CN114210965A - Metallic silver and preparation method and application thereof - Google Patents
Metallic silver and preparation method and application thereof Download PDFInfo
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- CN114210965A CN114210965A CN202111401475.8A CN202111401475A CN114210965A CN 114210965 A CN114210965 A CN 114210965A CN 202111401475 A CN202111401475 A CN 202111401475A CN 114210965 A CN114210965 A CN 114210965A
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 233
- 239000004332 silver Substances 0.000 title claims abstract description 233
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 217
- 238000006243 chemical reaction Methods 0.000 claims abstract description 113
- 239000002245 particle Substances 0.000 claims abstract description 59
- 238000009826 distribution Methods 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 201
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 45
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 45
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 238000005303 weighing Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- -1 silver ions Chemical class 0.000 claims description 18
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 11
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 11
- 229940068041 phytic acid Drugs 0.000 claims description 11
- 235000002949 phytic acid Nutrition 0.000 claims description 11
- 239000000467 phytic acid Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 39
- 238000003756 stirring Methods 0.000 description 28
- 238000010586 diagram Methods 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- 230000002572 peristaltic effect Effects 0.000 description 10
- 238000005086 pumping Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 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
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses metallic silver and a preparation method and application thereof, belonging to the technical field of material synthesis; the metallic silver provided by the invention is powder, and D thereof50＝0.906‑2.960μm，D10≥0.612μm，D90Less than or equal to 4.723 mu m, and the particle size distribution coefficient P ═ D90‑D10)/D50Less than or equal to 1.003; the preparation method comprises the steps of adding reducing liquid into the circulating reaction liquid from the top of the reaction kettle at a constant speed to obtain a metal silver suspension; then, carrying out solid-liquid separation on the metallic silver suspension to obtain metallic silver; the circulating direction of the circulating reaction liquid is that the circulating reaction liquid flows out from the bottom of the reaction kettle and then flows in from the top of the reaction kettle; the adding or inflow angle of the reducing liquid and the circulating reaction liquid is 30-45 degrees; the preparation method provided by the invention is simple and suitable for industrial production, and the metal silver provided by the invention has narrow particle size distribution, high uniformity and capacity ofCan be widely applied to the field of electronic components.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to metallic silver and a preparation method and application thereof.
Background
The principle of preparing metallic silver by chemical liquid phase reduction method is that silver is deposited from silver salt and silver complex aqueous solution in the form of powder by using reducing agent, and then metallic silver is obtained by solid-liquid separation, solid washing and drying. Liquid phase reduction processes have significant advantages, such as: the method has the advantages of simple equipment and low preparation cost, the shape and the particle size of the silver powder formed by the metallic silver can be easily controlled by adjusting the technological parameters such as temperature, reaction time, reactant consumption and the like in the reaction process, the technological process is simple, and the prepared metallic silver powder can be widely applied to the field of electronic industry. However, the metal silver prepared by the chemical reduction method is easy to have the problems of poor uniformity of metal silver powder and wide particle size distribution in the placing process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the metallic silver with narrow particle size distribution as well as the preparation method and the application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: metallic silver, which is powder, and D thereof50＝0.906-2.960μm，D10≥0.612μm，D90Less than or equal to 4.723 mu m, and the particle size distribution coefficient P ═ D90-D10)/D50≤1.003。
The technical scheme of the invention provides metal silver which is powdery and has a particle size distribution coefficient P ═ D90-D10)/D50Less than or equal to 1.003, and the metal silver provided by the invention has narrow particle size distribution and high uniformity, so that the metal silver can be widely applied to the field of electronic components.
In addition, the invention also provides a preparation method of the metallic silver, which comprises the following steps: adding the reducing solution into the circulating reaction solution from the top of the reaction kettle at a constant speed to obtain a metal silver suspension; then, carrying out solid-liquid separation on the metallic silver suspension to obtain metallic silver; the circulating direction of the circulating reaction liquid is that the circulating reaction liquid flows out from the bottom of the reaction kettle and then flows in from the top of the reaction kettle; the addition or inflow angle of the reducing liquid and the circulating reaction liquid is 30-45 degrees.
The metal silver is prepared by a chemical liquid phase method, in the preparation process, the generation of the metal silver generally comprises two stages, one stage is the formation of a silver nucleus, and the other stage is the growth of the silver nucleus; according to the preparation method of the metallic silver, provided by the invention, the reaction liquid is set to be in a circulation mode from the bottom to the top of the reaction kettle, the angle between the addition of the reducing liquid and the inflow of the reaction liquid is controlled to be 30-45 degrees, and the feeding position is arranged in front of the stirring direction, so that the mass transfer and heat transfer properties in the reaction process can be well improved; the technical scheme provided by the invention can solve the problem that the difference of the metal silver particle size distribution is large due to the fact that the forming rate of upper and lower silver nuclei in non-circulating reaction liquid is not consistent or the forming rate of local silver nuclei is too high due to too much local reducing liquid in the reaction liquid on one hand, and can solve the problem that the growth of the silver nuclei is not uniform due to the fact that the fluidity of the bottom of the reaction liquid is poor due to the fact that the volume of the reaction liquid is increased and the viscosity of the reaction liquid is increased at the later stage on the other hand; the preparation method provided by the invention can balance the reaction rates of the reaction solution with different heights, can avoid the problem of nonuniform silver nucleus growth caused by excessively high local silver nucleus generation rate of the reaction solution or excessively high viscosity of the reaction solution, and can obtain the metal silver with the particle size distribution coefficient P ═ (D)90-D10)/D50≤1.003。
In a preferred embodiment of the preparation method of the present invention, the reducing solution is an aqueous solution of hydrazine hydrate, wherein the mass concentration of hydrazine hydrate in the reducing solution is 10-20 g/L.
As a preferable embodiment of the preparation method of the present invention, the duration of the uniform addition of the reducing solution is 30 to 60 minutes.
When the mass concentration of the hydrazine hydrate in the reducing solution is within the range, on one hand, the local reducing solution concentration can not be too high when the reducing solution is mixed with the reaction solution, so that the problem of too high instantaneous formation rate of silver nuclei is avoided, and on the other hand, the reducing solution has enough capacity to form the silver nuclei when being mixed with the reaction solution, so that the problem of low production efficiency of the metallic silver is avoided.
In a preferred embodiment of the preparation method of the present invention, the recycled reaction solution is a reduction solution and is obtained by reacting with a silver solution.
As a preferred embodiment of the preparation method of the present invention, the temperature of the silver solution is 30 to 40 ℃.
When the temperature of the silver solution is in the range, the problem of too high reaction rate due to too high temperature can be avoided, and the solute in the silver solution can be ensured to have better dissolution rate and not be separated out.
As a preferred embodiment of the preparation method of the present invention, the preparation method of the silver solution includes the steps of: weighing silver nitrate, a pH regulator and a surfactant, and dissolving in water to obtain a silver solution.
As a preferable embodiment of the preparation method, the mass concentration of silver ions formed by dissociation of the silver nitrate in the silver solution is 10-20 g/L.
When the concentration of the silver ions is in the range, the silver ions and the subsequently generated metallic silver can be ensured to have proper concentration in a solution system, and the problem of overlarge particle size caused by overhigh concentration or the problem of overlarge particle size caused by overlow concentration is avoided, so that the prepared metallic silver D50Between 0.906 and 2.960 μm.
As a preferred embodiment of the preparation method of the present invention, the pH adjusting agent includes at least one of sodium carbonate, sodium hydroxide, or ammonia water.
As a preferred embodiment of the preparation method of the present invention, the pH of the silver solution is 10 to 14.
When the pH value of the silver solution is in the range, the pH value of the system can be ensured to be favorable for the reduction reaction, and meanwhile, the pH value is set to be 10-14, so that a large number of generated silver nuclei can be agglomerated and grown to form a spherical structure, and the uniformity of particle size distribution is increased.
As a preferred embodiment of the preparation method of the present invention, the surfactant includes at least one of starch, polyvinyl alcohol, phytic acid, or gelatin.
The components have good dispersibility in water, and when the components are used as a surfactant for preparing metal silver by a chemical reduction method, the good dispersibility of the components can protect silver particles formed at an early stage, slow down the production rate of the silver particles, avoid the problem of wide particle size distribution range caused by excessive growth of the silver particles, and also can ensure that the generated metal silver D is50Between 0.906 and 2.960 μm.
In addition, the invention also provides application of the metallic silver in manufacturing electronic components.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the method comprises the following steps: the technical scheme of the invention provides metal silver which is powdery and has a particle size distribution coefficient P ═ D90-D10)/D50Less than or equal to 1.003, and the metal silver provided by the invention has narrow particle size distribution and high uniformity, so that the metal silver can be widely applied to the field of electronic components;
secondly, the method comprises the following steps: according to the preparation method of the metallic silver, provided by the invention, the reaction liquid is set to be in a circulation mode from the bottom to the top of the reaction kettle, the angle between the addition of the reducing liquid and the inflow of the reaction liquid is controlled to be 30-45 degrees, and the feeding position is arranged in front of the stirring direction, so that the mass transfer and heat transfer properties in the reaction process can be well improved, and the prepared metallic silver is narrow and uniform in particle size distribution;
thirdly, the method comprises the following steps: the preparation method of the metal silver provided by the invention is simple and is suitable for industrial production.
Drawings
FIG. 1: the preparation method of the invention uses the reaction device front schematic diagram;
FIG. 2: the reaction device used in the preparation method of the invention is a schematic plan view;
FIG. 3: a: SEM image of metallic silver prepared in example 1, B: particle size distribution diagram of metallic silver prepared in example 1;
FIG. 4: a: SEM image of metallic silver prepared in example 2, B: particle size distribution diagram of metallic silver prepared in example 2;
FIG. 5: a: SEM image of metallic silver prepared in example 3, B: particle size distribution diagram of metallic silver prepared in example 3;
FIG. 6: a: SEM image of metallic silver prepared in example 4, B: particle size distribution diagram of metallic silver prepared in example 4;
FIG. 7: a: SEM image of metallic silver prepared in example 5, B: particle size distribution diagram of metallic silver prepared in example 5;
FIG. 8: a: SEM image of metallic silver prepared in comparative example 1, B: the particle size distribution diagram of the metallic silver prepared in comparative example 1;
FIG. 9: a: SEM image of metallic silver prepared in comparative example 2, B: the particle size distribution diagram of the metallic silver prepared in comparative example 2;
FIG. 10: a: SEM image of metallic silver prepared in comparative example 3, B: the particle size distribution diagram of the metallic silver prepared in comparative example 3.
FIG. 11: a: SEM image of metallic silver prepared in comparative example 4, B: the particle size distribution diagram of the metallic silver prepared in comparative example 4;
FIG. 12: a: SEM image of metallic silver prepared in comparative example 5, B: the particle size distribution diagram of the metallic silver prepared in comparative example 5;
FIG. 13: a: SEM image of metallic silver prepared in comparative example 6, B: the particle size distribution diagram of the metallic silver prepared in comparative example 6.
FIG. 14: a: SEM image of metallic silver prepared in comparative example 7, B: the particle size distribution diagram of the metallic silver prepared in comparative example 7;
FIG. 15: a: SEM image of metallic silver prepared in comparative example 8, B: the particle size distribution diagram of the metallic silver prepared in comparative example 8.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The preparation steps of the examples and the comparative examples of the invention all adopt the reaction device shown in figure 1 to carry out the reaction; the reagents used in the examples of the present invention and comparative examples were obtained from conventional commercial sources unless otherwise specified.
Example 1
The preparation method of the metal silver of the embodiment of the invention comprises the following steps:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26% and 0.5g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 10.0g/L, and the pH value of the silver solution is 10;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 1.28L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 10.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 30 degrees, and keeping stirring reaction in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝0.997。
Example 2
The preparation method of the metal silver of the embodiment of the invention comprises the following steps:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26%, 12g of sodium hydroxide and 0.5g of polyvinyl alcohol, and dissolving in 3.3L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 15.2g/L, and the pH value of the silver solution is 14;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 0.85L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 15.1 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 35 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 45 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 30 degrees, and keeping stirring reaction in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝1.003。
Example 3
The preparation method of the metal silver of the embodiment of the invention comprises the following steps:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26%, 15g of sodium hydroxide, 0.2g of polyvinyl alcohol and 0.3g of gelatin, and dissolving in 2.5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 20.0g/L, and the pH value of the silver solution is 14;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 0.64L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 20.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 40 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 60 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 30 degrees, and the stirring reaction is kept in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝0.678。
Example 4
The preparation method of the metal silver of the embodiment of the invention comprises the following steps:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26% and 0.5g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 10.0g/L, and the pH value of the silver solution is 10;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 1.28L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 10.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 45 degrees, and the stirring reaction is kept in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝0.990。
Example 5
The preparation method of the metal silver of the embodiment of the invention comprises the following steps:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26% and 0.5g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 10.0g/L, and the pH value of the silver solution is 10;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 1.28L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 10.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 38 degrees, and keeping stirring reaction in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝0.969。
Comparative example 1
The preparation method of the metallic silver of the comparative example of the present invention is as follows:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26% and 0.5g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 10.0g/L, and the pH value of the silver solution is 10;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 1.28L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 10.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, uniformly dropwise adding a reducing solution into a circulating solution, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the cyclic adding of a reaction solution is 30 degrees, and the stirring reaction is kept in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝1.319。
Comparative example 2
The preparation method of the metallic silver of the comparative example of the present invention is as follows:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26%, 12g of sodium hydroxide and 0.5g of polyvinyl alcohol, and dissolving in 3.3L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 15.2g/L, and the pH value of the silver solution is 14;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 0.85L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 15.1 g/L;
(3) adding the silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 35 ℃, uniformly dropwise adding the reducing solution into the circulating solution, wherein the dropwise adding time is 45 minutes, the angle between the dropwise adding of the reducing solution and the cyclic adding of the reaction solution is 30 degrees, and the stirring reaction is kept in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝1.304。
Comparative example 3
The preparation method of the metallic silver of the comparative example of the present invention is as follows:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26%, 15g of sodium hydroxide, 0.2g of polyvinyl alcohol and 0.3g of gelatin, and dissolving in 2.5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 20.0g/L, and the pH value of the silver solution is 14;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 0.64L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 20.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 40 ℃, uniformly dropwise adding a reducing solution into a circulating solution, wherein the dropwise adding time is 60 minutes, the angle between the dropwise adding of the reducing solution and the cyclic adding of a reaction solution is 30 degrees, and stirring and reacting are kept in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝0.945。
Comparative example 4
The preparation method of the metallic silver of the comparative example of the present invention is as follows:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26% and 0.5g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 10.0g/L, and the pH value of the silver solution is 10;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 1.28L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 10.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 75 degrees, and the stirring reaction is kept in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝1.237。
Comparative example 5
The preparation method of the metallic silver of the comparative example of the present invention is as follows:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26% and 0.5g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 10.0g/L, and the pH value of the silver solution is 10;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 1.28L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 10.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 10 degrees, and keeping stirring reaction in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝1.195。
Comparative example 6
The preparation method of the metallic silver of the comparative example of the present invention is as follows:
(1) weighing 78.8g of silver nitrate, 100g of ammonia water with the mass fraction of 26% and 0.5g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 10.0g/L, and the pH value of the silver solution is 8;
(2) weighing 16g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 1.28L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 10.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 30 degrees, and keeping stirring reaction in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝1.279。
Comparative example 7
The preparation method of the metallic silver of the comparative example of the present invention is as follows:
(1) weighing 170.0g of silver nitrate, 252g of ammonia water with the mass fraction of 26% and 1.0g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 21.6g/L, and the pH value of the silver solution is 10;
(2) weighing 34.56g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the hydrazine hydrate in 2.76L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 10.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 30 degrees, and keeping stirring reaction in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metal silver with the particle size distribution coefficient P ═ D90-D10)/D50＝1.201。
Comparative example 8
The preparation method of the metallic silver of the comparative example of the present invention is as follows:
(1) weighing 78.8g of silver nitrate, 126g of ammonia water with the mass fraction of 26% and 0.5g of phytic acid, and dissolving in 5L of pure water to obtain a silver solution, wherein the mass concentration of silver ions in the silver solution is 10.0g/L, and the pH value of the silver solution is 10;
(2) weighing 48g of hydrazine hydrate with the mass fraction of 80 percent, and dissolving the 48g of hydrazine hydrate in 1.28L of pure water to obtain reducing solution, wherein the mass concentration of the hydrazine hydrate in the reducing solution is 30.0 g/L;
(3) adding a silver solution into a reaction device, stirring, maintaining the temperature of the reaction device at 30 ℃, pumping the silver solution from the bottom of the reaction by using a peristaltic pump, adding the silver solution from the top of the reaction device, uniformly dropwise adding a reducing solution into a circulating solution after the silver solution forms stable up-and-down circulation, wherein the dropwise adding time is 30 minutes, the angle between the dropwise adding of the reducing solution and the circulating addition of the reaction solution is 30 degrees, and keeping stirring reaction in the dropwise adding process;
(4) after the reaction is finished, standing for precipitation, and carrying out solid-liquid separation to obtain the metallic silver with the particle size distribution coefficient P ═(D90-D10)/D50＝1.661。
Examples of effects
The metallic silver prepared in examples 1 to 5 and comparative examples 1 to 8 was observed and recorded under a scanning electron microscope while the particle size distribution thereof was measured, and as can be seen from fig. 3 to 7 provided in examples 1 to 5, when the technical solutions adopted were within the range given in the present invention, the prepared metallic silver was spherical and the particle size distribution coefficient P was (D) as90-D10)/D50Less than or equal to 1.003; as can be seen from fig. 3 to 5 and fig. 8 to 10 provided in examples 1 to 3 and comparative examples 1 to 3, the particle size distribution coefficient P ═ D (D) of the metallic silver prepared when the cyclic feeding was not employed90-D10)/D50The corresponding general ratio is larger than that of the examples 1-3, and the increase range is 22.0-28.0%, which shows that the particle size distribution uniformity can be obviously improved by adopting the circulating liquid adding and the control of the charging angle of the invention;
as can be seen from fig. 3 and fig. 11 and 12 provided in example 1 and comparative examples 4 and 5, when the angle of addition was changed, whether the angle was increased or decreased, the particle size distribution coefficient P of the metallic silver obtained was (D ═ D)90-D10)/D50The particle size uniformity of the prepared metal silver is influenced by the angle;
as can be seen from fig. 3 and 13 provided in example 1 and comparative example 6, when the pH of the system is lowered, some of the prepared metallic silver is not spherical, and it is apparent from the figure that the size of the formed metallic silver is greatly different, i.e. the particle size distribution range of the formed metallic silver is wide;
as can be seen from fig. 3 and fig. 14 and 15 provided in example 1 and comparative examples 7 and 8, when the concentration of silver ions is increased, the metallic silver particles are made to be irregularly spherical and become large in particle size, and the particle size distribution range is widened; when the concentration of hydrazine hydrate is increased, the metal silver particles are also in an irregular sphere shape similar to shrinkage, the size distribution is extremely uneven, and the particle size distribution value is increased.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit 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 modifications and equivalent substitutions can be made to 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. The metallic silver is characterized in that the metallic silver is powder, and D is50＝0.906-2.960μm，D10≥0.612μm，D90Less than or equal to 4.723 mu m, and the particle size distribution coefficient P ═ D90-D10)/D50≤1.003。
2. The method of preparing metallic silver according to claim 1, comprising the steps of: adding the reducing solution into the circulating reaction solution from the top of the reaction kettle at a constant speed to obtain a metal silver suspension; then, carrying out solid-liquid separation on the metallic silver suspension to obtain metallic silver;
the circulating direction of the circulating reaction liquid is that the circulating reaction liquid flows out from the bottom of the reaction kettle and then flows in from the top of the reaction kettle;
the addition or inflow angle of the reducing liquid and the circulating reaction liquid is 30-45 degrees.
3. The preparation method according to claim 2, characterized in that the reducing solution is an aqueous solution of hydrazine hydrate, and the mass concentration of the hydrazine hydrate in the reducing solution is 10-20 g/L.
4. The preparation method according to claim 2, wherein the circulating reaction solution is obtained by reacting a reducing solution with a silver solution.
5. The method for preparing a silver solution according to claim 4, comprising the steps of: weighing silver nitrate, a pH regulator and a surfactant, and dissolving in water to obtain a silver solution.
6. The preparation method according to claim 5, wherein the mass concentration of silver ions formed by dissociation of the silver nitrate in the silver solution is 10-20 g/L.
7. The method of claim 5, wherein the pH adjuster comprises at least one of sodium carbonate, sodium hydroxide, or ammonia water.
8. The method according to claim 5, wherein the silver solution has a pH of 10 to 14.
9. The method of claim 5, wherein the surfactant comprises at least one of starch, polyvinyl alcohol, phytic acid, or gelatin.
10. Use of metallic silver according to claim 1 for the production of electronic components.
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| CN115464132A (en) * | 2022-08-18 | 2022-12-13 | 太原理工大学 | Controllable preparation method of phytate-coated silver nanoparticles |
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