CN113512209B - Preparation method of high-conductivity and high-sensitivity polyvinyl alcohol-based conductive hydrogel - Google Patents
Preparation method of high-conductivity and high-sensitivity polyvinyl alcohol-based conductive hydrogel Download PDFInfo
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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
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Abstract
The invention relates to a preparation method of high-conductivity and high-sensitivity polyvinyl alcohol-based conductive hydrogel, which is characterized in that polyvinyl alcohol-sodium lignosulfonate hydrogel with high mechanical strength characteristics is used as a matrix material, and a compact silver simple substance nanoparticle layer is formed on the outer surface of the hydrogel through reduction reaction based on the adsorption characteristic of a microphase separation structure of the hydrogel to silver ions, so that the conductive-sensing function with high conductivity, high sensitivity and high linearity is realized. The invention breaks through the traditional preparation idea of the conductive hydrogel, innovatively and innovatively improves the surface silver reduction process method and parameters of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel, realizes the firm combination of the silver nanoparticle layer with uniform size, uniform distribution and compactness and the hydrogel matrix, can effectively detect and distinguish the micro strain in real time, has simple, convenient, efficient, stable and repeatable preparation method and low cost, and provides an effective new idea for the conductive hydrogel in the fields of electronic skin, intelligent wearable equipment, flexible sensors and the like.
Description
Technical Field
The invention relates to the field of material science, in particular to a preparation method of high-conductivity and high-sensitivity polyvinyl alcohol-based conductive hydrogel.
Technical Field
As a typical flexible material, the conductive hydrogel combines the electrochemical performance of conductive macromolecules and the soft characteristic and biocompatibility of hydrogel, has the technical advantages of excellent electronics, mechanics, chemistry, biological characteristics and the like, and is an ideal material for constructing high-precision flexible electronic products such as wearable electronic equipment, flexible sensors, tissue engineering, flexible robots and the like and manufacturing technology. Therefore, conductive hydrogels have become an emerging, rapidly developing and important research direction in the field of flexible electronics.
Although the conductive hydrogel-based flexible sensing material has become one of the leading research hotspots in the field of flexible electronic technology, the defects of low conductivity, poor mechanical strength and low sensing sensitivity generally exist. Around the above disadvantages, scholars at home and abroad mainly improve the conductivity by modifying the conductive filler, improve the hydrogel network structure to improve the mechanical properties, and optimize the traditional method of the accessory function expansion application range to research on the aspects of basic materials, functional stability and application universality. Although the traditional preparation method has obvious effect to a certain extent, the preparation method still has a plurality of technical defects which are mainly reflected in that: (1) in the aspect of improving the conductivity, the conductive polymer, the carbon-based material and the derivatives thereof are added into the non-conductive hydrogel matrix as a main method, so that the sensing stability is reduced while the conductivity and the processability of the conductive hydrogel are improved. (2) The strength of the material is improved by only constructing a double-network structure, the influence of ion diffusion on the conductivity and the signal transmission stability of the hydrogel cannot be effectively avoided, and the mechanical property of the conductive hydrogel is reduced. (3) The diversified functional attributes improve the functionality of the conductive hydrogel, and simultaneously reduce the application universality due to weakened tensile strength and fatigue strength and specific application scenes. Therefore, the conventional design concept and preparation method cannot provide the technical advantages of high efficiency, stability and diversification, and cannot solve the existing technical defects of the conductive hydrogel at the same time, so that a brand new design method and preparation technology are urgently needed.
The invention sets up a high mechanical strength foundation by taking polyvinyl alcohol-sodium lignosulfonate-based hydrogel as a conductive hydrogel matrix material from the aspects of synthesis of the conductive hydrogel matrix material and improvement of a conductive process. Based on the adsorption characteristic of the matrix material microphase separation structure to silver ions, a compact silver nanoparticle layer is formed on the outer surface of the matrix material microphase separation structure through a reduction reaction, and the functional basis of high conductivity and high sensing sensitivity of the conductive hydrogel is constructed. The invention carries out surface reduction silver reaction on the cured and formed polyvinyl alcohol-sodium lignosulfonate-based hydrogel, realizes excellent electric conduction and sensing functions and simultaneously keeps the original material characteristics and high mechanical strength of the matrix material. The synthesis process and the conductive process of the hydrogel have the characteristics of high efficiency, convenience and repeatability, and the prepared polyvinyl alcohol-sodium lignosulfonate conductive hydrogel has high mechanical property, high conductivity, high sensitivity and high linearity, can effectively detect micro strain in real time, and provides an effective new method for the wide application of the conductive hydrogel.
Disclosure of Invention
The invention aims to effectively solve the technical bottlenecks of poor mechanical strength, low conductivity and low sensing sensitivity of the conventional conductive hydrogel, and the conductive hydrogel matrix material with high mechanical strength is prepared by establishing a firm physical crosslinking network formed by hydrogen bonds between polyvinyl alcohol and sodium lignosulfonate by a freeze-thaw cycle method based on optimized synthesis process parameters. Based on the optimized conductive process parameters, a compact and firm silver simple substance nano particle layer is formed on the outer surface of the matrix material through a reduction reaction by utilizing the adsorption characteristic of the microphase separation structure of the matrix material to silver ions, so that the functions of high conductivity and high sensing sensitivity of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel are realized.
The invention breaks through the technical disadvantages of the traditional design thought and the preparation method, innovatively realizes the high mechanical strength, high conductivity, high sensitivity, high linearity and high durability of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel through the high-efficiency, convenient and repeatable matrix material synthesis process and the conductive process, innovatively forms the technical advantages of high efficiency, stability and diversification, realizes the improvement of the mechanical property and the functional property of the conductive hydrogel, and provides a new method for promoting the development of the conductive hydrogel.
The invention discloses a preparation method of a high-conductivity and high-sensitivity polyvinyl alcohol-based conductive hydrogel, which adopts the technical scheme that polyvinyl alcohol-sodium lignosulfonate hydrogel is taken as a conductive hydrogel matrix material, silver ions are fixed on the surface of the matrix material by soaking the conductive hydrogel in a mixed solution of polyvinylpyrrolidone and silver nitrate and utilizing the adsorption effect of the matrix material on the silver ions, and then the conductive hydrogel is soaked in a mixed solution of polyvinylpyrrolidone and ascorbic acid to reduce the silver ions on the surface of the matrix material into a continuous and compact silver elementary substance nanoparticle layer, so that the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel with the functional characteristics of high conductivity, high sensitivity and high linearity is prepared.
The materials used in the invention are: polyvinyl alcohol (PVA), sodium Lignosulfonate (LS), dimethyl sulfoxide (DMSO), silver nitrate (AgNO)3) K30 polyvinylpyrrolidone (PVP), ascorbic acid (VC), deionized water (DI). Wherein, polyvinyl alcohol is used as a matrix, sodium lignosulfonate is used as a reinforcing phase, dimethyl sulfoxide is used as a sodium lignosulfonate dispersant, silver nitrate is used as a reducing agent, K30 polyvinylpyrrolidone is used as a solution dispersant, ascorbic acid is used as a reducing agent, and deionized water is used as a solvent.
The preparation method of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel comprises the following steps:
(1) preparing a polyvinyl alcohol-sodium lignin sulfonate hydrogel matrix material:
1) in volume ratio VDMSO：VDI4: 1, preparing a mixed solution of dimethyl sulfoxide and deionized water with the volume of 45ml-90 ml;
2) under the condition of magnetically stirring the mixed solution of dimethyl sulfoxide and deionized water, 0.05g to 0.65g of sodium lignosulfonate is added and then the stirring is continued until the sodium lignosulfonate is completely dissolved. Then, ultrasonically dispersing the mixed solution containing sodium lignosulfonate for 20min-30min, adding 4.35g-5g of polyvinyl alcohol, and mechanically stirring the polyvinyl alcohol in the sodium lignosulfonate solution for 2h-2.5h at the constant temperature of 140-150 ℃ and under the condition of 400r/min-450r/min to obtain a PVA-LS solution;
3) cooling the PVA-LS solution to 80-85 ℃, pouring the PVA-LS solution into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into a refrigerator with the temperature of-18-20 ℃ for 12-13 h, and unfreezing the PVA-LS solution for 2-2.5 h at room temperature. At this time, the PVA-LS solution in the mold is solidified into hydrogel;
4) the obtained hydrogel was placed in a beaker filled with deionized water, and dimethyl sulfoxide in the gel was replaced with deionized water. And replacing the deionized water every 6-6.5 h in the daytime and every other day at night, wiping off the water on the surface of the hydrogel in the replacement process, and weighing the mass of the hydrogel. When the quality of the hydrogel is not changed within 48h-49h, the solvent in the hydrogel is completely replaced, and the preparation of the polyvinyl alcohol-sodium lignin sulfonate hydrogel matrix material is completed.
(2) Preparing a silver layer on the surface of a polyvinyl alcohol-sodium lignin sulfonate hydrogel matrix material:
1) AgNO with concentration of 0.01M-1.0M3Respectively mixing the solution and 0.08-0.2M VC solution with 5-15 wt% PVP solution in equal volume to prepare AgNO3-PVP and VC-PVP solutions;
2) soaking the prepared polyvinyl alcohol-sodium lignosulfonate hydrogel matrix material in AgNO3And soaking the polyvinyl alcohol-sodium lignin sulfonate conductive hydrogel in the VC-PVP mixed solution for 48 hours after the-PVP mixed solution is soaked for 8 hours, so as to complete the preparation of the silver layer on the surface of the polyvinyl alcohol-sodium lignin sulfonate conductive hydrogel. Thus, the preparation of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel is completed.
The invention has the advantages of
(1) The polyvinyl alcohol and the sodium lignin sulfonate used in the invention can form intermolecular hydrogen bonds through freeze-thaw cycles, realize high tensile strength and high fatigue strength in a physical crosslinking mode, and provide a matrix material with good mechanical strength for the conductive hydrogel. As the reinforcing phase, the sodium lignosulfonate effectively improves the density of the matrix material, and the mechanical strength of the matrix material and the adsorption amount of the matrix material to silver ions can be effectively regulated and controlled by changing the content of the sodium lignosulfonate. Based on the innovatively adopted synthesis process parameters including the sodium lignosulfonate efficient dispersion method, the invention efficiently improves the mechanical strength and the functional basis of the conductive hydrogel by a simple, convenient and low-cost method.
(2) Based on the controllability of the microphase separation structure of the matrix material on the adsorption characteristic of silver ions, the firm and compact silver simple substance nano-particle layer is formed on the outer surface of the matrix material through a reduction reaction. By innovatively adopting conductive technological parameters including a silver nitrate solution efficient dispersion method and an ascorbic acid solution efficient dispersion method, the prepared conductive silver layer is uniformly, compactly and firmly combined on the surface of a matrix material in the form of simple substance silver nanoparticles, so that the high conductivity, high sensitivity, high linearity and high durability of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel are realized.
(3) The process of the conductive hydrogel prepared by the invention is divided into two steps, wherein the first step is to prepare the polyvinyl alcohol-sodium lignosulfonate hydrogel with high mechanical strength. And the second step is to perform silver reduction reaction on the surface of the polyvinyl alcohol-sodium lignosulfonate hydrogel. In the two preparation steps, the synthesis process and the conductive process adopted by the innovation of the invention are adopted. The conductive hydrogel prepared by the invention has high conductivity and high sensitivity, does not change the mechanical property of the matrix material, and innovatively considers the mechanical property and the functional property of the conductive hydrogel. The preparation method has the characteristics of simplicity, convenience, high efficiency and repeatability.
Drawings
FIG. 1 is a stress strain diagram of matrix materials with different sodium lignosulfonate contents
FIG. 2 is a diagram of ultimate tensile stress and Shore hardness of polyvinyl alcohol-sodium lignosulfonate conductive hydrogel
FIG. 3 is a distribution and energy spectrum of a silver layer of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel.
FIG. 4 is a diagram of the appearance and an enlarged view of a silver layer of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel.
FIG. 5 is an enlarged view of the interface between the silver layer of the PVA-lignosulfonate conductive hydrogel and the matrix.
Fig. 6 is a phase diagram of a silver layer of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel.
FIG. 7 is a distribution diagram of the resistance of the PVA-sodium lignosulfonate conductive hydrogel
FIG. 8 is a graph of the sensitivity gauge factor and linearity of a PVA-Lignosulfonate conductive hydrogel
FIG. 9 shows 100 cycles of 1% circulation of a polyvinyl alcohol-sodium lignosulfonate conductive hydrogelDelta R/R under ring strain0Variation diagram
FIG. 10 is a graph of the sounding signals of different persons detected by a polyvinyl alcohol-sodium lignosulfonate conductive hydrogel
FIG. 11 is a graph of pulse beat signals detected by the PVA-lignosulfonate conductive hydrogel
Detailed Description
Example 1:
the substrate material synthesis process and the feasibility of the conductive process are determined by analyzing the appearance, phase and mechanical properties of the silver layer on the surface of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel.
Please refer to a stress-strain diagram of a matrix material with different sodium lignosulfonate contents shown in fig. 1, an ultimate tensile stress and shore hardness diagram of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel shown in fig. 2, a silver layer distribution and energy spectrum diagram of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel shown in fig. 3, a morphology and an enlarged view of the silver layer of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel shown in fig. 4, an interface and an enlarged view of the silver layer of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel shown in fig. 5, and a phase diagram of the silver layer of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel shown in fig. 6.
The invention successfully synthesizes the polyvinyl alcohol-sodium lignin sulfonate with different sodium lignin sulfonate contents based on the preparation method in the claims. When the mass ratio of sodium lignosulfonate to polyvinyl alcohol was 3% (i.e., LS-3 in fig. 1), the matrix material prepared had the highest tensile strength, as shown in fig. 1. The sodium lignosulfonate effectively enhances the mechanical strength of the matrix material by comparison with a pure polyvinyl alcohol hydrogel without sodium lignosulfonate (i.e. the pure PVA hydrogel in fig. 2). After the conductive process is completed, the shore hardness of the matrix material is increased, as shown in fig. 2. Therefore, the present invention is based on LS-3 type hydrogel for subsequent operation. Based on the optimized technological parameters of silver reduction, the LS-3 type hydrogel has a silver layer on the surface, as shown in figure 3. The three-dimensional network structure is still kept in the hydrogel and silver is not contained. As shown in fig. 4, the silver layer is composed of a large number of silver nanoparticles with uniform size, and the silver layer is tightly combined with the interface of the substrate without any layering and separation phenomena, as shown in fig. 5. The phase analysis result shows that the silver on the surface of the LS-3 type hydrogel is a simple silver substance, and is shown in figure 6. The results of the morphology, phase and mechanical properties of the silver layer on the surface of the conductive hydrogel show that the preparation method of the conductive hydrogel has feasibility, the uniform and compact simple substance silver nanoparticles are firmly combined with the matrix material with good mechanical strength, and an efficient material basis is established for the conductive sensing function of the conductive hydrogel.
Example 2:
the effectiveness of the matrix material synthesis process and the conductive process is determined by analyzing the resistance, linearity, sensitivity gauge factors and signal detection performance of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel.
Please refer to the distribution diagram of the resistance of the conductive hydrogel of polyvinyl alcohol-sodium lignosulfonate shown in fig. 7, the sensitivity gauge factor and the linearity diagram of the conductive hydrogel of polyvinyl alcohol-sodium lignosulfonate shown in fig. 8, and the Δ R/R of the conductive hydrogel of polyvinyl alcohol-sodium lignosulfonate shown in fig. 9 under 100 times of 1% cyclic strain0The graph shows that the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel shown in fig. 10 detects the throat sounding signals of different people and the graph shows that the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel shown in fig. 11 detects the pulse beating signals.
According to the preparation method of the invention, the resistance value of the polyvinyl alcohol-sodium lignin sulfonate conductive hydrogel with the size parameter of 35mm multiplied by 3mm is only 1 omega, and the conductivity obtained by calculation is 3300Sm-1The conductivity value is at a higher level in the field of conductive hydrogel, which shows that the conductive hydrogel prepared by the invention has high conductivity. Meanwhile, the resistance value of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel is continuously measured in a segmented manner at intervals of every 5mm, and the obtained resistance value is distributed between 0.2 omega and 0.6 omega, which shows that the conductive hydrogel prepared by the invention has good conductivity stability, and is shown in figure 7. Resistance change (Δ R/R) with increasing strain through a conductive hydrogel0Δ R is the resistance at different strains relative to the initial resistance R0The amount of change) is effective to analyze the strain sensitivity of the conductive hydrogel. As shown in FIG. 8, Δ R @R0The value of (A) increases with increasing strain from 0% to 20%, and shows a good linear relationship at 5% strain (R)20.9949), which shows the high linearity of the conductive hydrogel prepared by the invention. In addition, in the strain range of 0% -5%, the sensitivity gauge factor of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel is 24.4, and the sensitivity value is at a higher level in the field of the conductive hydrogel, which shows that the conductive hydrogel prepared by the invention has high sensitivity. As shown in FIG. 9, the PVA-sodium lignosulfonate conductive hydrogel outputs a stable signal (Δ R/R) with small fluctuation under the condition of 100 times of 1% cyclic fixation strain0> 30%), which indicates that the conductive hydrogel prepared by the invention has the durability requirement as a strain sensor. As shown in fig. 10, the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel can effectively identify the throat fluctuation signals when different people respectively say "jilin university" for multiple times. The two sets of completely different signals acquired can effectively distinguish the identities of different persons. Meanwhile, the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel can sensitively capture the change of pulse, and can effectively distinguish different peak values in the pulse beating process. The conductive hydrogel prepared by the invention has the advantages of high sensitivity, high response speed, wide application range, reliable test result and the like.
Claims (1)
1. A preparation method of a high-conductivity and high-sensitivity polyvinyl alcohol-based conductive hydrogel is characterized in that the technical scheme of the scheme is that polyvinyl alcohol-sodium lignosulfonate hydrogel is used as a conductive hydrogel matrix material, silver ions are fixed on the surface of the matrix material by soaking in a mixed solution of polyvinylpyrrolidone and silver nitrate and utilizing the adsorption effect of the matrix material on the silver ions, and then the silver ions are soaked in a mixed solution of polyvinylpyrrolidone and ascorbic acid to reduce the silver ions on the surface of the matrix material into a continuous compact silver simple substance nanoparticle layer so as to prepare the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel with the functional characteristics of high conductivity, high sensitivity and high linearity;
the used materials in the scheme are as follows: polyvinyl alcohol PVA and sodium lignin sulfonateLS, dimethyl sulfoxide DMSO, silver nitrate AgNO3K30 polyvinylpyrrolidone PVP, ascorbic acid VC and deionized water DI, wherein polyvinyl alcohol is used as a matrix, sodium lignosulfonate is used as a reinforcing phase, dimethyl sulfoxide is used as a sodium lignosulfonate dispersant, silver nitrate is used as a reducer, K30 polyvinylpyrrolidone is used as a solution dispersant, ascorbic acid is used as a reducer, and deionized water is used as a solvent;
the preparation method of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel comprises the following steps:
(1) preparing a polyvinyl alcohol-sodium lignin sulfonate hydrogel matrix material:
1) in volume ratio VDMSO：VDI4: 1, preparing a mixed solution of dimethyl sulfoxide and deionized water with the volume of 45ml-90 ml;
2) under the condition of magnetically stirring the mixed solution of dimethyl sulfoxide and deionized water, adding 0.05g to 0.65g of sodium lignosulfonate, continuously stirring until the sodium lignosulfonate is completely dissolved, then ultrasonically dispersing the mixed solution containing the sodium lignosulfonate for 20min to 30min, adding 4.35g to 5g of polyvinyl alcohol, and mechanically stirring the polyvinyl alcohol in the sodium lignosulfonate solution for 2h to 2.5h at the constant temperature of 140 ℃ to 150 ℃ and at the speed of 400r/min to 450r/min to obtain a PVA-LS solution;
3) cooling the PVA-LS solution to 80-85 ℃, pouring the PVA-LS solution into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into a refrigerator with the temperature of 18-20 ℃ below zero for 12-13 h, and unfreezing the PVA-LS solution at room temperature for 2-2.5 h, wherein the PVA-LS solution in the mold is solidified into hydrogel;
4) placing the prepared hydrogel in a beaker filled with deionized water, replacing dimethyl sulfoxide in the hydrogel with the deionized water, replacing the deionized water every 6-6.5 h every day and every other day at night, wiping off water on the surface of the hydrogel in the replacement process, weighing the mass of the hydrogel, completely replacing the solvent in the hydrogel when the mass of the hydrogel is unchanged within 48-49 h, and finishing the preparation of the polyvinyl alcohol-sodium lignosulfonate hydrogel matrix material;
(2) preparing a silver layer on the surface of a polyvinyl alcohol-sodium lignin sulfonate hydrogel matrix material:
1) AgNO with concentration of 0.01M-1.0M3Respectively mixing the solution and 0.08-0.2M VC solution with 5-15 wt% PVP solution in equal volume to prepare AgNO3-PVP and VC-PVP solutions;
2) soaking the prepared polyvinyl alcohol-sodium lignosulfonate hydrogel matrix material in AgNO3And soaking the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel in the VC-PVP mixed solution for 48h after 8h in the-PVP mixed solution to complete the preparation of the silver layer on the surface of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel, thus completing the preparation of the polyvinyl alcohol-sodium lignosulfonate conductive hydrogel.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489716A (en) * | 2011-12-15 | 2012-06-13 | 湖南科技大学 | Preparation method for lignosulfonate nano-silver colloid |
| CN110240774A (en) * | 2019-06-21 | 2019-09-17 | 华南理工大学 | A kind of high-intensity wood quality/polyvinyl alcohol composite antibacterial hydrogel and preparation method |
| CN112521630A (en) * | 2020-08-28 | 2021-03-19 | 同济大学 | Preparation method and application of green flexible conductive anti-freezing hydrogel |
| CN113004543A (en) * | 2021-02-26 | 2021-06-22 | 江南大学 | Nano lignin/polyvinyl alcohol composite medical hydrogel and preparation method thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489716A (en) * | 2011-12-15 | 2012-06-13 | 湖南科技大学 | Preparation method for lignosulfonate nano-silver colloid |
| CN110240774A (en) * | 2019-06-21 | 2019-09-17 | 华南理工大学 | A kind of high-intensity wood quality/polyvinyl alcohol composite antibacterial hydrogel and preparation method |
| CN112521630A (en) * | 2020-08-28 | 2021-03-19 | 同济大学 | Preparation method and application of green flexible conductive anti-freezing hydrogel |
| CN113004543A (en) * | 2021-02-26 | 2021-06-22 | 江南大学 | Nano lignin/polyvinyl alcohol composite medical hydrogel and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| In situ reduction of silver nanoparticles in the lignin based hydrogel for enhanced antibacterial application;Man Li等;《Colloids and Surfaces B: Biointerfaces》;20190501;第177卷;第370–376页 * |
| PANI导电水凝胶的制备及其进展;隋立军;《高分子通报》;20200615(第06期);第29-37页 * |
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