CN113941711B - Preparation method and device of high-fluidity micron silver particles - Google Patents
Preparation method and device of high-fluidity micron silver particles Download PDFInfo
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- CN113941711B CN113941711B CN202111148544.9A CN202111148544A CN113941711B CN 113941711 B CN113941711 B CN 113941711B CN 202111148544 A CN202111148544 A CN 202111148544A CN 113941711 B CN113941711 B CN 113941711B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000004332 silver Substances 0.000 title claims abstract description 102
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 102
- 239000002245 particle Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 34
- 239000007791 liquid phase Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000000546 pharmaceutical excipient Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 26
- 238000006722 reduction reaction Methods 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
- -1 sorbitan fatty acid ester Chemical class 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229940070765 laurate Drugs 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 101
- 230000002776 aggregation Effects 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 8
- 238000004220 aggregation Methods 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000007363 regulatory process Effects 0.000 description 2
- 238000010900 secondary nucleation Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Abstract
The invention discloses a preparation method of high-fluidity micron silver particles, and belongs to the technical field of powder materials. The preparation method can effectively solve the problem of grain aggregation of silver powder in the liquid phase reaction in the traditional preparation method, and meanwhile, the solution is not required to be mixed in a stirring mode before the liquid phase reaction, so that the defect that larger crystal particles cannot be formed is avoided; the glidant is used for replacing a dispersing agent in the traditional liquid phase reaction, so that the problem of residual cleaning of the follow-up silver powder is effectively avoided, the effects of dispersing the silver powder and improving the surface properties of particles are achieved, and meanwhile, gas in silver particles can be preferentially adsorbed, so that the product is high in tap density and high in fluidity. The invention also discloses a point screen type dispersing device for preparing the strong-fluidity micron particles, which can effectively synchronously add the excipient silver source solution and the reducer solution into the glidant solution, improve the uniformity of the mixed solution and solve the problem of grain aggregation of the silver particles.
Description
Technical Field
The invention relates to the technical field of powder materials, in particular to a preparation method and a preparation device of high-fluidity micron silver particles.
Background
In the prior art, the principle of the liquid phase reduction method for preparing silver powder is that silver is deposited from silver salt, silver complex aqueous solution or organic system in a powder form by using a reducing agent, and the method has the following advantages: the method has the advantages of low equipment requirement, low preparation cost, easy control of the morphology and particle size of the silver powder by adjusting the technological parameters such as temperature, reaction time, reactant consumption and the like in the reaction process, and simple technological process. The liquid phase reduction method is widely applied to the field of electronic industry, but silver powder prepared by the chemical reduction method is easy to agglomerate, the pH value and the reaction temperature influence the reaction rate, the reaction rate is too high to cause secondary agglomeration, the rate is too low to cause the problems of serious agglomeration, reduced dispersibility, irregular shape, uneven shape and the like, and parameters need to be strictly controlled; in addition, the silver powder prepared at present can form a large number of air holes after being solidified into a film due to poor fluidity and contact in the sintering process, so that the problems of poor sintering compactness, large sheet resistance of a solidified film layer and the like are caused, and the application effect of the conductive paste is directly influenced.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide a preparation method of high-fluidity micron silver particles, and silver powder prepared by the preparation method can be closely piled in a vibration process and can be used for solving the problem that a large number of air holes exist after sintering and film forming of silver powder prepared in the prior art; the preparation method can effectively solve the problem of silver powder grain aggregation, can avoid the problem of residue in the silver powder cleaning process after liquid phase reaction, and is efficient and simple.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing high-fluidity micro silver particles, comprising the following steps:
(1) Dissolving a silver source and an excipient in deionized water to obtain a shaped silver source solution A;
(2) Respectively dissolving a reducing agent and a glidant in deionized water to respectively obtain a reducing agent solution B and a glidant solution C, and placing the glidant solution C in a container of an inclined cavity;
(3) Adjusting the pH value of the shaped silver source solution A to 1-6, and then carrying out liquid phase reduction reaction with the reducer solution B in an ultrasonic dispersion environment by rotating and dispersing the shaped silver source solution A into the glidant solution C through a point screen type dispersing device;
(4) And after the liquid phase reduction reaction is finished, sequentially carrying out vacuum filtration, centrifugation, washing, drying, crushing and grinding treatment on the turbid liquid obtained after the reaction to obtain the strong-fluidity micro silver particles.
According to the preparation method of the high-fluidity micro silver particles, a liquid adding mode that a point screen type dispersing device rotates and is added is utilized to uniformly disperse a silver source and a reducing agent solution in a glidant solution, so that the probability of forming crystal nuclei by crossing an energy barrier of the solution in a unit volume is the same, and the problem of crystal grain aggregation of silver powder in a liquid phase reaction is solved; the container with the inclined cavity is used as a liquid phase reaction container, so that the mixing degree of each solution can be improved, meanwhile, the solution is not required to be mixed in a stirring mode like the traditional liquid phase reaction, the secondary nucleation caused by stirring can be avoided, and the defect that larger crystal particles cannot be formed can be overcome. According to the preparation method, the glidant is used for replacing the dispersing agent in the traditional liquid phase reaction, so that the problem of residual cleaning of the follow-up silver powder is effectively avoided, the silver powder is dispersed and the effect of improving the surface property of particles is achieved, meanwhile, the gas in the silver particles is preferentially adsorbed, a large number of air holes are avoided being formed in the sintering process, and finally the product is high in tap density and strong in fluidity.
Preferably, the molar concentration of the silver source in the shaping silver source solution A is 0.4-2 mol/L, and the molar concentration of the excipient is 0.008-0.012 mol/L;
the excipient can furthest regulate the stability of the silver source in the subsequent reaction process, and ensures that the generated spheroidal silver particles have high dispersibility and size uniformity.
More preferably, the silver source comprises silver nitrate;
more preferably, the excipient comprises at least one of sorbitol, polyethylene glycol.
Preferably, the reducing agent comprises at least one of ferrous sulfate heptahydrate, hydroquinone, sodium citrate, ascorbic acid, and glucose.
Preferably, the mass concentration of the reducing agent in the glidant solution C is 25-35 g/L.
The glidant not only plays a role of a dispersing agent in the liquid phase reaction, but also fully wraps and modifies the surfaces of the silver particles after being uniformly mixed with the generated silver particles, so that the glidant can effectively absorb the gas in the silver particles and improve the quality of the silver particles. When the content of the glidant is too small, the modifying effect of the glidant on silver particles is poor, and meanwhile, agglomeration of the silver particles due to insufficient dispersion in the generating process can be caused; if the content of the glidant is too high, the particle size of the prepared silver particles may be too large, and the tap density may be rather small.
More preferably, the glidant comprises at least one of polyethylene glycol laurate, sorbitan fatty acid ester.
Preferably, the inclination of the container of the inclined cavity in the step (2) is 20-60 degrees.
Preferably, the temperature at the time of the liquid phase reduction reaction is 10 to 60 ℃.
Preferably, the point screen type dispersing device comprises a solution cavity, the lower end of the solution cavity is provided with a plurality of dispersing pipes communicated with the solution cavity, and the formed silver source solution A and the reducing agent solution B after the pH adjustment are firstly placed in the solution cavity when being added into the point screen type dispersing device, and then synchronously flow out of the communicated dispersing pipes into the glidant solution C.
Due to the design of the point screen type dispersing device, after the shaped silver source solution A and the reducer solution B are placed in the solution cavity, the shaped silver source solution A and the reducer solution B flow into the glidant solution C through a plurality of dispersing pipes in a rotating mode, so that the dispersive mixing of each component can be effectively realized, the excipient, the silver source and the reducer can be effectively dispersed in the glidant system, the probability that the solution passes over an energy barrier to form crystal nucleus is the same, and the problem of crystal grain agglomeration is further solved.
Another object of the invention is to provide a point-screen dispersion device for preparing high-fluidity microparticles, comprising a solution chamber (1) and a plurality of hollow dispersion conduits (2); one end of the hollow dispersion conduit is communicated with the bottom of the solution cavity.
Preferably, the solution chamber is a cylindrical chamber with an open top.
Preferably, the hollow dispersion pipes are fixed at the bottom of the solution cavity in a central symmetry mode, and the hollow dispersion pipes are parallel to each other.
More preferably, the space between the hollow dispersion pipes is 3cm, and the ratio of the length of the hollow dispersion pipes to the inner diameter of the solution cavity is 2:1.
When the device is used for preparing the strong-fluidity micron particles, the device can be used as a sample adding device to synchronously add the excipient silver source solution and the reducer solution into the glidant solution, so that the uniformity of the mixed solution is improved, and the problem of aggregation of silver particle grains is solved.
The preparation method of the high-fluidity micron silver particles has the beneficial effects that the method can effectively solve the problem of grain aggregation of silver powder in the liquid phase reaction in the traditional preparation method, and meanwhile, the solution is not required to be mixed in a stirring mode before the liquid phase reaction, so that the defect that secondary nucleation caused by stirring can be avoided, and larger crystal particles cannot be formed can be overcome. According to the preparation method, the glidant is used for replacing the dispersing agent in the traditional liquid phase reaction, so that the problem of residual cleaning of the follow-up silver powder is effectively avoided, the silver powder is dispersed and the effect of improving the surface property of particles is achieved, meanwhile, the gas in the silver particles is preferentially adsorbed, a large number of air holes are avoided being formed in the sintering process, and finally the product is high in tap density and strong in fluidity. The invention also provides a point screen type dispersing device for preparing the strong-fluidity micro-particles, compared with a sample adding device in the traditional silver particle preparation process, the device can effectively synchronously add the shaped silver source solution and the reducing agent solution into the glidant solution, improves the uniformity of the mixed solution, and solves the problem of grain aggregation of silver particles.
Drawings
FIG. 1 is a schematic view (left) and a plan view (right) of a point screen type dispersing device according to the present invention; the device comprises a solution cavity 1 and a plurality of hollow dispersion pipes 2;
FIG. 2 is an SEM image of micrometer silver particles prepared according to the method of example 1 of the present invention;
FIG. 3 is an SEM image of micrometer silver particles prepared according to the method of example 2 of the present invention;
FIG. 4 is an SEM image of micrometer silver particles prepared according to the method of example 3 of the present invention;
fig. 5 is an SEM electron microscope image of the micro silver particles prepared by the preparation method described in comparative example 1.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments designed in the practice and comparative examples of the present invention are common reagents and instruments unless otherwise specified.
Example 1
The invention relates to a preparation method of high-fluidity micron silver particles, which comprises the following steps:
(1) 255g of silver nitrate powder and 1.53g of sorbitol are dissolved in 1000mL of deionized water, and fully stirred to obtain a shaped silver source solution A;
(2) Dissolving 60g of hydroquinone white crystals and 26g of polyethylene glycol lunar silicate in 500mL and 1000mL of deionized water at 20 ℃ to obtain a reducer solution B and a glidant solution C respectively, and placing the glidant solution C in a container with an inclined cavity (the inclination is 40 ℃);
(3) Adjusting pH of the shaped silver source solution A to 3 by dilute nitric acid (the adjusting process is maintained at about 20 ℃), then dispersing the shaped silver source solution A and the reducing agent solution B in a 20 ℃ ultrasonic dispersion environment, and adding the shaped silver source solution A and the reducing agent solution B into the glidant solution C while rotating through a point screen type dispersing device to carry out liquid phase reduction reaction;
(4) After the liquid phase reduction reaction is finished, obtaining turbid liquid containing silver powder, sequentially carrying out vacuum filtration on the turbid liquid obtained after the reaction, loading the turbid liquid into a centrifuge tube containing absolute ethyl alcohol, centrifuging for 3-4 times, washing, drying in a baking oven at 60 ℃ for 6-8 hours, and crushing and grinding to obtain the strong-fluidity micron silver particles.
The structure schematic diagram of the point screen type dispersing device is shown in fig. 1, and the device comprises a solution cavity (1) and a plurality of hollow dispersing guide pipes (2); one end of the hollow dispersion conduit is communicated with the bottom of the solution cavity; the solution cavity is a cylindrical cavity with an opening at the top; the hollow dispersion pipes are fixed at the bottom of the solution cavity in a central symmetry mode, and the hollow dispersion pipes are mutually parallel.
The micrometer silver particles obtained in the embodiment are observed by a scanning electron microscope, as shown in fig. 2, the silver particles are uniformly dispersed and have a similar spherical shape, the particle size is about 2-3 micrometers, and no obvious impurities exist in the particles.
Example 2
The invention relates to a preparation method of high-fluidity micron silver particles, which comprises the following steps:
(1) Dissolving 306g of silver nitrate powder and 1.8g of polyethylene glycol in 1000mL of deionized water, and fully stirring to obtain a shaped silver source solution A;
(2) Dissolving 60g of hydroquinone white crystals and 30g of polyethylene glycol lunar silicate in 500mL and 1000mL of deionized water at 20 ℃ to obtain a reducer solution B and a glidant solution C respectively, and placing the glidant solution C in a container with an inclined cavity (the inclination is 35 ℃);
(3) Adjusting pH of the shaped silver source solution A to 4 by dilute nitric acid (the adjusting process is maintained at about 20 ℃), and then adding the shaped silver source solution A and the reducing agent solution B into the glidant solution C for liquid-phase reduction reaction under the condition of ultrasonic dispersion at 20 ℃ through a point screen type dispersing device while rotating and dispersing;
(4) After the liquid phase reduction reaction is finished, obtaining turbid liquid containing silver powder, sequentially carrying out vacuum filtration on the turbid liquid obtained after the reaction, loading the turbid liquid into a centrifuge tube containing absolute ethyl alcohol, centrifuging for 3-4 times, washing, drying in a baking oven at 60 ℃ for 6-8 hours, and crushing and grinding to obtain the strong-fluidity micron silver particles.
The point screen type dispersing device is the same as in example 1.
The micrometer silver particles obtained in this example were observed by a scanning electron microscope, and as shown in fig. 3, the size among the silver particles was uniform, and the particles were uniformly dispersed, and were generally spherical-like, similar to the product of example 1.
Example 3
The invention relates to a preparation method of high-fluidity micron silver particles, which comprises the following steps:
(1) Dissolving 68g of silver nitrate powder and 1.8g of polyethylene glycol in 1000mL of deionized water, and fully stirring to obtain a shaped silver source solution A;
(2) Dissolving 60g of hydroquinone white crystals and 30g of polyethylene glycol lunar silicate in 500mL and 1000mL of deionized water at 25 ℃ to obtain a reducer solution B and a glidant solution C respectively, and placing the glidant solution C in a container with an inclined cavity (the inclination is 35 ℃);
(3) Adjusting pH of the shaped silver source solution A to 4.2 by dilute nitric acid (the adjusting process is maintained at about 25 ℃), then dispersing the shaped silver source solution A and the reducing agent solution B in a 25 ℃ ultrasonic dispersion environment, and adding the shaped silver source solution A and the reducing agent solution B into the glidant solution C while rotating through a point screen type dispersing device to carry out liquid phase reduction reaction;
(4) After the liquid phase reduction reaction is finished, obtaining turbid liquid containing silver powder, sequentially carrying out vacuum filtration on the turbid liquid obtained after the reaction, loading the turbid liquid into a centrifuge tube containing absolute ethyl alcohol, centrifuging for 3-4 times, washing, drying in a baking oven at 60 ℃ for 6-8 hours, and crushing and grinding to obtain the strong-fluidity micron silver particles.
The point screen type dispersing device is the same as in example 1.
As shown in fig. 4, the micrometer silver particles obtained in this example were observed by a scanning electron microscope, and each silver particle was generally spherical-like in shape and uniform in size, but slightly increased in surface roughness, similar to the products of examples 1 and 2.
Example 4
The invention relates to a preparation method of high-fluidity micron silver particles, which comprises the following steps:
(1) 340g of silver nitrate powder and 2g of sorbitol are dissolved in 1000mL of deionized water, and fully stirred to obtain a shaped silver source solution A;
(2) At 20 ℃, 278g of ferrous sulfate heptahydrate and 35g of sorbitan fatty acid ester are respectively dissolved in 500mL and 1000mL of deionized water to respectively obtain a reducer solution B and a glidant solution C, and the glidant solution C is placed in a container with an inclined cavity (the inclination is 45 ℃);
(3) Adjusting pH of the shaped silver source solution A to 5 by dilute nitric acid (the adjusting process is maintained at about 30 ℃), then dispersing the shaped silver source solution A and the reducing agent solution B in a 20 ℃ ultrasonic dispersion environment, and adding the shaped silver source solution A and the reducing agent solution B into the glidant solution C while rotating through a point screen type dispersing device to carry out liquid phase reduction reaction;
(4) After the liquid phase reduction reaction is finished, obtaining turbid liquid containing silver powder, sequentially carrying out vacuum filtration on the turbid liquid obtained after the reaction, loading the turbid liquid into a centrifuge tube containing absolute ethyl alcohol, centrifuging for 3-4 times, washing, drying in a baking oven at 60 ℃ for 6-8 hours, and crushing and grinding to obtain the strong-fluidity micron silver particles.
The point screen type dispersing device is the same as in example 1.
Comparative example 1
The present comparative example differs from example 1 only in that the step (3) is replaced with: the pH value of the shaped silver source solution A is regulated to 3 by dilute nitric acid (the regulating process is maintained at about 20 ℃), and then the shaped silver source solution A and the reducing agent solution B are directly added into the glidant solution C for liquid-phase reduction reaction under the condition of ultrasonic dispersion at 20 ℃.
The micrometer silver particles obtained in the comparative example are observed by a scanning electron microscope, as shown in fig. 5, the silver particles prepared by adopting a direct dispersion sample adding mode show irregular (between flower-shaped and spherical) morphology, the surface roughness is increased, meanwhile, the density among particles is insufficient, and the particle size is also increased to 4-6 micrometers.
Comparative example 2
The present comparative example differs from example 2 only in that the step (3) is replaced with: the pH value of the shaped silver source solution A is regulated to 4 by dilute nitric acid (the regulating process is maintained at about 20 ℃), and then the shaped silver source solution A and the reducing agent solution B are directly added into the glidant solution C for liquid-phase reduction reaction under the condition of ultrasonic dispersion at 20 ℃.
Comparative example 3
The difference between this comparative example and example 1 is only that the glidant solution C of step (2) is placed in a common flat bottom vessel in which the subsequent liquid-phase reduction reaction is also carried out.
Effect example 1
In order to verify the performance of the products prepared by the preparation method and the device of the high-fluidity micron silver particles, the products obtained in the examples and the comparative examples are measured, and the tap density, the repose angle and the compressibility of the products are respectively detected; where the degree of compression is defined as (ρ2- ρ1)/ρ2, and ρ1 and ρ2 are the bulk density and tap density, respectively, of the prepared silver particles, and the angle of repose refers to the maximum angle formed by the free surface of the silver particles when naturally stacked with the horizontal plane in a state of resting equilibrium. Under the same conditions, the smaller the repose angle and the compression value, the better the fluidity of the powder. The test results are shown in Table 1.
TABLE 1
| Group of | Tap density (g/cm) 3 ) | Angle of repose (°) | Degree of compression (°) |
| Example 1 | 6.27 | 37 | 0.38 |
| Example 2 | 6.11 | 42 | 0.31 |
| Example 3 | 6.15 | 45 | 0.33 |
| Example 4 | 6.15 | 40 | 0.35 |
| Comparative example 1 | 5.90 | 53 | 0.56 |
| Comparative example 2 | 5.75 | 50 | 0.48 |
| Comparative example 3 | 5.69 | 47 | 0.60 |
As can be seen from Table 1, the tap densities of the micro silver particles obtained in examples 1 to 4 were all 6g/cm 3 The above results show that the products prepared by the preparation method of the high-fluidity micron silver particles have excellent fluidity and tap density, wherein the repose angle is below 45 degrees, and the compression degree is below 0.4 degrees. In contrast, the products obtained in comparative examples 1 to 3 were lower in tap density and also significantly weaker in flowability than the products obtained in examples 1 to 4.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A method for preparing high-fluidity micro silver particles, which is characterized by comprising the following steps:
(1) Dissolving a silver source and an excipient in deionized water to obtain a shaped silver source solution A; the molar concentration of a silver source in the shaping silver source solution A is 0.4-2 mol/L, and the molar concentration of an excipient is 0.008-0.012 mol/L;
(2) Respectively dissolving a reducing agent and a glidant in deionized water to respectively obtain a reducing agent solution B and a glidant solution C, and placing the glidant solution C in a container of an inclined cavity;
(3) Adjusting the pH value of the shaped silver source solution A to 1-6, and then dispersing and adding the shaped silver source solution A and the reducing agent solution B into the glidant solution C to perform liquid-phase reduction reaction in an ultrasonic dispersion environment through a point screen type dispersing device while rotating; the point screen type dispersing device comprises a solution cavity and a plurality of hollow dispersing guide pipes; one end of the hollow dispersion conduit is communicated with the bottom of the solution cavity; the mass concentration of the reducing agent in the glidant solution C is 25-35 g/L; the glidant comprises at least one of polyethylene glycol laurate and sorbitan fatty acid ester;
(4) And after the liquid phase reduction reaction is finished, sequentially carrying out vacuum filtration, centrifugation, washing, drying, crushing and grinding treatment on the turbid liquid obtained after the reaction to obtain the strong-fluidity micro silver particles.
2. The method of making high mobility micro silver particles of claim 1, wherein the silver source comprises silver nitrate; the excipient comprises at least one of sorbitol and polyethylene glycol.
3. The method of making high fluidity micro silver particles of claim 1, wherein the reducing agent comprises at least one of ferrous sulfate heptahydrate, hydroquinone, sodium citrate, ascorbic acid, glucose.
4. The method for preparing high-fluidity micro silver particles according to claim 1, wherein the inclination of the container of the inclined cavity in the step (2) is 20-60 °.
5. The method for preparing highly mobile micro silver particles according to claim 1, wherein the pH-adjusted shaped silver source solution a and the reducing agent solution B are introduced into the solution chamber when added to the screen-type dispersing device, and then simultaneously flow out of the connected dispersing tube into the glidant solution C.
6. The method for preparing the high-fluidity micro-silver particles according to any one of claims 1 to 5, wherein the solution cavity is a cylindrical cavity with an open top; the hollow dispersion pipes are fixed at the bottom of the solution cavity in a central symmetry mode, and the hollow dispersion pipes are mutually parallel.
7. The method of preparing high fluidity micro silver particles according to claim 6, wherein the space between the hollow dispersion pipes is 3cm, and the ratio of the length of the hollow dispersion pipes to the inner diameter of the solution chamber is 2:1.
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