CN110256760A - Reversible shape memory material with photoelectric respone and its preparation method and application - Google Patents
Reversible shape memory material with photoelectric respone and its preparation method and application Download PDFInfo
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- CN110256760A CN110256760A CN201910540387.2A CN201910540387A CN110256760A CN 110256760 A CN110256760 A CN 110256760A CN 201910540387 A CN201910540387 A CN 201910540387A CN 110256760 A CN110256760 A CN 110256760A
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/041—Carbon nanotubes
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Abstract
The present invention relates to functional polymer materials, and in particular to a kind of reversible shape memory material of double-response characteristic and its preparation method and application with electricity and light.The present invention provides a kind of reversible shape memory material with photoelectricity double-response characteristic, the material is the polymer base conductive composite material with isolation structure, wherein, the polymer is the semi-crystalline polymer with wide melting range, melting range silicon carbide >=20 DEG C of the i.e. described polymer, melting range silicon carbide=end melting temperatur-initial melting temperature.For the present invention by the way that simultaneously the reversible shape memory material of the double-response characteristic with electricity and light can be prepared in cooling and shaping with figuration through hot press molding again after physical blending, preparation method is simple；The isolation structure of conductive filler is constructed in material internal to obtain excellent electric conductivity；The conductive filler of isolation network will not influence the movement of reversible shape memory polymer strand, so that it is still able to maintain excellent driveability as driver.
Description
Technical field
The present invention relates to functional polymer materials, and in particular to a kind of reversible shape of the double-response characteristic with electricity and light
Shape memory material and its preparation method and application.
Background technique
It is rapidly developed instantly in artificial intelligence robot, environmental stimuli (heat, light, electricity etc.) can be converted to mechanic
The driver of work has received widespread attention.Bidirectional shape memory polymer (RSMP) is can to change that shape is presented by temperature
The intellectual material of variation, and RSMP have such as low-density, low energy consumption and excellent machinability the advantages of, present its
The application potential of field of drivers.And traditional RSMP can only respond the variation of environment temperature, this is just largely limited
Its application.Filler network is constructed in RSMP to increase it to the response of light and electricity and can further expand the application of RSMP.
Currently used for prepare electrically driven (operated) shape-memory polymer be usually conductive filler is introduced directly into be blended, although
This can actually realize electric drive, but there are many limitations: (1) Yao Shixian polymer draws from the transformation of insulator electrical conductor needs
Enter a large amount of filler, and needs to drive at higher voltages；(2) presence of mass filler will affect polymer molecule
The locomitivity of chain is to reduce the shape-memory properties of RSMP.
Summary of the invention
In view of the foregoing drawbacks, the present invention provide a kind of reversible shape memory material with light and electric double-response characteristic and
Preparation method and application, resulting materials can respond electricity and light stimulus simultaneously, that is, have light and electric double-response characteristic, and gained
Material has excellent driveability；And the preparation process of the material is simple.
Technical solution of the present invention:
The invention solves first technical problem be to provide a kind of reversible shape with photoelectricity double-response characteristic
Memory material, the material are the polymer base conductive composite material with isolation structure, wherein the polymer is with width
The semi-crystalline polymer of melting range, i.e., melting range silicon carbide >=20 DEG C of the described polymer, melting range silicon carbide=end melting temperatur-incipient melting
Temperature.
I.e. polymer selected by the present invention is wide melting range polymer (i.e. melting range silicon carbide >=20 DEG C)；Melting range refers to substance
Fusing point is not a point, but a temperature range, referred to as melting range section, and two limits are referred to as initial melting temperature and eventually molten temperature
Degree, initial melting temperature, that is, substance start the temperature of melting, the temperature that whole melting temperatur, that is, substance melts completely.
Further, the isolation structure refers to: polymer base conductive composite material is prepared by polymeric matrix and conductive filler
It forms, wherein conductive filler is on the interface between polymeric matrix, rather than random alignment in a polymer matrix.
Further, the polymeric matrix in the above-mentioned reversible shape memory material with photoelectricity double-response characteristic is tool
There is the semi-crystalline polymer in 20 DEG C or more wide melting range sections.
Further, the polymeric matrix are as follows: ethylene-octene copolymer (POE) or ethylene-vinyl acetate copolymer
At least one of (EVA).
The conductive filler is at least one of carbon black, carbon nanotube, graphene or the short fibre of carbon fiber；It is led in the present invention
Electric filler selects any one in the filler that composite material can be made to have energization joule heat effect and photo-thermal effect
Or at least two mixture.
Preferably, in the above-mentioned reversible shape memory material with photoelectricity double-response characteristic, the polymeric matrix is
Ethylene-octene copolymer, the conductive filler are carbon nanotube, the proportion of polymeric matrix and conductive filler are as follows: ethylene-octene
00 parts by volume of copolymer 1,0.1~6 parts by volume of conductive filler.
The invention solves second technical problems to be to provide a kind of reversible shape note with photoelectricity double-response characteristic
Recall the preparation method of material, the preparation method is that: polymer base particles and conductive filler are first made into conduction through physical blending
Filler is coated on polymer base particles surface, then passes through the hot-forming boundary for making conductive filler be fixed on polymer base particles
Between face, the composite material with isolation structure is obtained；Then gained composite material is subjected to figuration and cooling and shaping is had
There is the reversible shape memory material of photoelectricity double-response characteristic.
Further, the partial size of the polymer base particles is at 50~2000 μm, and preferably 200~600 μm.
Further, the mode of the physical blending are as follows: one of ball milling, grinding or high-speed stirred mixing.
Further, the hot-forming first temperature or more of melting in polymeric matrix thermally decomposes the following progress of indexing；Gained
The figuration of composite material carries out at a temperature of the end of polymeric matrix melts 3~20 DEG C of temperature or less.
Further, the method that figuration uses stationary fixture clamping.
The invention solves third technical problem be to point out: it is obtained above with photoelectricity double-response characteristic can
Inverse shape-memory material can be used as intelligent switch, mechanical gripper or flexible robot.
Beneficial effects of the present invention:
(1) present invention with figuration by that can be prepared the dual sound with electricity and light through hot press molding again after physical blending
The reversible shape memory material of characteristic is answered, preparation method is simple；
(2) preparation process of hot pressing can construct the isolation structure of conductive filler in material internal to obtain after physical blending
Obtain excellent electric conductivity；
(3) conductive filler of isolation network will not influence the movement of the strands such as POE, so that gained reversible shape remembers material
Material is still able to maintain excellent driveability；
(4) conductive filler of isolation network makes RSMP that can respond electric and light stimulation simultaneously.
Detailed description of the invention
Fig. 1 is that the optical microscopy of the reversible shape memory material obtained by embodiment one with photoelectricity double-response characteristic shines
Piece.
Fig. 2 is that there is the optical microscopy of the reversible shape memory material of photoelectricity double-response characteristic to shine obtained by example IV
Piece.
Fig. 3 is the scanning electron microscope (SEM) photograph of two gained composite material of comparative example.
Fig. 4 be the gained of embodiment one, two, three, four, five have photoelectricity double-response characteristic reversible shape memory material,
The conductivity of one, two, three gained composite material of comparative example.
Fig. 5 is to have the reversible shape memory material of photoelectricity double-response characteristic under the conditions of no external force obtained by example IV
Deformation variation with temperature figure.
Fig. 6 is two gained composite material of comparative example deformation variation with temperature figure under the conditions of no external force.
Fig. 7 is to have the reversible shape memory material of photoelectricity double-response characteristic in 20V, 30V, 36V obtained by example IV
DC voltage under and two gained composite material of comparative example temperature under the DC voltage of 200V change with time figure.
Fig. 8 is to have the reversible shape memory material of photoelectricity double-response characteristic in 250mWcm obtained by embodiment two-2's
Temperature changes with time figure under the illumination of optical power density.
Specific embodiment
The invention solves first technical problem be to provide a kind of reversible shape with photoelectricity double-response characteristic
Memory material, the material is the polymer base conductive composite material with isolation structure, also, the polymer is with width
The semi-crystalline polymer of melting range, melting range silicon carbide >=20 DEG C of the polymer, melting range silicon carbide=end melting temperatur-incipient melting temperature
Degree.The present invention points out to have for the first time isolation structure, specific polymer base conductive composite material can be as having photoelectricity double
The reversible shape memory material of weight response characteristic.
The invention solves second technical problems to be to provide a kind of reversible shape note with photoelectricity double-response characteristic
Recall the preparation method of material, the preparation method is that: polymer base particles and conductive filler are first made into conduction through physical blending
Filler is coated on polymer base particles surface, then passes through the hot-forming boundary for making conductive filler be fixed on polymer base particles
Between face, the composite material with isolation structure is obtained；Then gained composite material is subjected to figuration and cooling and shaping is had
There is the reversible shape memory material of photoelectricity double-response characteristic.In other words, simultaneously cooling and shaping refers in hot pressing the figuration in the present invention
It customizes a shape after sizing again according to actual needs and is fixed.
Further, the hot-forming first temperature or more of melting in polymeric matrix thermally decomposes the following progress of indexing；Gained
The figuration of composite material carries out at a temperature of the end of polymeric matrix melts 3~20 DEG C of temperature or less.
The technical scheme of the invention is further explained by means of specific implementation.Following embodiment is several allusion quotations
The embodiment of type, can not play and limit effect of the invention, and those skilled in the art is referred to embodiment to technology
Scheme is reasonably designed, and result of the invention can be equally obtained.
Embodiment one
Planetary ball mill is added in 400r/ in 100 parts of POE powders (200~600 μm of partial size) and 0.25 part of carbon nanotube
90min is mixed under min, then by the product being mixed to get compression moulding under 100 DEG C and 2.5MPa of pressure, then will be hot-forming
Product at 80 DEG C according to actual needs by stationary fixture clamping figuration again, and cooling and shaping obtain it is dual with photoelectricity
The reversible shape memory material of response characteristic.
Embodiment two
Planetary ball mill is added in 400r/ in 100 parts of POE powders (200~600 μm of partial size) and 0.5 part of carbon nanotube
90min is mixed under min, then by the product being mixed to get compression moulding under 100 DEG C and 2.5MPa of pressure, then will be hot-forming
Product at 80 DEG C by stationary fixture clamping figuration again, and cooling and shaping obtain having photoelectricity double-response characteristic can
Inverse shape-memory material.
Embodiment three
Planetary ball mill is added in 400r/min in 100 parts of POE powders (200~600 μm of partial size) and 1 part of carbon nanotube
Lower mixing 90min, then by the product being mixed to get compression moulding under 100 DEG C and 2.5MPa of pressure, then will be hot-forming
Product clamps figuration again by stationary fixture at 80 DEG C, and cooling and shaping obtains having the reversible of photoelectricity double-response characteristic
Shape-memory material.
Example IV
Planetary ball mill is added in 400r/min in 100 parts of POE powders (200~600 μm of partial size) and 2 parts of carbon nanotubes
Lower mixing 90min, then by the product being mixed to get compression moulding under 100 DEG C and 2.5MPa of pressure, then will be hot-forming
Product clamps figuration again by stationary fixture at 80 DEG C, and cooling and shaping obtains having the reversible of photoelectricity double-response characteristic
Shape-memory material.
Embodiment five
Planetary ball mill is added in 400r/min in 100 parts of POE powders (200~600 μm of partial size) and 3 parts of carbon nanotubes
Lower mixing 90min, then by the product being mixed to get compression moulding under 100 DEG C and 2.5MPa of pressure, then will be hot-forming
Product clamps figuration again by stationary fixture at 80 DEG C, and cooling and shaping obtains having the reversible of photoelectricity double-response characteristic
Shape-memory material.
Comparative example one
Mixer is added with 1 part of carbon nanotube in 100 parts of POE, 8min, then the production that blending is obtained are blended at 150 DEG C
Object compression moulding under 100 DEG C and 2.5MPa of pressure, then hot-forming product is clamped at 80 DEG C by stationary fixture
Again figuration, and cooling and shaping obtains composite material.
Comparative example two
Mixer is added with 2 parts of carbon nanotubes in 100 parts of POE, 8min, then the production that blending is obtained are blended at 150 DEG C
Object compression moulding under 100 DEG C and 2.5MPa of pressure, then hot-forming product is clamped at 80 DEG C by stationary fixture
Again figuration, and cooling and shaping obtains composite material.
Comparative example three
Mixer is added with 3 parts of carbon nanotubes in 100 parts of POE, 8min, then the production that blending is obtained are blended at 150 DEG C
Object compression moulding under 100 DEG C and 2.5MPa of pressure, then hot-forming product is clamped at 80 DEG C by stationary fixture
Again figuration, and cooling and shaping obtains composite material.
Performance test:
Fig. 1 and Fig. 2 is respectively the optical microscope photograph of embodiment one Yu example IV resulting materials, observes resulting materials
Microstructure, it is available as drawn a conclusion: perfect interrupter can be constructed in material internal by hot pressing after ball milling
Conductive network, and with the raising of filer content, conductive path broadens.
Fig. 3 is the scanning electron microscope (SEM) photograph of two resulting materials of comparative example, from the figure 3, it may be seen that by the way that obtained material will directly be blended
The dispersion of middle filler be it is random, material internal does not form perfect conductive path.
Fig. 4 is the conductivity of one, two, three resulting materials of one, two, three, four, five resulting materials of embodiment and comparative example, by
Obtained material is directly blended it is found that the conductivity of material can be made to be much larger than in the conductive network that material internal constructs isolation structure in figure
Material.
Fig. 5 and Fig. 6 be respectively example IV and two resulting materials of comparative example under the conditions of no external force deformation with temperature change
Change figure, as seen from the figure, the reversible deformation of example IV resulting materials is up to 2.5%, the reversible deformation of two resulting materials of comparative example
It is 0.9%, comparison can be obtained to be substantially better than by the driveability of the material of the conductive network of hot pressing introducing isolation structure after ball milling
Obtained material is directly blended；I.e. the conducting polymer based composites with isolation structure have good driveability.
Fig. 7 is example IV resulting materials under the DC voltage of 20V, 30V, 36V and two gained composite material of comparative example
Temperature changes with time under the DC voltage of 200V, and as seen from the figure, example IV resulting materials can add outside 36V is below
It is quickly heated under voltage, and with alive raising is applied, the heating rate of material becomes faster；And two resulting materials of comparative example are in phase
With can not be heated at 200V under filer content；Table 1 is under two resulting materials different voltages of example IV and comparative example
Time summary sheet needed for being warming up to 60 DEG C；As it can be seen that the conducting polymer based composites with isolation structure are with good
Thermal response property.
1 example IV of table and two resulting materials of comparative example are warming up to 60 DEG C of required times under different voltages
| Sample | The time required to being warming up to 60 DEG C (s) |
| Example IV -20V | 80 |
| Example IV -30V | 32 |
| Example IV -36V | 22 |
| Two -200V of comparative example | It can not heat |
Fig. 8 is two resulting materials of embodiment in 250mWcm-2Optical power density illumination under the change of temperature at any time
Change, as seen from the figure, resulting materials are in 250mWcm-2Optical power density illumination under be warming up to 60 DEG C and only need 50s.As it can be seen that tool
Having the conducting polymer based composites of isolation structure has good photo absorption property.
Claims (10)
1. a kind of reversible shape memory material with photoelectricity double-response characteristic, which is characterized in that the material be with every
Polymer base conductive composite material from structure, wherein the polymer is the semi-crystalline polymer with wide melting range, i.e., described poly-
Close melting range silicon carbide >=20 DEG C of object, melting range silicon carbide=end melting temperatur-initial melting temperature.
2. the reversible shape memory material according to claim 1 with photoelectricity double-response characteristic, which is characterized in that institute
State isolation structure to refer to: polymer base conductive composite material is prepared by polymeric matrix and conductive filler, wherein conductive filler
It is on the interface between polymeric matrix, rather than random alignment in a polymer matrix.
3. the reversible shape memory material according to claim 2 with photoelectricity double-response characteristic, which is characterized in that institute
It states polymeric matrix to be selected from: at least one of ethylene-octene copolymer or ethylene-vinyl acetate copolymer.
4. the reversible shape memory material according to claim 2 or 3 with photoelectricity double-response characteristic, feature exist
In the conductive filler is at least one of carbon black, carbon nanotube, graphene or the short fibre of carbon fiber.
5. the reversible shape memory material according to claim 4 with photoelectricity double-response characteristic, which is characterized in that institute
Stating polymeric matrix is ethylene-octene copolymer, and the conductive filler is carbon nanotube, and polymeric matrix and conductive filler are matched
Than are as follows: 100 parts by volume of ethylene-octene copolymer, 0.1~6 parts by volume of conductive filler.
6. the preparation method of the reversible shape memory material described in any one of Claims 1 to 5 with photoelectricity double-response characteristic,
It is characterized in that, the preparation method is that: polymer base particles and conductive filler are first made into conductive filler packet through physical blending
Overlay on polymer base particles surface, then by the hot-forming interface for making conductive filler be fixed on polymer base particles it
Between, obtain the composite material with isolation structure；Then gained composite material is subjected to figuration and cooling and shaping is obtained with light
The reversible shape memory material of electric double-response characteristic.
7. the preparation method of the reversible shape memory material with photoelectricity double-response characteristic according to claim 6, special
Sign is that the partial size of the polymer base particles is at 50~2000 μm, preferably 200~600 μm.
8. the preparation method of the reversible shape memory material described according to claim 6 or 7 with photoelectricity double-response characteristic,
It is characterized in that, the mode of physical blending are as follows: one of ball milling, grinding or high-speed stirred mixing.
9. the preparation of the reversible shape memory material according to any one of claim 6~8 with photoelectricity double-response characteristic
Method, which is characterized in that the hot-forming first temperature or more of melting in polymeric matrix thermally decomposes the following progress of indexing；Gained
The figuration of composite material carries out at a temperature of the end of polymeric matrix melts 3~20 DEG C of temperature or less.
10. the reversible shape memory material with photoelectricity double-response characteristic can be used as intelligent switch, mechanical gripper or flexibility
Robot, wherein the reversible shape memory material with photoelectricity double-response characteristic is any one of Claims 1 to 5 institute
Reversible shape memory material is stated, or remembers material for reversible shape made from the described in any item preparation methods of claim 6~9
Material.
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| CN113337033A (en) * | 2021-06-29 | 2021-09-03 | 哈尔滨工业大学 | Preparation of thermally-deformed support arm and method for regulating and controlling unfolding state of space reflector by using thermally-deformed support arm |
| CN113480798A (en) * | 2021-07-26 | 2021-10-08 | 中国兵器科学研究院 | Preparation of photoinduced deformation supporting arm and method for regulating and controlling unfolding state of space reflector by utilizing photoinduced deformation supporting arm |
| CN116063799A (en) * | 2023-01-06 | 2023-05-05 | 华南理工大学 | Ultra-wide melting range two-way shape memory polymer composite material without external force and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110746629A (en) * | 2019-11-12 | 2020-02-04 | 电子科技大学中山学院 | Electrically-driven shape memory polymer micro-layer composite material and preparation method thereof |
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| CN113337033B (en) * | 2021-06-29 | 2022-01-18 | 哈尔滨工业大学 | Preparation of thermally-deformed support arm and method for regulating and controlling unfolding state of space reflector by using thermally-deformed support arm |
| CN113480798A (en) * | 2021-07-26 | 2021-10-08 | 中国兵器科学研究院 | Preparation of photoinduced deformation supporting arm and method for regulating and controlling unfolding state of space reflector by utilizing photoinduced deformation supporting arm |
| CN113480798B (en) * | 2021-07-26 | 2022-05-13 | 中国兵器科学研究院 | Preparation of photoinduced deformation supporting arm and method for regulating and controlling unfolding state of space reflector by utilizing photoinduced deformation supporting arm |
| CN116063799A (en) * | 2023-01-06 | 2023-05-05 | 华南理工大学 | Ultra-wide melting range two-way shape memory polymer composite material without external force and preparation method thereof |
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