Low-melting-point gallium-based liquid alloy and preparation method and application thereof

Abstract

The invention belongs to the technical field of low-melting-point alloys, and provides a low-melting-point gallium-based liquid alloy and a preparation method and application thereof. The preparation raw materials of the gallium-based liquid alloy comprise gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metal with specific mass content. The rare earth metal comprises one or two of lanthanum, cerium and neodymium. A trace amount of one or two of lanthanum, cerium and neodymium is added into the gallium-based alloy, so that the purity of the alloy can be improved, the viscosity can be reduced, and the surface tension can be adjusted; by adjusting the formula of the alloy, the smelting time is shortened in the alloy smelting process stage, the efficiency is improved, the alloy cost is reduced, the alloy is more uniform macroscopically, the low-temperature stability of the alloy is further improved, and the alloy can be kept in a stable liquid state at the low temperature even 10 DEG C below zero and better meet the special climate requirements.

Description

Technical Field

[0001] The present invention relates to the technical field of low melting point alloys, and in particular to a low melting point gallium-based liquid alloy and a preparation method and application thereof. Background Art

[0002] Gallium-based liquid alloys have a wide range of applications, ranging from fast heat dissipation in modern high-end GPUs and data centers to traditional mechanical parts and cutting-edge technology. Gallium-based liquid alloys are not only used in the fields of electricity, thermodynamics, lubrication, medicine, optics, etc., but also show great potential in cutting-edge fields such as flexible electronics, magnetohydrodynamic power generation, and drug carriers. In the field of flexible electronics, gallium-based liquid alloys are widely used in the preparation of flexible electronic devices due to their excellent conductivity and fluidity. It can be used to print flexible electronic devices and even shows application prospects in the repair of damaged nerves. In addition, gallium-based liquid alloys can also be used as drug carriers in drug delivery systems to improve the targeting and effectiveness of drugs. In the field of batteries, the application of gallium-based liquid alloys as electrode materials in primary batteries, secondary batteries, and photovoltaic solar cells is also increasingly valued. Its unique electrochemical properties enable batteries to have higher energy density and better performance.

[0003] The thermal conductivity of liquid metal is much higher than that of water. Liquid metal can withstand high temperatures of 2000°C, has stable performance, long life, and can quickly dissipate heat through flowing liquid. Gallium-based liquid metal has become an ideal heat dissipation medium for the new generation of radiators, and has been used in the extreme heat dissipation fields of high-power, high-heat flux density integrated electronic chips and optoelectronic devices, as well as key national defense equipment.

[0004] Glass thermometer is an important basic medical device used to measure body temperature and evaluate physical health. Therefore, it is widely used and has a large market demand. However, traditional thermometers use mercury as the temperature-sensing liquid to make mercury thermometers. Since mercury is highly toxic, exposure to the environment is extremely harmful to human health. Liquid metal is the only choice to replace mercury as a glass thermometer.

[0005] Therefore, it is of great significance to study and obtain a low-melting-point gallium-based liquid alloy with good stability and reduced cost. Summary of the invention

[0006] The purpose of the present invention is to provide a gallium-based liquid alloy with a low melting point and a preparation method and application thereof in view of the deficiencies in the prior art.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a gallium-based liquid alloy with a low melting point, wherein the raw materials for preparing the gallium-based liquid alloy include gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals;

[0009] The mass content of gallium is 58-75%, the mass content of indium is 10-20%, the mass content of tin is 9-15%, the mass content of zinc is 0-5%, the mass content of bismuth is 0-2%, the mass content of antimony is 0-2%, the mass content of lead is 0-1%, and the mass content of rare earth metals is 0.2-1.5%.

[0010] Preferably, the rare earth metal includes one or two of lanthanum, cerium and neodymium.

[0011] Preferably, the purity of gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals is independently ≥ 99.99%.

[0012] The present invention also provides a method for preparing the low-melting-point gallium-based liquid alloy, comprising the following steps:

[0013] 1) In a protective atmosphere, gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals are mixed to obtain an alloy raw material;

[0014] 2) In a vacuum environment, the alloy raw materials are successively subjected to high-temperature alloying and natural cooling to obtain a gallium-based liquid alloy with a low melting point.

[0015] Preferably, the protective atmosphere in step 1) is a nitrogen atmosphere or an argon atmosphere.

[0016] Preferably, the heating rate of the high temperature alloying in step 2) is 1.5-2.5°C / min; the vacuum degree of the vacuum environment is ≥3×10 -3 Pa.

[0017] Preferably, the high temperature alloying temperature is 200-650° C., and the high temperature alloying time is ≥3 h.

[0018] Preferably, during the high-temperature alloying process in step 2), high-temperature vacuum thermal reduction and deoxidation treatment are performed to discharge oxygen in the alloy raw materials.

[0019] The present invention also provides application of the low-melting-point gallium-based liquid alloy in temperature-sensitive liquid.

[0020] The beneficial effects of the present invention include the following:

[0021] 1) The present invention prepares a new type of non-toxic, non-corrosive, low-melting-point gallium-based liquid alloy with high stability by improving the alloy formula and alloy smelting process.

[0022] 2) Since rare earth metals have the ability to deoxidize and improve the physical and chemical properties of metals, the present invention adds a trace amount of light rare earths such as one or two of lanthanum, cerium and neodymium to the gallium-based alloy, which can improve the purity of the alloy, reduce viscosity and adjust surface tension; by adjusting the alloy formula, not only the smelting time is shortened and the efficiency is improved during the alloy smelting process, but also the alloy cost is reduced, making the alloy more uniform in the macroscopic sense, further improving its low-temperature stability, and being able to maintain a stable liquid state at a lower temperature even at -10°C, better meeting special climate requirements.

[0023] 3) The present invention purifies the gallium-based alloy during alloy smelting, including high-temperature vacuum thermal reduction and heating degassing treatment, etc., to avoid the gallium-based alloy from being contaminated by acid liquid, and will not destroy the alloy components, so as to obtain a purer and more stable gallium-based alloy, so that the filling thermometer has a better effect, and the product quality and yield rate are improved. Finally, the natural cooling and slow cooling in a vacuum system are adopted to make the structural performance of the low-melting-point gallium-based liquid alloy more stable, and the macroscopic uniformity is good, which is suitable for application in different scenarios, including heat dissipation, mercury-free thermometers, etc. DETAILED DESCRIPTION

[0024] The present invention provides a gallium-based liquid alloy with a low melting point, wherein the raw materials for preparing the gallium-based liquid alloy include gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals;

[0025] The mass content of gallium is 58-75%, the mass content of indium is 10-20%, the mass content of tin is 9-15%, the mass content of zinc is 0-5%, the mass content of bismuth is 0-2%, the mass content of antimony is 0-2%, the mass content of lead is 0-1%, and the mass content of rare earth metals is 0.2-0.5%.

[0026] The gallium-based liquid alloy of the present invention uses a gallium-based alloy as a raw material, and the gallium-based alloy preferably contains gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals.

[0027] In the raw material for preparing the gallium-based liquid alloy of the present invention, the mass content of gallium is preferably 59.5-70.6%, more preferably 61-65%, and more preferably 63-64%. The mass content of indium is preferably 12-19.3%, more preferably 14-18%, and more preferably 15-16%. The mass content of tin is preferably 10-14.5%, more preferably 12.5-14%, and more preferably 13%. The mass content of zinc is preferably 1-4%, and more preferably 2-3%. The mass content of bismuth is preferably 0.2-1.8%, and more preferably 0.5-1.5%, and more preferably 1%. The mass content of antimony is preferably 0.5-1.5%, and more preferably 1%. The mass content of lead is preferably 0.2-0.8%, and more preferably 0.4-0.5%. The mass content of rare earth metals is preferably 0.3-1.2%, and more preferably 0.4-1%, and more preferably 0.5-0.7%.

[0028] In the present invention, the rare earth metal preferably includes one or two of lanthanum, cerium and neodymium.

[0029] In the present invention, the purity of the gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals is independently preferably ≥99.99%, more preferably ≥99.992%, and even more preferably ≥99.995%.

[0030] The present invention also provides a method for preparing the low-melting-point gallium-based liquid alloy, comprising the following steps:

[0031] 1) In a protective atmosphere, gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals are mixed to obtain an alloy raw material;

[0032] 2) In a vacuum environment, the alloy raw materials are successively subjected to high-temperature alloying and natural cooling to obtain a gallium-based liquid alloy with a low melting point.

[0033] In the present invention, the protective atmosphere in step 1) is preferably a nitrogen atmosphere or an argon atmosphere.

[0034] In the present invention, the heating rate of the high temperature alloying in step 2) is preferably 1.5 to 2.5°C / min, more preferably 1.8 to 2.2°C / min, and more preferably 2°C / min; the vacuum degree of the vacuum environment is preferably ≥3×10 -3 Pa, more preferably ≥4×10 -3 Pa, preferably ≥5×10 -3 Pa.

[0035] In the present invention, the high temperature alloying temperature is preferably 200 to 650° C., more preferably 300 to 550° C., and more preferably 400 to 450° C., and the high temperature alloying time is preferably ≥3 h, and more preferably ≥4 h.

[0036] In the present invention, stirring and heating are performed during the high temperature alloying process, and the stirring rate is preferably 30 to 80 r / min, more preferably 40 to 70 r / min, and even more preferably 50 to 60 r / min.

[0037] In the present invention, the gallium-based alloy is purified during the high-temperature alloying process in step 2), and the purification includes high-temperature vacuum thermal reduction and deoxidation treatment to discharge oxygen in the alloy raw materials.

[0038] In the present invention, the alloy raw material is kept at a high temperature alloying temperature, and the trace gas (oxygen) in the alloy raw material is fully discharged during the holding time, so that the composition of the alloy raw material is uniform.

[0039] The invention obtains a low-melting-point gallium-based liquid alloy with stable physical and chemical properties through high-temperature alloying and natural cooling steps.

[0040] The present invention also provides application of the low-melting-point gallium-based liquid alloy in temperature-sensitive liquid.

[0041] The temperature-sensitive liquid prepared from the low-melting-point gallium-based liquid alloy of the present invention has stable physical and chemical properties and can still maintain relatively stable liquid fluidity at -10°C.

[0042] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0043] Example 1

[0044] The gallium-based liquid alloy uses a gallium-based alloy as a raw material. The gallium-based alloy includes gallium, indium, tin, bismuth, lead and rare earth metals. In the gallium-based alloy, the mass content of gallium is 70.6%, the mass content of indium is 14%, the mass content of tin is 12.5%, the mass content of bismuth is 1.5%, the mass content of lead is 1.0%, and the rare earth metal is cerium, and the mass content of cerium is 0.4%; the purity of gallium, indium, tin, bismuth, lead and cerium is 99.99%.

[0045] Alloy batching and mixing: clean and dry gallium, indium, tin, bismuth, lead and rare earth metal cerium are weighed according to the above proportions under the protection of nitrogen and placed in a clean quartz crucible for batching to obtain initial alloy raw materials; the initial alloy raw materials are mixed under the protection of nitrogen to obtain uniform alloy raw materials.

[0046] High temperature alloying: When the system vacuum degree is 3×10 -3Pa environment, the alloy raw materials are subjected to high-temperature alloying; during the high-temperature alloying process, they are stirred and heated at a rate of 50 r / min, the temperature is raised to 400°C at a heating rate of 2°C / min, and they are kept at 400°C for 4 hours to fully discharge trace gases (mainly oxygen) in the alloy raw materials, so that the composition of the alloy raw materials is uniform.

[0047] Purification: During the high-temperature alloying process, the alloy raw materials are purified by high-temperature vacuum thermal reduction and heating deoxidation treatment. Finally, the high-temperature alloyed raw materials are naturally cooled. The natural cooling is carried out under vacuum environment (vacuum degree 3×10 -3 After natural cooling, a low melting point gallium-based liquid alloy is obtained.

[0048] The gallium-based liquid alloy of this embodiment is a low-melting-point gallium-based liquid alloy with stable physical and chemical properties; when used as a temperature-sensing liquid, it can still maintain relatively stable liquid fluidity at -10°C, meeting the normal use and storage of the liquid alloy in a low-temperature environment.

[0049] Example 2

[0050] The gallium-based liquid alloy uses a gallium-based alloy as a raw material. The gallium-based alloy includes gallium, indium, tin, zinc, bismuth, antimony and rare earth metals. In the gallium-based alloy, the mass content of gallium is 61.0%, the mass content of indium is 19.1%, the mass content of tin is 15%, the mass content of zinc is 3%, the mass content of bismuth is 0.2%, the mass content of antimony is 1.0%, and the rare earth metals are lanthanum and neodymium, the mass content of lanthanum is 0.4%, and the mass content of neodymium is 0.3%; the purity of gallium, indium, tin, zinc, bismuth, antimony, lanthanum and neodymium is 99.995%.

[0051] Alloy batching and mixing: clean and dry gallium, indium, tin, zinc, bismuth, antimony and rare earth metals lanthanum and neodymium are weighed according to the above proportions and placed in a clean quartz crucible for batching under the protection of argon to obtain initial alloy raw materials; the initial alloy raw materials are mixed under the protection of argon to obtain uniform alloy raw materials.

[0052] High temperature alloying: When the system vacuum degree is 3.5×10 -3 Pa environment, the alloy raw materials were subjected to high-temperature alloying; during the high-temperature alloying process, they were stirred and heated at a rate of 40 r / min, the temperature was raised to 550°C at a heating rate of 2°C / min, and they were kept at 550°C for 3 hours to fully discharge trace gases (mainly oxygen) in the alloy raw materials, so that the composition of the alloy raw materials was uniform.

[0053] Purification: During the high-temperature alloying process, the alloy raw materials are purified by high-temperature vacuum thermal reduction and heating deoxidation treatment. Finally, the high-temperature alloyed raw materials are naturally cooled. The natural cooling is carried out under vacuum (vacuum degree 3.5×10-3 After natural cooling, a low melting point gallium-based liquid alloy is obtained.

[0054] The gallium-based liquid alloy of this embodiment is a low-melting-point gallium-based liquid alloy with stable physical and chemical properties; when used as a temperature-sensing liquid, it can still maintain relatively stable liquid fluidity at -10°C, meeting the normal use and storage of mercury-free glass thermometers in low-temperature environments.

[0055] Example 3

[0056] The gallium-based liquid alloy uses a gallium-based alloy as a raw material. The gallium-based alloy includes gallium, indium, tin, zinc, bismuth, antimony and rare earth metals. In the gallium-based alloy, the mass content of gallium is 59.5%, the mass content of indium is 20%, the mass content of tin is 14.5%, the mass content of zinc is 2%, the mass content of bismuth is 1.8%, the mass content of antimony is 1.5%, and the rare earth metals are lanthanum and cerium, the mass content of lanthanum is 0.3%, and the mass content of cerium is 0.4%; the purity of gallium, indium, tin, zinc, bismuth, antimony, lanthanum and cerium is 99.992%.

[0057] Alloy batching and mixing: clean and dry gallium, indium, tin, zinc, bismuth, antimony and rare earth metals lanthanum and cerium are weighed according to the above proportions under the protection of nitrogen and placed in a clean quartz crucible for batching to obtain initial alloy raw materials; the initial alloy raw materials are mixed under the protection of nitrogen to obtain uniform alloy raw materials.

[0058] High temperature alloying: When the system vacuum degree is 4×10 -3 Pa environment, the alloy raw materials were subjected to high-temperature alloying; during the high-temperature alloying process, they were stirred and heated at a rate of 60 r / min, the temperature was raised to 450°C at a heating rate of 2°C / min, and they were kept at 450°C for 4 hours to fully discharge trace gases (mainly oxygen) in the alloy raw materials, so that the composition of the alloy raw materials was uniform.

[0059] Purification: During the high-temperature alloying process, the alloy raw materials are purified by high-temperature vacuum thermal reduction and heating deoxidation treatment. Finally, the high-temperature alloyed raw materials are naturally cooled. The natural cooling is carried out under vacuum environment (vacuum degree 4×10 -3 After natural cooling, a low melting point gallium-based liquid alloy is obtained.

[0060] The gallium-based liquid alloy of this embodiment is a low-melting-point gallium-based liquid alloy with stable physical and chemical properties; when used as a temperature-sensing liquid, it can still maintain relatively stable liquid fluidity at -8°C, meeting the normal use and storage of mercury-free glass thermometers in low-temperature environments.

[0061] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A low melting point gallium-based liquid alloy, characterized in that: The raw materials for preparing gallium-based liquid alloys include gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals; The mass content of gallium is 58-75%, the mass content of indium is 10-20%, the mass content of tin is 9-15%, the mass content of zinc is 0-5%, the mass content of bismuth is 0-2%, the mass content of antimony is 0-2%, the mass content of lead is 0-1%, and the mass content of rare earth metals is 0.2-1.5%.

2. The low melting point gallium-based liquid alloy according to claim 1, characterized in that: The rare earth metal includes one or both of lanthanum, cerium and neodymium.

3. The low melting point gallium-based liquid alloy according to claim 1 or 2, characterized in that: The purity of the gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals is independently ≥99.99%.

4. The method for preparing the low melting point gallium-based liquid alloy according to any one of claims 1 to 3, characterized in that: The following steps are included: 1) In a protective atmosphere, gallium, indium, tin, zinc, bismuth, antimony, lead and rare earth metals are mixed to obtain an alloy raw material; 2) In a vacuum environment, the alloy raw materials are successively subjected to high-temperature alloying and natural cooling to obtain a gallium-based liquid alloy with a low melting point.

5. The preparation method according to claim 4, characterized in that: Step 1) The protective atmosphere is a nitrogen atmosphere or an argon atmosphere.

6. The preparation method according to claim 4, characterized in that: Step 2) The heating rate of the high temperature alloying is 1.5-2.5°C / min; the vacuum degree of the vacuum environment is ≥3×10 -3 Pa.

7. The preparation method according to claim 6, characterized in that: The temperature of high temperature alloying is 200-650°C, and the time of high temperature alloying is ≥3h.

8. The preparation method according to claim 7, characterized in that: Step 2) During the high-temperature alloying process, high-temperature vacuum thermal reduction and deoxidation treatment are performed to discharge oxygen in the alloy raw materials.

9. Use of the low melting point gallium-based liquid alloy according to any one of claims 1 to 3 in temperature-sensitive liquid.