CN105713219B - A kind of composite material of shape memory and its preparation method and application - Google Patents
A kind of composite material of shape memory and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of composite material of shape memory and its preparation method and application.The composite material is alternately combined by liquid-metal layer and shape memory high molecule material layer.Preparation method includes the method using hierarchical composite, by liquid metal even application on shape memory high molecule material layer, liquid-metal layer is formed, another layer shape memory high molecule material layer is then coated on the liquid-metal layer, repeats above step to required thickness.The conductive flexible shape memory composites electric conductivity of the present invention is excellent and has flexible speciality, while can change its thickness as needed, and preparation method is simple and efficient efficiently and controllable, and flexibility ratio is high, has broad application prospects.
Description
Technical field
It is the present invention relates to a kind of multifunctional polymer composite material, in particular to a kind of high with liquid metal and shape memory
Molecularly Imprinted Polymer conductive flexible shape memory polymer composite material as main component and its preparation method and application.
Background technique
Shape memory high molecule is also known as shape-memory polymer (Shape Memory Polymers, abbreviation SMP), refers to
After product with original shape changes its primary condition under certain conditions and fixes, by external condition (as heat, electricity,
Light, chemical co-ordination etc.) stimulation can restore the high molecular material of its original shape again.Currently, shape memory high molecule material exists
Intellectual material field obtains extensive concern and research.Compared with marmem, shape-memory polymer is as a kind of
Novel functional polymer material has many advantages, such as that light, can to reply deformation quantity big, easy to process, cheap.But its function
Property it is relatively single, and do not have with application environment be adapted functional characteristic, significantly limit in the general of Practical Project field
And with application.Therefore, in order to expand practical engineering application, various types of filler is often added in shape-memory polymer and does forming shape note
Polymer composites are recalled, to achieve the purpose that enhance its properties.Currently, it is thermotropic shape memory that research is more
Polymer, but thermotropic shape-memory polymer is easy to be limited by environmental factors such as external heat sources, and further application is gone back
There are many problems.In recent years, conductive material is added to this as the shape-memory polymer collective of insulator by researcher
In, electroluminescent type shape memory polymer composite material has been made.This material can be such that system temperature increases by electric current heat, real
Existing deformation restores, and is not had preferable stability by the interference of outside environmental elements.
Electroluminescent type shape-memory polymer can be divided into the memory of metal packing filling shape according to the difference of packing material and gather
Compound composite material and carbon filler filling shape memory composites.It is commonly carbon filler, what is utilized is carbon
Black, carbon nanotube, carbon fiber etc. influence the electrical property and shape note of shape memory polymer composite material as conductive filler
Recall effect.But carbon filler filling shape memory composite material is easy to appear the phenomenon that resistance increases in energization temperature-rise period,
To make composite material lose conductive capability.Therefore for conductive angle, the shape-memory polymer composite wood of metal packing
Expect that performance is more excellent.But currently used metal packing is gold, silver, copper etc., and hardness is higher at normal temperature, cannot flexibly convert
Shape.Simultaneously as carbon filler and the deformation recovery rate of metal packing are lower, when shape memory polymer composite material occurs
Easily and matrix stripping, this significantly limits the application of shape memory polymer composite material to filler when large deformation.Therefore, urgently
The appearance for needing a kind of new packing.
Summary of the invention
In order to solve the above technical problems, it is an object of the present invention to provide a kind of conductive flexible shape memory composite materials.
Realize the object of the invention technical solution are as follows:
A kind of composite material of shape memory is alternately combined by liquid-metal layer and shape memory high molecule material layer.
Preferably, the thickness of the liquid-metal layer and shape memory high molecule material layer is respectively 10 μm -100 μm.
Preferably, the thickness proportion of the liquid-metal layer and shape memory high molecule material layer is 0.5-1.5: 0.5-
1.5, further preferably 1: 1.
The composite material of shape memory includes multiple alternate liquid-metal layers and shape memory high molecule material layer.
Preferably, in the composite material of shape memory, liquid-metal layer is 3-10 layers or the shape memory high molecule
Material is 4-11 layers.
The composite material of shape memory can be actually needed according to different occasions and adjust to required thickness.
Preferably, the composite material of shape memory with a thickness of 70 μm of -2mm.
Preferably, its outermost layer of the composite material of shape memory is shape memory high molecule material layer.
Preferably, the liquid metal is one or more of gallium, the bianry alloy of gallium, the ternary alloy three-partalloy of gallium.
Preferably, the liquid metal is gallium indium bianry alloy, wherein the content of gallium is mass fraction 50%-90%,
Remaining is indium；
Or the liquid metal is gallium indium tin ternary alloy three-partalloy, wherein the content of gallium is mass fraction 60%-80%, and indium contains
Amount is mass fraction 10%-30%, remaining is tin.
Shape memory high molecule material of the present invention can be the common all kinds of shape memory high molecule materials of industry, including but
Be not limited to polystyrene shape-memory polymer, epoxy resin shape polymer, styrene-butadiene system shape polymer,
One or more of trans-polyisoprene system shape polymer, cyanate system shape polymer etc..Preferred shape memory
High molecular material is polybutylene terephthalate (PBT), polyethylene to this ethylene glycol, polyetherimide, polymethylacrylic acid isobutyl
One or more of ester etc..
Preferred version of the invention is a kind of composite material of shape memory, by liquid-metal layer and shape memory high molecule
Material layer is alternately combined；The thickness of the liquid-metal layer and shape memory high molecule material layer is respectively 10 μm of -100 μ
M, wherein the thickness proportion of the liquid-metal layer and shape memory high molecule material layer is 1:1；The liquid-metal layer is 3-
10 layers；Or shape memory high molecule material layer is 4-11 layers；Or the composite material with a thickness of 70 μm of -2mm；Its outermost layer is
Shape memory high molecule material layer.The liquid metal is one of gallium, gallium indium bianry alloy, gallium indium tin ternary alloy three-partalloy or several
Kind；Wherein, the content of gallium is mass fraction 50%-90% in the gallium indium bianry alloy, remaining is indium；The gallium indium tin ternary
The content of gallium is mass fraction 60%-80% in alloy, and the content of indium is mass fraction 10%-30%, remaining is tin.The shape
It is polybutylene terephthalate (PBT), polyethylene to this ethylene glycol, polyetherimide, polymethyl that shape, which remembers high molecular material,
One or more of sour isobutyl ester.
The present invention also provides the preparation methods of above-mentioned electrically conductive flexible shape memory composites, including use and divide
The compound method of layer forms liquid metal by above-mentioned liquid metal even application on above-mentioned shape memory high molecule material layer
Layer, another layer shape memory high molecule material layer is then coated on the liquid-metal layer, repeats above step to institute
Need thickness.
Since the shape-memory polymer overwhelming majority is insulator, itself does not have conductive capability.Therefore, conductive soft
Property shape memory polymer composite material transmitted by liquid-metal layer it is conductive, to have conductive capability.
The invention also includes the application of above-mentioned conductive flexible shape memory composites, the application includes
For space industry, medical equipment, sensor or intelligent packaging fabric etc..
The invention also includes the equipment or device that contain above-mentioned conductive flexible shape memory composites, institutes
It states equipment or device includes but is not limited to Spacecraft Launch device, Statellite antenna or artificial-muscle etc..
The beneficial effects of the present invention are:
Conductive flexible shape memory composites provided by the invention get rid of conventional shape-memory polymerization
The deficiencies of filler and matrix poor compatibility, deformation-recovery power are poor in object composite material, conduction power is weak.Since liquid metal has pole
High thermal coefficient, excellent surface tension, therefore can be perfectly bonded with shape memory high molecule material, to improve whole
The electric conductivity of body material.And the characteristic flowed based on liquid metal itself, the flexible shape memory of conduction provided by the invention are poly-
Compound composite material has better flexible characteristic.Simultaneously as can be realized according to different occasions using the method for hierarchical composite
Thickness adjustability greatly improves its application range.
Detailed description of the invention
Fig. 1 is shape of the present invention memory composite material material structural schematic diagram.Wherein, 1 is shape memory high molecule material；2
For liquid metal.
Fig. 2 is that shape of the present invention memory composite material deforms and reply schematic diagram.Wherein, 1 is original state；2 be deformation
Bending state afterwards；3 be state after reply.
Fig. 3 is that shape of the present invention memory composite material deforms and replys angle schematic diagram (experimental example 3).Wherein, 1 is initial
State；2 be bending state after deformation；3 be state after reply.α is deformation angle；β is to reply angle.
Specific embodiment
The present invention is now illustrated with following most preferred embodiment, but is not intended to limit the scope of the invention.In embodiment, such as nothing
Specified otherwise, used technological means are this field conventional technology.
Embodiment 1
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polybutylene terephthalate (PBT)；2 be liquid metal gallium.It is described
The thickness of liquid-metal layer and shape memory high molecule material layer is respectively 10 μm, the former (referring to liquid-metal layer, similarly hereinafter) number of plies
It is 9 layers, the latter's (referring to shape memory polymer material layer, similarly hereinafter) number of plies is 10 layers.
Embodiment 2
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polyethylene to this ethylene glycol；2 be liquid metal gallium-indium alloy,
The content of middle gallium is mass fraction 90%, remaining is indium；The thickness of the liquid-metal layer and shape memory high molecule material layer
Respectively 10 μm, the former number of plies is 3 layers, and the latter's number of plies is 4 layers.
Embodiment 3
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polyetherimide；2 be liquid metal gallium-indium alloy, wherein gallium
Content is mass fraction 70%, remaining is indium；The thickness of the liquid-metal layer and shape memory high molecule material layer is respectively
10 μm, the former number of plies is 5 layers, and the latter's number of plies is 6 layers.
Embodiment 4
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polyisobutyl methacrylate；2 close for liquid metal gallium indium tin
Gold, wherein the content of gallium is mass fraction 70%, and the content of indium is mass fraction 25%, remaining is tin；The liquid-metal layer
Thickness with shape memory high molecule material layer is respectively 10 μm, the former number of plies is 4 layers, and the latter's number of plies is 5 layers.
Embodiment 5
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polybutylene terephthalate (PBT)；2 be liquid metal gallium.It is described
The thickness of liquid-metal layer and shape memory high molecule material layer is respectively 100 μm, the former number of plies is 9 layers, and the latter's number of plies is 10
Layer.
Embodiment 6
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polybutylene terephthalate (PBT)；2 be liquid metal gallium.It is described
The thickness of liquid-metal layer and shape memory high molecule material layer is respectively 50 μm, the former number of plies is 9 layers, and the latter's number of plies is 10
Layer.
Embodiment 7
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polybutylene terephthalate (PBT)；2 be liquid metal gallium.It is described
The thickness of liquid-metal layer and shape memory high molecule material layer is respectively 70 μm, the former number of plies is 9 layers, and the latter's number of plies is 10
Layer.
Embodiment 8
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polyethylene to this ethylene glycol；2 be liquid metal gallium-indium alloy,
The content of middle gallium is mass fraction 90%, remaining is indium；The liquid-metal layer is with a thickness of 50 μm, shape memory high molecule material
The thickness of layer is 100 μm, the former number of plies is 3 layers, and the latter's number of plies is 4 layers.
Embodiment 9
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polyetherimide；2 be liquid metal gallium-indium alloy, wherein gallium
Content is mass fraction 70%, remaining is indium；The thickness of the liquid-metal layer is 20 μm, shape memory high molecule material layer
Thickness is 60 μm, the former number of plies is 5 layers, and the latter's number of plies is 6 layers.
Embodiment 10
A kind of composite material of shape memory, as shown in Figure 1, it is handed over by liquid-metal layer and shape memory high molecule material layer
For being combined；Wherein, 1 is shape memory high molecule material polyisobutyl methacrylate；2 close for liquid metal gallium indium tin
Gold, wherein the content of gallium is mass fraction 70%, and the content of indium is mass fraction 25%, remaining is tin；The liquid-metal layer
Thickness be 90 μm, the thickness of shape memory high molecule material layer is 30 μm, the former number of plies is 4 layers, and the latter's number of plies is 5 layers.
Embodiment 11
The present embodiment provides the preparation methods of composite material of shape memory described in embodiment 1, including by the shape memory
High molecular material is prepared into film layer (the i.e. shape macromolecule material of required thickness (10 μm) using general macromolecule film means
The bed of material), liquid metal is sprayed on the shape polymer material layer using spray gun then, forms the liquid of required thickness (10 μm)
State metal layer.Continue the shape memory high molecule material film layer of preparation required thickness (10 μm) on the liquid-metal layer, after
Continue the liquid-metal layer of spraying required thickness (10 μm).Process above is repeated to required thickness.
The preparation method Yu embodiment 11 of conductive flexible shape memory composites described in embodiment 2-10
It is similar.
Comparative example 1
A kind of composite material, the difference with embodiment 1 are only that the liquid-metal layer and shape memory high molecule material
The thickness of the bed of material is respectively 150 μm.At this point, composite material integral thickness is 2.85mm, which is deteriorated.
Comparative example 2
A kind of composite material, the difference with embodiment 2 are only that the liquid-metal layer and shape memory high molecule material
The thickness of the bed of material is respectively 5 μm.At this point, composite material integral thickness is 35 μm, the strength reduction of the composite material, it is easy to broken
It splits.
Experimental example 1
Attached drawing 2 is to composite material electroluminescent deformation Recovery Process schematic diagram.Wherein, 1 is original state；2 be curved after deformation
Curved state；3 be state after reply.Its shape recovery process are as follows:
1) it is warming up to the glass transition temperature of shape memory high molecule material or more, applying external force to material makes its deformation；
2) keep external force constant, it can be with freezing stress and deformation after reduction temperature；
3) voltage is applied to conductive flexible shape memory composites and makes it through liquid-metal layer conduction.Electricity
Stream can make the temperature of composite material rise to shape memory high score by heat caused by composite inner liquid-metal layer
More than the glass transition temperature of sub- material, to discharge freezing stress, composite material is made to be returned to the state before deformation.
Embodiment 1-10 and each composite material of comparative example 1-2 are tested respectively using above method, the results showed that real
It is good to apply each compound material flexible of a 1-10, it can good deformation-recovery；But 1 compound material flexible of comparative example is poor, it is not easy to
Deformation-recovery；The strength reduction of 2 composite material of comparative example, it is easy to rupture.
Experimental example 2
Deformation-recovery experiment (pressing 1 method of experimental example) is carried out to embodiment 1-10 and comparative example 1,2 composite materials respectively,
Angle after measuring its bending angle and replying, schematic diagram are as shown in Figure 3.Specific measurement result is as shown in table 1.It can be with by table 1
Find out, each composite material of embodiment 1-10 can good deformation-recovery；But comparative example 1, the deformation recovery situation of 2 composite materials
It is poor.
Table 1
Above embodiment be only preferred embodiments of the present invention will be described, not to the scope of the present invention into
Row limits, and without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to technical side of the invention
The all variations and modifications that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (14)
1. a kind of composite material of shape memory, which is characterized in that replaced by liquid-metal layer and shape memory high molecule material layer
It is combined；
The thickness of the liquid-metal layer and shape memory high molecule material layer is respectively 10 μm -100 μm；
The liquid-metal layer is 3-10 layers；Or the shape memory high molecule material layer is 4-11 layers.
2. composite material according to claim 1, which is characterized in that the composite material with a thickness of 70 μm of -2mm.
3. composite material according to claim 2, which is characterized in that the liquid-metal layer and shape memory high molecule material
The thickness proportion of the bed of material is 0.5-1.5: 0.5-1.5.
4. composite material according to claim 3, which is characterized in that the liquid-metal layer and shape memory high molecule material
The thickness proportion of the bed of material is 1: 1.
5. composite material according to claim 1-4, which is characterized in that its outermost layer of the composite material is shape
Shape remembers polymer material layer.
6. composite material according to claim 1-4, which is characterized in that the liquid metal be gallium, gallium two
One or more of first alloy, ternary alloy three-partalloy of gallium.
7. composite material according to claim 6, which is characterized in that the liquid metal is gallium indium bianry alloy, wherein
The content of gallium is mass fraction 50%-90%, remaining is indium；Or the liquid metal is gallium indium tin ternary alloy three-partalloy, wherein gallium contains
Amount is mass fraction 60%-80%, and the content of indium is mass fraction 10%-30%, remaining is tin.
8. composite material according to claim 1-4, which is characterized in that the shape memory high molecule material packet
Include polystyrene shape-memory polymer, epoxy resin shape polymer, trans-polyisoprene system shape polymer, cyanic acid
One or more of ester system shape polymer.
9. according to right want 8 described in composite material, which is characterized in that the shape memory high molecule material be styrene-fourth
Diene series shape polymer.
10. according to right want 1-4 described in composite material, which is characterized in that the shape memory high molecule material is poly- to benzene
One or more of dioctyl phthalate butanediol ester, polyetherimide, polyisobutyl methacrylate.
11. composite material according to claim 1, which is characterized in that the liquid-metal layer and shape memory high molecule
The thickness of material layer is respectively 10 μm -100 μm, wherein the thickness of the liquid-metal layer and shape memory high molecule material layer
Ratio is 1:1；The liquid-metal layer is 3-10 layers；Or shape memory high molecule material layer is 4-11 layers；Its outermost layer is shape
Shape remembers polymer material layer；
The liquid metal is one or more of gallium, gallium indium bianry alloy, gallium indium tin ternary alloy three-partalloy；Wherein, the gallium indium
The content of gallium is mass fraction 50%-90% in bianry alloy, remaining is indium；The content of gallium is matter in the gallium indium tin ternary alloy three-partalloy
Score 60%-80% is measured, the content of indium is mass fraction 10%-30%, remaining is tin；
The shape memory high molecule material is polybutylene terephthalate (PBT), polyetherimide, polymethylacrylic acid isobutyl
One or more of ester.
12. the preparation method of any one of the claim 1-11 composite material, including the method using hierarchical composite, by liquid
Metal even application forms liquid-metal layer, then applies on the liquid-metal layer on shape memory high molecule material layer
Another layer shape memory high molecule material layer is covered, repeats above step to required thickness.
13. composite material prepared by any one of the claim 1-11 composite material or claim 12 the method is answered
With the application includes being used for space industry, medical equipment, sensor or intelligent packaging fabric.
14. containing any one of the claim 1-11 composite material, or containing the compound of claim 12 the method preparation
The equipment or device of material, the equipment or device include Spacecraft Launch device, Statellite antenna or artificial-muscle.
Priority Applications (1)
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| CN107819069B (en) * | 2017-10-30 | 2019-07-12 | 清华大学 | The memory that phase-change memory cell and the unit based on nanometer liquid metallic particles are constituted |
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| CN109016771B (en) * | 2018-07-20 | 2019-12-10 | 北京梦之墨科技有限公司 | plastic part and manufacturing method thereof |
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| CN109637698B (en) * | 2018-11-06 | 2020-07-14 | 中国科学院理化技术研究所 | Liquid metal flexible film with two-sided different characteristics and preparation method thereof |
| CN109627769B (en) * | 2018-12-03 | 2021-11-30 | 深圳大学 | Liquid metal-based deformation memory composite material and preparation method and application thereof |
| CN113529075B (en) * | 2020-04-20 | 2022-05-03 | 厦门大学 | Liquid metal composite porous membrane and preparation method and application thereof |
| CN112233869A (en) * | 2020-10-30 | 2021-01-15 | 江苏普隆磁电有限公司 | Neodymium-iron-boron magnet and preparation method thereof |
| CN113043288B (en) * | 2020-12-25 | 2023-06-23 | 天津大学 | Liquid metal-polymer composite soft driver and preparation method thereof |
| CN114621498B (en) * | 2022-04-14 | 2022-11-11 | 哈尔滨工业大学 | Fine controllable heat transfer body with shape memory characteristic and preparation method and application thereof |
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