CN114149595A - High-elasticity hydrogel sensor and preparation method thereof - Google Patents
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Abstract
The invention discloses a high-elasticity hydrogel sensor and a preparation method thereof. The invention adopts a one-step method to prepare the double-network hydrogel sensor with the interpenetrating structure, which not only has high elasticity, but also can accurately and effectively sense the size, the shape and the position of force.
Description
Technical Field
The invention relates to a preparation method of a sensor, in particular to a high-elasticity hydrogel sensor and a preparation method thereof.
Background
The traditional sensor can only sense tiny deformation and cannot meet the requirements of large mechanical deformation such as bending, folding, twisting, stretching and the like. Hydrogel sensors have good flexibility, ductility, and biocompatibility, and can overcome the inherent rigidity of conventional sensors made of metallic or semiconducting materials. Therefore, the hydrogel sensor has wide application prospects in the fields of remote health monitoring, body motion tracking, electronic skin, wearable electronic equipment, soft robots and the like.
However, the existing hydrogel has poor mechanical properties, can be broken under low strain, and cannot be repaired and rebounded by self. The preparation of hydrogel with good mechanical properties is of great significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a high-elasticity hydrogel sensor with excellent mechanical properties.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-elasticity hydrogel sensor comprises the following steps:
step 1, adding a first monomer into water, and uniformly stirring at 45-55 ℃ to obtain a solution A;
step 2, adding a conductive filler into the solution A, and uniformly mixing at normal temperature to obtain a solution B;
step 3, adding a second monomer into the solution B, and uniformly mixing at normal temperature to obtain a solution C;
step 4, adding an initiator, a cross-linking agent and a catalyst into the solution C, and uniformly mixing at normal temperature to obtain a solution D;
and 5, pouring the solution D into a sealed mould, and putting the sealed mould into a drying oven with the temperature of 35-65 ℃ for heat preservation and solidification for 3-6 h to obtain the high-elasticity hydrogel sensor.
Further: and (2) making the total mass of the first monomer, the second monomer, the conductive filler, the initiator, the cross-linking agent and the catalyst M be M, then: the mass of the first monomer accounts for 5-20% of that of M, the mass of the second monomer accounts for 56.8-91.35% of that of M, the mass of the conductive filler accounts for 0.1-5% of that of M, the mass of the initiator accounts for 0.5-2% of that of M, the mass of the cross-linking agent accounts for 0.05-0.2% of that of M, and the mass of the catalyst accounts for 3-16% of that of M.
Further, in the solution D, the mass percentage of water is 75-95%.
Further, the first monomer is one of sodium alginate, chitosan, Gelatin (Gelatin), carrageenan and curdlan gum.
Further, the second monomer is one of acrylamide, acrylic acid, isopropyl acrylamide and acrylamide methyl propane sulfonic acid.
Further, the conductive filler is at least one of lithium chloride, calcium chloride, ferric chloride, sodium sulfate, aluminum chloride, polypyrrole, polyaniline, liquid metal, carbon black, graphene oxide and carbon nanotubes.
Further, the initiator is one of ammonium persulfate and potassium persulfate.
Further, the cross-linking agent is one of methylene-bis-propyl amide, polyethylene glycol methyl methacrylate and cetyl methacrylate.
Further, the catalyst is one of tetramethylethylenediamine and hexadecyltrimethylammonium bromide.
Compared with the prior art, the invention has the beneficial effects that:
1. when the hydrogel sensor is prepared, the first monomer and the second monomer are respectively crosslinked in a physical crosslinking mode and a chemical crosslinking mode, the physical crosslinking forms a first network, the chemical crosslinking forms a second network, and the two network structures are interpenetrating and play a good synergistic role. The single chemical crosslinking structure has better strength, but can not be repaired by self after being damaged by stress; the single physical cross-linked structure has good elasticity and can be repaired by itself after being damaged by stress. The invention is formed by two structures which complement each other, and the double-network high-elasticity hydrogel with an interpenetrating structure is obtained.
2. The invention obtains hydrogel with good mechanical property, especially the elastic property. After the deformation caused by external force, the deformation can be recovered quickly after the external force is removed, and the attenuation of stress is less than or equal to 25 percent after 20 times of repeated compression.
3. The hydrogel sensor can quickly and accurately sense the size, shape and position of force, and the response time is 5-10 s.
4. The hydrogel is added with inorganic salt as a conductive filler during preparation, and the inorganic salt can effectively prevent the loss of water of the hydrogel sensor, thereby further expanding the application range and application conditions of the hydrogel sensor.
5. The preparation process of the hydrogel is simple and is easy to popularize in a large range.
Drawings
FIG. 1 is a stress-strain diagram of the highly elastic hydrogel sensor prepared in example 1 after repeated 20 compressions;
FIG. 2 is a graph showing the response of the highly elastic hydrogel sensor prepared in example 1 to the magnitude, shape, and position of a force.
Detailed Description
To further illustrate the features and advantages of the present invention, the following examples are described in detail, which are only a part of the present invention, and the scope of the present invention is not limited to the following examples.
Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
This example prepares a highly elastic hydrogel sensor as follows:
(1) 20g of Gelatin was added to 400mL of deionized water, and the mixture was stirred at 50 ℃ for 30min to obtain solution A.
(2) Adding 4.8g of liquid gallium indium tin metal and 0.2g of short-walled carbon nanotubes into the solution A, firstly using ultrasonic oscillation for 5min, and then stirring and mixing at normal temperature for 30min to obtain a solution B.
(3) 56.8g of isopropylacrylamide was added to the solution B, and the mixture was stirred at room temperature to obtain a solution C.
(4) Adding 16g of tetramethylethylenediamine, 0.2g of methylenedipropylamide and 2g of potassium persulfate into the solution C in sequence, and stirring uniformly at normal temperature to obtain a solution D.
(5) And pouring the solution D into a sealed mould, putting the sealed mould into a 60 ℃ oven, preserving heat, curing for 5 hours, taking out the sealed mould, and naturally cooling to room temperature to obtain the high-elasticity hydrogel sensor.
FIG. 1 is a stress-strain diagram of the highly elastic hydrogel sensor prepared in this example after being compressed 20 times, and it can be seen that the hydrogel rapidly rebounds after the pressure is removed.
The right side of figure 2 is the 20cm by 20cm hydrogel sensor prepared in this example, and the left side is the computer that collects the data and images. A silica gel mold with the length and the width of 20cm is prepared in advance, and 16 electrodes are pre-buried in the mold. And pouring the prepared solution D into a silica gel mold, sealing the solution by using a preservative film, and curing in an oven to obtain the hydrogel sensor. As can be seen from fig. 2, the sensor is pressed using a plastic cylinder to clearly image.
Example 2
This example prepares a highly elastic hydrogel sensor as follows:
(1) gelatin (5 g) was added to deionized water (400 mL) and the mixture was stirred at 50 ℃ for 30min to obtain solution A.
(2) Adding 0.1g of ferric trichloride into the solution A, and stirring for 20min at normal temperature to obtain a solution B.
(3) 91.35g of acrylamide was added to the solution B, and stirred uniformly at normal temperature to obtain a solution C.
(4) Adding 3g of tetramethylethylenediamine, 0.05g of methylenedipropylamide and 0.5g of potassium persulfate into the solution C in sequence, and stirring uniformly at normal temperature to obtain a solution D.
(5) And pouring the solution D into a sealed mould, putting the sealed mould into a 60 ℃ oven, preserving heat, curing for 5 hours, taking out the sealed mould, and naturally cooling to room temperature to obtain the high-elasticity hydrogel sensor.
Tests show that the hydrogel obtained in the embodiment has good mechanical properties, particularly elastic properties.
Example 3
This example prepares a highly elastic hydrogel sensor as follows:
(1) 8.42g of sodium alginate is added into 400mL of deionized water, and stirred for 20min at 45 ℃ to obtain a solution A.
(2) Adding 1.754g of ferric trichloride and 0.35g of graphene oxide into the solution A, firstly using ultrasonic oscillation for 5min, and then stirring and mixing for 30min at normal temperature to obtain a solution B.
(3) 23.9128g of acrylic acid was added to the solution B, and the mixture was stirred at normal temperature to obtain a solution C.
(4) 6.736g of cetyltrimethylammonium bromide, 0.0842g of methylenebisacrylamide and 0.842g of ammonium persulfate were sequentially added to the solution C and stirred uniformly at normal temperature to obtain a solution D.
(5) And pouring the solution D into a sealed mould, putting the sealed mould into a 55 ℃ oven, preserving heat, curing for 4h, taking out the sealed mould, and naturally cooling to room temperature to obtain the high-elasticity hydrogel sensor.
Tests show that the hydrogel obtained in the embodiment has good mechanical properties, particularly elastic properties.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-elasticity hydrogel sensor is characterized by comprising the following steps:
step 1, adding a first monomer into water, and uniformly stirring at 45-55 ℃ to obtain a solution A;
step 2, adding a conductive filler into the solution A, and uniformly mixing at normal temperature to obtain a solution B;
step 3, adding a second monomer into the solution B, and uniformly mixing at normal temperature to obtain a solution C;
step 4, adding an initiator, a cross-linking agent and a catalyst into the solution C, and uniformly mixing at normal temperature to obtain a solution D;
and 5, pouring the solution D into a sealed mould, and putting the sealed mould into a drying oven with the temperature of 35-65 ℃ for heat preservation and solidification for 3-6 h to obtain the high-elasticity hydrogel sensor.
2. The method of claim 1, wherein: and (2) making the total mass of the first monomer, the second monomer, the conductive filler, the initiator, the cross-linking agent and the catalyst M be M, then: the mass of the first monomer accounts for 5-20% of that of M, the mass of the second monomer accounts for 56.8-91.35% of that of M, the mass of the conductive filler accounts for 0.1-5% of that of M, the mass of the initiator accounts for 0.5-2% of that of M, the mass of the cross-linking agent accounts for 0.05-0.2% of that of M, and the mass of the catalyst accounts for 3-16% of that of M.
3. The method of claim 1, wherein: in the solution D, the mass percent of water is 75-95%.
4. The method of claim 1, wherein: the first monomer is one of sodium alginate, chitosan, gelatin, carrageenan and curdlan gum.
5. The method of claim 1, wherein: the second monomer is one of acrylamide, acrylic acid, isopropyl acrylamide and acrylamide methyl propane sulfonic acid.
6. The method of claim 1, wherein: the conductive filler is at least one of lithium chloride, calcium chloride, ferric trichloride, ferric dichloride, sodium chloride, sodium sulfate, aluminum chloride, polypyrrole, polyaniline, liquid metal, carbon black, graphene oxide and carbon nano tubes.
7. The method of claim 1, wherein: the initiator is one of ammonium persulfate and potassium persulfate.
8. The method of claim 1, wherein: the cross-linking agent is one of methylene-bis-propyl amide, polyethylene glycol methyl methacrylate and cetyl methacrylate.
9. The method of claim 1, wherein: the catalyst is one of tetramethylethylenediamine and hexadecyl trimethyl ammonium bromide.
10. A highly elastic hydrogel sensor obtained by the production method according to any one of claims 1 to 9.
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