Liquid metal composite and method for producing the same

Abstract

The application 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, 3-(3,5-dicarboxyphenyl) pyridine-2,6-dicarboxylic acid and zinc nitrate hexahydrate are added into a solvent, and stirring treatment is performed to obtain a reaction solution; S2, after the reaction solution is subjected to a heating reaction, a block-shaped product is collected, and washing and drying treatment are performed on the block-shaped product to obtain a zinc complex; and S3, the liquid metal is mixed with the zinc complex, and ultrasonic treatment is performed to obtain the liquid metal composite material.The liquid metal composite material is obtained by mixing the liquid metal with the zinc complex and then performing ultrasonic treatment, the coordination number of the zinc complex is high, and the crystallinity of the zinc complex is good, so that the liquid metal composite material has high viscosity, and the liquid metal composite material is more likely to form effective adhesion with a base material.

Description

Technical Field

[0001] This invention relates to the field of liquid metal materials technology, and more specifically, to a liquid metal composite material and its preparation method. Background Technology

[0002] Liquid metals refer to a class of metals or alloys that exist in a liquid state at room temperature, encompassing single-phase liquid metals (such as gallium) and multi-phase liquid metal alloys (such as gallium-indium alloys). Given their low toxicity, excellent biocompatibility, significant electrical and thermal conductivity, and extremely high fluidity, liquid metals show great potential in biomedical fields such as therapeutics, bioimaging, biosensors, and tissue repair. However, the high surface tension of liquid metals makes it difficult for them to form effective adhesion with substrates, limiting their applications. Summary of the Invention

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

[0004] To address the above problems, this invention provides a method for preparing a liquid metal composite material, comprising:

[0005] Step S1: Add 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid and zinc nitrate hexahydrate to the solvent, stir and treat to obtain a reaction solution;

[0006] Step S2: After heating the reaction solution, collect the blocky product and wash and dry it to obtain the zinc complex;

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

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

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

[0010] Optionally, in step S1, the stirring speed is 1300-1500 rpm and the time is 20-40 min.

[0011] Optionally, in step S2, the heating reaction temperature is 150-170℃ and the time is 92-100h.

[0012] Optionally, in step S2, the drying process is carried out at a temperature of 70-80°C for 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 ultrasonic treatment time is 1-5 minutes.

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

[0017] Compared with existing technologies, this invention obtains a zinc complex through the reaction of the organic ligand 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid (H4ddp) and zinc nitrate hexahydrate. The organic ligand H4ddp has a higher number of carboxyl groups, making it easier for zinc nitrate hexahydrate to coordinate. Zinc nitrate hexahydrate has a higher coordination number and better crystallinity. The resulting zinc complex also has a high coordination number and good crystallinity. The liquid metal composite material provided in this invention is formed by mixing liquid metal with this zinc complex and then ultrasonically treating the mixture. Due to the high coordination number and good crystallinity of the zinc complex, the liquid metal composite material exhibits high viscosity, making it easier to form effective adhesion with the substrate. Furthermore, ultrasonic treatment helps reduce the particle size of the liquid metal composite material, thereby further improving its viscosity. In summary, the liquid metal composite material provided by this invention has high viscosity and is more likely to form effective adhesion with the substrate. Attached Figure Description

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

[0019] Figure 2 Scanning electron microscope (SEM) images of the liquid metal composite material prepared in Example 1. Detailed Implementation

[0020] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Although some embodiments of the present invention are shown in the drawings, it should be understood that the present invention can be implemented in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the present invention. It should be understood that the accompanying drawings and embodiments of the present invention are for illustrative purposes only 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 meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used in the description of this application is for the purpose of describing particular embodiments only and is not intended to limit this application.

[0022] The term "comprising" and its variations as used herein are open-ended, meaning "including but not limited to"; the term "based on" means "at least partially based on"; the term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one additional embodiment"; the term "some embodiments" means "at least some embodiments"; and the term "optionally" means "optional embodiments". Definitions of other terms will be given in the description below. It should be noted that the concepts of "first," "second," etc., mentioned in this invention are used to distinguish different objects, not to describe a specific order or hierarchy. Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined with "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, unless otherwise stated, "a plurality of" means two or more.

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

[0024] Step S1: Add 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid (H4ddp) and zinc nitrate hexahydrate to the solvent, stir, and obtain the reaction solution;

[0025] Step S2: After heating the reaction solution, collect the blocky product and wash and dry it to obtain the zinc complex;

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

[0027] This invention relates to a zinc complex obtained by reacting the organic ligand 3-(3,5-dicarboxyphenyl)pyridine-2,6-dicarboxylic acid (H4ddp) with zinc nitrate hexahydrate. The organic ligand H4ddp has a higher number of carboxyl groups, making it easier for zinc nitrate hexahydrate to coordinate. Zinc nitrate hexahydrate has a higher coordination number and better crystallinity. The resulting zinc complex also has a high coordination number and good crystallinity. The liquid metal composite material provided in this invention is formed by mixing liquid metal with this zinc complex and then ultrasonically treating the mixture. Due to the high coordination number and good crystallinity of the zinc complex, the liquid metal composite material exhibits high viscosity, making it easier to form effective adhesion with a substrate. Furthermore, ultrasonic treatment helps reduce the particle size of the liquid metal composite material, thereby further improving its viscosity. In summary, the liquid metal composite material provided in this invention exhibits high viscosity and is more likely to form effective adhesion with a substrate.

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

[0029] In some embodiments of the present invention, in step S1, for example, the solvent is composed 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 speed is 1300-1500 rpm and the time is 20-40 min.

[0031] In some embodiments of the present invention, in step S2, the heating reaction temperature is 150-170°C and the time is 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 for 10-14 hours.

[0033] In some embodiments of the present invention, in step S3, for example, 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 ultrasonic treatment time is 1-5min.

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

[0037] The present invention will be further described below with reference to specific embodiments.

[0038] Example 1

[0039] A1. 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 were added to a solvent consisting of 6 mL of water and 2 mL of acetonitrile. The mixture was stirred to obtain a reaction solution. The stirring speed was 1400 rpm and the stirring time was 30 min.

[0040] A2. After heating the reaction solution, collect the block product, and wash and dry the block product to obtain the zinc complex; wherein the heating reaction temperature is 160℃ and the time is 96h, and the drying treatment temperature is 75℃ and the time is 12h.

[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 750W, and the ultrasonic treatment time is 2min.

[0042] Example 2

[0043] A1. 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 were added to a solvent consisting of 6 mL of water and 2 mL of acetonitrile. The mixture was stirred to obtain a reaction solution. The stirring speed was 1300 rpm and the stirring time was 40 min.

[0044] A2. After heating the reaction solution, collect the block product, and wash and dry the block product to obtain the zinc complex; wherein the heating reaction temperature is 150℃ and the time is 100h, and the drying treatment temperature is 70℃ and the time is 14h.

[0045] A3. The liquid metal is mixed with the zinc complex and then subjected to ultrasonic treatment 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 700W, and the ultrasonic treatment time is 5min.

[0046] Example 3

[0047] A1. 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 were added to a solvent consisting of 6 mL of water and 2 mL of acetonitrile. The mixture was stirred to obtain a reaction solution. The stirring speed was 1500 rpm and the stirring time was 20 min.

[0048] A2. After heating the reaction solution, collect the block product, and wash and dry the block product to obtain the zinc complex; wherein the heating reaction temperature is 170℃ and the time is 92h, and the drying treatment temperature is 80℃ and the time is 10h.

[0049] A3. The liquid metal is mixed with the zinc complex and then subjected to ultrasonic treatment 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 800W, and the ultrasonic treatment time is 1min.

[0050] Comparative Example 1

[0051] Liquid metal is mixed with polyvinylpyrrolidone (PVP) and then subjected to ultrasonic treatment 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 ultrasonic treatment time is 2min.

[0052] Experimental Example

[0053] The liquid metal composite material prepared in Example 1 was characterized by scanning electron microscopy, and the results are shown in the figure. Figure 2 ,from Figure 2 As can be seen, the liquid metal composite material has a small particle size, ranging from 200 to 500 nm. The liquid metal composite materials prepared in Examples 1-3 and Comparative Example 1 were coated onto a 300 μm thick PET film for peel testing. The results are shown in Table 1. Table 1 shows that the stress required to peel the liquid metal composite materials prepared in Examples 1-3 from the PET film was 1.21 kPa, 1.15 kPa, and 1.25 kPa, respectively, while the stress required to peel the liquid metal composite material prepared in Comparative Example 1 from the PET film was 0.67 kPa. This indicates that the liquid metal prepared in Examples 1-3 has better adhesion to the PET film and exhibits better tack.

[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] While the present invention has been disclosed above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and all such changes and modifications will fall within the scope of protection of the present invention.

Claims

1. A method of producing a liquid metal composite material, characterized by, The preparation method comprises the following steps: S1, 3-(3, 5-dicarboxyphenyl) pyridine-2, 6-dicarboxylic acid, zinc nitrate hexahydrate are added into a solvent, and stirring treatment is performed to obtain a reaction solution; the molar ratio of the 3-(3, 5-dicarboxyphenyl) pyridine-2, 6-dicarboxylic acid to the zinc nitrate hexahydrate is (1-2) :(1-2); S2, after the reaction solution is subjected to heating reaction, a blocky product is collected and is subjected to washing and drying treatment to obtain a zinc complex; S3, liquid metal is mixed with the zinc complex, and ultrasonic treatment is performed to obtain a liquid metal composite material.

2. The method of claim 1, wherein the liquid metal composite is prepared by a method comprising: In the step S1, the solvent is composed of water and acetonitrile in a volume ratio of (3-4) :

1.

3. The method of claim 1, wherein the liquid metal composite is prepared by a method comprising: In the step S1, the stirring treatment is performed at a speed of 1300-1500 rpm for 20-40 min.

4. The method of claim 1, wherein the liquid metal composite is prepared by a method comprising: In the step S2, the heating reaction is performed at a temperature of 150-170 ℃ for 92-100 h.

5. The method of claim 1, wherein the liquid metal composite is prepared by a method comprising: In the step S2, the drying treatment is performed at a temperature of 70-80 ℃ for 10-14 h.

6. The method of claim 1, wherein the liquid metal composite is prepared by a method comprising: In the step S3, the liquid metal is a eutectic gallium-indium alloy.

7. The method of claim 6, wherein the liquid metal composite is prepared by a method comprising: In the step S3, the mass ratio of the liquid metal to the zinc complex is (90-110) :

1.

8. The method of claim 1, wherein the liquid metal composite is prepared by a method comprising: In the step S3, the ultrasonic treatment uses an ultrasonic power of 700-800 W, and the ultrasonic treatment is performed for 1-5 min.

9. A liquid metal composite, characterized in that The liquid metal composite material is prepared by using the preparation method according to any one of claims 1-8.

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