CN109722699A - A kind of color liquid metal and preparation method thereof - Google Patents
A kind of color liquid metal and preparation method thereof Download PDFInfo
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- CN109722699A CN109722699A CN201711027068.9A CN201711027068A CN109722699A CN 109722699 A CN109722699 A CN 109722699A CN 201711027068 A CN201711027068 A CN 201711027068A CN 109722699 A CN109722699 A CN 109722699A
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 30
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 58
- 239000002184 metal Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 33
- 239000008151 electrolyte solution Substances 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 238000007743 anodising Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000846 In alloy Inorganic materials 0.000 claims description 5
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 10
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 238000002845 discoloration Methods 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 244000061458 Solanum melongena Species 0.000 abstract 1
- 229940021013 electrolyte solution Drugs 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 239000003086 colorant Substances 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 239000005030 aluminium foil Substances 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910000573 alkali metal alloy Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229910052730 francium Inorganic materials 0.000 description 2
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 241000665112 Zonitoides nitidus Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000960 colored gold Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910000743 fusible alloy Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- -1 yellow Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Cosmetics (AREA)
Abstract
The present invention provides a kind of color liquid metals and preparation method thereof.The color liquid metal includes liquid metal and is wrapped in the liquid metal surface and has coloured oxide skin(coating).Color liquid metal of the invention is preferably discoloration liquid metal material of the surface in yellow, gold, black, aubergine, blue, green etc., different from the gallium and the silvery whites room temperature liquid metal such as gallium-base alloy without processing, it is preferable to use electrochemical oxidation methods, and liquid metal surface to be made to wrap up one layer of oxidation film for being different from the very thin micro-nano-scale of self-assembling formation, scale is 1 μm or so, can show the gloss of required color.Preparation method provided by the invention is simple, does not damage liquid metal electric conductivity, has broken the single of previous silvery white liquid metal, and realize that liquid metal colored drawing provides possibility to produce color liquid metal.
Description
Technical field
The present invention relates to liquid metal material fields, more particularly, to a kind of color liquid metal and preparation method thereof.
Background technique
In recent years, liquid metal enters the visual field of people as a kind of brand-new material.Liquid metal is commonly referred to as
It is at room temperature the metal of liquid, it had not only had good mobility, but also had the electric conductivity of metal brilliance, thermal conductivity.However it can
Keep the metal of liquid and few in room temperature or close to room temperature under conditions of, mainly have mercury, gallium and its alloy, alkali metal alloy,
Rubidium, caesium, francium etc., in these metals, rubidium, caesium, francium are radioactive metal, and alkali metal alloy chemical property is very active, save,
It is extremely stringent to environmental requirement when use, it is difficult to be utilized in daily life by people.Mercury is the most common liquid metal,
Pharmacy, electronic device manufacture, thermometer and optical instrument manufacture etc. are widely used, but the steam of mercury forces down,
It is easy to volatilize at room temperature, and the mercuryvapour generated that volatilizees has severe toxicity, improper use is easy to generate harm to human body.And gallium and
Its alloy becomes the hot spot of application because the stable advantage of its safety and low toxicity, property is shown one's talent in this few fluid-like state metal.
With a series of acquirement of important breakthroughs and progress, around room temperature liquid metal basis and application technical research by
Gradually become international popular great Environment Science, and is just the high-new energy of the mankind, electronic information, advanced manufacture, flexible circuit, state
The development of anti-military security and biologic medical health approach brings subversive change.However, having coloured gold compared to traditional
Belonging to showed rich colors, gallium and its alloy material inevitably seems relatively simple once sinking constant silvery white, at present electricity
It is also more more and more intense, current not a kind of colored liquid of realization for the demand of color liquid metal in terms of child print and colored drawing
The standby short-cut method of state made of metal.
Summary of the invention
For the single color defect of liquid metal, the present invention provides a kind of color liquid metal, by liquid metal
Surface wrap the colorful one oxide layer obtains the metal material of expected color, and it is dull to change liquid metal color, Zhi Nengcheng
Existing argenteous status, under the premise of not damaged electric conductivity, surface a system such as yellow, gold, purplish red, bluish-green or black
The liquid metal of column gloss meets the requirement when the fields such as electronic printable use liquid metal to its colorful property.
The present invention provides a kind of color liquid metal, comprising: liquid metal has color with liquid metal surface is wrapped in
Oxide skin(coating).
Wherein, oxide skin(coating) with a thickness of 0.5 μm -20 μm, preferably 1 μm.
Wherein, the resistance value of color liquid metal of the invention is still the good conductor of electricity within 10 ohm.
Wherein, oxide skin(coating) is by being wrapped in liquid metal surface using electrochemical method in electrolyte environment.
Make the oxide of liquid metal surface attachment diverse microcosmic structure by electrochemical method, not according to degree of oxidation
Together, oxide can in the colors such as yellow, gold, purplish red, bluish-green or black so that liquid metal show yellow, gold,
The colors such as purplish red, bluish-green or black.
Wherein it is possible to realized using electrochemical method commonly used in the art, the preferably highly conductive substrate of chemical stabilization
Sacrificial metal method or anodizing.
Use the above method that liquid metal is made to generate silvery white-yellowish-gold-purplish red-bluish-green-black at any time a series of
The liquid metal of the variation of continuous color, those skilled in the art can regulate and control the reaction time according to required color.
In the present invention, liquid metal includes low-melting alloy, generally includes gallium, indium, tin, bismuth, zinc, one in lead-containing alloy
Kind is a variety of, preferably gallium, gallium-indium alloy or gallium-indium-tin alloy, further preferably gallium-indium alloy, more preferably Ga90In10、
Ga80In20、Ga75.5In24.5、Ga70In30Or Ga60In40, most preferably Ga75.5In24.5.Wherein, gallium, gallium-indium alloy, gallium indium tin
Commercially available all products can be selected in other gallium-base alloys such as alloy, can also pass through according to the preparation method of alloy in the prior art
Heating mixed method is prepared.
In a preferred embodiment of the invention, the highly conductive substrate sacrificial metal method of chemical stabilization specifically:
The liquid metal is instilled in electrolyte solution, sacrificial metal is added in Xiang Suoshu liquid metal, in electrolyte
The liquid metal that joined sacrificial metal is transferred in environment and makes its infiltration in conductive substrates, so that the liquid metal
Wrap up oxide skin(coating) in surface;
The sacrificial metal is more active than the liquid metal.
In above-mentioned steps, liquid metal is usually molten condition.
In above-mentioned steps, sacrificial metal is the metal more active than liquid metal.When the alloy that liquid metal is gallium or gallium
When, sacrificial metal is preferably aluminium, further preferably thin aluminium foil.
In above-mentioned steps, when sacrificial metal is aluminium foil, the ratio of liquid metal and aluminium foil is preferred are as follows: the liquid of 0.75mL
State metal, it is preferable to use 1cm × 1cm size aluminium foil, the aluminium foil of experiment is commercially available wonderful clean board aluminium foil, 1cm ×
The corresponding quality of 1cm aluminium foil is about 0.004g.During the experiment, when taking the liquid metal of 0.75mL, take respectively 0.2mm ×
Find that liquid metal shows constant color respectively, yellow wadding occurs when the aluminium foil of 0.2mm, 0.5mm × 0.5mm and 2cm × 2cm
Shape object and do not infiltrate non-discolouring phenomenon.
In above-mentioned steps, electrolyte solution can be acid, neutral or alkaline electrolyte solution, preferably hydroxide
Sodium, sodium sulphate, sodium chloride, oxalic acid, hydrochloric acid or sulfuric acid solution.Wherein, the preferred 0.5mol/L of electrolyte solution, further preferably
0.5mol/L, the sodium hydroxide, sodium sulphate, sodium chloride, oxalic acid, hydrochloric acid and sulfuric acid solution concentration are respectively preferably 0.5mol/
L.In preferred implementation, it is respectively provided with the concentration gradient of 0.1mol/L, 0.5mol/L, 1mol/L and 2mol/L, discovery is when electricity
Occur respectively when solution constant color, chatoyance iridescence, from it is colored rapidly turn black with turn black rapidly after chatoyance iridescence after dissolve
Phenomenon.
In above-mentioned steps, in order to react liquid metal sufficiently in electrolyte solution with sacrificial metal, sacrificial metal
10min is preferably greater than with the liquid reactant metal time.The additional amount of sacrificial metal preferably so that its with the liquid metal in electricity
It solves subject to cmpletely being reacted in matter environment.
In above-mentioned steps, the additional amount of electrolyte solution is preferably with by the liquid in conductive substrates and the conductive substrates
Subject to metal is totally submerged.
In above-mentioned steps, conductive substrates are usually chemically stable highly conductive substrate, i.e. chemical property stabilization, conductivity
High baseplate material, preferably graphite plate or copper sheet.
In above-mentioned steps, when the liquid metal that joined sacrificial metal is transferred in conductive substrates, liquid metal is very
It infiltrates in conductive substrates well, and its color will show silvery white-yellowish-gold-purplish red-bluish-green-black at any time
A series of color of consecutive variations.
Use a series of consecutive variations such as available presentation silvery white-yellowish-gold-purplish red-bluish-green-black of the above method
Color color liquid metal, the present invention also provides the preparation method of above-mentioned color liquid metal, this method is above-mentionedization
Stablize highly conductive substrate sacrificial metal method.The color liquid metal oxide film that this method obtains can show golden yellow colour system
Gloss, the resistance of obtained color liquid metal film is preferably in 1 ohm of magnitude.
In a preferred embodiment of the invention, anodizing specifically: the liquid is instilled in electrolyte solution
The anode of power supply is connect by state metal with the liquid metal, and the cathode of power supply is placed in close in solution but does not contact the liquid
State metal powers on so that the liquid metal surface wraps up oxide skin(coating).
It is yellowish-purplish red-bluish-green-golden in order to obtain silvery white-in liquid metal surface in above-mentioned anodizing step
A series of variation of continuous colors of color-black, when electrolyte solution solubility is 0.5mol/l, voltage value is preferably 10V-20V.
Color changeable effect is optimal when voltage is greater than 10V, and when voltage is greater than 20V, liquid metal rapid oxidation becomes black, and colour film stops
Stay the time too short, the voltage of power supply is preferably 12V.
In above-mentioned anodizing step, to avoid liquid from moving under the action of electric field, preparation process is influenced, is preferably existed
Liquid metal is fixed in a slot in electrolyte solution.
In above-mentioned anodizing step, electrolyte solution can be acid, neutral or alkaline electrolyte solution.Its
In, acidic electrolyte solution can be inorganic acid solution or organic acid soln, preferably sodium hydroxide, sodium sulphate, sodium chloride, grass
Acid, hydrochloric acid or sulfuric acid solution, further preferably sodium hydroxide, sodium sulphate or sulfuric acid solution.Wherein, concentration of electrolyte solutions is excellent
It is selected as 0.5mol/L, i.e., the described sodium hydroxide, sodium sulphate, sodium chloride, oxalic acid, hydrochloric acid and sulfuric acid solution concentration are respectively preferably
0.5mol/L。
Use a series of consecutive variations such as available presentation silvery white-yellowish-gold-purplish red-bluish-green-black of the above method
Color color liquid metal, the present invention also provides the preparation method of above-mentioned color liquid metal, this method is above-mentioned sun
Pole oxidizing process.The color liquid metal that this method obtains is the coloured silk that can show purple, red, yellow, green and blue simultaneously
Colour circle, and show same color on each ring and seven colored pools are integrally presented;The electricity applied in anodizing by control
Size and time are pressed to control the color category of the colour circle of appearance.
In the method for realizing package using chemical method in electrolyte environment of the invention, when having wrapped up oxide skin(coating)
Liquid metal color when developing to required color, preferably by the liquid metal for having wrapped up oxide skin(coating) be transferred to deionized water or
In neutral buffer, clean.Wherein, neutral buffer is preferably sodium chloride solution or metabisulfite solution.
Resistance measurement, the present invention are carried out by colourshifting process of the setting 15-25V voltage to the liquid metal that the present invention obtains
The resistance of color liquid metal is smaller, is the good electric body of electricity.
Color liquid metal material proposed by the present invention is that a kind of surface is golden in the discoloration liquid of yellow, gold or black
Belong to material, different from the gallium and the silvery whites room temperature liquid metal such as gallium-base alloy without processing, liquid gold proposed by the present invention
Belong to the very thin micro-nano for being enclosed with that one layer is about 1 μm or so by the scale different from self-assembling formation that electrochemical oxidation process is formed
The oxidation film of metrical scale can show yellow, gold, purplish red, bluish-green or black gloss.Color liquid metal of the invention
Color is more lasting, and color is very stable after extracting in electrolyte solution, and the color liquid metal film extracted passes through
Find that, still without any variation, color gloss is as before after two months.The resistance control of color liquid metal proposed by the invention
System is within 10 magnitudes.
Yellow proposed by the present invention, gold, purplish red, bluish-green or black liquid state metal material preparation method, it is obtained
Color liquid metal has gloss possessed by script liquid metal, still has the texture of metal, and method of the invention has
The characteristics of preparation is simple, and coloring process does not damage liquid metal electric conductivity, has broken the single of previous silvery white liquid metal, and
It realizes that liquid metal colored drawing provides possibility to produce color liquid metal, has expanded previous traditional single color liquid metal
Use scope, especially for liquid metal color electric printing, electronic printing, polychromy etc..
Detailed description of the invention
Fig. 1 is the preparation method schematic diagram according to liquid metal colored in the embodiment of the present invention 1;
Fig. 2 is the preparation method schematic diagram according to liquid metal colored in the embodiment of the present invention 2;
Fig. 3 is the sectional view of the color liquid metal according to obtained in the embodiment of the present invention 1;
Fig. 4 be according in the embodiment of the present invention apply different voltages in the case of to resistance in color liquid metal colourshifting process
Experiment curv figure.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
Unless otherwise specified, the routine techniques hand that technological means used in embodiment is well known to those skilled in the art
Section.Unless otherwise specified, reagent used in embodiment is commercially available.
Liquid metal in raw material is prepared according to following technical scheme, with Ga75.5In24.5For:
(a) gallium that purity is 99.9% is weighed with indium, takes out corresponding matter according to mass ratio 74.5:24.5
The liquid metal gallium of amount is put into beaker;
(b) heated constant temperature magnetic stirring apparatus is placed the beaker, heating temperature is set as 80 DEG C, revolving speed 200r/min, so
Load weighted indium block is added in backward beaker;
(c) after the dissolution of indium block, to liquid metal in two magnetic stir bars are added, stirring molten metal body 10min is allowed to
As even phase.
Change the mass ratio of gallium and indium, Ga can be made in same operation90In10、Ga80In20、Ga70In30、
Ga60In40Alloy.
Embodiment 1
The present embodiment is a kind of preparation method of liquid metal that changes colour, specifically includes the following steps: the preparation of liquid metal:
(1) it takes 4.6g sodium hydroxide to be placed in 400ml beaker, the hydroxide that deionized water is configured to 0.5mol/l is added
Sodium solution;
(2) appropriate sodium hydroxide solution is taken out in small glassware 1, takes 0.75mL liquid metal (Ga75.5In24.5), it inserts
Enter 1cm*1cm flake aluminum to react into liquid metal;
(3) graphite plate is put into a glassware and the sodium hydroxide solution for preparing is added in step 1 to being totally submerged stone
Black plate will react substantially complete liquid metal and be drawn on graphite plate.
(4) after to liquid metal discoloration, liquid metal is transferred in neutral buffer, washes clean, is collected
Complete the preparation of material.
The schematic diagram of the present embodiment is as shown in Figure 1, wherein 1 is liquid metal, and 2 be graphite plate, and 3 be sodium hydroxide solution;
Finally obtained discoloration liquid metal is as shown in Figure 3.
Embodiment 2
(1) it takes 4.6g sodium hydroxide to be placed in 400ml beaker, the hydroxide that deionized water is configured to 0.5mol/l is added
Sodium solution;
(2) appropriate sodium hydroxide solution is taken out in small glassware, is taken 1ml liquid metal (Ga75.5In24.5), is put
On the PVC being immersed in sodium hydroxide solution.
(3) anode of power supply is connected into liquid metal by electrode, cathode is placed in close in solution but does not contact liquid gold
Belong to.Voltage is adjusted to 12V, is powered on.
(4) when liquid metal surface is developed to required color, liquid metal is transferred in neutral buffer, is washed
Clean electrolyte solution completes the preparation of material.
The schematic diagram of the present embodiment is as shown in Figure 2, wherein 4 be power cathode, and 5 be positive pole, and 6 is molten for sodium hydroxide
Liquid, 7 be liquid metal;Prepare the variation that surface generates a series of silvery white-yellowish-gold-black continuous colors at any time
Liquid metal.
The present embodiment carries out resistance measurement, discovery to colourshifting process by setting tri- voltage gradients of 15V, 20V and 25V
The resistance of discoloration liquid metal is smaller, within 10 Ω, is still the good conductor of electricity, as shown in Figure 4.
Embodiment 3
The present embodiment and the difference of embodiment 1 are only that, the sodium hydroxide in 1 step of embodiment (1) is replaced with
The metabisulfite solution of 0.5mol/l.
The present embodiment prepares the variation that surface generates a series of silvery white-yellowish-gold-black continuous colors at any time
Liquid metal.
Embodiment 4
The present embodiment and the difference of embodiment 1 are only that, the sodium hydroxide in 1 step of embodiment (1) is replaced with
The sodium chloride solution of 0.5mol/l.
The present embodiment prepares the variation that surface generates a series of silvery white-yellowish-gold-black continuous colors at any time
Liquid metal.
Embodiment 5
The present embodiment and the difference of embodiment 1 are only that, the liquid metal in 1 step of embodiment (2) is replaced with Ga.
The present embodiment prepares the variation that surface generates a series of silvery white-yellowish-gold-black continuous colors at any time
Liquid metal.
Embodiment 6
The present embodiment and the difference of embodiment 1 are only that, the liquid metal in 1 step of embodiment (2) is replaced with
Ga90In10。
The present embodiment prepares the variation that surface generates a series of silvery white-yellowish-gold-black continuous colors at any time
Liquid metal.
Embodiment 7
The present embodiment and the difference of embodiment 1 are only that, the liquid metal in 1 step of embodiment (2) is replaced with
Ga66In20.5Sn13.5。
The present embodiment prepares the variation that surface generates a series of silvery white-yellowish-gold-black continuous colors at any time
Liquid metal.
Embodiment 8
The present embodiment and the difference of embodiment 1 are only that, the sodium hydroxide in 1 step of embodiment (1) is replaced with
The dilution heat of sulfuric acid of 0.5mol/l.
The present embodiment prepares the variation that surface generates a series of silvery white-yellowish-gold-black continuous colors at any time
Liquid metal.
Embodiment 9
The present embodiment and the difference of embodiment 1 are only that, the sodium hydroxide in 1 step of embodiment (1) is replaced with
The dilute hydrochloric acid solution of 0.5mol/l.
The present embodiment prepares the liquid metal that surface generates black variation at any time.
Embodiment 10
The present embodiment and the difference of embodiment 2 are only that, the sodium hydroxide in 2 step of embodiment (1) is replaced with
The metabisulfite solution of 0.5mol/l.
The present embodiment prepares the variation that surface generates a series of silvery white-yellowish-gold-black continuous colors at any time
Liquid metal.
Embodiment 11
The present embodiment and the difference of embodiment 2 are only that, the sodium hydroxide in 2 step of embodiment (1) is replaced with
The dilution heat of sulfuric acid of 0.5mol/l.
Finally, method of the invention is only preferable embodiment, it is not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of color liquid metal characterized by comprising liquid metal has face with the liquid metal surface is wrapped in
The oxide skin(coating) of color.
2. color liquid metal according to claim 1, which is characterized in that the oxide skin(coating) passes through in electrolyte environment
It is middle to be wrapped in the liquid metal surface using chemical method.
3. color liquid metal according to claim 2, which is characterized in that the chemical method includes that chemical stabilization height is led
Electric substrate sacrificial metal method or anodizing.
4. color liquid metal according to claim 3, which is characterized in that the highly conductive substrate of chemical stabilization sacrifices gold
Category method specifically:
The liquid metal is instilled in electrolyte solution, sacrificial metal is added in Xiang Suoshu liquid metal, in electrolyte environment
It is middle that the liquid metal that joined sacrificial metal is transferred to and makes its infiltration in conductive substrates, so that the liquid metal surface
Wrap up oxide skin(coating);
The sacrificial metal is more active than the liquid metal;The reaction time that the sacrificial metal is added is preferably greater than 10min;
The conductive substrates are preferably graphite plate or copper sheet.
5. color liquid metal according to claim 3, which is characterized in that the anodizing specifically:
The liquid metal is instilled in electrolyte solution, the anode of power supply is connect with the liquid metal, the cathode of power supply
It is placed in close in solution but does not contact the liquid metal, power on so that the liquid metal surface wraps up oxide skin(coating);
The voltage of the power supply is preferably 12V.
6. color liquid metal according to claim 4 or 5, which is characterized in that the electrolyte solution is sodium hydroxide
Solution, sulfuric acid solution, hydrochloric acid solution, sodium chloride solution, metabisulfite solution or oxalic acid solution.
7. color liquid metal according to claim 1 to 6, which is characterized in that the liquid metal be gallium,
Gallium-indium alloy or gallium-indium-tin alloy, preferably gallium-indium alloy, more preferably Ga90In10、Ga80In20、Ga75.5In24.5、Ga70In30
Or Ga60In40。
8. a kind of preparation method of color liquid metal as claimed in claim 1 or 2 characterized by comprising
The liquid metal is instilled in electrolyte solution, sacrificial metal is added in Xiang Suoshu liquid metal, in electrolyte environment
It is middle that the liquid metal that joined sacrificial metal is transferred to and makes its infiltration in conductive substrates;
The sacrificial metal is more active than the liquid metal, preferably aluminium.
9. a kind of preparation method of color liquid metal as claimed in claim 1 or 2 characterized by comprising
The liquid metal is instilled in electrolyte solution, the anode of power supply is connect with the liquid metal, the cathode of power supply
It is placed in close in solution but does not contact the liquid metal, power on so that liquid metal surface wraps up oxide skin(coating).
10. preparation method according to claim 8 or claim 9, which is characterized in that the method also includes:
The liquid metal for having wrapped up oxide skin(coating) is transferred in deionized water or neutral buffer, is cleaned;It is described neutral slow
Rushing solution is preferably sodium chloride solution or metabisulfite solution.
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CN114150197A (en) * | 2021-11-11 | 2022-03-08 | 烟台南山学院 | Physical contact rapid reversible color change liquid metal composite material and preparation method and application thereof |
CN114263594A (en) * | 2021-11-18 | 2022-04-01 | 北京机械设备研究所 | Liquid metal dynamic driving method based on pressure and voltage |
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CN108395886A (en) * | 2017-02-07 | 2018-08-14 | 云南科威液态金属谷研发有限公司 | A kind of fluorescence liquid metal and preparation method thereof |
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CN108395886A (en) * | 2017-02-07 | 2018-08-14 | 云南科威液态金属谷研发有限公司 | A kind of fluorescence liquid metal and preparation method thereof |
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CN114150197A (en) * | 2021-11-11 | 2022-03-08 | 烟台南山学院 | Physical contact rapid reversible color change liquid metal composite material and preparation method and application thereof |
CN114150197B (en) * | 2021-11-11 | 2022-09-13 | 烟台南山学院 | Physical contact rapid reversible color change liquid metal composite material and application thereof |
CN114263594A (en) * | 2021-11-18 | 2022-04-01 | 北京机械设备研究所 | Liquid metal dynamic driving method based on pressure and voltage |
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