CN112321862B - Simple process for high-transparency multifunctional ultrathin ionized skin - Google Patents

Simple process for high-transparency multifunctional ultrathin ionized skin Download PDF

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CN112321862B
CN112321862B CN202011252869.7A CN202011252869A CN112321862B CN 112321862 B CN112321862 B CN 112321862B CN 202011252869 A CN202011252869 A CN 202011252869A CN 112321862 B CN112321862 B CN 112321862B
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朱雨田
姜妞
常晓华
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Hangzhou Normal University
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    • C08J2379/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract

The invention discloses a simple process for high-transparency multifunctional ultrathin ionized skin. Adding the ionic liquid solution into the elastomer precursor solution, uniformly stirring the ionic liquid solution and the elastomer precursor solution at a high speed, and then standing for a period of time; and pouring the mixed solution after standing into a mould, and putting into an oven for vacuum drying to obtain the product. The method for blending the solution and volatilizing the solvent is simple and easy to implement, has high feasibility, is easy to realize industrial production, and widens the application range.

Description

Simple process for high-transparency multifunctional ultrathin ionized skin
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a simple process for a high-transparency multifunctional ultrathin ionic skin.
Background
The wearable flexible sensor has potential application prospects in emerging fields such as touch screens, electronic skins, human health monitoring and the like. The traditional flexible sensor generally changes a resistance value based on mechanical deformation of the outside of a material, and converts a physical signal into a quantifiable electric signal. In order to obtain excellent sensing performance, some functionalized inorganic conductive particles, metal materials and carbon materials are usually introduced into a polymer elastomer, however, the difference between the young modulus of the inorganic particles and the young modulus of the polymer matrix is too large, so that the compatibility of the inorganic particles and the polymer matrix is poor, and the rigidity of the sensor as a whole is increased. Meanwhile, the introduction of inorganic particles also causes the light transmittance of the sensor to be greatly reduced. In addition, bacteria are easy to breed under human sweat or a humidity environment, so that human health is harmed, and the existing wearable flexible sensor has no substantial antibacterial performance. Based on the problems of the traditional wearable strain sensor, the flexible sensor with high sensitivity, high transparency and good antibacterial property prepared by utilizing the ion conduction mechanism gradually enters the visual field of people.
Ionic skin is a type of flexible sensor that uses ionic liquids, ionic gels, hydrogels, and other materials as elastic dielectrics. It is known that flexible sensors should have high sensitivity, maintain stable electrical signals along with the deformation of the outside of the material, and be able to recover itself after many deformations. In recent years, the variety of conductive gel sensors has been increasing, and mainly includes polyaniline, polypyrrole, polystyrene sulfonate, and the like. However, in order to obtain a highly sensitive, repeatable and stable sensor based on conductive gel, a complicated preparation process is usually involved, a lot of time and energy are consumed, the production cost is high, and the industrial production is difficult to realize.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art, provides a simple process for preparing a high-transparency multifunctional ultrathin ionized skin, and provides the multifunctional ultrathin ionized skin which has high antibacterial property, high sensitivity and good stability and can be used for sensing temperature and external acting force.
In order to solve the technical problem, the solution of the invention is as follows:
a method for preparing multifunctional ultrathin ionic skin with the thickness of 0.05-0.6 mm comprises the following steps:
adding a polymer elastomer into an organic solvent, and stirring to obtain an elastomer precursor solution;
the polymer elastomer is one or more of stretchable elastomers such as Polyimide (PI), polyurethane (PU), polydimethylsiloxane (PDMS), rubber (BR) and the like;
the organic solvent is a good solvent of the corresponding polymer elastomer.
Preferably, the stirring rate is 100 to 500r/min.
Adding the ionic liquid into an organic solvent, and stirring to obtain a diluted ionic liquid solution;
the ionic liquid is one or more of conductive ionic liquids such as 1-ethyl-3-methylimidazole tetrafluoroborate (EMIMBF 4), N-methyl, methoxyethyl pyrrolidine bis (trifluoromethanesulfonyl) imide salt (MEMPTFSI), 1-ethyl-3-methylimidazole bis (fluorosulfonyl) imide salt (EMIMTFSI), N-methylpropyl piperidine bis (trifluoromethanesulfonyl) imide salt (PP 13 TFSI) and the like;
the organic solvent is a good solvent of the corresponding ionic liquid;
preferably, the stirring rate is 100 to 500r/min.
Step (3), adding the ionic liquid solution obtained in the step (2) into the elastomer precursor solution obtained in the step (1), uniformly stirring the two solutions at a high speed, and then standing for a period of time;
preferably, the high-speed stirring speed is 800-1500 r/min;
preferably, the standing time is 0.5 to 2 hours;
and (4) pouring the mixed solution after standing into a mould, and putting the mould into an oven for vacuum drying to obtain the antibacterial multifunctional ionic skin based on the ionic liquid.
Preferably, the mass fraction of the ionic liquid in the electronic skin is 10% to 90%.
Preferably, the drying temperature is 80 to 250 ℃ and the drying time is 1 to 2 hours.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts the method of solution blending and solvent volatilization to prepare the multifunctional ionic skin with antibacterial property, is simple and easy to implement, has high implementability, is easy to realize industrial production and widens the application range.
(2) The polymer elastomer used in the invention has stretchability, excellent repeatability and stability, and endows the ionized skin with high sensitivity and larger deformability.
(3) The invention utilizes an ion transmission mechanism to endow the material with excellent conductivity, and simultaneously, the transparency and the antibacterial property of the ionic liquid endow the ionic skin with multiple functions.
Drawings
Fig. 1 is a diagram of a conductive mechanism of antibacterial multifunctional ionic skin based on ionic liquid.
Fig. 2 is a schematic view of the structure of the ionic skin of example 2.
FIG. 3 is a graph showing the resistance versus the change in the tensile strength in example 2.
FIG. 4 is a graph showing the resistance versus temperature change at an elevated temperature in example 4.
FIG. 5 is a graph of the resistance versus change for a finger touch in accordance with example 4.
FIG. 6 is a SEM image of example 2 and example 3.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Examples 1 to 8
In examples 1 to 8, a polymer elastomer of a certain mass was dissolved in a good solvent with reference to table 1, and an elastomer precursor solution was obtained after stirring; dissolving a certain mass of ionic liquid in a good solvent, and stirring to obtain a uniform ionic liquid solution; adding the ionic liquid solution into the polymer elastomer precursor solution, stirring the ionic liquid solution and the polymer elastomer precursor solution uniformly at a high speed, wherein the stirring speed is 800-1500 r/min, and then standing for 0.5-2 h; and pouring the mixed solution after standing into a mould, putting into an oven, and carrying out vacuum drying for 1-2 h at the temperature of 80-250 ℃ to obtain the antibacterial multifunctional ionic skin based on the ionic liquid.
In comparative example 1, a polymer film was prepared using the same method using a polymer elastomer to which no ionic liquid was added as a raw material. The polymer elastomer and ionic liquid ratios, solvent types, drying temperatures, etc. in examples 1 to 8 and comparative example 1 are shown in table 1.
Table 1: examples 1-8 and comparative example 1 conditions for preparing antibacterial multifunctional ionic skin based on ionic liquid
Figure BDA0002772160850000031
Figure BDA0002772160850000041
The sample of the invention is tested for the antibacterial performance of escherichia coli by a bacteriostatic circle method, the sample with the diameter of 0.5cm is put into a 50 mu l escherichia coli plank, incubated for 24h at 37 ℃, and the diameter of the bacteriostatic circle is observed. The results are shown in table 2, and the larger the inhibition zone diameter, the more significant the antibacterial effect of the ionic skin, with the increase of the mass fraction of the ionic liquid.
TABLE 2 antibacterial effect of ionized skin on Escherichia coli
Sample (I) Concentration of Escherichia coli (CFU/ml) Diameter of bacteriostatic circle (mm)
Example 1 1×10 6 9.2
Example 2 1×10 6 15.3
Example 4 1×10 6 18.5
Example 5 1×10 6 20.3
Example 6 1×10 6 25.7
Example 7 1×10 6 29.3
Example 8 1×10 6 35.5
Comparative example 1 1×10 6 0
Fig. 1 is a diagram of a conductive mechanism of antibacterial multifunctional ionic skin based on ionic liquid.
As shown in FIG. 2, the ionized skin obtained in example 2 was cut into a rectangular strip of 3cm by 0.5cm, silver paste was applied to both ends of the strip, the strip was wrapped with a copper sheet, and copper was bonded to the copper sheet. The tensile property of the sample strip is tested by using a universal tester, and a digital multimeter is used for recording the change signal of the resistance of the ionic skin under 10% strain in real time, wherein the resistance increases along with the increase of the strain, and the R/R is stretched in a reciprocating way for 10 cycles of the sensor under the strain along with the reduction of the recovery resistance of the strain, as shown in figure 3 0 The curves all showed the same response trend, indicating repeatability and stability.
As shown in FIG. 4, when the ionic skin obtained in example 4 is placed in silicone oil at 80 ℃, the rapid increase of the external temperature accelerates the movement rate of cations and anions in the ionic skin conduction path, so that the resistance decreases rapidly with the increase of the temperature, and the resistance changes to a greater extent with higher temperature.
As shown in fig. 5, when the volunteer touches the ionized skin with a finger, the ionized skin is deformed under the action of a slight pressure, the resistance decreases with the increase of the deformation, when the finger leaves, the resistance returns to the initial value, and the actions are repeated for several times, so that the resistance signals all show the same and stable variation trend.
As shown in fig. 6, the microstructure of the samples of example 2 and example 3 was characterized by using a scanning electron microscope, and as can be seen from fig. 6 (a), when the stirring rate of the mixed solution is 800r/min, the dispersion of the ionic liquid in the substrate is not uniform enough, and the size of the ionic liquid droplet is different, and when the stirring rate is increased to 1200r/min, the distribution of the ionic liquid in the substrate is more uniform, and the size is also more uniform, as shown in fig. 6 (b).
According to the analysis of the test results, the following steps are carried out: the antibacterial multifunctional ionic skin with the ionic liquid as the conductive filler and the polymer elastomer as the substrate material has high light transmittance, and solves the problems of poor ionic skin interface compatibility, complex preparation process, high cost and the like. In addition, the ultrathin ionized skin has higher sensitivity to temperature, stress and pressure, and can capture signals of resistance change generated under the action of tiny temperature and pressure in real time. Meanwhile, the ionic skin also has a stronger antibacterial function, and the characteristic provides more possibility for the application of the invention.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (5)

1. The application of the high-transparency ultrathin ionic skin on a sensor for sensing temperature and external acting force is characterized in that the thickness of the ionic skin is 0.05-0.6 mm, and the preparation process of the ionic skin comprises the following steps:
adding a polymer elastomer into an organic solvent, and stirring to obtain an elastomer precursor solution;
the polymer elastomer is one or more of polyimide PI, polyurethane PU, polydimethylsiloxane PDMS and rubber BR;
adding the ionic liquid into an organic solvent, and stirring to obtain a diluted ionic liquid solution;
the ionic liquid is one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate EMIMBF4, N-methyl, methoxyethyl pyrrolidine bistrifluoromethanesulfonyl imide salt MEMPTFSI, 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonyl imide salt EMIMTFSI and N-methylpropyl piperidine bistrifluoromethanesulfonyl imide salt PP13 TFSI;
step (3), adding the ionic liquid solution obtained in the step (2) into the elastomer precursor solution obtained in the step (1), uniformly stirring the two solutions at a high speed, and then standing for a period of time;
pouring the mixed solution after standing into a mould, and putting the mould into an oven for vacuum drying to obtain the antibacterial multifunctional ionic skin based on the ionic liquid;
the mass fraction of the ionic liquid in the electronic skin is 10-90%.
2. The use according to claim 1, wherein the stirring rate in steps (1) to (2) is from 100 to 500r/min.
3. The use according to claim 1, wherein the high speed stirring rate in step (3) is 800 to 1500r/min.
4. The use according to claim 1, wherein the standing time in step (3) is 0.5 to 2 hours.
5. Use according to claim 1, characterized in that the drying temperature is 80-250 ℃ and the drying time is 1-2 h.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108318162A (en) * 2018-01-10 2018-07-24 中山大学 A kind of flexible sensor and preparation method thereof
CN109945996A (en) * 2019-03-21 2019-06-28 苏州大学 A kind of novel robot electronic skin and preparation method thereof
CN110358297A (en) * 2018-12-29 2019-10-22 钛深科技(深圳)有限公司 Ionic rubber elastomer and preparation method thereof, from electronic type electronic skin

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WO2014169119A1 (en) * 2013-04-10 2014-10-16 President And Fellows Of Harvard College Stretchable ionics for transparent sensors and actuators

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108318162A (en) * 2018-01-10 2018-07-24 中山大学 A kind of flexible sensor and preparation method thereof
CN110358297A (en) * 2018-12-29 2019-10-22 钛深科技(深圳)有限公司 Ionic rubber elastomer and preparation method thereof, from electronic type electronic skin
CN109945996A (en) * 2019-03-21 2019-06-28 苏州大学 A kind of novel robot electronic skin and preparation method thereof

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