CN109238312A - A kind of preparation method of composite fibre base flexible piezoelectric sensors - Google Patents
A kind of preparation method of composite fibre base flexible piezoelectric sensors Download PDFInfo
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- G—PHYSICS
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- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
- G01D5/12—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable using electric or magnetic means
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to sensor fields, disclose a kind of preparation method of composite fibre base flexible piezoelectric sensors, the present invention is nanocrystalline with samarium doping lead titanates, the Curie temperature for mixing the rare earth modified lead titanate piezoelectric ceramics of samarium is higher, mechanical-electric coupling anisotropy is big, more suitable for the various energy converters to work under production high temperature, by its ball milling at nano particle, enlarged contact areas.Then surface functionalization is carried out with amino, it is ensured that with the maleic anhydride molecule covalent coupling in polymer substrate.After the coating of electroactive carbon ink, fiber base flexible piezoelectric sensors are obtained through wet spinning, improve flexible and stability, and its stitchability expands the scope of application of sensor, and has more excellent detection performance.Finally by itself and the compound torsion of silver nanowires, composite fibre base flexible piezoelectric sensors are obtained.Inventive sensor is flexible, can be applied to medical biological monitoring, the fields such as environment and the monitoring of hygiene.
Description
Technical field
The present invention relates to sensor field more particularly to a kind of preparation methods of composite fibre base flexible piezoelectric sensors.
Background technique
Sensor is that mankind itself finds out the various sensory informations of nature, can be turned to unlike signal and perception information
Turn to can digitize, intelligentized important devices.During human civilization rapid development of information technology, sensor is played
Increasingly heavier effect is mankind's exploration outfield, while being also that the mankind understand real world, observes the important of peripheral information
One of means.Sensor be it is a kind of the non-electrical signal such as electricity, light, temperature and chemical action can be converted into electrical signal can
The component of regulation.
Lead titanates series electron ceramics belong to function ceramics, mainly have Electricity Functional, as dielectricity, piezoelectricity, ferroelectricity and
Pyroelectric etc., some also has the function of light.Lead titanates is that calcium is admired the ferroelectric material of mine structure, because its curie point is high, relatively
Dielectric constant is small, and pyroelectricity constant is big, laterally and longitudinally there is very big anisotropy between electromechanical coupling factor, is well suited for making
High-frequency transducer and get more and more people's extensive concerning.
In recent years, as the fast development of flexible wearable formula electronic product, flexible sensor and flexible energy-storage travelling wave tube draw
Extensive concern is played.The important component of flexible sensor and flexible energy-storage travelling wave tube as wearable electronic, in people
There is huge application prospect in the fields such as body motion detection, personalized health monitoring and intelligent human-machine interaction.Wherein, flexible to pass
Sensor should have both high sensitivity, wide detection range, high flexibility and high stability, and flexible energy-storage travelling wave tube should have excellent electrification
Learn performance, good mechanical flexibility etc..So far, preparing these ideal flexible devices is still a no small challenge.It is logical
It crosses and material select and is expected to obtain the flexible device of excellent combination property using new technology of preparing and mentality of designing.It leads
Electric macromolecular fibre base flexible piezoelectric sensors because its flexibility is good, light weight, foldable bending, can weave, it is at low cost and
The features such as large specific surface area, has become one of the important directions of flexible device research
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation sides of composite fibre base flexible piezoelectric sensors
Method.The method of the present invention improves its Curie temperature by nanocrystalline, the modified lead titanate piezoelectric ceramic for preparing samarium doping lead titanates,
Lattice anisotropy becomes larger, and ball milling is at nano particle, then with amido modified samarium doping lead titanates nano particle, with covalently even
Connection realizes surface functionalization, after the coating of electroactive carbon ink, obtains a kind of fiber base flexible piezoelectric sensors by wet spinning,
Finally by itself and the compound torsion of silver nanowires, composite fibre base flexible piezoelectric sensors are obtained, are had compared with traditional sensors
More excellent detection performance.
The specific technical proposal of the invention is: a kind of preparation method of composite fibre base flexible piezoelectric sensors, including such as
Lower step:
(1) the nanocrystalline preparation of samarium doping lead titanates: deionized water is added in butyl titanate under agitation, is suspended
After liquid, the aqueous solution of lead acetate, samarium trichloride, sodium hydroxide is sequentially added under agitation, with deionized water constant volume, is mixed
Close solution；Mixed solution is added in reaction kettle and heats and stirs 4-5 minutes, rises insulation reaction 8-10h after temperature；Wait react
After the completion, room temperature is naturally cooled to；It takes out product to impregnate, makes soluble ion that sufficiently exchange occur, filtering and washing product removes
Soluble ion, then the dry 6-8h at 80-100 DEG C, is cooled to room temperature, it is nanocrystalline to obtain samarium doping lead titanates.
Lead titanates series electron ceramics belong to function ceramics, mainly have Electricity Functional, as dielectricity, piezoelectricity, ferroelectricity and
Pyroelectric etc., some also has the function of light.Lead titanates is that calcium is admired the ferroelectric material of mine structure, because its curie point is high, relatively
Dielectric constant is small, and pyroelectricity constant is big, laterally and longitudinally there is very big anisotropy between electromechanical coupling factor, is well suited for making
High-frequency transducer and get more and more people's extensive concerning, but since the crystal boundary energy that lead titanates becomes ceramics is high, cubic coercive field is big, brilliant
Lattice structural anisotropy is big, makes pure lead titanate ceramics material in annealing process by being easy to produce micro-crack when curie point, difficult
In densified sintering product, the invention of this hair is doped modification to it to solve the above-mentioned problems.With the lead titanates pressure being widely used at present
Electroceramics is compared, and the Curie temperature for mixing the rare earth modified lead titanate piezoelectric ceramics of samarium is higher, and mechanical-electric coupling anisotropy is big, more suitable
Together in the various energy converters to work under production high temperature.
(2) preparation of samarium doping lead titanates nano particle: samarium doping lead titanates is nanocrystalline with zirconia balls and ethyl alcohol
Samarium doping lead titanates nano particle is made in ball milling in a reservoir, dry at 70-80 DEG C.
Ball-milling method is a kind of mechanical stripping technology, environmentally protective, easy to operate, low cost.It avoids due to redox
Method uses reducing agents potential hazards caused by experiment operator and environment such as strong acid and hydrazine hydrate.
(3) preparation of amido modified samarium doping lead titanates nano particle: by samarium doping lead titanates nano particle and poly- Asia
Ethylimido difference ultrasonic disperse is adjusted to 9-11 in deionized water, and by pH value of solution respectively, and it is sub- to respectively obtain poly- ethylidene
Amine aqueous solution and samarium doping metatitanic acid lead solution；Polyethylene imine solution is added dropwise in samarium doping metatitanic acid lead solution, 1- is stirred
3h, centrifuge separation, obtains amido modified samarium doping lead titanates nano particle, and it is sub- that excessive poly- ethylidene is washed with deionized water
Amine, then after being washed with dehydrated alcohol and removing distilled water, pass through centrifugation and obtain pure amido modified samarium doping lead titanates nanometer
Particle.
Samarium doping lead titanates piezoelectric nano-particles carry out surface functionalization with amino, it is ensured that with the Malaysia in polymer substrate
Anhydride molecule covalent coupling.It, can be multiple in polymer containing amido modified nano particle compared with unmodified nanoparticles
Being uniformly distributed in condensation material, and therefore improve piezo-electric generating.Flexible device based on this unique composite material manufacture exists
The voltage generated during Cyclic flexion and not bending motion significantly improves.In addition, this achievement is based on this composite material
It is unprecedented in terms of the reasonably optimizing of flexible device, and presents the method using Chemical enhancement composite systems.
(4) preparation of the fiber base flexible piezoelectric sensors of electroactive carbon ink coating: by amido modified samarium doping metatitanic acid
Lead nano particle is scattered in tetrahydrofuran solution and ultrasonic disperse 4-6h；Then, spinning solution is added in gained suspension,
24-36h is stirred at 25-35 DEG C, is transferred in reaction kettle and reacts 9-10h, after the reaction was completed, room temperature is cooling, obtains mixing and spins
Silk liquid, is ultrasonically treated 1-2h in a water bath, and blend spinning liquid is injected 5- using the 10-20mL syringe with empty needle in No. 23
In the alcohol solidification bath of 10Hz rotation, gained fiber is vertically pulled out and is wrapped on spool, obtains electroactive carbon ink coating
Fiber base flexible piezoelectric sensors.
Electroactive material is the mixed conductor of electron-ion, and it is special that insulator is presented when being in complete oxidation or reducing condition
Sign can reversibly be placed in from solution and discharge ion (ion exchange or charge and discharge when converting between oxidation and reducing condition
Electric process) become electric conductor.Electroactive carbon ink is a kind of porous carbonaceous material, and has very strong adsorption capacity.
(5) preparation of composite fibre base flexible piezoelectric sensors: 40-60 μm of silver nanoparticle winding steps (4) are resulting
The fiber base flexible piezoelectric sensors torsion of electroactive carbon ink coating, is then impregnated with electrolyte, is put into transparent and soft modeling
In expects pipe, which is 0.6mm, outer diameter 0.7mm, finally uses glue sealing, obtains composite fibre base flexible piezoelectric
Sensor.
Silver is the good conductor of electricity, and resistivity is low, and conductivity is high, and nano-silver thread is applied to conductive layer for the electric current of collection
Export, can reduce energy loss compared with TCO semiconductor.Silver nanowires is because of its excellent electric conductivity, conductivity of heat, low surface electricity
The features such as resistance, high transparency and good biocompatibility.
Preferably, in step (1), [OH]=1.0-2.0molL in the mixed solution after constant volume-1, [3/2Sm+Pb]=
0.15-0.20mol·L-l, [Ti]=0.1-0.2molL-1。
Preferably, being warming up to 220-300 DEG C in step (1)；Product is taken out after cooling in deionized water and dehydrated alcohol
Middle immersion, and wash 3-4 times repeatedly respectively.
Preferably, ball milling frequency is 15-45Hz in step (2), Ball-milling Time is 60-100 minutes.
Preferably, the mass ratio of polyethylene imine and samarium doping lead titanates is 1:10 in step (3).
Preferably, in step (3), centrifugal rotational speed 8000-10000rpm；Deionized water is washed 1-2 times, dehydrated alcohol
Washing 3-4 times.
Preferably, the dosage of the tetrahydrofuran solution is 20-40mL, content 99% in step (4).
Preferably, being ultrasonically treated the model S-450D-1/2 of ultrasonic processor used in step (4).
Preferably, the spinning solution is that the electroactive carbon ink solution of 0.85wt/v% is introduced 8wt/ in step (4)
It is made in v% Styrene-Butadiene-Styrene Block Copolymer solution；Wherein the solvent of electroactive carbon ink solution is volume ratio
For the distilled water and ethyl alcohol of 7:3；The solvent of Styrene-Butadiene-Styrene Block Copolymer solution is the second that volume ratio is 6:4
Pure and mild dimethylformamide.
Preferably, in step (5), the electrolyte be 1, the 2- dimethyl -3- propyl iodate imidazoles containing 0.6M,
The chloroacetonitrile solution of 0.03M iodine solution, 0.5 μM of 4- tert .-butylpyridine and 0.03 μM of guanidinium isothiocyanate.
It is compared with the prior art, the beneficial effects of the present invention are:
1, modified lead titanate piezoelectric ceramic nanocrystalline with samarium doping lead titanates of the invention, with the lead titanates pressure being widely used at present
Electroceramics is compared, and the Curie temperature for mixing the rare earth modified lead titanate piezoelectric ceramics of samarium is higher, and mechanical-electric coupling anisotropy is big, more suitable
Together in the various energy converters to work under production high temperature, and use ball mill ball milling at nano particle, enlarged contact areas it.
2, samarium doping lead titanates piezoelectric nano-particles carry out surface functionalization with amino, it is ensured that with the horse in polymer substrate
Carry out anhydride molecule covalent coupling.It, can be in polymer containing amido modified nano particle compared with unmodified nanoparticles
Being uniformly distributed in composite material, and therefore improve piezo-electric generating.
3, this flexible sensor is spun into fiber based sensor using wet spinning after the coating of electroactive carbon ink, is mentioned
High flexibility and stability, and its stitchability expands the scope of application of sensor.
4, composite fibre base flexible piezoelectric sensors obtained pass through and silver nanowires it is compound, improve its electric conductivity, pass
Hot and biocompatibility.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1
(1) the nanocrystalline preparation of samarium doping lead titanates:
Butyl titanate is added in ptfe autoclave, deionized water is added under stirring conditions, is suspended
After liquid, the aqueous solution of lead acetate, samarium trichloride, sodium hydroxide is sequentially added under stirring conditions, and all reactions are all made of with water
Deionized water, last constant volume is to 250ml, wherein [OH]=1.0molL-1, [3/2Sm+Pb]=0.15molL-l, [Ti]=
0.1mol·L-1,.Reaction kettle is heated and is stirred 4 minutes, is stirred for after heating 4 minutes, 220 DEG C at a temperature of keep the temperature 8h.
To after the reaction was completed, reaction kettle be made to naturally cool to room temperature.It takes out in product and impregnates certain time, fill soluble ion
Divide exchange, filtering and washing product washs 3 times repeatedly respectively in deionized water and dehydrated alcohol, removes soluble ion, then exist
Dry 6h, it is nanocrystalline to obtain samarium doping lead titanates in 80 DEG C of baking oven.
(2) preparation of samarium doping lead titanates nano particle:
Samarium doping lead titanates it is nanocrystalline with zirconia balls and ethyl alcohol in polyethylene bottle with ball mill ball milling to form samarium doping
Lead titanates nano particle, ball mill rotational speed of ball-mill are 15Hz, and Ball-milling Time is 60 minutes, then that it is dry at 70 DEG C.
(3) preparation of amido modified samarium doping lead titanates nano particle:
Samarium doping lead titanates nano particle and polyethylene imine powder the difference ultrasonic disperse that step (2) is obtained are in deionization
In water, and the pH of solution is adjusted to 10 respectively, then polyethylene imine solution is added dropwise to the samarium doping metatitanic acid of dispersion
In lead solution, the ratio of the samarium doping metatitanic acid lead solution of the polyethylene imine solution dispersed in mixed solution and dispersion is 1:
10, and mixed solution is stirred into 1h, after stirring, the centrifuge for being 8000 turns by revolving speed separates the amido modified samarium prepared
Doped with Titanium lead plumbate nano particle, and be washed with deionized 1 time and wash away excessive polyethylene imine, then washed with dehydrated alcohol
After 3 times to remove distilled water, the luxuriant scheming centrifugation for being 8000 turns by revolving speed obtains pure amido modified samarium doping titanium
Lead plumbate nano particle.
(4) preparation of the fiber base flexible piezoelectric sensors of electroactive carbon ink coating:
It is prepared by wet spinning, it is in 99% tetrahydrofuran solution that nano particle prepared by step (3), which is dispersed in 20mL content,
And with ultrasonic disperse 4h, ultrasonic processor is the processor of S-450D-1/2.Then, spinning solution is added in gained suspension
Formula, spinning solution formula is by drawing the electroactive carbon ink solution of 0.85wt/v% (being made of distilled water: ethyl alcohol (7:3) solution)
Enter 8wt/v% Styrene-Butadiene-Styrene Block Copolymer solution and (prepares) system with ethyl alcohol: dimethylformamide=6:4
It is standby.Mixture stirs 24 hours at 25 DEG C, then feeds the mixture into ptfe autoclave high temperature reaction 9h, reaction
After the completion, it cools down, is finally ultrasonically treated in a water bath before fibre spinning 1 hour at room temperature.Using hollow with No. 23
Gained fiber is vertically pulled out in the alcohol solidification bath of spinning solution injection 5Hz rotation and is wrapped in by the 10mL syringe of needle
On spool, the fiber base flexible piezoelectric sensors of electroactive carbon ink coating are obtained.
(5) preparation of composite fibre base flexible piezoelectric sensors:
The fiber base piezoelectric transducer torsion that 40 μm of silver nanowires is manufactured around above-mentioned steps (4), is then impregnated with electrolyte,
Electrolyte be the 1,2- dimethyl -3- propyl iodate imidazoles containing 0.6M, 0.03M iodine solution, 0.5 μM of 4- tert .-butylpyridine and
The chloroacetonitrile solution of 0.03 μM of guanidinium isothiocyanate, is put into transparent and soft plastic tube, and the internal diameter of the plastic tube is 0.6mm,
Outer diameter is 0.7mm, finally uses glue sealing, obtains composite fibre base flexible piezoelectric sensors.
Embodiment 2
(1) the nanocrystalline preparation of samarium doping lead titanates:
Butyl titanate is added in ptfe autoclave, deionized water is added under stirring conditions, is suspended
After liquid, the aqueous solution of lead acetate, samarium trichloride, sodium hydroxide is sequentially added under stirring conditions, and all reactions are all made of with water
Deionized water, last constant volume is to 300ml, wherein [OH]=2.0molL-1, [3/2Sm+Pb]=0.20molL-l, [Ti]=
0.2mol·L-1,.Reaction kettle is heated and is stirred 5 minutes, is stirred for after heating 4 minutes, 220 DEG C at a temperature of keep the temperature 10h.
To after the reaction was completed, reaction kettle be made to naturally cool to room temperature.It takes out in product and impregnates certain time, fill soluble ion
Divide exchange, filtering and washing product washs 4 times repeatedly respectively in deionized water and dehydrated alcohol, removes soluble ion, then exist
Dry 6h, it is nanocrystalline to obtain samarium doping lead titanates in 80 DEG C of baking oven.
(2) preparation of samarium doping lead titanates nano particle:
Samarium doping lead titanates it is nanocrystalline with zirconia balls and ethyl alcohol in polyethylene bottle with ball mill ball milling to form samarium doping
Lead titanates nano particle, ball mill rotational speed of ball-mill are 15Hz, and Ball-milling Time is 100 minutes, then that it is dry at 80 DEG C.
(3) preparation of amido modified samarium doping lead titanates nano particle:
Samarium doping lead titanates nano particle and polyethylene imine powder the difference ultrasonic disperse that step (2) is obtained are in deionization
In water, and the pH of solution is adjusted to 10 respectively, then polyethylene imine solution is added dropwise to the samarium doping metatitanic acid of dispersion
In lead solution, the ratio of the samarium doping metatitanic acid lead solution of the polyethylene imine solution dispersed in mixed solution and dispersion is 1:
10, and mixed solution is stirred into 3h, after stirring, the centrifuge separation for being 10000 turns by revolving speed prepares amido modified
Samarium doping lead titanates nano particle, and be washed with deionized 2 times and wash away excessive polyethylene imine, then washed with dehydrated alcohol
After 4 times are washed to remove distilled water, the luxuriant scheming centrifugation for being 10000 turns by revolving speed obtains pure amido modified samarium doping
Lead titanates nano particle.
(4) preparation of the fiber base flexible piezoelectric sensors of electroactive carbon ink coating:
It is prepared by wet spinning, it is in 99% tetrahydrofuran solution that nano particle prepared by step (3), which is dispersed in 30mL content,
And with ultrasonic disperse 5h, ultrasonic processor is the processor of S-450D-1/2.Then, spinning solution is added in gained suspension
Formula, spinning solution formula is by drawing the electroactive carbon ink solution of 0.85wt/v% (being made of distilled water: ethyl alcohol (7:3) solution)
Enter 8wt/v% Styrene-Butadiene-Styrene Block Copolymer solution and (prepares) system with ethyl alcohol: dimethylformamide=6:4
It is standby.Mixture stirs 29 hours at 30 DEG C, then feeds the mixture into ptfe autoclave high temperature reaction 9.5h, instead
It after the completion of answering, cools down, is finally ultrasonically treated in a water bath before fibre spinning 1.2 hours at room temperature.Using with No. 23
Gained fiber is vertically pulled out in the alcohol solidification bath of spinning solution injection 7Hz rotation and is twined by the 16mL syringe of middle empty needle
It is wound on spool, obtains electroactive carbon ink coating fiber base flexible piezoelectric sensors.
(5) preparation of composite fibre base flexible piezoelectric sensors:
The fiber base piezoelectric transducer torsion that 50 μm of silver nanowires is manufactured around above-mentioned steps (4), is then impregnated with electrolyte,
Electrolyte be the 1,2- dimethyl -3- propyl iodate imidazoles containing 0.6M, 0.03M iodine solution, 0.5 μM of 4- tert .-butylpyridine and
The chloroacetonitrile solution of 0.03 μM of guanidinium isothiocyanate, is put into transparent and soft plastic tube, and the internal diameter of the plastic tube is 0.6mm,
Outer diameter is 0.7mm, finally uses glue sealing, obtains composite fibre base flexible piezoelectric sensors.
Embodiment 3
(1) the nanocrystalline preparation of samarium doping lead titanates:
Butyl titanate is added in ptfe autoclave, deionized water is added under stirring conditions, is suspended
After liquid, the aqueous solution of lead acetate, samarium trichloride, sodium hydroxide is sequentially added under stirring conditions, and all reactions are all made of with water
Deionized water, last constant volume is to 250ml, wherein [OH]=2.0molL-1, [3/2Sm+Pb]=0.15molL-l, [Ti]=
0.1mol·L-1,.Reaction kettle is heated and is stirred 4-5 minutes, is stirred for after heating 4 minutes, 300 DEG C at a temperature of keep the temperature
8h.To after the reaction was completed, reaction kettle be made to naturally cool to room temperature.It takes out in product and impregnates certain time, send out soluble ion
Raw sufficiently exchange, filtering and washing product wash 3 times repeatedly respectively in deionized water and dehydrated alcohol, remove soluble ion, so
The dry 8h in 100 DEG C of baking oven afterwards, it is nanocrystalline to obtain samarium doping lead titanates.
(2) preparation of samarium doping lead titanates nano particle:
Samarium doping lead titanates it is nanocrystalline with zirconia balls and ethyl alcohol in polyethylene bottle with ball mill ball milling to form samarium doping
Lead titanates nano particle, ball mill rotational speed of ball-mill are 15Hz, and Ball-milling Time is 100 minutes, then that it is dry at 70 DEG C.
(3) preparation of amido modified samarium doping lead titanates nano particle:
Samarium doping lead titanates nano particle and polyethylene imine powder the difference ultrasonic disperse that step (2) is obtained are in deionization
In water, and the pH of solution is adjusted to 10 respectively, then polyethylene imine solution is added dropwise to the samarium doping metatitanic acid of dispersion
In lead solution, the ratio of the samarium doping metatitanic acid lead solution of the polyethylene imine solution dispersed in mixed solution and dispersion is 1:
10, and mixed solution is stirred into 3h, after stirring, the centrifuge separation for being 10000 turns by revolving speed prepares amido modified
Samarium doping lead titanates nano particle, and be washed with deionized 1 time and wash away excessive polyethylene imine, then washed with dehydrated alcohol
After 3 times are washed to remove distilled water, the luxuriant scheming centrifugation for being 10000 turns by revolving speed obtains pure amido modified samarium doping
Lead titanates nano particle.
(4) preparation of the fiber base flexible piezoelectric sensors of electroactive carbon ink coating:
It is prepared by wet spinning, it is in 99% tetrahydrofuran solution that nano particle prepared by step (3), which is dispersed in 40mL content,
And with ultrasonic disperse 6h, ultrasonic processor is the processor of S-450D-1/2.Then, spinning solution is added in gained suspension
Formula, spinning solution formula is by drawing the electroactive carbon ink solution of 0.85wt/v% (being made of distilled water: ethyl alcohol (7:3) solution)
Enter 8wt/v% Styrene-Butadiene-Styrene Block Copolymer solution and (prepares) system with ethyl alcohol: dimethylformamide=6:4
It is standby.Mixture stirs 36 hours at 35 DEG C, then feeds the mixture into ptfe autoclave high temperature reaction 10h, instead
It after the completion of answering, cools down, is finally ultrasonically treated in a water bath before fibre spinning 2 hours at room temperature.Using in No. 23
Gained fiber is vertically pulled out in the alcohol solidification bath of spinning solution injection 10Hz rotation and is wound by the 20mL syringe of empty needle
On spool, electroactive carbon ink coating fiber base flexible piezoelectric sensors are obtained.
(5) preparation of composite fibre base flexible piezoelectric sensors:
The fiber base piezoelectric transducer torsion that 60 μm of silver nanowires is manufactured around above-mentioned steps (4), is then impregnated with electrolyte,
Electrolyte be the 1,2- dimethyl -3- propyl iodate imidazoles containing 0.6M, 0.03M iodine solution, 0.5 μM of 4- tert .-butylpyridine and
The chloroacetonitrile solution of 0.03 μM of guanidinium isothiocyanate, is put into transparent and soft plastic tube, and the internal diameter of the plastic tube is 0.6mm,
Outer diameter is 0.7mm, finally uses glue sealing, obtains composite fibre base flexible piezoelectric sensors.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (10)
1. a kind of preparation method of composite fibre base flexible piezoelectric sensors, it is characterised in that include the following steps:
(1) the nanocrystalline preparation of samarium doping lead titanates: deionized water is added in butyl titanate under agitation, is suspended
After liquid, the aqueous solution of lead acetate, samarium trichloride, sodium hydroxide is sequentially added under agitation, with deionized water constant volume, is mixed
Close solution；Mixed solution is added in reaction kettle and heats and stirs 4-5 minutes, rises insulation reaction 8-10h after temperature；Wait react
After the completion, room temperature is naturally cooled to；It takes out product to impregnate, makes soluble ion that sufficiently exchange occur, filtering and washing product removes
Soluble ion, then the dry 6-8h at 80-100 DEG C, is cooled to room temperature, it is nanocrystalline to obtain samarium doping lead titanates；
(2) preparation of samarium doping lead titanates nano particle: holding with zirconia balls and ethyl alcohol by samarium doping lead titanates is nanocrystalline
Samarium doping lead titanates nano particle is made in ball milling in device, dry at 70-80 DEG C；
(3) preparation of amido modified samarium doping lead titanates nano particle: by samarium doping lead titanates nano particle and poly- ethylidene
Imines difference ultrasonic disperse is adjusted to 9-11 in deionized water, and by pH value of solution respectively, and it is molten to respectively obtain polyethylene imine
Liquid and samarium doping metatitanic acid lead solution；Polyethylene imine solution is added dropwise in samarium doping metatitanic acid lead solution, 1-3h is stirred, from
Heart separation, obtains amido modified samarium doping lead titanates nano particle, excessive polyethylene imine is washed with deionized water, then
It is washed with dehydrated alcohol after removing distilled water, pure amido modified samarium doping lead titanates nano particle is obtained by centrifugation；
(4) preparation of the fiber base flexible piezoelectric sensors of electroactive carbon ink coating: amido modified samarium doping lead titanates is received
Rice grain is scattered in tetrahydrofuran solution and ultrasonic disperse 4-6h；Then, spinning solution is added in gained suspension,
24-36h is stirred at 25-35 DEG C, is transferred in reaction kettle and reacts 9-10h, after the reaction was completed, room temperature is cooling, obtains blend spinning
Liquid is ultrasonically treated 1-2h in a water bath, and blend spinning liquid is injected 5- using the 10-20mL syringe with empty needle in No. 23
In the alcohol solidification bath of 10Hz rotation, gained fiber is vertically pulled out and is wrapped on spool, obtains electroactive carbon ink coating
Fiber base flexible piezoelectric sensors；
(5) preparation of composite fibre base flexible piezoelectric sensors: the resulting electricity of 40-60 μm of silver nanoparticle winding steps (4) is living
Property carbon ink coating fiber base flexible piezoelectric sensors torsion, then impregnated with electrolyte, be put into transparent and soft plastic tube
In, which is 0.6mm, outer diameter 0.7mm, finally uses glue sealing, obtains composite fibre base flexible piezoelectric sensing
Device.
2. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
(1) in, [OH]=1.0-2.0molL in the mixed solution after constant volume-1, [3/2Sm+Pb]=0.15-0.20molL-l,
[Ti]=0.1-0.2mol·L-1。
3. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
(1) in, it is warming up to 220-300 DEG C；Product is taken out after cooling to impregnate in deionized water and dehydrated alcohol, and is washed repeatedly respectively
3-4 times.
4. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
(2) in, ball milling frequency is 15-45Hz, and Ball-milling Time is 60-100 minutes.
5. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
(3) in, the mass ratio of polyethylene imine and samarium doping lead titanates is 1:10.
6. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
(3) in, centrifugal rotational speed 8000-10000rpm；Deionized water is washed 1-2 times, and dehydrated alcohol washs 3-4 times.
7. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
(4) in, the dosage of the tetrahydrofuran solution is 20-40mL, content 99%.
8. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
(4) in, it is ultrasonically treated the model S-450D-1/2 of ultrasonic processor used.
9. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
(4) in, the spinning solution is that the electroactive carbon ink solution of 0.85wt/v% is introduced 8wt/v% s-B-S
It is made in block copolymer solution；Wherein the solvent of electroactive carbon ink solution is the distilled water and ethyl alcohol that volume ratio is 7:3；Benzene second
Alkene-butadiene-styrene block copolymer solution solvent is the ethyl alcohol and dimethylformamide that volume ratio is 6:4.
10. a kind of preparation method of composite fibre base flexible piezoelectric sensors as described in claim 1, which is characterized in that step
Suddenly in (5), the electrolyte is 1,2- dimethyl -3- propyl iodate imidazoles, 0.03M iodine solution, 0.5 μM containing 0.6M
The chloroacetonitrile solution of 4- tert .-butylpyridine and 0.03 μM of guanidinium isothiocyanate.
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