CN111471348B - Wax-dispersed liquid metal solid ink and preparation method and application thereof - Google Patents
Wax-dispersed liquid metal solid ink and preparation method and application thereof Download PDFInfo
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- CN111471348B CN111471348B CN202010349401.3A CN202010349401A CN111471348B CN 111471348 B CN111471348 B CN 111471348B CN 202010349401 A CN202010349401 A CN 202010349401A CN 111471348 B CN111471348 B CN 111471348B
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- liquid metal
- wax
- solid ink
- paper
- dispersant
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/12—Printing inks based on waxes or bitumen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/40—Printing on bodies of particular shapes, e.g. golf balls, candles, wine corks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Abstract
The invention discloses wax-dispersed liquid metal solid ink and a preparation method and application thereof. The preparation method comprises the following steps: firstly, heating the solid wax dispersant to a molten state, adding the solid wax dispersant into the liquid wax dispersant, stirring to obtain a mixture, and quickly freezing at a low temperature. The method for printing the paper-based electronic circuit comprises the following steps: loading the liquid metal solid ink on a paper substrate, heating the paper substrate to remove the wax dispersant, and rolling the paper substrate without the wax dispersant to realize a passage. The preparation process utilizes the low melting point characteristic of the wax dispersant, the liquid phase is uniformly dispersed under the assistance of heat, the dispersion effect is maintained by simple quick freezing, and the difficulty that the liquid metal is not easy to store after being dispersed is solved. During printing, the relation between paper and wax and the respective characteristics are benefited, large-scale rapid printing of the liquid metal on the paper base can be realized, and a new possibility is provided for the application of the liquid metal in the field of paper base flexible electronic circuits.
Description
Technical Field
The invention belongs to the field of electronic devices, and particularly relates to wax-dispersed liquid metal solid ink as well as a preparation method and application thereof.
Background
The liquid metal is a metal which is liquid at normal temperature, and plays a great role in the design of the flexible electronic circuit due to the unique liquidity of the metal. In order to realize controllable printing of liquid metal, microchannel perfusion and injector 3D printing are the most common printing means at present. However, these methods are complex processes and are limited by the extremely strong surface tension of the liquid metal, and have a strong selectivity for the printing substrate, especially not easy to adhere to the paper substrate.
However, paper substrates are an indispensable place in the field of flexible electronics as a flexible material that is inexpensive and easy to print. In order to realize the printing possibility of the liquid metal on various materials, part of scholars perform blending modification of the liquid metal and realize the printing on rough paper. In fact, due to the fluidity and strong surface tension of the liquid metal, long residence times of the liquid metal on the paper cannot be achieved by blending. In addition, the direct drawing of complex patterns is realized by combining liquid phase dispersion of liquid metal and an ejector by a scholars. However, the dispersed liquid metal is difficult to uniformly store in a liquid phase for a long time, and is easy to precipitate, so that the printing efficiency and effect are greatly limited.
The wax printing technology is an important component in the current paper-based electronics, perfectly combines the capillary effect of the paper substrate and the low-melting-point characteristic of wax, is often applied to the design of microfluidic channels on paper or the packaging of electronic circuits, but cannot realize the printing of the electronic circuits independently, and the application scene is very limited.
In summary, the invention provides a wax-dispersed liquid metal solid ink, which aims to solve the problems of dispersion and printing of liquid metal, and provides a paper-based electronic circuit design method using the wax-dispersed liquid metal solid ink, so as to provide a new idea for printing liquid metal on paper.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a wax-dispersed liquid metal solid ink and a preparation method and application thereof.
The invention adopts the following specific technical scheme:
a wax-dispersed liquid metal solid ink is composed of a liquid metal and a wax dispersant, wherein the liquid metal is uniformly dispersed in the form of particles in the solid wax dispersant.
Preferably, the liquid metal is 25 to 75 mass% and the wax dispersant is 25 to 75 mass%.
Preferably, the liquid metal is in a non-volatile state at normal temperature, and the melting point is 10-25 ℃; the liquid metal is preferably a gallium indium alloy or an alloy of gallium indium with other metals.
Preferably, the wax dispersant comprises one or more of a vegetable wax, a mineral wax, a petroleum wax and a synthetic wax, preferably beeswax or soy wax.
Another object of the present invention is to provide a method for preparing a liquid metal solid ink according to any of the above aspects, which comprises the following steps:
s11: heating the solid wax dispersant to a molten state to form a liquid wax dispersant;
s12: adding liquid metal into the liquid wax dispersant obtained in the step S11, and uniformly mixing to obtain a uniformly dispersed mixture;
s13: and quickly freezing the mixture at low temperature in the step S12, so that the liquid metal in the mixture is uniformly dispersed in the form of particles in the gaps of the solid wax dispersing agent to form the wax-dispersed liquid metal solid ink.
Preferably, the blending manner in S12 is ultrasonic stirring, and the stirring time is 2 hours.
Another object of the present invention is to provide a method for printing paper-based electronic circuit by using liquid metal solid ink according to any of the above schemes, which comprises the following steps:
s21: loading the liquid metal solid ink on a paper substrate, wherein the paper substrate is made of a material with a rough surface and multiple holes;
s22: heating the paper substrate loaded with the liquid metal solid ink in the step S21 to completely remove the wax dispersant;
s23: rolling the paper substrate from which the wax dispersant is removed in step S22, so that the liquid metal particles in the liquid metal solid ink are reconnected, thereby realizing the passage.
Preferably, the loading method in step S21 is: and forming a film or an electronic circuit pattern on the paper substrate by directly coating or adopting a mask mode by using the liquid metal solid ink.
Preferably, the heating temperature in the step S22 is higher than the melting point of the wax dispersant, and preferably 50 to 150 ℃.
Preferably, the rolling operation in step S23 is performed by a roller.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method is different from normal-temperature liquid-phase dispersion, fully utilizes the low-melting-point characteristic of the wax, uniformly disperses the liquid metal and the liquid wax dispersant at high temperature, and quickly freezes to ensure that liquid metal particles are uniformly dispersed in gaps of the solid wax and cannot be precipitated.
(2) When the liquid metal solid ink is used for printing electronic circuits, the relationship between paper and wax is fully utilized. During printing, the ink can be drawn on paper by utilizing the interaction between the liquid metal solid ink dispersed by the wax and the paper; and the wax can be removed by heating only by utilizing the low-melting-point characteristic of the wax and the capillary effect of the paper, and a liquid metal layer is left. The process not only solves the difficulty that the liquid metal on the paper is not easy to draw, but also has very simple manufacturing process.
(3) The liquid metal solid ink is used for printing electronic circuits. Paper can be used as a substrate, so that the paper has the advantages of low price and easy obtainment; the printing method is a direct coating or mask method, and has the advantage of simple operation; the combination of the two can realize the large-scale electronic circuit printing with lower cost.
(4) The liquid metal solid ink disclosed by the invention has the advantage of being more advantageous than the existing ink in the aspects of transportation, storage and the like due to the normal-temperature solid property of the wax.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a liquid metal solid ink according to the present invention;
FIG. 2 is a schematic representation of the application of the liquid metal solid ink of the present invention in paper-based electronic circuit printing;
FIG. 3 is a microscopic schematic diagram of the application of the liquid metal solid ink of the present invention in paper-based electronic circuit printing.
The reference numbers in the figures are:
the printing ink comprises a first heating device 101, a liquid wax dispersing agent 102, a liquid metal 103, a mixture 104, a mould 105, a wax dispersed liquid metal solid ink 201, an electronic circuit pattern 202, a mask 203, a blank paper substrate 301, a paper substrate 204, a second heating device 205, a roller 206, an ink layer 302, a wax dispersing agent 303, liquid metal particles 304 and a liquid metal thin layer 305.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
The invention relates to wax-dispersed liquid metal solid ink which consists of liquid metal and a wax dispersant, wherein the liquid metal is uniformly dispersed in the solid wax dispersant in a particle form. The mass percent of the liquid metal is 25-75%, the mass percent of the wax dispersant is 25-75%, and in the actual application process, a proper amount of other metals can be added into the liquid metal main body according to the requirement to adjust parameters such as melting point and the like.
In the two components, the liquid metal is in a non-volatile state at normal temperature and has a melting point of 10-25 ℃. The liquid metal may be a gallium-indium alloy, and a metal such as tin may be added to the gallium-indium alloy as necessary to adjust the melting point. In the liquid metal solid ink, the liquid metal is uniformly dispersed in the form of particles in the solid wax dispersant, so that the liquid metal is in a continuous and uniform state during subsequent melting. The wax dispersant may be one or more of vegetable wax, mineral wax, petroleum wax and synthetic wax, which should be solid at normal temperature and melt after heating, preferably beeswax or soybean wax.
Therefore, the liquid metal solid ink utilizes the characteristic that the wax is solid at normal temperature but has low melting point, and the liquid metal is dispersed in the solid wax dispersant, so that the spatial position of the liquid metal is limited, and the liquid metal can be uniformly dispersed. When the wax is used, the wax dispersant containing liquid metal is directly coated on the surface of the substrate, and then the wax is heated to be infiltrated into the substrate.
The preparation of the liquid metal solid ink can uniformly disperse the liquid metal and the liquid wax dispersant at high temperature, and then quickly freeze to solidify the wax dispersant, so that liquid metal particles are uniformly dispersed in gaps of solid wax. As shown in fig. 1, the method for preparing the liquid metal solid ink specifically comprises the following steps:
1) heating the solid wax dispersant to a molten state by using a first heating device 101 to form a liquid wax dispersant 102;
2) adding the liquid metal 103 with the corresponding mass into the liquid wax dispersant 102 according to the proportion of the liquid metal 103 (25-75%) to the liquid wax dispersant 102 (25-75%) to be uniformly mixed to obtain a mixture 104, wherein the liquid metal 103 in the mixture 104 is uniformly dispersed in the liquid wax dispersant 102 in a particle form; the mode of mixing can select ultrasonic stirring 2 hours, or ultrasonic vibration certain time.
3) The mixture 104 is placed into a mold 105 with a proper shape according to the requirement for low-temperature quick freezing, and the quick cooling is required to be ensured in the quick freezing operation, so that the liquid metal in the mixture is uniformly dispersed in the gaps of the solid wax dispersant in a particle form to form the wax-dispersed liquid metal solid ink 201, and if the speed is too low, the liquid metal particles can be settled in the wax dispersant due to the action of gravity, so that the distribution is not uniform, and the subsequent application is influenced.
As shown in fig. 2, the method for printing paper-based electronic circuits using the liquid metal ink of the present invention comprises the steps of:
1) drawing a corresponding pattern on a blank paper substrate 301 by using the liquid metal solid ink 201 provided by the invention through a mask 203 (which can also be directly coated and drawn) designed with an electronic circuit pattern 202; the paper substrate is made of rough and porous material, and can be filter paper, common A4 paper and the like;
2) the above-mentioned paper substrate 204 carrying the electronic circuit pattern 202 is placed on a second heating device 205 and heated at a temperature higher than the melting point of the wax dispersant to completely remove the wax dispersant.
The heating temperature is generally set to be 50-150 ℃, because the melting point of the wax dispersant is generally about 50 ℃, and when the heating temperature is 50-150 ℃, the wax dispersant can be ensured to be in a molten state, and the paper substrate can not be carbonized and damaged.
The liquid metal is heated in the air, so that the surface of the liquid metal can form a metal oxidation state. Taking gallium-indium alloy as an example, gallium-indium alloy is exposed to air and heated to oxidize the gallium-indium alloy, gallium oxide is generated on the surface of metal, particle shape is formed due to the tension between atoms, and the gallium oxide is very stable at normal temperature, and at the moment, liquid metal particles cannot be in conductive communication.
3) The paper substrate 204 is rolled completely de-waxed using a roller 206 to re-bond the liquid metal particles to complete the passage. The roller 206 may be coated with a special material or surface to ensure that the roller 206 has a low coefficient of friction surface, is smooth, and is not prone to stick materials. Thus, when the paper substrate 205 with complete wax removal is rolled by the roller 206, the liquid metal particles do not stick to the surface of the roller 206.
As shown in fig. 3, it can be seen from the microscopic schematic diagram of the application of the liquid metal solid ink of the present invention in paper-based electronic circuit printing that there are a large number of voids on the surface of the blank paper substrate 301, which has a capillary effect. The liquid metal solid ink 201 with dispersed wax forms a thin ink layer 302 on the surface of the blank paper substrate 301 by using a mask or direct coating. . The ink layer 302 contains a wax dispersant 303 and uniformly dispersed liquid metal particles 304. After heating, the solid wax dispersant 303 becomes liquid and penetrates into the interior of the blank paper base 301 first due to the capillary action of the surface of the blank paper base 301, forming a thin layer of wax dispersant. At this time, the liquid metal particles 304 are left on the surface of the blank paper substrate 301, and the electric conduction cannot be achieved due to the oxide layer therebetween. The thin layer of liquid metal particles 304 is rolled by roller 206 to rejoin the particles to form a thin layer 305 of liquid metal for conducting electricity.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (7)
1. A method of printing a paper-based electronic circuit using a wax dispersed liquid metal solid ink, comprising the steps of:
s21: loading liquid metal solid ink on a paper substrate, wherein the paper substrate is made of a material with a rough surface and multiple holes;
s22: heating the paper substrate loaded with the liquid metal solid ink in the step S21 to completely remove the wax dispersant;
s23: rolling the paper substrate with the wax dispersant removed in the step S22 to reconnect the liquid metal particles in the liquid metal solid ink, thereby realizing a passage;
the liquid metal solid ink consists of liquid metal and a wax dispersant, and the liquid metal is uniformly dispersed in the solid wax dispersant in a particle form;
the liquid metal is in a non-volatile state at normal temperature, and the melting point is 10-25 ℃; the liquid metal is gallium-indium alloy or alloy of gallium-indium and other metals; the wax dispersant comprises one or more of a vegetable wax, a mineral wax, a petroleum wax, and a synthetic wax;
the preparation method of the liquid metal solid ink comprises the following steps:
s11: heating the solid wax dispersant to a molten state to form a liquid wax dispersant;
s12: adding liquid metal into the liquid wax dispersant obtained in the step S11, and uniformly mixing to obtain a uniformly dispersed mixture;
s13: and quickly freezing the mixture at low temperature in the step S12, so that the liquid metal in the mixture is uniformly dispersed in the form of particles in the gaps of the solid wax dispersing agent to form the wax-dispersed liquid metal solid ink.
2. The method of printing paper-based electronic circuits with wax-dispersed liquid metal solid ink as claimed in claim 1 wherein the liquid metal is 25% to 75% by mass and the wax dispersant is 25% to 75% by mass.
3. The method of printing a paper-based electronic circuit with a wax-dispersed liquid metal solid ink as in claim 1, wherein the wax dispersant is beeswax or soy wax.
4. The method for printing paper-based electronic circuit with wax-dispersed liquid metal solid ink according to claim 1, wherein the blending manner in S12 is ultrasonic stirring for 2 hours.
5. The method for printing paper-based electronic circuit using wax dispersed liquid metal solid ink as claimed in claim 1, wherein the loading method in step S21 is: and forming a film or an electronic circuit pattern on the paper substrate by directly coating or adopting a mask mode by using the liquid metal solid ink.
6. The method for printing paper-based electronic circuit by using wax dispersed liquid metal solid ink as claimed in claim 1, wherein the heating temperature in the step S22 is 50-150 ℃ higher than the melting point of the wax dispersant.
7. The method for printing paper-based electronic circuits using wax dispersed liquid metal solid inks as claimed in claim 1 wherein the rolling operation in step S23 is performed by a roller.
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