Liquid metal composite material and preparation method thereof

Abstract

The invention provides a liquid metal composite material and a preparation method thereof, and relates to the technical field of liquid metal materials, the preparation method comprises the following steps: S1, adding 3-(3, 5-dicarboxyphenyl) pyridine-2, 6-dicarboxylic acid and zinc nitrate hexahydrate into a solvent, and stirring to obtain a reaction solution; s2, after the reaction solution is subjected to a heating reaction, blocky products are collected and washed and dried, and the zinc complex is obtained; and S3, the liquid metal and a zinc complex are mixed, ultrasonic treatment is conducted, and the liquid metal composite material is obtained. The liquid metal composite material provided by the invention is formed by mixing the liquid metal and the zinc complex and then performing ultrasonic treatment, and the zinc complex is relatively high in coordination number and relatively good in crystallinity, so that the liquid metal composite material has relatively high viscosity, and the liquid metal composite material is relatively easy to form effective adhesion with a base material.

Description

Technical Field

[0001] The present invention relates to the technical field of liquid metal materials, and in particular to a liquid metal composite material and a preparation method thereof. Background Art

[0002] Liquid metal refers to a type of metal or alloy that is liquid at room temperature, including single-phase liquid metal (such as metallic gallium) and multiphase liquid metal alloys (such as gallium-indium alloys). Liquid metal has low toxicity, excellent biocompatibility, significant electrical and thermal conductivity, and strong fluidity, and has great potential in biomedical fields such as therapeutics, bioimaging, biosensors, and tissue repair. However, due to the high surface tension of liquid metal, it is difficult for liquid metal to form effective adhesion with the substrate, which limits the application of liquid metal. Summary of the invention

[0003] The problem solved by the present invention is that due to the large surface tension of liquid metal, it is difficult for liquid metal to form effective adhesion with a substrate.

[0004] In order to solve the above problems, the present invention provides a method for preparing a liquid metal composite material, comprising:

[0005] Step S1, adding 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid and zinc nitrate hexahydrate into a solvent, stirring to obtain a reaction solution;

[0006] Step S2, after heating the reaction solution for reaction, collecting the block product and washing and drying it to obtain a zinc complex;

[0007] Step S3: After mixing the liquid metal and the zinc complex, ultrasonic treatment is performed to obtain a liquid metal composite material.

[0008] Optionally, in step S1, the molar ratio of the 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid to the zinc nitrate hexahydrate is (1-2): (1-2).

[0009] Optionally, in step S1, the solvent consists of water and acetonitrile in a volume ratio of (3-4):1.

[0010] Optionally, in step S1, the stirring process is performed at a speed of 1300-1500 rpm for 20-40 min.

[0011] Optionally, in step S2, the heating reaction is carried out at a temperature of 150-170° C. and for a time of 92-100 h.

[0012] Optionally, in step S2, the drying process is performed at a temperature of 70-80°C and for a time of 10-14 hours.

[0013] Optionally, in step S3, the liquid metal is a eutectic gallium-indium alloy.

[0014] Optionally, in step S3, the mass ratio of the liquid metal to the zinc complex is (90-110):1.

[0015] Optionally, in step S3, the ultrasonic power used in the ultrasonic treatment is 700-800W, and the time of the ultrasonic treatment is 1-5min.

[0016] The present invention also provides a liquid metal composite material, which is made by the preparation method of the liquid metal composite material as described above.

[0017] Compared with the prior art, the present invention obtains a zinc complex by reacting an organic ligand 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid (H4ddp) with a zinc salt zinc nitrate hexahydrate, wherein the organic ligand H4ddp has more carboxyl groups, which is easier to coordinate with zinc nitrate hexahydrate, and the coordination number of zinc nitrate hexahydrate is higher and the crystallinity is better. The coordination number of the zinc complex obtained by the reaction of the two is higher and the crystallinity is better. The liquid metal composite material provided in the present invention is formed by ultrasonic treatment after mixing liquid metal with the zinc complex. Since the coordination number of the zinc complex is higher and the crystallinity is better, the liquid metal composite material has a higher viscosity, and the liquid metal composite material is easier to form effective adhesion with the substrate. In addition, ultrasonic treatment is beneficial to reducing the particle size of the liquid metal composite material, thereby further improving the viscosity of the liquid metal composite material. In summary, the liquid metal composite material provided by the present invention has a higher viscosity and is easier to form effective adhesion with the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 Schematic diagram of the preparation method of the liquid metal composite material in an embodiment of the present invention;

[0019] Figure 2 This is a scanning electron microscope image of the liquid metal composite material prepared in Example 1. DETAILED DESCRIPTION

[0020] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. Although certain embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be interpreted as being limited to the embodiments described herein. On the contrary, these embodiments are provided to provide a more thorough and complete understanding of the present invention. It should be understood that the drawings and embodiments of the present invention are only for exemplary purposes and are not intended to limit the scope of protection of the present invention.

[0021] Unless otherwise defined, all technical and scientific terms used in this application have the same meanings as those commonly understood by those skilled in the art to which this application belongs; the terms used in the specification of this application are only for the purpose of describing specific implementation methods and are not intended to limit this application;

[0022] The term "including" and its variations used in this article are open inclusions, that is, "including but not limited to"; the term "based on" is "based at least in part on"; the term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one other embodiment"; the term "some embodiments" means "at least some embodiments"; the term "optionally" means "optional embodiments". The relevant definitions of other terms will be given in the following description. It should be noted that the concepts of "first" and "second" mentioned in the present invention are used to distinguish different objects, rather than to describe a specific order or a primary and secondary relationship. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, unless otherwise specified, the meaning of "multiple" is two or more.

[0023] like Figure 1 As shown, an embodiment of the present invention provides a method for preparing a liquid metal composite material, comprising:

[0024] Step S1, adding 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid (H4ddp) and zinc nitrate hexahydrate into a solvent, stirring to obtain a reaction solution;

[0025] Step S2, after heating the reaction solution for reaction, collecting the block product and washing and drying it to obtain a zinc complex;

[0026] Step S3: After mixing the liquid metal and the zinc complex, ultrasonic treatment is performed to obtain a liquid metal composite material.

[0027] The embodiment of the present invention obtains a zinc complex by reacting an organic ligand 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid (H4ddp) with a zinc salt zinc nitrate hexahydrate, wherein the organic ligand H4ddp has more carboxyl groups, which is easier to coordinate with zinc nitrate hexahydrate, and the coordination number of zinc nitrate hexahydrate is higher and the crystallinity is better. The coordination number of the zinc complex obtained by the reaction of the two is higher and the crystallinity is better. The liquid metal composite material provided in the present invention is formed by ultrasonic treatment after mixing liquid metal with the zinc complex. Since the coordination number of the zinc complex is higher and the crystallinity is better, the liquid metal composite material has a higher viscosity, and the liquid metal composite material is easier to form effective adhesion with the substrate. In addition, ultrasonic treatment is beneficial to reducing the particle size of the liquid metal composite material, thereby facilitating further improving the viscosity of the liquid metal composite material. In summary, the liquid metal composite material provided in the embodiment of the present invention has a higher viscosity and is easier to form effective adhesion with the substrate.

[0028] In some embodiments of the present invention, in step S1, the molar ratio of the 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid to the zinc nitrate hexahydrate is (1-2): (1-2).

[0029] In some embodiments of the present invention, in step S1, illustratively, the solvent consists of water and acetonitrile in a volume ratio of (3-4):1.

[0030] In some embodiments of the present invention, in step S1, the stirring process is performed at a speed of 1300-1500 rpm for a time of 20-40 min.

[0031] In some embodiments of the present invention, in step S2, the heating reaction is carried out at a temperature of 150-170° C. and for a time of 92-100 h.

[0032] In some embodiments of the present invention, in step S2, the drying process is carried out at a temperature of 70-80° C. and for a time of 10-14 hours.

[0033] In some embodiments of the present invention, in step S3, illustratively, the liquid metal is a eutectic gallium-indium alloy (EGaIn), in which the mass fraction of Ga is 75% and the mass fraction of In is 75%.

[0034] In some embodiments of the present invention, in step S3, the mass ratio of the liquid metal to the zinc complex is (90-110):1.

[0035] In some embodiments of the present invention, in step S3, the ultrasonic power used in the ultrasonic treatment is 700-800W, and the time of the ultrasonic treatment is 1-5min.

[0036] The present invention also provides a liquid metal composite material, which is made by the preparation method of the liquid metal composite material as described above.

[0037] The present invention is further described below in conjunction with specific embodiments.

[0038] Example 1

[0039] A1. Add 33.1 mg (0.10 mmol) of 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid and 29.8 mg (0.10 mmol) of zinc nitrate hexahydrate to a solvent consisting of 6 mL of water and 2 mL of acetonitrile, and stir to obtain a reaction solution; the stirring speed is 1400 rpm, and the time is 30 min.

[0040] A2. After heating the reaction solution, collecting the block product, washing and drying the block product to obtain a zinc complex; wherein the heating reaction temperature is 160° C., the time is 96 h, and the drying temperature is 75° C., and the time is 12 h.

[0041] A3. After mixing the liquid metal with the zinc complex, ultrasonic treatment is performed to obtain a liquid metal composite material; wherein the liquid metal is a eutectic gallium-indium alloy (EGaIn), the mass ratio of the liquid metal to the zinc complex is 100:1, the ultrasonic power used in the ultrasonic treatment is 750 W, and the time of the ultrasonic treatment is 2 min.

[0042] Example 2

[0043] A1. Add 66.2 mg (0.20 mmol) of 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid and 29.8 mg (0.10 mmol) of zinc nitrate hexahydrate to a solvent consisting of 6 mL of water and 2 mL of acetonitrile, and stir to obtain a reaction solution; the stirring speed is 1300 rpm, and the time is 40 min.

[0044] A2. After heating the reaction solution, collecting the block product, washing and drying the block product to obtain a zinc complex; wherein the heating reaction temperature is 150° C., the time is 100 h, and the drying temperature is 70° C., and the time is 14 h.

[0045] A3. After mixing the liquid metal and the zinc complex, ultrasonic treatment is performed to obtain a liquid metal composite material; wherein the liquid metal is a eutectic gallium-indium alloy (EGaIn), the mass ratio of the liquid metal to the zinc complex is 90:1, the ultrasonic power used in the ultrasonic treatment is 700 W, and the time of the ultrasonic treatment is 5 min.

[0046] Example 3

[0047] A1. Add 33.1 mg (0.10 mmol) of 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid and 59.6 mg (0.10 mmol) of zinc nitrate hexahydrate to a solvent consisting of 6 mL of water and 2 mL of acetonitrile, and stir to obtain a reaction solution; the stirring speed is 1500 rpm, and the time is 20 min.

[0048] A2. After heating the reaction solution, collecting the block product, washing and drying the block product to obtain a zinc complex; wherein the heating reaction temperature is 170° C., the time is 92 h, and the drying temperature is 80° C., and the time is 10 h.

[0049] A3. After mixing the liquid metal with the zinc complex, ultrasonic treatment is performed to obtain a liquid metal composite material; wherein the liquid metal is a eutectic gallium-indium alloy (EGaIn), the mass ratio of the liquid metal to the zinc complex is 110:1, the ultrasonic power used in the ultrasonic treatment is 800 W, and the time of the ultrasonic treatment is 1 min.

[0050] Comparative Example 1

[0051] After mixing liquid metal with polyvinyl pyrrolidone (PVP), ultrasonic treatment is performed to obtain a liquid metal composite material; wherein the liquid metal is a eutectic gallium-indium alloy (EGaIn), the mass ratio of the liquid metal to the zinc complex is 100:1, the ultrasonic power used in the ultrasonic treatment is 750W, and the time of the ultrasonic treatment is 2 minutes.

[0052] Experimental example

[0053] The liquid metal composite material prepared in Example 1 was characterized by scanning electron microscopy. Figure 2 ,from Figure 2 It can be seen that the particle size of the liquid metal composite material is relatively small, which is 200-500nm. The liquid metal composite materials prepared in Examples 1-3 and Comparative Example 1 were coated on a PET film with a thickness of 300μm for peeling test. The results are shown in Table 1. It can be seen from Table 1 that the stress required to peel the liquid metal composite materials prepared in Examples 1-3 from the PET film is 1.21kPa, 1.15kPa and 1.25kPa, and the stress required to peel the liquid metal composite material prepared in Comparative Example 1 from the PET film is 0.67kPa, indicating that the liquid metal prepared in Examples 1-3 has better adhesion to the PET film and has better viscosity.

[0054] Table 1

[0055] serial number Stress required for peeling (kPa) Example 1 1.21 Example 2 1.15 Example 3 1.25 Comparative Example 1 0.67

[0056] Although the present invention is disclosed as above, the protection scope of the present invention is not limited thereto. Those skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. A method for preparing a liquid metal composite material, characterized in that: include: Step S1, adding 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid and zinc nitrate hexahydrate into a solvent, stirring to obtain a reaction solution; Step S2, after heating the reaction solution for reaction, collecting the block product and washing and drying it to obtain a zinc complex; Step S3: After mixing the liquid metal and the zinc complex, ultrasonic treatment is performed to obtain a liquid metal composite material.

2. The method for preparing the liquid metal composite material according to claim 1, characterized in that: In the step S1, the molar ratio of the 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid to the zinc nitrate hexahydrate is (1-2): (1-2).

3. The method for preparing the liquid metal composite material according to claim 1, characterized in that: In the step S1, the solvent is composed of water and acetonitrile in a volume ratio of (3-4):

1.

4. The method for preparing the liquid metal composite material according to claim 1, characterized in that: In the step S1, the stirring process is performed at a speed of 1300-1500 rpm for 20-40 min.

5. The method for preparing the liquid metal composite material according to claim 1, characterized in that: In the step S2, the heating reaction temperature is 150-170°C and the time is 92-100 hours.

6. The method for preparing the liquid metal composite material according to claim 1, characterized in that: In step S2, the drying process is carried out at a temperature of 70-80°C and for a time of 10-14 hours.

7. The method for preparing the liquid metal composite material according to claim 1, characterized in that: In the step S3, the liquid metal is a eutectic gallium-indium alloy.

8. The method for preparing the liquid metal composite material according to claim 7, characterized in that: In the step S3, the mass ratio of the liquid metal to the zinc complex is (90-110):

1.

9. The method for preparing the liquid metal composite material according to claim 1, characterized in that: In step S3, the ultrasonic power used in the ultrasonic treatment is 700-800W, and the time of the ultrasonic treatment is 1-5min.

10. A liquid metal composite material, characterized in that: The liquid metal composite material is prepared by the preparation method of any one of claims 1 to 9.

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