CN115401203B - Method for reducing particle size of tin microspheres prepared based on molten salt metal emulsion method - Google Patents
Method for reducing particle size of tin microspheres prepared based on molten salt metal emulsion method Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 107
- 239000002184 metal Substances 0.000 title claims abstract description 107
- 239000002245 particle Substances 0.000 title claims abstract description 99
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000004005 microsphere Substances 0.000 title claims abstract description 83
- 150000003839 salts Chemical class 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004945 emulsification Methods 0.000 title claims abstract description 16
- 229910003480 inorganic solid Inorganic materials 0.000 claims abstract description 36
- 239000000374 eutectic mixture Substances 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 10
- 239000002612 dispersion medium Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 60
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000007795 chemical reaction product Substances 0.000 claims description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 28
- 239000010453 quartz Substances 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 26
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000005496 eutectics Effects 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 50
- 239000001103 potassium chloride Substances 0.000 description 25
- 235000011164 potassium chloride Nutrition 0.000 description 25
- 238000005303 weighing Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 7
- 239000013528 metallic particle Substances 0.000 description 6
- 229910021392 nanocarbon Inorganic materials 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 150000003841 chloride salts Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000879 optical micrograph Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
Abstract
The invention discloses a method for reducing the grain size of tin microspheres prepared based on a molten salt metal emulsion method, which takes a molten chloride eutectic mixture as a dispersion medium, liquid metal tin as a dispersion phase, adds a proper amount of nano inorganic solid particles, utilizes ultrasonic cavitation to provide energy to disperse liquid metal in molten salt, quickly cools and washes away salt to obtain metal microspheres with controllable grain size, and the added nano inorganic solid particles can effectively reduce the grain size of the metal microspheres.
Description
Technical Field
The invention relates to the technical field of metal emulsion preparation, in particular to a method for reducing the particle size of tin microspheres prepared based on a molten salt metal emulsion method.
Background
A metal emulsion is a special dispersion system with liquid metal as the dispersed phase. A typical example is increasing the interfacial area between metal and slag by emulsifying droplets of metal into slag during refining of molten steel, so-called "metal emulsions", which play an important role in controlling the reaction rate between molten steel and slag. Researchers have studied bubbling assisted emulsification of liquid metal with molten chloride salt as the slag phase, and have shown that small-sized emulsified metal droplets can be extracted by rapidly cooling the chloride salt and then dissolving the salt in water.
In common emulsions, such as oil-in-water emulsions, the emulsion is stable in a dispersed state for a long time after emulsification under ultrasonic irradiation due to a relatively small density difference. Compared with the traditional oil-water emulsion, the metal emulsion is unstable because of the factors of high interfacial tension between liquid metal and molten salt, influence of ionic property of the molten salt, incapability of adding surfactant at high temperature and the like.
It has been reported that Sn microspheres （Friedman, H.; Reich, S.; Popovitz–Biro, R.; Huth, V .P .; Halevy , I.; Koltypin, Y .; Gedanken, A.; Porat, Z. Micro–and nano–spheres of low melting point metals and alloys formed by ultrasonic cavitation. Ultrason. Sonochem. 2013, 20, 432–444.）, having good shape can be prepared by ultrasonic dispersion of liquid Sn into silicone oil, but the use of silicone oil as a dispersion medium is not perfectly compatible with the metal emulsion method, silicone oil is easily evaporated or even decomposed at high temperature, and is harmful. And because of its extremely high viscosity, it is also necessary to remove it from the surface of the metal particles by means of organic substances.
It is found that the micro-sized metal droplets can be extracted by using chloride salt as a dispersion medium, dispersing the metal droplets in molten salt by ultrasonic cavitation, and then rapidly cooling the molten salt and washing the salt. The particle size ,（Zheng, X.; Luo, W.; Yu, Y.; Xue, Z.; Zheng, Y.; Liu, Z., Metal Emulsion-Based Synthesis, Characterization, and Properties of Sn-Based Microsphere Phase Change Materials. Molecules 2021, 26 (24).） of the metal microspheres can be reduced by increasing the ultrasonic power and the ultrasonic time and increasing the volume ratio of the salt to the metal in a certain range, and the method consumes energy although the particle size of the metal microspheres can be reduced to a certain extent by increasing the ultrasonic time. Therefore, the method for controlling the particle size of the metal microspheres by searching for a method which is simple to operate, energy-saving and environment-friendly has important significance.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a method for reducing the particle size of tin microspheres prepared by a molten salt metal emulsion method, the particle size of the metal tin microspheres can be regulated and controlled by changing the selection and the addition amount of nano inorganic solid particles, and the device is simple and easy to operate.
The technical scheme of the invention is as follows:
A method for reducing the grain diameter of tin microspheres prepared based on molten salt metal emulsion method is characterized in that a molten chloride eutectic mixture is used as a dispersion medium, liquid metal tin is used as a dispersion phase, nano inorganic solid particles are added, ultrasonic cavitation is utilized to provide energy, liquid metal is dispersed in molten salt, salt is washed out after rapid cooling, and the metal tin microspheres with controllable grain diameter are obtained, and the method specifically comprises the following steps:
1) Heating molten salt: putting the eutectic mixture into a quartz test tube, and putting the quartz test tube into a high-temperature heating furnace for heating and melting;
2) Adding metallic tin: after the step 1) is finished in melting, taking metal tin and adding the metal tin into a quartz test tube filled with high-temperature molten salt;
3) Adding nano inorganic solid particles: after the temperature of the high-temperature molten salt in the step 2) is reduced, specifically, the temperature is reduced from 365-370 ℃ to 285-300 ℃, nano inorganic solid particles are taken and put into a quartz test tube in the step 2) to be slightly shaken and dispersed, ultrasonic treatment is carried out after the uniform dispersion, and liquid tin is dispersed in the molten salt;
4) After the ultrasonic treatment of the step 3), rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product after cleaning, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
Further, the eutectic mixture in step 1) includes two or three of CsCl, liCl and KCl.
Further, the eutectic mixture is LiCl and KCl, wherein the molar ratio of LiCl to KCl is 3:2.
Further, the eutectic mixture is LiCl and CsCl, wherein the molar ratio of LiCl to CsCl is 3:2.
Further, the eutectic mixture is CsCl, liCl and KCl, and when the CsCl mole percentage is 25%, the LiCl mole percentage is 50% -61%, and the KCl mole percentage is 14% -41%.
Further, the nano inorganic solid particles in the step 3) are nano titanium dioxide, nano carbon powder or nano silicon dioxide.
Further, the nano-inorganic solid particles are preferably nano-titania.
Further, in the step 3), the mass ratio of the metal tin to the nano inorganic solid particles is 1:0.0022-0.448.
Further, the temperature point of the nano inorganic solid particles added in the step 3) is the lowest eutectic point of the eutectic mixture in the step 1).
Further, in the step 3), the ultrasonic power is 540-840 w, and the ultrasonic time is 3-8 min.
Compared with the prior art, the invention has the following beneficial effects:
1) By adopting the technical scheme of the invention, the molten chloride eutectic mixture is used as a dispersion medium, the liquid metal is used as a dispersion phase, and the metal microspheres with controllable particle size can be obtained by controlling the addition amount of nano inorganic solid particles and utilizing ultrasonic cavitation dispersion;
2) The preparation method is simple, has universality on most metals, and can effectively reduce the particle size of the metal microspheres by adding a proper amount of nano inorganic solid particles under the conditions of not improving ultrasonic power and not prolonging ultrasonic time.
Drawings
FIG. 1 is an optical microscope image of metal microspheres obtained without adding nano inorganic solid particles in example 1;
FIG. 2 is a graph showing the particle diameter statistics of metal microspheres obtained without adding nano inorganic solid particles in example 1;
FIG. 3 is an optical microscope image of metal microspheres obtained by adding 0.04g of nano-silica in example 2;
FIG. 4 is a graph showing the particle size statistics of metal microspheres obtained by adding 0.04g of nano-silica in example 2;
FIG. 5 is an optical microscope image of the metal microsphere obtained by adding 0.04g of nano carbon powder in example 3;
FIG. 6 is a graph showing the particle size statistics of metal microspheres obtained by adding 0.04g of nano carbon powder in example 3;
FIG. 7 is an optical microscopic image of metal microspheres obtained by adding 0.005g of nano-titania in example 4;
FIG. 8 is a graph showing the particle diameter statistics of metal microspheres obtained by adding 0.005g of nano-titania in example 4;
FIG. 9 is an optical microscopic image of metal microspheres obtained by adding 0.02g of nano-titania in example 5;
FIG. 10 is a graph showing the particle size statistics of metal microspheres obtained by adding 0.02g of nano-titania in example 5;
FIG. 11 is an optical microscopic image of metal microspheres obtained by adding 0.03g of nano-titania in example 6;
FIG. 12 is a graph showing the particle diameter statistics of metal microspheres obtained by adding 0.03g of nano-titania in example 6;
FIG. 13 is an optical microscopic image of metal microspheres obtained by adding 0.04g of nano-titania in example 7;
FIG. 14 is a graph showing the particle diameter statistics of metal microspheres obtained by adding 0.04g of nano titanium dioxide in example 7;
FIG. 15 is an optical microscopic image of metal microspheres obtained by adding 0.05g of nano-titania in example 8;
FIG. 16 is a graph showing the particle diameter statistics of metal microspheres obtained by adding 0.05g of nano titanium dioxide in example 8;
FIG. 17 is an SEM image of metal microspheres obtained by adding 0.07g of nano-titania according to example 9;
FIG. 18 is a graph showing the particle diameter statistics of metal microspheres obtained by adding 0.07g of nano-titania in example 9;
FIG. 19 is an SEM image of metal microspheres obtained by adding 0.1g of nano-titania according to example 10;
FIG. 20 is a graph showing the particle size statistics of metal microspheres obtained by adding 0.1g of nano-titania in example 10;
Detailed Description
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to the above.
Example 1
The ultrasonic power is 600w, the ultrasonic time is 5min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the mass of the metal tin is 2.23g, and the metal tin microsphere is prepared under the condition of no nano inorganic solid particles.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metallic tin: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, setting the ultrasonic power to be 600w and starting ultrasonic treatment for 5min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
From fig. 1-2, it can be seen that the metal particles are all uniform spheres, the particle size is larger, and particles with diameters of 80-100 mu m are dominant in the product.
Example 2
The ultrasonic power is 600w, the ultrasonic time is 5min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.04g of nano silicon dioxide.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metallic tin: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.04g of nano silicon dioxide, uniformly dispersing, and setting the ultrasonic power to be 600w to start ultrasonic treatment for 5min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
It can be seen from fig. 3 to 4 that the particle size of the metallic tin microspheres is significantly reduced compared to the condition without the addition of nano inorganic solid particles, but the metallic particles have a wider particle size distribution, and particles with diameters of 12.5 to 25 μm are dominant in the product.
Example 3
The ultrasonic power is 600w, the ultrasonic time is 5min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.04g of nano carbon powder.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metal: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.04g of nano carbon powder for uniform dispersion, and setting the ultrasonic power to be 600w for starting ultrasonic treatment for 5min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
From fig. 5 to 6, it can be seen that the particle size of the metal tin microspheres is significantly reduced, and the metal particles have a narrower particle size distribution, and particles with diameters of 5 to 7 μm are dominant in the product, compared with the condition that no nano inorganic solid particles are added.
Example 4
The ultrasonic power is 600w, the ultrasonic time is 5min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.005g of nano titanium dioxide.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metal: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.005g of nano titanium dioxide, uniformly dispersing, and setting the ultrasonic power to be 600w to start ultrasonic treatment for 5min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
From fig. 7 to 8, it can be seen that the particle size of the metal tin microspheres is reduced compared with the condition that no nano inorganic solid particles are added, the particle size distribution of the metal particles is narrower, and the particles with the diameters of 60-75 mu m are dominant in the product.
Example 5
The ultrasonic power is 600w, the ultrasonic time is 5min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.02g of nano titanium dioxide.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metal: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.02g of nano titanium dioxide, uniformly dispersing, and setting the ultrasonic power to 600w to start ultrasonic treatment for 5min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
It can be seen from fig. 9 to 10 that the particle size of the metallic tin microspheres is significantly reduced, and the metallic particles have a narrower particle size distribution, with particles having diameters of 20 to 30 μm being dominant in the product, compared to the condition without adding the nano inorganic solid particles.
Example 6
The ultrasonic power is 540w, the ultrasonic time is 3min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.03g of nano titanium dioxide.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metal: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.03g of nano titanium dioxide, uniformly dispersing, and setting the ultrasonic power to be 540w to start ultrasonic treatment for 3min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
From fig. 11 to 12, it can be seen that, compared with the condition without adding nano inorganic solid particles, although the ultrasonic power is reduced and the ultrasonic time is shortened, the particle size of the metal tin microsphere is obviously reduced, and the particles with the diameters of 15-25 mu m are dominant in the product.
Example 7
The ultrasonic power is 600w, the ultrasonic time is 5min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.04g of nano titanium dioxide.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metal: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.04g of nano titanium dioxide, uniformly dispersing, and setting the ultrasonic power to be 600w to start ultrasonic treatment for 5min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
From FIGS. 13 to 14, it can be seen that the particle size of the metallic tin microspheres is significantly reduced, and the metallic particles have a narrower size distribution, with particles having diameters of 10 to 17 μm being dominant in the product, compared to the condition without the addition of nano inorganic solid particles.
Example 8
The ultrasonic power is 840w, the ultrasonic time is 8min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.05g of nano titanium dioxide.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metal: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.05g of nano titanium dioxide, uniformly dispersing, and setting the ultrasonic power to 840w to start ultrasonic treatment for 8min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
From FIGS. 15 to 16, it can be seen that the particle size of the metallic tin microspheres is significantly reduced, and the metallic particles have a narrower size distribution, with particles having diameters of 6 to 10 μm being dominant in the product, compared to the condition without the addition of nano inorganic solid particles.
Example 9
The ultrasonic power is 600w, the ultrasonic time is 5min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.07g of nano titanium dioxide.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metal: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.07g of nano titanium dioxide, uniformly dispersing, and setting the ultrasonic power to be 600w to start ultrasonic treatment for 5min;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
From FIGS. 17 to 18, it can be seen that the particle size of the metallic tin microspheres is significantly reduced, and the metallic particles have a narrower size distribution, with particles having diameters of 8 to 14 μm being dominant in the product, compared to the condition without the addition of nano inorganic solid particles.
Example 10
The ultrasonic power is 600w, the ultrasonic time is 5min, the molten salt molar ratio (potassium chloride: lithium chloride: cesium chloride) is 5:14:6, the metal amount is 2.23g, and the metal tin microsphere is prepared under the condition of adding 0.1g of nano titanium dioxide.
1) Heating molten salt: 4.161g of potassium chloride, 6.351g of lithium chloride and 11.388g of cesium chloride are taken and are put into a quartz test tube, and are placed into a high-temperature heating furnace for heating and melting;
2) Adding metal: weighing 2.23g of metallic tin, and adding the metallic tin into the quartz test tube filled with the high-temperature molten salt in the step 1);
3) When the temperature is reduced to 290 ℃, adding 0.1 g nanometer titanium dioxide to uniformly disperse, and setting the ultrasonic power to be 600w to start ultrasonic treatment for 5 minutes;
4) And after the ultrasonic treatment is finished, rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing the reaction product into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product, and placing the washed product in a vacuum oven for drying to obtain the metal tin microspheres.
It can be seen from FIGS. 19 to 20 that the particle size of the metallic tin microspheres is significantly reduced, and the metallic particles have a narrower size distribution, with particles having diameters of 6 to 12 μm being dominant in the product, compared to the condition without the addition of nano inorganic solid particles.
It can be seen from comparative examples 1, 2, 3 and 7 that the addition of the nano inorganic solid particles can significantly reduce the particle size of the metallic tin microspheres, and that the addition of different nano inorganic solid particles of the same addition amount has different effects on reducing the particle size of the metallic tin microspheres while maintaining the consistency of ultrasonic power and ultrasonic time.
When nano silicon dioxide is used as nano inorganic solid particles to be added, the particle size of the metal tin microspheres is reduced, but the particle size distribution is wider, and particles with the diameter of 12.5-25 mu m are dominant in the product. When nano titanium dioxide is used as nano inorganic solid particles to be added, the particle size of the metal tin balls can be obviously reduced, particles with the diameters of 10-17 mu m are dominant in the product, and the particle size is uniform. When nano carbon powder is used as nano inorganic solid particles to be added, the particle size of the metal tin microspheres can be obviously reduced, the particles with the diameters of 5-7 mu m are dominant in the product, and the particle size is most uniform.
As can be seen from comparison of examples 4, 5, 7 and 9, the metallic tin microspheres prepared in different examples have uniform spherical morphology, but different particle sizes, and the particle sizes of the metallic tin microspheres gradually decrease with the gradual increase of the addition amount of the nano titanium dioxide when the addition amount of the nano titanium dioxide is changed under other conditions.
Claims (8)
1. A method for reducing the grain diameter of tin microspheres prepared based on molten salt metal emulsion method is characterized in that a molten chloride eutectic mixture is used as a dispersion medium, liquid metal tin is used as a dispersion phase, nano inorganic solid particles are added, ultrasonic cavitation is utilized to provide energy, liquid metal is dispersed in molten salt, salt is washed out after rapid cooling, and the metal tin microspheres with controllable grain diameter are obtained, and the method specifically comprises the following steps:
1) Heating molten salt: putting the eutectic mixture into a quartz test tube, and putting the quartz test tube into a high-temperature heating furnace for heating and melting;
2) Adding metallic tin: after the melting of the step 1) is finished, adding metal tin into a quartz test tube filled with high-temperature molten salt;
3) Adding nano inorganic solid particles: after the temperature of the high-temperature molten salt in the step 2) is reduced, putting nano inorganic solid particles into a quartz test tube in the step 2), slightly shaking for dispersion, carrying out ultrasonic treatment after uniform dispersion, and dispersing liquid tin into molten salt;
4) After the ultrasonic treatment of the step 3), rapidly placing the reaction product in a cooling container, cooling, washing salt with distilled water, placing into an ultrasonic cleaner for ultrasonic cleaning, centrifugally separating the reaction product after cleaning, and placing the washed product in a vacuum oven for drying to obtain the product, namely the metallic tin microspheres;
The eutectic mixture in the step 1) comprises two or three of CsCl, liCl and KCl;
the nanometer inorganic solid particles in the step 3) are nanometer titanium dioxide, nanometer carbon powder or nanometer silicon dioxide.
2. A method of reducing the particle size of tin microspheres produced based on molten salt metal emulsion process according to claim 1, characterized in that the eutectic mixture is LiCl and KCl, wherein the molar ratio of LiCl to KCl is 3:2.
3. A method of reducing the particle size of tin microspheres produced based on molten salt metal emulsion process according to claim 1 wherein the eutectic mixture is LiCl and CsCl, wherein the molar ratio of LiCl to CsCl is 3:2.
4. The method of claim 1, wherein the eutectic mixture is CsCl, liCl and KCl, and the LiCl is 50% -61% and the KCl is 14% -41% when CsCl is 25%.
5. The method for reducing the particle size of tin microspheres prepared by a molten salt metal emulsion process according to claim 1, wherein the nano inorganic solid particles are nano titanium dioxide.
6. The method for reducing the particle size of tin microspheres prepared by a molten salt metal emulsion method according to claim 1, wherein the mass ratio of metal tin to nano inorganic solid particles in the step 3) is 1:0.0022-0.448.
7. The method for reducing the particle size of tin microspheres prepared by a molten salt metal emulsion process according to claim 1, wherein the temperature point of the nano inorganic solid particles added in the step 3) is the lowest eutectic point of the eutectic mixture in the step 1).
8. The method for reducing the particle size of tin microspheres prepared by a molten salt metal emulsion method according to claim 1, wherein the ultrasonic power in the step 3) is 540-840 w, and the ultrasonic time is 3-8 min.
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