CN105220013B - 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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- CN105220013B CN105220013B CN201510592158.7A CN201510592158A CN105220013B CN 105220013 B CN105220013 B CN 105220013B CN 201510592158 A CN201510592158 A CN 201510592158A CN 105220013 B CN105220013 B CN 105220013B
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- liquid metal
- indium
- pigment
- color liquid
- bismuth
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 170
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000049 pigment Substances 0.000 claims abstract description 72
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000008187 granular material Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 41
- 229910045601 alloy Inorganic materials 0.000 claims description 28
- 239000000956 alloy Substances 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 21
- 229910052738 indium Inorganic materials 0.000 claims description 18
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 17
- 229910052733 gallium Inorganic materials 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910000743 fusible alloy Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 239000007769 metal material Substances 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- COHYTHOBJLSHDF-UHFFFAOYSA-N Indigo Chemical compound N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 6
- MPZNMEBSWMRGFG-UHFFFAOYSA-N bismuth indium Chemical compound [In].[Bi] MPZNMEBSWMRGFG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000001040 synthetic pigment Substances 0.000 claims description 4
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011370 conductive nanoparticle Substances 0.000 claims description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001710 laterite Inorganic materials 0.000 claims description 3
- 239000011504 laterite Substances 0.000 claims description 3
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052957 realgar Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 241001005836 Euchloe ausonia Species 0.000 claims description 2
- 241000692870 Inachis io Species 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- UCYSETLJZJSHFR-UHFFFAOYSA-N [Bi].[Cd].[In] Chemical compound [Bi].[Cd].[In] UCYSETLJZJSHFR-UHFFFAOYSA-N 0.000 claims description 2
- MXCODEAYRFLVOQ-UHFFFAOYSA-N [Zn].[Bi].[In] Chemical compound [Zn].[Bi].[In] MXCODEAYRFLVOQ-UHFFFAOYSA-N 0.000 claims description 2
- WGCXSIWGFOQDEG-UHFFFAOYSA-N [Zn].[Sn].[In] Chemical compound [Zn].[Sn].[In] WGCXSIWGFOQDEG-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 239000011050 natural pearl Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 claims description 2
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 235000014692 zinc oxide Nutrition 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 claims 1
- 241000123069 Ocyurus chrysurus Species 0.000 claims 1
- DVZGHANHGMAGPI-UHFFFAOYSA-N [Bi].[Zn].[Cu].[Ag] Chemical compound [Bi].[Zn].[Cu].[Ag] DVZGHANHGMAGPI-UHFFFAOYSA-N 0.000 claims 1
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 230000005496 eutectics Effects 0.000 claims 1
- 239000003086 colorant Substances 0.000 abstract description 8
- 238000007639 printing Methods 0.000 abstract description 3
- 229910000846 In alloy Inorganic materials 0.000 description 23
- 230000008859 change Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- -1 Cinnabaris Substances 0.000 description 5
- 230000000295 complement effect Effects 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001446187 Kermes Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 239000001023 inorganic pigment Substances 0.000 description 1
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- CXORMDKZEUMQHX-UHFFFAOYSA-N kermesic acid Chemical compound O=C1C2=C(O)C(O)=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C CXORMDKZEUMQHX-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
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- 230000004630 mental health Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
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Abstract
The present invention provides a kind of color liquid metal and preparation method thereof, and the color liquid raw metal includes liquid metal, pigment and/or conductive nano granule, and various specific colors can be also presented while realizing conductive.The present invention provides the rich colors for having liquid metal satisfactory electrical conductivity and pigment simultaneously concurrently first, can open colored printing electronic channel, can be obviously improved the aesthetic property and experience sense of printed electronic；Meanwhile, also improve the non-oxidizability and rust-preventing characteristic of conventional liquid metal.
Description
Technical field
The invention belongs to liquid metal material field, specifically related to a kind of color liquid metal and preparation method thereof.
Background technology
Liquid metal typically refers to a kind of in the metal that near room temperature is liquid, such as gallium of the fusing point below 30 DEG C or its conjunction
Gold, can also or in such as 40 DEG C -200 DEG C of periods of slightly higher some temperature ranges be presented the low-melting point metal alloy such as bismuth indium stannum of liquid
The materials such as zinc.In the past, as many attributes and purposes of liquid metal are rarely known by the people for a long time, big class functional material is less receives for this
Academia and industrial circle in global range is paid attention to.In recent years, with a series of acquirement of major progresses, the weight of liquid metal
Using value is wanted progressively to draw attention.In a variety of applications where, due to being worked with liquid states of matter, mobility is very for liquid metal material
It is good, and itself there is natural electric conductivity, thus emerging printed electronic, functional device 3D printing are introduced in recent years
Field, becomes unique important printable formula electronic material.
However, existing liquid metal is limited due to its own physical property or alloy composition, the liquid metal for being formed itself
Gloss is silvery white in color mostly, and color is very single, and this is for industrial many printings higher to color and aesthetic measure requirement
Or coating application scenario, formed circuit is apart from each other with the aesthetic conceptions of people.In fact, with social development and material and culture
Growth in the living standard, for many new electronics and consumption electronic product, user is no longer only satisfied with acquisition, and which is basic
Electrical functions, the color embodied for product and experience are it is also proposed that wilderness demand.To a great extent, color is determined really
Effects of many products.The ever-changing and form and aspect of nature color, constitute WANZIQIANHONG, the multicoloured world.From
For Psychological Angle, different colours can cause different senses to regard to human body, such as：Soft, bright colors, meeting band give happiness
The beautiful enjoyment such as happy, happy, relaxing；Conversely, color imbalance even extreme embodiment can then allow people to feel dull, lose heart, very
And have influence on physical and mental health.
Regrettably, so far, the liquid metal printed electronic ink for being developed in recent years there is no method to present in itself
Color function, it more difficult to reach the ever-changing of color.Obviously, it is color if which can be given to the liquid metal principle with printability
Color function, will greatly promote its special performance, be achieved in coloury printed electronic or 3D metals make, significantly increase then
The experience sense and artistic value of strong product.For this purpose, present invention firstly provides the technological concept of color liquid metal, its purpose is just
It is that liquid metal with various colors and preparation method thereof is provided, to the existing skill of take on a new look existing liquid metal and pigment
Art category.
It is known that pigment refers to the material that object can be made to catch color, the mankind are known that very early and use pigment, such as profit
With coloured soil and Ore, draw a picture on crag and smear body.Equally, to make liquid metal keep electric conductivity and mobility
Bright-colored color can also be presented simultaneously, the invention provides pigment loading measure, by the preparation of specific pigment and liquid metal,
The liquid metal of color of all kinds can be obtained.
In view of this, it is special to propose the present invention.
The content of the invention
(1) technical problem to be solved
To overcome the shortcoming of current material technology and to change conventional liquid metal color single and conventional pigment does not have
The present situation of standby electric conductivity, the present invention provides a kind of color liquid metal material, by loading per se with color in liquid metal
Color pigment can be used to making electronic circuit lucuriant in design or 3D metallic prints or more obtaining the metal material of expected color
Multipurpose, present invention also offers the manufacture method of the color liquid metal.
(2) technical scheme
For achieving the above object, the present invention provides a kind of color liquid metal, and the raw material of the color liquid metal includes
Liquid metal and pigment.
The liquid metal includes low-melting alloy.
Low-melting alloy of the present invention, refers to fusible alloy of the fusing point less than 232 DEG C；Generally by Ga, In, Sn, Bi,
The low-melting-point metals such as Pb, Zn are elementary composition.
The low-melting alloy includes one or more in gallium, indium, stannum, bismuth, zinc, lead-containing alloy；
Further, the low-melting alloy include one kind in bianry alloy gallium indium, gallium stannum, bismuth stannum, indium bismuth, indium stannum or
It is several；Or the low-melting alloy includes ternary alloy three-partalloy gallium indium tin, bismuth indium stannum, bismuth indium zinc, indium stannum zinc, bismuth stannum copper, bismuth indium cadmium
In one or more；Or the low-melting alloy includes quaternary alloy gallium indium tin zinc, indium stannum zinc bismuth, bismuth indium stannum silver, zinc bismuth
One or more in silver-bearing copper.
Wherein, in the gallium-base alloy, gallium content is 10wt%-100wt%；In bismuth-base alloy, bi content is 10wt%-
95wt%；In indium-base alloy, indium content is 10wt%-95wt%.
Preferably, in the gallium-base alloy, gallium content is 50wt%-90wt%；In bismuth-base alloy, bi content is 50wt%-
90wt%, in indium-base alloy, indium content is 50wt%-90wt%.
The pigment includes one or more in natural pigment, synthetic pigment.
Further, the natural pigment includes natural minerals pigment, such as Cinnabaris, laterite, Realgar, peacock green, heavy carbon
One or more in sour calcium, wollastonite, blanc fixe, Pulvis Talci, mica powder, Kaolin etc.；Or animal origin pigment, kermes
One or more in dried female insect, natural pearl white etc.；Or plant origin pigment, such as：One kind in Resina garciniae, alizarin red, indigo-blue etc.
Or it is several.
One or more in the synthetic pigment, including the inorganic pigment such as titanium white, Griffith's zinc white., lead chromate yellow, barba hispanica；
Or one or more in the organic pigment such as red, even yellowish, phthalocyanine blue, quinacridone.
Further, the liquid metal and the mass ratio of the pigment are 10-100: 1-10.
Further to reduce adverse effect of the pigment to liquid metal, it is an unexpected discovery of the invention that working as granules of pigments diameter
For 1nm-900nm when minimum is affected on liquid metal electric conductivity；And can also be lifted liquid metal itself rust-preventing characteristic and
Antioxygenic property.
It is further preferred that a diameter of 10nm-500nm of the granules of pigments.
The pigment can be directly appended in the liquid metal；The pigment can also be added to some in advance molten
Mix with liquid metal after liquid paint is made in agent again；Solvent described here can for transparent silicone rubber, epoxy resin,
The materials such as PDMS (polydimethylsiloxane), it might even be possible to be the solvent mixed colours by colored paint and coating；Preferably,
The pigment is 5wt%-90wt% with the mass ratio of the solvent；It is possible thereby to the liquid of different colourities is obtained according to concrete proportioning
State metal material.
For the electric conductivity for further lifting color liquid metal, it is preferable that the raw material of the color liquid metal is also wrapped
Include conductive nano granule.
Preferably, the conductive nano granule includes nano level gold, silver, copper, ferrum, ferrum oxide, nickel, cobalt, gadolinium and carbon
One or more in nanotube, Graphene etc..
Preferably, the conductive nano particle diameter is 1nm-900nm；Preferably 10nm-500nm.
It is further preferred that the liquid metal is 10-100: 1-10 with the mass ratio of the conductive nano granule.
Wherein, for example nano level ferrum of the conductive nano granule, ferrum oxide, nickel, cobalt, gadolinium etc. can also change color liquid
The magnetism characteristic of metal；The conductive nano granule such as copper, golden and CNT, Graphene etc. also have regulation liquid metal
Effect of color.
On the other hand, the manufacture method that the present invention also provides above-mentioned color liquid metal, comprises the following steps,
S1：Needed raw material, i.e. liquid metal, pigment, and/or conductive nano granule are chosen on demand；
S2：The liquid metal is processed as into liquid condition；
S3：The pigment is added in the liquid metals of the liquid condition, is stirred；And/or add described
Conductive nano granule, stirs.
In above-mentioned manufacture method step S1：
According to the color of required color liquid metal, the usage ratio of the liquid metal and pigment is determined.
In above-mentioned manufacture method step S2：
It is described the method that the liquid metal is processed as liquid condition is included the liquid metal is placed in air or
In vacuum, constant temperature is processed.
The constant temperature process time is changed into liquid condition with the liquid metal and is advisable；Preferably, the constant temperature is processed
Time is 1-4h.
The constant temperature treatment temperature is changed into liquid condition with the liquid metal and is advisable；Preferably, the constant temperature is processed
Fusing point of the temperature greater than or equal to the liquid metal；It is further preferred that the constant temperature treatment temperature is higher than liquid gold
30-600 DEG C of the fusing point of category.
Preferably, step S3 will be carried out again after the liquid metal stirring for being changed into liquid condition；It is further preferred that
Use magnetic stirrer 0.5-5h.
In above-mentioned manufacture method step S3：
The mixing time is preferably 0.5-5h.
The stirring means can be with mechanical agitation, electromagnetic agitation, ultrasonic agitation, vibrations stirring etc.；Preferably electromagnetic agitation.
As needed, obtained two or more chromatic metallics as stated above can be mixed once again, is made spy
The color color liquid metal of fixation.
Preferably, the color liquid metal can be modulated in shades of colour scope.The liquid metal toning can pass through
Man-made Color Matching or computerized color matching realize that color matching principle can follow subtractive process principle, such as based on three primary colories as yellow, blue or green, purple and its
Corresponding complementary color is for example blue, red, green, can be that two kinds of coloured light are mixed to get white coloured light by a certain percentage by complementary color, according to Jing
The color theory of allusion quotation obtains required color liquid metal by that analogy, and such as red complementary color is cyan, and the complementary color of yellow is blueness,
The complementary color of green is purple, and the subtractive process mixed principle being achieved in can be followed：Yellow=white-blue；Purple=white-green
Color；Cyan=white-redness；Yellow+purple=white-blue-green=redness；Yellow+cyan=white-blue-redness
=green；Purple+cyan=white-green-redness=blueness；Yellow+purple+cyan=white-blue-green etc..
Following table lists the fusing point of some common liquid metals：
| Gallium, 29.28 DEG C | Ga75.5In24.5, 16 DEG C | Ga62.5In21.5Sn16, 11 DEG C |
| Bi49In21Pb18Sn12, 58 DEG C | In66.3Bi33.7, 72 DEG C | Bi52Pb30Sn18, 96 DEG C |
| Bi58Sn42, 138 DEG C |
(3) beneficial effect
The above-mentioned technical proposal that the present invention is provided has the advantage that：
1st, taken on a new look the existing concept and technology category of existing liquid metal and pigment, first there is provided color liquid metal
The material of this brand new conception, has the rich colors of liquid metal satisfactory electrical conductivity and pigment concurrently；
2nd, different from existing liquid metal, color liquid metal increased bright and colourful speciality, may be used on big
Amount cultural creative electron trade；Colored printing electronic channel can be opened；The aesthetic property and experience sense of printed electronic can be obviously improved；
3rd, different from conventional pigment or paint, color liquid metal possesses the electric conductivity not available for convention pigment
Matter, thus conventional pigment industry of can taking on a new look；
4th, color liquid metal further improves non-oxidizability and rust-preventing characteristic of conventional liquid metal etc.；
5th, compared with traditional liquid metal, degree of oxidation is greatly reduced, advantageously in the application of liquid metal itself；
6th, thus the proposition of color liquid metal material is the ideational innovation to traditional metal materials and printed electronic, can be
Amplify out a large amount of whole new set of applications.
Description of the drawings
Fig. 1 is the structural representation of color liquid metal of the present invention.
In figure：1st, liquid metal；2nd, granules of pigments.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
A kind of color liquid metal, its raw material include liquid metal and pigment；The liquid metal is gallium-indium alloy
Ga24.5In, the pigment are Cinnabaris, wherein the mass ratio of the liquid metal and pigment is 10: 1.
The manufacture method that the present embodiment also provides the color liquid metal, comprises the following steps：
S1：The liquid metal gallium-indium alloy Ga is taken by proportioning24.5In and pigment Cinnabaris；
S2：The liquid metal is placed in constant temperature in air ambient to process, treatment temperature is 50 DEG C, and process time is 1h；
Then it is stirred, stir speed (S.S.) is 500rpm, and mixing time is 5h；Obtain the liquid metal of liquid condition；
S3：The pigment Cinnabaris are made into the granule of a diameter of 600nm, the liquid metals of above-mentioned liquid condition is added to
In, 80min is mechanically stirred to stirring.
Described in the present embodiment, color liquid metal is as shown in Figure 1.
Embodiment 2-11
Color liquid metal, its raw material include liquid metal and pigment, from embodiment 1 to differ only in pigment different.
The manufacture method of the color liquid metal is with embodiment 1.
| Numbering | Liquid metal | Pigment |
| Embodiment 2 | Gallium-indium alloy Ga24.5In | Laterite |
| Embodiment 3 | Gallium-indium alloy Ga24.5In | Alizarin red |
| Embodiment 4 | Gallium-indium alloy Ga24.5In | Red |
| Embodiment 5 | Gallium-indium alloy Ga24.5In | Realgar |
| Embodiment 6 | Gallium-indium alloy Ga24.5In | Resina garciniae |
| Embodiment 7 | Gallium-indium alloy Ga24.5In | Lead chromate yellow |
| Embodiment 8 | Gallium-indium alloy Ga24.5In | It is even yellowish |
| Embodiment 9 | Gallium-indium alloy Ga24.5In | It is indigo-blue |
| Embodiment 10 | Gallium-indium alloy Ga24.5In | Barba hispanica |
| Embodiment 11 | Gallium-indium alloy Ga24.5In | Phthalocyanine blue |
Embodiment 12
A kind of color liquid metal, its raw material include liquid metal, pigment and conductive nano granule；The liquid metal is
Gallium-indium alloy Ga24.5In, the pigment are Cinnabaris, and the conductive nano granule is the nanometer gold of a diameter of 300nm；It is wherein described
The mass ratio of liquid metal, pigment and conductive nano granule is 40: 4: 6.
The manufacture method that the present embodiment also provides the color liquid metal, comprises the following steps：
S1：The liquid metal gallium-indium alloy Ga is taken by proportioning24.5In, pigment Cinnabaris and conductive nano granule it is (a diameter of
The nanometer gold of 300nm)；
S2：The liquid metal is placed in constant temperature in air ambient to process, treatment temperature is 50 DEG C, and process time is 1h；
Then it is stirred, stir speed (S.S.) is 500rpm, and mixing time is 5h；Obtain the liquid metal of liquid condition；
S3：The pigment Cinnabaris are made into the granule of a diameter of 600nm, the liquid metals of above-mentioned liquid condition is added to
In, 80min is mechanically stirred to stirring；Conductive nano granule (nanometer gold of a diameter of 300nm) is being added, machine is being used
Tool mode stirs 80min to stirring.
Embodiment 13-21
Color liquid metal, its raw material include the conductive particle of liquid metal, pigment and a diameter of 300nm nanometers, with reality
That applies example 12 differs only in conductive nano granule difference.The manufacture method of the color liquid metal is with embodiment 12.
| Numbering | Liquid metal | Pigment | Conductive nano granule |
| Embodiment 13 | Gallium-indium alloy Ga24.5In | Cinnabaris | Silver |
| Embodiment 14 | Gallium-indium alloy Ga24.5In | Cinnabaris | Copper |
| Embodiment 15 | Gallium-indium alloy Ga24.5In | Cinnabaris | CNT |
| Embodiment 16 | Gallium-indium alloy Ga24.5In | Cinnabaris | Graphene |
| Embodiment 17 | Gallium-indium alloy Ga24.5In | Cinnabaris | Ferrum oxide |
| Embodiment 18 | Gallium-indium alloy Ga24.5In | Cinnabaris | Ferrum |
| Embodiment 19 | Gallium-indium alloy Ga24.5In | Cinnabaris | Nickel |
| Embodiment 20 | Gallium-indium alloy Ga24.5In | Cinnabaris | Cobalt |
| Embodiment 21 | Gallium-indium alloy Ga24.5In | Cinnabaris | Gadolinium |
Embodiment 22
Color liquid metal, its raw material include liquid metal and pigment, differ only in liquid metal not with embodiment 1
Together, the liquid metal of the color liquid metal is indium-base alloy InSn49.2。
The manufacture method of the present embodiment color liquid metal with embodiment 1 to differ only in step S2 different.This enforcement
Manufacture method step S2 of example color liquid metal is included indium-base alloy InSn49.2It is placed in 230 DEG C of vacuum constant-temperature container permanent
Temperature 1 hour, then with magnetic stirrer 100 minutes, is obtained the indium-base alloy InSn of liquid condition49.2。
Wherein, indium-base alloy InSn49.2Manufacture method include：Ratio according to mass ratio 50.8: 49.2 is weighed respectively
Pure indium and pure tin, are put in rustless steel container, and container is placed in constant temperature 1 hour in 230 DEG C of vacuum constant-temperature container, magnetic force is subsequently used
Agitator is stirred 100 minutes, that is, indium-base alloy InSn is obtained49.2, its fusing point is 120 DEG C.
Embodiment 23
Color liquid metal, its raw material include liquid metal and pigment, also include directly with differing only in for embodiment 22
Conductive nano granule silver of the footpath for 300nm；Wherein, wherein the mass ratio of the liquid metal, pigment and conductive nano Argent grain
Example is 40: 4: 6.
The preparation method of the color liquid metal is with embodiment 12.
Embodiment 24
Color liquid metal, its raw material include liquid metal and pigment, differ only in liquid metal not with embodiment 1
Together, the liquid metal of the color liquid metal is bismuth-base alloy BiIn21Sn12Pb18。
The manufacture method of the present embodiment color liquid metal with embodiment 1 to differ only in step S2 different.This enforcement
Manufacture method step S2 of example color liquid metal is included bismuth-base alloy BiIn21Sn12Pb18It is placed in 250 DEG C of vacuum constant-temperature container
Middle constant temperature 4 hours, then with magnetic stirrer 50 minutes, is obtained the bismuth-base alloy BiIn of liquid condition21Sn12Pb18。
Wherein, bismuth-base alloy BiIn21Sn12Pb18Manufacture method include：According to mass ratio 49:21:12:18 ratio point
Another name takes pure bismuth, pure indium, pure tin and pure lead, is put in rustless steel container, container is placed in constant temperature in 250 DEG C of vacuum constant-temperature container
4 hours, subsequently use magnetic stirrer 50 minutes, that is, bismuth-base alloy BiIn is obtained21Sn12Pb18, its fusing point is 58 DEG C.
Embodiment 25
Color liquid metal, its raw material include liquid metal and pigment, differs only in pigment class with embodiment 1-11
Type is different.The present embodiment is added to the pigment (granule of a diameter of 600nm) in some solvents in advance makes liquid paint,
Required color liquid metal is made after mixing with liquid metal again afterwards.Solvent described here can be transparent silicone rubber, ring
The materials such as oxygen tree fat, PDMS (polydimethylsiloxane) even through colored paint and coating toning form, the raw material with
The mass ratio of solvent is 1：10.
Embodiment 26
Color liquid metal, its raw material include liquid metal and pigment, with embodiment 1 differ only in liquid metal with
The mass ratio of pigment is 20: 1.The color liquid metal fabrication methods are same as Example 1.
Embodiment 27
Color liquid metal, the difference with embodiment 26 are that its raw material also includes diameter 500nm nano-Ag particles, wherein
Liquid metal is 10: 3 with the mass ratio of nano-Ag particles.The color liquid metal fabrication methods are identical with embodiment 12.
Embodiment 28
The present embodiment is configured to the liquid metal of required color by toning based on existing color liquid metal.Specifically will
As obtained in above-described embodiment 1-25,2-6 classes color liquid metal mixes once again, the mass ratio between different color liquid metals
For 1-10 scopes, to the liquid metal for mixing colours into specific color.
Experimental example
The conductive characteristic and corrosive nature method of testing list of references of color liquid metal is " a kind of by by liquid metal
Grain is uniformly blended into obtained high heat conduction, electric insulation silicone grease in polydimethylsiloxane " (Mei Shengfu, high rosy clouds, Deng Zhongshan, Liu
It is quiet), American Society of Mechanical Engineers's proceedings《Electronic Packaging journal》, 2014,136,011009；, Ying Yi：Mei S.F.,Gao
Y.X.,Deng Z.S.,Liu J.Thermally conductive and electrically highly resistive
grease through homogeneously dispersing liquid metal droplets inside dimethyl
Siloxane.ASME Journal of Electronic Packaging, 2014,136,011009) described in realize liquid
The method of state metal heat-conducting fat is carried out.In the present invention, using liquid metal as material based on packing material, pigment, Jing exists
In air, directly the color liquid metal of different ratio is prepared in blending, then by testing leading for measurement analysis color liquid metal
Electrical characteristics and corrosive nature.
As the resistivity of composite is larger, test platform is built using Agilent 34972A data collecting instruments.
The measurement range of resistance grade is 0～100MOhm.Resistance measurement probe has been set up in this experiment self-control, and the probe is by two copper electrodes
With a politef annular shim pack into.The size of copper electrode is diameter D=30mm, height H=30mm.Polytetrafluoroethylene ring
The size of shape pad is：Internal diameter d=20mm, outer diameter D=30mm, thickness t=0.3mm.Thus, by Agilent34972A data
Acquisition Instrument obtains resistance value R of the big small samples of 0.3mm × φ 20mm, then by classical Ohm's law ρ=R π d2/ 4t can be calculated
Go out the size of resistivity of material ρ.In experiment measurement process, in order to ensure measurement accuracy, need sample evacuation again
Bubble therein is removed, with the resistivity error for avoiding being brought by bubble.From representative experimental data, Ga can be obtained24.5In
After blending Cinnabaris pigment, the resistivity of color liquid metal is with the situation of change of liquid metal volume fraction, one of case
For, if the mass ratio of liquid metal and pigment is 20: 1 (embodiment 26), made color liquid metallic resistance rate is
3.2×10-6Ohmm, is still the good conductor of electricity.On this basis, then in mass ratio 10：3 loading 500nm diameter nanometer silvers are (real
Apply example 27), the resistivity of color liquid metal that can obtain preparing through hybrid technique lifts about 8.3 × 10-7Ohmm,
Illustrate the loading of nano-particle so that electric conductivity also illustrates the feasibility of the present invention better than color liquid metal before.Its
It is remaining, by more different liquid metal matrix components and the color liquid metal prepared of pigment or even nano-particle, also obtain class
As component relation.It is numerous herein.
With regard to rust-preventing characteristic, non-oxidizability, can be assessed using Experiments of Optics.Now, by testing sample (about 0.3ml)
It is even to be applied on a frosting.By quantifying optical surface, can be with color liquid of the qualitative assessment after oxidation gold
The rust-preventing characteristic of category, non-oxidizability.The EDS energy spectrum analysiss of Jing surfaces, can obtain the element ratio not in the same time through material.Experiment is sent out
It is existing, Ga24.5After In blending Cinnabaris pigment, color liquid metal includes the liquid metal for loading nano-particle once again without obvious oxygen
Change and get rusty.Its reason is：The addition of not oxidizable pigment makes liquid metal surface be difficult to form oxide-film, it is possible to find institute
There is no significant change in the color liquid metal surface of formation before and after experiment, while elemental composition is also without significant change.It is similar
Rule is also easy to realize in other embodiment 1-24 color liquid metal.
Although above having used general explanation, specific embodiment and test, the present invention having been made to retouch in detail
State, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (19)
1. a kind of color liquid metal, it is characterised in that its raw material includes liquid metal and pigment；The liquid metal is eutectic
Point alloy；The low-melting alloy is gallium, indium, stannum, bismuth, zinc, one or more in lead-containing alloy；Gallium in the gallium-base alloy
Content is 10wt%-100wt%；In bismuth-base alloy, bi content is 10wt%-95wt%；In indium-base alloy, indium content is
10wt%-95wt%；The low-melting alloy is 10-100: 1-10 with the mass ratio of the pigment；The granules of pigments diameter
For 1nm-900nm.
2. color liquid metal according to claim 1, it is characterised in that the low-melting alloy includes bianry alloy gallium
One or more in indium, gallium stannum, bismuth stannum, indium bismuth, indium stannum；Or the low-melting alloy includes ternary alloy three-partalloy gallium indium tin, bismuth
One or more in indium stannum, bismuth indium zinc, indium stannum zinc, bismuth stannum copper, bismuth indium cadmium；Or the low-melting alloy includes quaternary alloy
One or more in gallium indium tin zinc, indium stannum zinc bismuth, bismuth indium stannum silver, zinc bismuth silver copper.
3. color liquid metal according to claim 1, it is characterised in that gallium content is in the gallium-base alloy
50wt%-90wt%；In bismuth-base alloy, bi content is 50wt%-90wt%, and in indium-base alloy, indium content is 50wt%-
90wt%.
4. the color liquid metal according to any one of claim 1-3, it is characterised in that the pigment includes natural face
One or more in material, synthetic pigment.
5. color liquid metal according to claim 4, it is characterised in that the natural pigment includes natural minerals pigment
One kind in Cinnabaris, laterite, Realgar, peacock green, ground calcium carbonate, wollastonite, blanc fixe, Pulvis Talci, mica powder, Kaolin
Or it is several；Or one or more in animal origin pigment alkermes, natural pearl white；Or plant origin pigment Resina garciniae, madder
One or more during element is red, indigo-blue；The synthetic pigment include the one kind in titanium white, Griffith's zinc white., lead chromate yellow, barba hispanica or
It is several；Or one or more in red, even yellowish, phthalocyanine blue, quinacridone.
6. the color liquid metal according to any one of claim 1-3, it is characterised in that the granules of pigments is a diameter of
10nm-500nm。
7. the color liquid metal according to any one of claim 1-3, it is characterised in that the original of the color liquid metal
Material also includes conductive nano granule.
8. color liquid metal according to claim 7, it is characterised in that the conductive nano granule includes nano level
One or more in gold, silver, copper, ferrum, ferrum oxide, nickel, cobalt, gadolinium and CNT, Graphene.
9. color liquid metal according to claim 7, it is characterised in that the conductive nano particle diameter is 1nm-
900nm。
10. color liquid metal according to claim 8, it is characterised in that the conductive nano particle diameter is 10nm-
500nm。
11. color liquid metals according to claim 7, it is characterised in that the liquid metal and the conductive nano
The mass ratio of granule is 10-100: 1-10.
The manufacture method of color liquid metal described in 12. any one of claim 1-11, it is characterised in that comprise the following steps,
S1：Needed raw material is chosen on demand；
S2：The liquid metal is processed as into liquid condition；
S3：The pigment is added in the liquid metals of the liquid condition, is stirred；And/or add the nanometer
Conductive particle, stirs.
13. manufacture methods according to claim 12, it is characterised in that in manufacture method step S2：It is described by institute
State liquid metal be processed as liquid condition method include by the liquid metal be placed in air or in vacuum constant temperature process.
14. manufacture methods according to claim 13, it is characterised in that the constant temperature process time is 1-4h.
15. manufacture methods according to claim 13, it is characterised in that the constant temperature treatment temperature is greater than or equal to described
The fusing point of liquid metal.
16. manufacture methods according to claim 13, it is characterised in that the constant temperature treatment temperature is higher than liquid gold
30-600 DEG C of the fusing point of category.
17. manufacture methods according to claim 12 or 13, it is characterised in that by the liquid for being changed into liquid condition
Step S3 is carried out again after metal stirring.
18. manufacture methods according to claim 17, it is characterised in that the stirring is to use magnetic stirrer 0.5-
5h。
19. manufacture methods according to claim 12 or 13, it is characterised in that in manufacture method step S3：It is described
Mixing time is 0.5-5h.
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| CN107337964B (en) * | 2017-08-25 | 2020-07-07 | 北京梦之墨科技有限公司 | Colored liquid metal printing ink and preparation method thereof |
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| CN111534282A (en) * | 2019-12-16 | 2020-08-14 | 有研工程技术研究院有限公司 | Phase-change heat storage material with low melting point and high volume latent heat, and preparation method and application thereof |
| CN117866484A (en) * | 2024-03-12 | 2024-04-12 | 成都先进金属材料产业技术研究院股份有限公司 | Liquid metal printing ink and preparation method thereof |
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