CN110256760B - Reversible shape memory material with photoelectric responsiveness and preparation method and application thereof - Google Patents
Reversible shape memory material with photoelectric responsiveness and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a functional polymer material, in particular to a reversible shape memory material with electrical and optical dual response characteristics, and a preparation method and application thereof. The invention provides a reversible shape memory material with photoelectric dual response characteristics, which is a polymer-based conductive composite material with an isolation structure, wherein the polymer is a semi-crystalline polymer with a wide melting range, namely the melting range temperature of the polymer is more than or equal to 20 ℃, and the melting range temperature is equal to the final melting temperature-initial melting temperature. The reversible shape memory material with electric and optical dual response characteristics can be prepared by physical blending, hot press molding, shaping, cooling and shaping, and the preparation method is simple; an isolation structure of the conductive filler is constructed in the material so as to obtain excellent conductive performance; the conductive filler of the isolation network does not influence the movement of the molecular chain of the reversible shape memory polymer, so that the reversible shape memory polymer can still keep excellent driving performance when used as a driver.
Description
Technical Field
The invention relates to a functional polymer material, in particular to a reversible shape memory material with electrical and optical dual response characteristics, and a preparation method and application thereof.
Background
When the artificial intelligent robot is rapidly developed, a driver capable of converting external stimuli (heat, light, electricity, etc.) into mechanical work is receiving wide attention. The two-way shape memory polymer (RSMP) is a smart material capable of exhibiting a shape change by a temperature change, and RSMP has advantages such as low density, low power consumption and excellent processability, showing its application potential in the field of drives. The conventional RSMP can only respond to the change of the ambient temperature, which greatly limits its application. The application of RSMP can be further expanded by building a filler network in the RSMP to increase its response to light and electricity.
The shape memory polymers currently used for the preparation of electrically actuated are generally blended by directly introducing electrically conductive fillers, which, although it does enable electrical actuation, have a number of limitations: (1) the transition of the polymer from the insulator to the conductor requires the introduction of a large amount of filler and the actuation at a higher voltage; (2) the presence of a large amount of filler can affect the mobility of the polymer molecular chains and thereby reduce the shape memory properties of the RSMP.
Disclosure of Invention
Aiming at the defects, the invention provides a reversible shape memory material with optical and electric dual response characteristics and a preparation method and application thereof, the obtained material can simultaneously respond to electric and optical stimulation, namely, the material has the optical and electric dual response characteristics, and the obtained material has excellent driving performance; and the preparation process of the material is simple.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a reversible shape memory material with photoelectric dual response characteristics, wherein the material is a polymer-based conductive composite material with an isolation structure, the polymer is a semi-crystalline polymer with a wide melting range, namely the melting range temperature of the polymer is not less than 20 ℃, and the melting range temperature is the final melting temperature-initial melting temperature.
Namely, the polymer selected by the invention is a wide melting range polymer (namely the temperature of a melting range interval is more than or equal to 20 ℃); the melting range refers to a temperature range, called melting range, where the melting point of a substance is not a point, and two limits are called initial melting temperature, i.e. the temperature at which the substance starts to melt, and final melting temperature, i.e. the temperature at which the substance completely melts.
Further, the isolation structure refers to: the polymer-based conductive composite is prepared from a polymer matrix and conductive fillers, wherein the conductive fillers are located at the interface between the polymer matrix, rather than being randomly arranged in the polymer matrix.
Furthermore, the polymer matrix in the reversible shape memory material with the photoelectric dual response characteristic is a semi-crystalline polymer with a wide melting range of more than 20 ℃.
Still further, the polymer matrix is: at least one of ethylene-octene copolymer (POE) or ethylene-vinyl acetate copolymer (EVA).
The conductive filler is at least one of carbon black, carbon nano tubes, graphene or carbon fiber short fibers; the conductive filler in the invention is selected from any one of fillers or a mixture of at least two of fillers which can enable the composite material to have an electrified Joule heating effect and a photothermal effect.
Preferably, in the reversible shape memory material with photoelectric dual response characteristics, the polymer matrix is an ethylene-octene copolymer, the conductive filler is a carbon nanotube, and the ratio of the polymer matrix to the conductive filler is as follows: 100 parts by volume of ethylene-octene copolymer and 0.1-6 parts by volume of conductive filler.
The invention aims to solve the second technical problem and provides a preparation method of a reversible shape memory material with photoelectric dual response characteristics, which comprises the following steps: firstly, physically blending polymer matrix particles and conductive filler to enable the conductive filler to be coated on the surfaces of the polymer matrix particles, and then fixing the conductive filler between the interfaces of the polymer matrix particles through hot-pressing molding to obtain a composite material with an isolation structure; and then shaping and cooling the obtained composite material to obtain the reversible shape memory material with photoelectric dual response characteristics.
Further, the particle size of the polymer matrix particles is 50-2000 μm, preferably 200-600 μm.
Further, the physical blending mode is as follows: one of ball milling, grinding or high speed stirring and mixing.
Further, the hot press molding is performed at a temperature not lower than the initial melting temperature of the polymer matrix but not higher than the thermal decomposition index; the shaping of the composite material is carried out at a temperature which is 3-20 ℃ below the final melting temperature of the polymer matrix.
Further, the shaping adopts a method of clamping by a fixed clamp.
The third technical problem to be solved by the present invention is to point out: the reversible shape memory material with photoelectric dual response characteristics can be used as an intelligent switch, a mechanical gripper or a flexible robot.
The invention has the beneficial effects that:
(1) the reversible shape memory material with electric and optical dual response characteristics can be prepared by physical blending and then hot press molding and shaping, and the preparation method is simple;
(2) the preparation process of hot pressing after physical blending can construct an isolation structure of the conductive filler in the material so as to obtain excellent conductive performance;
(3) the conductive filler of the isolation network does not influence the movement of molecular chains such as POE (polyolefin elastomer) and the like, so that the obtained reversible shape memory material can still keep excellent driving performance;
(4) the conductive filler of the isolating network allows the RSMP to respond to both electrical and optical stimuli.
Drawings
FIG. 1 is an optical microscope photograph of the reversible shape memory material with photoelectric dual response characteristics obtained in the first embodiment.
FIG. 2 is an optical microscope photograph of the reversible shape memory material with photoelectric dual response characteristics obtained in example four.
FIG. 3 is a scanning electron micrograph of a composite material obtained in comparative example II.
FIG. 4 shows the electrical conductivity of the reversible shape memory material with photoelectric dual response characteristics obtained in the first, second, third, fourth and fifth examples, and the composite material obtained in the first, second and third comparative examples.
FIG. 5 is a graph showing the temperature dependence of deformation of the reversible shape-memory material with photoelectric dual response characteristics obtained in the fourth embodiment without external force.
FIG. 6 is a graph showing the change of deformation with temperature of the composite material obtained in comparative example without external force.
FIG. 7 is a graph showing the temperature changes with time of the reversible shape memory material with photoelectric dual response characteristics obtained in example four under DC voltages of 20V, 30V and 36V and the composite material obtained in comparative example two under DC voltage of 200V.
FIG. 8 shows that the reversible shape-memory material with photoelectric dual response characteristics obtained in example two is 250mW cm-2Is a graph of temperature under illumination versus time for optical power density.
Detailed Description
The first technical problem to be solved by the invention is to provide a reversible shape memory material with photoelectric dual response characteristics, the material is a polymer-based conductive composite material with an isolation structure, the polymer is a semi-crystalline polymer with a wide melting range, the temperature of the melting range of the polymer is not less than 20 ℃, and the temperature of the melting range is equal to or higher than a final melting temperature-an initial melting temperature. The invention indicates for the first time that a specific polymer-based conductive composite material with an isolation structure can be used as a reversible shape memory material with photoelectric dual response characteristics.
The invention aims to solve the second technical problem and provides a preparation method of a reversible shape memory material with photoelectric dual response characteristics, which comprises the following steps: firstly, physically blending polymer matrix particles and conductive filler to enable the conductive filler to be coated on the surfaces of the polymer matrix particles, and then fixing the conductive filler between the interfaces of the polymer matrix particles through hot-pressing molding to obtain a composite material with an isolation structure; and then shaping and cooling the obtained composite material to obtain the reversible shape memory material with photoelectric dual response characteristics. In other words, the shaping and cooling shaping in the present invention means to re-customize a shape and fix it according to actual needs after hot press shaping.
Further, the hot press molding is performed at a temperature not lower than the initial melting temperature of the polymer matrix but not higher than the thermal decomposition index; the shaping of the composite material is carried out at a temperature which is 3-20 ℃ below the final melting temperature of the polymer matrix.
The technical solution of the present invention is further explained by the following embodiments. The following examples are only exemplary embodiments and are not intended to limit the present invention, and those skilled in the art can reasonably design the technical solutions with reference to the examples and can also obtain the results of the present invention.
Example one
Adding 100 parts of POE powder (with the particle size of 200-600 mu m) and 0.25 part of carbon nano tube into a planetary ball mill, mixing for 90min at the speed of 400r/min, then performing compression molding on the mixed product at the temperature of 100 ℃ and under the pressure of 2.5MPa, then clamping and reshaping the hot-press molded product at the temperature of 80 ℃ through a fixing clamp according to actual needs, and cooling and shaping to obtain the reversible shape memory material with photoelectric dual response characteristics.
Example two
Adding 100 parts of POE powder (with the particle size of 200-600 mu m) and 0.5 part of carbon nano tube into a planetary ball mill, mixing for 90min at the speed of 400r/min, then performing compression molding on the mixed product at the temperature of 100 ℃ and under the pressure of 2.5MPa, clamping the hot-press molded product at the temperature of 80 ℃ through a fixed clamp, reshaping, and cooling and sizing to obtain the reversible shape memory material with photoelectric dual response characteristics.
EXAMPLE III
Adding 100 parts of POE powder (with the particle size of 200-600 mu m) and 1 part of carbon nano tube into a planetary ball mill, mixing at 400r/min for 90min, then performing compression molding on the mixed product at 100 ℃ and under the pressure of 2.5MPa, clamping the hot-pressed product at 80 ℃ through a fixing clamp, reshaping, and cooling and sizing to obtain the reversible shape memory material with photoelectric dual response characteristics.
Example four
Adding 100 parts of POE powder (with the particle size of 200-600 mu m) and 2 parts of carbon nano tubes into a planetary ball mill, mixing at 400r/min for 90min, then performing compression molding on the mixed product at 100 ℃ and under the pressure of 2.5MPa, clamping the hot-pressed product at 80 ℃ through a fixing clamp, reshaping, and cooling and sizing to obtain the reversible shape memory material with photoelectric dual response characteristics.
EXAMPLE five
Adding 100 parts of POE powder (with the particle size of 200-600 mu m) and 3 parts of carbon nano tubes into a planetary ball mill, mixing at 400r/min for 90min, then performing compression molding on the mixed product at 100 ℃ and under the pressure of 2.5MPa, clamping the hot-pressed product at 80 ℃ through a fixing clamp, reshaping, and cooling and sizing to obtain the reversible shape memory material with photoelectric dual response characteristics.
Comparative example 1
Adding 100 parts of POE and 1 part of carbon nano tube into an internal mixer, blending for 8min at 150 ℃, then performing compression molding on a product obtained by blending at 100 ℃ and under the pressure of 2.5MPa, clamping the product obtained by hot-press molding at 80 ℃ through a fixing clamp, reshaping, and cooling and shaping to obtain the composite material.
Comparative example No. two
Adding 100 parts of POE and 2 parts of carbon nano tubes into an internal mixer, blending for 8min at 150 ℃, then performing compression molding on a product obtained by blending at 100 ℃ and under the pressure of 2.5MPa, clamping the product obtained by hot-press molding at 80 ℃ through a fixing clamp, reshaping, and cooling and shaping to obtain the composite material.
Comparative example No. three
Adding 100 parts of POE and 3 parts of carbon nano tubes into an internal mixer, blending for 8min at 150 ℃, then performing compression molding on a product obtained by blending at 100 ℃ and under the pressure of 2.5MPa, clamping the product obtained by hot-press molding at 80 ℃ through a fixing clamp, reshaping, and cooling and shaping to obtain the composite material.
And (3) performance testing:
fig. 1 and 2 are optical micrographs of the materials obtained in the first and fourth examples, respectively, and the following conclusions can be obtained by observing the microstructure of the obtained materials: a perfect conductive network of an isolation mechanism can be constructed in the material through hot pressing after ball milling, and a conductive path becomes wider along with the increase of the content of the filler.
Fig. 3 is a scanning electron micrograph of the material obtained in the comparative example, and it can be seen from fig. 3 that the dispersion of the filler in the material obtained by direct blending is random and a perfect conductive path is not formed inside the material.
Fig. 4 shows the electrical conductivity of the materials obtained in the first, second, third, fourth and fifth examples and the materials obtained in the first, second and third comparative examples, and it can be seen that the electrical conductivity of the materials can be much higher than that of the materials obtained by direct blending by constructing the conductive network of the isolation structure in the interior of the materials.
FIGS. 5 and 6 are graphs showing the deformation of the materials obtained in the fourth example and the second comparative example along with the change of temperature under the condition of no external force, respectively, and it can be seen from the graphs that the reversible deformation of the material obtained in the fourth example can reach 2.5%, the reversible deformation of the material obtained in the second comparative example can reach 0.9%, and the driving performance of the material of the conductive network introduced into the isolation structure by hot pressing after ball milling is obviously better than that of the material obtained by direct blending; namely, the conductive polymer matrix composite material with the isolation structure has good driving performance.
FIG. 7 is a graph showing the temperature of the composite material obtained in example four, which is rapidly heated at an applied voltage of 36V or less, with a direct current voltage of 20V, 30V, 36V and a direct current voltage of 200V, as compared with the composite material obtained in comparative example two, and the temperature rising rate of the material is increased as the applied voltage is increased; the material obtained in comparative example can not be heated even at 200V under the same filler content; table 1 is a summary of the time required for the materials obtained in example four and comparative example two to heat to 60 ℃ at different voltages; therefore, the conductive polymer matrix composite material with the isolation structure has good thermal response performance.
TABLE 1 time required for the materials obtained in example four and comparative example two to heat up to 60 ℃ at different voltages
| Sample (I) | Time(s) required for heating to 60 ℃ |
| Examples four to 20V | 80 |
| Examples four to 30V | 32 |
| Examples four to 36V | 22 |
| Comparative example No. two to 200V | Can not be heated |
FIG. 8 shows the material obtained in example two at 250mW cm-2The change of the temperature under light irradiation with the optical power density of (1) with time, it can be seen from the graph that the obtained material is250mW·cm-2The temperature is raised to 60 ℃ in the light of the optical power density of the light for only 50 s. Therefore, the conductive polymer matrix composite material with the isolation structure has good light response performance.
Claims (12)
1. The reversible shape memory material with the photoelectric dual-response characteristic is characterized in that the material is a polymer-based conductive composite material with an isolation structure, wherein the polymer is a semi-crystalline polymer with a wide melting range, namely the melting range temperature of the polymer is not less than 20 ℃, and the melting range temperature is the final melting temperature-initial melting temperature; the isolation structure refers to: the polymer-based conductive composite material is prepared from a polymer matrix and conductive fillers, wherein the conductive fillers are positioned on an interface between the polymer matrix and are not randomly arranged in the polymer matrix; and the proportion of the polymer matrix to the conductive filler is as follows: 100 parts by volume of a polymer matrix and 0.1-6 parts by volume of a conductive filler; wherein the polymer matrix is an ethylene-octene copolymer;
the reversible shape memory material with photoelectric dual response characteristics is prepared by adopting the following method: firstly, physically blending polymer matrix particles and conductive filler to enable the conductive filler to be coated on the surfaces of the polymer matrix particles, and then fixing the conductive filler between the interfaces of the polymer matrix particles through hot-pressing molding to obtain a composite material with an isolation structure; then shaping and cooling the obtained composite material to obtain the reversible shape memory material with photoelectric dual response characteristics; wherein, the physical blending mode is as follows: one of ball milling, grinding or high speed stirring and mixing.
2. The reversible shape memory material with photoelectric dual response characteristic according to claim 1, wherein the conductive filler is at least one of carbon black, carbon nanotubes, graphene or carbon fiber short fiber.
3. The reversible shape memory material with photoelectric dual-response characteristic according to claim 2, wherein the polymer matrix is an ethylene-octene copolymer, the conductive filler is carbon nanotubes, and the ratio of the polymer matrix to the conductive filler is as follows: 100 parts by volume of ethylene-octene copolymer and 0.1-6 parts by volume of conductive filler.
4. A method for preparing a reversible shape memory material with photoelectric dual response characteristics as claimed in any one of claims 1 to 3, wherein the method comprises: firstly, physically blending polymer matrix particles and conductive filler to enable the conductive filler to be coated on the surfaces of the polymer matrix particles, and then fixing the conductive filler between the interfaces of the polymer matrix particles through hot-pressing molding to obtain a composite material with an isolation structure; and then shaping and cooling the obtained composite material to obtain the reversible shape memory material with photoelectric dual response characteristics.
5. The method for preparing a reversible shape memory material with photoelectric dual response characteristics according to claim 4, wherein the particle size of the polymer matrix particles is 50-2000 μm.
6. The method for preparing a reversible shape memory material with photoelectric dual response characteristics according to claim 5, wherein the particle size of the polymer matrix particles is 200-600 μm.
7. The method for preparing the reversible shape memory material with photoelectric dual response characteristic according to claim 4, wherein the physical blending mode is as follows: one of ball milling, grinding or high speed stirring and mixing.
8. The method for preparing the reversible shape memory material with photoelectric dual response characteristic according to claim 5 or 6, wherein the physical blending mode is as follows: one of ball milling, grinding or high speed stirring and mixing.
9. The method for preparing a reversible shape memory material with photoelectric dual response characteristics as claimed in claim 4, wherein the hot press molding is performed at a temperature higher than the initial melting temperature of the polymer matrix and lower than the thermal decomposition temperature; the shaping of the composite material is carried out at a temperature which is 3-20 ℃ below the final melting temperature of the polymer matrix.
10. The method for preparing a reversible shape memory material with photoelectric dual response characteristics according to any one of claims 5 to 7, wherein the hot press molding is performed at a temperature higher than the initial melting temperature of the polymer matrix and lower than the thermal decomposition temperature; the shaping of the composite material is carried out at a temperature which is 3-20 ℃ below the final melting temperature of the polymer matrix.
11. The method for preparing a reversible shape memory material with photoelectric dual response characteristics as claimed in claim 8, wherein the hot press molding is performed at a temperature higher than the initial melting temperature of the polymer matrix and lower than the thermal decomposition temperature; the shaping of the composite material is carried out at a temperature which is 3-20 ℃ below the final melting temperature of the polymer matrix.
12. The reversible shape memory material with the photoelectric dual response characteristic can be used as an intelligent switch, a mechanical gripper or a flexible robot, wherein the reversible shape memory material with the photoelectric dual response characteristic is the reversible shape memory material disclosed by any one of claims 1-3 or the reversible shape memory material prepared by the preparation method disclosed by any one of claims 4-11.
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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 |
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