CN104894750B - Force-sensitive stretchable electro-spinning patterning conductive nanofiber membrane and preparation method thereof - Google Patents
Force-sensitive stretchable electro-spinning patterning conductive nanofiber membrane and preparation method thereof Download PDFInfo
- Publication number
- CN104894750B CN104894750B CN201510334084.7A CN201510334084A CN104894750B CN 104894750 B CN104894750 B CN 104894750B CN 201510334084 A CN201510334084 A CN 201510334084A CN 104894750 B CN104894750 B CN 104894750B
- Authority
- CN
- China
- Prior art keywords
- spinning
- masterplate
- fibrous membrane
- quick
- stretchable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method of a force-sensitive stretchable electro-spinning patterning conductive nanofiber membrane. The preparation method comprises the following steps that (1) a high-molecular polymer and a conductive polymer are fully mixed and dissolved in an organic solvent, and therefore a spinning precursor solution is formed; (2) a patterning collection template is used for electrostatic spinning to collect electrospunpolymer nanofibers, a patterning conductive nanofiber membrane in a non-woven mode is formed on the collection template, and is taken from the collection template, and therefore the force-sensitive stretchable electro-spinning patterning conductive nanofiber membrane can be obtained, wherein the collection template is a metal template, a semiconductor template or an insulating plastic template, and a hollow or protruding pattern structure is arranged on the collection template. The nanofiber membrane prepared through the preparation method can achieve the purposes of high conductivity, good force-sensitive performance and good stability, and can bear large-scale two-dimensional stretching strain. The preparation method is simple and low in cost, and has the good application prospect.
Description
Technical field
The present invention relates to Electrospun nano-fibers, and in particular to a kind of quick stretchable electrospinning pattern conductive Nanowire of power
Dimension film and preparation method thereof.
Background technology
Electrostatic spinning is a kind of method for preparing one-dimensional function micro nanometer fiber, compared with conventional method, electrostatic spinning tool
Have that manufacture device is simple, cost of spinning is cheap, can woven material species is more, unique ease for operation and broad applicability, preparation is received
Rice fiber film material has that specific surface area is big, aperture size is little, excellent adsorption, strong filter capacity the features such as, thus in tissue work
The fields such as journey, filtering material, bio-medical dressing, sensor, opto-electronic device, catalyst carrier, protective materials have very well
Application prospect.During electrostatic spinning, receiver board plays vital effect to nanofiber accumulation shape.Conventional electrostatic
The modal product of spinning is two-dimentional non-woven fabrics fiber structure, and this limits to a certain extent it and further applies.For
This problem is solved, the arrangement and assembling of fiber can be controlled with various methods recently, such as in order to prepare orientation
Array structure electrospinning fibre, cylinder collecting method, flywheel collecting method, auxiliary electric field method, framework collecting method, parallel pole can be adopted
The double shower nozzle methods of collecting method, water surface receiving screen method, positive or negative high voltage, compound frame collecting method, spinning nozzle linear reciprocating motion electrostatic
Spinning, centrifugation electrostatic spinning etc..Electrostatic spinning technique is equally the important method for preparing conductive polymer micro-nano rice fibrous material,
Electrospinning conducting polymer (such as polyaniline PANI, poly- (3,4- ethylenedioxy thiophenes) PEDOT, polypyrrole PPY etc.) is micro-nano
, in microelectronic component, especially flexible extensible electronic device is significant for materials application.But, obtained in conventional method
The mechanical property of conducting polymer materials is poor, the nonwoven fabric construct electrospinning conductive polymer micro-nano rice by obtained in method of electrostatic spinning
Tunica fibrosa, its extensibility is less than 2% (J.Mater.Chem., 21 (2011) 18962-18966), and this tensile property is poor
Micro nanometer fiber film, it is impossible to well adapt to requirement of the flexible extensible electronic device to material, limit electrospinning conducting polymer
Application of the thing material in field of microelectronic devices.
During electrostatic spinning, the electrostatic field point that the shape characteristic of masterplate can be directly affected in spinning process is collected
Cloth, and then affect to collect the pattern of the tunica fibrosa obtained on masterplate.Can be obtained with spy using the collection masterplate of special appearance
The nano fibrous membrane of the patterning of different accumulation rule, a kind of preparation method (the patent Shen of patterned nano-fiber film of Chinese patent
Please number：200910013772.8) disclose a kind of collection masterplate preparation patterning zinc acetate/PVP using patterning to be combined
The method of micro nanometer fiber film.Because researchers generally believe the nano fibrous membrane of patterning in physics and chemistry properties and tradition
Nonwoven fabric construct Random fiber film it is essentially identical, at present, to pattern electrospinning micro nanometer fiber film research focus mostly on
The characteristics of motion of the nanofiber in electrostatic field is proved by studying the special accumulation rule research of fiber on film, or, it is special
Application the two in terms of of the different shape characteristic at the aspect such as biological support and packing engineering.It is existing to electrospinning patterned fibrous film
Research more be confined to non-conducting material aspect, electrospinning patterned conducting polymer (such as polyaniline PANI, poly- (3,4- ethylenes
Dioxy thiophene) PEDOT, polypyrrole PPY etc.) nano fibrous membrane almost do not report, for electrospinning patterned nano-fiber film
The research of performance and application is still in blank stage.
Compare, the nano fibrous membrane of patterning has extensibility (can be more than 100%) bigger on two-dimensional directional, therefore,
Based on the stretchable electronic device of electrospinning patterned conducting polymer nano fibrous membrane be expected to be applied to test knee bend and stretch, finger
The fields such as the actions such as activity, stretchable display screen, skin sensor.
The content of the invention
It is an object of the invention to provide a kind of quick stretchable electrospinning pattern conductive nano fibrous membrane of power and its preparation side
Method, the conductive-nano-fibers film be capable of achieving high conductivity, the good quick performance of power, good stability, can bear on a large scale dimensional tensile should
Become, and preparation method is simple, with low cost, stretchable electronic device is bent in test knee by made by the conductive-nano-fibers film
Stretch, there is good application prospect in the field such as action, stretchable display screen, the skin sensor such as finger movement.
A kind of preparation method of the quick stretchable electrospinning pattern conductive nano fibrous membrane of power, comprises the following steps：
(1) spinning precursor solution is prepared：High molecular polymer and conducting polymer are sufficiently mixed and are dissolved in organic solvent
It is configured to spinning precursor solution；
(2) loaded in the spinning solution container with Metallic Nozzle At The Ingot, metal sprays the spinning precursor solution for preparing step (1)
The injection mouth down of head is simultaneously connected with the positive pole of DC high-voltage power supply, and the masterplate of collecting of patterning is placed in Metallic Nozzle At The Ingot jet
Immediately below and be connected with the negative pole of DC high-voltage power supply, adjustment spinning distance, precursor solution is under gravity in jet
Place forms hemispherical drop, opens DC high-voltage power supply and arranges spinning voltage, and electrified jet is under electric field force effect from shower nozzle spray
Go out, the pattern conductive nano fibrous membrane of non-woven fabrics form is formed on masterplate is collected, DC high-voltage power supply is then shut off, from receipts
Capable quick stretchable electrospinning pattern conductive nano fibrous membrane by pattern conductive nano fibrous membrane is removed on collection masterplate；It is described
Collection masterplate is metal matrix, semiconductor masterplate or ambroin masterplate, collects the pattern that hollow out or projection are provided with masterplate
Structure.
Further, the conducting polymer described in step (1) be polyaniline, polypyrrole, poly- (3,4-ethylene dioxythiophene),
Polythiophene, poly- (3- hexyl thiophenes), polyacetylene, poly- to one or more in styrene, polyphenylene sulfide, polyphenylacetylene, or
Person its with polyethylene glycol oxide, Kynoar, polycaprolactone, polystyrene, polymethyl methacrylate in one or more
Compound；Described high molecular polymer is polyethylene glycol oxide, Kynoar, polycaprolactone, polystyrene, poly- methyl-prop
One or more in e pioic acid methyl ester；Collection masterplate described in step (2) is metal grill masterplate.
Further, step (1) prepares spinning precursor solution：By the polyvinylpyrrolidone of 1.0 gram-molecular weights 1,300,000
Powder and poly- (3,4-ethylene dioxythiophene)/polystyrolsulfon acid aqueous solution that 3.0 gram mass fractions are 2.8wt%, and 2 grams
Absolute ethyl alcohol mixes, and is subsequently adding 0.2 gram of dimethyl sulfoxide (DMSO), and magnetic agitation 5 hours under room temperature are well mixed solution, then
90 minutes are stood, homogeneous electrostatic spinning precursor solution is obtained；Spinning distance is 8 centimetres in step (2), and spinning voltage is 8
Kilovolt, the spinning time is 10 minutes.
The invention also discloses the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power by obtained in said method, described
The quick stretchable electrospinning pattern conductive nano fibrous membrane of power collects electrospinning conduction composite nano fiber by the collection masterplate for patterning
It is obtained, the conductive-nano-fibers film is made up of conducting polymer composite nano fiber, in non-woven fabrics form, the electrical-conductive nanometer is fine
Dimension film has the regular aggregation pattern corresponding with the pattern of the collection masterplate used in its preparation process.
Further, the extensibility of the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power by obtained in said method is big
In 20%, the conductive-nano-fibers film has different electrical conductivity in different level of stretch, when extensibility is 20% still
So there is electric conductivity, and remove pulling force, conductive-nano-fibers film quick recoverable former state, the electrical conductivity of conductive-nano-fibers film
Recover therewith.
Except using the direct electrospinning pattern conductive nano fibrous membrane of electrospinning process, similar method can also be used
The non-conductive high molecular polymer nano fibrous membrane of patterning is prepared, then with the high molecular polymer nano fibrous membrane as masterplate
In one layer of conducting polymer integument of high polymer fiber in situ Polymerization, conducting polymer/high molecular polymerization is formed
The coaxial composite nano fiber of thing, and then pattern conductive nano fibrous membrane is obtained, this method is comprised the following steps：
(1) spinning precursor solution is prepared：Nonconducting high molecular polymer is dissolved in organic solvent and being configured to before spinning
Drive liquid solution；
(2) loaded in the spinning solution container with Metallic Nozzle At The Ingot, metal sprays the spinning precursor solution for preparing step (1)
The injection mouth down of head is simultaneously connected with the positive pole of DC high-voltage power supply, and the masterplate of collecting of patterning is placed in Metallic Nozzle At The Ingot jet
Immediately below and be connected with the negative pole of DC high-voltage power supply, adjustment spinning apart from spinning (Metallic Nozzle At The Ingot jet and collection masterplate between
Vertical spacing), precursor solution under gravity at jet formed hemispherical drop, open DC high-voltage power supply set
Spinning voltage is put, electrified jet sprays under electric field force effect from shower nozzle, and the pattern of non-woven fabrics form is formed on masterplate is collected
Change high molecular polymer nano fibrous membrane, be then shut off DC high-voltage power supply, remove patterning polyphosphazene polymer on masterplate from collecting
Compound nano fibrous membrane；The collection masterplate is metal matrix, semiconductor masterplate or ambroin masterplate, is collected on masterplate
It is provided with the patterning of hollow out or projection；
(3) conducting polymer polymerization reaction solution is configured, by the obtained patterning high molecular polymer Nanowire of step (2)
Dimension film is paved and is fixed on hollow out frame, then is completely immersed in configuration conducting polymer polymerization reaction solution, until high score
The fiber surface in-situ polymerization of sub- polymer nanofibre film forms conducting polymer composite integument, and tunica fibrosa is taken out, and washes
Remove capable quick stretchable electrospinning pattern conductive nano fibrous membrane by its surface impurity.
Further, the step (1) prepares spinning precursor solution：By the polyvinylidene fluoride that 2.2 gram-molecular weights are 270,000
Alkene is added in the mixed solution of 3.9 grams of DMFs and 3.9 grams of acetone, and heating magnetic agitation obtains spinning after 3 hours
Precursor solution；Spinning distance is 10 centimetres in step (2), and spinning voltage is 14 kilovolts, and the spinning time is 15 minutes, described
Collection masterplate is metal grill masterplate；In step (3) with 0.93 gram of aniline, 4.56 grams of ammonium persulfate, 1.28 grams of sulfosalicylic acid,
70 milliliters of mixing of distilled water are sufficiently stirred for, and are configured to conducting polymer polymerization reaction solution, and reaction temperature is kept for 0～4 DEG C, configuration
It is rapid by the patterning high molecular polymer nanofiber being fixed on hollow out frame after good conducting polymer polymerization reaction solution
Film is immersed, and immersion takes out nano fibrous membrane after 6 hours, and deionized water is rinsed under 3 times, room temperature in vacuo dries, i.e.,
Can capable quick stretchable electrospinning pattern conductive nano fibrous membrane.
Further, the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power is collected with the collection masterplate for patterning
Nonconducting electrospinning high molecular polymer nanofiber be masterplate fiber, by conducting polymer composite in masterplate fiber surface
Hard carbon via in-situ polymerization integument is obtained, and the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power is not lead by inside
The macromolecular material of electricity, outside is constituted for the conducting polymer composite nano fiber of conducting polymer, described in non-woven fabrics form
The quick stretchable electrospinning pattern conductive nano fibrous membrane of power has relative with the pattern of the collection masterplate used in its preparation process
The regular aggregation pattern answered.
Further, the extensibility of the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power by obtained in said method is big
In 110%, the conductive-nano-fibers film has different electrical conductivity in different level of stretch, when extensibility is 110%
Still there is electric conductivity, and removes pulling force, tunica fibrosa quick recoverable as former state, also recover therewith by the electrical conductivity of tunica fibrosa.
Beneficial effects of the present invention are：The invention provides a kind of quick stretchable electrospinning pattern conductive nano fibrous membrane of power
And preparation method thereof, the nano fibrous membrane be capable of achieving high conductivity, the good quick performance of power, good stability, can bear on a large scale two dimension
Elongation strain, and preparation method is simple, with low cost, stretchable electronic device is in test knee by made by the nano fibrous membrane
Bend and stretch, there is good application prospect in the field such as action, stretchable display screen, the skin sensor such as finger movement.Specifically：1)
The addition of conducting polymer makes being more widely applied for patterned fibrous film；2) method and apparatus for being adopted is all fairly simple,
It is easy to operate and repeats, cost is relatively low, practicality is stronger；3) nano fibrous membrane of the invention has stretching (bending) well extensive
Multiple characteristic, can be used as strain transducer；4) presence of patterning makes tunica fibrosa have higher extensibility and high conductivity so as to
With the quick performance of more preferable power, the quick test of power of larger range of stretch, the stretchable electronics by made by the nano fibrous membrane are suitable for
The fields such as device is bent and stretched in test knee, action, stretchable display screen, the skin sensor such as finger movement have well using front
Scape；Even if 5) sensor draws in repeatedly bending by made by the power of the invention quick stretchable electrospinning pattern conductive nano fibrous membrane
Stretch and the high electrical conductivity of comparison is remained in that after test, elasticity is strong, it is high durable, it is high sensitive.
Description of the drawings
The optical imagery of patterned conductive nano fibrous membrane prepared by Fig. 1 present invention；
The C-V characteristic of pattern conductive nanofiber film sensors prepared by Fig. 2 present invention in the case of different stretch is bent
Line；
The response curve of flexible extensible patterned nano-fiber film sensors prepared by Fig. 3 present invention to pressure.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
Apply the specific material proportion described by example, process conditions and its result be merely to illustrate the present invention and should not also without limitation on
The present invention described in detail in claims.
Embodiment 1
A kind of preparation method of the quick stretchable electrospinning pattern conductive nano fibrous membrane of power, comprises the following steps：
(1) spinning precursor solution is prepared：By the polyvinylpyrrolidonepowder powder of 1.0 gram-molecular weights 1,300,000 and 3.0 grams of matter
Poly- (the 3,4-ethylene dioxythiophene)/polystyrolsulfon acid aqueous solution of the fraction for 2.8wt%, and 2 grams of absolute ethyl alcohols mixing are measured,
0.2 gram of dimethyl sulfoxide (DMSO) is subsequently adding, magnetic agitation 5 hours under room temperature are well mixed solution, then stand 90 minutes, obtain
Obtain homogeneous electrostatic spinning precursor solution；
(2) loaded in the spinning solution container with Metallic Nozzle At The Ingot, metal sprays the spinning precursor solution for preparing step (1)
The injection mouth down of head is simultaneously connected with the positive pole of DC high-voltage power supply, and the masterplate of collecting of patterning is placed in Metallic Nozzle At The Ingot jet
Immediately below and be connected with the negative pole of DC high-voltage power supply, adjustment spinning distance, precursor solution is under gravity in jet
Place forms hemispherical drop, opens DC high-voltage power supply and arranges spinning voltage, and electrified jet is under electric field force effect from shower nozzle spray
Go out, the pattern conductive nano fibrous membrane of non-woven fabrics form is formed on masterplate is collected, spinning distance is 8 centimetres, spinning voltage
For 8 kilovolts, the spinning time is 10 minutes, is then shut off DC high-voltage power supply, remove pattern conductive nanometer on masterplate from collecting
Capable quick stretchable electrospinning pattern conductive nano fibrous membrane by tunica fibrosa, the quick stretchable electrospinning pattern conductive of power of gained
The shape characteristic of nano fibrous membrane is as shown in the optical microscope photograph of Fig. 1；Described collection masterplate is metal grill masterplate.
The quick stretchable electrospinning pattern conductive nano fibrous membrane of the power by obtained in said method, the quick stretchable electrospinning of the power
Pattern conductive nano fibrous membrane is collected electrospinning conducting polymer composite nano fiber and is obtained by the collection masterplate for patterning, and this is led
Conducting nanofiber film is made up of conducting polymer composite nano fiber, and in non-woven fabrics form, the conductive-nano-fibers film has
The cross aggregation pattern of the rule distribution corresponding with the pattern of the collection masterplate used in its preparation process；Jing is tested, institute
The extensibility of the quick stretchable electrospinning pattern conductive nano fibrous membrane of power is stated more than 42%, the conductive-nano-fibers film is different
There are different electrical conductivity during level of stretch, still there is electric conductivity when extensibility is 42.4%, and remove pulling force, tunica fibrosa
Quick recoverable as former state, also recover therewith by the electrical conductivity of tunica fibrosa.
Embodiment 2
The preparation method of the quick stretchable electrospinning pattern conductive nano fibrous membrane of power of embodiment 2 is similar to Example 1, area
It is not：Step (1) prepares spinning precursor solution：By 1.0 grams of polyaniline in eigenstate without doping, (molecular weight is
120000) mix with 1.29 grams of camphorsulfonic acids, in being dissolved in 100 milliliters of chloroforms, room temperature magnetic agitation 4 hours.By the depth for obtaining
Green solution (doped polyaniline) is filtered, and 32 milligrams of PEO (molecular weight are then added in filtrate
2000000), room temperature magnetic agitation again filtered solution after 2 hours, obtained homogeneous Electrospun precursor solution；Step (2)
In spinning distance be 10 centimetres, spinning voltage be 14 kilovolts, the spinning time be 15 minutes, it is described collection masterplate be ambroin
Net, ambroin side off the net is lined with aluminium foil.
The quick stretchable electrospinning pattern conductive nano fibrous membrane pattern of the power by obtained in said method and performance and embodiment 1
Nano fibrous membrane it is similar；Jing is tested, and the extensibility of the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power is more than
65%, the conductive-nano-fibers film has different electrical conductivity in different level of stretch, when extensibility is 65.6% still
So there is electric conductivity, and remove pulling force, tunica fibrosa quick recoverable as former state, also recover therewith by the electrical conductivity of tunica fibrosa.
Embodiment 3：
The preparation method of the quick stretchable electrospinning pattern conductive nano fibrous membrane of power of embodiment 3 is similar to Example 1, area
It is not：Step (1) prepares spinning precursor solution：By 0.5 gram of polypyrrole powder (molecular weight is more than 1000) and 1.0 gram 12
Alkyl benzene sulphonate mixes, and ultrasonic agitation is dissolved in 10 milliliters of chloroforms.The solution for obtaining (doped polypyrrole) is used into Teflon
Filter membrane is filtered, and filtrate is evaporated and is concentrated into the mass percent of polypyrrole and is about 35wt%, is subsequently adding poly- meat
Laurate, polypyrrole is 4 with the mass ratio of poly- vinyl cinnamate:1, room temperature magnetic agitation 2 hours obtains homogeneous electricity
Spinning precursor solution；Spinning distance in step (2) is 10 centimetres, and spinning voltage is 14 kilovolts, and the spinning time is 20 minutes,
Described collection masterplate is metal grill masterplate.
The quick stretchable electrospinning pattern conductive nano fibrous membrane pattern of the power by obtained in said method and performance and embodiment 1
Nano fibrous membrane it is similar；Jing is tested, and the extensibility of the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power is more than
21%, the conductive-nano-fibers film has different electrical conductivity in different level of stretch, when extensibility is 21.76% still
So there is electric conductivity, and remove pulling force, tunica fibrosa quick recoverable as former state, also recover therewith by the electrical conductivity of tunica fibrosa.
Embodiment 4
A kind of preparation method of the quick stretchable electrospinning pattern conductive nano fibrous membrane of power, comprises the following steps：
(1) spinning precursor solution is prepared：The Kynoar that 2.2 gram-molecular weights are 270,000 is added into 3.9 grams of N, N- bis-
In the mixed solution of NMF and 3.9 grams of acetone, heating magnetic agitation obtains spinning precursor solution after 3 hours；
(2) loaded in the spinning solution container with Metallic Nozzle At The Ingot, metal sprays the spinning precursor solution for preparing step (1)
The injection mouth down of head is simultaneously connected with the positive pole of DC high-voltage power supply, and the masterplate of collecting of patterning is placed in Metallic Nozzle At The Ingot jet
Immediately below and be connected with the negative pole of DC high-voltage power supply, adjustment spinning apart from spinning, precursor solution under gravity spraying
Hemispherical drop is formed at loophole, DC high-voltage power supply is opened and spinning voltage is set, electrified jet is under electric field force effect from spray
Head sprays, and the patterning high molecular polymer nano fibrous membrane of non-woven fabrics form is formed on masterplate is collected, and spinning distance is 10
Centimetre, spinning voltage is 14 kilovolts, and the spinning time is 15 minutes, is then shut off DC high-voltage power supply, is removed on masterplate from collecting
Patterning high molecular polymer nano fibrous membrane；Described collection masterplate is metal grill masterplate；
(3) it is abundant with 0.93 gram of aniline, 4.56 grams of ammonium persulfate, 1.28 grams of sulfosalicylic acid, 70 milliliters of mixing of distilled water
Stirring, is configured to conducting polymer polymerization reaction solution, and reaction temperature is kept for 0～4 DEG C, has configured conducting polymer polymerization reaction
After solution the patterning high molecular polymer nano fibrous membrane being fixed on hollow out frame is immersed rapidly, is soaked 6 hours
After take out nano fibrous membrane, deionized water is rinsed under 3 times, room temperature in vacuo dries, you can capable quick stretchable electrospinning figure
Case conductive-nano-fibers film.
Collection masterplate of the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power by obtained in said method to pattern
The nonconducting electrospinning high molecular polymer nanofiber collected is masterplate fiber, by conducting polymer composite in masterplate fiber
In situ Polymerization conducting polymer integument is obtained, and the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power is by inside
Nonconducting macromolecular material, outside is constituted for the conducting polymer composite nano fiber of conducting polymer, in non-woven fabrics form,
The quick stretchable electrospinning pattern conductive nano fibrous membrane of the power have and collection masterplate used in its preparation process pattern
Corresponding regular aggregation pattern；Jing is tested, the stretching of the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power
Rate is more than 110%, and the conductive-nano-fibers film has different electrical conductivity in different level of stretch, is in extensibility
Still there is electric conductivity when 110.53%, and remove pulling force, as former state, the electrical conductivity of tunica fibrosa is also therewith for tunica fibrosa quick recoverable
Recover.
The performance test of embodiment 5
The quick performance of its power is tested by taking the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power of embodiment 4 as an example.First
2 electrodes are processed at pattern conductive Nanowire film two ends, is encapsulated in sample with dimethyl silicone polymer glue film；Then connect
Voltage source and ammeter, are characterized with stretchable electrical measurement platform to device performance.The experimental result of survey such as Fig. 2 and Tu
Shown in 3, Fig. 2 is that C-V characteristic of the pattern conductive nanofiber film sensors of present invention preparation in the case of different stretch is bent
Line (I-V curve), it can be seen that when elongation strain reaches 110.53%, tunica fibrosa still keeps good electric conductivity and can
Restorability；Fig. 3 is response curve (in test process holding voltage 5 volt constant) of the sensor under stress, can be seen
Arrive, with the increase of stress, its electric current changes rapidly；Once and remove stress and be allowed to recover former length, current value also can be returned rapidly
To (or being close to) without the initial value under stress.Illustrate stability and the spirit of the flexible extensible strain transducer of present invention preparation
Sensitivity is fine.
Test result indicate that, the flexible extensible pattern conductive nano fibrous membrane prepared by the method, with good
Strain sensing performance, and stable performance, sensitivity is high, with broad prospect of application.
Embodiment of above technology design only to illustrate the invention and feature, its object is to allow and are familiar with technique
People understands present invention and is carried out, and can not be limited the scope of the invention with this, all real according to spirit of the invention
Equivalence changes or modification that matter is done, all should cover within the scope of the present invention.
Claims (2)
1. a kind of quick stretchable electrospinning pattern conductive nano fibrous membrane of power, it is characterised in that the quick stretchable electrospinning figure of the power
Case conductive-nano-fibers film is collected electrospinning conducting polymer composite nano fiber and is obtained by the collection masterplate for patterning, the conduction
Nano fibrous membrane is made up of conducting polymer composite nano fiber, in non-woven fabrics form, the conductive-nano-fibers film have with
The corresponding regular aggregation pattern of pattern of the collection masterplate used in its preparation process；The quick stretchable electrospinning figure of the power
The extensibility of case conductive-nano-fibers film is more than 20%, and the film has different electrical conductivity in different level of stretch,
Still there is electric conductivity when extensibility is 20%, and remove pulling force, tunica fibrosa quick recoverable former state, the electrical conductivity of tunica fibrosa
Recover therewith；The preparation method of the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power is comprised the following steps：
(1) spinning precursor solution is prepared：By the polyvinylpyrrolidonepowder powder of 1.0 gram-molecular weights 1,300,000 and 3.0 gram masses point
Poly- (the 3,4-ethylene dioxythiophene)/polystyrolsulfon acid aqueous solution for 2.8wt%, and 2 grams of absolute ethyl alcohols mixing are counted, then
0.2 gram of dimethyl sulfoxide (DMSO) is added, magnetic agitation 5 hours under room temperature are well mixed solution, then stand 90 minutes, obtain equal
One electrostatic spinning precursor solution；
(2) the spinning precursor solution for preparing step (1) is loaded in the spinning solution container with Metallic Nozzle At The Ingot, Metallic Nozzle At The Ingot
Injection mouth down is simultaneously connected with the positive pole of DC high-voltage power supply, the collection masterplate of patterning be placed in Metallic Nozzle At The Ingot jet just under
Side and be connected with the negative pole of DC high-voltage power supply, adjustment spinning distance, the precursor solution shape at jet under gravity
Into hemispherical drop, open DC high-voltage power supply and spinning voltage is set, electrified jet sprays under electric field force effect from shower nozzle,
The pattern conductive nano fibrous membrane that non-woven fabrics form is formed on masterplate is collected, DC high-voltage power supply is then shut off, from collection mould
Capable quick stretchable electrospinning pattern conductive nano fibrous membrane by pattern conductive nano fibrous membrane is removed in version；The collection
Masterplate is metal grill masterplate, and spinning distance is 8 centimetres, and spinning voltage is 8 kilovolts, and the spinning time is 10 minutes.
2. a kind of quick stretchable electrospinning pattern conductive nano fibrous membrane of power, it is characterised in that the quick stretchable electrospinning figure of the power
Case conductive-nano-fibers film with pattern collect masterplate collect nonconducting electrospinning high molecular polymer nanofiber be
Masterplate fiber, is obtained by conducting polymer composite in masterplate fiber surface hard carbon via in-situ polymerization integument, and the power is quick
Stretchable electrospinning pattern conductive nano fibrous membrane is by internal for nonconducting macromolecular material, outside leading for conducting polymer
Electric polymer composite nano fiber is constituted, in non-woven fabrics form, the quick stretchable electrospinning pattern conductive nano fibrous membrane of the power
With the regular aggregation pattern corresponding with the pattern of the collection masterplate used in its preparation process；The power is quick stretchable
The extensibility of electrospinning pattern conductive nano fibrous membrane is more than 110%, and the film has different electricity in different level of stretch
Conductance, still has electric conductivity when extensibility is 110%, and removes pulling force, tunica fibrosa quick recoverable former state, tunica fibrosa
Electrical conductivity is also recovered therewith；The preparation method of the quick stretchable electrospinning pattern conductive nano fibrous membrane of described power includes following step
Suddenly：
(1) spinning precursor solution is prepared：The Kynoar that 2.2 gram-molecular weights are 270,000 is added into 3.9 grams of N, N- dimethyl
In the mixed solution of formamide and 3.9 grams of acetone, heating magnetic agitation obtains spinning precursor solution after 3 hours；
(2) the spinning precursor solution for preparing step (1) is loaded in the spinning solution container with Metallic Nozzle At The Ingot, Metallic Nozzle At The Ingot
Injection mouth down is simultaneously connected with the positive pole of DC high-voltage power supply, the collection masterplate of patterning be placed in Metallic Nozzle At The Ingot jet just under
It is connected just and with the negative pole of DC high-voltage power supply, apart from spinning, precursor solution is under gravity in jet for adjustment spinning
Place forms hemispherical drop, opens DC high-voltage power supply and arranges spinning voltage, and electrified jet is under electric field force effect from shower nozzle spray
Go out, the patterning high molecular polymer nano fibrous membrane of non-woven fabrics form is formed on masterplate is collected, be then shut off high direct voltage
Power supply, from collecting patterning high molecular polymer nano fibrous membrane is removed on masterplate；Spinning distance is 10 centimetres, spinning electricity
Press as 14 kilovolts, the spinning time is 15 minutes, described collection masterplate is metal grill masterplate；
(3) it is sufficiently stirred for 0.93 gram of aniline, 4.56 grams of ammonium persulfate, 1.28 grams of sulfosalicylic acid, 70 milliliters of mixing of distilled water,
Conducting polymer polymerization reaction solution is configured to, reaction temperature is kept for 0～4 DEG C, has configured conducting polymer polymerization reaction solution
Afterwards, the obtained patterning high molecular polymer nano fibrous membrane of step (2) is paved and is fixed on hollow out frame, rapidly will be fixed
Patterning high molecular polymer nano fibrous membrane on hollow out frame is immersed, and immersion takes out nano fibrous membrane after 6 hours,
Deionized water is rinsed under 3 times, room temperature in vacuo dries, you can capable quick stretchable electrospinning pattern conductive nanofiber
Film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510334084.7A CN104894750B (en) | 2015-06-16 | 2015-06-16 | Force-sensitive stretchable electro-spinning patterning conductive nanofiber membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510334084.7A CN104894750B (en) | 2015-06-16 | 2015-06-16 | Force-sensitive stretchable electro-spinning patterning conductive nanofiber membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104894750A CN104894750A (en) | 2015-09-09 |
| CN104894750B true CN104894750B (en) | 2017-05-03 |
Family
ID=54027686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510334084.7A Active CN104894750B (en) | 2015-06-16 | 2015-06-16 | Force-sensitive stretchable electro-spinning patterning conductive nanofiber membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104894750B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101703095B1 (en) | 2010-06-17 | 2017-02-06 | 워싱톤 유니버시티 | Biomedical patches with aligned fibers |
| SG11201502207WA (en) | 2012-09-21 | 2015-04-29 | Univ Washington | Biomedical patches with spatially arranged fibers |
| CN106606805B (en) * | 2015-10-22 | 2020-05-19 | 中国科学院上海硅酸盐研究所 | Nano-bioglass coated patterned electrospun fibrous membrane and preparation method and application thereof |
| US10632228B2 (en) | 2016-05-12 | 2020-04-28 | Acera Surgical, Inc. | Tissue substitute materials and methods for tissue repair |
| EP3454915A4 (en) * | 2016-05-12 | 2020-01-01 | Acera Surgical, Inc. | Tissue substitute materials and methods for tissue repair |
| CN106978670A (en) * | 2017-04-01 | 2017-07-25 | 佛山轻子精密测控技术有限公司 | The Nanofiber filter net and its preparation facilities of a kind of recycling, method |
| CN107287684B (en) * | 2017-05-31 | 2019-08-20 | 华南理工大学 | It is a kind of high to stretch highly sensitive quick sensing fiber of flexible force and preparation method thereof |
| CN107574493B (en) * | 2017-07-25 | 2020-04-10 | 青岛农业大学 | Flexible tensile strain sensor of spiral winding structure based on electrospinning |
| CN108385283A (en) * | 2018-03-29 | 2018-08-10 | 深圳市四清空气技术有限公司 | The forming method of 3-D nano, structure |
| CN110274713B (en) * | 2019-06-13 | 2020-12-25 | 东华大学 | Fiber-based shape-adaptive passive electronic skin and preparation method thereof |
| CN110499647A (en) * | 2019-08-18 | 2019-11-26 | 裘国良 | A kind of preparation method based on PPy-PMMA nanofiber composite air-sensitive material |
| CN110841102B (en) * | 2019-11-29 | 2022-02-25 | 青岛农业大学 | Composite nanofiber elastic bandage and preparation method thereof |
| CN113279071A (en) * | 2021-05-20 | 2021-08-20 | 大连理工大学 | In-situ forming manufacturing method for electrostatic spinning fiber support on polymer device |
| CN113638128A (en) * | 2021-08-13 | 2021-11-12 | 大连理工大学 | Preparation method of thin film material capable of realizing temperature and strain dual-function self-driven sensing |
| CN115161782B (en) * | 2022-07-14 | 2023-12-19 | 华南理工大学 | Electrospun fiber composite electrode structure and patterning manufacturing method thereof |
| CN116005363A (en) * | 2023-01-17 | 2023-04-25 | 河北科技大学 | Stretchable boron-nitrogen doped manganese dioxide nanofiber membrane and preparation method and application thereof |
| CN116254615B (en) * | 2023-05-15 | 2023-08-04 | 诺一迈尔（苏州）医学科技有限公司 | Preparation method of endometrium repair membrane and prepared endometrium repair membrane |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360592C (en) * | 2005-03-10 | 2008-01-09 | 中国科学院化学研究所 | Conductive type polyaniline composite film, prepn. method and use thereof |
| CN102978721A (en) * | 2007-10-30 | 2013-03-20 | 上海昊海生物科技股份有限公司 | Preparation method for controllable patterned electrospinning fiber aggregate |
| CN101463532B (en) * | 2009-01-14 | 2010-11-17 | 青岛大学 | Method for producing patterned nano-fiber |
| JP2012533657A (en) * | 2009-07-15 | 2012-12-27 | ザ ユニバーシティ オブ アクロン | Manufacture of multifunctional conductive / transparent / flexible membranes |
| CN102443870B (en) * | 2011-09-13 | 2013-07-24 | 青岛大学 | Method for preparing ordered coaxial structural micro and nano fibers |
| CN102691176A (en) * | 2012-06-14 | 2012-09-26 | 东华大学 | Method for preparing patterning nanofiber membrane by utilizing insulating receiving template static spinning |
| KR20140030975A (en) * | 2012-09-04 | 2014-03-12 | 삼성전자주식회사 | Strechable conductive nano fiber and method for producing the same |
| CN103076031B (en) * | 2013-01-04 | 2015-04-22 | 青岛大学 | Preparation method of flexible tensile strain type sensor |
| CN103397402A (en) * | 2013-07-23 | 2013-11-20 | 青岛大学 | Preparation method of ionic liquid-doped conductive nanofiber |
| CN104120546B (en) * | 2014-08-08 | 2017-03-29 | 青岛大学 | A kind of preparation method of two-dimensional network structure flexible extensible device |
-
2015
- 2015-06-16 CN CN201510334084.7A patent/CN104894750B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104894750A (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104894750B (en) | Force-sensitive stretchable electro-spinning patterning conductive nanofiber membrane and preparation method thereof | |
| Yu et al. | Patterned, highly stretchable and conductive nanofibrous PANI/PVDF strain sensors based on electrospinning and in situ polymerization | |
| Gao et al. | Continuous wet-spinning of flexible and water-stable conductive PEDOT: PSS/PVA composite fibers for wearable sensors | |
| Zhong et al. | Self-powered human-interactive transparent nanopaper systems | |
| Dutta et al. | NiO@ SiO2/PVDF: A flexible polymer nanocomposite for a high performance human body motion-based energy harvester and tactile e-skin mechanosensor | |
| Ding et al. | Flexible and compressible PEDOT: PSS@ melamine conductive sponge prepared via one-step dip coating as piezoresistive pressure sensor for human motion detection | |
| CN104897316B (en) | A kind of condenser type ultrathin flexible strain gauge and preparation method thereof | |
| CN107192485B (en) | A kind of multifunctional nano fiber sensor of flexible extensible and preparation method thereof | |
| Rana et al. | Cation functionalized nylon composite nanofibrous mat as a highly positive friction layer for robust, high output triboelectric nanogenerators and self-powered sensors | |
| CN109137105B (en) | Flexible stretchable multifunctional sensor based on graphene nanofiber yarn and preparation method thereof | |
| He et al. | P–N junction-based ZnO wearable textile nanogenerator for biomechanical energy harvesting | |
| CN106787931B (en) | A kind of stretchable coaxial fibrous triboelectricity and senser element and preparation method thereof | |
| CN105970350B (en) | A kind of preparation method and applications of Stretchable polymeric composite material | |
| CN107574493A (en) | A kind of spiral winding structure flexible extensible strain transducer based on electrospinning | |
| CN102719927B (en) | Preparation method of polyvinylidene fluoride (PVDF)/carbon nanotube composite nanofibers | |
| Zhang et al. | Enhanced piezoelectric performance of various electrospun PVDF nanofibers and related self-powered device applications | |
| Kim et al. | Characterization of PI/PVDF-TrFE composite nanofiber-based triboelectric nanogenerators depending on the type of the electrospinning system | |
| CN103076031B (en) | Preparation method of flexible tensile strain type sensor | |
| Lei et al. | New insight into gap electrospinning: toward meter-long aligned nanofibers | |
| CN104916448A (en) | Hierarchical structure micro-nano porous fiber electrode material and preparing method thereof | |
| Li et al. | Continuous preparation of chitosan-based self-powered sensing fibers recycled from wasted materials for smart home applications | |
| CN103280337B (en) | Fibrous supercapacitor and preparation method thereof | |
| Jiang et al. | A wearable strain sensor based on polyurethane nanofiber membrane with silver nanowires/polyaniline electrically conductive dual-network | |
| Guan et al. | Flexible energy harvester based on aligned PZT/SMPU nanofibers and shape memory effect for curved sensors | |
| CN104120546B (en) | A kind of preparation method of two-dimensional network structure flexible extensible device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |