CN109180962A - A kind of preparation method of PAA class pectin self-healing hydrogel and its capacitance type sensor - Google Patents
A kind of preparation method of PAA class pectin self-healing hydrogel and its capacitance type sensor Download PDFInfo
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Abstract
The invention belongs to new material and sensor technical fields, disclose the preparation method of a kind of PAA class pectin self-healing hydrogel and its capacitance type sensor, by using acrylic acid and pectin as substrate, iron ion is added and forms coordination, Raolical polymerizable occurs after heating and generates the uniform double-deck tridimensional network, the mechanical performance that obtained polyacrylic pectin self-healing hydrogel has had, but also the characteristic closed with rapidly self-healing.In order to make full use of hydrogel, it is made into capacitance pressure transducer, or condenser type strain transducer that both ends are the sandwich structure that self-healing hydrogel intermediate dielectric layer is dimethyl silicone polymer (PDMS) or VHB adhesive tape (3M4920).The present invention is easy to operate using the method that PAA class pectin self-healing hydrogel prepares capacitance type sensor, and raw material sources are extensive, and has good electrochemistry and mechanical performance, has broad application prospects in flexible energy storage material field.
Description
Technical field
The invention belongs to new material and sensor technical fields, and in particular to a kind of PAA class pectin self-healing hydrogel and
The preparation method of its capacitance type sensor.
Background technique
Since the 1940s, hydrogel is in bionical, chemical, medicine and other fields researchs from uninterrupted.Hydrogel
As a kind of soft wet stock, it is that have hydrophily and not soluble in water, and can absorb a large amount of water using water as decentralized medium
Point, the high molecular polymer with cross-linked structure.Hydrogel has good water permeability and biocompatibility, plants as human body
Adverse reaction can be reduced by entering object, hydrogel also with many active mass of human body, such as the joint lubrication cartilage of people, musculature etc.
There is very much like property, so that the alternative materials that hydrogel is ideal as joint prosthesis, and exploitation class are artificial
The ideal alternative materials in joint, thus hydrogel is widely used as excellent bio-medical material.
In recent years, requirement of the people to portable electronic device is continuously improved, and wearable electronic, electronic skin etc. are soft
Property device material research it is more and more, and it is environmental-friendly, performance is stable, service life the features such as be concerned.20th century 80
Age, scientist by self-regeneration biosystem triggering and one kind for developing can be carried out the new material of self-regeneration, it is this kind of
Self-healing material helps to improve service life and the safety of device.But its high-moisture leads to poor mechanical performance and stability
Application and development that gel is substituted as load bearing soft tissue are limited, therefore prepares high-intensitive self-healing hydrogel mesh
Before still remain very big challenge.
Sensor is a kind of common but critically important device.New material etc. is high-tech to be continued to bring out, sensor
Diversified trend is showed, such as: simulating human skin, the tactile of novel sensor using biomaterial；Utilize MEMS technology
Intelligent miniature sensor is researched and developed, to be conducive to the integrated of complication system；Laser thunder is created using high-precision laser technology
It reaches, to be conducive to system real-time perception periphery barrier and environment etc..A kind of sensor is required to have while era development more
Kind identification function, but also the ability for needing the material to have self-healing, this is still an arduous challenge.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of with tensile strength is high, the self-healing time is short, self-healing
High-efficient hydrogel, and capacitance pressure transducer, and condenser type strain transducer are produced using self-healing hydrogel.
Mentality of designing of the invention is: being monomer using acrylic acid (AA), N, N '-methylene-bisacrylamide (MBAA) are
Crosslinking agent, ferric chloride hexahydrate (FeCl3·6H2It O) is metal ion network mixture, Ammonium Persulfate 98.5 (APS) is initiator, water-soluble
In liquid occur polymerization reaction obtain polyacrylic acid, due to carboxyl all rich in polyacrylic acid and pectin can and Fe3+Into
Row coordination forms the double-deck tridimensional network of physics and chemical crosslinking, makes it have the property of very strong stretching and self-healing.
Using the ionic conductivity of hydrogel, it can form that conductive layer is self-healing hydrogel, intermediate dielectric layer is polydimethylsiloxanes
The capacitive pressure or condenser type strain transducer of " sandwich " structure of alkane (PDMS) or VHB adhesive tape.
PAA class pectin self-healing hydrogel and its capacitance type sensor of the present invention the preparation method is as follows:
(1) by acrylic acid (AA), pectin (PE), ferric chloride hexahydrate (FeCl3·6H2O), N, N '-methylene bisacrylamide acyl
Amine (MBAA), Ammonium Persulfate 98.5 (APS) are added water and stir 30 minutes, lead to the 30 minutes gas removed in solution of nitrogen after mixing
Body reacts 60 minutes at 60 DEG C, forms the double-deck tridimensional network self-healing water-setting of PAA class pectin physics and chemical crosslinking
Glue.
(2) dimethyl silicone polymer (taking PDMS) is used as intermediate dielectric layer, the identical hydrogel conduct of upper and lower area coverage
Conductive layer, three, which is fitted closely, makes that bubble is not present between hydrogel and PDMS layer, and respectively between hydrogel and PDMS
Upper conducting wire is pressed from both sides respectively to export as electric signal.It is prepared that upper and lower level is the identical self-healing hydrogel of area, middle layer is
The capacitance pressure transducer, of " sandwich " structure of PDMS.VHB adhesive tape (3M 4920) can also be used as intermediate dielectric layer,
Conductive layer is the condenser type strain transducer of " sandwich " structure of self-healing hydrogel；Wherein, dimethyl silicone polymer dielectric
The area of layer is greater than the area of hydrogel layer, and with a thickness of 0.352mm；The area of VHB adhesive tape (3M4920) dielectric layer is greater than water
The area of gel layer, and with a thickness of 0.488mm.
(3) by step (2) capacitance pressure transducer, and condenser type strain transducer it is right with VHB adhesive tape (3M4910)
Device is packaged.
Hydrogel described in step (1) in the course of the polymerization process, acrylic acid (AA) and N, N '-methylene-bisacrylamide
(MBAA) polymerization reaction occurs under Ammonium Persulfate 98.5 (APS) initiation and generates polyacrylic acid, in ferric chloride hexahydrate (FeCl3.6H2O)
Under the action of, polyacrylic acid and pectin (PE) and Fe3+Between complex reaction occurs, form the bilayer of a kind of physics and chemical crosslinking
Tridimensional network self-healing hydrogel.
The dosage of step (1) described pectin is that 1.55~15.5%, the MBAA dosage of acrylic acid quality is acrylic acid quality
0.2%, APS dosage be acrylic acid quality 2%, FeCl3·6H2O dosage is the 0~2.5% of the amount of acrylic substance.
It is preferred that are as follows: when 6.2%, the MBAA dosage that the dosage of pectin is acrylic acid quality is the 0.2% of acrylic acid quality,
APS dosage is 2%, FeCl of acrylic acid quality3·6H2O dosage is the 1.25% of the amount of acrylic substance, can prepare self-healing
Close fast speed, the maximum hydrogel of elongation at break.
It is food containing 65% galacturonic acid and 34% methylation galacturonic acid in step (1) described pectin
Grade low-fat pectin.
The production of PDMS layer described in step (2) method particularly includes: by PDMS according to mass ratio: 10:1 (U.S. Dao Kang
The two-component external member that peaceful 184 silicon rubber of Sylgard is made of liquid component, density 1.04g/ml) it is uniformly mixed and to obtain
Mixture, then degassing removes bubble, and uncured mixture is poured into Teflon mould, and 1 is heated at 80 DEG C
After hour, the PDMS film of 10mm × 20mm and 0.352mm thickness can be formed.
The size of VHB (3M4920) layer described in step (2) is 20mm × 40mm × 0.488mm.
The capacitance type sensor of two kinds of " sandwich " structures described in step (3) is after completing, water in order to prevent
Gel dries out, and is packaged processing to sensor using VHB (3M4910) adhesive tape.
Elongation at break is restored to 195% in self-healing hydrogel 0.5 hour made from step (1), and self-healing efficiency is
Elongation at break is restored to 544% after 16.0%, 1h, and elongation at break is restored to after self-healing efficiency is 53.0%, 1.5 hours
964%, elongation at break is restored to 1148% after self-healing efficiency is 79.3%, 2 hours, and self-healing efficiency is 94.4%.
The utility model has the advantages that compared with prior art, the present invention is mainly reflected in easy to operate, and process conditions are mild, are produced into
This is low, and cost of material is low.The method of the present invention uses the pectin to human body close friend, and increases three-dimensional netted between acrylic acid
The crosslinking degree of structure enhances the tensile strength of hydrogel, shortens the self-healing time.The hydrogel that this method obtains breaks
It splits elongation and is up to 1216%, maximum stress 67.8kPa；Self-healing recovery time is most 2 hours fastly, self-healing efficiency
It is 94.4%；Performance still maintains stable after 12 circulations.The condenser type of hydrogel " sandwich " structure that the present invention makes
Not only there is high resolution ratio, performance to stablize, but also have self-healing energy for pressure sensor and condenser type strain transducer
Power.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the hydrogel prepared according to embodiment 1,2.
Fig. 2 is that the SEM of the different concentration of pectin hydrogels prepared according to embodiment 2 schemes, and (a) concentration of pectin is 1.5wt%,
(b) concentration of pectin is 3.1wt%, and (c) concentration of pectin is 6.2wt%.
Fig. 3 is the different proportion Fe prepared according to embodiment 13+The stress-strain curve of hydrogel.
Fig. 4 is the hydrogel stress-strain curve of the different concentration of pectin prepared according to embodiment 2.
Fig. 5 is the PAA-PE/Fe prepared according to embodiment 23+The continuous cyclic tension stress-strain curve of hydrogel.
Fig. 6 is the PAA-PE/Fe prepared according to embodiment 23+Cyclic tension stress-of the hydrogel after rest different time
Strain curve figure.
Fig. 7 is the PAA-PE/Fe prepared according to embodiment 23+The photo of hydrogel hydrogel before and after healing, (a) cutting
Hydrogel can stretch after hydrogel (c) healing after being divided into the healing of two parts (b).
Fig. 8 is the PAA-PE/Fe prepared according to embodiment 23+Hydrogel self-healing tensile stress-strain curve figure.
Fig. 9 is the capacitor and the curve of time of the capacitance pressure transducer, that is prepared according to embodiment 3 at various pressures
Figure.
Figure 10 be capacitor under 12 uniform pressures effects of the capacitance pressure transducer, that prepare according to embodiment 3 and when
Between cyclic curve figure.
Figure 11 is the condenser type strain transducer that prepare according to embodiment 4 rate of change of capacitance in the case where different tension strains act on
Curve graph
Specific embodiment
The present invention is described in further details below by embodiment, these embodiments are only used to illustrate the present invention, and
It does not limit the scope of the invention, illustrates embodiment in conjunction with example, the specific process is as follows:
Embodiment 1
2g acrylic acid, 0.031g pectin are taken, the amount concentration relative to acrylic substance is added in 4mg MBAA, 40mg APS
For the FeCl of 0-2.5mol%3.6H2O stirs 30 minutes after mixing in the aqueous solution of 10mL, leads to nitrogen 30 minutes and removes
Gas in solution, solution is poured into the mold of polytetrafluoroethylene (PTFE), is occurred polymerization reaction 60 minutes at 60 c, cooling
After obtain different Fe3+The hydrogel of concentration.When pectin content is 6.2wt%, FeCl in hydrogel3.6H2O content is 0mol%
When be labeled as PAA-PE hydrogel.
Embodiment 2
Embodiment 1 is changed to take 2g acrylic acid, 4mg MBAA, 40mg APS, 1.25mol%FeCl3.6H2O is added opposite
In the pectin that acrylic acid mass concentration is 1.55-15.5wt%, 30 minutes are stirred in the aqueous solution of 10mL after mixing, are led to
The nitrogen 30 minutes gas removed in solution, occurs polymerization reaction 60 minutes under 60 degrees Celsius, obtains the water of different concentration of pectin
Gel.When pectin content is 0wt%, FeCl3.6H2PAA hydrogel is labeled as when O content is 0mol%.When pectin content is
1.55wt%, FeCl3.6H2PAA-PE/Fe is labeled as when O content is 1.25mol%3+Hydrogel.
Embodiment 3
The production of PDMS layer first method particularly includes: by PDMS according to mass ratio: 10:1 (Dow corning Sylgard
The two-component external member that 184 silicon rubber are made of liquid component, density 1.04g/ml) it is uniformly mixed obtained mixture, so
Degassing removes bubble afterwards, and uncured mixture is poured into Teflon mould, can after heating 1 hour at 80 DEG C
Form the PDMS film of 10mm × 20mm and 0.352mm thickness.Take above-mentioned PDMS as middle layer, both sides are the PAA- of same size
PE/Fe3+Hydrogel fits closely three, presss from both sides a copper conductor among the interlayer of hydrogel and PDMS respectively, makes two copper
The conducting wire position opposite at two ends.It is dimethyl silicone polymer (PDMS) that obtain both ends, which be self-healing hydrogel intermediate dielectric layer,
The capacitance pressure transducer, of " sandwich " structure.Finally by the capacitance pressure transducer, of production VHB (3M 4910) adhesive tape
Processing is packaged to device.
Embodiment 4
VHB adhesive tape (3M 4920) is used as middle layer first, both sides are the PAA-PE/Fe of same size3+Hydrogel, will
Three, which fits closely, to stick together, and presss from both sides a copper conductor among the interlayer of hydrogel and VHB respectively, makes two copper conductors two
Hold opposite position.Obtain the electricity that both ends are " sandwich " structure that self-healing hydrogel intermediate dielectric layer is VHB (3M 4920)
Appearance formula strain transducer.The condenser type strain transducer of production is finally packaged place to device with VHB adhesive tape (3M 4910)
Reason.
Using Fourier infrared spectrograph to PAA hydrogel, PAA-PE hydrogel and PAA-PE/Fe3+The structure of hydrogel
It is analyzed, as shown in Figure 1, PAA hydrogel is in 3375,1647,1450 and 1024cm-1Amide groups is attributed to the fact that at peak everywhere respectively
The flexible vibration peak of middle N-H, the flexible vibration of C=O, the flexible vibration of the deformation vibration and C-O of O-H.PAA-PE hydrogel
In infrared spectrogram, 1636cm-1The flexible vibration peak that place is marked as C=O transits to 1640cm-1Place, this be likely to be by
In the addition of pectin, the effect of hydrogen bond in hydrogel is enhanced.Simultaneously, PAA-PE/Fe3+Occurs 1042cm in hydrogel-1
New peak, this is most likely due to Fe3+Addition promote between metal and carboxyl formed coordinate bond result.
Hydrogel to the different pectin contents prepared in embodiment 2, after carrying out freeze-drying 12 hours, using scanning electricity
Mirror (SEM, FEI Quanta650) observes hydrogel surface appearance structure, it is found that the aperture of the hydrogel of different pectin contents is big
Small inconsistent, when pectin content is 1.5wt%, minimum-value aperture can reach 1um or less (Fig. 2 a), and with the increasing of pectin content
Add pore size to be gradually increased, a kind of uniform porous network structure is showed when 6.2wt% to pectin content, such as Fig. 2 institute
Show.The aperture of hydrogel is more uniform, and structure is more stable, and mechanical stretching performance can be stronger.
Study on Mechanical Properties is carried out to hydrogel in embodiment 1,2 respectively using universal testing machine.What tension test used
Sample size are as follows: 50mm × 10mm × 2mm cuboid, tensile loads rate are as follows: 10mm/min, test result are five tests
Average value (following test condition is all the same, unless otherwise specified).As shown in Figures 3 and 4, the respectively Fe of various concentration3+Water
The tensile stress-strain curve figure of the pectin hydrogel of gel and various concentration.It was found that working as FeCl3·6H2O is compared to acrylic acid
Substance withdrawl syndrome be 1.25%, pectin compared to acrylic acid mass concentration be 6.2%, MBAA compared to acrylic acid matter
It compared to the mass concentration of acrylic acid is 2% that amount concentration, which is 0.2%, APS, the PAA-PE/Fe of preparation3+The fracture of hydrogel is stretched
Long rate and maximum stress reach best.
By to PAA-PE/Fe3+Hydrogel circulation pulling force stress-strain curve is it is found that disconnected when being stretched to hydrogel
It splits when 60% i.e. the 730% of elongation (1216%) continuously elongated 5 times, apparent hysteresis phenomenon occurs in discovery hydrogel, such as
Shown in Fig. 5.In order to be contrasted, is stretched at once second after first time stretches, apparent hysteresis phenomenon occur, but work as
Hydrogel is gradually restored to original state after sixty minutes for rest, and this is mainly due to can be with there are a large amount of carboxyl in hydrogel
Hydrogen bond is formed, hydrogel is gradually restored to original shape by hydrogen bond after stretching, and maximum stress is restored to 96.7%, such as schemes
Shown in 6.
From figure 7 it can be seen that by PAA-PE/Fe3+After hydrogel cutting (Fig. 7 a), two part Hydrogel contact at room temperature
Hydrogel realizes selfreparing, smooth (Fig. 7 b) that incision position becomes after 2h, and can stretch middle section and fracture (figure does not occur
7c).Self-healing degree is judged by the elongation at break of hydrogel recovery known to pulling force load-deformation curve, and hydrogel exists
Elongation at break is restored to 195% in 0.5 hour after cutting, and elongation at break restores after self-healing efficiency is 16.0%, 1 hour
To 544%, elongation at break is restored to 964% after self-healing efficiency is 53.0%, 1.5 hours, and self-healing efficiency is 79.3%,
Elongation at break is restored to 1148% after 2 hours, and self-healing efficiency is 94.4%, as shown in Figure 8.
Fig. 9 is PAA-PE/Fe3+The size of the capacitance pressure transducer, of hydrogel production is 20mm × 10mm × 5mm, point
Capacitor and time not at 2000Pa, 1000Pa, 1000Pa and 2500Pa through the test of same favour 2829C automatic component analyzer
Relationship, show stable increase at various pressures as can be seen from Figure 9, and still be able to after removing pressure
Return to initial state.Figure 10 is PAA-PE/Fe3+Hydrogel production capacitance pressure transducer, uniform pressure effect under 12
Secondary cyclic curve figure, no change has taken place for property after the state that can be returned to after each pressure and circulation 12 times,
Show good stability and repeatability.
Figure 11 is PAA-PE/Fe3+The condenser type strain transducer of hydrogel production is in same favour 2829C automatic component analyzer
The tension strain and capacitance variations curve graph tested jointly with omnipotent machine on probation.The size of the condenser type strain transducer of production is
20mm × 10mm × 5mm, and tensile loads rate are as follows: 2mm/min.As can be seen from Figure 11, with the variation of the enhancing capacitor of strain
Rate is smaller and smaller, and it is respectively 0-240% and 240-343% that strain curve can be substantially divided into two sections.Respectively to this two sections into
The linearity curve equation that row line integral obtains is respectively as follows: y=0.233x-3.33 and y=0.09x+29.9, wherein two sections of line
Property equation slope it is corresponding be respectively sensitivity of the sensor between 0-240% and 240-343% be 0.233 and 0.09.
Claims (9)
1. a kind of method that PAA class pectin self-healing hydrogel prepares capacitance type sensor, it is characterised in that: the preparation method
Steps are as follows:
(1) by acrylic acid (AA), pectin (PE), N, N '-methylene-bisacrylamide (MBAA), six water and iron chloride (FeCl3·
6H2O it) stirs 30 minutes, after completely dissolution, leads in 30 minutes removing solution of nitrogen with Ammonium Persulfate 98.5 (APS) mixing, addition water
Gas carries out polymerization reaction 60 minutes at 60 DEG C, obtains polyacrylic acid and pectin self-healing hydrogel；
(2) being fabricated to both ends is " sandwich " structure that self-healing hydrogel intermediate dielectric layer is dimethyl silicone polymer (PDMS)
Capacitance pressure transducer, or using VHB adhesive tape (3M 4920) as intermediate dielectric layer, both ends be self-healing hydrogel " three
The condenser type strain transducer of Mingzhi " structure；
(3) processing finally is packaged to sensor with VHB adhesive tape (3M 4910).
2. the method that PAA class pectin self-healing hydrogel as described in claim 1 prepares capacitance type sensor, feature exist
In: step (1) pectin is food-grade low-fat pectin, wherein contains 65% galacturonic acid and 34% methylation half
Lactobionic acid.
3. the method that PAA class pectin self-healing hydrogel as described in claim 1 prepares capacitance type sensor, feature exist
In: the dosage of step (1) described pectin is that 1.55%~15.5%, the MBAA dosage of acrylic acid quality is acrylic acid quality
0.2%, APS dosage are the 2% of acrylic acid quality, six water and iron chloride (FeCl3·6H2O) dosage is the amount of acrylic substance
0~2.5%.
4. the method that PAA class pectin self-healing hydrogel as described in claim 1 prepares capacitance type sensor, feature exist
In: elongation at break is restored to 195% in self-healing hydrogel 0.5 hour made from step (1), and self-healing efficiency is
Elongation at break is restored to 544% after 16.0%, 1h, and elongation at break is restored to after self-healing efficiency is 53.0%, 1.5 hours
964%, elongation at break is restored to 1148% after self-healing efficiency is 79.3%, 2 hours, and self-healing efficiency is 94.4%.
5. the method that PAA class pectin self-healing hydrogel as described in claim 1 prepares capacitance type sensor, feature exist
In: the composition of step (2) hydrogel for preparing capacitance type sensor in mass ratio are as follows: dosage of pectin is acrylic acid quality
6.2%, MBAA dosage be 0.2%, the APS dosage of acrylic acid quality be 2%, FeCl of acrylic acid quality3·6H2O dosage is
The 1.25% of the amount of acrylic substance.
6. the method that PAA class pectin self-healing hydrogel as described in claim 1 prepares capacitance type sensor, feature exist
In: the preparation method of capacitance pressure transducer, described in step (2) and condenser type strain transducer is equal are as follows: size is identical
Hydrogel is fitted tightly over dielectric layer both sides, and presss from both sides a conducting wire in hydrogel and the intermediate of dielectric layer respectively, makes two conducting wires
In the opposite position in both ends.
7. the method that PAA class pectin self-healing hydrogel as described in claim 1 prepares capacitance type sensor, feature exist
In: the area of dimethyl silicone polymer dielectric layer described in step (2) is greater than the area of hydrogel layer, and with a thickness of 0.352mm；
The area of VHB adhesive tape (3M4920) dielectric layer is greater than the area of hydrogel layer, and with a thickness of 0.488mm.
8. the method that PAA class pectin self-healing hydrogel as described in claim 1 prepares capacitance type sensor, feature exist
In the production of PDMS layer described in step (2) method particularly includes: by the PDMS (184 silicon rubber of Sylgard) of bi-component according to
Mass ratio: 10:1 is uniformly mixed, and then degassing removes bubble and obtains mixture, and uncured mixture is poured into polytetrafluoroethyl-ne
In alkene mold, after heating 1 hour at 80 DEG C, the PDMS film of 10mm × 20mm and 0.352mm thickness are formed.
9. the method that PAA class pectin self-healing hydrogel as described in claim 1 prepares capacitance type sensor, feature exist
In: the size of VHB (3M4920) layer described in step (2) is 20mm × 40mm × 0.488mm.
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| CN109974905A (en) * | 2019-04-03 | 2019-07-05 | 南开大学 | A kind of strain gauge and preparation method thereof with self-reparing capability |
| CN110702147A (en) * | 2019-09-09 | 2020-01-17 | 江苏大学 | Flexible stretchable sensor and preparation method and application thereof |
| CN110736420A (en) * | 2019-09-19 | 2020-01-31 | 北京科技大学 | Preparation method of portable self-powered hydrogel strain sensor |
| CN112067175A (en) * | 2020-09-27 | 2020-12-11 | 天津工业大学 | Flexible capacitive sensor and preparation method and application thereof |
| CN115368638A (en) * | 2022-08-10 | 2022-11-22 | 河南师范大学 | Preparation method and application of multifunctional modified starch-based hydrogel material |
| CN115463622A (en) * | 2022-08-03 | 2022-12-13 | 广东纤友朵美生物科技有限公司 | Gel based on oxidized pectin and preparation method thereof |
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| CN110702147A (en) * | 2019-09-09 | 2020-01-17 | 江苏大学 | Flexible stretchable sensor and preparation method and application thereof |
| CN110736420A (en) * | 2019-09-19 | 2020-01-31 | 北京科技大学 | Preparation method of portable self-powered hydrogel strain sensor |
| CN110736420B (en) * | 2019-09-19 | 2020-09-11 | 北京科技大学 | Preparation method of portable self-powered hydrogel strain sensor |
| CN112067175A (en) * | 2020-09-27 | 2020-12-11 | 天津工业大学 | Flexible capacitive sensor and preparation method and application thereof |
| CN115463622A (en) * | 2022-08-03 | 2022-12-13 | 广东纤友朵美生物科技有限公司 | Gel based on oxidized pectin and preparation method thereof |
| CN115368638A (en) * | 2022-08-10 | 2022-11-22 | 河南师范大学 | Preparation method and application of multifunctional modified starch-based hydrogel material |
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