CN114621483B - Electric response shape memory composite material capable of driving three-dimensional structure and preparation method and application thereof - Google Patents

Electric response shape memory composite material capable of driving three-dimensional structure and preparation method and application thereof Download PDF

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CN114621483B
CN114621483B CN202210205086.6A CN202210205086A CN114621483B CN 114621483 B CN114621483 B CN 114621483B CN 202210205086 A CN202210205086 A CN 202210205086A CN 114621483 B CN114621483 B CN 114621483B
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shape memory
electric heating
heating layer
shape
conductive
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CN114621483A (en
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冷劲松
胡容祥
张风华
刘彦菊
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

An electric response shape memory composite material capable of driving a three-dimensional structure and a preparation method and application thereof belong to the technical field of intelligent materials. The invention provides an electric response shape memory composite material and a preparation method and application thereof. The shape memory conductive heating layer in the electric response shape memory composite material has good conductive stability and conductivity, can perform shape memory and shape recovery with the same trend along with the deformation of a device, reduces the resistance from the electric heating layer in the deformation process of the device, improves the shape fixing rate and the shape recovery rate, keeps the interface stability and the structural integrity of the electric heating layer, the composite material and the device, and can realize the electric response driving of a specific path.

Description

Electric response shape memory composite material capable of driving three-dimensional structure and preparation method and application thereof
Technical Field
The invention belongs to the technical field of intelligent materials, and relates to an electric response shape memory composite material capable of driving a three-dimensional structure, and a preparation method and application thereof.
Background
The shape memory polymer material can spontaneously change the shape under the stimulation of external energy as an intelligent material, combines the advantages of light weight, low cost and the like of high polymer materials, and has wide application prospect in the fields of wearable intelligent equipment, brakes, deployable structures, biomedical treatment and the like.
The conventional driving mode of the SMP generally carries out heat transfer driving structural change by increasing the ambient temperature, so that the application range of the SMP device is limited. The electric response shape memory polymer can provide energy for stimulating the SMP to change shape through electric heating, gets rid of the limitation of environmental temperature and enlarges the application range of the SMP material. The preparation method of the electrically-responsive SMP is generally that a certain amount of conductive material is filled in the SMP, however, the SMP with low content of conductive material has larger resistance and needs high voltage to generate enough driving heat, and the SMP with high content of conductive material can reduce the shape recovery rate of the structure, thereby limiting the engineering application of the electrically-responsive SMP. Although the conductive copper wire laid in the SMP material can be heated and driven under a lower voltage, the interface bonding force between metal and polymer is poor, and a part of restoring force needs to be provided to apply work to the conductive copper wire in the shape restoring process of the SMP device, so that the shape restoring rate of the device can be reduced. In addition, in engineering, a mode of attaching an electric heating film to the surface of an SMP device is often adopted as an external heat source to provide deformation driving energy for the SMP, but the electric heating film and the SMP are heterogeneous materials, so that the interface bonding stability is poor, the electric heating film and the SMP are peeled off and separated in the SMP deformation process, heat cannot be effectively transferred, and the normal operation of the device is influenced. In addition, the electrically-driven SMP device in the background of the prior art is mostly of a two-dimensional structure, and few technical methods capable of electrically-driving the deformation of the three-dimensional SMP device are available.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to an electrically responsive shape memory composite capable of driving a three-dimensional structure, and a method for preparing the same and an application thereof. The shape memory conductive heating layer in the electric response shape memory composite material has good conductive stability and conductivity; the polymer substrate used for preparing the electric heating layer and the preparation device are made of the same SMP material, the electric heating layer with the shape memory effect can carry out shape memory and shape recovery with the same trend along with the deformation of the shape memory composite device, the resistance from the electric heating layer in the deformation process of the device is reduced, the shape fixing rate and the shape recovery rate are improved, and meanwhile, the interface stability and the structural integrity of the electric heating layer, the composite material and the device can be better maintained. Before the electric heating layer is compounded with the shape memory material, the shape of the matched conductive heating path can be edited according to the structure and the function of the device, the electric response driving of the specific path of the device is realized, and particularly, the electric heating layer can be compounded with the shape memory composite material with a three-dimensional structure, and the electric response driving of the obtained device is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an electric response shape memory composite material capable of driving a three-dimensional structure is characterized by comprising the following steps:
(1) Preparing conductive slurry: taking the shape memory polymer solution/prepolymer solution, adding a volatile solvent to regulate the concentration and viscosity of the shape memory polymer solution/prepolymer solution, adding a conductive material, and dispersing to form uniform conductive slurry;
(2) Coating the conductive slurry formed in the step (1) into a groove die with a designed path, and solidifying after volatilizing a volatile solvent to obtain an electric heating layer with a conductive path;
or, coating the conductive slurry formed in the step (1) into a demolding material, volatilizing a volatile solvent, solidifying, and then dividing to form a conductive path to obtain an electric heating layer with the conductive path; before the electric heating layer and the shape memory material are further compounded, the path shape of the electric heating layer can be restored by heating, and the shape editing step is repeated to re-edit the path shape of the electric heating layer.
(3) Heating the electric heating layer obtained in the step (2) to the deformation temperature of the electric heating layer, editing the shape and the conductive path of the electric heating layer which are matched according to the structure and the function of the device, keeping the shape editing and cooling to the room temperature to obtain the shape memory electric heating layer with a fixed shape;
(4) And (3) uniformly mixing the shape memory polymer solution/prepolymer solution which is the same as the shape memory polymer solution/prepolymer solution obtained in the step (1) with a selectively added functional filling material, compounding the mixture with the shape memory electric heating layer obtained in the step (3) in a two-dimensional/three-dimensional/special-shaped structure mould matched with the shape of the device, and curing and forming to obtain the electric response shape memory composite material with the two-dimensional/three-dimensional/special-shaped structure.
The preparation method is characterized in that the shape memory polymer solution in the step (1) and the shape memory polymer material in the step (4) both comprise one or a mixture of more of shape memory polylactic acid, shape memory polycaprolactone, shape memory polyurethane, shape memory polystyrene, shape memory epoxy resin, shape memory cyanate ester resin, shape memory polyimide and shape memory polymaleimide, the conductive material in the step (1) comprises at least one of conductive carbon black, graphite, graphene, carbon nano tubes, carbon fiber materials and nano metals, and the dispersion mode comprises stirring or ultrasound.
The preparation method is characterized in that the weight percentage of the shape memory polymer solution/prepolymer solution in the conductive paste in the step (1) is 20-90 wt%, the weight percentage of the conductive material is 10-80 wt%, the concentration of the shape memory polymer solution/prepolymer solution is controlled to be 20-100 wt%, and the viscosity of the shape memory polymer solution/prepolymer solution is controlled to be 1mPa & s-100 Pa & s.
The manufacturing method is characterized in that the thickness of the electric heating layer in the step (2) is 10-1000 μm, and the shape memory electric heating layer with a fixed shape in the step (3) has the characteristic of restoring to the original shape by heating to a deformation temperature and re-editing the shape of the fixed electric heating layer.
The preparation method is characterized in that the distribution and the layer number of the shape memory electric heating layer are designed and adjusted in the compounding process in the step (4).
The preparation method is characterized in that the functionalized filling material in the step (4) comprises at least one of a continuous fiber material, a chopped fiber material, a particle material and a functionalized nano material, and the compounding method comprises the following steps: dipping, coating and pouring, wherein the mass ratio of the shape memory electric heating layer to the shape memory polymer solution/prepolymer solution to the functionalized filling material is 1:1-20.
The electric response shape memory composite material is characterized by comprising an electric heating layer with an editable shape, wherein the shape of a path of the electric heating layer is designed and edited according to the structure and the function of a device, and the structure of the device is a two-dimensional structure/a three-dimensional structure/an irregular special-shaped structure.
The electric response shape memory composite material is characterized by being prepared by any one of the preparation methods.
The electric response shape memory composite material is applied to an electric drive shape memory polymer material with low resistance and high stability.
The electrically-responsive shape memory composite is used in an electrically-driven SMP device.
When the functional filling material which is selectively added has better conductivity, a layer of shape memory polymer needs to be pre-cured or semi-cured on two sides of the electric heating layer, so that shape memory polymer matrix isolation layers are formed on two sides of the electric heating layer, and then the shape memory polymer matrix isolation layers are compounded with the prepolymer containing the functional filling material.
The design method of the shape of the electric heating path of the electric heating layer comprises the steps of obtaining the electric heating layer with the expected path and shape by a mould and a segmentation conducting layer when the electric heating layer is prepared, or editing the required path shape by means of the shape memory effect of the electric heating layer after the electric heating layer is obtained.
The invention constructs a conductive network by using high-content conductive filler, and fixes the conductive network by using a shape memory polymer; pouring a solution, volatilizing a solvent, and performing post-curing molding to obtain a shape memory electric heating layer, and editing a conductive path and a shape of the electric heating layer matched with the shape memory electric heating layer according to the structure and the function of the device; and finally, compounding the electric heating layer and the shape memory material to obtain the electric response shape memory polymer composite material capable of driving the three-dimensional structure, wherein the electric heating layer is designed according to the device structure, and the electric heating driving of the two-dimensional/three-dimensional/special-shaped structure can be realized after compounding.
The electric heating layer is made of the conductive shape memory composite material, the shape memory polymer contained in the electric heating layer and the polymer matrix used by the SMP device are the same, the surface energy of the electric heating layer and the SMP device is reduced while the shape memory effect is endowed to the electric heating layer, and the interface stability is improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the conductive filler content in the electric heating layer of the product is high, a large number of stable conductive paths are formed among the conductive fillers, the thickness of the conductive layer is thin, the contact among the conductive fillers is better, the conductive stability and the conductivity of the electric heating layer can be improved, and the stable resistance can be kept in the structural change process, so that the stable heat is provided.
2. The SMP substrate contained in the electric heating layer is consistent with the SMP substrate forming the device, the electric heating layer can carry out shape memory and shape recovery with the same trend along with the deformation of the device, the resistance of the electric heating layer in the deformation process is reduced, and the shape fixing rate and the recovery rate of the device are improved; meanwhile, the interface stability and the structural integrity of the electric heating layer and the SMP device in the deformation process of the device are ensured, and the problem of easy separation caused by poor interface stability of heterogeneous materials is solved.
3. The electric heating layer has the shape memory effect, can flexibly edit the required shape before being compounded and molded with the SMP device, and can customize the conductive path and the shape of the electric heating layer according to the structure and the function of the device to realize the electric response driving of a specific path.
4. The invention can realize the electric response drive of the three-dimensional SMP device by editing the shape of the electric heating layer and compounding the special shape and the three-dimensional SMP structure.
Drawings
FIG. 1 is a schematic view of an electrically responsive shape memory composite capable of driving a three-dimensional structure according to embodiment 1 of the present invention;
FIG. 2 is a schematic diagram of a three-dimensional solid cylindrical shape change driven by an electrical layer in embodiment 1 of the present invention;
FIG. 3 is an electron microscope image of the internal structure of an electric heating layer in example 2;
FIG. 4 is an electron micrograph of the internal structure of the electrically responsive shape memory composite material according to example 2;
FIG. 5 is a schematic view of an electrically responsive shape memory composite material according to embodiment 2 of the present invention;
in the figure, 1-shape memory polymer matrix, 2-electric heating layer, 3-heat conducting BN particles and 4-continuous carbon fibers.
Detailed Description
The invention will be further explained with reference to the drawings and examples.
Example 1:
a preparation method of an electric response shape memory composite material capable of driving a three-dimensional structure comprises the following steps:
(1) Taking 0.5g of conductive carbon black and 0.5g of chopped carbon fibers with the length of 0.5mm and the diameter of 7 mu m, and carrying out dry mixing and stirring for 0.5h to obtain a uniformly mixed conductive material;
(2) Adding the mixed conductive material into 10mL of N, N-dimethylformamide solution of 15 mass percent of shape memory epoxy resin prepolymer with Tg of 80 ℃, ultrasonically dispersing for 0.5h, and stirring at room temperature for 15min to obtain uniformly mixed conductive slurry;
(3) Uniformly coating the dispersed conductive paste in a mold, volatilizing the solvent, and curing at 100 ℃ for 8 hours to obtain an electric heating layer;
(4) Editing the shape of the electric heating layer to obtain a fixed double-spiral structure;
(5) Placing the double-spiral structure electric heating layer in a cylindrical mold, dispersing 5% of heat conduction particles BN in the shape memory epoxy resin prepolymer, pouring the prepolymer liquid into the mold, adjusting the position of the electric heating layer, curing for 8h at 60 ℃, curing for 4h at 80 ℃ and curing for 4h at 100 ℃ to obtain the three-dimensional shape memory composite material capable of driving the three-dimensional structure. The structure of the electrically responsive shape memory composite that can actuate a three-dimensional structure is shown in FIG. 1.
(6) Giving 36V direct current to be connected with the spiral electric heating layer, applying external force to deform after 90s, and performing power-off cooling to obtain a temporary shape; and the original shape is recovered 120s after the power is supplied again. The electrical layer driven three-dimensional volumetric cylindrical shape change is shown in figure 2.
Example 2:
the preparation method of the electric response shape memory composite material capable of driving the three-dimensional structure comprises the following steps:
(1) Taking 0.7g of multi-walled carbon nanotube and 0.3g of graphene, and carrying out dry mixing and grinding for 0.5h to obtain a uniformly mixed conductive material;
(2) Adding the mixed conductive material into 15mL of tetrahydrofuran solution of 10% shape memory styrene prepolymer by mass fraction, ultrasonically dispersing for 0.5h, and stirring for 15min at room temperature; obtaining evenly mixed conductive slurry;
(3) Uniformly coating the dispersed conductive paste in an S-shaped mould, volatilizing the solvent, and curing at 100 ℃ for 8 hours to obtain an electric heating layer; the internal structure of the electrical heating layer, i.e. the conductive layer, is shown in fig. 3.
(4) Respectively coating a layer of shape memory styrene prepolymer on two sides of the electric heating layer, and performing thermocuring;
(5) Respectively paving a layer of continuous carbon fiber on the upper side and the lower side of an electric heating layer with the surface isolated by shape memory styrene, soaking a shape memory styrene prepolymer in a mold, and carrying out vacuum hot-pressing curing at 100 ℃ for 8 hours to obtain the electric response shape memory composite material. An electron microscope image of the internal structure of the electric response shape memory composite material is shown in fig. 4, and a structural image of the electric response shape memory composite material is shown in fig. 5.

Claims (8)

1. A preparation method of an electric response shape memory composite material capable of driving a three-dimensional structure is characterized by comprising the following steps:
preparing conductive slurry: taking the shape memory polymer solution/prepolymer solution, adding a volatile solvent to regulate the concentration and viscosity of the shape memory polymer solution/prepolymer solution, adding a conductive material, and dispersing to form uniform conductive slurry;
coating the conductive slurry formed in the step (1) into a groove die with a designed path, and solidifying after volatilizing a volatile solvent to obtain an electric heating layer with a conductive path;
or, coating the conductive slurry formed in the step (1) into a demolding material, volatilizing a volatile solvent, solidifying, and then dividing to form a conductive path to obtain an electric heating layer with the conductive path;
(3) Heating the electric heating layer obtained in the step (2) to the deformation temperature of the electric heating layer, editing the shape and the conductive path of the matched electric heating layer according to the structure and the function of the device, keeping the shape editing, and cooling to the room temperature to obtain the shape memory electric heating layer with a fixed shape;
(4) Taking the shape memory polymer solution/prepolymer solution which is the same as the shape memory polymer solution/prepolymer solution obtained in the step (1), uniformly mixing the shape memory polymer solution/prepolymer solution with the selectively added functional filling material, compounding the shape memory polymer solution/prepolymer solution with the shape memory electric heating layer obtained in the step (3) in a three-dimensional die matched with the shape of the device, and curing and forming to obtain a three-dimensional electric response shape memory composite material;
the shape memory polymer solution in the step (1) and the shape memory polymer material in the step (4) both comprise one or a mixture of more of shape memory polylactic acid, shape memory polycaprolactone, shape memory polyurethane, shape memory polystyrene, shape memory epoxy resin, shape memory cyanate resin, shape memory polyimide and shape memory polymaleimide;
the conductive material in the step (1) comprises at least one of conductive carbon black, graphite, graphene, carbon nano tubes, carbon fiber materials and nano metal;
means of dispersion include stirring or sonication.
2. The preparation method of claim 1, wherein the weight percentage of the shape memory polymer solution/prepolymer solution in the conductive paste in the step (1) is 20wt% -90 wt%, the weight percentage of the conductive material is 10wt% -80 wt%, the concentration of the shape memory polymer solution/prepolymer solution is adjusted to 20wt% -100 wt%, and the viscosity of the shape memory polymer solution/prepolymer solution is adjusted to 1 mPa-s-100 Pa-s.
3. The production method according to claim 1, wherein the thickness of the electric heating layer in the step (2) is 10 to 1000 μm, and the shape-fixed electric heating layer in the step (3) has a property of recovering to an original shape by heating to a deformation temperature, and re-editing the shape of the electric heating layer.
4. The production method according to claim 1, wherein the distribution and number of layers of the shape memory electric heating layer are designed and adjusted during the compounding in the step (4).
5. The method according to claim 1, wherein the functionalized filler material in step (4) comprises at least one of a continuous fiber material, a chopped fiber material, a particulate material and a functionalized nano material, and the method for compounding comprises: dipping, coating and pouring, wherein the mass ratio of the shape memory electric heating layer to the shape memory polymer solution to the prepolymer solution to the functional filling material is 1 to 20.
6. An electrically responsive shape memory composite material obtained by the production method according to any one of claims 1 to 5, wherein the electrically responsive shape memory composite material has an electrically heatable layer of editable shape, and the shape of the path of the electrically heatable layer is edited according to the structural and functional design of the device, and the structure of the device is a three-dimensional structure.
7. Use of the electrically responsive shape memory composite of claim 6 as a low resistance, high stability electrically actuated shape memory polymer material.
8. Use of an electrically responsive shape memory composite material according to claim 6 in an electrically driven SMP device.
CN202210205086.6A 2022-03-02 2022-03-02 Electric response shape memory composite material capable of driving three-dimensional structure and preparation method and application thereof Active CN114621483B (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
DE102015014291A1 (en) * 2015-11-06 2017-05-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process and apparatus for the production of polymer moldings from polymers having shape memory or thermoresponsive properties
CN109096699A (en) * 2018-07-10 2018-12-28 哈尔滨工业大学 A kind of electric drive shape memory polymer composite material and preparation method thereof
CN112898756A (en) * 2021-03-09 2021-06-04 电子科技大学 Electric response shape memory composite material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015014291A1 (en) * 2015-11-06 2017-05-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process and apparatus for the production of polymer moldings from polymers having shape memory or thermoresponsive properties
CN109096699A (en) * 2018-07-10 2018-12-28 哈尔滨工业大学 A kind of electric drive shape memory polymer composite material and preparation method thereof
CN112898756A (en) * 2021-03-09 2021-06-04 电子科技大学 Electric response shape memory composite material and preparation method thereof

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