CN111069606B - Continuous forming method of low-melting-point metal - Google Patents
Continuous forming method of low-melting-point metal Download PDFInfo
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Abstract
The invention discloses a continuous forming method of low-melting-point metal, which comprises the steps of uniformly injecting liquid low-melting-point metal into neutral conductive matrix liquid in a power-on state, controlling an injection head to move at a constant speed in the injection process, and controlling the moving speed to be 5-100 mm/s, so that the liquid low-melting-point metal forms continuous metal in the conductive matrix liquid. The method is simple and easy to operate, and can effectively solve the problem that low-melting-point metal is difficult to continuously form due to strong surface tension.
Description
Technical Field
The invention belongs to the technical field of metal forming, and particularly relates to a continuous forming method of low-melting-point metal.
Background
The low-melting-point metal/alloy is a metal or alloy thereof having a melting point of 300 ℃ or less, typically 60 to 200 ℃. The low melting point metals include bismuth, tin, lead, indium, gallium, rubidium, cesium, and the like. Such metals are also referred to as liquid metals because they have a low melting point and are readily converted to a fluid form upon heating.
The metal has the characteristics of low melting point, strong conductivity, strong fluidity and the like, can be used for preparing and repairing various deformed devices, and has been widely applied to the fields of medical treatment, electronics and the like.
However, through research and experiments, the liquid metal is usually in a spherical liquid drop state due to the strong surface tension, and the application of continuous forming is limited to a great extent.
In chinese patent application publication No. CN 108837719a, yunnan kowei liquid metal valley research and development limited discloses a liquid metal droplet forming apparatus, which includes a liquid metal droplet generator and a first micro-injection pump, the liquid metal droplet generator includes a generation block, a first pipe and a second pipe; a through hole is formed in the generating block, the first end of the first pipeline and the first end of the second pipeline respectively extend into the through hole from two ends of the through hole, and the first end of the first pipeline and the first end of the second pipeline are coaxial and are arranged oppositely; the output end of the first micro-injection pump is connected with the second end of the first pipeline so as to input liquid metal into the first pipeline and push the liquid metal into the second pipeline from the first end of the second pipeline. The device can accurately control the size and the distribution of the liquid metal droplets, so that the sizes of the liquid metal droplets formed by the device are uniform, but the continuous forming of the liquid metal cannot be realized.
Chinese patent application with publication number CN 106654503a discloses a gas accuse deformation antenna based on liquid metal, including flexible runner, liquid metal, gasbag and air pump, liquid metal with the gasbag all sets up inside the flexible runner, the air pump sets up outside the flexible runner, be used for the gasbag is aerifyd or is breathed in. The air pump is used for inflating the air bag to expand the volume of the air bag, or the air bag inhales the air to contract the volume of the air bag, so that the liquid metal in the flexible flow channel is controlled to move in the internal flow channel, and a specific shape is formed. On one hand, the air control process is relatively complex and difficult to control, and on the other hand, liquid metal is easy to form liquid drops, and an oxide film is easy to form among the liquid drops, so that the conductivity of the antenna is affected.
Another chinese utility model patent with publication number CN 209183284U discloses a liquid metal conductor, which includes a hollow elastic insulation shell, a plurality of conductive metal balls that set up at intervals in the elastic insulation shell, cooperate between per two adjacent conductive metal balls in a plurality of conductive metal balls the elastic insulation shell forms a sealed space, it has metal conductive liquid to fill in the sealed space, sets up two electrodes at the opposite both ends of elastic insulation shell. The utility model discloses a just because receive liquid metal surface tension strong and be difficult to continuous forming's restriction, only can adopt liquid metal to form the metal ball and adopt the mode of conducting liquid with the electric current conduction between the metal ball to realize the function of wire. The structure of the conducting wire is complex, and the problem of conducting liquid leakage after the elastic insulating shell is damaged exists, so that the conducting wire is greatly limited in the actual use process.
In the prior art, a casting method is generally adopted for forming low-melting point metal, namely, metal which is heated and melted into fluid is poured into a mold with a specific shape, and the metal is taken out of the mold after being cooled and transformed into solid, so as to obtain a metal device which is expected to be processed. However, the manufacturing process is increased by the die casting, and the problem of surface tension of the liquid metal cannot be solved. Thus, continuous forming of liquid metal is achieved without the use of a mold, becoming a problem to be solved.
Disclosure of Invention
The invention aims to provide a continuous forming method of low-melting-point metal, which is simple and easy to operate and can effectively solve the problem that the low-melting-point metal is difficult to continuously form due to strong surface tension.
The purpose of the invention is realized by the following technical scheme:
a continuous forming method of low-melting-point metal is characterized in that liquid low-melting-point metal is uniformly injected into neutral conductive matrix liquid in a power-on state, an injection head is controlled to move at a constant speed in the injection process, and the moving speed is controlled to be 5-100 mm/s, so that the liquid low-melting-point metal forms continuous metal in the conductive matrix liquid.
The neutrality is the neutrality of acid and alkali.
The continuous forming method of the low melting point metal may include the specific steps of:
(1) preparing neutral conductive matrix liquid;
(2) heating and melting the low-melting-point metal to form a liquid state;
(3) electrifying the conductive matrix solution prepared in the step (1), and controlling the voltage to be 20.0-50.0V;
(4) and (3) uniformly injecting the liquid low-melting-point metal obtained in the step (2) into the conductive matrix liquid by using an injection device, and controlling an injection head of the injection device to move at a constant speed in the injection process, wherein the moving speed is controlled to be 25-100 mm/s, so that the liquid low-melting-point metal forms continuous metal in the conductive matrix liquid.
The method of the present invention is suitable for bismuth and bismuth-based alloys, gallium and gallium-based alloys, indium and indium-based alloys, tin and tin-based alloys, etc. with a melting point below 200 ℃. The above low melting point metals are shaped by the above method with little difference in effect.
Hair brushThe conductive matrix solution is a working solution which has a conductive matrix in liquid and can realize conductivity, and can be NaCl solution or NH4Cl solution or CaCl2The difference of solute has little influence on the forming effect of the solution or the solution containing electrolyte matrix such as conductive gel.
Different from the existing low-melting-point metal forming process, the low-melting-point metal is easy to form liquid drops, and the low-melting-point metal obtained by the method is continuously formed without the defects of interruption, air holes and the like. It is inferred from the experimental results that this is probably due to the fact that after the power is applied, an electric field is formed in the conductive matrix liquid, and the electric field influences the low-melting-point metal in the liquid state, so that the surface tension of the low-melting-point metal is reduced, and the generation of an oxide layer on the surface of the low-melting-point metal is inhibited.
As a result, when the liquid low-melting-point metal is injected into the conductive matrix liquid, spherical droplets are not easily formed under the action of the electric field, but a continuous fluid state is formed, so that the low-melting-point metal forms continuous metal in the conductive matrix liquid. Moreover, because the electric field inhibits the formation of an oxide layer, the homogeneity of the formed metal is ensured, and the continuity of the metal is further ensured.
In the forming process, the moving speed of the injection head is a key, and the metal is broken due to the excessively high speed, so that the continuous forming cannot be performed; the speed is too slow, the metal is not uniformly formed, the thickness is difficult to control, and the metal is easy to aggregate into balls after being stacked.
On the other hand, the extrusion speed of the liquid low melting point also has a certain influence on the molding. The extrusion rate refers to the amount of liquid low-melting metal injected from the injection head per unit time. Preferably, the extrusion speed is 50-800 mu L/min.
The suitable concentration range of the conductive matrix liquid is 1 mmol/L-10 mol/L, preferably 10 mmol/L-1 mol/L. After experiments, the concentration of the conductive matrix liquid influences the line-forming voltage. The higher the concentration, the lower the line voltage. The line-forming voltage refers to the lowest voltage required for continuously forming the liquid low-melting-point metal injected into the conductive matrix liquid, and the voltage lower than the lowest voltage cannot be continuously formed.
Compared with the prior art, the invention has the following beneficial effects:
1. the device used by the continuous forming method of the low-melting-point metal is simple, and a die required in the traditional forming method is not needed;
2. the method has the advantages of few steps, low operation difficulty, convenient extraction and easy recovery, can directly extract the formed metal by transferring electrolyte or heating and the like, and greatly simplifies the forming process of the low-melting-point metal;
3. the method has strong reliability, enables the low-melting-point metal to be continuously and uniformly molded, and solves the problem that the application of the low-melting-point metal is limited because liquid low-melting-point metal is easy to form liquid drops due to excessively strong surface tension in the prior art;
4. the low-melting-point metal device prepared by the method has wide application range, can be applied to firstly preparing a conductive antenna, and utilizes continuously formed liquid metal to wrap an insulating layer outside so as to prepare a conductive circuit; preparing a linear electrode for electrochemical detection; preparing flexible electronic material for circuit preparation; preparing an intelligent robot material; the method is used for the 3D printing additive manufacturing technology, and expands the space for the research and development of new technologies.
Drawings
The invention is further illustrated by the following figures.
FIG. 1 is a schematic view of an apparatus for continuously forming a low melting point metal.
FIG. 2 is a drawing of a low melting point metal forming metal line.
FIG. 3 is a graph of concentration of conductive matrix fluid versus line voltage.
FIG. 4 is a graph showing the effect of injection head movement speed on voltage on molding.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The device used in the embodiment is shown in figure 1 and comprises a reaction tank for containing conductive matrix liquid and a power supply, wherein the negative pole of the power supply is connected with a conductive cathode, the electrolytic cathode is soaked in the conductive matrix liquid, the positive pole of the power supply is connected with a metal injection head of an injection device, and the metal injection head is soaked in the conductive matrix liquid to simultaneously serve as the anode.
When the low-melting-point metal is required to be continuously formed, the power supply is turned on to be electrified so as to form an electric field in the conductive matrix liquid, the molten low-melting-point metal is injected into the conductive matrix liquid through the metal injection head, and the metal injection head moves at a constant speed to complete the forming of the low-melting-point metal.
Example 1
The forming method of the low-melting-point metal comprises the following steps:
(1) preparing 1mmol/L NH4Cl solution is used as conductive matrix liquid;
(2) heating to melt the indium-based alloy into a liquid state;
(3) turning on a power supply to enable the NH prepared in the step (1)4Electrifying the Cl solution, and controlling the voltage to be 50V;
(4) starting an injection device, and uniformly injecting the molten indium-based alloy obtained in the step (2) into NH at an extrusion speed of 50 mu L/min4In the Cl solution, the injection head of the injection device is controlled to move at a constant speed in the injection process, and the moving speed is controlled to be 25mm/s, so that NH is added4Continuous indium-based alloy metal lines are formed in the Cl solution.
Example 2
The forming method of the low-melting-point metal comprises the following steps:
(1) preparing 5mol/L NaCl solution as conductive matrix solution;
(2) heating to melt the gallium-based alloy into a liquid state;
(3) turning on a power supply to electrify the NaCl solution prepared in the step (1), and controlling the voltage to be 1.5V;
(4) and (3) starting an injection device, uniformly injecting the molten gallium-based alloy obtained in the step (2) into a NaCl solution at an extrusion speed of 600 mu L/min, and controlling an injection head of the injection device to move at a constant speed in the injection process, wherein the moving speed is controlled to be 50mm/s, so that continuous gallium-based alloy metal wires are formed in the NaCl solution.
After the completion of the molding, the gallium-based alloy metal wire taken out from the NaCl solution was continuous and uniform, and had no black oxide layer on the surface, as shown in fig. 2.
Example 3
The forming method of the low-melting-point metal comprises the following steps:
(1) preparing 10mol/L conductive gel liquid as conductive matrix liquid;
(2) heating to melt the tin-based alloy into a liquid state;
(3) turning on a power supply to electrify the conductive gel liquid prepared in the step (1), and controlling the voltage to be 20V;
(4) and (3) starting an injection device, uniformly injecting the molten tin-based alloy obtained in the step (2) into the conductive gel liquid at the extrusion speed of 800 mu L/min, controlling an injection head of the injection device to move at a constant speed in the injection process, and controlling the moving speed to be 100mm/s, so as to form a continuous tin-based alloy metal wire in the conductive gel liquid.
Example 4
Relationship between concentration of conductive matrix liquid and linear voltage
In different concentrations of CaCl2Using the solution as a conductive matrix solution, forming the gallium-based alloy at the same concentration by using different voltages, and recording the concentration at which CaCl can be injected2The lowest voltage required for continuously forming the gallium-based alloy in the solution into the metal wire is the wire-forming voltage.
The results of the experiment are shown in FIG. 3, from which it can be seen that CaCl is accompanied by2The increase of the solution concentration leads to the decrease of the line-forming voltage, and the decrease amplitude is more obvious under the condition of low concentration.
Example 5
Influence of injection head moving speed and voltage on forming
At 5mol/L of CaCl2The solution is used as conductive matrix liquid, the extrusion speed of an injection device is controlled to be constant at 200 mu L/min, the moving speed of an injection head and the power voltage are changed, and the gallium-based alloy is formedAnd (4) performing type operation, and recording the properties of the formed gallium-based alloy.
As shown in fig. 4, the gallium-based alloy in the black region on the left side of the figure cannot form a continuous metal line, i.e., the gallium-based alloy in the region cannot be molded; in the middle gray area part, the gallium-based alloy forms a continuous metal wire, and the surface of the metal wire is not provided with a black oxide layer; in the right pattern area part, the gallium-based alloy forms a continuous metal wire, but the surface of the metal wire is a black oxide layer.
It should be noted that the above-mentioned embodiments are only illustrative and not restrictive, and any modifications or changes within the meaning and range of equivalents to the technical solutions of the present invention by those skilled in the art should be considered to be included in the protection scope of the present invention.
Claims (2)
1. A continuous forming method of low-melting-point metal is characterized in that liquid low-melting-point metal is uniformly injected into neutral conductive matrix liquid in a power-on state, an injection head is controlled to move at a constant speed in the injection process, and the moving speed is controlled to be 25-100 mm/s, so that the liquid low-melting-point metal forms continuous metal in the conductive matrix liquid; the method comprises the following specific steps:
(1) preparing neutral conductive matrix liquid;
(2) heating and melting the low-melting-point metal to form a liquid state;
(3) electrifying the conductive matrix solution prepared in the step (1), and controlling the voltage to be 20.0-50.0V;
(4) uniformly injecting the liquid low-melting-point metal obtained in the step (2) into the conductive matrix liquid by using an injection device, and controlling an injection head of the injection device to move at a constant speed in the injection process;
the low-melting point metal comprises bismuth and bismuth-based alloy, gallium and gallium-based alloy, indium and indium-based alloy and tin-based alloy with the melting point below 200 ℃;
the conductive matrix solution is NaCl solution and NH4Cl solution, CaCl2A solution, or a solution containing a conductive gel;
in the process of uniformly spraying the liquid low-melting-point metal, the extrusion speed is 50-800 mu L/min;
the concentration of the conductive matrix liquid is 1 mmol/L-10 mol/L.
2. The continuous forming method of a low melting point metal according to claim 1, wherein the concentration of the conductive matrix liquid is 10mmol/L to 1 mol/L.
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| CN114147224A (en) * | 2020-09-08 | 2022-03-08 | 中国科学院理化技术研究所 | Forming method and application of metal powder |
| CN112647156B (en) * | 2020-12-21 | 2023-02-03 | 苏州菲拓生物科技有限公司 | Method for electrochemically assisting preparation of liquid metal hydrogel fiber |
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| US9415590B2 (en) * | 2013-04-26 | 2016-08-16 | The Regents Of The University Of Michigan | Electrohydrodynamic jet printing device with extractor |
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| CN103127608A (en) * | 2013-01-22 | 2013-06-05 | 清华大学 | Manufacturing method of inner body injecting and molding type electronic device |
| CN105798306A (en) * | 2014-12-31 | 2016-07-27 | 中国科学院理化技术研究所 | 3D metal printing system and method thereof |
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