阅读说明：本技术 一种彩色液态金属及其制备方法 (Colored liquid metal and preparation method thereof ) 是由 朱唐 董仕晋 郑翰 于洋 于 2019-02-20 设计创作，主要内容包括：本发明提供一种彩色液态金属及其制备方法,涉及材料技术领域。本发明提供的彩色液态金属包括：均匀混合的预氧化的液态金属和金属络合染料溶液,所述金属络合染料溶液包括溶剂、金属络合染料和助剂。本发明的技术方案能够使彩色液态金属显色效果好且导电性好。(The invention provides a colored liquid metal and a preparation method thereof, and relates to the technical field of materials. The invention provides a colored liquid metal comprising: the pre-oxidized metal complex dye comprises a pre-oxidized liquid metal and a metal complex dye solution which are uniformly mixed, wherein the metal complex dye solution comprises a solvent, a metal complex dye and an auxiliary agent. The technical scheme of the invention can ensure that the color liquid metal has good color development effect and good conductivity.)

1. A colored liquid metal, comprising: the pre-oxidized metal complex dye comprises a pre-oxidized liquid metal and a metal complex dye solution which are uniformly mixed, wherein the metal complex dye solution comprises a solvent, a metal complex dye and an auxiliary agent.

2. The colored liquid metal as claimed in claim 1, wherein the mass ratio of the liquid metal to the metal complex dye is 100: 1 to 5: 1.

3. The colored liquid metal according to claim 1, wherein in the metal complex dye solution, the weight percentage of the metal complex dye is 10-40%, the weight percentage of the solvent is 30-70%, and the weight percentage of the auxiliary agent is 1-30%.

4. The colored liquid metal according to any one of claims 1 to 3, wherein the solvent comprises at least one of water, ethanol, ethylene glycol, glycerol, N-butanol, isobutanol, N-propanol, isopropanol, isoamyl alcohol, 1, 3-butanediol, methoxypropanol, acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, diisobutyl ketone, ethylene glycol ethyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol phenyl ether, glycidyl ether, ethyl acetate, butyl acetate, isoamyl acetate, N-butyl glycolate, N-hexane, cyclohexane, N-heptane, N-octane, isooctane, toluene, xylene, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, and N-methylpyrrolidone.

5. The colored liquid metal of any one of claims 1-3, wherein the additive comprises at least one of a pH adjuster, a surfactant, a cosolvent, a humectant, and a preservative.

6. A coloured liquid metal as claimed in any one of claims 1 to 3, characterised in that it further comprises a coupling agent and/or a conductive filler.

7. A method for preparing a colored liquid metal, which is used for preparing the colored liquid metal as claimed in any one of claims 1 to 6, and which comprises the following steps:

step S1, carrying out pre-oxidation treatment on the liquid metal;

step S2, preparing a metal complex dye solution through a metal complex dye, a solvent and an auxiliary agent;

step S3, adding the metal complex dye solution into the pre-oxidized liquid metal, and uniformly mixing to obtain the colored liquid metal;

wherein, the operation temperature of the steps S1 to S3 is higher than the melting point of the liquid metal.

8. The method of claim 7, wherein the liquid metal is pre-oxidized by a mechanical stirring method, a magnetic stirring method or a ball milling method in step S1.

9. The method according to claim 8, wherein the stirring speed is 300-3000 r/min and the stirring time is 0.5-60 min during the mechanical stirring or magnetic stirring process; in the ball milling process, the rotating speed is 50 r/min-500 r/min, and the ball milling time is 0.5 min-5 min.

10. The method for preparing colored liquid metal according to any one of claims 7 to 9, wherein in step S3, the metal complex dye solution and the pre-oxidized liquid metal are uniformly mixed by at least one of a mechanical stirring method, a magnetic stirring method, an ultrasonic dispersion method and a ball milling method.

Technical Field

The invention relates to the technical field of materials, in particular to a colored liquid metal and a preparation method thereof.

Background

Liquid metal generally refers to metal or alloy with a melting point below 300 ℃, has excellent properties of electrical conductivity, thermal conductivity, fluidity, stretchability, chemical inertness and the like, and is a promising new electronic material. The liquid metal has metallic luster, is usually silvery white and has a single color, and cannot meet the requirements of customers on colors in various application scenes.

At present, there are patents which propose the technology of directly blending liquid metal with natural pigments such as cinnabar, realgar and the like or artificially synthesized pigments such as titanium white, lead chrome yellow, phthalocyanine blue and the like to prepare colored liquid metal. However, the inventor finds that when the liquid metal is directly blended with the pigment due to the special properties of large surface tension, easy oxidation and the like, the pigment is easily wrapped in the metal, and the formed colored liquid metal is light in color or even hardly develops color.

Disclosure of Invention

The invention provides a colored liquid metal and a preparation method thereof, which can ensure that the colored liquid metal has good color development effect and good conductivity.

In a first aspect, the present invention provides a colored liquid metal, which adopts the following technical scheme:

the colored liquid metal includes: the pre-oxidized metal complex dye comprises a pre-oxidized liquid metal and a metal complex dye solution which are uniformly mixed, wherein the metal complex dye solution comprises a solvent, a metal complex dye and an auxiliary agent.

Optionally, the mass ratio of the liquid metal to the metal complex dye is 100: 1-5: 1.

Optionally, in the metal complex dye solution, the weight percentage of the metal complex dye is 10% to 40%, the weight percentage of the solvent is 30% to 70%, and the weight percentage of the auxiliary agent is 1% to 30%.

Optionally, the solvent comprises at least one of water, ethanol, ethylene glycol, glycerol, N-butanol, isobutanol, N-propanol, isopropanol, isoamyl alcohol, 1, 3-butanediol, methoxypropanol, acetone, butanone, cyclohexanone, methyl isobutyl ketone, diisobutyl ketone, ethylene glycol ethyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol phenyl ether, glycidyl ether, ethyl acetate, butyl acetate, isoamyl acetate, N-butyl glycolate, N-hexane, cyclohexane, N-heptane, N-octane, isooctane, toluene, xylene, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, N-methylpyrrolidone.

Optionally, the auxiliary agent comprises at least one of a pH adjuster, a surfactant, a cosolvent, a humectant, and a preservative.

Optionally, the colored liquid metal further comprises a coupling agent and/or a conductive filler.

In a second aspect, the present invention provides a method for preparing a colored liquid metal, which is used for preparing any one of the colored liquid metals described above, and adopts the following technical scheme:

the preparation method of the colored liquid metal comprises the following steps:

step S1, carrying out pre-oxidation treatment on the liquid metal;

step S2, preparing a metal complex dye solution through a metal complex dye, a solvent and an auxiliary agent;

step S3, adding the metal complex dye solution into the pre-oxidized liquid metal, and uniformly mixing to obtain the colored liquid metal;

wherein, the operation temperature of the steps S1 to S3 is higher than the melting point of the liquid metal.

Alternatively, in step S1, the liquid metal is subjected to pre-oxidation treatment by a mechanical stirring method, a magnetic stirring method, or a ball milling method.

Further, in the process of mechanical stirring or magnetic stirring, the stirring speed is 300r/min to 3000r/min, and the stirring time is 0.5min to 60 min; in the ball milling process, the rotating speed is 50 r/min-500 r/min, and the ball milling time is 0.5 min-5 min.

Optionally, in step S3, the metal complex dye solution and the pre-oxidized liquid metal are mixed uniformly by at least one of a mechanical stirring method, a magnetic stirring method, an ultrasonic dispersion method, and a ball milling method.

The invention provides a colored liquid metal and a preparation method thereof, wherein the colored liquid metal comprises the following components: the pre-oxidized metal complex dye solution comprises a solvent, a metal complex dye and an auxiliary agent. The metal complex dye is a dye containing coordination metal atoms in molecules, is also called as a chromogen, and is soluble in solvents such as water, alcohols, aromatics, esters and the like. Compared with common inorganic pigments, the metal complex dye has the excellent characteristics of easy dispersion, easy permeation, easy coloring, bright color, good transparency and the like. The inventor finds that if liquid metal and metal complex dye solution are directly mixed, the liquid metal is easily dispersed into small particles in the mixing process due to the existence of the solvent in the metal complex dye solution, the surfaces of the small particles are easily wrapped by the solvent, oxides and the like, so that the finally formed colored liquid metal is not conductive, after creative work, the liquid metal is subjected to pre-oxidation treatment to obtain the pre-oxidized liquid metal, the content and viscosity of the oxides of the liquid metal are improved, the liquid metal is not easily dispersed into the small particles when the liquid metal and the metal complex dye solution are mixed, and the liquid metal is uniformly mixed with the metal complex dye solution as a continuous phase, so that the colored liquid metal with good color rendering effect and good conductivity is obtained.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

Fig. 1 is a flowchart of a method for preparing a colored liquid metal according to an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It should be noted that the technical features in the embodiments of the present invention may be combined with each other without conflict.

The embodiment of the invention provides a colored liquid metal, which specifically comprises: the pre-oxidized metal complex dye solution comprises a solvent, a metal complex dye and an auxiliary agent.

The term "pre-oxidation" refers to a process step of reacting a liquid metal with oxygen to form a metal oxide by a chemical or physical method before a certain process, thereby improving the dispersion state of the liquid metal in the subsequent process.

The reason for selecting the metal complex dye is that: the metal complex dye is a dye containing coordination metal atoms in molecules, is also called as a dye extract, is soluble in solvents such as water, alcohols, aromatics and esters, and has the excellent characteristics of easy dispersion, easy permeation, easy coloring, bright color, good transparency and the like compared with common inorganic pigments. It should be noted that, in the metal complex dye, an acidic metal complex dye, a metal complex disperse dye, a metal complex neutral dye, and the like are all suitable for the colored liquid metal provided in the embodiment of the present invention.

The reason for selecting the metal complex dye solution is that: if metal complex dye powder is directly selected for use, when the metal complex dye powder is mixed with liquid metal, the metal complex dye powder can be wrapped by the liquid metal, so that the color developing effect is poor or even no color is developed, although the content of the metal complex dye powder is improved to a certain extent, the liquid metal and the metal complex dye powder cannot form an even fluid mixture.

The reason for choosing the pre-oxidized liquid metal is: if the liquid metal is directly mixed with the metal complex dye solution, the liquid metal is easily dispersed into small particles in the mixing process due to the existence of the solvent in the metal complex dye solution, and the surfaces of the small particles are easily wrapped by the solvent, the oxide and the like, so that the finally formed colored liquid metal is not conductive. The liquid metal is subjected to pre-oxidation treatment to obtain pre-oxidized liquid metal, the content and viscosity of oxides of the liquid metal are improved, so that the liquid metal is not easily dispersed into small particles when the liquid metal is mixed with the metal complex dye solution, and the liquid metal is used as a continuous phase to be uniformly mixed with the metal complex dye solution, and further the colored liquid metal with good color rendering effect and good conductivity is obtained.

From the above, the colored liquid metal in the embodiment of the invention has good color rendering effect and good conductivity.

Optionally, in the colored liquid metal provided by the embodiment of the invention, the mass ratio of the liquid metal to the metal complex dye is 100: 1-5: 1, so that not only the phenomenon of poor color development effect due to too little metal complex dye does not occur, but also the phenomenon of poor conductivity due to too much metal complex dye does not occur, and the comprehensive performance of the colored liquid metal is good. Illustratively, the mass ratio of liquid metal to metal complex dye is 100: 1, 50: 1, 20: 1, 10: 1, or 5: 1.

Optionally, in the metal complex dye solution, the weight percentage of the metal complex dye is 10% to 40%, the weight percentage of the solvent is 30% to 70%, and the weight percentage of the auxiliary agent is 1% to 30%. The weight percentages herein are based on the metal complex dye solution used in preparing the colored liquid metal.

Illustratively, the metal complex dye is Yellow-20, Yellow-57, Yellow-45kk, Orange-10, Orange-09, Red-04, Red-35, Red-06, Red-95, Red-10, Red-16, Brown-02, Brown-05, Blue-04, Blue-06, Green-20, Green-575, Black-04, Black-20, Black-55, and the like.

Illustratively, the solvent includes at least one of water, ethanol, ethylene glycol, glycerol, N-butanol, isobutanol, N-propanol, isopropanol, isoamyl alcohol, 1, 3-butanediol, methoxypropanol, acetone, butanone, cyclohexanone, methyl isobutyl ketone, diisobutyl ketone, ethylene glycol ethyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol phenyl ether, glycidyl ether, ethyl acetate, butyl acetate, isoamyl acetate, N-butyl glycolate, N-hexane, cyclohexane, N-heptane, N-octane, isooctane, toluene, xylene, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, N-methylpyrrolidone.

Optionally, the auxiliary agent comprises at least one of a pH adjuster, a surfactant, a cosolvent, a humectant, and a preservative. The preservative, the cosolvent and the like in the auxiliary agent are needed for the stability of the metal complex dye solution, and the surfactant and the like can make the metal complex dye and other materials have better compatibility, so that the metal complex dye can be more easily and uniformly mixed with liquid metal.

Optionally, the liquid metal comprises a simple metal or an alloy having a melting point below 300 ℃. Preferably, the liquid metal is one or more of a gallium simple substance, an indium simple substance, a tin simple substance, a mercury simple substance, a gallium-indium alloy, a gallium-indium-tin alloy, a gallium-zinc alloy, a gallium-indium-zinc alloy, a gallium-tin-zinc alloy, a gallium-indium-tin-zinc alloy, a gallium-tin-cadmium alloy, a gallium-zinc-cadmium alloy, a bismuth-indium alloy, a bismuth-tin alloy, a bismuth-indium-zinc alloy, a bismuth-tin-zinc alloy, a bismuth-indium-tin-lead alloy, a bismuth-tin-cadmium alloy, a bismuth-lead-tin alloy, a bismuth-tin-lead-cadmium alloy, a tin-copper alloy, a tin-zinc alloy, a tin.

Optionally, the colored liquid metal may further include a coupling agent and/or a conductive filler, so that the properties of the colored liquid metal may be adjusted according to actual needs.

In addition, an embodiment of the present invention further provides a method for preparing a colored liquid metal, which is used to prepare any one of the colored liquid metals described above, specifically, as shown in fig. 1, fig. 1 is a flowchart of a method for preparing a colored liquid metal provided in an embodiment of the present invention, where the method for preparing a colored liquid metal includes:

and step S1, carrying out pre-oxidation treatment on the liquid metal.

Alternatively, in step S1, the liquid metal is subjected to pre-oxidation treatment by a mechanical stirring method, a magnetic stirring method, or a ball milling method. During the process of mechanical stirring, magnetic stirring or ball milling, the compact oxide on the surface of the liquid metal can be damaged, and then new oxygen is introduced into the liquid metal, so that the liquid metal is pre-oxidized.

Further, in the process of mechanical stirring or magnetic stirring, the stirring speed is 300r/min to 3000r/min, and the stirring time is 0.5min to 60 min; in the ball milling process, the rotating speed is 50 r/min-500 r/min, and the ball milling time is 0.5 min-5 min. The stirring speed and the stirring time can control the oxidation degree and the viscosity of the liquid metal, the faster the stirring speed is, the longer the stirring time is, the greater the oxidation degree and the viscosity of the liquid metal are, and the ball milling rotating speed and the ball milling time are also similar. The selection of the process parameters can ensure that the oxidation degree of the liquid metal is proper when the liquid metal is subjected to pre-oxidation treatment, and the problem of overlarge viscosity or poor conductivity caused by excessive oxidation can be avoided.

And step S2, preparing a metal complex dye solution through the metal complex dye, the solvent and the auxiliary agent.

And step S3, adding the metal complex dye solution into the pre-oxidized liquid metal, and uniformly mixing to obtain the colored liquid metal.

Alternatively, in step S3, the metal complex dye solution and the pre-oxidized liquid metal are uniformly mixed by at least one of a mechanical stirring method, a magnetic stirring method, an ultrasonic dispersion method, and a ball milling method. The mixing time may be 1min to 60 min.

Wherein, the operation temperature of the steps S1 to S3 is higher than the melting point of the liquid metal. If the melting point of the liquid metal is lower than the room temperature, the steps S1 to S3 may be performed at room temperature, and if the melting point of the liquid metal is higher than the room temperature, the steps S1 to S3 may be performed by heating the liquid metal to ensure that the liquid metal has fluidity and is higher than the melting point.

In the method, the liquid metal is firstly subjected to pre-oxidation treatment to obtain the pre-oxidized liquid metal, the content and the viscosity of the oxide of the liquid metal are improved, so that the liquid metal is not easily dispersed into small particles when the liquid metal is mixed with the metal complex dye solution, and is uniformly mixed with the metal complex dye solution as a continuous phase, and further the colored liquid metal with good color development effect and good conductivity is obtained. .

The following embodiments of the present invention are illustrated in a number of specific examples to facilitate understanding and implementation by those skilled in the art.

Unless otherwise stated, the raw material addition amounts used in the following examples are calculated by mass.