reduced by using an electrochemical method, so that the formation of dispersed liquid metal drops in the microfluidic spinning process is avoided, the liquid metal can be continuously filled in hydrogel fibers, and the construction of a high-conductivity hydrogel fiber device is facilitated. The method has the advantages of simple and efficient operation, low cost, large-scale production, environmental protection and the like. The structural size of the liquid metal hydrogel fiber can be accurately regulated and controlled by controlling parameters of microfluidic spinning, such as the flow velocity of the inner phase and the outer phase, the inner diameter of the inner phase and the outer phase and the applied potential.
Drawings
FIG. 1 is a schematic view of a microfluidic chip device used in the present invention;
FIG. 2 is a micrograph of a liquid metal hydrogel fiber prepared in example 1;
FIG. 3 is a pictorial view of a liquid metal hydrogel fiber prepared in example 2;
FIG. 4 is a micrograph of a liquid metal hydrogel fiber prepared in example 2.
Detailed Description
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to make the technical solutions of the present invention practical in accordance with the content of the specification, the following detailed description of the embodiments of the present invention is given with reference to the examples. The following examples are intended to illustrate the invention without limiting its scope.
Referring to fig. 1-4, in the following embodiments of the present invention, the structure of the microfluidic chip device is as follows:
the liquid metal hydrogel precursor solidifying device comprises an inner phase channel 1 and an outer phase channel 2 which are communicated with each other through fluid and are coaxial, wherein the inner phase channel is used for accommodating liquid metal 6, the outer phase channel is used for accommodating a hydrogel 7 precursor liquid, an outlet of the inner phase channel is arranged in the outer phase channel, the inner phase channel and the outer phase channel are respectively provided with an injection port, the inner diameter of the inner phase channel is 100 micrometers, the inner diameter of the outer phase channel is 1000 micrometers, and an outlet of the outer phase channel is inserted into a solidifying liquid 5. An inert electrode 3 is placed in the solidification liquid, the inert electrode is connected with the negative electrode of a direct current power supply 4, and liquid metal 6 is connected with the positive electrode of the direct current power supply through a stainless steel needle of an injector. And the liquid metal is injected from an injection port of the inner phase channel and flows into the outer phase channel from an outlet of the inner phase channel, and the liquid metal is wrapped by the hydrogel precursor liquid of the outer phase and flows into the solidification liquid from an outlet of the outer phase channel.
Example 1
Weighing 2g of sodium alginate and 5.8g of sodium chloride, adding 100g of deionized water, and placing on a magnetic stirrer to stir continuously to fully dissolve the sodium alginate and the sodium chloride, wherein the temperature is set to be 60 ℃. Finally preparing the sodium alginate aqueous solution with the concentration of 2 wt%. Sodium chloride was added to increase the ionic strength of the solution, which was used as a hydrogel precursor.
20g of anhydrous calcium chloride and 5.8g of sodium chloride are weighed, 1000g of deionized water is added, and the mixture is stirred until the anhydrous calcium chloride and the sodium chloride are dissolved to be used as a solidification solution.
76.5g of gallium metal and 23.5g of indium metal are weighed and placed in a glass beaker, and the glass beaker is placed in an oven and heated for 5 hours at 250 ℃ to obtain gallium-indium alloy liquid metal with the melting point of 15.6 ℃.
After the solution is prepared, performing micro-fluidic spinning, injecting the prepared hydrogel precursor solution into the outer phase channel from an injection port of the outer phase channel, and injecting liquid metal into the inner phase channel from an injection port of the inner phase channel, wherein the injection speed of the hydrogel precursor solution is 15mL/h, the injection speed of the liquid metal is 10mL/h, the applied voltage is 3V, the liquid metal flows out from the inner phase channel, and then the liquid metal is wrapped by sodium alginate solution and enters the coagulating liquid, and the sodium alginate solution is subjected to gelation reaction after meeting calcium chloride in the coagulating liquid, and then is converted into fibers to be separated out, so as to form fiber filaments wrapping continuous liquid metal. In order to avoid the continuous oxidation of the liquid metal, the fluorosilicone oil which is higher in density than water and insoluble in water is added into the solidification liquid, and finally the liquid metal hydrogel fibers enter the fluorosilicone oil under the action of gravity so as to be collected.
FIG. 2 is a micrograph of the liquid metal hydrogel fiber obtained in this example, and it can be seen that the liquid metal is continuously filled in the hydrogel fiber.
Example 2
3g of PEGDA,1g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (HMPP) and 5.8g of sodium chloride are weighed and added with 100g of deionized water to be uniformly mixed in a dark place. Finally preparing the PEGDA aqueous solution with the concentration of 3 wt%. Sodium chloride was added to increase the ionic strength of the solution, which was used as a hydrogel precursor.
68.5g of gallium metal, 21.5g of indium metal and 10g of tin metal are weighed and placed in a glass beaker, and the glass beaker is placed in an oven and heated for 5 hours at 300 ℃ to obtain gallium indium tin alloy liquid metal, wherein the melting point of the liquid metal is-19 ℃.
58g of sodium chloride was weighed, and 1000g of deionized water was added thereto and sufficiently dissolved to obtain a solidification solution.
And after the solution is prepared, carrying out micro-fluidic spinning, injecting the prepared PEGDA aqueous solution into the outer phase channel from an injection port of the outer phase channel, and injecting liquid metal into the inner phase channel from an injection port of the inner phase channel, wherein the injection speed of the hydrogel precursor solution is 6mL/h, the injection speed of the liquid metal is 12mL/h, the applied voltage is 3.5V, the liquid metal flows out from the inner phase channel, then the liquid metal is wrapped by the PEGDA solution and enters the solidification solution, 365nm ultraviolet curing and the like are used for irradiating the outlet of the outer phase channel, so that the PEGDA is subjected to photopolymerization reaction, and then the PEGDA is converted into fibers to be separated out, and the fiber filaments wrapping the continuous liquid metal are formed. This example illustrates that the electrochemical-assisted preparation of liquid metal fibers is applicable not only to ionically crosslinked sodium alginate hydrogels, but also to photo-cured hydrogel systems.
FIG. 3 is a schematic representation of a liquid metal hydrogel fiber obtained in this example;
FIG. 4 is a micrograph of a liquid metal hydrogel fiber obtained in this example.
Example 3
In this embodiment, the adopted microfluidic chip device includes two inner phase channels, both of which are used for accommodating liquid metal, the inner diameters of the two inner phase channels are 100 micrometers, the channel outlets of the two inner phase channels are located inside the outer phase channel, the inner diameter of the outer phase channel is 1000 micrometers, the distance between the axes of the two inner phase channels is 300 micrometers, and the outlet of the outer phase channel is placed in a solidification liquid. The liquid metal of the two internal phase channels is connected with the anode of a power supply through a stainless steel needle of the injector, and the gold electrode in the solidification liquid is connected with the cathode of the power supply.
3g of sodium alginate and 11.6g of sodium chloride are weighed, 100g of deionized water is added, and the mixture is placed on a magnetic stirrer to be stirred continuously to be fully dissolved, wherein the temperature is set to be 60 ℃. Finally preparing the sodium alginate aqueous solution with the concentration of 3 wt%. Sodium chloride was added to increase the ionic strength of the solution, and the mixed solution was used as a hydrogel precursor.
40g of anhydrous calcium chloride and 5.8g of sodium chloride are weighed, 1000g of deionized water is added, and the mixture is stirred until dissolved to be used as a solidification solution.
76.5g of gallium metal and 23.5g of indium metal are weighed and placed in a glass beaker, and the glass beaker is placed in an oven and heated for 5 hours at 250 ℃ to obtain gallium-indium alloy liquid metal with the melting point of 15.6 ℃.
After the solution is prepared, performing micro-fluidic spinning, injecting the prepared hydrogel precursor solution into the outer phase channel from an injection port of the outer phase channel, and injecting liquid metal into the inner phase channel from injection ports of the two inner phase channels, wherein the injection speed of the hydrogel precursor solution is 18mL/h, the injection speed of the liquid metal is 8mL/h, the applied voltage is 2.5V, the liquid metal flows out from the two inner phase channels, and then the liquid metal is wrapped by the sodium alginate solution and enters the solidification solution, and the sodium alginate solution is subjected to gelation reaction after encountering calcium chloride in the solidification solution, and then is converted into fibers to be separated out, so as to form the fiber filament wrapping the double-core continuous liquid metal. In order to avoid continuous oxidation of the liquid metal, carbon tetrachloride which is higher in density than water and insoluble in water is added into the solidification liquid, and finally, the liquid metal hydrogel fibers enter the carbon tetrachloride under the action of gravity so as to be collected.
This example illustrates that by increasing the number of internal phase channels, more multicore liquid metal hydrogel fibers can be prepared, which facilitates the construction of integrated hydrogel sensors, such as capacitance-responsive hydrogel strain sensors.
Claims (7)
1. A method for preparing liquid metal hydrogel fibers by electrochemical assistance is characterized by comprising the following steps: respectively injecting liquid metal and hydrogel precursor liquid from an injection port of a microfluidic chip device, allowing the liquid metal and the hydrogel precursor liquid to flow into a solidification liquid through an outlet of the microfluidic chip device, solidifying or photocuring the hydrogel, applying a potential between the liquid metal and the solidification liquid, and reducing the surface tension of the liquid metal to prepare a liquid metal-filled hydrogel fiber; the micro-fluidic chip device comprises an inner phase channel and an outer phase channel which are communicated by fluid, the inner phase channel is used for containing liquid metal, the outer phase channel is used for containing hydrogel precursor liquid, and the inner phase channel and the outer phase channel are respectively connected with the injection port; the hydrogel precursor solution is a sodium alginate aqueous solution or a polyethylene glycol diacrylate aqueous solution, when the concentration of the hydrogel precursor solution is the sodium alginate aqueous solution, the concentration of sodium alginate is 1-5wt%, the solidification solution is a calcium chloride aqueous solution, the concentration of calcium chloride is 1-5wt%, and an organic reagent which is insoluble in water and has a density larger than that of water is added into the solidification solution, wherein the organic reagent comprises dichloromethane, trichloromethane, chloroform and fluorosilicone oil; when the polyethylene glycol diacrylate aqueous solution is used, the concentration of the polyethylene glycol diacrylate aqueous solution is 1-4wt%, the photoinitiator is mixed with the polyethylene glycol diacrylate aqueous solution, and ultraviolet lamp irradiation is arranged at the outlet of the external phase channel to realize rapid photocuring; the specific method for applying the potential between the liquid metal and the solidification liquid comprises the following steps: and placing an inert electrode in the solidification liquid, wherein the inert electrode is connected with the negative electrode of a direct current power supply, and the liquid metal is connected with the positive electrode of the direct current power supply.
2. The method of claim 1, wherein: the inner phase channel is provided with an inner phase channel outlet, the outlet of the inner phase channel is positioned in the outer phase channel, the outer phase channel is provided with an outer phase channel outlet, and liquid metal flows into the outer phase channel from the inner phase channel outlet, is coated by hydrogel precursor liquid in the outer phase channel and flows into the solidification liquid from the outlet of the outer phase channel.
3. The method of claim 1, wherein: the ratio of the inner phase channel to the outer phase channel is 1.
4. The production method according to claim 1, characterized in that: the liquid metal is gallium-indium alloy or gallium-indium-tin alloy; the coagulating liquid comprises one or two of a calcium chloride solution and a sodium chloride solution.
5. The method of claim 1, wherein: the flow rate of the liquid metal is 6-12mL/h; the flow rate of the hydrogel precursor liquid is 12-20mL/h.
6. The method of claim 1, wherein: the inner phase channel is provided with a plurality of channels.
7. The method of claim 1, wherein: the magnitude of the applied potential is 1-6V.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109338716A (en) * | 2018-09-28 | 2019-02-15 | 成都新柯力化工科技有限公司 | A kind of fibrous composite and preparation method for robot electronic skin |
| CN110016725A (en) * | 2019-03-25 | 2019-07-16 | 绍兴钠钇光电有限公司 | A method of there is the fiber of heat insulation function based on microflow control technique preparation |
| CN111069606A (en) * | 2019-12-06 | 2020-04-28 | 北京航空航天大学 | Continuous forming method of low-melting-point metal |
| CN111101214A (en) * | 2020-01-09 | 2020-05-05 | 苏州大学 | Coaxial skin-core layer structure color fiber and microfluidic preparation method thereof |
| CN111485296A (en) * | 2020-05-19 | 2020-08-04 | 南京鼓楼医院 | Preparation method and application of bionic multi-component fiber |
| CN111549396A (en) * | 2020-05-29 | 2020-08-18 | 南京鼓楼医院 | Fiber wrapping liquid metal and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015175989A2 (en) * | 2014-05-16 | 2015-11-19 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona, Acting For And On Behalf Of Arizona State University | Methods of rapid 3d nano/microfabrication of multifunctional shell-stabilized liquid metal pipe networks and insulating/metal liquids electro-mechanical switch and capacitive strain sensor |
-
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- 2020-12-21 CN CN202011518377.8A patent/CN112647156B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109338716A (en) * | 2018-09-28 | 2019-02-15 | 成都新柯力化工科技有限公司 | A kind of fibrous composite and preparation method for robot electronic skin |
| CN110016725A (en) * | 2019-03-25 | 2019-07-16 | 绍兴钠钇光电有限公司 | A method of there is the fiber of heat insulation function based on microflow control technique preparation |
| CN111069606A (en) * | 2019-12-06 | 2020-04-28 | 北京航空航天大学 | Continuous forming method of low-melting-point metal |
| CN111101214A (en) * | 2020-01-09 | 2020-05-05 | 苏州大学 | Coaxial skin-core layer structure color fiber and microfluidic preparation method thereof |
| CN111485296A (en) * | 2020-05-19 | 2020-08-04 | 南京鼓楼医院 | Preparation method and application of bionic multi-component fiber |
| CN111549396A (en) * | 2020-05-29 | 2020-08-18 | 南京鼓楼医院 | Fiber wrapping liquid metal and preparation method thereof |
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