CN113214621B - Preparation and recovery method of anisotropic liquid metal composite material - Google Patents
Preparation and recovery method of anisotropic liquid metal composite material Download PDFInfo
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- CN113214621B CN113214621B CN202110725685.6A CN202110725685A CN113214621B CN 113214621 B CN113214621 B CN 113214621B CN 202110725685 A CN202110725685 A CN 202110725685A CN 113214621 B CN113214621 B CN 113214621B
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Abstract
A liquid metal composite material is prepared through mixing Liquid Metal (LM) with Polycaprolactone (PCL), stirring while heating to 170-180 deg.C to obtain a flowing composite, and cooling at ordinary temp. The method is simple and easy to obtain, and the prepared liquid metal composite material (LM-PCL) has excellent stretchability and plasticity; the conductive film has excellent anisotropy of one surface being conductive and one surface being insulating, and the conductivity of the conductive surface is high; has degradable recoverability and simple recovery method.
Description
Technical Field
The invention belongs to the technical field of liquid metal materials, and particularly relates to a preparation and recovery method of a liquid metal composite material.
Background
The liquid metal has excellent properties such as low melting point, high electrical conductivity, high thermal conductivity, low viscosity, fluidity and the like, and has good thermal conductivity and fluidity macroscopically. Therefore, the conductive paste can flow freely and keep good conductive performance. Meanwhile, liquid metal is also the best material for microfluidics. The gallium-based liquid metal is nontoxic and harmless to human bodies due to low toxicity and biocompatibility, can be applied to the field of biological materials, and can be used as a drug transport carrier. Through phase change, the liquid metal can realize reversibility between solid state and liquid state, thereby adjusting the rigidity of the composite material. Because the atoms in the liquid metal can not move freely as in the solid state and vibrate around the position of the equilibrium node, the vibration energy and the frequency of the liquid metal are millions of times higher than those of the solid atoms.
The liquid metal composite material has good application prospect by virtue of the manufacturing advantages of stretchability, flexibility, impact resistance, high efficiency, low cost and the like. The liquid metal is used as a modified filler and permeates into the flexible high molecular polymer, and the liquid metal can be reoriented along with the deformation of the matrix. The stretchable composite material has good application prospect in the fields of wearable implantable materials, self-healing materials, electromagnetic shielding materials and the like. The high molecular polymer has the characteristics of flexibility, light weight and the like, and polycaprolactone (PCL/(C) 6 H 10 O 2 ) n ) Has better biocompatibility and biodegradability, and is applied to surgical sutures, drug-releasing carriers, tumor treatment carriers and the like in the medical field. The material compounded by the liquid metal and the high molecular polymer has very high design flexibility. At present liquid metalThe composite material is synthesized with most other high molecular polymers, and the composite material cannot be degraded and recycled due to the properties of the polymers, has anisotropic characteristics, and is limited in application in the fields of medical treatment and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a liquid metal composite material.
It is another object of the present invention to provide a method for recovering the liquid metal composite prepared by the above method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a liquid metal composite material is characterized by comprising the following steps: mixing Liquid Metal (LM) and Polycaprolactone (PCL), heating to 170-180 ℃ while stirring to form a flowing compound, then placing the flowing compound on the surface of a PET film, and cooling and curing at normal temperature.
Further, the mixing is to heat the Liquid Metal (LM) to 80 to 90 ℃, and then to add the Polycaprolactone (PCL) particle by particle while stirring.
And further stirring by using a glass rod at the stirring speed of 50 to 60rpm, placing the tail end of the glass rod in a mixture formed by LM and PCL and close to 1/3 of the surface of the mixture after the temperature is raised, and continuously stirring for 30 to 60min.
In the preparation process, the prepared composite material loses conductivity due to the excessive consumption of the PCL, but the PCL and the Liquid Metal (LM) which are few are difficult to completely permeate into the PCL and are easy to attach to a stirrer due to the high viscosity of the PCL, and the liquid metal is difficult to uniformly distribute in the PCL.
According to the invention, the LM is heated to a melting point slightly higher than that of the PCL, the PCL is slowly added and stirred, then the temperature is slowly increased to a higher temperature, the viscosity of the PCL is cooperatively regulated and controlled along with the slow change of the temperature and the participation of liquid metal in the process, the EGaIn is completely infiltrated into the PCL by stirring of the stirring rod made of glass, and the excellent hardness and toughness of the EGaIn are ensured. According to the larger density difference of PCL and LM, the stirring position of the glass stirring rod in the mixture is adjusted at high temperature, the liquid metal is promoted to form a structure that most of LM in the PCL sinks and the component content gradually decreases from bottom to top under the slow stirring speed, PCL moves upwards and gradually decreases from top to bottom, the anisotropy of front (upper) insulation and back (lower) conduction is formed, and the LM is mainly gathered on the back of the material, so that the structure that the conducting end of the LM is uniformly dispersed in the composite material has more excellent conducting performance.
Further, the liquid metal is preferably a gallium indium alloy (EGaIn).
Further, the mass ratio of the gallium-indium alloy to the polycaprolactone is 7 to 9.
Further, the temperature rise rate is 1 to 1.5 ℃/min.
Most specifically, the preparation method of the liquid metal composite material is characterized by comprising the following steps of:
step (1): heating Liquid Metal (LM) to 80-90 ℃, and adding Polycaprolactone (PCL) into the metal liquid while stirring by using a glass rod at 50-60rpm, wherein the mass ratio of LM to PCL is 7-9;
step (2): after the addition is finished, continuously stirring, and slowly raising the temperature to 170-180 ℃;
and (3): after the temperature rise is finished, moving the tail end of the glass rod to a position, close to 1/3 of the surface of the mixture, in the mixture formed by the LM and the PCL, and continuously stirring for 30-60min to obtain a flow dynamic compound with the LM completely coated by the PCL;
and (4): and (3) placing the liquid compound on the surface of PET, and cooling and solidifying the liquid compound in a room-temperature environment.
The method for recovering the liquid metal composite material prepared by the method is characterized by comprising the following steps: and the recovery is to place the liquid metal composite material in a 3mol/L hydrochloric acid solution, stand for 12 to 18h, remove the solution and the surface floats thereof, and collect the liquid metal settled at the bottom.
The invention has the following technical effects:
the method is simple and easy to obtain, and the prepared liquid metal composite material (LM-PCL) has excellent stretchability and plasticity and can be prepared into different shapes; the conductive film has excellent anisotropy of one surface being conductive and one surface being insulated, and the conductivity of the conductive surface is high, so that the conductive film can be effectively applied to the fields with special anisotropic requirements, such as Chinese medicine acupuncture and moxibustion; has degradable recoverability and simple recovery method.
Drawings
FIG. 1: the invention discloses a process schematic diagram for preparing a liquid metal composite material.
FIG. 2: front and back and longitudinal cross-sectional views of the liquid metal composite material prepared by the invention.
FIG. 3: the anisotropy of the liquid metal composite material prepared by the invention is shown schematically.
FIG. 4: the liquid metal composite material prepared by the invention has a section scanning electron microscope image.
FIG. 5: the liquid metal composite material prepared by the method has a drawable state and a fiber state.
FIG. 6: the infrared spectrum analysis chart of the liquid metal composite material prepared by the invention.
FIG. 7: the front surface energy spectrum analysis chart of the liquid metal composite material prepared by the invention.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
The preparation method of the liquid metal composite material comprises the following steps:
step (1): heating gallium indium alloy (EGaIn) to 80 ℃, adding Polycaprolactone (PCL) into the gallium indium alloy (EGaIn) one by one while stirring the gallium indium alloy with a glass rod at 50rpm, wherein the mass ratio of the EGaIn to the PCL is 7:1;
step (2): after the addition was complete, stirring was continued and the temperature was slowly raised to 170 ℃;
and (3): after the temperature rise is finished, moving the tail end of the glass rod to a position, close to 1/3 of the surface of the mixture, in the mixture formed by the LM and the PCL, and continuously stirring for 30min to obtain a flow state compound of which the LM is completely coated by the PCL;
and (4): and (3) placing the liquid compound on the surface of PET, and cooling and solidifying the liquid compound in a room-temperature environment.
Example 2
The preparation method of the liquid metal composite material is characterized by comprising the following steps of:
step (1): heating gallium indium alloy (EGaIn) to 90 ℃, adding Polycaprolactone (PCL) into the gallium indium alloy (EGaIn) one by one while stirring the gallium indium alloy with a glass rod at 60rpm, wherein the mass ratio of the EGaIn to the PCL is 8:1;
step (2): after the addition was complete, stirring was continued and the temperature was slowly raised to 175 ℃;
and (3): after the temperature rise is finished, moving the tail end of the glass rod to a position, close to 1/3 of the surface of the mixture, in the mixture formed by the LM and the PCL, and continuously stirring for 60min to obtain a flow state compound of which the LM is completely coated by the PCL;
and (4): and (3) placing the liquid compound on the surface of PET, and cooling and solidifying the liquid compound in a room-temperature environment.
Example 3
The preparation method of the liquid metal composite material is characterized by comprising the following steps of:
step (1): heating gallium indium alloy (EGaIn) to 85 ℃, adding Polycaprolactone (PCL) one by using a glass rod while stirring at 55rpm, wherein the mass ratio of EGaIn to PCL is 9:1;
step (2): after the addition was complete, stirring was continued and the temperature was slowly raised to 180 ℃;
and (3): after the temperature rise is finished, moving the tail end of the glass rod to a position, close to 1/3 of the surface of the mixture, in the mixture formed by the LM and the PCL, and continuously stirring for 50min to obtain a flow state compound of which the LM is completely coated by the PCL;
and (4): and (3) placing the liquid compound on the surface of PET, and cooling and solidifying the liquid compound in a room-temperature environment.
The liquid metal composite material prepared by the invention has a black surface state, contains PCL as a main component and gray back surface, and contains a large amount of liquid metal. The cross section is a composite material of a plurality of granular liquid metals mixed with PCL, as shown in figure 2. The internal components of the PCL are distributed in the upper part of the composite material, the liquid metal is deposited in the lower part of the composite material, and the content of the liquid metal is higher downwards, so that the anisotropy of front conductivity and back conductivity is realized.
FIG. 4 is a scanning electron microscope view showing a transverse cross section near the back surface of a liquid metal composite material prepared by the present invention and a comparative example, wherein FIG. 4 (a) is an LM-PCL composite material prepared by mixing 90wt% liquid metal to 10wt% PCL in example 3 of the present invention, from which smooth liquid droplets are in the form of liquid metal, the size of the liquid droplets is relatively uniform, the average size is about 80 μm, the coarse portion is PCL, the liquid metal and PCL are mixed, the liquid droplets of the liquid metal are connected with each other, and the liquid metal is uniformly distributed. FIG. 4 (b) is a scanning electron micrograph of a cross section of an LM-PCL composite prepared at a liquid metal content of 80wt% to mass ratio of 2 wt% PCL, showing poor droplet size uniformity of the liquid metal and an average size of about 150 μm. The connection between the liquid drops is blocked by PCL, and the liquid drops are distributed unevenly, and the detection shows that the liquid drops have no conductivity. FIG. 4 (c) LM-PCL composite material prepared by 40wt% liquid metal to mass ratio of PCL, with a cross section of small amount of liquid metal distributed in large amount of PCL material. The liquid metal composite material has no conductivity and is an insulator.
At high temperature, the composite material is in a dark gray fluid state and has high viscosity and plasticity, and different morphological structures at room temperature can be obtained by performing compression molding, wire drawing or injection on the LM-PCL composite material at high temperature, as shown in figure 5.
As can be seen from FIG. 6, the values are 1729 to 1239cm -1 The infrared image of PCL has stronger peak position and belongs to the characteristic absorption peak of ester group, which shows that the pure PCL and the LM-PCL composite material prepared by the invention all contain ester group
，1471~1396cm -1 Is provided with (-CH) 2 A-) a deformation vibration absorption peak just occurs; 2943 to 2867cm -1 With (-CH) 2 -) occurrence of a stretching vibration absorption peak; 1364cm -1 And 1418cm -1 All have (-CH) 3 ) The appearance of a characteristic absorption peak of-CH indicates 3 The existence of the structure. The black peak of PCL is 3341cm -1 The peak has a stretching vibration peak of-OH, and a red peak in the LM-PCL composite material has no-OH structure.
Fig. 7 is a front scanning electron micrograph of the liquid metal composite material, and composition distribution diagrams of C, ga, in, and O elements on the front surface of the composite material, in order from fig. 7 (a) to fig. 7 (e). In the front element composition, the atomic composition content was 77.23% of C atoms, 20.27% of O atoms, 2.16% of Ga atoms, and 0.34% of In atoms, and the front liquid metal content was very small and the PCL content was high. Therefore, the front surface of the composite material has no conductivity, and the resistance test is sequentially carried out on the front surface and the longitudinal section of the liquid metal composite material, and the test result shows that the resistance of the front surface of the liquid metal composite material is infinite, the middle resistance value of the longitudinal section is 4.03 omega, and the resistance value is gradually reduced closer to the back surface, which is consistent with the expression of the structural schematic diagram in fig. 3.
Comparative example 1:
the preparation method of 100% pure PCL comprises the following specific steps:
50ml of water was placed in a 100ml beaker and heated to 60 ℃ to obtain 5g of solid PCL particles, which were then stirred with glass in a glass vessel. And (3) heating the PCL in the beaker to 180 ℃ slowly until the PCL becomes mucus, taking out the PCL with a medicine spoon, placing the PCL on a solid PET film, and waiting for solidification at normal temperature.
At temperatures above 60 ℃, PCL melts into a liquid state, but its viscosity is extremely high.
During the stirring at elevated temperature, we found that the viscosity of PCL did not change significantly with increasing temperature, forming a viscous liquid that adhered to the glass container and the glass rod.
Comparative example 2:
the preparation method of the liquid metal composite material is characterized by comprising the following steps of:
heating gallium indium alloy (EGaIn) to 180 ℃, adding Polycaprolactone (PCL) into the alloy by one while stirring with a glass rod close to the bottom of the container at 55rpm, wherein the mass ratio of the EGaIn to the PCL is 9:1, continuously stirring for 50min, completely penetrating the EGaIn into the PCL to form a flowing mixture, placing the flowing mixture on the surface of PET, and cooling and solidifying at room temperature.
At a lower temperature (lower than 170 ℃), high-content EGaIn is difficult to permeate into low-content PCL, the high-content EGaIn can be permeated into the low-content PCL only at the temperature of 170 ℃ or above, in the comparative example 2, the LM-PCL composite material is directly prepared in a high-temperature environment, but the composite material is fragile, difficult to deform and stretch, and cannot form structures such as a wire drawing state, a fiber state and the like, the distribution uniformity of EGaIn liquid drops in the PCL is poor, a large amount of liquid metal is gathered in some places in the same transverse section of the composite material, and the liquid metal is not gathered in some places.
We also tried to prepare LM-PCL material in water using water as the vehicle, although PCL was less viscous in water and easier to stir, LM was extremely fluid in water, hardly formed dispersed droplets, and it was still difficult for LM to completely enter PCL.
Example 4
Degrading and recycling the liquid metal composite material:
the LM-PCL composite material prepared in example 3 was placed in a glass container, 3mol/L HCl solution was added to completely submerge the composite material, and after soaking for 16.5 h.
In the process, the edges of the composite material gradually become white, more white substances emerge to the surface of the hydrochloric acid solution, and more droplets settle at the bottom of the container and are gathered. Therefore, ester groups in the PCL are hydrolyzed under an acidic condition, so that the liquid metal is separated from the PCL.
Claims (3)
1. The preparation method of the liquid metal composite material is characterized by comprising the following steps of:
step (1): heating liquid metal LM to 80-90 ℃, and adding polycaprolactone PCL into the liquid metal LM by a glass rod while stirring at 50-60rpm;
step (2): after the addition is finished, continuously stirring, and slowly raising the temperature to 170-180 ℃;
and (3): after the temperature rise is finished, moving the tail end of the glass rod to a position, close to 1/3 of the surface of the mixture, in the mixture formed by the LM and the PCL, and continuously stirring for 30-60min to obtain a flow dynamic compound with the LM completely coated by the PCL;
and (4): and (3) placing the liquid compound on the surface of PET, and cooling and solidifying the liquid compound in a room-temperature environment.
2. The method of preparing a liquid metal composite of claim 1, wherein: the liquid metal is gallium-indium alloy, and the mass ratio of the gallium-indium alloy to the polycaprolactone is 7 to 9.
3. A method of recycling a liquid metal composite produced by the method of claim 1, wherein: and the recovery is to place the liquid metal composite material in a 3mol/L hydrochloric acid solution, stand for 12 to 18h, remove the solution and the surface floats thereof, and collect the liquid metal settled at the bottom.
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| CN108410001A (en) * | 2018-03-22 | 2018-08-17 | 河南科技学院 | Application of the low-melting point metal alloy in preparing organic polymer sponge and foam |
| CN112076352A (en) * | 2020-08-25 | 2020-12-15 | 云南科威液态金属谷研发有限公司 | Medical liquid metal thermoplastic functional composite material and preparation method and application thereof |
| CN112280284A (en) * | 2020-09-24 | 2021-01-29 | 深圳大学 | Liquid metal composite material, preparation method, remodeling method and recovery method |
| CN113024929A (en) * | 2021-04-08 | 2021-06-25 | 东南大学 | Preparation method of conductive polymer composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108410001A (en) * | 2018-03-22 | 2018-08-17 | 河南科技学院 | Application of the low-melting point metal alloy in preparing organic polymer sponge and foam |
| CN112076352A (en) * | 2020-08-25 | 2020-12-15 | 云南科威液态金属谷研发有限公司 | Medical liquid metal thermoplastic functional composite material and preparation method and application thereof |
| CN112280284A (en) * | 2020-09-24 | 2021-01-29 | 深圳大学 | Liquid metal composite material, preparation method, remodeling method and recovery method |
| CN113024929A (en) * | 2021-04-08 | 2021-06-25 | 东南大学 | Preparation method of conductive polymer composite material |
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