CN116393713A - Preparation method of small-particle-size flake silver powder for fine line printing - Google Patents
Preparation method of small-particle-size flake silver powder for fine line printing Download PDFInfo
- Publication number
- CN116393713A CN116393713A CN202310516441.6A CN202310516441A CN116393713A CN 116393713 A CN116393713 A CN 116393713A CN 202310516441 A CN202310516441 A CN 202310516441A CN 116393713 A CN116393713 A CN 116393713A
- Authority
- CN
- China
- Prior art keywords
- silver powder
- ball
- silver
- agent
- particle size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- 238000000227 grinding Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 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 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 7
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 7
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- 235000021314 Palmitic acid Nutrition 0.000 claims description 6
- 239000002826 coolant Substances 0.000 claims description 6
- -1 fatty acid salt Chemical class 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000000126 substance Substances 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
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-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
- 150000002989 phenols Chemical class 0.000 claims description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000843 powder Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 239000000498 cooling water Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 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
-
- 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
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like 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
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention relates to a preparation method of flake silver powder with small grain size for fine line printing, which comprises the following steps: preparing silver powder for ball milling: adding silver nitrate solution into ammonia water to obtain silver ammonia oxidation solution, and adding the silver ammonia oxidation solution into a reducing agent solution containing a dispersing agent A within 5-10 seconds for reaction; the silver powder is obtained through solid-liquid separation, washing, coating and ultrasonic dispersion; ball-milling of the following materials: adding grinding balls into an vertical ball mill, adding a ball milling auxiliary agent to annihilate the grinding balls, and then adding silverAdding the powder and the dispersing agent B into a ball mill; firstly starting an external circulation system of the ball mill, then starting the ball mill, controlling the temperature in the ball milling process to be not more than 20 ℃, uniformly mixing the ball materials after stirring, and then separating the ball liquid to obtain silver powder slurry; and (3) performing aftertreatment: filtering, drying, crushing and screening the silver powder slurry to obtain the silver powder slurry with the average particle diameter of 3-4 mu m and the tap density of 4.0-5.0 g/cm 3 Small-diameter flake silver powder. The invention has simple process, controllable parameter index, stable production, easy realization of industrial production, no pollution and low cost.
Description
Technical Field
The invention relates to the field of metal powder material preparation, in particular to a preparation method of flake silver powder with small particle size for fine line printing.
Background
Conductive silver paste is the most basic and critical functional material in the electronics industry, and is a thick paste of a mechanical mixture consisting of silver powder, conductive adhesive, solvent and auxiliary agent. The electronic paste composed of silver powder as the conductive phase has the characteristics of high quality, high benefit, advanced technology, wide application and the like, and has an irreplaceable position in the electronic paste industry.
The flake silver powder is used as a special silver powder in the silver powder, and the spherical silver powder and the flake silver powder are mixed according to a certain proportion in the production process of the electronic paste, so that the performance of the electronic paste is greatly improved, and the performance of a finally formed electronic product is directly or indirectly influenced. The morphology of the flake silver powder is not standard round, the thickness of different parts is different, the flake silver powder with larger diameter-thickness ratio generally shows lower apparent density, the silver powder particle quantity per unit volume is more, the flake silver powder is generally applied to the field of thin film switch conductive silver paste, and excellent conductive performance can be shown under the condition of lower silver content; while the flake silver powder with smaller diameter and thickness often shows higher tap density and is generally applied to conductive paste with high precision and fine line printing.
At present, the production of the flake silver powder mainly adopts a ball milling method, wherein the mechanical ball milling method comprises the modes of vertical stirring ball milling, horizontal ball milling, planetary ball milling and the like, and the particle size of the flake silver powder prepared by adopting the mechanical ball milling method is generally micron-sized or submicron-sized powder.
The ball milling method is to grind spherical or spheroidal silver powder into flake silver powder by taking silver powder prepared by a chemical method as a precursor, adding a grinding aid and adopting a ball milling mode.
The key point of the mechanical ball milling method is how to control the uniform ball milling of the feed liquid in the ball milling process, how to ensure that the ball milling process of the flake silver powder can not agglomerate due to heat release in the ball milling process, ensure the stable production process of the flake silver powder, be favorable for preparing flake silver powder with different specifications and stable physical and chemical indexes, and have excellent application performance in the subsequent slurry application.
Disclosure of Invention
The invention aims to solve the technical problem of providing the preparation method for the fine line printing small-particle-size flake silver powder, which has the advantages of simple process, controllable parameter indexes, stable production and easy realization of industrial production.
In order to solve the problems, the preparation method of the flake silver powder with small grain size for fine line printing comprises the following steps:
preparing silver powder for ball milling:
adding a silver nitrate solution with the mass concentration of 600-650 g/L into ammonia water to obtain silver ammonia oxidation solution, adding the silver ammonia oxidation solution into a reducing agent solution containing a dispersing agent A within 5-10 seconds, and ending the reaction after reacting for 30-60 seconds; solid-liquid separation and washing are carried out to obtain silver powder slurry A; coating the silver powder slurry A by a surface coating agent, and dispersing the silver powder slurry A in an ethanol medium by ultrasonic waves to obtain silver powder;
ball-milling of the following materials:
adding grinding balls into an vertical ball mill, adding a ball milling auxiliary agent to annihilate the grinding balls, and then adding the silver powder and the dispersing agent B into the ball mill; firstly starting an external circulation system of the ball mill, starting circulation of a cooling medium in the external circulation system, starting the ball mill again, controlling the temperature of the ball milling process to be not more than 20 ℃, uniformly mixing the ball materials after stirring, and then separating the ball liquid to obtain silver powder slurry B;
and (3) performing aftertreatment:
filtering, drying, crushing and screening the silver powder slurry B to obtain the silver powder slurry B with the average particle diameter of 3-4 mu m and the tap density of 4.0-5.0 g/cm 3 Small-diameter flake silver powder.
In the step, the mass ratio of silver nitrate to ammonia water is 1:1.2-1.3.
The reducing agent solution containing the dispersing agent A in the step (A) is mixed solution which is formed by mixing the dispersing agent A and the reducing agent and has the concentration of 25-32 g/L; the dispersing agent A is at least one of fatty acid, fatty acid salt, a high molecular compound and a surfactant, and the adding amount of the dispersing agent A is 0.1-0.5% of the mass of the silver powder; the reducing agent refers to one or more of formaldehyde, hydrazine hydrate, ascorbic acid and phenolic compounds.
The dispersing agent A is one or more of polyvinylpyrrolidone, tween, gelatin, succinic acid and polyethylene glycol 4000.
The surface coating agent in the step (A) refers to fatty acid or fatty acid salt substances, and the addition amount of the surface coating agent is 0.1-0.5% of the mass of the silver powder.
The surface coating agent is one or more of oleic acid, erucic acid, isostearic acid and n-octanoic acid.
In the step (II), the grinding balls are graded 1-5: 1. zirconia balls with the particle size of 0.5-2 mm; the ball material mass ratio of the grinding balls to the silver powder is 10-15:1.
The ball milling auxiliary agent is 98% absolute ethyl alcohol, and the adding amount of the ball milling auxiliary agent is 2-3L per kilogram of silver powder.
In the step (II), the dispersing agent B refers to one of saturated fatty acid, unsaturated fatty acid and surfactant, and the addition amount of the dispersing agent B is 0.1-1.0% of the total mass of the silver powder.
The dispersing agent B is one or two of hexadecanoic acid, hexadecanol, stearic acid, erucic acid or oleic acid.
The external circulation speed of the ball mill is 500-1000 mL/min.
The ball milling speed is 200-400 rpm, and the time is 4-7 h.
And in the step III, the drying temperature is 50-60 ℃ and the drying time is 5-10 hours.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the ball-milling raw powder is prepared by adopting a liquid phase chemical reduction method, the silver ammoxidation liquid is added into the reducing agent solution within 30-60 seconds, and the flocculent soft aggregate composed of the monocrystal small-particle silver powder can be produced in a large quantity by the instant reaction of the reducing agent and silver, so that the solid-liquid separation and the washing are convenient.
2. The invention adopts 98% absolute ethyl alcohol as a ball milling auxiliary agent, adopts a dispersing agent as a ball milling medium, adopts grinding balls with specific grading particle size to form ball milling conditions, strictly controls the proportion of the grinding balls to silver powder raw materials, and analyzes and controls key factors influencing the ball milling process in the ball milling process under the action of the ball milling medium; then the external circulation system with the cooling medium is added to obtain the material with the average grain diameter of 3-4 mu m and the tap density of 4.0-5.0 g/cm 3 And the surface is smooth and flat, and the small-diameter flake silver powder is free of impurities.
3. The invention adopts the absolute ethyl alcohol with the mass percent concentration of more than 98 percent, has better dispersity, simultaneously ensures no impurity introduction and ensures the purity of silver powder.
4. The invention adopts the 1-S type vertical stirring ball mill, the ball mill has a unique stirring structure, the materials and the grinding medium exert shearing force and pressure on the materials under the high-speed stirring action, so that the energy transmitted by the stirrer is uniformly dispersed in the materials, the fine grinding efficiency is high, the overgrinding is less, the materials are uniformly mixed, and no dead angle exists; meanwhile, the external circulation is added, so that no residual dead angle exists in the ball milling process, the silver powder is fully contacted with the grinding medium and fully ground, and the ball milling efficiency is improved.
5. According to the invention, by adding the external circulation system with the cooling medium, the temperature in the ball milling process is controlled to be not more than 20 ℃, the heat dissipation in the ball milling process is maintained, the aggregation of silver powder caused by overhigh ball milling heat and the cold welding in the ball milling process are prevented, and the dispersibility of the silver powder is improved.
6. The invention has simple production process, controllable parameter index, stable production, easy realization of industrial production, no pollution and low cost.
7. The silver powder prepared by the method has smooth and flat surface, no impurity, small diameter-thickness ratio and good dispersibility, and is suitable for high-precision and fine-line printing conductive paste.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 is an SEM image of the plate-like silver powder prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the plate-like silver powder prepared in comparative example 1 of the present invention.
Detailed Description
A preparation method of flake silver powder with small particle size for fine line printing comprises the following steps of
Preparing silver powder for ball milling:
adding a silver nitrate solution with the mass concentration of 600-650 g/L into ammonia water to obtain silver ammonia oxidation solution, adding the silver ammonia oxidation solution into a reducing agent solution containing a dispersing agent A within 5-10 seconds, and ending the reaction after reacting for 30-60 seconds; solid-liquid separation and washing are carried out to obtain silver powder slurry A; coating the silver powder slurry A by a surface coating agent, and dispersing the silver powder slurry A in an ethanol medium by ultrasonic waves to obtain the silver powder.
Wherein: the mass ratio (g/g) of the silver nitrate to the ammonia water is 1:1.2-1.3.
The reducing agent solution containing the dispersing agent A is a mixed solution of the dispersing agent A and the reducing agent, wherein the concentration of the mixed solution is 25-32 g/L. The dispersing agent A is at least one of fatty acid, fatty acid salt, high molecular compound and surfactant, preferably one or more of polyvinylpyrrolidone, tween, gelatin, succinic acid and polyethylene glycol 4000, and the addition amount of the dispersing agent A is 0.1-0.5% of the mass of silver powder. The reducing agent is one or more of formaldehyde, hydrazine hydrate, ascorbic acid and phenolic compounds.
The surface coating agent is fatty acid or fatty acid salt, preferably one or more of oleic acid, erucic acid, isostearic acid and n-octanoic acid, and the addition amount of the surface coating agent is 0.1-0.5% of the mass of the silver powder.
Ball-milling of the following materials:
adding grinding balls into a 1-S type vertical stirring ball mill, adding a ball milling auxiliary agent to annihilate the grinding balls, and then adding silver powder and a dispersing agent B into the ball mill; firstly, an external circulation system of the ball mill is started, and a cooling medium (cooling water is used as the cooling medium) in the external circulation system starts to circulate, wherein the external circulation speed is 500-1000 mL/min; and then starting the ball mill, preventing the temperature of the cold welding ball milling process from being higher than 20 ℃, controlling the ball milling rotating speed to be 200-400 rpm, stirring for 4-7 hours, uniformly mixing the ball materials, and then separating the ball liquid to obtain silver powder slurry B.
Wherein: the grinding ball is graded 1-5: 1. zirconia balls with the particle size of 0.5-2 mm; the ball mass ratio (g/g) of the grinding balls to the silver powder is 10-15:1.
The ball milling auxiliary agent is 98% absolute ethyl alcohol, and the adding amount of the ball milling auxiliary agent is 2-3L per kilogram of silver powder.
The dispersing agent B is one of saturated fatty acid, unsaturated fatty acid and surfactant, preferably one or two of hexadecanoic acid, hexadecanol, stearic acid, erucic acid or oleic acid, and the addition amount of the dispersing agent B is 0.1-1.0% of the total mass of the silver powder.
And (3) performing aftertreatment:
filtering silver powder slurry B, drying at 50-60 ℃ for 5-10 hours, crushing and screening to obtain the silver powder slurry B with the average particle diameter of 3-4 mu m and the tap density of 4.0-5.0 g/cm 3 Small-diameter flake silver powder.
Example 1A method for producing flake silver powder having a small particle diameter for fine line printing comprising the steps of
Preparing silver powder for ball milling:
20kg of silver nitrate was dissolved in 32L of pure water, and 16.35kg of an aqueous ammonia solution was added to obtain an oxidized solution, which was kept at 35 ℃.
6.06kg of ascorbic acid was dissolved in 200L of pure water, and 32g of polyvinylpyrrolidone was added to obtain a reducing agent solution, and the temperature was kept constant to 35 ℃.
Adding silver ammonia oxidation solution into reducer solution within 5s, stirring and reacting for 60s, and stopping the reaction; solid-liquid separation and washing are carried out to obtain silver powder slurry A; adding 25g of isomerism stearic acid into the silver powder slurry A, uniformly mixing, and then dispersing in an ethanol medium by ultrasonic to obtain the silver powder.
Ball-milling of the following materials:
adding grinding balls into a 1-S type vertical stirring ball mill according to the proportion phi 1mm: phi 0.8mm is 1:3, adding 13kg of zirconia balls into 2.5L of absolute ethyl alcohol with the mass percentage concentration of 98 percent to annihilate the grinding balls, and adding 1000g of silver powder, 5g of stearic acid and 3g of hexadecanoic acid into a ball mill; firstly, an external circulation system of the ball mill is started, cooling water in the external circulation system starts to circulate, and the speed of the cooling water is 800mL/min; and then starting the ball mill, stirring for 4 hours at the ball milling rotating speed of 200rpm, uniformly mixing the ball materials, and then separating the ball liquid by a method of filtering and washing with absolute ethyl alcohol to obtain silver powder slurry B.
And (3) performing aftertreatment:
filtering silver powder slurry B, drying at 60deg.C for 16 hr, crushing, and sieving to obtain silver powder slurry with average particle diameter of 3.25 μm and tap density of 4.5g/cm 3 The high tap small-plate-diameter particle size flake silver powder is shown in fig. 1.
Example 2A process for producing a flake silver powder having a small particle diameter for fine line printing comprising the steps of
Preparation of ball-milled silver powder the same as in example 1.
Ball-milling of the following materials:
adding grinding balls into a 1-S type vertical stirring ball mill according to the proportion phi 1mm: phi 0.8mm is 1:4, adding 2.5L of absolute ethyl alcohol into the zirconium oxide balls 13 and kg, annihilating the grinding balls, and adding 5000g of silver powder, 40g of stearic acid and 10g of hexadecanoic acid into a ball mill; firstly, an external circulation system of the ball mill is started, cooling water in the external circulation system starts to circulate, and the cooling water speed is 600mL/min; and then starting the ball mill, stirring for 5 hours at the ball milling speed of 250rpm, uniformly mixing the ball materials, and then separating the ball liquid by a method of filtering and washing with absolute ethyl alcohol to obtain silver powder slurry B.
And (3) performing aftertreatment:
filtering silver powder slurry B, drying at 60deg.C for 16 hr, crushing, and sieving to obtain silver powder slurry with average particle diameter of 4.0 μm and tap density of 4.0g/cm 3 High tap small-diameter particle-size flake silver powder.
Example 3A method for producing flake silver powder having a small particle diameter for fine line printing comprising the steps of
Preparation of ball-milled silver powder the same as in example 1.
Ball-milling of the following materials:
adding grinding balls into a 1-S type vertical stirring ball mill according to the proportion phi 1mm: phi 0.8mm is 1:3, adding 15L of absolute ethyl alcohol into the zirconia balls 70 and kg, annihilating the grinding balls, and adding 5000g of silver powder, 40g of stearic acid and 10g of hexadecanoic acid into a ball mill; firstly, an external circulation system of the ball mill is started, cooling water in the external circulation system starts to circulate, and the cooling water speed is 600mL/min; and then starting the ball mill, stirring for 5 hours at the ball milling speed of 250rpm, uniformly mixing the ball materials, and then separating the ball liquid by a method of filtering and washing with absolute ethyl alcohol to obtain silver powder slurry B.
And (3) performing aftertreatment:
filtering silver powder slurry B, drying at 60deg.C for 16 hr, crushing, and sieving to obtain silver powder slurry with average particle diameter of 3.65 μm and tap density of 4.2g/cm 3 High-tap small-sheet-diameter particle-size flake silver powder
Comparative example 1A process for producing flake silver powder having a small particle diameter for fine line printing comprising the steps of
Preparation of ball-milled silver powder the same as in example 1.
Ball-milling of the following materials:
adding grinding ball into a ball mill, wherein the proportion of the grinding ball is phi 2mm: phi 1mm is 1:3, adding 3L of absolute ethyl alcohol into the zirconium oxide balls 18 and kg, annihilating the grinding balls, and adding 1500g of silver powder, 75g of stearic acid and 15g of erucic acid into a ball mill; firstly uniformly mixing materials at a low speed, then ball-milling for 3 hours at a ball milling rotation speed of 250rpm, and then separating the ball liquid by a method of filtering and washing with absolute ethyl alcohol to obtain silver powder slurry B.
And (3) performing aftertreatment:
filtering silver powder slurry B, drying at 60deg.C for 16 hr, crushing, and sieving to obtain silver powder slurry with average particle diameter of 2.1 μm and tap density of 4.5g/cm 3 Is not uniform in ball milling, and is mixed with a large amount of spherical-like silver powder, as shown in figure 2.
Claims (10)
1. The preparation method of the flake silver powder with small particle size for fine line printing comprises the following steps:
preparing silver powder for ball milling:
adding a silver nitrate solution with the mass concentration of 600-650 g/L into ammonia water to obtain silver ammonia oxidation solution, adding the silver ammonia oxidation solution into a reducing agent solution containing a dispersing agent A within 5-10 seconds, and ending the reaction after reacting for 30-60 seconds; solid-liquid separation and washing are carried out to obtain silver powder slurry A; coating the silver powder slurry A by a surface coating agent, and dispersing the silver powder slurry A in an ethanol medium by ultrasonic waves to obtain silver powder;
ball-milling of the following materials:
adding grinding balls into an vertical ball mill, adding a ball milling auxiliary agent to annihilate the grinding balls, and then adding the silver powder and the dispersing agent B into the ball mill; firstly starting an external circulation system of the ball mill, starting circulation of a cooling medium in the external circulation system, starting the ball mill again, controlling the temperature of the ball milling process to be not more than 20 ℃, uniformly mixing the ball materials after stirring, and then separating the ball liquid to obtain silver powder slurry B;
and (3) performing aftertreatment:
filtering, drying, crushing and screening the silver powder slurry B to obtain the silver powder slurry B with the average particle diameter of 3-4 mu m and the tap density of 4.0-5.0 g/cm 3 Small-diameter flake silver powder.
2. The process for producing a fine line-printed small particle size plate-like silver powder according to claim 1, wherein: in the step, the mass ratio of silver nitrate to ammonia water is 1:1.2-1.3.
3. The process for producing a fine line-printed small particle size plate-like silver powder according to claim 1, wherein: the reducing agent solution containing the dispersing agent A in the step (A) is mixed solution which is formed by mixing the dispersing agent A and the reducing agent and has the concentration of 25-32 g/L; the dispersing agent A is at least one of fatty acid, fatty acid salt, a high molecular compound and a surfactant, and the adding amount of the dispersing agent A is 0.1-0.5% of the mass of the silver powder; the reducing agent refers to one or more of formaldehyde, hydrazine hydrate, ascorbic acid and phenolic compounds.
4. A process for producing a fine-line printed small particle size plate-like silver powder according to claim 3, characterized in that: the dispersing agent A is one or more of polyvinylpyrrolidone, tween, gelatin, succinic acid and polyethylene glycol 4000.
5. The process for producing a fine line-printed small particle size plate-like silver powder according to claim 1, wherein: the surface coating agent in the step (A) refers to fatty acid or fatty acid salt substances, and the addition amount of the surface coating agent is 0.1-0.5% of the mass of the silver powder.
6. The process for producing a fine line-printed small particle size plate-like silver powder according to claim 5, wherein: the surface coating agent is one or more of oleic acid, erucic acid, isostearic acid and n-octanoic acid.
7. The process for producing a fine line-printed small particle size plate-like silver powder according to claim 1, wherein: in the step (II), the grinding balls are graded 1-5: 1. zirconia balls with the particle size of 0.5-2 mm; the ball material mass ratio of the grinding balls to the silver powder is 10-15:1.
8. The process for producing a fine line-printed small particle size plate-like silver powder according to claim 1, wherein: the ball milling auxiliary agent is 98% absolute ethyl alcohol, and the adding amount of the ball milling auxiliary agent is 2-3L per kilogram of silver powder.
9. The process for producing a fine line-printed small particle size plate-like silver powder according to claim 1, wherein: in the step (II), the dispersing agent B refers to one of saturated fatty acid, unsaturated fatty acid and surfactant, and the addition amount of the dispersing agent B is 0.1-1.0% of the total mass of the silver powder.
10. The process for producing a fine line-printed small particle size plate-like silver powder according to claim 9, wherein: the dispersing agent B is one or two of hexadecanoic acid, hexadecanol, stearic acid, erucic acid or oleic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310516441.6A CN116393713A (en) | 2023-05-09 | 2023-05-09 | Preparation method of small-particle-size flake silver powder for fine line printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310516441.6A CN116393713A (en) | 2023-05-09 | 2023-05-09 | Preparation method of small-particle-size flake silver powder for fine line printing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116393713A true CN116393713A (en) | 2023-07-07 |
Family
ID=87012374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310516441.6A Pending CN116393713A (en) | 2023-05-09 | 2023-05-09 | Preparation method of small-particle-size flake silver powder for fine line printing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116393713A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116571753A (en) * | 2023-07-13 | 2023-08-11 | 长春黄金研究院有限公司 | Preparation method of flaky metal powder |
-
2023
- 2023-05-09 CN CN202310516441.6A patent/CN116393713A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116571753A (en) * | 2023-07-13 | 2023-08-11 | 长春黄金研究院有限公司 | Preparation method of flaky metal powder |
| CN116571753B (en) * | 2023-07-13 | 2023-10-20 | 长春黄金研究院有限公司 | Preparation method of flaky metal powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7329878B2 (en) | Silicon nitride, ceramic slurry and preparation method | |
| US5401701A (en) | Ito sintered body and method of manufacturing the same | |
| CN111097922A (en) | Nano silver particle and preparation method and application thereof | |
| CN116393713A (en) | Preparation method of small-particle-size flake silver powder for fine line printing | |
| CN108213456B (en) | Preparation method of cubic nanometer copper powder | |
| CN111774575A (en) | Preparation method of high-tap-density large-sheet-diameter flaky silver powder | |
| CN1837055A (en) | Indium oxide powder and method for producing same | |
| CN112605394B (en) | Preparation method of silver powder for conductive paste | |
| CN110355382B (en) | Preparation method of microcrystalline silver powder containing hollow structure | |
| CN112939576A (en) | IGZO powder, target material and preparation method thereof | |
| CN116251961A (en) | Method for preparing silver powder with assistance of ultrasonic waves, silver powder prepared by method and application of silver powder | |
| CN113666380B (en) | Preparation method of spherical silicon dioxide | |
| CN112756617B (en) | Preparation method of flake silver powder for conductive silver adhesive | |
| CN109877336A (en) | A kind of preparation method of flake copper powder | |
| KR20170038467A (en) | The manufacturing method of flake silver powder using the agglomerated silver powder | |
| CN111663061A (en) | Method for preparing Al-Si alloy grain refiner | |
| CN112264629A (en) | Preparation method and application of low-cost high-dispersion silver powder | |
| KR20170038465A (en) | The manufacturing method of flake silver powder using the agglomerated silver powder | |
| CN111889695A (en) | Preparation method of micro-nano silver powder with controllable particle size | |
| CN116237533A (en) | Silver powder for PERC battery front silver paste and preparation method and application thereof | |
| CN115196970A (en) | Preparation method of high-fluidity AlON spherical powder | |
| CN113292053B (en) | Process for preparing high-dispersity aluminum nitride powder by carbothermic method based on polymer dispersant | |
| CN115805305A (en) | Spherical composite powder and preparation method thereof | |
| CN112846213B (en) | Preparation method of low-oxygen high-dispersion nano spherical cobalt powder | |
| CN109550933B (en) | Ultrathin silver sheet and chemical synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |