CN101342596B - Process for preparing nm-class silver powder - Google Patents
Process for preparing nm-class silver powder Download PDFInfo
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- CN101342596B CN101342596B CN200810029739XA CN200810029739A CN101342596B CN 101342596 B CN101342596 B CN 101342596B CN 200810029739X A CN200810029739X A CN 200810029739XA CN 200810029739 A CN200810029739 A CN 200810029739A CN 101342596 B CN101342596 B CN 101342596B
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Abstract
The present invention discloses a method for preparing the nanometer-level silver powder, and comprises the steps such as the reduction reaction, the surface chemical treatment and the drying, wherein, the reduction reaction: (1) organic acid dispersing agent is added into the organic alcohol solution to be mixed, and then is added with silver-contained material and neovaricaine reducer to be uniformly mixed, and to obtain the suspension solution; (2) the suspension solution that is obtained in the mixing step (1) is heated to 80 to 100 DEG C; (3) within 2 to 4 hours, neovaricaine reducer is dropped into the suspension solution that is obtained in step (2), and is continued to be mixed for 0.5 to 1 hour, and is cooled to 50 DEG C plus or minus 5 DEG C, and is kept still to precipitate the silver powder; the silver-contained material is one or two mixtures of silver carbonate and silver oxide. The method of the present invention is simple and easy to be done; the produced nanometer silver powder has high purity, good dispersing property, and small grain large specific surface and wide drying temperature range; the powder can be effectively prevented from being self sintered or clustered, and is easy to be dispersed to be organic carrier.
Description
Technical field
The present invention relates to the liquid phase preparation process of nano-scale silver powder, relate in particular to a kind of liquid phase preparation process that is applied to the nano-scale silver powder of electric slurry.
Background technology
Silver powder is most widely used a kind of noble metal powder in electric industry, and Traditional industrial greater than 0.2 micron, can be used for making isotropic conductive adhesive, electrically-conducting paint with the silver powder particle diameter; Also can be used for the slug type silver paste; Like the functional electrode slurry of capacitor, inductor, resistor and other ceramic components, typical sintering temperature is 650～850 ℃, and sintering temperature is high; Energy consumption is high, and is also high to the ceramic substrate performance requirement.The nano-silver powder that is used for the electric slurry industry requires good dispersion, and tap density is high, yet active high just because of nano-silver powder, very easily takes place from sintering or reunion; The general unresolved agglomeration traits of commercially available so-called nano-silver powder, bad dispersibility, surface-active are not high, and tap density is low; Preparation during slurry organic carrier be difficult to the complete wetting powder, silver layer is not fine and close behind the big and sintering of particle diameter, shrinkage factor is big; Hole is many, and poor electrical performance can't satisfy the demand that electronics industry further develops.This silver powder is used for electric slurry, and the printed silver layer thickness is big, shown in accompanying drawing 1.
Chinese patent CN101214555 discloses a kind of preparation method of spherical nano-silver powder; It comprises the steps: 1) spray pyrolysis: a. is silver nitrate and one of following three kinds: 1. magnesium nitrate, 2. nickel nitrate, 3. copper nitrate; Soluble in waterly be mixed with the aqueous solution that concentration is 10～40wt.%, the mol ratio of silver ion and magnesium ion, nickel ion or copper ion is 0.05～1: 4 in the solution; Spray pyrolysis then; B. in the presence of dispersant and protective agent, add ultrasonic dispersion in the absolute ethyl alcohol, get mixture; 2) preparation of spherical nano-silver powder: a. is added drop-wise to acid solution in the mixture, and regulating the pH value is 3～5, must contain the suspension of spherical nano-silver powder; B. suction filtration, washing, drying obtain spherical nano-silver powder.
Summary of the invention
The technical problem that the present invention will solve provides that a kind of purity is high, particle diameter is little, size is even, good dispersion, specific area are big, the baking temperature wide ranges of activity height, powder, can control effectively that powder does not take place from sintering or reunion, very easily secondary is scattered in the nanometer-level silver powder, preparation method thereof of organic carrier.
The technical problem that the present invention will solve realizes through following technical scheme: a kind of preparation method of nano-scale silver powder; Comprise reduction reaction, chemical surface treatment, drying steps; Described reduction reaction process does; 1. earlier the organic acid dispersant is added in organic alcoholic solution and stir, add again and contain ag material and ethanolamines reducing agent and stir and obtain suspension; 2. whipping process 1. suspension and the heat temperature raising of gained up to 80～100 ℃; 3. in 2～4 hours, in the suspension of 2. process gained, drip the ethanolamines reducing agent again, add continued and stirred 0.5～1 hour, stop to stir after being cooled to 50 ℃ ± 5 ℃, staticly settle silver powder; Described organic acid dispersant is one or more in oleic acid, stearic acid, the rosin acid; The described ag material that contains is a kind of or both mixtures in silver carbonate, the silver oxide; Described ethanolamines reducing agent is one or more in MEA, diethanol amine and the triethanolamine.Reaction speed is effectively controlled in the reduction of employing weak reductant, guarantees that gained silver powder particle diameter is little, size is even.Organic alcohols is made reaction dissolvent, can effectively reduce the generation of reunion, and powder dispersity is good, and specific area is big, and surface-active is high, can significantly reduce the slurry sintering temperature.For the organic resin of liquid phase carries out chemical surface treatment to powder, the baking temperature wide ranges of powder can effectively be controlled powder and not take place from sintering or reunion under the employing room temperature, and very easily secondary is scattered in organic carrier.
Further: said process is 80～130 ℃ of pure boiling points in the alcoholic solution 1..The heating rate of said process in 2. is 1～2 ℃/min.Described reduction reaction principle is:
6Ag
2CO
3+N(X
a-OH)
3＝12Ag+N(X
a-1COOH)
3+6CO
2+3H
2O
6Ag
2O+N(X
a-OH)
3＝12Ag+N(X
a-1-COOH)
3+3H
2O
Wherein X is an alkyl chain, and a representes the alkyl carbon number in the alkyl chain, the natural number of a >=2.
Described chemical surface treatment step is in the silver powder after washing, and adding weight percentage is liquid phase organic resin or the long-chain solvent of 1～5wt%, and 20～50min is soaked in the back that stirs, and is beneficial to the dry and dried secondary of wide temperature range and disperses.And described organic resin or middle long-chain solvent are in liquid pinene resin, mineral oil and the bisphenol-A liquid-state epoxy resin one or more, can with electric slurry organic carrier matched well.
Among the preparation method of above-mentioned nano-scale silver powder, the cost of raw material is low, simple for process, easy suitability for industrialized production, and productive rate is high.By nano-silver powder purity height, the good dispersion of this method gained, particle diameter is little, size is even, good dispersion; The baking temperature wide ranges of big, active high, the powder of specific area, can effectively control powder and do not take place from sintering or reunion, tap density high; Be suitable for electric slurry, be specially adapted to be lower than the silver slurry of 600 ℃ of sintering and the place that needs ultra-thin printing silver layer, practices thrift silver-colored consumption.
Description of drawings
Fig. 1 influences the design sketch of printed layers thickness and silver-colored consumption for general industry silver powder diameter of particle; Fig. 2 influences the design sketch of printed layers thickness and silver-colored consumption for diameter of particle of the present invention; Fig. 3 is the SEM figure of the nano-silver powder of the present invention's preparation; Fig. 4 is the XRD figure of the nano-silver powder of the present invention's preparation.
The specific embodiment
Purport of the present invention be through control temperature, time and select for use weak reductant, organic alcohols to make reaction dissolvent, organic resin carries out surface treatment to powder and prepares a kind of nano-scale silver powder; In this method; The used cost of raw material is low, simple for process, easy suitability for industrialized production, and productive rate is high.By nano-silver powder purity height, the good dispersion of this method gained, particle diameter is little, size is even, good dispersion; The baking temperature wide ranges of big, active high, the powder of specific area, can effectively control powder and do not take place from sintering or reunion, tap density high; Be suitable for electric slurry, be specially adapted to be lower than the silver slurry of 600 ℃ of sintering and the place that needs ultra-thin printing silver layer, practices thrift silver-colored consumption.Below in conjunction with embodiment content of the present invention is done further to detail, mentioned content is not to qualification of the present invention among the embodiment, and temperature, time and material chosen can be suited measures to local conditions and the result is not had substantial effect among the preparation method.
At first; Summary preparation method's of the present invention basic scheme: a kind of preparation method of nano-scale silver powder; Comprise reduction reaction, chemical surface treatment, drying steps; Described reduction reaction process does, 1. earlier the organic acid dispersant added in organic alcoholic solution and stirs, and adds to contain ag material and ethanolamines reducing agent and stir and obtain suspension again; 2. whipping process 1. suspension and the heat temperature raising of gained up to 80～100 ℃; 3. in 2～4 hours, in the suspension of 2. process gained, drip the ethanolamines reducing agent again, add continued and stirred 0.5～1 hour, stop to stir after being cooled to 50 ℃ ± 5 ℃, staticly settle silver powder; Described organic acid dispersant is one or more in oleic acid, stearic acid, the rosin acid; The described ag material that contains is a kind of or both mixtures in silver carbonate, the silver oxide; Described ethanolamines reducing agent is one or more in MEA, diethanol amine and the triethanolamine.
Embodiment 1
Take by weighing 0.8g gum rosin and join the 50ml butanols, stirring and dissolving adds 25.5g Ag
2CO
3Powder and 0.5g triethanolamine, stirring obtains suspension, this suspension of warming while stirring heating, the control programming rate is 1 ℃/min; Keep 80～100 ℃ of temperature, Dropwise 5 g triethanolamine in 2～4h stirs 0.5～1h again after adding, be cooled to below 50 ℃; Stop to stir, staticly settle silver powder, stack filter cloth and filter paper in Bu Shi pan suction filtration; Alcohol is washed precipitated powder more than 3 times, uses the liquid resin chemical surface treatment ,≤80 ℃ of dry nano-silver powders that get.Powder characteristic analysis in table 1, diameter of particle influence the design sketch of printed layers thickness and silver-colored consumption shown in accompanying drawing 2, and powder size evenly, good dispersion, specific area be big, shown in accompanying drawing 3.The purity of powder is high, shown in accompanying drawing 4.
Embodiment 2
In embodiment 1, with Ag
2CO
3Change Ag into
2O, consumption are 21.5g.Powder characteristic analysis in table 1, diameter of particle influence the design sketch of printed layers thickness and silver-colored consumption shown in accompanying drawing 2, and powder size evenly, good dispersion, specific area be big, shown in accompanying drawing 3.The purity of powder is high, shown in accompanying drawing 4.
Embodiment 3
In embodiment 1, change programming rate into 2 ℃/min by 1 ℃/min.Powder characteristic analysis in table 1, diameter of particle influence the design sketch of printed layers thickness and silver-colored consumption shown in accompanying drawing 2, and powder size evenly, good dispersion, specific area be big, shown in accompanying drawing 3.The purity of powder is high, shown in accompanying drawing 4.
Embodiment 4
In embodiment 2, change programming rate into 2 ℃/min by 1 ℃/min.Powder characteristic analysis in table 1, diameter of particle influence the design sketch of printed layers thickness and silver-colored consumption shown in accompanying drawing 2, and powder size evenly, good dispersion, specific area be big, shown in accompanying drawing 3.The purity of powder is high, shown in accompanying drawing 4.
Embodiment 5
In like embodiment 1, change gum rosin into oleic acid, consumption is constant.Powder characteristic analysis in table 1, diameter of particle influence the design sketch of printed layers thickness and silver-colored consumption shown in accompanying drawing 2, and powder size evenly, good dispersion, specific area be big, shown in accompanying drawing 3.The purity of powder is high, shown in accompanying drawing 4.
Embodiment 6
In like embodiment 2, change gum rosin into oleic acid, consumption is constant.Powder characteristic analysis in table 1, diameter of particle influence the design sketch of printed layers thickness and silver-colored consumption shown in accompanying drawing 2, and powder size evenly, good dispersion, specific area be big, shown in accompanying drawing 3.The purity of powder is high, shown in accompanying drawing 4.
Table 1: powder characteristic analysis
Claims (5)
1. the preparation method of a nano-scale silver powder comprises reduction reaction, chemical surface treatment, drying steps, it is characterized in that: described reduction reaction process does,
1. earlier the organic acid dispersant is added in organic alcoholic solution and stir, add again and contain ag material and ethanolamines reducing agent and stir and obtain suspension;
2. the 1. suspension of gained of whipping process, heat temperature raising is up to 80～100 ℃;
3. in 2～4 hours, in the suspension of 2. process gained, drip the ethanolamines reducing agent again, add continued and stirred 0.5～1 hour, stop to stir after being cooled to 50 ℃ ± 5 ℃, staticly settle silver powder;
Described organic acid dispersant is one or more in oleic acid, stearic acid, the rosin acid; The described ag material that contains is a kind of or both mixtures in silver carbonate, the silver oxide; Described ethanolamines reducing agent is one or more in MEA, diethanol amine and the triethanolamine;
Said process is 80～130 ℃ of pure boiling points in the alcoholic solution 1.;
The heating rate of said process in 2. is 1～2 ℃/min.
2. the preparation method of nano-scale silver powder according to claim 1, it is characterized in that: described reduction reaction principle is:
6Ag
2CO
3+N(X
a-OH)
3＝12Ag+N(X
a-1COOH)
3+6CO
2+3H
2O
6Ag
2O+N(X
a-OH)
3＝12Ag+N(X
a-1-COOH)
3+3H
2O
Wherein X is an alkyl chain, and a representes the alkyl carbon number in the alkyl chain, the natural number of a >=2.
3. the preparation method of nano-scale silver powder according to claim 2; It is characterized in that: described chemical surface treatment step is in the silver powder after washing; Adding weight percentage is liquid phase organic resin or the middle long-chain solvent of 1～5wt%, and 20～50min is soaked in the back that stirs.
4. the preparation method of nano-scale silver powder according to claim 3, it is characterized in that: described organic resin or middle long-chain solvent are one or more in liquid pinene resin, mineral oil and the bisphenol-A liquid-state epoxy resin.
5. the preparation method of nano-scale silver powder according to claim 4 is characterized in that: described baking temperature≤80 ℃.
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| CN101342596B true CN101342596B (en) | 2012-02-22 |
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| CN101872653A (en) * | 2010-06-28 | 2010-10-27 | 彩虹集团公司 | Nano silver conductive paste and preparation method thereof |
| CN102784924B (en) * | 2012-07-16 | 2013-12-18 | 燕山大学 | Water phase preparation method for chain platinum nanosphere by taking octreotide acetate as template |
| CN102896326A (en) * | 2012-10-30 | 2013-01-30 | 东华大学 | Method for preparing cubic crystal type nano-silver material by utilizing oil-water interface method of oleic acid |
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| CN105817644A (en) * | 2016-05-13 | 2016-08-03 | 浙江光达电子科技有限公司 | Preparation method of high-concentration superfine silver powder |
| CN105798327B (en) * | 2016-05-13 | 2018-06-26 | 浙江光达电子科技有限公司 | Improve the preparation method of the hygrometric state silver powder of slurry fineness |
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| CN108480658A (en) * | 2018-06-10 | 2018-09-04 | 江苏经贸职业技术学院 | A method of synthesis silver nanoclusters are heat-treated based on complexing |
| CN109732102B (en) * | 2019-03-18 | 2020-09-01 | 湘潭市泽宇新材料科技有限公司 | Monodisperse conductive silver powder suitable for high-temperature and low-temperature silver pastes and preparation method thereof |
| CN110919025B (en) * | 2019-12-04 | 2022-08-30 | 郴州市金贵银业股份有限公司 | Preparation method of nano paillette silver powder |
| CN115283691B (en) * | 2022-09-28 | 2022-12-16 | 长春黄金研究院有限公司 | Preparation method of silver powder for printing paste |
| CN116511520B (en) * | 2023-04-23 | 2024-03-15 | 东方电气集团科学技术研究院有限公司 | Mixed silver powder with large and small particle sizes, preparation method thereof and conductive silver paste |
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