CN111992734B - Preparation method of nano-silver with controllable particle size - Google Patents
Preparation method of nano-silver with controllable particle size Download PDFInfo
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- CN111992734B CN111992734B CN202010848330.1A CN202010848330A CN111992734B CN 111992734 B CN111992734 B CN 111992734B CN 202010848330 A CN202010848330 A CN 202010848330A CN 111992734 B CN111992734 B CN 111992734B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000002245 particle Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 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 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 37
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 26
- 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 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 13
- 239000011668 ascorbic acid Substances 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 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 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 74
- 239000000843 powder Substances 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The application discloses a preparation method of nano silver with controllable particle size, which comprises the following steps: 1) dissolving soluble silver salt in dihydric alcohol to obtain solution A; 2) mixing and dissolving a dispersing agent and a reducing agent in the dihydric alcohol, and adjusting the pH to 2-8 by using a pH regulator to obtain a solution B; 3) adding the solution A into the stirred solution B at the temperature of 100-180 ℃, wherein the feeding rate is 4-10mL/min, and obtaining a solution C; 4) and cooling and separating the solution C to obtain the nano silver. The preparation method adopts a liquid phase reduction method which is nontoxic, pollution-free, low in energy consumption and easy to operate, spherical nano silver with excellent dispersity, controllable and uniform particle size is obtained, and the method is simple, rapid and efficient.
Description
Technical Field
The application relates to a preparation method of nano silver with controllable particle size, belonging to the technical field of nano material preparation.
Background
The metallic silver has excellent physical and chemical properties, such as conductivity, thermal conductivity, strongest reflection characteristic, relatively stable chemical property and the like, and is widely applied to the fields of antibacterial materials, medical materials, electronic paste, decorative materials, catalysts and the like. The nano silver powder has the specific quantum size effect, volume effect, surface effect and the like of the nano material, shows the special effects which are not achieved by the common silver powder in the aspects of antibiosis, medicine, superconduction, optics and the like, and is a novel material with wide application prospect.
The existing preparation method of the nano silver powder can be simply divided into a physical method and a chemical method. Physical methods include ion vapor condensation, vacuum evaporation, sputter plating, ion plating, and the like; the chemical method includes a liquid phase reduction method, a thermal decomposition method, and the like. The physical method needs special equipment and has high and fussy operating condition requirements, large investment, low production efficiency and high difficulty of industrial amplification and industrial application. The liquid phase reduction method is the most thorough and widely applied method in academic circles and industrial circles, and the method is simple to prepare, easy to operate and low in cost. However, the existing liquid phase reduction method still has some defects, such as poor stability and consistency of particle size control, low purity of the produced nano silver, complex and complicated preparation process, low production efficiency, difficult industrial amplification and the like. For example, in patent CN102407342B, a method of seed crystal growth and step-by-step control is adopted to prepare the nano silver powder with controllable particle size, but the process is complicated and takes long time, and the concentration of the precursor for seed crystal growth is low, which results in low production efficiency and is not beneficial to industrial application; in patent CN1557163A, the particle size and the dispersibility of nano-silver are controlled by adding a large amount of surfactant, the process is relatively complex, and the produced silver powder contains a large amount of organic matters, and the silver content is only 60-90%; in patent CN103909273A, a dispersant is dissolved in an alcohol solvent, chloride ions are added, and silver nitrate is added to react at a high temperature to prepare nano silver, but the product is a mixed particle of triangle, polygon and sphere.
Therefore, it is very important to develop a simple, efficient and rapid preparation method of spherical nano silver powder with controllable product particle size and uniform appearance.
Disclosure of Invention
In order to solve the problems, the preparation method of the nano silver with the controllable particle size adopts a liquid phase reduction method which is non-toxic, pollution-free, low in energy consumption and easy to operate, spherical nano silver with excellent dispersibility, controllable and uniform particle size is obtained, and the method is simple, rapid and efficient.
The preparation method of the nano silver with the controllable particle size comprises the following steps:
1) dissolving soluble silver salt in dihydric alcohol to obtain solution A;
2) mixing and dissolving a dispersing agent and a reducing agent in the dihydric alcohol, and adjusting the pH to 2-8 by using a pH regulator to obtain a solution B;
3) adding the solution A into the stirred solution B at the temperature of 100-180 ℃, wherein the feeding rate is 4-10mL/min, and obtaining a solution C;
4) and cooling and separating the solution C to obtain the nano silver.
Optionally, the soluble silver salt is selected from silver nitrate, silver acetate or silver sulfate.
Preferably, the soluble silver salt is silver nitrate.
Optionally, the glycol is ethylene glycol, propylene glycol, butylene glycol, or pentylene glycol.
Preferably, the diol is ethylene glycol, propylene glycol or butylene glycol.
More preferably, the glycol is ethylene glycol.
Optionally, the silver content in the solution a is 5-10%.
Preferably, the silver content in the solution A is 8-10 wt%.
Optionally, the dispersing agent is polyvinylpyrrolidone K10, polyvinylpyrrolidone K30, polyvinylpyrrolidone K90, polyethylene glycol, polyvinyl alcohol or sodium dodecyl benzene sulfonate, the reducing agent is ascorbic acid, glucose, citric acid, sodium borohydride, formaldehyde, hydrazine hydrate, hydroquinone or hydrogen peroxide, and the PH regulator is nitric acid, ammonia water, a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, the dispersing agent is polyvinylpyrrolidone K30 or polyvinyl alcohol, the reducing agent is ascorbic acid, citric acid or glucose, and the pH regulator is nitric acid or ammonia water.
More preferably, the dispersant is polyvinylpyrrolidone K30 and the reducing agent is ascorbic acid.
Optionally, the mass of the dihydric alcohol in the solution B is 1.5-2.8 times of that of the dihydric alcohol in the solution A, the mass of the dispersing agent is 5-15 times of that of the soluble silver salt, and the mass of the reducing agent is 0.3-0.8 time of that of the soluble silver salt.
Preferably, the mass of the dihydric alcohol in the solution B is 2-2.5 times of that of the dihydric alcohol in the solution A, the mass of the dispersing agent is 5-8 times of that of the soluble silver salt, and the mass of the reducing agent is 0.3-0.5 time of that of the soluble silver salt.
Optionally, the pH of solution B is 2-4.
Optionally, in the step 3), the solution A is uniformly added into the stirred solution B at the temperature of 100-160 ℃, and the adding rate is 5-7mL/min, so as to obtain a solution C.
Preferably, the solution A is uniformly added into the stirred solution B at the temperature of 140 ℃ at 100 ℃ in the step 3), and the adding speed is 5-7mL/min, so as to obtain a solution C.
Optionally, step 4) further includes: and (3) keeping the temperature of the solution C and stirring for at least 3 minutes, cooling and separating to obtain the nano silver.
Preferably, the solution C is stirred for 5 minutes at incubation.
According to another aspect of the present application, there is provided a nano-silver paste, wherein the nano-silver paste is obtained by dispersing the nano-silver paste prepared by the above preparation method in a specified solvent and centrifuging, and the solid content of the nano-silver paste is not less than 80 wt%.
Benefits of the present application include, but are not limited to:
1. according to the preparation method of the nano-silver, the dihydric alcohol is used as a solvent, the dihydric alcohol is used as a reducing agent, in addition, reducing agents such as ascorbic acid, glucose, citric acid, sodium borohydride, formaldehyde, hydrazine hydrate, hydroquinone or hydrogen peroxide are added, the reducing capabilities of different types of dihydric alcohol and reducing agents are different, so that the nucleation speed of nano-silver particles in the dihydric alcohol is different, and the synthesis of the spherical nano-silver with controllable particle size in the range of 30-300nm can be realized.
2. According to the preparation method of the nano-silver, the polyvinylpyrrolidone K30 is used as the dispersing agent, the polyvinylpyrrolidone K30 has good adhesion and can be firmly coated on the surface of the generated nano-silver to prevent the nano-silver from agglomerating, so that the prepared nano-silver has good dispersibility, uniform appearance and stability.
3. According to the preparation method of the nano-silver, parameters such as the feeding sequence, the feeding speed, the reaction temperature and the pH value of the solution are strictly controlled, so that the growth process of the nano-silver is controlled, the preparation of the nano-silver with controllable particle size is realized, and the obtained nano-silver is uniform in shape and good in dispersity.
4. According to the preparation method of the nano-silver, different post-treatments are carried out on the prepared nano-silver, so that different nano-silver products can be obtained, such as freeze drying to obtain high-purity nano-silver powder, or dispersing by using a solvent to obtain a nano-silver paste.
5. According to the preparation method of the nano-silver, the adopted equipment and the process are simple, rapid and efficient, and industrial amplification and industrial application are facilitated.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a scanning electron microscope image of nano-silver prepared in example 1 of the present application;
FIG. 2 is a scanning electron microscope image of nano-silver prepared in example 2 of the present application;
FIG. 3 is a scanning electron microscope image of nano-silver prepared in example 3 of the present application;
FIG. 4 is a scanning electron microscope image of nano-silver prepared in example 4 of the present application;
FIG. 5 is a scanning electron microscope image of nano-silver prepared in example 5 of the present application;
FIG. 6 is a scanning electron microscope image of nano-silver prepared in example 6 of the present application;
FIG. 7 is a scanning electron microscope image of nano-silver prepared in comparative example 1 of the present application;
FIG. 8 is a scanning electron microscope image of the nano-silver prepared in comparative example 2 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
Example 1
1) Solution A having a silver content of about 5.7% by weight was prepared by weighing 4 g of silver nitrate and dissolving it in 40 ml of solvent butanediol.
2) 60 g of dispersant polyvinylpyrrolidone K30 is weighed and dissolved in 100 ml of solvent butanediol, 3 g of reducing agent ascorbic acid is added and mixed evenly, then 3 ml of ammonia water is added to adjust the PH, so as to form a mixed solution B of the dispersant and the reducing agent, and the PH of the solution B is about 8.
3) Adding the solution A into the solution B at a constant speed under the condition of stirring at 160 ℃, wherein the adding time is about 4 minutes to obtain a solution C.
4) And (3) keeping the temperature of the solution C and stirring for 5 minutes, then cooling to normal temperature, carrying out sedimentation and centrifugal cleaning to obtain the nano silver, wherein the centrifugal cleaning is the alternate washing of deionized water and ethanol.
5) The centrifuged nano silver is cooled, freeze-dried and dried to obtain about 2.5 g of nano silver powder with good dispersibility, or the nano silver powder is dispersed by a specified solvent and then centrifuged to obtain a nano silver paste with solid content of more than 80 percent and dispersed by the solvent.
The microscopic morphology of the nano-silver prepared in this example was analyzed by a scanning electron microscope, and the result is shown in fig. 1, from which it can be seen that the prepared nano-silver particles have uniform morphology, good dispersibility, and an average particle size of about 30 nm.
Example 2
1) 6 g of silver nitrate was weighed and dissolved in 40 ml of propylene glycol as a solvent to prepare a solution A having a silver content of about 8 wt%.
2) 45 g of dispersant polyvinyl alcohol is weighed and dissolved in 100 ml of solvent propylene glycol, 3 g of reducing agent ascorbic acid is added and mixed evenly to form a mixed solution B of the dispersant and the reducing agent, and the pH value of the solution B is about 4.
3) Adding the solution A into the solution B at a constant speed under the condition of stirring at 140 ℃, wherein the adding time is about 6 minutes to obtain a solution C.
4) And (3) keeping the temperature of the solution C and stirring for 5 minutes, then cooling to normal temperature, carrying out sedimentation and centrifugal cleaning to obtain the nano silver, wherein the centrifugal cleaning is the alternate washing of deionized water and ethanol.
5) The centrifuged nano silver is cooled, freeze-dried and dried to obtain about 3.8 g of nano silver powder with good dispersibility, or the nano silver powder is dispersed by a specified solvent and then centrifuged to obtain a nano silver paste with solid content of more than 80 percent and dispersed by the solvent.
The microscopic morphology of the nano-silver prepared in this example was analyzed by a scanning electron microscope, and the result is shown in fig. 2, from which it can be seen that the prepared nano-silver particles have uniform morphology, good dispersibility, and an average particle size of about 50 nm.
Example 3
1) 8 g of silver nitrate was weighed and dissolved in 40 ml of ethylene glycol as a solvent to prepare a solution A having a silver content of about 9.6 wt%.
2) 60 g of dispersant polyvinylpyrrolidone K30 is weighed and dissolved in 100 ml of solvent ethylene glycol, 3.2 g of reducing agent citric acid is added and mixed evenly to form a mixed solution B of the dispersant and the reducing agent, and the pH value of the solution B is about 4.
3) Adding the solution A into the solution B at a constant speed under the condition of stirring at 140 ℃, wherein the adding time is about 6 minutes to obtain a solution C.
4) And (3) keeping the temperature of the solution C and stirring for 5 minutes, then cooling to normal temperature, carrying out sedimentation and centrifugal cleaning to obtain the nano silver, wherein the centrifugal cleaning is the alternate washing of deionized water and ethanol.
5) The centrifuged nano silver is cooled, freeze-dried and dried to obtain about 5 g of nano silver powder with good dispersibility, or the nano silver powder is dispersed by a specified solvent and then centrifuged to obtain the nano silver paste with solid content of more than 80 percent and dispersed by the solvent.
The microscopic morphology of the nano-silver prepared in this example was analyzed by a scanning electron microscope, and the result is shown in fig. 3, from which it can be seen that the prepared nano-silver particles have uniform morphology, good dispersibility, and an average particle size of about 80 nm.
Example 4
1) 8 g of silver nitrate was weighed and dissolved in 40 ml of ethylene glycol as a solvent to prepare a solution A having a silver content of about 9.6 wt%.
2) 40 g of dispersant polyvinyl alcohol is weighed and dissolved in 100 ml of solvent ethylene glycol, 2.4 g of reducing agent ascorbic acid is added and mixed evenly, then 0.5 ml of nitric acid is added to adjust the pH value, so as to form a mixed solution B of the dispersant and the reducing agent, wherein the pH value of the solution B is about 3.
3) Adding the solution A into the solution B at a constant speed under the condition of stirring at 140 ℃, wherein the adding time is about 6 minutes to obtain a solution C.
4) And (3) keeping the temperature of the solution C and stirring for 5 minutes, then cooling to normal temperature, carrying out sedimentation and centrifugal cleaning to obtain the nano silver, wherein the centrifugal cleaning is the alternate washing of deionized water and ethanol.
5) The centrifuged nano silver is cooled, freeze-dried and dried to obtain about 5 g of nano silver powder with good dispersibility, or the nano silver powder is dispersed by a specified solvent and then centrifuged to obtain the nano silver paste with solid content of more than 80 percent and dispersed by the solvent.
The microscopic morphology of the nano-silver prepared in this example was analyzed by a scanning electron microscope, and the result is shown in fig. 4, from which it can be seen that the prepared nano-silver particles have uniform morphology, good dispersibility, and an average particle size of about 100 nm.
Example 5
1) 10 g of silver nitrate was dissolved in 50 ml of ethylene glycol as a solvent to prepare a solution A having a silver content of about 9.6 wt%.
2) 60 g of dispersant polyvinylpyrrolidone K30 is weighed and dissolved in 100 ml of solvent ethylene glycol, 3 g of reducing agent ascorbic acid is added and mixed evenly, then 1.5 ml of nitric acid is added to adjust the pH value to form a mixed solution B of the dispersant and the reducing agent, and the pH value of the solution B is about 2.
3) Adding the solution A into the solution B at a constant speed under the condition of stirring at 120 ℃, wherein the adding time is about 8 minutes to obtain a solution C.
4) And (3) keeping the temperature of the solution C and stirring for 5 minutes, then cooling to normal temperature, carrying out sedimentation and centrifugal cleaning to obtain the nano silver, wherein the centrifugal cleaning is the alternate washing of deionized water and ethanol.
5) The centrifuged nano silver is cooled, freeze-dried and dried to obtain about 6.3 g of nano silver powder with good dispersibility, or the nano silver powder is dispersed by a specified solvent and then centrifuged to obtain a nano silver paste with solid content of more than 80 percent and dispersed by the solvent.
The microscopic morphology of the nano-silver prepared in this example was analyzed by a scanning electron microscope, and the result is shown in fig. 5, from which it can be seen that the prepared nano-silver particles have uniform morphology, good dispersibility, and an average particle size of about 200 nm.
Example 6
1) 10 g of silver nitrate was dissolved in 50 ml of ethylene glycol as a solvent to prepare a solution A having a silver content of about 9.6 wt%.
2) 60 g of dispersant polyvinylpyrrolidone K30 is weighed and dissolved in 100 ml of solvent ethylene glycol, then 3 g of reducing agent glucose is added and mixed evenly, and then 1.5 ml of nitric acid is added to adjust the pH value to form a mixed solution B of the dispersant and the reducing agent, wherein the pH value of the solution B is about 2.
3) Adding the solution A into the solution B at a constant speed under the condition of stirring at 100 ℃, wherein the adding time is about 10 minutes to obtain a solution C.
4) And (3) keeping the temperature of the solution C and stirring for 5 minutes, then cooling to normal temperature, carrying out sedimentation and centrifugal cleaning to obtain the nano silver, wherein the centrifugal cleaning is the alternate washing of deionized water and ethanol.
5) The centrifuged nano silver is cooled, freeze-dried and dried to obtain about 6.3 g of nano silver powder with good dispersibility, or the nano silver powder is dispersed by a specified solvent and then centrifuged to obtain a nano silver paste with solid content of more than 80 percent and dispersed by the solvent.
The microscopic morphology of the nano-silver prepared in this example was analyzed by a scanning electron microscope, and the result is shown in fig. 6, from which it can be seen that the prepared nano-silver particles have uniform morphology, good dispersibility, and an average particle size of about 300 nm.
Comparative example 1
1) 10 g of silver nitrate is weighed and dissolved in 50 ml of solvent ethylene glycol to prepare a solution with silver content of about 9.6 wt%, and 60 g of dispersant polyvinylpyrrolidone K30 is weighed and dissolved in the solution to form solution A.
2) Solution B was prepared by weighing 3 grams of the reducing agent ascorbic acid in 100 milliliters of solvent ethylene glycol and adjusting the pH by adding 1.5 milliliters of nitric acid, the pH of solution B being about 2.
3) Adding the solution A into the solution B at a constant speed under the condition of stirring at 120 ℃, wherein the adding time is about 8 minutes to obtain a solution C.
4) And (3) keeping the temperature of the solution C and stirring for 5 minutes, then cooling to normal temperature, carrying out sedimentation and centrifugal cleaning to obtain the nano silver, wherein the centrifugal cleaning is the alternate washing of deionized water and ethanol.
5) The centrifuged nano silver is freeze-dried to obtain about 6.3 g of comparative silver powder, or the centrifugal silver powder is dispersed by a specified solvent and then centrifuged to obtain the silver-containing paste with the solid content of more than 80 percent and dispersed by the solvent.
The microscopic morphology of the nano-silver prepared in the comparative example was analyzed by a scanning electron microscope, and the results are shown in fig. 7, from which it can be seen that the particle size range of the prepared nano-silver particles is varied from 100-500 nm, and the morphology is not uniform.
Comparative example 2
1) 6 g of silver nitrate was weighed and dissolved in 40 ml of propylene glycol as a solvent to prepare a solution A having a silver content of about 8 wt%.
2) 45 g of dispersant polyvinyl alcohol is weighed and dissolved in 100 ml of solvent propylene glycol, 3 g of reducing agent ascorbic acid is added and mixed evenly to form a mixed solution B of the dispersant and the reducing agent, and the pH value of the solution B is about 4.
3) Adding the solution A into the solution B at a constant speed under the condition of stirring at 140 ℃, wherein the adding time is about 12 minutes to obtain a solution C.
4) And (3) keeping the temperature of the solution C and stirring for 5 minutes, then cooling to normal temperature, carrying out sedimentation and centrifugal cleaning to obtain the nano silver, wherein the centrifugal cleaning is the alternate washing of deionized water and ethanol.
5) The centrifuged nano silver is subjected to freeze drying to obtain about 3.8 g of comparative silver powder, or the centrifugal silver powder is dispersed by using a specified solvent and then centrifuged to obtain the silver-containing paste with the solid content of more than 80 percent and dispersed by using the solvent.
The microscopic morphology of the nano-silver prepared in this comparative example was analyzed by a scanning electron microscope, and the result is shown in fig. 8, from which it can be seen that the particle size of the prepared nano-silver particles is about 100 nm, but the particle size distribution morphology is not uniform, and the agglomeration phenomenon is relatively obvious.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (13)
1. A preparation method of nano silver with controllable particle size is characterized by comprising the following steps:
1) dissolving soluble silver salt in dihydric alcohol to obtain solution A; the dihydric alcohol is ethylene glycol, propylene glycol, butanediol or pentanediol, and the silver content in the solution A is 5-10%;
2) mixing and dissolving a dispersing agent and a reducing agent in the dihydric alcohol, and adjusting the pH to 2-8 by using a pH regulator to obtain a solution B;
the mass of the dihydric alcohol in the solution B is 1.5-2.8 times of that of the dihydric alcohol in the solution A, the mass of the dispersing agent is 5-15 times of that of the soluble silver salt, the mass of the reducing agent is 0.3-0.8 time of that of the soluble silver salt, the dispersing agent is polyvinylpyrrolidone K10, polyvinylpyrrolidone K30, polyvinylpyrrolidone K90, polyethylene glycol, polyvinyl alcohol or sodium dodecyl benzene sulfonate, and the reducing agent is ascorbic acid, glucose, citric acid, sodium borohydride, formaldehyde, hydrazine hydrate, hydroquinone or hydrogen peroxide;
3) adding the solution A into the stirred solution B at the temperature of 100-180 ℃, wherein the feeding rate is 4-10mL/min, and obtaining a solution C;
4) and cooling and separating the solution C to obtain the nano silver.
2. The method of claim 1, wherein the soluble silver salt is selected from silver nitrate, silver acetate, or silver sulfate.
3. The method of claim 2, wherein the soluble silver salt is silver nitrate.
4. The method according to claim 1, wherein the diol is ethylene glycol.
5. The method for preparing nano silver according to claim 4, wherein the silver content in the solution A is 8 to 10 wt%.
6. The method according to claim 1, wherein the pH adjuster is nitric acid, ammonia water, a sodium hydroxide solution, or a potassium hydroxide solution.
7. The method according to claim 6, wherein the dispersant is polyvinylpyrrolidone K30, the reducing agent is ascorbic acid, and the pH adjuster is nitric acid or aqueous ammonia.
8. The production method according to any one of claims 1 to 7, wherein the mass of the glycol in the solution B is 2 to 2.5 times the mass of the glycol in the solution A, the mass of the dispersing agent is 5 to 8 times the mass of the soluble silver salt, and the mass of the reducing agent is 0.3 to 0.5 times the mass of the soluble silver salt.
9. The method according to claim 8, wherein the solution B has a pH of 2 to 4.
10. The preparation method as claimed in claim 9, wherein the solution A is uniformly added to the stirred solution B at the temperature of 100-160 ℃ in step 3) at the feeding rate of 5-7mL/min to obtain the solution C.
11. The method according to claim 10, wherein the step 4) further comprises: and (3) keeping the temperature of the solution C and stirring for at least 3 minutes, cooling and separating to obtain the nano silver.
12. The method according to claim 11, wherein the solution C is stirred for 5 minutes under heat.
13. A nano-silver paste, characterized in that the nano-silver paste is obtained by dispersing the nano-silver prepared by the preparation method of any one of claims 1 to 12 in a specified solvent and centrifuging, wherein the solid content of the nano-silver paste is not less than 80 wt%.
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Denomination of invention: A preparation method for controllable particle size nano silver Effective date of registration: 20230327 Granted publication date: 20220222 Pledgee: Jinan Branch of Qingdao Bank Co.,Ltd. Pledgor: SHANDONG JIANBANG COLLOID MATERIAL CO.,LTD. Registration number: Y2023980036193 |
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