CN111041708A - Composite membrane, preparation method thereof and pressure sensor - Google Patents
Composite membrane, preparation method thereof and pressure sensor Download PDFInfo
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- CN111041708A CN111041708A CN201911400207.7A CN201911400207A CN111041708A CN 111041708 A CN111041708 A CN 111041708A CN 201911400207 A CN201911400207 A CN 201911400207A CN 111041708 A CN111041708 A CN 111041708A
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- 239000012528 membrane Substances 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 81
- 239000002121 nanofiber Substances 0.000 claims abstract description 45
- 239000006185 dispersion Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000007590 electrostatic spraying Methods 0.000 claims abstract description 26
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 36
- 239000007921 spray Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 7
- 229920002301 cellulose acetate Polymers 0.000 claims description 6
- 239000004677 Nylon Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 229920001778 nylon Polymers 0.000 claims description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 3
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000009489 vacuum treatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01D5/00—Formation of filaments, threads, or the like
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- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
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- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/18—Measuring force or stress, in general using properties of piezo-resistive materials, i.e. materials of which the ohmic resistance varies according to changes in magnitude or direction of force applied to the material
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Abstract
The invention provides a preparation method of a composite membrane, which comprises the steps of carrying out electrostatic spinning on a solution containing a polymer and carrying out electrostatic spraying on a dispersion liquid containing graphene oxide, and collecting the solution at the same position to obtain a prefabricated membrane, wherein the prefabricated membrane comprises a nanofiber membrane and an aggregate embedded in the nanofiber membrane, the nanofiber membrane is made of the polymer, and the aggregate is made of graphene oxide; and reducing the graphene oxide to obtain the composite membrane. The invention also provides a composite film obtained based on the preparation method and a pressure sensor based on the composite film. The composite membrane has excellent flexibility and mechanical stability, and the pressure sensor has the characteristics of high sensitivity, wide range and stable performance.
Description
Technical Field
The invention relates to the technical field of pressure sensors, in particular to a composite membrane, a preparation method of the composite membrane and a pressure sensor.
Background
The piezoresistive pressure sensor is composed of a substrate providing mechanical properties and an active material providing sensing properties, and in order to meet the sensitivity requirement, micro-nano structures such as micro-groove type, hemispherical type, pyramid type, interlocking type and the like are usually introduced into the active material through a template method. However, the structural design method based on the template method usually requires more complicated processes, is extremely high in cost and is not suitable for large-scale manufacturing, and the microstructure obtained by the template method is only suitable for detection in a small range. Along with the increasing degree of intellectualization of human life style, it is very important to design a flexible pressure sensor with high sensitivity, wide range, stable performance and simple preparation process.
Disclosure of Invention
In view of the above, it is necessary to provide a composite membrane having high sensitivity, wide range, stable performance and simple process, a method for preparing the same, and a pressure sensor.
The preparation method of the composite membrane comprises the following steps:
providing a dispersion liquid containing graphene oxide and a solution containing a polymer;
carrying out electrostatic spinning on the solution, carrying out electrostatic spraying on the dispersion liquid at the same time, and collecting at the same position to obtain a prefabricated film, wherein the prefabricated film comprises a nanofiber film and an aggregate embedded in the nanofiber film, the nanofiber film is made of a polymer, and the aggregate is made of graphene oxide;
and reducing the graphene oxide to obtain the composite membrane.
In one embodiment, the electrostatic spinning process parameters include: the voltage is 10kV to 30kV, the liquid supply speed is 0.1mL/h to 5mL/h, and the receiving distance is 5cm to 20 cm;
and/or the technological parameters of the electrostatic spraying comprise: the voltage is 10kV to 30kV, the liquid supply speed is 0.1mL/h to 5mL/h, and the receiving distance is 5cm to 20 cm.
In one embodiment, during the electrostatic spinning, the first spray head reciprocates within the range of 5 cm-10 cm;
and/or during electrostatic spraying, the second spray head reciprocates within the range of 5 cm-10 cm.
In one embodiment, the electrostatic spinning and the electrostatic spraying are performed in the same chamber, the temperature of the chamber is between room temperature and 100 ℃, and the humidity is between 10 and 70 percent.
In one embodiment, the graphene oxide is reduced to graphene using silane.
In one embodiment, the amount of the silane is 2 μ L to 5 μ L based on 1mg of graphene oxide.
In one embodiment, the graphene oxide is reduced to the graphene at a temperature of 140 ℃ to 180 ℃.
In one embodiment, the silane comprises one or more of methyltriethoxysilane and 3-aminopropyltriethoxysilane.
In one embodiment, the concentration of the graphene oxide in the dispersion liquid is 3 mg/mL-5 mg/mL, and the mass percentage of the polymer in the solution is 5% -20%.
In one embodiment, the dispersion liquid further includes an auxiliary agent, and the auxiliary agent includes polyvinylpyrrolidone.
In one embodiment, the polymer comprises one or more of thermoplastic polyurethane, nylon, polylactic acid, polymethyl methacrylate, cellulose acetate, and polyvinyl alcohol.
The composite membrane is obtained by the preparation method and comprises a nanofiber membrane and an aggregate embedded in the nanofiber membrane, wherein the nanofiber membrane is made of a polymer, and the aggregate is made of graphene.
In one embodiment, the aggregate has a shape including one or more of flower, microsphere, and sheet.
A pressure sensor comprises a composite membrane and a lead arranged on the composite membrane, wherein the lead extends out of the composite membrane.
According to the preparation method of the composite membrane, the nanofiber membrane is obtained through electrostatic spinning and serves as a flexible matrix of the composite membrane, the graphene oxide aggregate is embedded into the nanofiber membrane through electrostatic spraying, a stacked multi-stage structure is formed in the nanofiber membrane along with the process during embedding, and then graphene is reduced to serve as an active material. Therefore, the composite membrane with the multilevel composite microstructure is obtained through the combination of electrostatic spinning and electrostatic spraying, and the process is simple.
Meanwhile, the composite membrane has excellent flexibility, and the graphene aggregate and the nanofiber membrane have good bonding strength through in-situ reduction and crosslinking of the graphene aggregate, so that the composite membrane has good mechanical stability.
When the composite membrane is applied to a pressure sensor, under the action of external force, the contact condition between the graphene aggregates is changed, so that the resistance of the graphene aggregates and the nanofiber membrane is changed, and high-sensitivity and wide-range detection on pressure is realized. Therefore, the pressure sensor can be well attached to the surface of a human body, is very suitable for monitoring physiological indexes such as human body pulse and the like, and is suitable for various fields such as wearable medical equipment, motion monitoring, intelligent clothes, intelligent robots, electronic skins and the like.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a composite membrane.
Detailed Description
The composite membrane, the preparation method thereof and the pressure sensor provided by the invention will be further explained below.
As shown in fig. 1, a method for preparing a composite film according to the present invention includes:
s1, providing a dispersion liquid containing graphene oxide and a solution containing a polymer;
s2, performing electrostatic spinning on the solution, performing electrostatic spraying on the dispersion liquid, and collecting at the same position to obtain a prefabricated film a, wherein the prefabricated film a comprises a nanofiber membrane and an aggregate embedded in the nanofiber membrane, the nanofiber membrane is made of a polymer, and the aggregate is made of graphene oxide;
and S3, reducing the graphene oxide to obtain a composite film b.
In step S1, the graphene oxide may be prepared by using a principle of a hummer method in which graphite powder is modified, and specifically, the method may include the following steps:
s11, mixing K2S2O8And P2O5Dispersed in concentrated H2SO4Forming a dispersion;
s12, slowly adding graphite powder while stirring the dispersion liquid;
s13, continuously reacting for 5-8 h, cooling to room temperature, slowly diluting, standing and layering; the diluent used can be deionized water and the like.
The reaction temperature in step S13 is preferably 50 to 90 ℃, and more preferably 75 to 85 ℃, and when the pre-oxidation temperature is 80 ℃, the dielectric loss and hysteresis loss of the obtained graphene oxide are optimal, the micro-lamellar structure of the prepared graphene oxide is relatively complete, the secondary oxidation effect is relatively good, and therefore, the secondary oxidation temperature is more preferably 80 ℃.
And S14, removing the supernatant obtained in the step S13, performing suction filtration, washing the upper filter cake, naturally standing and drying to obtain the pre-oxidized graphene. The filtration can be specifically carried out by a polytetrafluoroethylene filter membrane, preferably, the pore diameter of the polytetrafluoroethylene filter membrane is 0.22 μm, and the polytetrafluoroethylene filter membrane can be washed by deionized water.
Further, the steps further include:
s15, dispersing the preoxidation product obtained in the step S14 in concentrated H2SO4To obtain a dispersion liquid; continuously stirring the dispersion in an ice salt bath to reduce the temperature to 0-3 ℃, and slowly adding KMnO in the stirring process4And always maintaining a low temperature, preferably, the low temperature is maintained below 5 ℃.
S16, heating the mixed reaction liquid obtained in the step S15 to 35 ℃, stirring, diluting with deionized water, heating to 85 ℃, and continuing stirring. Preferably, the first stirring time is 1.5-2.5 h, the second stirring time is 2-3 h, the low-temperature stirring time is lower than the high-temperature stirring time, the oxidation degree of the graphene is favorably improved, and the prepared graphene oxide has a complete micro lamellar structure.
S17, sequentially adding ionized water and H2O2The reaction was terminated and the reaction solution was allowed to cool naturally to room temperature. And (3) standing the product for two days for layering, removing supernatant, centrifugally separating bottom precipitate, and washing with an acidic solution and deionized water in sequence to reach the pH value of 6 to obtain the graphene oxide aqueous dispersion, wherein the acidic solution is preferably 1M hydrochloric acid.
And (3) carrying out the Hummer method of the steps S15 to S17 on the graphene after the pre-oxidation stage of the steps S11 to S14 to prepare the graphene oxide, wherein the obtained graphene oxide is attached with a large amount of oxygen-containing functional groups.
Further, the graphene oxide can be dispersed in an organic solvent by a solvent exchange method, wherein the organic solvent comprises one or more of N, N-dimethylformamide and ethanol, and is preferably N, N-dimethylformamide.
Further, the concentration of the graphene oxide in the dispersion liquid is 3 mg/mL-5 mg/mL.
Further, the method also comprises the step of adding an auxiliary agent into the dispersion liquid of the graphene oxide, wherein the auxiliary agent comprises polyvinylpyrrolidone. Polyvinylpyrrolidone can easily form a microsphere structure under an electric field, so that the graphene oxide aggregate prepared by adding polyvinylpyrrolidone has a wrinkled microspherical composite structure.
Further, in the solution containing the polymer, the mass percent of the polymer is 5-20%, and the polymer comprises one or more of thermoplastic polyurethane, nylon, polylactic acid, polymethyl methacrylate, cellulose acetate and polyvinyl alcohol. The polymer is preferably nylon, because nylon is used as a base material for electrostatic spinning, the material is easy to obtain, the raw material cost is low, and the polymer is suitable for large-scale production, and the produced nano-fibers also have the advantages of large specific surface area, small pore size and low corrosion to equipment.
In step S2, specifically, electrospinning the solution with an electrospinning device to form a nanofiber membrane, and embedding graphene oxide in the nanofiber membrane with an electrostatic spraying device.
Specifically, during electrostatic spinning, the solution is placed in a first injector, the first injector is placed on a micro propulsion pump, the first injector is connected to a spray head of electrostatic spinning equipment through a conduit, electrostatic spinning is carried out through the first spray head, and the technological parameters of electrostatic spinning comprise: the voltage is 10kV to 30kV, the liquid supply speed is 0.1mL/h to 5mL/h, and the receiving distance is 5cm to 20 cm.
During electrostatic spraying, the dispersion liquid is placed in a second injector, the second injector is placed on a micro propulsion pump, the second injector is connected to a spray head of electrostatic spraying equipment through a guide pipe, electrostatic spraying is carried out through the second spray head, and the technological parameters of the electrostatic spraying comprise: the voltage is 10kV to 30kV, the liquid supply speed is 0.1mL/h to 5mL/h, and the receiving distance is 5cm to 20 cm.
Further, in order to ensure that the graphene oxide aggregates and the nanofiber membrane are uniformly collected, during electrostatic spinning, the first spray head reciprocates within the range of 5 cm-10 cm, during electrostatic spraying, the second spray head also reciprocates within the range of 5 cm-10 cm, and the reciprocating distances of the first spray head and the second spray head are the same. It is understood that the first and second nozzles may be arranged in parallel and simultaneously during the reciprocating movement, or may be arranged in front and rear to reciprocate during the reciprocating movement.
In addition, in the reciprocating motion process, the nanofiber membrane and the graphene oxide aggregate can be stacked layer by layer to form a multi-stage composite microstructure.
Further, the electrostatic spinning and the electrostatic spraying are carried out in the same chamber, the temperature of the chamber is between room temperature and 100 ℃, and the humidity is between 10 and 70 percent. Under the combined action of temperature and humidity environment, the volatilization speeds of the solvents contained in the graphene oxide droplets formed in the electrostatic spraying process of the dispersion liquid are different, and the shapes of the formed aggregates are different.
Specifically, for example, at a temperature of 80 ℃ to 100 ℃, the humidity is controlled to be 10% to 20% by using dry air, so that in an electrostatic spraying process, a dispersion liquid is atomized into small droplets at high pressure, and a solvent in the droplets is rapidly volatilized under the combined action of high temperature and low humidity, wherein when the solvent sandwiched between two different graphene oxide sheets is volatilized, a capillary force is generated on the graphene oxide sheets, so that the graphene oxide sheets are wrinkled to form a flower-shaped structure.
At the temperature of room temperature to 50 ℃, the humidity is controlled to be 30-70% by using dry air, and when the dispersion liquid contains the assistant polyvinylpyrrolidone, the polyvinylpyrrolidone dilute solution can not be filamentized under an electric field and only forms microspheres, so that the obtained graphene oxide aggregate is a microspherical composite structure with folds.
At the temperature of 30-60 ℃, when the humidity is controlled to be 20-40% by using dry air, the solvent of the liquid drops can not be completely and quickly volatilized due to lower temperature, the smaller liquid drops are quickly volatilized to form a wrinkled flower-shaped aggregate, and the larger liquid drops are slowly volatilized to form a flaky aggregate.
Therefore, the graphene oxide aggregates with different morphologies can be obtained by regulating and controlling the temperature and the humidity and using the auxiliary agent.
In step S3, silane may be used to reduce the graphene oxide to graphene at a temperature of 140 ℃ to 180 ℃, so that the graphene oxide is reduced and crosslinked in situ, so that the obtained graphene aggregate and the nanofiber membrane have a good bonding strength, thereby providing the composite membrane with good mechanical stability.
The silane comprises one or more of methyl triethoxysilane and 3-aminopropyl triethoxysilane, and the dosage of the silane is 2-5 muL calculated by 1mg graphene oxide.
Therefore, the composite membrane of the invention obtains the nanofiber membrane as the flexible matrix of the composite membrane through electrostatic spinning, and simultaneously embeds the graphene oxide aggregate into the nanofiber membrane through electrostatic spraying and then reduces the graphene into graphene as an active material, namely the composite membrane with the multilevel composite microstructure is obtained through the combination of electrostatic spinning and electrostatic spraying, and the process is simple.
The invention also provides a composite membrane, which is obtained by the preparation method and comprises a nanofiber membrane and an aggregate embedded in the nanofiber membrane, wherein the nanofiber membrane is made of a polymer, and the aggregate is made of graphene. The composite membrane has excellent flexibility, and the aggregate and the nanofiber membrane have high bonding strength and good mechanical stability.
Specifically, the shape of the aggregate comprises one or more of flower shape, micro-sphere shape and sheet shape.
The invention also provides a pressure sensor, which comprises the composite film and a lead arranged on the composite film, wherein the lead extends out of the composite film.
Based on the better flexibility and the multi-stage composite microstructure of the composite membrane, when the composite membrane is applied to a pressure sensor, under the action of external force, the contact condition between graphene aggregates is changed, so that the resistance of the graphene aggregates and a nanofiber membrane is changed, and high-sensitivity and wide-range detection on pressure is realized.
Therefore, the pressure sensor can be well attached to the surface of a human body, is very suitable for monitoring physiological indexes such as human body pulse and the like, and is suitable for various fields such as wearable medical equipment, motion monitoring, intelligent clothes, intelligent robots, electronic skins and the like.
Hereinafter, the flexible pressure sensor and the method for manufacturing the same will be further described with reference to the following specific examples.
Preparing graphene oxide:
16.8gK2S2O8And 16.8gP2O5Dispersion in 80mL of concentrated H at 60 deg.C2SO4Stirring while slowly adding 20g of graphite powder, reacting at 80 ℃ for 5 hours, cooling to room temperature, slowly diluting with deionized water, standing and layering. And (3) removing the supernatant, performing suction filtration by using a polytetrafluoroethylene filter membrane with the aperture of 0.22 mu m, washing the upper filter cake by using 3L of deionized water, and naturally drying to obtain the pre-oxidized graphene. Pre-oxidation product was dispersed in 460mL of concentrated H2SO4Neutralizing and continuously stirring in ice salt bath to reduce the temperature to 0-3 deg.C, continuously stirring, and slowly adding 60g KMnO4And the temperature is kept below 5 ℃ all the time in the process to obtain mixed reaction liquid. The mixed reaction solution was then heated to 35 ℃ and stirred for 2h, diluted with 1.5L deionized water, warmed to 85 ℃ and stirred for 2.5 h. 1.5L of deionized water and 500mLH were then added in that order2O2And stopping the reaction, naturally cooling the reaction solution to room temperature, standing the product for two days for layering, removing the supernatant, centrifugally separating the precipitate at the bottom, and washing the precipitate with 1MHCl solution and deionized water in sequence to reach the pH value of 6 to obtain the graphene oxide aqueous dispersion.
Example 1:
and dispersing graphene oxide in an N, N-dimethylformamide solvent by a solvent exchange method to obtain a dispersion liquid containing the graphene oxide, wherein the concentration of the graphene oxide in the dispersion liquid is 5 mg/mL.
Dissolving nylon 6 in formic acid to obtain a solution containing nylon 6, and controlling the mass percent of the nylon 6 to be 15%.
The dispersion and the solution were placed in 10mL syringes respectively, equipped with a metal needle having an outer diameter of 0.7mm, and the flow rate was controlled with a microsyringe, and the preformed film was collected with a flat receiver laid with aluminum foil. Electrostatic spinning of the solution is carried out under the voltage of 15kV, the flow rate of 0.1mL/h and the receiving distance of 15cm, electrostatic spraying of the dispersion is carried out under the voltage of 20kV, the flow rate of 1mL/h and the receiving distance of 5cm synchronously with the electrostatic spinning, the air temperature in the cavity is controlled to be 100 ℃ by an electric heating wire, the relative humidity is controlled to be 20% by dry air, the first spray head and the second spray head are controlled to reciprocate within the range of 10cm by a motion control system of the spray heads, and the processing duration is 12h, so that the prefabricated film is obtained.
The resulting pre-formed film was dried under vacuum at 40 ℃ for 24 h. Placing a culture dish containing 200 mu L of methyltriethoxysilane in a dryer, sealing, reacting at 180 ℃ for 3h, taking out the prefabricated membrane after the reaction is finished, and carrying out vacuum treatment for three times to obtain the composite membrane. The composite membrane comprises a nanofiber membrane and an aggregate embedded in the nanofiber membrane, wherein the nanofiber membrane is made of nylon 6, the aggregate is made of graphene, and the aggregate is in a flower shape.
Example 2:
adding a polyvinylpyrrolidone solution with the concentration of 3% into the graphene oxide aqueous dispersion, wherein the concentration of the graphene oxide in the dispersion is 3mg/mL, and the mass ratio of the graphene oxide to the polyvinylpyrrolidone is 1: 10.
Dissolving cellulose acetate in a mixed solvent with the volume ratio of N, N-dimethylacetamide to acetone being 1:2 to obtain a solution containing cellulose acetate, and controlling the mass percent of the cellulose acetate to be 15%.
The dispersion and the solution were placed in 10mL syringes respectively, equipped with a metal needle having an outer diameter of 0.7mm, and the flow rate was controlled with a microsyringe, and the preformed film was collected with a flat receiver laid with aluminum foil. Electrostatic spinning of the solution is carried out under the voltage of 12kV, the flow rate of 0.1mL/h and the receiving distance of 15cm, electrostatic spraying of the dispersion is carried out under the voltage of 20kV, the flow rate of 1mL/h and the receiving distance of 5cm synchronously with the electrostatic spinning, the air temperature in the cavity is controlled to be 100 ℃ by an electric heating wire, the relative humidity is controlled to be 10% by dry air, the first spray head and the second spray head are controlled to reciprocate within the range of 8cm by a motion control system of the spray heads, and the processing duration is 12h, so that the prefabricated film is obtained.
The resulting pre-formed film was dried under vacuum at 40 ℃ for 24 h. Placing a culture dish containing 200 mu L of ethyl triethoxysilane in a dryer, sealing, reacting at 180 ℃ for 3h, taking out the prefabricated membrane after the reaction is finished, and carrying out vacuum treatment for three times to obtain the composite membrane. The composite membrane comprises a nanofiber membrane and an aggregate embedded in the nanofiber membrane, wherein the nanofiber membrane is made of cellulose acetate, the aggregate is made of graphene, and the aggregate is in a microspherical shape with folds.
Example 3:
and dispersing graphene oxide in an ethanol solvent by a solvent exchange method to obtain a dispersion liquid containing the graphene oxide, wherein the concentration of the graphene oxide in the dispersion liquid is 5 mg/mL.
Thermoplastic polyurethane is dissolved in N, N-dimethylformamide to obtain a solution containing the thermoplastic polyurethane, and the mass percent of the thermoplastic polyurethane is controlled to be 15%.
The dispersion and the solution were placed in 10mL syringes respectively, equipped with a metal needle having an outer diameter of 0.7mm, and the flow rate was controlled with a microsyringe, and the preformed film was collected with a flat receiver laid with aluminum foil. Electrostatic spinning of the solution is carried out under the voltage of 12kV, the flow rate of 0.1mL/h and the receiving distance of 15cm, electrostatic spraying of the dispersion is carried out under the voltage of 20kV, the flow rate of 1mL/h and the receiving distance of 5cm synchronously with the electrostatic spinning, the air temperature in the cavity is controlled to be 50 ℃ by an electric heating wire, the relative humidity is controlled to be 30% by dry air, the first spray head and the second spray head are controlled to reciprocate within the range of 5cm by a motion control system of the spray heads, and the processing duration is 12h, so that the prefabricated film is obtained.
The resulting pre-formed film was dried under vacuum at 40 ℃ for 24 h. Placing a culture dish containing 200 mu L of methyltriethoxysilane in a dryer, sealing, reacting at 140 ℃ for 3h, taking out the prefabricated membrane after the reaction is finished, and carrying out vacuum treatment for three times to obtain the composite membrane. The composite membrane comprises a nanofiber membrane and an aggregate embedded in the nanofiber membrane, wherein the nanofiber membrane is made of thermoplastic polyurethane, the aggregate is made of graphene, and the aggregate is flaky and partially flower.
And respectively leading out two ends of the composite film obtained in the embodiment 1-3 by using conductive silver paste and a copper wire to prepare the pressure sensor. And is connected to a digital multimeter, and the composite sponge is stuck to the position of wrist where the pulse can be detected by using the transparent medical dressing. And recording the resistance change of the composite membrane in real time by using a digital multimeter to obtain a real-time monitoring signal of the human pulse.
The pressure sensor of the invention can show the characteristics of good sensitivity, wide range, stable performance and the like, is suitable for large-area popularization and application, can be used as a pulse sensor, and can also be used for detecting various micro deformations such as laryngeal vibration, finger bending and falling of micro objects, the preparation and detection processes are similar, and the shape and the size of the composite membrane in the pressure sensor are cut and attached to an area to be detected.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. A method of making a composite membrane, comprising:
providing a dispersion liquid containing graphene oxide and a solution containing a polymer;
carrying out electrostatic spinning on the solution, carrying out electrostatic spraying on the dispersion liquid at the same time, and collecting at the same position to obtain a prefabricated film, wherein the prefabricated film comprises a nanofiber film and an aggregate embedded in the nanofiber film, the nanofiber film is made of a polymer, and the aggregate is made of graphene oxide;
and reducing the graphene oxide to obtain the composite membrane.
2. The method for preparing the composite film according to claim 1, wherein the process parameters of the electrostatic spinning comprise: the voltage is 10kV to 30kV, the liquid supply speed is 0.1mL/h to 5mL/h, and the receiving distance is 5cm to 20 cm;
and/or the technological parameters of the electrostatic spraying comprise: the voltage is 10kV to 30kV, the liquid supply speed is 0.1mL/h to 5mL/h, and the receiving distance is 5cm to 20 cm.
3. The method for preparing the composite film according to claim 1, wherein the first nozzle reciprocates within a range of 5cm to 10cm during the electrospinning;
and/or during electrostatic spraying, the second spray head reciprocates within the range of 5 cm-10 cm.
4. The method for preparing the composite film according to claim 1, wherein the electrospinning and the electrostatic spraying are performed in the same chamber, and the temperature of the chamber is between room temperature and 100 ℃ and the humidity of the chamber is between 10 and 70 percent.
5. The method of claim 1, wherein the graphene oxide is reduced to graphene using silane.
6. The method for preparing the composite film according to claim 5, wherein the amount of the silane is 2 to 5 μ L based on 1mg of graphene oxide.
7. The method of claim 5, wherein the graphene oxide is reduced to the graphene at a temperature of 140 ℃ to 180 ℃.
8. The method of claim 5, wherein the silane comprises one or more of methyltriethoxysilane and 3-aminopropyltriethoxysilane.
9. The method for preparing the composite membrane according to claim 1, wherein the concentration of the graphene oxide in the dispersion liquid is 3 mg/mL-5 mg/mL, and the mass percentage of the polymer in the solution is 5% -20%.
10. The method of claim 1, wherein the dispersion further comprises an auxiliary agent, wherein the auxiliary agent comprises polyvinylpyrrolidone.
11. A method of making a composite film according to claim 1 wherein said polymer comprises one or more of thermoplastic polyurethane, nylon, polylactic acid, polymethylmethacrylate, cellulose acetate, polyvinyl alcohol.
12. A composite membrane obtained by the preparation method of any one of claims 1 to 11, comprising a nanofiber membrane and an aggregate embedded in the nanofiber membrane, wherein the nanofiber membrane is made of a polymer, and the aggregate is made of graphene.
13. The composite membrane of claim 12 wherein the aggregate shape comprises one or more of flower, microsphere, and platelet.
14. A pressure sensor comprising the compound membrane of claim 12 or 13 and a conductive wire disposed on the compound membrane, the conductive wire extending out of the compound membrane.
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