CN108752815A - Using PVDF/PVP/IL as the preparation method and application of the through-hole phase transfer type IPMC of basilar memebrane - Google Patents
Using PVDF/PVP/IL as the preparation method and application of the through-hole phase transfer type IPMC of basilar memebrane Download PDFInfo
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- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
Abstract
The invention discloses a kind of high performance using PVDF/PVP/IL as the preparation method and application of the through-hole phase transfer type IPMC of basilar memebrane, by basilar memebrane, the carbon nanotube membrane electrode that is fixed on basilar memebrane both sides, external electric signal input system form, hole phase transfer type IPMC has the vesicularity of height, PVDF/PVP/IL basilar memebranes are by phase transfer technique and hypochlorous acid except PVP Duplex treatments obtain, therefore voidage is very big, so that IPMC is drawn more ionic liquids, is conducive to maintain the prolonged stabilized drivings of IPMC；Through-hole phase transfer type IPMC has hydrophobicity, so passing through ionic liquid（IL）Obtained IPMC drivings are driven more to stablize.Through-hole phase transfer type IPMC has a large amount of channel, improves the ionic transporting quantity of material internal, forms the pressure difference and ion stream of bigger in material internal, is conducive to the driving that electric actuator forms bigger, while also providing the mechanical property of bigger.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of high performance using PVDF/PVP/IL as basilar memebrane
Through-hole phase transfer type IPMC preparation method and application.
Background technology
Perfluorinated sulfonic acid product is mainly made of carbon fluorine main chain and sulfonate radical side chain, and chemical constitution is as follows：
The structure of its carbon fluorine main chain is similar to the chemical constitution of polytetrafluoroethylene (PTFE), the performance with hydrophobic, and due to its side
The hydrophily of the sulfonate functional of chain, perfluorinated sulfonic acid have hydrophilic performance.Presently mainly DuPont Corporation's production is complete
Fluosulfonic acid product includes Nafion membrane and Nafion solution series of products.
Noble metal such as platinum is plated by the method for electroless plating in the both sides of Nafion membrane, ionic polymerization can be made in gold etc.
Object metal composite (Ionic Polymer Metal Composite, IPMC), also known as artificial-muscle.The material is made in electric field
It can bend under, and electric microfield can be generated under alternating bending state, thus can be applied to actuator and sensor,
Due to its light weight, driving voltage is low, is similar to the performance of biological muscles, and this material leavens dough to obtain in actuator at present
Extensive research and application.Its drive mechanism is as follows：
Cation (the Na under electric field action+,Li+,K+) certain hydrone is carried to movable cathode, so as to cause anode
Contraction and cathode expansion so that material bends.The driving voltage of this material is low, usually in 1-3V or so, so
And the driving of ionic polymer metal compound is since the cation in base material (Nafion) is in electric field action lower band
Dynamic hydrone is to movable cathode, so that material is bent to anode.As it can be seen that in braking process, hydrone plays crucial
Effect, the loss of moisture content can influence power output and the displacement of IPMC artificial muscle material, so current IPMC artificial muscle is answered
With mainly in water or wet environment, the working time of IPMC artificial muscle is also comparable short in dry environments.
In recent years, in order to improve the mechanics output performance of IPMC artificial muscle, domestic and foreign scholars, which have done this, largely to grind
Study carefully, including the preparation method by improving electroless plating, i.e., improves surface using PVP during electroless plating
The dispersion of nano metal electrode, the loss to reduce moisture content improve the mechanical property of IPMC.Due to the Nafion membrane of business
Thickness between 100-300um, thicker Nafion membrane can be prepared by the method for Nafion solution-casts, to
The mechanics output performance of raising IPMC artificial muscle, but IPMC prepared by thicker Nafion membrane, driving voltage also can phase
Should be higher, the generation of hydrolytic process will be increased, the hydrolysis voltage of water is generally 1.23V.Presently preferred method is by right
The modification of base material (Nafion) prepares IPMC with modified Nafion membrane, can preferably improve IPMC in this way
Mechanical property and the working time.
In terms of modification, South Korea scholar Vinh Khanh Nguyen et al. add nano particle in Nafion solution
(nanoparticulates) silicate such as high phosphorus stone (layered silicate (montmorillonite)) or tripoli
(fumed silica), to form the Nafion of nanometer compound state, thus it is possible to vary Nafion internal networks channel (Nafion
Matrix performance), to improve the mechanical property of Nafion.
The features such as IPMC made of Nafion has voltage small, and repercussion is fast, it is deep to be applied by each field of science and technology, still
It exists simultaneously the shortcomings of porosity is low, and water imbibition is poor, and shift length is short, the displacement period is short, and mechanical property is small.
Invention content
For problems of the prior art, the present invention provides a kind of high performance using PVDF/PVP/IL as basilar memebrane
Through-hole phase transfer type IPMC, this PVDF/PVP/IL composite membranes due to by phase transfer and it is hypochlorous immersion so that it is had
Highly porous degree and large scale aperture, this finger-like pore and big porosity can form a large amount of ion channel, be conducive to electricity
Actuator ionic liquid environment intermediate ion migration, to high displacement characteristic.
In order to solve the above technical problems, the present invention uses following technical scheme：
It is a kind of high performance using PVDF/PVP/IL as the through-hole phase transfer type IPMC of basilar memebrane, by basilar memebrane, it is fixed on
The carbon nanotube membrane electrode of basilar memebrane both sides, external electric signal input system composition, the basilar memebrane by Kynoar,
Polyvinylpyrrolidone and 2- imidazoles -1- base ethamine ionic liquids are made, and the carbon nanotube membrane electrode is by carbon nano tube-doped
Kynoar disperses to constitute by ionic liquid, and the electric signal of electric signal input system is 0.1-10Hz, the sine of 0.5-5V
Wave, square wave or triangular wave.
100-800 microns of the thickness of the basilar memebrane, carbon nanotube electrode thickness are 10-60 microns.
The surface resistance of the carbon nanotube membrane electrode is 0.5-300 Ω.
Described is high performance using PVDF/PVP/IL as the preparation method of the through-hole phase transfer type IPMC of basilar memebrane, step
It is as follows：
(1) PVDF/PVP/IL substrate coating solutions are prepared：By in PVDF and PVP mixtures, DMF solvents are added, heating is stirred
Mixing is mixed, 1- ethyl-3-methylimidazole tetrafluoroborate ionic liquids are then added and are uniformly mixed, standing vacuumizes removal solution
In bubble, obtain PVDF/PVP/IL coating solutions；
(2) PVDF/PVP/IL basilar memebranes are prepared：It drops in PVDF/PVP/IL coating solutions are quantitative made from step (1)
It on glass plate, is then placed on sol evenning machine and tiles, 30s is stood after running 80s, be then placed on the ethyl alcohol that mass fraction is 20%
It in solidification liquid, completes inversion of phases process and film forming is precipitated, film is put in deionized water, a water is changed per 5-8h, removal is remaining
Solvent on film finally dries to obtain PVDF/PVP/IL basilar memebranes in 70 DEG C of baking ovens；
(3) PVP in PVDF/PVP/IL basilar memebranes is removed：PVDF/PVP/IL basilar memebranes made from step (2) are placed on
In the hypochlorite solution that mass concentration is 0.5%, pH value of solution=5-7,50 DEG C of heating water bath, heated at constant temperature 48h are adjusted；Every five
It checks a pH value of solution situation of change within a hour, is then adjusted to prescribed limit, periodically as water-bath adds water, avoid water-bath
In water dryout, taking-up is dried for standby；
(4) PVDF/PVP/IL basilar memebranes are chimeric prepares IPMC：By the carbon nanotube prepared/ionic liquid gel integration electricity
Pole liquid uniformly be coated in drying basement membrane surface both sides, then put baking oven into, temperature is transferred to 70 DEG C, be made after drying with
PVDF/PVP/IL is the IPMC of basilar memebrane.
In the step (1) in PVDF/PVP/IL coating solutions, the mass fraction of PVDF is 14%, 1- ethyl -3- methyl
The mass fraction of tetrafluoroborate ionic liquid is that the quality of 5%, PVP accounts for the 15% of PVDF mass.
PVDF/PVP/IL coating solutions drip 2-7mL on a glass in the step (2), and the rotating speed of sol evenning machine is 40-
80r/min。
Remaining pore-foaming agent PVP is removed through chloric acid in the step (3) so that the total pore volume (P/P of film0=0.954)
For 0.5-0.85.
The preparation method of carbon nanotube/ionic liquid gel integrated electrode liquid is as follows in the step (4)：It is received using carbon
Mitron aoxidizes grafting, weighs original MWCNTs, is added in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, flows back at 100 DEG C
5h, cooling, dilution, is filtered, being washed to filtrate with distillation is in neutrality with teflon membrane filter；In in 100 DEG C of vacuum drying chambers
Dry 4h, obtains CNT-COOH after oxidation, then again Jia Ru oxanes as solvent by CNT-COOH ultrasonic disperse 15min, addition
EDC/NHS reacts 30min, and CNT-NHS is obtained after centrifugation, adds triethylamine and makees solvent, adjusts solution Ph=6-7, so
2- imidazoles -1- base ethamine the ionic liquids after drying are added afterwards, are mixed evenly, carbon nanotube/ion is formed after reacting 6h
It is for use finally to put storage at low temperature for lyogel integrated electrode liquid.
The CNT-NHS and the mass ratio of 2- imidazoles -1- base ethamine ionic liquids are 13:54.
It is described it is high performance using PVDF/PVP/IL be that the IPMC of basilar memebrane is applied to electric actuator.
The phase transfer that the present invention uses prepares PVDF/PVP/IL basilar memebranes, may be implemented in coating solution in phase transition behavior
Organic solvent DMF in coagulating bath water and ethyl alcohol swap, PVP with organic solvent to solidification liquid shift, coagulating bath
Into in film, PVP's loses, and makes to cause a large amount of gap in film, to realize the highly porous of film.
Since the mode of phase transfer can not obtain the through-hole structure that we want, found using secondary by studying
Chloric acid can be removed according to the parts carried out again the different PVP by PVDF/PVP/IL basilar memebranes of concentration and pH, be carried out
Secondary pore-creating is more conducive to the formation in hydrated ion channel to obtain desired highly porous through-hole structure, to
Improve the actuating performance of IPMC.
Prepare carbon nanotube/ionic liquid gel integrated electrode liquid：Glyoxaline cation base ionic liquid is a kind of good carbon
Nanotube dispersant.Ionic liquid is fluid at room temperature, is sent out in the form of cation-π or π-π with the pi-electron of carbon nano tube surface
Raw crosslinking, can dispersing Nano carbon tubes, and will not reunite, form spawn easy to process, have very strong steady
It is qualitative, its physical property can be also kept at low temperature.In addition, ionic liquid acts not only as a kind of dispersant, and can be with
Carbon nanotube crosslinks, and forms more stable gel.Carbon nanotube/ionic liquid gel is prepared using following 2 kinds of technologies：a
Carbon nanotube aoxidizes grafting.If Fig. 3 illustrates, carbon nanotube aoxidized first, is then activated by EDC, NHS, then with amido
Ionic liquid is coupled, and forms gel；B carbon nanotube electrochemistry graftings.Alkenyl ionic liquid cation is placed in carbon nanotube
It is crosslinked under electric field, is then acted on ion solution anion and generate carbon nanotube/ionic liquid gel.This is using carbon nanometer
Pipe aoxidizes grafting, weighs the original MWCNTs of 2.0g, is added in the mixed solution of the 150mL concentrated sulfuric acids and 50mL concentrated nitric acids,
Flow back 5h at 100 DEG C, and cooling, dilution is filtered with 0.22 μm of teflon membrane filter, is washed to filtrate with distillation and is in neutrality；In
Dry 4h in 100 DEG C of vacuum drying chambers.CNT-COOH is obtained after oxidation, then again Jia Ru oxanes as solvent by CNT-COOH
Ultrasonic disperse 15min, be added EDC/NHS react 30min, obtain CNT-NHS after centrifugation, add triethylamine make it is molten
Agent adjusts pH value of solution=6-7 and 2- is then added after 2- imidazoles -1- base ethamine ionic liquids (IL) are put into 80 DEG C of dryings of baking oven
Imidazoles -1- base ethamine ionic liquids, are mixed evenly, and reaction 6h forms carbon nanotube/ionic liquid gel integrated electrode, most
After to put storage at low temperature for use.
Beneficial effects of the present invention：1. IPMC proposed by the present invention has the vesicularity of height, PVDF/PVP/IL substrates
Film is by phase transfer technique and hypochlorous acid except PVP Duplex treatments obtain, therefore voidage is very big, and vesicularity is very high, makes
IPMC draws more ionic liquids, is conducive to maintain the prolonged stabilized drivings of IPMC.
2. proposed by the present invention have hydrophobicity by the through-hole phase transfer type IPMC of basilar memebrane of PVDF/PVP/IL, so
We can be driven by ionic liquid (IL), and obtained IPMC drivings are more stablized, and driving time is longer.
3. proposed by the present invention have a large amount of channel by the through-hole phase transfer type IPMC of basilar memebrane of PVDF/PVP/IL,
A large amount of channel can greatly improve the ionic transporting quantity of material internal, and the pressure difference and ion of bigger are formed in material internal
Stream is conducive to the driving that electric actuator forms bigger, while also providing the mechanical property of bigger.
4. the IPMC of the present invention has more wide field in purposes.For example, due to the IPMC mass of the present invention
Gently, energy consumption is few, therefore can be used on flapping wing aircraft, can significantly reduce the weight of aircraft itself, high machine
Dynamic performance can provide enough power for flight, and excellent mechanical property can provide enough mechanics for flight and support, high
It spends porous structure and ionic liquid driving also provides lasting continuation of the journey for flight and ensures (such as Fig. 1)
5, IPMC of the invention is driven by 1- ethyl-3-methylimidazole tetrafluoroborate ionic liquids, ionic liquid driving
The motion state of IPMC is set more to stablize, simultaneously because ionic liquid is during the motion without volatilization and consumption so that the present invention
IPMC can long-term stable work 2.2h, be 2 times of the time under water-driven.
Description of the drawings
Fig. 1 flapping wing aircraft models.
Four structural schematic diagram of Fig. 2 inventive samples (a is PVDF/PVP/IL basilar memebranes, and b is SWCNT/ ionic liquids electrode).
Fig. 3 carbon nanotubes oxidation grafting ionic liquid synthetic route.
Section, the electrode plane SEM pictures of Fig. 4 SWCNT/IL electrodes IPMC.
Fig. 5 electric actuator schematic devices.1, --- signal generator module, 2, --- power measurement module, 3, --- at signal
Reason module, 4, --- ion-exchange polymer.
The specific surface area and porosity figure of Fig. 6 PVDF/PVP/IL basilar memebranes
Deflection figure of Fig. 7 samples four under different voltages：The working condition b work items that a operating conditions are 0.5Hz 2.5V
Part is the working condition of 0.5Hz 3V.
Fig. 8 infrared spectrograms compare, and a is sample one, and b is sample two, and c is sample three, and d is sample four.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described.It should be understood that following embodiment is merely to illustrate
The person skilled in the art of the range of the present invention and is not intended to limit the present invention, the field can make according to the content of foregoing invention
Go out some nonessential modifications and adaptations.
Embodiment 1 (casting method prepares basilar memebrane)
The basilar memebrane of IPMC is prepared using casting method：2.196gPVDF solution, 0.3876gPVP and the 20mlDMF of weighing
Solvent adds 1ml1- ethyl-3-methylimidazole tetrafluoroborate ionic liquids, is mixed evenly, will mix in beaker
Coating solution low-pressure pumping steam bubble, then the solution for taking out aerobic bubble is put to stand in air and obtains a coating solution in, then will
Coating solution is coated on glass slide at shakeouing, and is put into 70 DEG C of baking ovens dry 6h, PVDF/PVP/IL basilar memebranes are made.
Embodiment 2 (phase transfer mode prepares basilar memebrane)
PVDF/PVP/IL basilar memebranes are prepared using phase transfer mode：The 2.196g PVDF powder of weighing be (solution quality
14%), 0.3876gPVP powder (the 15% of PVDF content of powder) and 20mlDMF solvents add 1ml ionic liquids in beaker,
The coating solution mixed is removed in vacuum steam bubble, then will take out the solution of aerobic bubble by 60 DEG C of mechanical agitation 10h after mixing
It puts and stands one minute in air, transparent uniform casting solution is obtained, by the quantitative drop of PVDF/PVP/IL casting solutions obtained
On a glass, it is then placed on evenly laid out on the glass plate on sol evenning machine, the uniform coating solution of thickness is obtained, then in sky
It after stopping 30s in gas, is placed in 20% alcohol solidification liquid, completes inversion of phases process and film forming is precipitated, the thickness for obtaining film is about
100-800 microns.Film is put in deionized water, a water is changed per 5-8h, removes the remaining solvent on film.Finally exist
70 DEG C of baking oven dries film, obtains phase transfer mode and prepares IPMC basilar memebranes.
Embodiment 3 (prepares through-hole casting type IPMC basilar memebranes)
The sodium chlorate solution of time a concentration of 5000ppm is chosen to remove the pore former PVP in PVDF/PVP/IL cast membranes,
2x2cm shapes are made in the PVDF/PVP/IL cast membranes that example 1 obtains, it are put into prepared 5000ppm times a concentration of
In sodium chloride solution, 50 DEG C are heated, 3d is impregnated, is flushed three times with ionized water after then taking out, deionized water is placed on and impregnates 6h,
It is placed in 70 DEG C of baking ovens and dries.The through-hole IPMC basilar memebranes for having high-performance activating profile needed for us are made.
Embodiment 4 (prepares through-hole phase transfer type IPMC basilar memebranes)
The PVDF/PVP/IL phase transfer films obtained in example 2 are chosen, the shape of 2x2cm is made, it then can according to example 3
To choose the secondary sodium chloride of a concentration of 5000ppm, PVDF/PVP/IL phase transfer films are put in liquor natrii hypochloritis, heating 50
DEG C, it after impregnating 3d, is flushed three times with deionized water, taking-up is put impregnates 6h in deionized water, is finally placed in 70 DEG C of baking ovens and does
Dry, drying obtains through-hole phase transfer type IPMC basilar memebranes needed for us.
Embodiment 5 (preparation of IPMC electrode solutions)
The preparation of ordinary electrode liquid：It is 2 in mass ratio：1 weighs a certain amount of graphite powder and PVDF powder in beaker,
20ml DMF solvents are added, is placed on heating furnace and temperature 60 C heating is set, mechanical agitation, after mixing, low pressure filter
Bubble obtains the electrode solution of IPMC.
The preparation of carbon nanotube electrode：This aoxidizes grafting using carbon nanotube, and it is original to weigh 2.0g
MWCNTs is added in the mixed solution of the 150mL concentrated sulfuric acids and 50mL concentrated nitric acids, and flow back 5h at 100 DEG C, cooling, dilution,
It is filtered with 0.22 μm of teflon membrane filter, is washed to filtrate with distillation and is in neutrality；In dry 4h in 100 DEG C of vacuum drying chambers.
CNT-COOH is obtained after oxidation, then again Jia Ru oxanes as solvent by CNT-COOH ultrasonic disperse 15min, EDC/NHS is added
30min is reacted, CNT-NHS is obtained after centrifugation, triethylamine is added and makees solvent, pH value of solution=6-7 is adjusted, by 2- imidazoles
After -1- base ethamine ionic liquids (IL) are put into 80 DEG C of dryings of baking oven, 2- imidazoles -1- base ethamine ionic liquids are then added, are mixed
Uniformly, reaction 6h forms carbon nanotube/ionic liquid gel integrated electrode, and it is for use finally to put storage at low temperature.
If Fig. 3 is electrode layer scanning electron microscope (SEM) photograph, the square resistance for testing to obtain electrode by four probe instruments is such as table 1
Shown in table 2.
The square resistance of 1 ordinary electrode liquid of table
| 1 | 2 | 3 | 4 | 5 | 6 | It is average | |
| Electrode solution resistance (Ω) | 4.60 | 5.95 | 5.14 | 5.12 | 5.19 | 4.94 | 5.16 |
The square resistance of 2 carbon nanotube electrode liquid of table
| 1 | 2 | 3 | 4 | 5 | 6 | It is average | |
| Electrode solution resistance (Ω) | 2.31 | 3.15 | 2.86 | 3.22 | 2.64 | 2.56 | 2.79 |
The preparation of embodiment 6IPMC
The basilar memebrane dried in example 1-4, which is placed in ionic liquid, impregnates 5h, and the carbon that embodiment 5 prepares is received in 70 DEG C of drying
Mitron electrode solution is uniformly coated in the basilar memebrane both side surface of drying, and the top and the bottom of film are then clipped with two clips, hangs down
Straight hangs in baking oven, and temperature is transferred to 70 DEG C, be made after drying be cast into using PVDF/PVP/IL as the IPMC (samples of basilar memebrane
Product one)；With phase transfer mode obtain using PVDF/PVP/IL as the IPMC (sample two) of basilar memebrane；Cast membrane is removed with hypochlorous acid
The mode of middle PVP obtain using PVDF/PVP/IL as the through-hole casting type IPMC (sample three) of basilar memebrane；Phase is removed with hypochlorous acid
PVP in transfer membrane obtains the through-hole phase transfer type IPMC (sample four) using PVDF/PVP/IL as basilar memebrane.
The IPMC of above-mentioned preparation observes the thickness of basilar memebrane fibre diameter and basement membrane layer with scanning electron microscope (SEM),
In obtained using PVDF/PVP/IL as the through-hole phase transfer type IPMC's of basilar memebrane using the PVP removed with hypochlorous acid in phase transfer film
SEM pictures are listed in Fig. 4.
The electric signal of embodiment 7IPMC
Experimental provision is mainly made of signal generation unit, signal amplification unit, force snesor (see Fig. 5).Signal generates
The hardware of unit is made of the 6024E multifunctional data acquisition cards of NI companies；Software is programmed to obtain by LabVIEW；Signal amplifies
Unit is made of the power amplifier chip OPA548 of TI companies；Force snesor has selected the one-dimensional force snesor that can survey micro-ox level,
The voltage signal that force snesor is surveyed is read in by amplifying circuit, then by 6024E multifunctional data acquisition cards in computer, through place
Force signal is obtained after reason.
Electric actuation performance test：IPMC is placed in the two poles of the earth of power supply, control voltage is between 0.5~5 volt, and electric current is strong
Degree is between 0.01~0.20 ampere, and working frequency is 0.1~20 hertz, with high-speed camera (Olympus) and laser position
Displacement sensor (Keynce) observes the working time of the displacement and material of electric drive, with force snesor (0.01 milli of sensitivity
Ox) size of its power output is surveyed, and carry out power and displacement output and the comparison of working time.As a result table 3 and table 4 are listed in.
The relevant parameter of table 3PVDF/PVP/IL ion-exchange polymers actuator (sample three)
The relevant parameter of table 4PVDF/PVP/IL ion-exchange polymers actuator (sample four)
The performance test of embodiment 8IPMC
Ion-exchange equivalent is tested：The ion-exchange equivalent (IEC) of 6 sample of embodiment and business Nafion membrane is tested
(table 5).Prepared drying membrane sample is immersed in 8h in the NaCl solution of 2mol/L, makes sodium ion will be in sulfonic acid group
Hydrogen ion exchanges, and is titrated later using the standard NaOH solution of 0.1mol/L, and the calculation formula of IEC is as follows：
V in formulaNaOHIt is the volume for the NaOH solution being consumed, MNaOHIt is the concentration of NaOH, W is the weight of dry film.
Electromechanics performance test：Electromechanical Testing Platform includes signal generator, force snesor and multi-functional number
It is formed according to capture card.Signal generator (SP864, Nanjing) can in 0~10V voltages, 0.1~100Hz frequency downconverteds are sinusoidal,
Square wave and triangular signal；Force snesor (FEMTO-10000, Switzerland) range is 10mN, and sensitivity is 1 μ N；Multi-functional number
Lapview (v14.0) support programs are used according to capture card (NI, 6024E).The size of 5 sample IPMC samples of embodiment be 20 ×
2×0.33mm3, test under air atmosphere, the results are shown in Table 6.
The IEC of each IPMC, mechanical property result in 5 embodiment 6 of table
The electric actuation performance and relevant parameter of each IPMC in 6 embodiment 6 of table
Specific surface area and porosity is tested：Sample about 100mg is put into sample bottle, in adsorption instrument de-aeration stage 250'C and low
In 6.67 × 10-2Pa deaerated under vacuum is sympathized, and is then transferred to analysis station and is carried out nitrogen absorption under low temperature, and absorption etc. is obtained using volumetric method
Warm money.Specific surface area is obtained using BET model linear regressions；With N2It is only using BJH on the basis of adsorption isotherm desorption branch
The middle pore size distribution of vertical cylindrical model parsing sample；With N2On the basis of adsorption isotherm money low pressure adsorbent branch, using HK methods to sample
The micropore of product is parsed, and the curve (such as Fig. 5) of specific surface area and porosity is obtained
Examination of infrared spectrum：
Model IRAFFINITY-1S；Test condition：Measuring resolution is 4cm-1, scanning times are 64 times, test model
It encloses for 400~4500cm-1.Temperature：Under room temperature.Humidity：45% or less dry environment.By sample one, sample two, sample
Product four are cut into the shape of 2x2mm, are placed on 70 DEG C of drying in baking oven, then test sample, obtain infrared spectrum (as schemed
8) the characteristic peak integral area (such as table 7) of each sample, is obtained
The characteristic peak integral area of each sample in 7 embodiment 6 of table
By table 5 and table 6 it is known that the present invention with phase transfer method and add hypochlorous acid except the PVDF/ obtained after PVP
The IPMC that PVP/IL does basilar memebrane has big displacement, and under 3V voltages, deflection angle is common PVDF/PVP/IL cast membranes
Do the IPMC deflection angles of basilar memebrane 2 times are 3 times of the IPMC deflection angles that Nafion product films do basilar memebrane.
It can be obtained by sample one, sample two, sample three, the infrared spectrogram of sample four and to the integral of characteristic peak
Film is obtained by way of phase transfer, compared to most pore-foaming agent PVP can will be removed for cast membrane, to make film
Porosity be greatly improved, from the test result of porosity we it is also seen that coming.Sample passes through hypochlorous effect
The strength reduction of PVP characteristic spectrums, therefore remaining PVP can be further removed, be conducive to the braking for improving actuator
Performance extends the actuating time of actuator.
The present invention obtain with phase transfer method and add hypochlorous acid to do basilar memebrane except the PVDF/PVP/IL obtained after PVP
IPMC has the characteristic of long-term stable work, and due to being driven under ionic liquid, ionic liquid drives the motion state for making IPMC
More stablize, simultaneously because ionic liquid is during the motion without volatilization and consumption, the mode and hypochlorous acid of phase transfer are except residue
PVP, obtain highly porous structure IPMC allow to store drawing more ionic liquids, so ionic liquid driving time is more
It lengthens.The IPMC of basilar memebrane is in voltage 3V, frequency 0.5HZ conditions with the PVDF/PVP/IL cast membranes obtained with phase transfer method
The lower stable motion time will be 1.9h, with phase transfer method and hypochlorous acid be added to do basilar memebrane except the PVDF/PVP obtained after PVP
IPMC stable motion times under the conditions of voltage 3V, frequency 0.5HZ are 2.2h.
The present invention obtain with phase transfer method and add hypochlorous acid to do basilar memebrane except the PVDF/PVP/IL obtained after PVP
IPMC has higher ion-exchange equivalent, is 2 times of Nafion product films, is 3 times of Nafion cast membranes.
The IPMC (sample four) that the present invention obtains is driven by ionic liquid (IL), and ionic liquid driving is compared to water drive
The dynamic motion state that can make IPMC is more stablized, and the working time is greatly improved, and IPMC of the invention can be in ionic liquid
Middle steady operation 2.2h is 2 times of the time under water-driven.
The basic principles and main features and advantages of the present invention of the present invention have been shown and described above.The industry
For technical staff it should be appreciated that the present invention is not limited to the above embodiments, what is described in the above embodiment and the description is only say
Bright the principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention,
These changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention is wanted by appended right
Ask book and its equivalent thereof.
Claims (10)
1. a kind of using PVDF/PVP/IL as the through-hole phase transfer type IPMC of basilar memebrane, it is characterised in that：By basilar memebrane, it is fixed on
The carbon nanotube membrane electrode of basilar memebrane both sides, external electric signal input system composition, the basilar memebrane by Kynoar with
1- ethyl-3-methylimidazole tetrafluoroborates ionic liquid, polyvinylpyrrolidone copolymer are formed a film by way of phase transfer, and
Bis- pore-creating of part pvp is removed by hypochlorous acid to be made, the carbon nanotube membrane electrode passes through 2- imidazoles -1- bases by carbon nanotube
The dispersion of ethamine ionic liquid is constituted, and the electric signal of electric signal input system is 0.1-10Hz, sine wave, square wave or the triangle of 0.5-5V
Wave.
2. according to claim 1 using PVDF/PVP/IL as the through-hole phase transfer type IPMC of basilar memebrane, it is characterised in that：
The thickness of the basilar memebrane is 100-800 microns, and carbon nanotube electrode thickness is 10-60 microns.
3. according to claim 1 using PVDF/PVP/IL as the through-hole phase transfer type IPMC of basilar memebrane, it is characterised in that：
The surface resistance of the carbon nanotube membrane electrode is 0.5-300 Ω.
4. any described using PVDF/PVP/IL as the preparation of the through-hole phase transfer type IPMC of basilar memebrane according to claim 1-3
Method, it is characterised in that steps are as follows：
（1）Prepare PVDF/PVP/IL substrate coating solutions：In PVDF and PVP mixtures, DMF solvent will be added, heating stirring is mixed
It closes, 1- ethyl-3-methylimidazole tetrafluoroborate ionic liquids is then added and are uniformly mixed, stand the gas vacuumized in removal solution
Bubble, obtains PVDF/PVP/IL coating solutions；
（2）Prepare PVDF/PVP/IL basilar memebranes：By step（1）PVDF/PVP/IL coating solutions obtained it is quantitative drop in glass plate
On, it is then placed on sol evenning machine and tiles, 30s is stood after running 80s, be then placed in the alcohol solidification liquid that mass fraction is 20%,
It completes inversion of phases process and film forming is precipitated, film is put in deionized water, a water is changed per 5-8h, removal is remaining molten on film
Agent finally dries to obtain PVDF/PVP/IL basilar memebranes in 70 DEG C of baking ovens；
（3）Remove the PVP in PVDF/PVP/IL basilar memebranes：By step（2）PVDF/PVP/IL basilar memebranes obtained are placed on quality
In a concentration of 0.5% hypochlorite solution, pH value of solution=5-7,50 DEG C of heating water bath, heated at constant temperature 48h are adjusted；
（4）PVDF/PVP/IL basilar memebranes are chimeric to prepare IPMC：By the carbon nanotube prepared/ionic liquid gel integrated electrode liquid
The uniform basement membrane surface both sides coated in drying, then put baking oven into, temperature is transferred to 70 DEG C, is made with PVDF/ after drying
PVP/IL is the IPMC of basilar memebrane.
5. it is according to claim 4 using PVDF/PVP/IL as the preparation method of the through-hole phase transfer type IPMC of basilar memebrane,
It is characterized in that：The step（1）In middle PVDF/PVP/IL coating solutions, the mass fraction of PVDF is 14%, 1- ethyl -3- methyl miaows
The mass fraction of azoles tetrafluoroborate ionic liquid is that the quality of 5%, PVP accounts for the 15% of PVDF mass.
6. it is according to claim 4 using PVDF/PVP/IL as the preparation method of the through-hole phase transfer type IPMC of basilar memebrane,
It is characterized in that：The step（2）Middle PVDF/PVP/IL coating solutions drip 2-7mL on a glass, and the rotating speed of sol evenning machine is 40-
80r/min。
7. it is according to claim 4 using PVDF/PVP/IL as the preparation method of the through-hole phase transfer type IPMC of basilar memebrane,
It is characterized in that：The step（3）It is middle that remaining pore-foaming agent PVP is removed through chloric acid so that the total pore volume of film（P/P0= 0.954）
For 0.5-0.85.
8. it is according to claim 4 using PVDF/PVP/IL as the preparation method of the through-hole phase transfer type IPMC of basilar memebrane,
It is characterized in that：The step（4）The preparation method of middle carbon nanotube/ionic liquid gel integrated electrode liquid is as follows：It is received using carbon
Mitron aoxidizes grafting, weighs original MWCNTs, is added in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, flows back at 100 DEG C
5 h, cooling, dilution, are filtered, being washed to filtrate with distillation is in neutrality with teflon membrane filter；In in 100 DEG C of vacuum drying chambers
Dry 4 h, obtain CNT-COOH after oxidation, then again Jia Ru oxanes as solvent by CNT-COOH ultrasonic disperse 15min, addition
EDC/NHS reacts 30min, and CNT-NHS is obtained after centrifugation, adds triethylamine and makees solvent, adjusts solution Ph=6-7, then
2- imidazoles -1- base ethamine the ionic liquids after drying are added, are mixed evenly, formation carbon nanotube/ionic liquid is solidifying after reacting 6h
It is for use finally to put storage at low temperature for glue integrated electrode liquid.
9. it is according to claim 8 using PVDF/PVP/IL as the preparation method of the through-hole phase transfer type IPMC of basilar memebrane,
It is characterized in that：The CNT-NHS and the mass ratio of 2- imidazoles -1- base ethamine ionic liquids are 13:54.
10. being applied to by the through-hole phase transfer type IPMC of basilar memebrane of PVDF/PVP/IL according to claim 1-3 is any described
Electric actuator.
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