CN102816462B - Preparation method for nano-silver particles coated with organic protection agent on surfaces - Google Patents
Preparation method for nano-silver particles coated with organic protection agent on surfaces Download PDFInfo
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Abstract
The present invention discloses a preparation method for nano-silver particles coated with an organic protection agent on surfaces. The preparation method comprises the following steps: 1) mixing and stirring 1 part by mass of an organic protection agent, 8-20 parts by mass of a reducing agent, and 2-5 parts by mass of deionized water; 2) adding 2-7 parts by mass of deionized water and 2-8 parts by mass of a metal silver salt, and continuously stirring; 3) carrying out ultrasonic oscillation on the resulting solution; 4) adding 30-125 parts by mass of anhydrous ethanol, and keeping stirring during the adding process; 5) carrying out a centrifugation treatment on the obtained solution; and 6) drying the product obtained by the centrifugation treatment to obtain nano-silver particles coated with the organic protection agent on the surfaces. According to the present invention, the preparation method of the present invention has characteristics of simple operation and low cost; the prepared nano-silver particles can be long-termly and stably stored at a room temperature in a solid form; during preparation of nano-silver electricity conductive ink, the nano-silver particles can be directly taken and metered, and added to an ink solvent, wherein the nano-silver particles can be automatically dispersed into the solvent.
Description
Technical field
The present invention relates to nano material and manufacture field; be specifically related to a kind of surface and be coated the preparation method of the nano-Ag particles of organic protective agent, the nano-Ag particles that surface prepared by the method is being coated organic protective agent can be used as the raw material of the nano silver conductive ink of preparation based on ink jet printing flexible electronic.
Background technology
Flexible electronic, claims again printed electronic or organic electronic, is organic/inorganic electron device is deposited on to flexible substrate as formed the technology of circuit in the substrates such as paper, plastics or fabric.Because flexible electronic performance is suitable with traditional microelectronics, and there is portable, transparent, lightweight, extension/flexion and be easy to the features such as rapid large-area printing, make some become possibility, such as flexible flexible display, Electronic Paper, big area sensor array, intelligent label, thin film solar cell etc. by the special applications that traditional electronic circuit is realized.The key of flexible electronic manufacture is exactly the manufacture of pattern conductive circuit, and the desirable Patternized technique of flexible electronic should meet: low cost, big area, batchprocess, low temperature, " adding " formula, contactless, can adjust in real time, three-dimensional structure, be easy to the requirements such as multilayer alignment.And at present common patterning techniques is as in the technology such as photoetching, shadow mask, micro-contact printing and ink jet printing, only have ink-jet printing technology can finely meet these requirements.In addition, under computer-aided control condition, inkjet technology is more easily realized the design and implementation of figure in be situated between sight and microcosmic rank, can realize accurate, quantitative, location deposition, the imaging precision of assurance conductive pattern.And the technique of inkjet technology is relatively simple, do not need harsh especially environmental requirement, cost of manufacture is lower, reduces the pollution of environment and raw-material waste.
Utilize inkjet technology to prepare in the technique of conducting channel, one of gordian technique is the conductive ink that preparation is applicable to spray ink Printing.The performance index that are applicable to the conductive ink of spray ink Printing mainly comprise: (1) spray property: particle size, viscosity and three indexs of surface tension of showing as ink.Generally speaking, particle size should be less than 1 μ m, and viscosity is 5 ~ 35cP, and surface tension is 10 ~ 50mN/m.For different brands piezoelectric type printer, these indexs of ink are also slightly different.(2) reliability: do not block shower nozzle; Between ink composition and between ink and nozzle component, there is consistency; There is package stability.(3) printed patterns quality: printing quality is good; On print media, there are certain rate of drying, adhesivity etc.(4) security: require conductive ink can use green solvent as far as possible, there is nontoxicity, nonflammable, odorlessness.Common conductive ink can be divided into organic polymer conductive ink and metallic conduction ink, but general organic polymer conductive ink is than low three or four orders of magnitude of the electric conductivity of metallic conduction ink, and expensive, be not applicable to the preparation of common big area conducting channel very much.It is several that metallic conduction ink common are golden conductive ink, silver-colored conductive ink and copper conductive ink etc.But to have cost ratio gold cheap many due to silver, and chemical property is than features such as copper are stable, and while considering conductivity, the production cost of conductive ink, silver-colored conductive ink has higher cost performance.
And nano-Ag particles is the crucial constitutive material of conductive ink, the preparation of nano-Ag particles is chosen and is had important impact for the conductivity of conductive ink and the solvent of ink.The method of preparing nano-Ag particles can be divided into Physical and chemical method, wherein Physical is by physical grinding silver block materials, prepare nano-Ag particles, the silver-colored particle that the method prepares, specific surface energy is higher, easily produce and reunite, cannot well be dispersed in and take water in main solvent, and then be difficult to be applied in ink-jet printing process.And chemical rule is divided into gas-phase reaction method and liquid-phase precipitation method.Gas-phase reaction method is divided into spray method, pyrolysis method and method of evaporation etc., and these methods are higher to the environmental requirement of manufacture, as needs high temperature or high pressure, can produce more toxic and harmful in production process simultaneously; Liquid-phase precipitation method, its principle is exactly first to prepare silver-colored compound solution, then chooses certain reductive agent; restore nano-Ag particles, finally choose certain organic protective agent, stop silver-colored particle to occur to reunite and precipitation; preparation process is fairly simple comparatively speaking, and cost is lower.Existing surface is being coated the preparation method of the nano-Ag particles of organic protective agent; its nano-Ag particles preparing is general all to be left in certain solvent with the form of disperseing; cannot be directly with solid-state nanometer silver form prolonged storage and transportation; also cannot realize it in needs simultaneously; directly add in ink solvent, automatically disperse to form conductive ink.
Summary of the invention
Technical problem to be solved by this invention is; for the deficiencies in the prior art; provide a kind of surface being coated the preparation method of the nano-Ag particles of organic protective agent; simple to operate; cost is low, and the nano-Ag particles that the method prepares can be deposited with solid-state form normal temperature at ordinary times steadily in the long term, when preparing nano silver conductive ink; directly taken amount adding in ink solvent, can be distributed in solvent automatically.
In view of this, a kind of surface provided by the invention is being coated the preparation method of the nano-Ag particles of organic protective agent, comprises the following steps:
1) deionized water of the reductive agent of the organic protective agent of 1 part of quality, 8 ~ 20 parts of quality, 2 ~ 5 parts of quality is mixed, under 50 ~ 70 ℃ of conditions, stir 1 ~ 3 hour;
2) add the deionized water of 2 ~ 7 parts of quality and the metal silver salt of 2 ~ 8 parts of quality, continue to stir 2 ~ 10 hours;
3) solution is carried out to sonic oscillation 20 ~ 60 minutes;
4) with the speed of 5 ~ 20 gram/minute, add the dehydrated alcohol of 30 ~ 125 parts of quality, in adition process, keep stirring;
5) solution obtaining is carried out to centrifugal treating 20 ~ 40 minutes with the centrifugal speed of 3000 ~ 8000 rpm;
6) product centrifugal treating being obtained is dried 2 ~ 7 hours at 50 ~ 70 ℃, obtains the nano-Ag particles that surface is being coated organic protective agent.
Preferably, in step 1), described organic protective agent is selected from one or both in polyglutamic acid, polyacrylic acid, polymethyl acrylic acid, polyoxypropylene, fatty alcohol-polyoxyethylene ether, polyxyethylated alkylphenol.
Preferably, in step 1), described reductive agent is selected from a kind of in thanomin, diethanolamine, trolamine.
Preferably, in step 2) in, described metal silver salt is selected from a kind of in Silver monoacetate, Silver Nitrate, silver tetrafluoroborate.
Compared with prior art; the inventive method is simple to operate; cost is low, and the surface of preparation is being coated the nano-Ag particles of organic protective agent and can preserving with the form normal temperature sealing darkness of solid at ordinary times, and when printing needs; solid content that can be on demand; directly take and be then scattered in ink solvent, the stability of ink finally obtaining can be good, places 6 months in air ambient; can there is not obviously heavy poly-phenomenon, go for common piezoelectric ink jet printer.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that the surface for preparing in the embodiment of the present invention 1 is being coated the nano-Ag particles of organic protective agent;
Fig. 2 is differential thermal-thermogravimetric analysis figure that the surface for preparing in the embodiment of the present invention 2 is being coated the nano-Ag particles of organic protective agent.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment 1: get 3 grams of polyacrylic acid, 24 grams of thanomins and 10 grams of deionized waters and mix, utilize magnetic stirring apparatus to stir under 60 ℃ of conditions 1 hour; And then add 10 grams of deionized waters and 15 grams of Silver Nitrates, and continue to stir 2 hours; Then the solution obtaining is carried out to sonic oscillation 50 minutes, obtain deep brown solution; In this solution, the speed with 15 gram/minute adds 250 grams of ethanol again, in adition process, keeps stirring, and the nanometer metallic silver ion in solution is reunited, and sedimentation occurs part; Finally the solution obtaining is carried out to centrifugal treating, centrifugal speed is 4000 rpm, and the time is 20 minutes; The centrifugal product obtaining after dry 4 hours, obtains the nano-Ag particles that surface is being coated organic protective agent at 50 ℃.The nano-Ag particles that the surface making is being coated to organic protective agent carries out scanning electron microscopic observation, and result as shown in Figure 1.
Embodiment 2: get 5 grams of polyacrylic acid, 40 grams of diethanolamine and 10 grams of deionized waters and mix, utilize magnetic stirring apparatus to stir under 60 ℃ of conditions 2 hours; And then add 20 grams of deionized waters and 10 grams of Silver monoacetates, and continue to stir 4 hours; Then the solution obtaining is carried out to sonic oscillation 30 minutes, obtain deep brown solution; In this solution, the speed with 20 gram/minute adds 300 grams of ethanol again, in adition process, keeps stirring, and the nanometer metallic silver ion in solution is reunited, and sedimentation occurs part; Finally the solution obtaining is carried out to centrifugal treating, centrifugal speed is 8000rpm, and the time is 20 minutes; The centrifugal product obtaining after dry 3 hours, obtains the nano-Ag particles that surface is being coated organic protective agent at 50 ℃.The nano-Ag particles that the surface making is being coated to organic protective agent carries out differential thermal-thermogravimetric analysis, and as shown in Figure 2, visible surface is being coated in the nano-Ag particles of organic protective agent result, and the shared weight ratio of protective material is 0.5% left and right.
Embodiment 3: get 6 grams of polymethyl acrylic acid, 116 grams of trolamines and 20 grams of deionized waters and mix, utilize magnetic stirring apparatus to stir under 60 ℃ of conditions 3 hours; And then add 20 grams of deionized waters and 30 grams of Silver Nitrates, and continue to stir 2 hours; Then the solution obtaining is carried out to sonic oscillation 30 minutes, obtain deep brown solution; In this solution, the speed with 10 gram/minute adds 600 grams of ethanol again, in adition process, keeps stirring, and the nanometer metallic silver ion in solution is reunited, and sedimentation occurs part; Finally the solution obtaining is carried out to centrifugal treating, centrifugal speed is 6000 rpm, and the time is 20 minutes; The centrifugal product obtaining after dry 5 hours, obtains the nano-Ag particles that surface is being coated organic protective agent at 50 ℃.
Embodiment 4: get 5 grams of polyglutamic acids, 40 grams of diethanolamine and 25 grams of deionized waters and mix, utilize magnetic stirring apparatus to stir under 60 ℃ of conditions 3 hours; And then add 10 grams of deionized waters and 10 grams of silver tetrafluoroborates, and continue to stir 2 hours; Then the solution obtaining is carried out to sonic oscillation 30 minutes, obtain deep brown solution; In this solution, the speed with 5 gram/minute adds 600 grams of ethanol again, in adition process, keeps stirring, and the nanometer metallic silver ion in solution is reunited, and sedimentation occurs part; Finally the solution obtaining is carried out to centrifugal treating, centrifugal speed is 3000 rpm, and the time is 20 minutes; The centrifugal product obtaining after dry 5 hours, obtains the nano-Ag particles that surface is being coated organic protective agent at 50 ℃.
Claims (2)
1. surface is being coated a preparation method for the nano-Ag particles of organic protective agent, it is characterized in that comprising the following steps:
1) deionized water of the reductive agent of the organic protective agent of 1 part of quality, 8～20 parts of quality, 2～5 parts of quality is mixed, under 50～70 ℃ of conditions, stir 1～3 hour, described organic protective agent is selected from one or both in polyglutamic acid, polyacrylic acid, polymethyl acrylic acid, polyoxypropylene, fatty alcohol-polyoxyethylene ether, polyxyethylated alkylphenol, and described reductive agent is selected from a kind of in thanomin, diethanolamine, trolamine;
2) add the deionized water of 2～7 parts of quality and the metal silver salt of 2～8 parts of quality, continue to stir 2～10 hours;
3) solution is carried out to sonic oscillation 20～60 minutes;
4) with the speed of 5～20 gram/minute, add the dehydrated alcohol of 30～125 parts of quality, in adition process, keep stirring;
5) solution obtaining is carried out to centrifugal treating 20～40 minutes with the centrifugal speed of 3000～8000rpm;
6) product centrifugal treating being obtained is dried 2～7 hours at 50～70 ℃, obtains the nano-Ag particles that surface is being coated organic protective agent.
2. a kind of surface according to claim 1 is being coated the preparation method of the nano-Ag particles of organic protective agent, it is characterized in that: in step 2) in, described metal silver salt is selected from a kind of in Silver monoacetate, Silver Nitrate, silver tetrafluoroborate.
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| CN104419921B (en) * | 2013-08-26 | 2017-07-21 | 比亚迪股份有限公司 | A kind of water-soluble silver protecting agent and preparation method thereof, chemical silver plating method and electroplate workpiece |
| CN104479463B (en) * | 2015-01-09 | 2017-07-21 | 东北大学 | A kind of electrically conducting transparent containing silver oxalate is without particle silver-based inks and preparation method thereof |
| CN104817891B (en) * | 2015-04-13 | 2017-03-22 | 中国科学院宁波材料技术与工程研究所 | Write-through nano-silver conductive ink and preparation method thereof |
| CN108372310B (en) * | 2018-03-19 | 2021-03-30 | 电子科技大学 | Preparation method of small-size nano silver for water-based conductive ink |
| CN110586952B (en) * | 2018-06-22 | 2022-06-24 | 天津理工大学 | Room temperature preparation method of nano metal powder and conductive ink thereof |
| CN108998006B (en) * | 2018-07-20 | 2021-06-08 | 合肥工业大学 | Environment-friendly strain response type fluorescent supramolecular material and preparation method thereof |
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| JP2002334611A (en) * | 2001-05-07 | 2002-11-22 | Kawakado Kimiko | Conductive particle composite |
| KR100545288B1 (en) * | 2003-03-28 | 2006-01-25 | 주식회사 잉크테크 | Organic silver conpound and it's preparation method, organic silver ink and it's direct wiring method |
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