CN109265643A - A kind of sunlight selfreparing transparent flexible strain sensing composite material and preparation method and application - Google Patents
A kind of sunlight selfreparing transparent flexible strain sensing composite material and preparation method and application Download PDFInfo
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- CN109265643A CN109265643A CN201810887218.1A CN201810887218A CN109265643A CN 109265643 A CN109265643 A CN 109265643A CN 201810887218 A CN201810887218 A CN 201810887218A CN 109265643 A CN109265643 A CN 109265643A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The present invention relates to a kind of sunlight selfreparing transparent flexible strain sensing composite material and preparation method and applications.The composite material includes polyurethane bottom and coated in the metal nanometer line on polyurethane bottom；The polyurethane is grouped as by the group of following parts by weight: 15 ~ 28 parts of diisocyanate monomer, 10 ~ 50 parts of polyalkylene glycol monomer, 5 ~ 15 parts of monomer containing cystine linkage, 0.5 ~ 2.5 part of crosslinking agent.Sunlight selfreparing transparent flexible strain sensing composite material provided by the invention has excellent light transmittance, elongation strain is responded sensitive, and display linear response, when by scratch or fracture damage, the multiple reparation of mechanical property and electric conductivity can be realized under light illumination, and repair time is short, remediation efficiency is high.
Description
Technical field
The invention belongs to selfreparing strain transducer fields, and in particular to a kind of sunlight selfreparing transparent flexible strain biography
Feel composite material and preparation method and application.
Background technique
In recent years, the development of flexible strain sensing devices is very fast, can be used to detect various physical activities, including compared with
Significantly hand, arms and legs bending is mobile and breathing more by a small margin, swallow, sounding when muscle vibration and blood pressure
Deng.Flexible strain transducer can effectively convert outside stimulus to visual electric signal, comment in physical activity detection, health
Estimate, the fields such as flexible electronic skin and industrial robot are gathered around has broad application prospects.
With the development of transparent visual wearable device, the transparence of the flexible sensor as core component becomes hair
Exhibition trend.In addition, flexible strain transducer faces problem at high cost, that the service life is short, in use, vulnerable to various environment
The influence of factor, or by repeatedly bending, extruding or stretch the effects of, cause micro-damage, cause the electric conductivity of material big
Width reduces, and device performance failure, an urgent demand material has self-repair function, repairs micro-damage in time, avoid element and equipment
Major accident and loss caused by failure.Smart self-repairing polymer or polymer composites can be automatically or in external conditions
The micro-damage of stimulation lower healing material inside and outside, ensures the long-time service stability and reliability of material, extends the use of material
Service life.
Currently, polymer matrix self-repair material can be divided into outer adding type and intrinsic according to the mode for repairing substance and energy supply
Type self-repair material two major classes.Compared to outer adding type self-repair material, Intrinsical selfreparing by itself chemical bond (covalent bond/
Non-covalent bond), physically or chemically reversible reaction is carried out by modes such as light, thermal and magnetic or pH, realizes repairing repeatedly for material micro-crack
It is multiple.The energy resource supply of sunlight selfreparing comes from sunlight, environmental-friendly and cheap and easy to get, operates compared to other repair modes
It is more simple and convenient, belong to the scope being automatically repaired.
Therefore, design synthesis has weight with the transparent flexible strain sensing composite material of similar organism self-repair function
The theory and actual application value wanted.
Summary of the invention
It is an object of the invention to overcome flexible strain sensing composite material light transmittance and self-reparing capability in the prior art
Deficiency, a kind of sunlight selfreparing transparent flexible strain sensing composite material is provided.Composite material provided by the invention has
Excellent light transmittance, it is sensitive to elongation strain response, and show linear response, when by scratch or fracture damage, under light illumination
The multiple reparation of mechanical property and electric conductivity can be achieved, and repair time is short, remediation efficiency is high.
Another object of the present invention is to provide the systems of above-mentioned sunlight selfreparing transparent flexible strain sensing composite material
Preparation Method.
Another object of the present invention is to provide above-mentioned sunlight selfreparing transparent flexible strain sensing composite materials soft
Application in property sensor.
Another object of the present invention is to provide repairing for above-mentioned sunlight selfreparing transparent flexible strain sensing composite material
Compound method.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of sunlight selfreparing transparent flexible strain sensing composite material, including polyurethane bottom and be coated in polyurethane
Metal nanometer line in substrate；The polyurethane is grouped as by the group of following parts by weight:
The present inventor passes through the study found that cystine linkage can carry out the reversible exchange of light in the polyurethane of the specific composition
Reaction.With self-repair function.In addition to this, which also has excellent light transmittance and draftability as substrate,
And metal nanometer line is coated, and obtained composite material has excellent light transmittance, and it is sensitive to elongation strain response, and show linear
Response, when by scratch or fracture damage, under light illumination, after the plane of disruption docks again, between plane of disruption polyurethane coating
Phase counterdiffusion occurs for strand, the reversible exchange reaction of cystine linkage occurs, the cystine linkage of fracture re-forms, to make material crack
It repairs, silver nanowire layer overlaps again, and then the electric conductivity and mechanical property of repair materials, and repair time is short, repairs effect
Rate is high, can repeatedly repair.
Preferably, the polyurethane is grouped as by the group of following parts by weight:
Preferably, the monomer containing cystine linkage is one or more of following structural formula compound:
Preferably, the diisocyanate monomer is one or more of following structural formula compound:
Preferably, the polyalkylene glycol monomer is polyethylene glycol 200, polyethylene glycol 400, Macrogol 600, polyethylene glycol
800, one or more of cetomacrogol 1000.
Preferably, the crosslinking agent is one or more of following structural formula compound:
Preferably, polyurethane is prepared via a method which to obtain:
S001: cystine linkage monomer, polyalkylene glycol monomer and diisocyanate monomer will be contained, polymerization reaction occurs, generated containing double
The polyurethane line style prepolymer of sulfide linkage；
S002: polyurethane line style prepolymer of the gained containing cystine linkage in S1 is reacted with crosslinking agent to get the poly- ammonia is arrived
Ester.
Preferably, the S1 reaction carries out in nitrogen, and the reaction temperature is 60 DEG C, and the reaction time of the S1 is 7
~9h；The reaction time of the S2 is 3~5h.
Preferably, the metal nanometer line is one or more of silver nanowires, nanowires of gold or copper nano-wire.
Preferably, metal nanometer line is silver nanowires, and the draw ratio of the silver nanowires is 667:1~1500:1.
Silver nanowires with more high length-diameter ratio will further promote the electric conductivity and light transmission of composite material.
The present invention provides a kind of method for preparing more high length-diameter ratio.
Preferably, the silver nanowires is reacted by the raw material of following parts by weight and is obtained:
The present invention is reacted using each reaction raw materials, and the silver nanowires of size uniformity, high length-diameter ratio can be obtained.
Preferably, the silver nanowires is prepared via a method which to obtain: using silver nitrate as presoma, polyvinylpyrrolidine
Ketone is inducer, and hydrochloric acid is controlling agent, be added polyol solvent in, after completely dissolution, at 130~180 DEG C react 12~
Silver nanowires solution is made in 16h, filters, separation, washs to get silver nanowires is arrived.
Preferably, the polyvinylpyrrolidone is PVP K-30, polyvinylpyrrolidone K-60 or poly-
One or more of vinylpyrrolidone K-90.
Preferably, the polyalcohol is one or more of ethylene glycol, propylene glycol or glycerine.
Preferably, the composite material includes polyurethane bottom, coated on the metal nanometer line on the polyurethane bottom
With another polyurethane bottom for being coated on the metal nanometer line.
The composite material is " sandwich structure " of more stability, can be made to metal nanometer line with good protection
With further promotion bending resistance and fatigue resistance performance.
The preparation method of above-mentioned sunlight selfreparing transparent flexible strain sensing composite material, includes the following steps:
S1: polyurethane solutions are poured on planar substrate, polyurethane bottom is obtained after solidification；
S2: it disperses metal nanometer line in solvent and obtains metal nanometer line dispersion liquid, by the metal nanometer line dispersion liquid
It is uniformly coated on polyurethane bottom, forms conductive network after the solvent is volatilized and obtain the sunlight selfreparing transparent flexible
Strain sensing composite material；
Or S3: it disperses metal nanometer line in solvent and obtains metal nanometer line dispersion liquid, the metal nanometer line is dispersed
Liquid is coated on planar substrate, forms conductive network after the solvent is volatilized；
S4: being coated with polyurethane solutions on the conductive network described in S3, arrives the sunlight certainly after solidification demoulding
Repair transparent flexible strain sensing composite material.
Preferably, the method for coating described in S2 or S3 is Meyer stick method, drop-coating, spray coating method or spin-coating method.
Specifically, Meyer stick method refers to by Meyer stick in planar substrate or polyurethane substrate material surface even spread one
Layer has certain thickness metal nanometer line dispersion liquid；Drop-coating refers to metal nanometer line dispersant liquid drop in planar substrate or poly-
Urethane substrate material surface, spray coating method, which refer to, to be atomized by high-pressure spray gun by metal nanometer line dispersion liquid and is injected in planar substrate
Or polyurethane substrate material surface；Spin-coating method, which refers to, is fixed on high-speed rotating platform for planar substrate or polyurethane bottom material
On, so that metal nanometer line homogeneous dispersion is dispersed in above.
Preferably, the planar substrate is glass.
Preferably, the planar substrate is using preceding carry out prerinse.
Preferably, further include the steps that being surface-treated the conductive network after S2 the or S4 step.
Surface treatment can further remove the insulation phase on metal nanometer line surface, further increase electric conductivity.
Preferably, the method for the surface treatment is plasma technology or thermal anneal process.
It is further preferable that the method for the surface treatment is plasma technology.
Plasma technology can be sintered metal nanometer line, further increase electric conductivity.
Preferably, the solvent of metal nanometer line dispersion liquid described in S2 or S3 is in ethyl alcohol, methylene chloride, isopropanol or water
One or more.
Preferably, when the composite material includes polyurethane bottom, coated on the metal nano on the polyurethane bottom
When line and another polyurethane bottom coated on the metal nanometer line, the preparation method further includes answering what S2 or S4 were obtained
Polyurethane solutions are coated on the conductive network of condensation material, the step of solidification.
Application of the above-mentioned sunlight selfreparing transparent flexible strain sensing composite material in flexible sensor is also in this hair
In bright protection scope.
The restorative procedure of above-mentioned sunlight selfreparing transparent flexible strain sensing composite material, when the composite material occurs
When scratch, by the composite material be placed under solar irradiation repair 1~for 24 hours；When the composite material is broken, alignment
The fracture of the composite material, under solar irradiation repair 1~for 24 hours.
The repair mechanisms of sunlight selfreparing transparent flexible strain sensing composite material provided by the invention are to be utilized
The reversible exchange reaction of cystine linkage light in polyurethane bottom.Under light illumination, after the plane of disruption docks again, plane of disruption polyurethane bottom
Between strand occur phase counterdiffusion, occur the reversible exchange reaction of cystine linkage, the cystine linkage of fracture re-forms, to make material
Expect crack forming mechanism, metal nanometer line layer overlaps again, and then the electric conductivity and mechanical property of repair materials.
Compared with prior art, the invention has the following beneficial effects:
Sunlight selfreparing transparent flexible strain sensing composite material provided by the invention has excellent light transmittance, to drawing
Stretching strain response is sensitive, and shows linear response, when by scratch or fracture damage, can realize mechanical property under light illumination and lead
The multiple reparation of electrical property, and repair time is short, remediation efficiency is high.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture for the silver nanowires that embodiment 4 provides；
Fig. 2 is the cross-sectional scans electromicroscopic photograph that the sandwich structure flexibility that embodiment 4 provides answers change composite material；
Fig. 3 is the light transmittance of the flexible strain sensing composite material for the sandwich structure that embodiment 4 provides；
Fig. 4 is the scratch of the silver nanowires thin polyurethane film surface for the non-sandwich structure that embodiment 4 provides by the sun
It disappears after light illumination, wherein (a) is the scratch of film surface；(b) for after sunlight irradiates 12 hours, film surface is drawn
Trace is repaired；
Fig. 5 is the stretching mechanical before and after the flexible strain sensing composite repair for the sandwich structure that embodiment 4 provides
Performance test；
Fig. 6 is that the flexible strain sensing composite material for the sandwich structure that embodiment 4 provides shows outlet to elongation strain
Property response, straight slope represents sensitivity；
Fig. 7 is the silver nanowires polyurethane film and (b) sandwich structure of (a) non-sandwich structure that embodiment 4 provides
Flexible strain sensing composite material bending resistance test.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replacement belongs to scope of the present invention.
Embodiment 1
(1) preparation of polyurethane solutions
Polyurethane is by 15~28 parts of diisocyanate monomer, 10~50 parts of polyalkylene glycol monomer, monomer containing cystine linkage 5~15
Part, 0.5~2.5 part of crosslinking agent reaction is made, specific preparation process are as follows: it is different will to contain cystine linkage monomer, polyalkylene glycol monomer and two
Polymerization reaction occurs for cyanate ester monomer, generates the polyurethane line style prepolymer containing cystine linkage；By the polyurethane line style containing cystine linkage
Prepolymer reacts to arrive the polyurethane with crosslinking agent.The preparation of polyurethane specifically refers in patent CN105669932A
Each embodiment.
In the present embodiment, weigh 9.96g isophorone diisocyanate, bis- (2- hydroxyethyl) disulfides of 3.20g and
8.00g polyethylene glycol 400 (PEG400, molecular weight 400) is dissolved in 150mL anhydrous methylene chloride, under protection of argon gas, 60 DEG C
10h is reacted, 0.2g triethanolamine is added, the reaction was continued 3h obtains polyurethane solutions.
(2) preparation of silver nanowires
1.0g silver nitrate is weighed, 1.5g polyvinylpyrrolidone (K-60) is added in 100mL ethylene glycol, is sufficiently stirred
Dissolution.It is subsequently poured into the hydrothermal reaction kettle of 250mL, 0.002g concentrated hydrochloric acid is added, is heated to 140 DEG C after mixing, instead
Answer 15h.Be cooled to room temperature after reaction, using 200~1000 mesh standard sieves separate, and with industry ethanol wash, finally divide
It dissipates in ethyl alcohol, obtains the alcohol dispersion liquid of nano-silver thread.
The present embodiment provides a kind of non-sandwich structure silver nanowires polyurethane films and the strain of sandwich structure flexibility to pass
Feel composite material.
Wherein, non-sandwich structure includes polyurethane bottom and coated in the silver nanowires on polyurethane bottom.
Sandwich structure includes polyurethane bottom, coated on the metal nanometer line on the polyurethane bottom and coated on institute
State another polyurethane bottom of metal nanometer line.In other embodiments the composition of non-sandwich structure and sandwich structure and this
It is identical.
Specific preparation process is as follows: the silver nanowires homogeneous dispersion of above-mentioned preparation being coated on cleaning using Meyer stick method
On glass plate, 100 DEG C of dry 2h obtain the glass of surface coating silver nanowires；Then polyurethane solutions are coated on silver nanoparticle
The upper layer of line, the dry vacuum drying oven for being placed on 60 DEG C that slowly volatilizees to solvent is dry for 24 hours, and it is multiple that demoulding obtains silver nanowires polyurethane
Film, Surface Treatment with Plasma 2min under argon atmosphere are closed, the silver nanowires polyurethane that can be obtained i.e. non-sandwich structure is answered
Close film；One layer of polyurethane solutions finally are poured on silver nanowires upper layer again, slowly volatilizing to solvent dry is placed on 60 DEG C true
Empty oven drying for 24 hours, obtains the flexible strain sensing composite material of sandwich structure.Non- sandwich structure silver nanowires polyurethane
Electric conductivity, the transparency and the mechanical property of film and sandwich structure flexibility strain sensing composite material are shown in Table 1.
Embodiment 2
(1) preparation of polyurethane solutions
Weigh 9.96g isophorone diisocyanate, bis- (2- hydroxyethyl) disulfides of 3.20g and 8.00g polyethylene glycol
400 (PEG400, molecular weight 400) are dissolved in 150mL anhydrous methylene chloride, and under protection of argon gas, 60 DEG C of reaction 10h are added
0.2g triethanolamine, the reaction was continued 3h obtain polyurethane solutions.
(2) preparation of silver nanowires
1.0g silver nitrate is weighed, 1.0g polyvinylpyrrolidone (K-90) is added in 100mL ethylene glycol, is sufficiently stirred
Dissolution.It is subsequently poured into the hydrothermal reaction kettle of 250mL, 0.005g concentrated hydrochloric acid is added, is heated to 140 DEG C after mixing, instead
Answer 16h.Be cooled to room temperature after reaction, using 200~1000 mesh standard sieves separate, and with industry ethanol wash, finally divide
It dissipates in methylene chloride, obtains the methylene chloride dispersion liquid of nano-silver thread.
The present embodiment provides a kind of non-sandwich structure silver nanowires polyurethane films and the strain of sandwich structure flexibility to pass
Feel composite material.
Specific preparation process is as follows: the silver nanowires homogeneous dispersion of above-mentioned preparation being coated on cleaning using Meyer stick method
On glass plate, 100 DEG C of dry 2h obtain the glass of surface coating silver nanowires；Then it will be closed according to patent CN105669932A
At polyurethane solutions be cast in and be coated in silver nanowire layer, the dry vacuum drying oven for being placed on 60 DEG C that slowly volatilizees to solvent is dry
It is dry for 24 hours, demoulding obtain silver nanowires polyurethane laminated film, Surface Treatment with Plasma 2min, can be obtained i.e. under argon atmosphere
The silver nanowires polyurethane laminated film of non-sandwich structure；One layer of polyurethane solutions finally are poured on silver nanowires upper layer again,
The dry vacuum drying oven for being placed on 60 DEG C that slowly volatilizees to solvent is dry for 24 hours, and the flexible strain sensing for obtaining sandwich structure is compound
Material.The electric conductivity of non-sandwich structure silver nanowires polyurethane film and sandwich structure flexibility strain sensing composite material,
The transparency and mechanical property are shown in Table 1.
Embodiment 3
(1) preparation of polyurethane solutions
Weigh 9.96g isophorone diisocyanate, bis- (2- hydroxyethyl) disulfides of 3.20g and 8.00g polyethylene glycol
400 (PEG400, molecular weight 400) are dissolved in 150mL anhydrous methylene chloride, and under protection of argon gas, 60 DEG C of reaction 10h are added
0.2g triethanolamine, the reaction was continued 3h obtain polyurethane solutions.
(2) preparation of silver nanowires
1.0g silver nitrate is weighed, 1.5g polyvinylpyrrolidone (K-60) is added in 100mL ethylene glycol, is sufficiently stirred
Dissolution.It is subsequently poured into the hydrothermal reaction kettle of 250mL, 0.002g concentrated hydrochloric acid is added, is heated to 140 DEG C after mixing, instead
Answer 15h.Be cooled to room temperature after reaction, using 200~1000 mesh standard sieves separate, and with industry ethanol wash, finally divide
It dissipates in ethyl alcohol, obtains the alcohol dispersion liquid of nano-silver thread.
The present embodiment provides a kind of non-sandwich structure silver nanowires polyurethane films and the strain of sandwich structure flexibility to pass
Feel composite material.
Specific preparation process is as follows: polyurethane solutions being cast in glass mold, slowly it is solvent-free to be allowed to surface for volatilization；
Then use high-pressure spray gun by the methylene chloride dispersion liquid high-pressure atomization even application of silver nanowires in thin polyurethane film surface, and
Surface solvent is set to volatilize naturally dry, continuation is dry for 24 hours in 60 DEG C of vacuum drying ovens, and it is poly- to obtain silver nanowires for demoulding after being cooled to room temperature
Urethane laminated film, Surface Treatment with Plasma 3min under argon atmosphere, the silver nanowires that can be obtained i.e. non-sandwich structure are poly-
Urethane laminated film；One layer of polyurethane solutions finally are poured on silver nanowires upper layer again, slowly volatilizing to solvent dry is placed on 60
DEG C vacuum drying oven it is dry for 24 hours, obtain the flexible strain sensing composite material of sandwich structure.Non- sandwich structure silver nanowires
Electric conductivity, the transparency and the mechanical property of polyurethane film and sandwich structure flexibility strain sensing composite material are shown in Table 1.
Embodiment 4
(1) preparation of polyurethane solutions
Weigh 9.96g isophorone diisocyanate, bis- (2- hydroxyethyl) disulfides of 3.20g and 8.00g polyethylene glycol
400 (PEG400, molecular weight 400) are dissolved in 150mL anhydrous methylene chloride, and under protection of argon gas, 60 DEG C of reaction 10h are added
0.2g triethanolamine, the reaction was continued 3h obtain polyurethane solutions.
(2) preparation of silver nanowires
1.0g silver nitrate is weighed, 1.0g polyvinylpyrrolidone (K-90) is added in 100mL ethylene glycol, is sufficiently stirred
Dissolution.It is subsequently poured into the hydrothermal reaction kettle of 250mL, 0.005g concentrated hydrochloric acid is added, is heated to 140 DEG C after mixing, instead
Answer 16h.Be cooled to room temperature after reaction, using 200~1000 mesh standard sieves separate, and with industry ethanol wash, finally divide
It dissipates in methylene chloride, obtains the methylene chloride dispersion liquid of nano-silver thread.
The present embodiment provides a kind of non-sandwich structure silver nanowires polyurethane films and the strain of sandwich structure flexibility to pass
Feel composite material.
Specific preparation process is as follows: polyurethane solutions being cast in glass mold, slowly it is solvent-free to be allowed to surface for volatilization；
Then use high-pressure spray gun by the methylene chloride dispersion liquid high-pressure atomization even application of silver nanowires in thin polyurethane film surface, and
Surface solvent is set to volatilize naturally dry, continuation is dry for 24 hours in 60 DEG C of vacuum drying ovens, and it is poly- to obtain silver nanowires for demoulding after being cooled to room temperature
Urethane laminated film, Surface Treatment with Plasma 3min under argon atmosphere, the silver nanowires that can be obtained i.e. non-sandwich structure are poly-
Urethane laminated film；One layer of polyurethane solutions finally are poured on silver nanowires upper layer again, slowly volatilizing to solvent dry is placed on 60
DEG C vacuum drying oven it is dry for 24 hours, obtain the flexible strain sensing composite material of sandwich structure.Non- sandwich structure silver nanowires
Electric conductivity, the transparency and the mechanical property of polyurethane film and sandwich structure flexibility strain sensing composite material are shown in Table 1.
Following performance test is carried out to Examples 1 to 4:
(1) cross section of silver nanowires pattern and flexible strain sensing composite material sandwich structure passes through Japan
Hitachi S-4800 type scanning electron microscope carries out morphology observation.
(2) composite material light transmittance is tested by 750 ultraviolet-visible spectrophotometer of PerkinElmer-Lambda,
With the transparency of the transmitance characterization composite material at 550nm.
(3) the silver nanowires polyurethane laminated film surface of non-sandwich structure manufactures scratch using Ultrathin blade, too
Sunlight shines lower reparation 1-24h, and scratch disappears, and electric property restores.Pass through Japanese Hitachi S-4800 type scanning electron microscopy
Mirror is observed.Its film resistor for repairing front and back is shown using the method for four probes by ST-2258A digital multi simultaneously
Instrument measures, and electric conductivity remediation efficiency is calculated, the results are shown in Table 2.
(4) the flexible strain sensing composite material of sandwich structure is cut off using Ultrathin blade, after being aligned fracture, in the sun
1-24h is repaired under illumination, the mechanical property and electric property of material are restored.Test its mechanical property for repairing front and back and electricity
Performance is learned, the remediation efficiency of mechanical property and electric conductivity is calculated, the results are shown in Table 2.
The remediation efficiency of mechanical property carries out quantitatively characterizing: the remediation efficiency (η of mechanical property with the following methodT) definition
Tensile strength (σ after being repaired for materialHealed) and material green tensile intensity (σvirgin) ratio, it may be assumed that
ηT=σHealed/σvirgin
In formula: σHealedTo repair post-tensioning intensity, σvirginFor green tensile intensity.
Electric conductivity remediation efficiency (ηC) be defined as material repair after sheet resistance or resistance and it is impaired when sheet resistance or resistance
Difference (RCrack-RHealed) with the original sheet resistance of material or resistance and it is impaired when sheet resistance or resistance difference (RCrack-Rvirgin) ratio
Value, it may be assumed that
ηC=(RCrack-RHealed)/(RCrack-Rvirgin)
In formula: Rvirgin、RCrackAnd RHealedRespectively the original sheet resistance of material or resistance, it is impaired when sheet resistance or resistance and repair
Sheet resistance or resistance after multiple.
The non-sandwich structure silver nanowires polyurethane film of table 1 and sandwich structure flexibility strain sensing composite material are led
Electrically, the transparency and mechanical property
The electric conductivity self-repair efficiency and sandwich structure of the non-sandwich structure silver nanowires polyurethane film of table 2 are flexible
The mechanical property and electric conductivity selfreparing remediation efficiency of strain sensing composite material compare
2 result of consolidated statement, it can be deduced that, transparent flexible strain sensing composite material provided by the present invention shines in light at room temperature
Under can be achieved with selfreparing, remediation efficiency is high, and same area has multiplicating repair ability.In addition, sandwich structure
Flexible strain sensing composite material has higher electric conductivity compared to the silver nanowires polyurethane film of non-sandwich structure
Remediation efficiency, and remediation efficiency variation is smaller three times, can weaken even to be eliminated this is mainly due to stable sandwich structure and split
The layering of caused crackle two sides silver nanowires, is conducive to the overlap joint again of silver nanowires when line generates, to restore conductive logical
Road.Meanwhile it can be seen from figure 7 that compared to non-sandwich structure silver nanowires polyurethane film, sandwich structure it is soft
Property strain sensing composite material when recycling bend test, not only have the longer service life resistant to bending, and increased resistance value compared with
Small, this also illustrates that sandwich structure has good protective effect to silver nanowires conductive network from another point of view.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of sunlight selfreparing transparent flexible strain sensing composite material, which is characterized in that including polyurethane bottom and painting
Overlay on the metal nanometer line on polyurethane bottom；The polyurethane is grouped as by the group of following parts by weight:
15 ~ 28 parts of diisocyanate monomer
10 ~ 50 parts of polyalkylene glycol monomer
5 ~ 15 parts of monomer containing cystine linkage
0.5 ~ 2.5 part of crosslinking agent.
2. sunlight selfreparing transparent flexible strain sensing composite material according to claim 1, which is characterized in that the gold
Category nano wire is one or more of silver nanowires, nanowires of gold or copper nano-wire.
3. sunlight selfreparing transparent flexible strain sensing composite material according to claim 2, which is characterized in that the gold
Category nano wire is silver nanowires, and the draw ratio of the silver nanowires is 667:1 ~ 1500:1.
4. sunlight selfreparing transparent flexible strain sensing composite material according to claim 3, which is characterized in that the silver
Nano wire is reacted by the raw material of following parts by weight to be obtained:
1 ~ 5 part of silver nitrate
1 ~ 5 part of polyvinylpyrrolidone
0.001 ~ 0.05 part of hydrochloric acid
50 ~ 200 parts of polyalcohol.
5. sunlight selfreparing transparent flexible strain sensing composite material according to claim 4, which is characterized in that the silver
Nano wire is prepared via a method which to obtain: using silver nitrate as presoma, polyvinylpyrrolidone is inducer, and hydrochloric acid is control
Agent is added in polyol solvent, after completely dissolution, 12 ~ 16h is reacted at 130 ~ 180 DEG C, silver nanowires solution is made, filtered,
Separation is washed to get silver nanowires is arrived.
6. sunlight selfreparing transparent flexible strain sensing composite material according to claim 1, which is characterized in that described multiple
Condensation material includes polyurethane bottom, coated on the metal nanometer line on the polyurethane bottom and coated on the metal nanometer line
Another polyurethane bottom.
7. the preparation method of any sunlight selfreparing transparent flexible strain sensing composite material of claim 1 ~ 6, special
Sign is, includes the following steps:
S1: polyurethane solutions are poured on planar substrate, polyurethane bottom is obtained after solidification；
S2: it disperses metal nanometer line in solvent and obtains metal nanometer line dispersion liquid, by the metal nanometer line homogeneous dispersion
It is coated on polyurethane bottom, forms conductive network after the solvent is volatilized and obtain the sunlight selfreparing transparent flexible strain
Sensing composite material；
Or S3: dispersing metal nanometer line in solvent and obtain metal nanometer line dispersion liquid, and the metal nanometer line dispersion liquid is applied
It is distributed on planar substrate, forms conductive network after the solvent is volatilized；
S4: polyurethane solutions are coated on the conductive network described in S3, to get transparent to the sunlight selfreparing after solidification demoulding
Flexible strain sensing composite material.
8. preparation method according to claim 7, which is characterized in that when the composite material includes polyurethane bottom, coating
In the metal nanometer line on the polyurethane bottom and when coated on another polyurethane bottom of the metal nanometer line, the system
The step of Preparation Method further includes that polyurethane solutions are coated on the conductive network of the composite material obtained to S2 or S4, solidification.
9. any sunlight selfreparing transparent flexible strain sensing composite material of claim 1 ~ 6 is in flexible sensor
Using.
10. the restorative procedure of any sunlight selfreparing transparent flexible strain sensing composite material of claim 1 ~ 6, special
Sign is, when there is scratch in the composite material, by the composite material be placed under solar irradiation repair 1 ~ for 24 hours；Work as institute
When stating composite material and being broken, it is aligned the fracture of the composite material, repair 1 under solar irradiation ~ for 24 hours.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105532A (en) * | 2019-05-05 | 2019-08-09 | 湖北三江航天江河化工科技有限公司 | Thermoplasticity selfreparing polyurethane resin and preparation method thereof for 3D printing composite material |
| CN110498895A (en) * | 2019-08-05 | 2019-11-26 | 南京理工大学 | Poly- (urea-urethane) selfreparing elastomer of tridimensional network and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860013A (en) * | 2016-06-28 | 2016-08-17 | 朱弟 | Preparation method of polyurethane/silica nanowire composite material |
| CN106336669A (en) * | 2016-09-14 | 2017-01-18 | 中山大学 | Silicone sealant polymer capable of self-repairing and being recycled by virtue of sunlight as well as preparation method and application of silicone sealant polymer |
| CN106674998A (en) * | 2017-01-05 | 2017-05-17 | 广东工业大学 | Shape memory-based multi-stimulated sensing conductive polymer material and preparation method and application thereof |
| CN107216643A (en) * | 2017-08-03 | 2017-09-29 | 四川大学 | A kind of selfreparing polyurethane nano composite material and its production and use |
| CN107805314A (en) * | 2017-10-14 | 2018-03-16 | 深圳赢特科技有限公司 | A kind of antireflecting coating based on nano silver wire and preparation method thereof |
-
2018
- 2018-08-06 CN CN201810887218.1A patent/CN109265643A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860013A (en) * | 2016-06-28 | 2016-08-17 | 朱弟 | Preparation method of polyurethane/silica nanowire composite material |
| CN106336669A (en) * | 2016-09-14 | 2017-01-18 | 中山大学 | Silicone sealant polymer capable of self-repairing and being recycled by virtue of sunlight as well as preparation method and application of silicone sealant polymer |
| CN106674998A (en) * | 2017-01-05 | 2017-05-17 | 广东工业大学 | Shape memory-based multi-stimulated sensing conductive polymer material and preparation method and application thereof |
| CN107216643A (en) * | 2017-08-03 | 2017-09-29 | 四川大学 | A kind of selfreparing polyurethane nano composite material and its production and use |
| CN107805314A (en) * | 2017-10-14 | 2018-03-16 | 深圳赢特科技有限公司 | A kind of antireflecting coating based on nano silver wire and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 容敏智 等: "太阳光诱导本征型自修复聚氨酯及其导电复合材料", 《2017全国高分子学术论文报告会》 * |
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