CN113941711A - 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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- CN113941711A CN113941711A CN202111148544.9A CN202111148544A CN113941711A CN 113941711 A CN113941711 A CN 113941711A CN 202111148544 A CN202111148544 A CN 202111148544A CN 113941711 A CN113941711 A CN 113941711A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 99
- 239000004332 silver Substances 0.000 title claims abstract description 99
- 239000002245 particle Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 31
- 239000007791 liquid phase Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims description 25
- 238000006722 reduction reaction Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-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
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 8
- 239000011859 microparticle Substances 0.000 claims description 7
- 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
- -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
- 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 2
- 229940070765 laurate Drugs 0.000 claims description 2
- 238000010979 pH adjustment 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 1
- 239000000243 solution Substances 0.000 abstract description 95
- 239000013078 crystal Substances 0.000 abstract description 12
- 238000005054 agglomeration Methods 0.000 abstract description 10
- 230000002776 aggregation Effects 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 9
- 239000000843 powder Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 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 13
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000001000 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
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010900 secondary nucleation Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time 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
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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 crystal grain agglomeration of the silver powder in the traditional preparation method during liquid phase reaction, and simultaneously, the solution does not need 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 flow aid is used for replacing a dispersing agent in the traditional liquid phase reaction, so that the problem of subsequent silver powder cleaning residue is effectively avoided, the effects of dispersing the silver powder and improving the surface property of particles are achieved, gas in the silver particles can be preferentially adsorbed, and finally the prepared product is high in tap density and strong in flowability. The invention also discloses a point sieve type dispersing device for preparing the high-fluidity micron particles, which can effectively and synchronously add the shaped silver source solution and the reducing agent solution into the flow aid solution, improve the uniformity of the mixed solution and solve the problem of agglomeration of silver particle grains.
Description
Technical Field
The invention relates to the technical field of powder materials, in particular to a method and a device for preparing high-fluidity micron silver particles.
Background
In the prior art, the principle of preparing silver powder by a liquid phase reduction method is that silver is deposited in a powder form from a silver salt, a silver complex aqueous solution or an organic system by using a reducing agent, and the method has the following advantages: the equipment requirement is low, the preparation cost is low, the morphology and the particle size of the silver powder can be easily controlled by adjusting the technological parameters such as temperature, reaction time, reactant consumption and the like in the reaction process, and the technological process is simple. 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, secondary agglomeration can be caused when the reaction rate is too high, the agglomeration is serious, the dispersity is reduced, the shape is irregular, the shape is uneven and the like when the reaction rate is too low, and parameters need to be strictly controlled; in addition, the silver powder prepared at present can form a large number of pores after being solidified into a film due to poor fluidity and contact property in the sintering process, so that the problems of poor sintering compactness, large sheet resistance of a solidified film layer and the like are brought, and the application effect of the conductive paste is directly influenced.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide the preparation method of the high-fluidity micron silver particles, and the silver powder prepared by the preparation method can realize tight packing in the vibration process and can be used for solving the problem that a large number of air holes exist after the silver powder prepared by the prior art is sintered into a film; the preparation method can effectively solve the problem of agglomeration of silver powder crystal grains, can avoid the residue problem in the silver powder cleaning process after liquid phase reaction, and is efficient, simple and convenient.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of high-fluidity micron silver particles comprises the following steps:
(1) dissolving a silver source and an excipient in deionized water to obtain a forming silver source solution A;
(2) respectively dissolving a reducing agent and a flow aid in deionized water to respectively obtain a reducing agent solution B and a flow aid solution C, and placing the flow aid solution C in a container with an inclined cavity;
(3) adjusting the pH value of the shaped silver source solution A to 1-6, then adding the shaped silver source solution A and the reducing agent solution B into the flow aid solution C in a dispersing manner while rotating through a point-sieve type dispersing device under an ultrasonic dispersing environment, and carrying out liquid phase reduction reaction;
(4) and after the liquid phase reduction reaction is finished, sequentially carrying out vacuum filtration, centrifugation, washing, drying, crushing and grinding on turbid liquid obtained after the reaction to obtain the high-fluidity micron silver particles.
In the preparation method of the high-fluidity micron silver particles, a silver source and a reducing agent solution are uniformly dispersed in a flow aid solution by using a liquid adding mode of adding while rotating a point sieve type dispersing device, so that the probability that the solution in unit volume exceeds an energy barrier to form crystal nuclei is the same, and the problem of crystal grain agglomeration during liquid phase reaction of silver powder is further 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, the solution is not required to be mixed in a stirring mode like the traditional liquid phase reaction, secondary nucleation caused by stirring can be avoided, and the defect of larger crystal particles cannot be formed. According to the preparation method, the flow aid is used for replacing a dispersing agent in the traditional liquid phase reaction, so that the problem of subsequent silver powder cleaning residue is effectively avoided, the effects of dispersing the silver powder and improving the surface property of particles are achieved, gas in the silver particles can be preferentially adsorbed, a large number of air holes are prevented from being formed in the sintering process, and finally the prepared product is high in tap density and strong in flowability.
Preferably, the molar concentration of the silver source in the shaped 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 in the proportion can adjust the stability of the silver source in the subsequent reaction process to the maximum extent, and ensure that the generated sphere-like 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 and 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 flow aid not only plays a role of a dispersing agent in liquid phase reaction, but also fully wraps and modifies the surface of the silver particles by the flow aid after the flow aid and the generated silver particles are uniformly mixed, so that gas in the silver particles can be effectively absorbed, and the quality of the silver particles is improved. When the content of the flow aid is too low, the flow aid has poor modification effect on the silver particles, and can cause the silver particles to agglomerate due to insufficient dispersion in the generation process; if the content of the glidant is too high, the particle size of the prepared silver particles is too large, and the tap density becomes smaller.
More preferably, the glidant comprises at least one of polyethylene glycol laurate and sorbitan fatty acid esters.
Preferably, the inclination of the container of the inclined cavity in the step (2) is 20-60 degrees.
Preferably, the temperature during the liquid phase reduction reaction is 10-60 ℃.
Preferably, the dot-sieve 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 shaped silver source solution a and the reducing agent solution B after the pH adjustment are firstly placed in the solution cavity and then synchronously flow out of the communicated dispersing pipes into the flow aid solution C when added into the dot-sieve type dispersing device.
Due to the design of the dot sieve type dispersing device, after the shaped silver source solution A and the reducing agent solution B are placed in the solution cavity, the shaped silver source solution A and the reducing agent solution B flow into the glidant solution C through the plurality of dispersing pipes in a rotating mode, so that the dispersing and mixing of all components can be effectively realized, the excipient, the silver source and the reducing agent can also be effectively dispersed in a glidant system, the probability that the solution crosses an energy barrier to form crystal nuclei is the same, and the problem of grain agglomeration is solved.
Another object of the present invention is to provide a dot sieve type dispersing apparatus for preparing high-flowability microparticles, said apparatus comprising a solution chamber (1) and a plurality of hollow dispersing 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 ducts are fixed at the bottom of the solution chamber in a centrosymmetric manner, and the hollow dispersion ducts are parallel to each other.
More preferably, the distance between the hollow dispersion conduits is 3cm, and the ratio of the length of the hollow dispersion conduits to the inner diameter of the solution chamber is 2: 1.
When the device is used for preparing the high-fluidity micron particles, the device can be used as a sample adding device to synchronously add the shaped silver source solution and the reducing agent solution into the flow aid solution, so that the uniformity of the mixed solution is improved, and the problem of agglomeration of silver particle grains is solved.
The preparation method of the micron silver particles with the strong fluidity has the beneficial effects that the method can effectively solve the problem of crystal grain agglomeration of the silver powder in the traditional preparation method during liquid phase reaction, and simultaneously, the solution does not need to be mixed in a stirring mode before the liquid phase reaction, so that the defects that secondary nucleation is caused by stirring, and then larger crystal particles cannot be formed can be avoided. According to the preparation method, the flow aid is used for replacing a dispersing agent in the traditional liquid phase reaction, so that the problem of subsequent silver powder cleaning residue is effectively avoided, the effects of dispersing the silver powder and improving the surface property of particles are achieved, gas in the silver particles can be preferentially adsorbed, a large number of air holes are prevented from being formed in the sintering process, and finally the prepared product is high in tap density and strong in flowability. Compared with a sample adding device in the traditional silver particle preparation process, the device can effectively and synchronously add the shaped silver source solution and the reducing agent solution into the flow aid solution, improve the uniformity of the mixed solution and solve the problem of agglomeration of silver particle grains.
Drawings
FIG. 1 is a schematic view (left) and a top view (right) of a dot screen type dispersing apparatus according to the present invention; the device comprises a solution cavity 1 and a plurality of hollow dispersion conduits 2;
FIG. 2 is an SEM electron microscope image of micron silver particles prepared by the preparation method described in example 1 of the invention;
FIG. 3 is an SEM electron microscope image of micron silver particles prepared by the preparation method described in example 2 of the invention;
FIG. 4 is an SEM electron microscope image of micron silver particles prepared by the preparation method described in example 3 of the invention;
fig. 5 is an SEM electron micrograph of the micro silver particles prepared according to the preparation method described in comparative example 1.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents and instruments designed for the practice of the present invention and the comparative examples 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) dissolving 255g of silver nitrate powder and 1.53g of sorbitol in 1000mL of deionized water, and fully stirring to obtain a forming silver source solution A;
(2) respectively dissolving 60g of hydroquinone white crystal and 26g of polyethylene glycol monthly silicate in 500mL of deionized water and 1000mL of deionized water at the temperature of 20 ℃ to respectively obtain a reducing agent solution B and a flow aid solution C, and placing the flow aid solution C in a container with an inclined cavity (the inclination is 40 ℃);
(3) adjusting the pH value of the shaped silver source solution A to 3 by using dilute nitric acid (the adjusting process is maintained at about 20 ℃), then adding the shaped silver source solution A and the reducing agent solution B into the flow aid solution C in a point-sieve type dispersing device to perform liquid phase reduction reaction in an ultrasonic dispersing environment at 20 ℃ while rotating;
(4) and 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, putting the turbid liquid into a centrifugal tube containing absolute ethyl alcohol, centrifuging for 3-4 times, washing, drying in an oven at 60 ℃ for 6-8 h, crushing and grinding to obtain the high-fluidity micron silver particles.
The structural schematic diagram of the point-sieve type dispersing device is shown in figure 1, and the device comprises a solution cavity (1) and a plurality of hollow dispersing conduits (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 conduits are fixed at the bottom of the solution cavity in a centrosymmetric mode and are parallel to each other.
Scanning electron microscope observation is carried out on the micron silver particles obtained in the embodiment, as shown in fig. 2, the silver particles are uniformly dispersed and are similar to spheres in shape, the particle size is about 2-3 microns, and no obvious impurity exists 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 forming silver source solution A;
(2) respectively dissolving 60g of hydroquinone white crystal and 30g of polyethylene glycol monthly silicate in 500mL of deionized water and 1000mL of deionized water at the temperature of 20 ℃ to respectively obtain a reducing agent solution B and a flow aid solution C, and placing the flow aid solution C in a container with an inclined cavity (the inclination is 35 ℃);
(3) adjusting the pH value of the shaped silver source solution A to 4 by using dilute nitric acid (the adjusting process is maintained at about 20 ℃), then adding the shaped silver source solution A and the reducing agent solution B into the flow aid solution C in a point-sieve type dispersing device to perform liquid phase reduction reaction in an ultrasonic dispersing environment at 20 ℃ while rotating;
(4) and 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, putting the turbid liquid into a centrifugal tube containing absolute ethyl alcohol, centrifuging for 3-4 times, washing, drying in an oven at 60 ℃ for 6-8 h, crushing and grinding to obtain the high-fluidity micron silver particles.
The point screen type dispersing apparatus was the same as in example 1.
The micron silver particles obtained in the embodiment are observed by a scanning electron microscope, and as shown in fig. 3, similar to the product of the embodiment 1, the silver particles have uniform size and uniform dispersion, and are in a sphere-like shape as a whole.
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 forming silver source solution A;
(2) respectively dissolving 60g of hydroquinone white crystal and 30g of polyethylene glycol monthly silicate in 500mL of deionized water and 1000mL of deionized water at 25 ℃ to respectively obtain a reducing agent solution B and a flow aid solution C, and placing the flow aid solution C in a container with an inclined cavity (the inclination is 35 ℃);
(3) adjusting the pH value of the shaped silver source solution A to 4.2 by using dilute nitric acid (the adjusting process is maintained at about 25 ℃), then adding the shaped silver source solution A and the reducing agent solution B into the flow aid solution C in a dispersing manner while rotating through a point-sieve type dispersing device at 25 ℃ under an ultrasonic dispersing environment, and carrying out liquid phase reduction reaction;
(4) and 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, putting the turbid liquid into a centrifugal tube containing absolute ethyl alcohol, centrifuging for 3-4 times, washing, drying in an oven at 60 ℃ for 6-8 h, crushing and grinding to obtain the high-fluidity micron silver particles.
The point screen type dispersing apparatus was the same as in example 1.
When the micron silver particles obtained in this example are observed by a scanning electron microscope, as shown in fig. 4, similar to the products of examples 1 and 2, the silver particles are all sphere-like and uniform in size, but the surface roughness is slightly increased.
Example 4
The invention relates to a preparation method of high-fluidity micron silver particles, which comprises the following steps:
(1) dissolving 340g of silver nitrate powder and 2g of sorbitol in 1000mL of deionized water, and fully stirring to obtain a forming silver source solution A;
(2) at the temperature of 20 ℃, 278g of p-heptahydrate ferrous sulfate and 35g of sorbitan fatty acid ester are respectively dissolved in 500mL of deionized water and 1000mL of deionized water to respectively obtain a reducing agent solution B and a flow aid solution C, and the flow aid solution C is placed in a container with an inclined cavity (the inclination is 45 ℃);
(3) adjusting the pH value of the shaped silver source solution A to 5 by using dilute nitric acid (the adjusting process is maintained at about 30 ℃), then adding the shaped silver source solution A and the reducing agent solution B into the flow aid solution C in a point-sieve type dispersing device to perform liquid phase reduction reaction in an ultrasonic dispersing environment at 20 ℃ while rotating;
(4) and 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, putting the turbid liquid into a centrifugal tube containing absolute ethyl alcohol, centrifuging for 3-4 times, washing, drying in an oven at 60 ℃ for 6-8 h, crushing and grinding to obtain the high-fluidity micron silver particles.
The point screen type dispersing apparatus was the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that the step (3) is replaced by: the pH value of the shaped silver source solution A is adjusted to 3 by dilute nitric acid (the adjusting 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 flow aid solution C for liquid phase reduction reaction at 20 ℃ under the ultrasonic dispersion environment.
The micron silver particles obtained in the comparative example are observed by a scanning electron microscope, and as shown in fig. 5, the silver particles prepared by adopting a direct dispersion sample adding mode have irregular (between flower shape and spherical shape) appearance, the surface roughness is increased, meanwhile, the density between the particles is insufficient, and the particle size is also increased to 4-6 microns.
Comparative example 2
This comparative example differs from example 2 only in that the step (3) is replaced by: the pH value of the shaped silver source solution A is adjusted to 4 by dilute nitric acid (the adjusting 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 flow aid solution C for liquid phase reduction reaction at 20 ℃ under the ultrasonic dispersion environment.
Comparative example 3
The comparative example differs from example 1 only in that the flow aid solution C described in step (2) was placed in a common flat-bottomed vessel in which the subsequent liquid phase reduction reaction was also carried out.
Effect example 1
In order to verify the performance of the product prepared by the method and the device for preparing the high-fluidity micron silver particles, the products obtained in the examples and the comparative examples are measured, and the tap density, the angle of repose and the degree of compression of the products are respectively detected; wherein the degree of compression is defined as (ρ 2- ρ 1)/ρ 2, and ρ 1 and ρ 2 are the bulk density and tap density, respectively, of the prepared silver particles, and the angle of repose is the maximum angle that the free surface of the silver particles naturally piled up forms with the horizontal plane in a static equilibrium state. Under the same conditions, the smaller the angle of repose and the compressibility value, the better the flowability 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 silver microparticles obtained in examples 1 to 4 are all 6g/cm3Above, the angle of repose is below 45 ° and the degree of compression is below 0.4 °, which indicates that the product prepared by the method for preparing the high-fluidity micro silver particles of the invention has excellent fluidity and tap density. In contrast, the tap density of the products obtained in comparative examples 1 to 3 was lower, and the flowability was also significantly lower than that of the products obtained in examples 1 to 4.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of high-fluidity micron silver particles is characterized by comprising the following steps:
(1) dissolving a silver source and an excipient in deionized water to obtain a forming silver source solution A;
(2) respectively dissolving a reducing agent and a flow aid in deionized water to respectively obtain a reducing agent solution B and a flow aid solution C, and placing the flow aid solution C in a container with an inclined cavity;
(3) adjusting the pH value of the shaped silver source solution A to 1-6, then adding the shaped silver source solution A and the reducing agent solution B into the flow aid solution C in a dispersing manner while rotating through a point-sieve type dispersing device under an ultrasonic dispersing environment, and carrying out liquid phase reduction reaction;
(4) and after the liquid phase reduction reaction is finished, sequentially carrying out vacuum filtration, centrifugation, washing, drying, crushing and grinding on turbid liquid obtained after the reaction to obtain the high-fluidity micron silver particles.
2. The method for preparing high-fluidity micron silver particles according to claim 1, wherein the molar concentration of the silver source in the shaped silver source solution A is 0.4-2 mol/L, and the molar concentration of the excipient is 0.008-0.012 mol/L.
3. The method of making high flow silver microparticles of claim 2 wherein the silver source comprises silver nitrate; the excipient comprises at least one of sorbitol and polyethylene glycol.
4. The method of preparing high-flowability silver microparticles as claimed in claim 1, wherein the reducing agent includes at least one of ferrous sulfate heptahydrate, hydroquinone, sodium citrate, ascorbic acid, and glucose.
5. The preparation method of the high-fluidity micron silver particles as claimed in claim 1, wherein 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.
6. 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 ° to 60 °.
7. The method for preparing high-fluidity micron silver particles according to claim 1, wherein the dot-sieve type dispersing device comprises a solution cavity, a plurality of dispersing pipes communicated with the solution cavity are arranged at the lower end of the solution cavity, and the forming silver source solution A and the reducing agent solution B after the pH adjustment are firstly placed into the solution cavity and then synchronously flow out of the communicated dispersing pipes into the flow aid solution C when being added into the dot-sieve type dispersing device.
8. A dot-screen dispersing device for preparing high-flowability microparticles, which is characterized by comprising a solution cavity and a plurality of hollow dispersing conduits; one end of the hollow dispersion conduit is communicated with the bottom of the solution cavity.
9. The dot sieve type dispersing apparatus for preparing high-flowability microparticles as claimed in claim 8, wherein said solution chamber is a cylindrical chamber with an open top; the hollow dispersion conduits are fixed at the bottom of the solution cavity in a centrosymmetric mode and are parallel to each other.
10. A dot sieve type dispersing apparatus for preparing microparticles with strong flowability as claimed in claim 9, wherein the interval between the hollow dispersing conduits is 3cm, and the ratio of the length of the hollow dispersing conduit to the inner diameter of the solution chamber is 2: 1.
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