CN116178865A - Transparent conductive hydrogel with high compressive strength and low energy dissipation and preparation method thereof - Google Patents
Transparent conductive hydrogel with high compressive strength and low energy dissipation and preparation method thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 92
- 230000021715 photosynthesis, light harvesting Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 41
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 36
- 230000006835 compression Effects 0.000 claims abstract description 16
- 238000007906 compression Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000004254 Ammonium phosphate Substances 0.000 claims description 21
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 21
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 19
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010257 thawing Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005185 salting out Methods 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 15
- 239000012266 salt solution Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 abstract description 5
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- 239000011540 sensing material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 238000007405 data analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/251—Means for maintaining electrode contact with the body
- A61B5/256—Wearable electrodes, e.g. having straps or bands
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
- A61B5/6802—Sensor mounted on worn items
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/32—Phosphorus-containing compounds
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Abstract
The invention discloses a transparent conductive hydrogel with high compressive strength and low energy dissipation and a preparation method thereof, and belongs to the technical field of functional polymer preparation. According to the invention, the high-density polymer chains are obtained by increasing the dosage of the polyvinyl alcohol, meanwhile, the high-concentration ammonium phosphate salt solution is introduced to promote the mutual entanglement among the polymer chains, promote the generation of more hydrogen bonds, and improve the overall strength of the hydrogel, and meanwhile, the high-entangled polymer chains can effectively and greatly reduce the energy dissipation generated when the hydrogel is subjected to the load of reciprocating loading and unloading. The hydrogel prepared by the invention has excellent conductivity and compression mechanical property, the conductivity is as high as 1.4S/m, and the energy dissipation generated by unloading after compressing to 1MPa is only 15.67%. The invention has simple technical process, short preparation period and wide application range, and can be widely applied to flexible electronic devices such as flexible strain sensors and the like.
Description
Technical Field
The invention belongs to the technical field of functional polymer preparation, and relates to a transparent conductive hydrogel with high compressive strength and low energy dissipation and a preparation method thereof.
Background
At present, the main sensing module of the wearable sensing device needs to be able to sensitively distinguish the force when loaded, and the strength of the sensing material needs to be high enough to bear the force generated by pressing by a human hand, and meanwhile, the sensing material needs to be soft enough to be better attached to an irregular surface and not to hinder pressing of the human hand on the acupuncture points.
For the existing conductive sensing material, the elastic modulus of the conductive elastomer material filled with the ionic liquid is too high, so that the conductive elastomer material is not soft enough, and meanwhile, the deformation of the conductive elastomer material under the stress is limited, so that the conductive elastomer material is not sensitive enough to the sensing of the loading force. The hydrogel material with the conductivity enhanced by adding conductive fillers such as nano silver, graphene, carbon nano tube and the like has weak mechanical properties and low tensile breaking strength, is not enough to support a large load, and cannot meet daily use requirements.
The strength of the hydrogel with the mechanical property enhanced by selecting the salt solution is enough to bear the force of pressing by hands, but the energy dissipation rate is higher (more than 60 percent), and the hydrogel can not transfer enough force during massage, so that the hydrogel is not suitable for a wearable device for massage.
In order to improve the energy dissipation condition by improving the substrate density of the high polymer material in the hydrogel, during the process of heating and dissolving the polyvinyl alcohol with relatively large mass ratio based on deionized water, the polyvinyl alcohol can adhere to the inner wall of the heating container in a large amount, so that the polyvinyl alcohol cannot be taken out in a sufficient amount after the heating and dissolving are completed; in addition, the polyvinyl alcohol with high density cannot successfully carry out entanglement reinforcement on the polymer chains by immersing the polyvinyl alcohol hydrogel in a salt solution and allowing the salt solution to permeate into the hydrogel by the salt solution immersing reinforcement method.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a transparent conductive hydrogel with high compression strength and low energy dissipation and a preparation method thereof, wherein the high-strength conductive hydrogel is prepared by using polyvinyl alcohol with relatively large mass ratio based on deionized water and a high-concentration ammonium phosphate salt solution, and the hydrogel can keep low energy dissipation when bearing the pressing force of a human hand, so that the massage effect is not weakened due to the energy dissipation generated by the viscoelasticity of the hydrogel.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of transparent conductive hydrogel with high compression strength and low energy dissipation is characterized in that the use amount of polyvinyl alcohol is increased to obtain high-density polymer chains, meanwhile, high-concentration ammonium phosphate salt solution is introduced to promote mutual entanglement among the polymer chains, more hydrogen bonds are promoted to be generated, the overall strength of the hydrogel is improved, and meanwhile, the highly entangled polymer chains can effectively and greatly reduce the energy dissipation generated when the hydrogel is subjected to load of reciprocating loading and unloading. The method specifically comprises the following steps:
firstly, dissolving an ammonium phosphate monomer in deionized water at a temperature of 95-100 ℃ to obtain an ammonium phosphate aqueous solution with a mass concentration of 5-7 wt.%;
secondly, dissolving polyvinyl alcohol particles in an ammonium phosphate aqueous solution at the temperature of 95-100 ℃ to obtain a mixed solution, and continuously heating and stirring for 40-60 min at the temperature to fully generate physical crosslinking and high entanglement between polyvinyl alcohol polymer chains to obtain a hydrogel precursor; wherein the mass concentration ratio of the polyvinyl alcohol particles in the mixed solution is 33-37 wt.%.
And thirdly, taking the hydrogel obtained in the second step out of a heating container, shaping by using a die, standing in a refrigerator at the temperature of minus 30 ℃ to minus 20 ℃ for freezing for 16 to 24 hours, taking the hydrogel out of the refrigerator after freezing, thawing for 4 to 8 hours at the room temperature of 15 ℃ to 30 ℃, and performing freeze-thawing cycle for 3 to 6 times to obtain the transparent conductive hydrogel.
The transparent conductive hydrogel with high compression strength and low energy dissipation is prepared by the method, is a single-network hydrogel formed by a polyvinyl alcohol-ammonium phosphate system, and is characterized in that polyvinyl alcohol high molecular chains are highly entangled under the salting-out effect of an ammonium phosphate aqueous solution.
The technical principle analysis of the invention:
in order to improve the strength of the hydrogel to the greatest extent, the invention uses the polyvinyl alcohol with relatively large mass ratio based on deionized water to ensure the density of the polymer material substrate in the hydrogel, and adopts the high-concentration ammonium phosphate salt solution to enhance the mutual entanglement effect between polyvinyl alcohol polymer chains.
The invention firstly dissolves to obtain high-concentration ammonium phosphate solution, and then the polyvinyl alcohol with relatively large mass ratio based on deionized water is heated and dissolved in ammonium phosphate aqueous solution, and in the process, the ammonium phosphate has the following functions:
1) The ammonium phosphate salt solution can enhance the entanglement effect between polyvinyl alcohol polymer chains through salting-out effect;
2) Because the aqueous solution contains ammonium phosphate, the density is higher, polyvinyl alcohol particles are not easy to sink in the process of heating and dissolving the polyvinyl alcohol, so that the polyvinyl alcohol is completely dissolved and is not adhered to the inner wall of a heating container, and the hydrogel can be taken out sufficiently.
The beneficial effects of the invention are as follows:
(1) The hydrogel prepared by the invention has excellent conductivity and compression mechanical property, and the conductivity is as high as 1.4S/m; the sensitivity is high enough, the compression strength can be used for a long time in the range of the human hand massage force, the energy dissipation rate (15.67%) is low, and enough force can be transmitted during massage; i.e. the energy dissipation resulting from unloading after compression to 1MPa is only 15.67%.
(2) The preparation method provided by the invention has the advantages of one-step in place, no need of complex operation steps, simple process, short preparation period and wide application range, can be widely applied to flexible electronic devices such as flexible strain sensors and the like, and has a wide application prospect in the aspect of electronic skin.
Drawings
FIG. 1 (a) is a stress-strain plot of the hydrogel prepared in example 1 of the present invention compressed to 90% strain at a rate of 50 mm/min; FIG. 1 (b) is a stress-strain curve diagram showing that the hydrogel prepared in example 1 of the present invention in FIG. 1 (a) is compressed at a rate of 50mm/min to a compression strain of 0 to 40%.
FIG. 2 is a stress-time graph of the hydrogel prepared in example 1 according to the present invention unloaded after being compressed to 40% strain (1 MPa) at a rate of 50mm/min and reciprocated 1000 times;
FIG. 3 is a stress-strain graph of the hydrogel prepared in example 1 of the present invention and a hydrogel of the same polyvinyl alcohol concentration without the ammonium phosphate solution introduced compressed to 40% strain at a rate of 50mm/min, unloaded, and reciprocated 10 times;
FIG. 4 is a graph showing the relative voltage ratio change at a rate of 50mm/min for the hydrogel prepared in example 1 of the present invention compressed to 60% strain.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Comparative example 1
In the first step, 35g of polyvinyl alcohol particles are weighed, added into 60mL of deionized water and stirred uniformly, and the mixture is heated and stirred continuously for 45 minutes at 98 ℃ to obtain a hydrogel precursor.
And secondly, taking out the hydrogel precursor obtained in the first step, fixing the hydrogel precursor in a standard sample mold, and wrapping the hydrogel precursor with a preservative film to avoid water loss. Freezing in a refrigerator at-20deg.C for 16 hr, taking out, thawing at room temperature for 5 hr, and repeating the above steps for three times to obtain pure PVA hydrogel.
Example 1
A preparation method of transparent conductive hydrogel with high compressive strength and low energy dissipation comprises the following steps:
in the first step, 5g of ammonium phosphate powder was weighed into 60mL of deionized water, and magnetically stirred at 95℃for 10 minutes until all dissolution gave an aqueous ammonium phosphate solution having a mass concentration ratio of 7.7 wt.%.
And secondly, weighing 33g of polyvinyl alcohol particles, adding the polyvinyl alcohol particles into the solution, stirring uniformly to obtain a mixed solution, and continuously heating and stirring the mixed solution at 95 ℃ for 40 minutes to obtain the hydrogel precursor. The mass concentration ratio of the polyvinyl alcohol particles in the mixed solution was 33.7wt.%.
And thirdly, taking out the hydrogel precursor obtained in the second step, fixing the hydrogel precursor in a standard sample mold, and wrapping the hydrogel precursor with a preservative film to avoid water loss. Freezing in a refrigerator at-30deg.C for 16 hr, taking out, thawing at room temperature for 4 hr, and repeating the above steps for three times to obtain hydrogel.
Example 2
In the first step, 5g of ammonium phosphate powder was weighed into 60mL of deionized water, and magnetically stirred at 98 ℃ for 10 minutes until all dissolution gave an aqueous ammonium phosphate solution having a mass concentration ratio of 7.7 wt.%.
Step two, weighing 35g of polyvinyl alcohol particles, adding the polyvinyl alcohol particles into the solution, and uniformly stirring to obtain a mixed solution; the mixed solution is heated and stirred for 45 minutes at 98 ℃ to obtain the hydrogel precursor. The mass concentration ratio of the polyvinyl alcohol particles in the mixed solution is 35wt.%.
And thirdly, taking out the hydrogel precursor obtained in the second step, fixing the hydrogel precursor in a standard sample mold, and wrapping the hydrogel precursor with a preservative film to avoid water loss. Freezing in a refrigerator at-20deg.C for 16 hr, taking out, thawing at room temperature for 5 hr, and repeating the above steps three times to obtain hydrogel.
Example 3
In the first step, 7g of ammonium phosphate powder was weighed into 60mL of deionized water, and magnetically stirred at 100℃for 10 minutes until all the powder was dissolved to obtain an aqueous ammonium phosphate solution having a mass concentration ratio of 10.4 wt.%.
Secondly, weighing 37g of polyvinyl alcohol particles, adding the polyvinyl alcohol particles into the solution, and uniformly stirring to obtain a mixed solution; the mixed solution is heated and stirred for 60 minutes at 100 ℃ to obtain the hydrogel precursor. The mass concentration ratio of the polyvinyl alcohol particles in the mixed solution is 35.6wt.%.
And thirdly, taking out the hydrogel precursor obtained in the second step, fixing the hydrogel precursor in a standard sample mold, and wrapping the hydrogel precursor with a preservative film to avoid water loss. Freezing in a refrigerator at-20deg.C for 24 hr, taking out, thawing at room temperature for 8 hr, and repeating the above steps for three times to obtain hydrogel.
Characterization data analysis:
in the compression mechanical property test performed on the examples, the hydrogels prepared in the examples were prepared into cylindrical test pieces having a radius of 5mm and a height of 6mm, and compressed to a strain of 90% at a compression rate of 50 mm/min. The strain of the strain sensor can be directly calculated by displacement data obtained by a tester, the stress value of the strain sensor calculates the real-time cross-sectional area according to the principle of constant volume, and the real-time stress is obtained by dividing the real-time cross-sectional area by the pressure at the moment. As shown in FIG. 1, the hydrogel of example 2 has a compressive stress of 100MPa when compressed to a strain of 90%, which is much higher than 1MPa of the hydrogel of comparative example 1, and slightly higher than 80MPa and 92MPa of the hydrogels of examples 1 and 3, mainly because the polymer chains of the hydrogels of comparative example 1 are not reinforced by the salt solution, the hydrogel of example 1 has a lower amount of polyvinyl alcohol and a lower density of polymer chains, and the hydrogel of example 3 has an insufficient amount of water for dissolving polyvinyl alcohol due to an excessively high amount of polyvinyl alcohol, and the entanglement of polymer chains becomes uneven due to an excessively high salt concentration during the preparation process
In the compression fatigue test performed on the examples, the hydrogels prepared in the examples were compressed to a strain of 40% at a compression rate of 50mm/min and then returned to the original state at the same rate. As shown in fig. 2, the hydrogel prepared in example 2 has a compressive stress of up to 1MPa when compressed to 40% strain, and is sufficient to carry the force generated by normal pressing by a human hand.
As shown in FIG. 3, the hydrogel prepared in example 2 was subjected to reciprocating compression to a strain of 40% (1 MPa) 1000 times, and the stress was not significantly attenuated, indicating that the hydrogel could be continuously operated for a long period of time under such a stress environment. The hydrogel prepared in example 2 showed little attenuation of stress after 500 and 1000 cycles of compression, and the stress-strain curves during multiple cycles of compression were very similar, indicating that the hydrogel was in a state of stress close during multiple cycles of loading, which would help the stable output of electrical signals from the hydrogel.
Comparing the hydrogel prepared in example 2 with the pure PVA hydrogel prepared in comparative example 1, the mechanical property curves of the hydrogel prepared in example 2 after being compressed to 40% strain and unloading for 10 times, it can be seen that the energy dissipation rate of the hydrogel prepared in example 2 is 15.67% and is far smaller than the energy dissipation rate of 57% of the pure PVA hydrogel, and this is mainly because the polymer chains in the hydrogel prepared in example 2 are entangled more tightly, the polymer chains are not easily separated after being stressed, the polymer chains are more easily pulled back to the original positions after being unloaded, and the polymer chains in the pure PVA hydrogel are not entangled tightly enough, once being loaded more, the polymer chains are not easily restored, so that the energy dissipation is serious in the loading and unloading process.
The conductivity of the hydrogel prepared in the embodiment is tested by using a resistor voltage division method, a direct current stabilized power supply with an output voltage of 10V is used for connecting the hydrogel with a standard resistor of 100 omega in series, and meanwhile, in order to protect a circuit from being damaged by short circuit, a resistor of 10 omega is connected in series at a power end to protect the circuit, and a data acquisition card is used for acquiring the voltages at two ends of the standard resistor. As shown in fig. 4, the conductivity of the hydrogel prepared in example 2 was calibrated by the ratio of the current voltage value to the initial voltage value. The hydrogel prepared in example 2 can reach 470% of relative voltage change within 60% of compressive strain, and can meet daily requirements.
The examples described above represent only embodiments of the invention and are not to be understood as limiting the scope of the patent of the invention, it being pointed out that several variants and modifications may be made by those skilled in the art without departing from the concept of the invention, which fall within the scope of protection of the invention.
Claims (3)
1. The transparent conductive hydrogel with high compression strength and low energy dissipation is characterized in that the transparent conductive hydrogel is a single-network hydrogel formed by a polyvinyl alcohol-ammonium phosphate system, wherein polyvinyl alcohol polymer chains can be highly entangled under the salting-out effect of an ammonium phosphate aqueous solution.
2. A method of preparing a high compressive strength low energy dissipating transparent conductive hydrogel according to claim 1, comprising the steps of:
firstly, dissolving an ammonium phosphate monomer in deionized water at a temperature of 95-100 ℃ to obtain an ammonium phosphate aqueous solution with a mass concentration of 5-7 wt.%;
secondly, dissolving polyvinyl alcohol particles in an ammonium phosphate aqueous solution at the temperature of 95-100 ℃ to obtain a mixed solution, and continuously heating and stirring for 40-60 min at the temperature to fully generate physical crosslinking and high entanglement between polyvinyl alcohol polymer chains to obtain a hydrogel precursor; wherein the mass concentration ratio of the polyvinyl alcohol particles in the mixed solution is 33-37 wt%;
and thirdly, taking the hydrogel obtained in the second step out of a heating container, shaping by using a die, and sequentially freezing and thawing for many times to obtain the transparent conductive hydrogel.
3. The method for preparing a transparent conductive hydrogel with high compressive strength and low energy dissipation according to claim 2, wherein in the third step, the transparent conductive hydrogel is obtained by freezing for 16-24 hours in a refrigerator with the temperature of minus 30-minus 20 ℃ and then thawing for 4-8 hours at room temperature, and the freezing-thawing cycle is performed for 3-6 times.
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| US20190009427A1 (en) * | 2016-03-28 | 2019-01-10 | Henkel Ag & Co. Kgaa | Aqueous bonding composition |
| CN111040197A (en) * | 2019-12-19 | 2020-04-21 | 华南理工大学 | High-strength multifunctional ion conductive hydrogel and preparation method and application thereof |
| CN111533928A (en) * | 2020-06-06 | 2020-08-14 | 南开大学 | Preparation method of polyvinyl alcohol ionic conductive hydrogel with high strength and high sensitivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190009427A1 (en) * | 2016-03-28 | 2019-01-10 | Henkel Ag & Co. Kgaa | Aqueous bonding composition |
| CN111040197A (en) * | 2019-12-19 | 2020-04-21 | 华南理工大学 | High-strength multifunctional ion conductive hydrogel and preparation method and application thereof |
| CN111533928A (en) * | 2020-06-06 | 2020-08-14 | 南开大学 | Preparation method of polyvinyl alcohol ionic conductive hydrogel with high strength and high sensitivity |
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| Title |
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| 白晴文;汪辉亮;: "基于协同氢键作用的高强度聚乙烯醇-聚丙烯酸水凝胶", 北京师范大学学报(自然科学版), no. 05, 15 October 2016 (2016-10-15), pages 561 - 565 * |
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