CN114150197B - Physical contact rapid reversible color change liquid metal composite material and application thereof - Google Patents
Physical contact rapid reversible color change liquid metal composite material and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional materials, and particularly relates to a physical contact rapid reversible color change liquid metal composite material, and a preparation method and application thereof. The invention can realize rapid reversible color change only through physical contact without an external excitation source. The material provides a new effective technical means for surface color camouflage of the liquid metal robot, and provides a new idea for development and industrial application of the low-power-consumption liquid metal color developing material. The invention uses simple material synthesis process, has no special condition requirement, is easy to operate, has simple equipment requirement and is easy for large-scale production.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a metal composite material which can realize rapid reversible color change only through physical contact without an external excitation source, and a preparation method and application thereof.
Technical Field
Liquid metals, such as gallium (Ga), eutectic gallium indium (GaIn), and gallium indium tin (GaInSn), are becoming increasingly important functional materials in liquid muscles and macroscopic biomimetic liquid robots due to their low melting points and low voltage deformability. However, in natural environment, the specific metal luster makes the liquid metal robot particularly easy to detect. Therefore, how to make the liquid robot naturally blend with the surrounding environment, such as the contact discoloration camouflage capability of the liquid metal robot T-1000 in the movie "terminator 2" is always the goal of the researchers. Inspired by nature, such as "electronic paper", "electrochemical" display methods and plasma inversion by metal/organic nanostructures, have been developed to disguise color-changing materials. However, these materials lack flexibility, are easily destroyed by external mechanical forces, and they are highly dependent on precise control of voltage/current by the chip, which severely limits the application of these methods to discolouration of liquid metal robots. In recent years, some researchers have proposed self-discoloration based on liquid gallium and its alloys, such as reversible discoloration caused by high temperature oxidation and deformation of gallium-copper/nickel microspheres by intense laser light. However, with the former, the discoloration caused by high temperature oxidation is irreversible, while the latter design is only suitable for small-sized materials, and furthermore, both designs rely on a higher external energy supply.
According to literature reports, gallium and its room temperature liquid alloy can show a series of mechanical behaviors due to the change of its surface tension, and researchers developed various liquid robot designs according to this characteristic. In mechanical behavior, phagocytosis of gallium liquid alloys often results in significant discoloration. Through regulation and control, the developed copper particles are spontaneously swallowed by the liquid metal droplets, so that the color of the liquid gallium alloy is rapidly changed from red/black to a shiny silver color. However, this discoloration has proven to be irreversible, one of the most important reasons being that the intermetallic compound formed between copper and gallium prevents the movement of the copper particles. However, the phenomenon inspires a new functional material design strategy that the reversible color change is hopeful to be realized through the accurate control of the motion of the color developing particles in the liquid gallium.
Disclosure of Invention
The invention provides a liquid metal composite material capable of rapidly and reversibly changing color by physical contact, which comprises gallium and graphite.
Graphite has similar properties to copper and is commonly used to reduce the surface tension of gallium in acidic or basic environments. Graphite and gallium can be easily converted from wet, partially wet to non-wet by appropriate control of ph concentration and/or electric field strength. At the same time, graphite is very stable at room temperature and does not react with acids or bases. More importantly, it cannot react with gallium to form any intermetallic compounds. In addition, graphite also has excellent light absorption capability in the visible spectrum, and thus graphite is an excellent dye for reversible discoloration of liquid metal gallium. Compared with the traditional color-changing functional material, the material does not depend on chip control and external energy supply, and has the advantages of mechanical force indestructibility and quick reversibility, so that the material has a wide application prospect in civil and military fields such as color camouflage and color development of liquid robots.
The gallium and graphite liquid metal composite material can realize the preparation process of the metal material with rapid reversible color change only through physical contact without an external excitation source. The gallium-graphite powder composite material is prepared by utilizing the autophagy characteristic of gallium in an acid solution on wetting particles due to the removal of a surface oxide layer. Then selecting proper acid environment, and adopting direct physical contact/separation of graphite paper/graphite block and metal gallium-graphite powder composite material to implement the goal of quickly changing colour of its surface. The contact surface of the material and graphite paper can be rapidly changed from metallic silvery white to gray black, and the use time is about 3-8 seconds; when the graphite paper is separated from the metal gallium-graphite powder composite material, the color of the composite material is rapidly restored to the original state, taking about 6 seconds. The material provides a new effective technical means for surface color camouflage of the liquid metal robot, and provides a new idea for development and industrial application of the low-power-consumption liquid metal color developing material. The invention uses simple material synthesis process, has no special condition requirement, is easy to operate, has simple equipment requirement and is easy for large-scale production.
The invention also provides a preparation method of the liquid metal composite material capable of rapidly reversibly changing color by physical contact, which comprises the following steps:
a. preparing scaly graphite powder: cutting 50 μm thick graphite paper into 5cm × 5cm square blocks, placing into 0.2-1.0mol/L hydrochloric acid solution, and electrolyzing with 4V direct current to strip scale graphite debris with electrode spacing of 5cm for 10-20 min; centrifuging the electrolyte at the rotation speed of 12000r/min for 5min, and evaporating the dry residual liquid to obtain scaly graphite powder;
b. compounding gallium metal and graphite powder: heating solid gallium with the purity of 99.95wt.% to 90 ℃ to obtain liquid gallium, taking out the liquid gallium by using a suction pipe, and placing the liquid gallium in distilled water at the temperature of 40-45 ℃; and (b) adding the scaly graphite powder obtained in the step (a) to the surface of liquid gallium, enabling the liquid gallium to phagocytose the scaly graphite powder spontaneously to obtain a metal gallium-graphite powder composite material, sucking the obtained metal gallium-graphite powder composite material out of distilled water through a suction pipe, and placing the metal gallium-graphite powder composite material in a plastic culture dish for drying.
Preferably, 12mol/L concentrated hydrochloric acid is dripped on the surface of the liquid gallium before the scaly graphite powder is added on the surface of the liquid gallium.
Preferably, the mass ratio of the scaly graphite powder in the metal gallium is 0.001-0.004 wt.%.
Preferably, the metallic gallium-graphite powder composite material is stored in an environment with the temperature of minus 20 ℃ to minus 24 ℃.
The invention also claims the application of the liquid metal composite material with physical contact and rapid reversible color change as a camouflage and color change material in the civil or military fields of liquid metal robots, toys, entertainment and the like.
Drawings
Fig. 1 is a microstructure diagram of a flaky graphite powder.
FIG. 2 is a schematic view showing the state in which gallium spontaneously phagocytizes flaky graphite powder.
Fig. 3 is a graph showing the color gradient caused by the contact/separation of the metal gallium-graphite powder composite material with the graphite paper.
Fig. 4 is a comparison graph of the color of the metal gallium liquid drop and the color of the metal gallium-graphite powder composite material on the surface of the graphite paper.
FIG. 5 is a diagram of the mechanism of color change in the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Example (b):
cutting graphite paper into 5cm × 5cm × 50 μm (length × width × thickness) blocks, placing into 0.2-1.0mol/L hydrochloric acid solution, and electrolyzing with 4V direct current to strip scale graphite debris with electrode spacing of 5cm for 10-20 min. The electrolyte was centrifuged (centrifuge speed 12000r/min, 5min treatment) and the dry residual liquid was evaporated to obtain a powder of exfoliated graphite flakes, which was placed in a desiccator for use as shown in fig. 1.
Heating solid gallium metal (purity 99.95 wt.%) to 90 deg.C to obtain liquid gallium, taking out 0.4-0.5 mL through a suction tube, and placing in distilled water at 40 deg.C. Adding the scaly graphite powder obtained in the above step to the surface of the liquid gallium. Preferably, by a method of directly dripping 12mol/L concentrated hydrochloric acid on the surface of the liquid gallium, a surface oxidation layer of the liquid gallium is removed to trigger the spontaneous phagocytosis function of the liquid Ga, so that liquid gallium drops spontaneously phagocytose scaly graphite powder, and the metal gallium-graphite powder composite material is obtained. At this time, the metal gallium-graphite powder composite material appears as liquid spheres with silvery white surfaces, and the mass percentage of the scaly graphite powder in the metal gallium is 0.004wt.%, as shown in fig. 2.
And (3) sucking the obtained gallium metal-graphite powder composite material out of the solution through a suction pipe, placing the gallium metal-graphite powder composite material into a plastic culture dish for drying, and placing the plastic culture dish into a refrigerator for storage, wherein the storage temperature is 24 ℃ below zero.
Graphite has similar properties to copper and is commonly used to reduce the surface tension of gallium in acidic or basic environments. Graphite and gallium can be easily converted from wet, partially wet to non-wet by appropriate ph concentration and/or electric field strength control. At the same time, graphite is very stable at room temperature and does not react with acids or bases. More importantly, it cannot react with gallium to form any intermetallic compounds. In addition, graphite also has excellent light absorption capability in the visible spectrum. Thus, graphite should be an excellent dye to achieve reversible color change of the liquid metal. Hydrochloric acid (HCl) solution has proven to be an effective solution to trigger the spontaneous phagocytic function of liquid Ga by removing the surface oxide layer of liquid Ga. While other commonly used solutions, such as sodium hydroxide (NaOH), sodium carbonate (Na 2CO 3), cannot support spontaneous phagocytosis without the aid of external electron injection (e.g., chemical reactions or external electric fields). Considering the requirement that rapid reversible color change can be realized through physical contact under the condition of not introducing an external field or materials, the invention selects an environment adopting HCl solution with certain concentration. Compared with the traditional color-changing functional material, the material does not depend on chip control and external energy supply, and has the advantages of mechanical force indestructibility and rapidness and reversibility, so that the material has a larger application prospect in the civil and military fields of color camouflage, color development and the like of liquid robots.
And (3) color change test:
preparing 0.4mol/L hydrochloric acid solution, adding the metal gallium-graphite powder composite material obtained in the embodiment into the prepared hydrochloric acid solution, and heating the hydrochloric acid solution to 40-45 ℃. Directly touching the metal gallium-graphite powder composite material with graphite paper with the size of 5cm multiplied by 50 mu m (length multiplied by width multiplied by thickness) in hydrochloric acid solution, wherein the surface of the metal gallium-graphite powder composite material is rapidly changed from silver white to grey black, and the use time is about 8 seconds; when the graphite paper is separated from the metal gallium-graphite powder composite material, the color of the composite material is rapidly restored to its original shape, taking about 6 seconds, as shown in fig. 3.
In the environment of 0.4mol/L hydrochloric acid solution, the metallic gallium-graphite powder composite material is directly dripped on the surface of graphite paper, the color of the metallic gallium-graphite powder composite material is rapidly changed into grey black, and the use time is only 3 seconds, as shown in figure 4. The color of the metal gallium liquid drops is opposite to that of the metal gallium-graphite powder composite material on the surface of the graphite paper as shown in FIG. 4.
The mechanism of discoloration is shown in fig. 5, and generally, liquid gallium forms a self-limiting, extremely thin oxide layer on its surface in a solution environment. In hydrochloric acid solution, the oxide layer will decrease with increasing acid concentration. However, the electronegativity of gallium and carbon is 1.81 and 2.55, respectively, and constitutes the galvanic reaction in an acidic environment. When the liquid metal gallium and the graphite powder are not contacted, in 0.4mol/L acid solution, the generation rate of an oxide layer on the surface of the gallium is lower than the dissolution rate, so that the liquid metal gallium keeps high surface tension, and the graphite powder is firmly locked in the liquid metal gallium, thereby showing the metallic luster of the gallium; however, when the two are contacted, electrons of the liquid metal gallium can be rapidly transferred to the graphite paper due to the potential difference, the growth rate of the oxide film on the surface of the metal gallium is greatly improved and exceeds the dissolution rate of the oxide film, and the surface tension of the gallium is not enough to lock the graphite powder in the graphite paper. Meanwhile, due to the polarization effect generated by the reaction, the upper surface of the gallium is charged with positive electricity, and the contact surface of the gallium and the graphite paper is charged with negative electricity. At this time, the graphite powder in the liquid metal gallium also traps part of electrons and shows electronegativity. Under the action of an electric field, graphite powder in the liquid metal gallium migrates towards the upper surface, and the result is contact discoloration. After the two are separated, the surface oxide film of the metal gallium is quickly dissolved, so that the liquid metal gallium has high surface tension again, and the carbon powder is firmly locked in the liquid metal gallium again, thereby completing color recovery.
The invention provides a new effective technical means for surface color camouflage of the liquid metal robot and provides a new idea for development and industrial application of the low-power-consumption liquid metal color developing material. The invention uses simple material synthesis process, has no special condition requirement, is easy to operate, has simple equipment requirement and is easy for large-scale production.
Claims (3)
1. A liquid metal composite material capable of rapidly and reversibly changing color by physical contact is characterized by comprising gallium and graphite, and the preparation method comprises the following steps:
a. preparing scaly graphite powder: cutting 50 μm thick graphite paper into 5cm × 5cm square blocks, placing into 0.2-1.0mol/L hydrochloric acid solution, and electrolyzing with 4V direct current to strip scale graphite debris with electrode spacing of 5cm for 10-20 min; centrifuging the electrolyte at the rotation speed of 12000r/min for 5min, and evaporating the dry residual liquid to obtain scaly graphite powder;
b. compounding gallium metal and graphite powder: heating solid gallium with the purity of 99.95wt.% to 90 ℃ to obtain liquid gallium, taking out the liquid gallium by using a suction pipe, and placing the liquid gallium in distilled water at the temperature of 40-45 ℃; b, adding the scaly graphite powder obtained in the step a to the surface of liquid gallium, enabling the liquid gallium to phagocytose the scaly graphite powder spontaneously to obtain a metal gallium-graphite powder composite material, sucking the obtained metal gallium-graphite powder composite material out of distilled water through a suction pipe, and placing the metal gallium-graphite powder composite material in a plastic culture dish for drying;
before adding the scaly graphite powder to the surface of the liquid gallium, dropwise adding 12mol/L concentrated hydrochloric acid to the surface of the liquid gallium;
the mass ratio of the scaly graphite powder in the gallium metal is 0.001-0.004 wt.%.
2. The liquid metal composite material with rapid reversible color change through physical contact as claimed in claim 1, wherein the metal gallium-graphite powder composite material is stored in an environment with a temperature of minus 20 ℃ to minus 24 ℃.
3. The use of the liquid metal composite material with physical contact rapid reversible color change as camouflage and color change material in civil or military fields according to claim 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4984994A (en) * | 1972-11-29 | 1974-08-15 | ||
| US5462821A (en) * | 1993-11-19 | 1995-10-31 | Dowa Mining Co., Ltd. | Gallium based active material for the negative electrode, a negative electrode using the same, and batteries using said negative electrode |
| CN106904570A (en) * | 2017-03-07 | 2017-06-30 | 烟台南山学院 | One kind is based on plasmon effect electric field-assisted Ag nano wire itself pattern restorative procedures |
| CN109722699A (en) * | 2017-10-27 | 2019-05-07 | 中国科学院理化技术研究所 | A kind of color liquid metal and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015508375A (en) * | 2011-12-15 | 2015-03-19 | ミッドサマー・アーベー | Recycling of copper indium gallium diselenide |
| GB2529411A (en) * | 2014-08-18 | 2016-02-24 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4984994A (en) * | 1972-11-29 | 1974-08-15 | ||
| US5462821A (en) * | 1993-11-19 | 1995-10-31 | Dowa Mining Co., Ltd. | Gallium based active material for the negative electrode, a negative electrode using the same, and batteries using said negative electrode |
| CN106904570A (en) * | 2017-03-07 | 2017-06-30 | 烟台南山学院 | One kind is based on plasmon effect electric field-assisted Ag nano wire itself pattern restorative procedures |
| CN109722699A (en) * | 2017-10-27 | 2019-05-07 | 中国科学院理化技术研究所 | A kind of color liquid metal and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "A general approach to composites containing nonmetallic fillers and liquid gallium";Chunhui Wang 等;《Science Advances》;20210131;第7卷(第1期);第1-2页 * |
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