CN106519939A - Self-repairing type conductive sensing high polymer material based on shape memory - Google Patents
Self-repairing type conductive sensing high polymer material based on shape memory Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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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
- C08J2327/00—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
- C08J2327/02—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
- 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
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention relates to the field of shape memory high polymer composites and conductive materials, in particular to a self-repairing type conductive sensing high polymer material based on shape memory. The material is prepared from a conductive material such as a metal nanowire, nanopowder, a carbon nano tube, graphene and carbon powder with a conductive network structure and a self-repairing material or a shape memory material such as polyurethane.
Description
Technical field
The present invention relates to shape memory macromolecule composite material and conductive material field, and in particular to a kind of to be remembered based on shape
Application of the self-repair type conductive sensor macromolecular material and the material recalled in terms of conductive sensor, such as smart mobile phone, it is convenient
The intellectual material application such as sensor of the flexibility of formula.
Background introduction
Material plays an important role for the production and life of the mankind.The development of science and technology has promoted mankind society
Can continuous progress, at the same time, people for the requirement more and more higher of material, therefore, various new materials arise at the historic moment, intelligence
Energy material is wherein important one kind, is with a wide range of applications.Used as the Typical Representative of new material, intellectual material is opened
Mankind's design is created and using the New Times of material.So-called intellectual material is that the external environment that itself can be perceived residing for which occurs
Change, and a class material of corresponding instantaneous active reaction is made to the change.It is simply that have OBD, from
A series of a kind of material of specific functions such as my adaptation, self-regeneration.Conventional intellectual material has automatically cleaning and self-repair material,
Magnetostriction materials, piezoelectric, marmem and shape-memory polymer etc.
Earliest shape-memory polymer (Shape Memory Polymer, abbreviation SMP) is the coalification of France in the world
(CDF-Chimie) polynorbornene that company succeeds in developing for 1984, Japan synthesized the poly- ammonia of shape memory in 1988, its
Its shape-memory polymer also have crosslinked polyethylene, ethylene-vinyl acetate copolymer, polycaprolactone, poly- fluoroolefin and trans-
1,4- polyisoprene etc..Compared with other shapes memory polymer, shape memory polyurethane (SMPU) has weatherability strong, anti-
Pinking is good, the features such as repeat good deformation effects, light refraction and excellent moisture vapor permeability, in engineering construction, clothes, health care
And the application potential of the aspect such as daily life is huge.Shape-memory polymer (Shape Memory Polymer) refers to one
Plant with original shape, after under the effect of certain external condition, deformation is fixed, by the outside stimulus such as heat, electricity, magnetic, light, can
Reply the polymer of its original shapes.Representative document has：Hayashi S etc. are by the heating power credit to SMPU and general SMP
Analysis (TMA) contrast, it is found which is different from general SMP, SMPU the upper and lower coefficient of expansion of shape memory temperature ratio up to 5～10.
Can be with preparation temperature sensor using this property.For example can be used for manufacturing the attachment means of fire-alarm, when first making connection
Shape, then post forming be disconnect when shape；When fire occurs, connector resiles automatically and makes circuit break
Open, alarm is just started working.
Self-repair material is a kind of new material that can carry out self-regeneration in object damage.This material is noted
Enter in high molecular polymer, when object is scratched, the material of injection can discharge the object to being damaged under multiple stimulation
Automatically repaired on surface.Conventional selfreparing mechanism includes microcapsule method, and representative document has：University of Illinois
White is applied to microcapsules selfreparing matrix in epoxide resin material, and he is coated on renovation agent dicyclopentadiene (DCPD)
In urea-formaldehyde resin microcapsule, and catalyst is dispersed in epoxy resin-base material, when matrix material occurs to damage, is caused micro-
There is rupture in capsule, renovation agent is released to the plane of disruption, meet generation polymerisation with catalyst, so as to repair the plane of disruption；Again
Such as reacted using the Diels-Alder of thermal reversion, representational document has：Chen etc. prepared it is a kind of have review one's lessons by oneself reactivation
The highly cross-linked polymer composites of power, under conditions of 120 DEG C of heating, crosslinking points therein break this composite
Open, but crosslinking points are after the cooling period, can re-close to form new chemical bond again, so as to repair crack face.Shape memory from
Reparation is the P.T in the U.S. in 2011
What Mather was proposed, over nearly 5 years, huge development is obtained based on the selfreparing of shape memory, it is considered to be the
Three generations's self-healing system.
Self-repair function based on shape memory is deepened continuously research, however, also less high with the sensing of compliant conductive
Molecule combines.Data in terms of wearable electronic, flexible sensing device.As recently, Beijing University of Chemical Technology Sun Xiao is bright
Professor, associate professor Wan Pengbo and Nanyang Technological University Chen Xiaodong professors, Shenzhen University professor Zhang Han etc. cooperate, in institute's structure
On the basis of the series of tasks such as flexible, transparent, the selfreparing thin film sensor built, looked back in recent years based on half comprehensive system
The flexibility of the material constructions such as conductor nano material, material with carbon element, Conductive polymers, transparent gas sensor；System summary is lifted
The flexible, transparency, the strategy of sensing capabilities, the assembling mode of control, material including sensing material pattern, the uniform of film sink
Product, selection and optimization of substrate etc.；Propose the existing flexible, deficiency of clear sensor, such as organic volatilization gas specificity
Quick detection is difficult, practical application when wearable property sensitive to environmental change, portable and signal radio transmission performance it is not good enough etc.；And open up
Flexibility towards wearable device, the further developing direction of clear sensor is hoped, has such as further been realized and is improved various
Gas is simultaneously detected, the environmental stability of sensing, the Multifunctional centralized of portable wearable device become second nature, the miniaturization of sensor and biography
Sense signal is wirelessly transferred integration etc. to equipment such as Ipad, mobile phone, Watch classes.This will be flexible, transparent, wearable for future
The development of gas sensor provides new Research Thinking and theoretical foundation.
Flexible material referred to herein, while contain selfreparing intelligent attributes and the electrical-conductive nanometer high score of shape memory
The strain of son relies on (strain-dependent) performance, final to obtain with new multifunctional sensing macromolecule.
The content of the invention
The purpose of the present invention is for the deficiencies in the prior art, there is provided a kind of self-repair type based on shape memory is conductive to be passed
Sense macromolecular material and preparation method thereof.
Concrete grammar of the present invention is as follows：
A kind of self-repair type conductive sensor macromolecular material based on shape memory, including the raw material of following mass percent
It is prepared from：
1. conductive material, consumption is 0.5%-1.5%.
2. self-repair material, consumption is 35%-45%.
3. shape-memory material, consumption is 53.5%-64.5%.
The preparation method of the above-mentioned self-repair type conductive sensor macromolecular material based on shape memory, comprises the steps：
1. conductive material is dissolved in solvent orange 2 A, is stirred and ultrasound a period of time.By its drop coating on matrix, dry
It is put in Muffle furnace that 24h obtains conducting film at 200 DEG C to after conducting film or drying.
2. self-repair material is dissolved in solvent B.Heating stirring ultrasound a period of time, make solution uniform.
3. shape-memory material is dissolved in solvent C.Heating stirring ultrasound a period of time, make solution uniform.
4. self-repair material solution and shape-memory material solution are blended in different proportions and ultrasound is uniform.Drop coating or
It is spin-coated on the conducting film of above-mentioned steps 1.Be placed in vacuum drying chamber first heating a period of time at 70-80 DEG C again, after take out
Vacuum 24h obtains composite membrane, i.e. the self-repair type conductive sensor macromolecular material based on shape memory.
Described conductive material is nano silver wire, CNT, graphene oxide, nano-Ag particles etc., solvent orange 2 A used
Including but not limited to ethanol, water etc.；Described self-repair material is pla-pcl (PCL).
And shape-memory material includes but is not limited to elastic epoxy macromolecule, shape memory polyurethane (SMPU) or elasticity
Siloxanes macromolecule, used solvent B and C is DMA, DMF, tetrahydrofuran etc..
Described matrix is polytetrafluoroethylene (PTFE), slide etc..Above-mentioned self-repair material solution and shape-memory material solution
Mixed proportion is 2-8:10.
The conductive flexible multifunctional material damage rehabilitation method of above-mentioned selfreparing：Keep 60-100 DEG C of scope of material or electricity
The modes such as triggering, near-infrared, can repair after 1-20min.
Compared with prior art, the method have the advantages that：
The present invention is prepared for a kind of self-repair type conductive sensor macromolecular material based on shape memory, its preparation method compared with
It is simple, resulting composite on the basis of shape-memory properties, while have conduction and certain self-healing properties, this
Kind of conductive and selfreparing be greatly improved in terms of intellectual material using and service life growth and increase the utilization in terms of sensing.
Special appearance increased mechanical property simultaneously.
Description of the drawings
Fig. 1 composites prepare schematic diagram
The surface texture of Fig. 2 conductive layers/SMPU/PCL composites
Wherein the surface of (a) for composite, is (b) section of composite
The self-healing properties of Fig. 3 conductive layers/SMPU/PCL composites
Wherein (a) is the composite that the composite (b) for scratching is selfreparing
Specific embodiment
In order that the technological means of the present invention, creation characteristic, reached purpose are readily apparent from effect, below by specific
Embodiment is described in further detail to the present invention.It is necessary to note that embodiment once is protection scope of the present invention.
Embodiment 1
1. nano silver wire 0.8-1.2mg is dissolved in ethanol solution, is stirred and ultrasound 10-20s.By its drop coating in matrix
On.And drying obtains conducting film.
2. self-repair material PCL is configured to concentration for 100mg/ml in being dissolved in DMAC N,N' dimethyl acetamide (DMAC).Plus
Thermal agitation ultrasound a period of time, make solution uniform.
3. shape memory polyurethane SMPU is dissolved in N, is configured to concentration for 100mg/ in N dimethyl acetamide (DMAC)
ml.Heating stirring ultrasound a period of time, make solution uniform.
4. by self-repair material solution and shape memory polyurethane solution with PCL:SMPU=6:The blending of 10 ratios ultrasound
Uniformly.Drop coating is on the conducting film of above-mentioned steps 1.Be placed in vacuum drying chamber and first heat 2-3h at 80 DEG C, after vacuumize
24h obtains composite membrane, i.e. the self-repair type conductive sensor macromolecular material based on shape memory.
The composite membrane repair time for obtaining and temperature are 10-20min and 60-100 degree.Conductive structure repairing effect exists
40%-80%.
Embodiment 2
1. the CNT of 10-20mg is dissolved in ethanol solution, is stirred and ultrasound 10-20s.By its drop coating in matrix
On.And drying obtains conducting film.
2. self-repair material PCL is configured to concentration for 100mg/ml in being dissolved in DMAC N,N' dimethyl acetamide (DMAC).Plus
Thermal agitation ultrasound a period of time, make solution uniform.
3. shape memory polyurethane SMPU is dissolved in N, is configured to concentration for 100mg/ in N dimethyl acetamide (DMAC)
ml.Heating stirring ultrasound a period of time, make solution uniform.
4. by self-repair material solution and shape memory polyurethane solution with PCL:SMPU=6:10 ratios are blended and surpass
Sound is uniform.Drop coating is on the conducting film of above-mentioned steps 1.Be placed in vacuum drying chamber and first heat 2-3h at 80 DEG C, after take out true
Empty 24h obtains composite membrane, the self-repair type conductive sensor macromolecular material based on shape memory.
The composite membrane repair time for obtaining and temperature are 10-20min and 60-100 degree.Conductive structure repairing effect exists
40%-80%.
Embodiment 3
1. by graphene oxide and CNT in varing proportions such as (0:10,1:9,2:8,3:7) so that gross mass is
10mg is dissolved in ethanol solution, is stirred and ultrasound 10-20s.By its drop coating on matrix.And dry.After be put in Muffle furnace
At 200 DEG C, 24h obtains conducting film.
2. self-repair material PCL is configured to concentration for 100mg/ml in being dissolved in DMAC N,N' dimethyl acetamide (DMAC).Plus
Thermal agitation ultrasound a period of time, make solution uniform.
3. shape memory polyurethane SMPU is dissolved in N, is configured to concentration for 100mg/ in N dimethyl acetamide (DMAC)
ml.Heating stirring ultrasound a period of time, make solution uniform.
4. by self-repair material solution and shape memory polyurethane solution with PCL:SMPU=6:The blending of 10 ratios ultrasound
Uniformly.Drop coating is on the conducting film of above-mentioned steps 1.Be placed in vacuum drying chamber and first heat 2-3h at 80 DEG C, after vacuumize
24h, obtains composite membrane, i.e. the self-repair type conductive sensor macromolecular material based on shape memory.
The repair time of its composite membrane and temperature are 10-20min and 60-100 degree.Conductive structure repairing effect is in 40%-
80%.
Embodiment 4
1. graphene oxide 8-20mg is dissolved in ethanol solution, 10min rotating speeds after stirring ultrasound 30min, are centrifuged
10000 turns, remove upper strata impurity.Afterwards by its drop coating on matrix such as (polytetrafluoroethylene (PTFE), slide etc.).And dry.After be put into
In Muffle furnace, at 200 DEG C, 24h obtains conducting film.
2. self-repair material PCL is configured to concentration for 100mg/ml in being dissolved in DMAC N,N' dimethyl acetamide (DMAC).Plus
Thermal agitation ultrasound a period of time, make solution uniform.
3. shape memory polyurethane SMPU is dissolved in N, is configured to concentration for 100mg/ in N dimethyl acetamide (DMAC)
ml.Heating stirring ultrasound a period of time, make solution uniform.
4. by self-repair material solution and shape memory polyurethane solution in different proportions with PCL:SMPU=6:10 ratios
Example blending is simultaneously ultrasonic uniform.Drop coating is on the conducting film of above-mentioned steps 1.First 2- is heated at 80 DEG C in being placed on vacuum drying chamber
3h, after vacuumize 24h, obtain composite membrane, i.e. the self-repair type conductive sensor macromolecular material based on shape memory.
The repair time of its composite membrane and temperature are 10-20min and 60-100 degree.Conductive structure repairing effect is in 40%-
80%.
Embodiment 5
1. nano-Ag particles 0.8-2mg is dissolved in ethanol solution, is stirred and ultrasound 10-20s.By its drop coating in matrix
On.And dry.
2. self-repair material PCL is configured to concentration for 100mg/ml in being dissolved in DMAC N,N' dimethyl acetamide (DMAC).Plus
Thermal agitation ultrasound a period of time, make solution uniform.
3. shape memory polyurethane SMPU is dissolved in N, is configured to concentration for 100mg/ in N dimethyl acetamide (DMAC)
ml.Heating stirring ultrasound a period of time, make solution uniform.
4. self-repair material solution and shape memory polyurethane solution are blended in different proportions with PCL:SMPU=6:
10 ratios are simultaneously ultrasonic uniform.Drop coating is on the conducting film of above-mentioned steps 1.First 2- is heated at 80 DEG C in being placed on vacuum drying chamber
3h, after vacuumize 24h, obtain composite membrane, i.e. the self-repair type conductive sensor macromolecular material based on shape memory.
The repair time of its composite membrane and temperature are 10-20min and 60-100 degree.Conductive structure repairing effect is in 60%-
80%.
Embodiment 6
1. by nano-silver thread and CNT with 1:9 are dissolved in ethanol solution, and the two consumption summation is 10mg, and stirring is simultaneously
Ultrasonic 10-20s.By its drop coating on matrix.And dry.
2. self-repair material PCL is configured to concentration for 100mg/ml in being dissolved in DMAC N,N' dimethyl acetamide (DMAC).Plus
Thermal agitation ultrasound a period of time, make solution uniform.
3. shape memory polyurethane SMPU is dissolved in N, is configured to concentration for 100mg/ in N dimethyl acetamide (DMAC)
ml.Heating stirring ultrasound a period of time, make solution uniform.
4. self-repair material solution and shape memory polyurethane solution are blended in different proportions with PCL:SMPU=6:
10 ratios are simultaneously ultrasonic uniform.Drop coating is on the conducting film of above-mentioned steps 1.First 2- is heated at 80 DEG C in being placed on vacuum drying chamber
3h, after vacuumize 24h, obtain composite membrane, i.e. the self-repair type conductive sensor macromolecular material based on shape memory.
The repair time of its composite membrane and temperature are 10-20min and 60-100 degree.Conductive structure repairing effect is in 40%-
80%.
Claims (8)
1. a kind of self-repair type conductive sensor macromolecular material based on shape memory, including following components and mass percent
Raw material is prepared from：
Conductive material, consumption are 0.5%-1.5%,
Self-repair material, consumption are 35%-45%,
Shape-memory material, consumption are 53.5%-64.5%,
The above-mentioned self-repair type conductive sensor macromolecular material based on shape memory, comprises the steps：
Conductive material is dissolved in solvent orange 2 A, is stirred and ultrasound a period of time, by its drop coating on matrix, and drying is led
At being put into 200 DEG C in Muffle furnace after electrolemma or drying, 24h obtains conducting film；
Self-repair material is dissolved in solvent B, simultaneously ultrasound for a period of time, makes solution uniform to heating stirring；
Shape-memory material is dissolved in solvent C, simultaneously ultrasound for a period of time, makes solution uniform to heating stirring；
Self-repair material solution and shape-memory material solution are blended in certain proportion and ultrasound is uniform, drop coating or be spin-coated on
On conducting film；
Be placed in vacuum drying chamber first heating a period of time at 70-80 DEG C, after vacuumize 24h and obtain composite membrane, that is, be based on
The self-repair type conductive sensor macromolecular material of shape memory.
2. a kind of self-repair type conductive sensor macromolecular material based on shape memory as claimed in claim 1, its feature exist
In, conductive material be nano silver wire, CNT, graphene oxide, nano-Ag particles.
3. a kind of self-repair type conductive sensor macromolecular material based on shape memory as claimed in claim 1, its feature exist
In described self-repair material is pla-pcl.
4. a kind of self-repair type conductive sensor macromolecular material based on shape memory as claimed in claim 1, its feature exist
In siloxanes high score of the shape-memory material for elastic epoxy macromolecule, shape memory polyurethane (SMPU) or elasticity
Son.
5. a kind of self-repair type conductive sensor macromolecular material based on shape memory as claimed in claim 1, its feature exist
In solvent orange 2 A used includes but is not limited to ethanol, water.
6. a kind of self-repair type conductive sensor macromolecular material based on shape memory as claimed in claim 1, its feature exist
In solvent B and C are DMAs, DMF, tetrahydrofuran.
7. a kind of self-repair type conductive sensor macromolecular material based on shape memory as claimed in claim 1, its feature exist
In the mixed proportion of self-repair material solution and shape-memory material solution is 2-8:10.
8. a kind of self-repair type conductive sensor macromolecular material based on shape memory as claimed in claim 1, its feature exist
In its damage rehabilitation method can be repaired after 1-20min for keeping 60-100 DEG C of scope of material or electricity triggering, near-infrared.
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| CN109735094A (en) * | 2019-01-11 | 2019-05-10 | 四川大学 | A kind of nitrogen phosphorus silicon is grapheme modified/preparation method of selfreparing polyurethane flame-proof composite material |
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| CN111205631A (en) * | 2020-02-28 | 2020-05-29 | 青岛科技大学 | Self-repairing polyurethane elastomer by electric heating and preparation method thereof |
| CN111564237B (en) * | 2020-05-21 | 2021-02-02 | 电子科技大学中山学院 | Preparation method of near-infrared thermal-repair flexible conductive film |
| CN112700908A (en) * | 2020-12-16 | 2021-04-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Intelligent composite material and preparation method and application thereof |
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