CN101254541A - Preparation of nano aluminum powder for conducting resin and storage method - Google Patents
Preparation of nano aluminum powder for conducting resin and storage method Download PDFInfo
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- CN101254541A CN101254541A CNA2008100305235A CN200810030523A CN101254541A CN 101254541 A CN101254541 A CN 101254541A CN A2008100305235 A CNA2008100305235 A CN A2008100305235A CN 200810030523 A CN200810030523 A CN 200810030523A CN 101254541 A CN101254541 A CN 101254541A
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- silver
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Abstract
The invention relates to the preparation and storage method of silver nano-particles for conductive adhesive, in particular to a method for preparing silver nano-particles by reducing high-concentration silver nitrate by adopting a chemical liquid-phase method. The method comprises the following steps: mixing sodium hypophosphite, polyvinyl pyrrolidone and sodium hexametaphosphate to obtain reduction solution, adding sulfuric acid dropwise to adjust pH value, adding silver nitrate solution into the reduction solution under magnetically stirring to obtain silver colloid, standing, centrifugally separating, recovering filtrate, concentrating, centrifugally separating, washing the solid, vacuum-drying to obtain silver nano-particles, sealing and packaging, and storing at low temperature. The method adopts high-concentration silver nitrate solution, and has the advantages of simple process flow, high yield of silver powder, short production cycle and good safety. In the separation process, the filtrate can be recovered to improve the coefficient of recovery of silver powder. The silver nano-particle has spherical shape, uniform particle diameter, narrow distribution, high purity, good dispersibility, good storage stability and long storage time without oxidization, and can be used for conductive filler such as conductive adhesive.
Description
Technical field
The present invention relates to preparation, the storage procedures of noble metal nano silver powder, particularly adopt the method for chemical liquid phase reaction reduction high concentrate silver nitrate development nano-silver powder.
Background technology
Nano-silver powder demonstrates wide application prospect: add a spot of nano-silver powder in chemical fibre, can improve some performance of chemical fibre product, and make it have very strong sterilizing ability; An amount of nano-silver powder of doping in silicon oxide film can make the glass of this film of plating that certain luminescence generated by light is arranged; It is high by 30% than traditional material to utilize nano-silver powder to make the effectiveness of heat exchanger of dilution refrigeration agent; Industrial with the catalyst of nano-silver powder as some chemical reaction, can improve reaction speed and efficient etc. greatly; In addition, nano-silver powder receives much concern in the application of electron trades such as conducting resinl, electrocondution slurry.Preparing at present both at home and abroad the method that nano-silver powder generally adopts has: thermal decomposition method, electrochemical process, physics method, chemical deposition etc.The physics method can access highly purified nano-silver powder, but equipment is required height and production cost is higher, the investment big, industrial production difficulty height.The liquid phase chemical reduction method is the oxidation-reduction method of utilizing in the chemical reaction, and the silver ion reduction in the silver salt is become atom silver, thereby prepares nano-silver powder.It is simple that the liquid phase chemical reduction method has technology, operation easily, and production cost is low, is to have one of method of practical value most.Employing formaldehyde such as Chou Kan-Sen reduction liquor argenti nitratis ophthalmicus prepares nano silver particles, be used for adding to conducting resinl (Effect of nano-sized silver particles on the resistivity of polymeric conductiveadhesives, International Journal ofAdhesion﹠amp then; Adhesives25 (2005)); the silver sol nano particle size of preparing can be stablized 24 hours for 7nm-20nm, but the silver nitrate concentration that is adopted only is 0.01M; protective agent polyvinylpyrrolidone optimum amount is 9.27 times of silver nitrate quality, and output is less.
But there is following shortcoming in above-mentioned liquid phase chemical reduction method:
(1) silver nitrate concentration of Cai Yonging is relatively low, is unfavorable for large-scale production.
(2) filtrate after the Separation of Solid and Liquid is not handled, and makes that the rate of recovery of silver is on the low side relatively.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method who reacts the nano-silver powder that silver nitrate concentration height, silver powder rate of recovery height, production technology are simple, operation is convenient, equipment investment is few, with short production cycle is provided.Preparation spherical nano-silver powder, particle size evenly, narrowly distributing, purity height, good dispersion, excellent storage stability is preserved for a long time and oxidation is not taken place.
Conducting resinl of the present invention adopts chemical liquid phase reaction reduction high concentrate silver nitrate to prepare nano-silver powder and low tempertaure storage with preparation, the storage procedures of nano-silver powder,
1. solid nitric acid silver is dissolved in distilled water, is made into silver nitrate oxidation liquid, place 35 ℃-45 ℃ water-soluble constant temperature; The sodium hypophosphite adding distil water is made into reducing solution, adds the protective agent polyvinylpyrrolidone, sodium hexametaphosphate dispersant mixes, be placed on and add thermal agitation on the magnetic stirrer it is dissolved fully; With sulfuric acid solution regulator solution pH value to 1-2;
2. reducing solution is heated in 40 ℃-45 ℃ the scope, under stirring condition liquor argenti nitratis ophthalmicus is dripped wherein, drip fully after, continue to stir and obtain the aubergine silver sol;
3. after silver sol being left standstill, carry out centrifugation, filtrate recovery concentrates and returns next centrifugation, and solid carries out next step washing;
4. the solid nano silver powder that separation is obtained is used passivator, acetone, absolute ethanol washing respectively;
5. the nano-silver powder after will washing is put in the vacuum drying chamber dries, and finally can obtain the black nano silver powder;
6. the black nano silver powder that obtains is sealed and packed, place low tempertaure storage standby.
Described silver nitrate concentration scope between 0.75mol/L-1.0mol/L, 1.0mol/L most preferably; The concentration of reducing agent sodium hypophosphite between 0.05mol/L-0.1mol/L, 0.1mol/L most preferably, for its used amount of substance be with the silver nitrate reduction completely theoretical consumption 2-4 doubly, 4 times of the bests wherein; Protective agent polyvinylpyrrolidone quality equates with the silver nitrate quality; The amount of sodium hexametaphosphate dispersant is the 10-13% of silver nitrate quality, most preferably 12.5%.
The liquor argenti nitratis ophthalmicus rate of addition most preferably is 20/min.Centrifuge speeds most preferably is 7000r/min.Used passivator is 1,2 of w=1.0%, the 3-BTA.Drying condition is 50 ℃-60 ℃.Silver nitrate oxidation liquid is constant temperature in 35 ℃-45 ℃ water-soluble, most preferably is 40 ℃.
After liquor argenti nitratis ophthalmicus drips fully, continue to stir 30min.Silver sol left standstill carry out centrifugation after 1 hour.
The nano-silver powder storage temperature for preparing is controlled at 1 ℃-10 ℃.
This method has following technical process and processing step:
A. prepare liquor argenti nitratis ophthalmicus and reducing solution respectively
Take by weighing a certain amount of silver nitrate and be dissolved in solution and 40 ℃ of constant temperature water baths that distilled water is made into 1.0mol/L; Sodium hypophosphite, polyvinylpyrrolidone, the mixing of calgon adding distil water are made into reducing solution, and wherein sodium hypophosphite concentration is 0.1mol/L, and amount of substance is 4 times of theoretical consumption; Polyvinylpyrrolidone adds quality and equates with the silver nitrate quality; It is 12.5% of silver nitrate quality that calgon adds quality; With concentration is the sulfuric acid solution adjusting reducing solution pH value 1-2 of 1.0mol/L.
B. reducing solution is placed on the magnetic stirrer to stir and it is dissolved fully and is warming up to 40 ℃-50 ℃, liquor argenti nitratis ophthalmicus is added with the speed of 20/min react, dripping fully, follow-up continuous stirring obtains the aubergine nano silver colloidal sol.The course of reaction equation is as follows:
4Ag
++H
3PO
2+2H
2O→4Ag↓+H
3PO
4+4H
+
C. carry out centrifugation after silver sol leaves standstill, Separation of Solid and Liquid comes, and filtrate recovery concentrates returns next centrifugation; The solid that obtains is used passivator (1,2, the 3-BTA), acetone, absolute ethanol washing respectively.
D. be placed in the vacuum drying chamber dry.
E. it is standby that dried nano-silver powder good seal is put in the refrigerator low tempertaure storage.
The present invention is suitable for preparation, the storage of conducting resinl with nano-silver powder.With other preparation method following advantage is arranged relatively:
1, production technology of the present invention is simple, is easy to control, operation, and equipment investment is few, and used silver nitrate concentration is for can reach 1.0mol/L, and the silver raising recovery rate height is easy to realize industrialization.
2, the filtrate after the Separation of Solid and Liquid is carried out effective processing, returned silver sol after recovery concentrates and carry out next centrifugation, improved the silver-colored rate of recovery.
3, prepared nano-silver powder particle diameter evenly, scope narrowly distributing, purity height, grain size is at 30nm-50nm.
4, prepared nano-silver powder can be preserved for a long time, is the desirable feedstock of silver conductive adhesive, electrocondution slurry.
Description of drawings
Fig. 1: preparation technology's flow chart of nano-silver powder of the present invention.
Fig. 2: the XRD analysis collection of illustrative plates of preparation nano-silver powder.
Fig. 3: the transmission electron microscope picture of preparation nano-silver powder.
Fig. 4: the energy spectrum analysis figure before and after nano-silver powder is stored.(a: newly prepare nano-silver powder; B: after depositing 1 month)
The specific embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further, and the present invention can implement by described any mode of summary of the invention.
Embodiment: used silver nitrate (analyzing pure), its main component (%) is: AgNO
3〉=99.8%, water-insoluble≤0.005%, chloride≤0.001%, sulfate≤0.004%, Fe≤0.0004%, Cu≤0.001%, Pb≤0.001%, hydrochloric acid is sediment≤0.02% not.
Take by weighing AgNO
33.4g be dissolved in the AgNO that 20mL distilled water is made into 1.0mol/L
3Oxidation liquid, and be positioned over constant temperature in 40 ℃ the water-bath; Take by weighing 1.06g sodium hypophosphite, 3.4g polyvinylpyrrolidone (PVP), 0.43g calgon respectively and be dissolved in 100mL distilled water and be made into reducing solution, add 2mL sulfuric acid (c (H simultaneously
2SO
4)=1.0mol/L) regulated pH value to 2; Reducing solution is positioned on the magnetic stirrer heating and stirs it is dissolved fully, be heated to 42 ℃ and keep constant temperature, under high-speed stirred with the speed of 20/min with AgNO
3The oxidation drop is added; Dripping fully, follow-up continuous stirring 30min obtains the aubergine silver sol; After silver sol leaves standstill 1h, centrifugation (rotating speed 7000r/min) 10min; Filtrate is reclaimed, and the solid nano silver powder that obtains uses 1,2 respectively, the aqueous solution of 3-BTA (w=1%), acetone, absolute ethanol washing, centrifugation once more; At last the silver powder that separates is placed in 52 ℃ of vacuum drying chambers dry 5 hours, obtains black nano silver powder; Package be placed in the refrigerating chamber store standby.
The sample that makes is carried out every performance test, and test case and result are as follows:
With X-ray diffraction analysis (XRD), can determine that from diffraction peak prepared black powder is pure nano-silver powder.Utilize Tecnai G
220 transmission electron microscopes (TEM) are observed, and prepared nano-silver powder is spherical in shape, even particle size, and narrow diameter distribution mainly concentrates between the 30nm-50nm.
Claims (11)
1, conducting resinl adopts chemical liquid phase reaction reduction high concentrate silver nitrate to prepare nano-silver powder and low tempertaure storage with preparation, the storage procedures of nano-silver powder, it is characterized in that:
1. solid nitric acid silver is dissolved in distilled water, is made into silver nitrate oxidation liquid, place 35 ℃-45 ℃ water-soluble constant temperature; The sodium hypophosphite adding distil water is made into reducing solution, adds the protective agent polyvinylpyrrolidone, sodium hexametaphosphate dispersant mixes, be placed on and add thermal agitation on the magnetic stirrer it is dissolved fully; With sulfuric acid solution regulator solution pH value to 1-2;
2. reducing solution is heated in 40 ℃-45 ℃ the scope, under the high-speed stirred condition liquor argenti nitratis ophthalmicus is dripped wherein, drip fully after, continue to stir and obtain the aubergine silver sol;
3. after silver sol being left standstill, carry out centrifugation, filtrate recovery concentrates and returns next centrifugation, and solid carries out next step washing;
4. the solid nano silver powder that separation is obtained is used passivator, acetone, absolute ethanol washing respectively;
5. the nano-silver powder after will washing is put in the vacuum drying chamber dries, and finally can obtain the black nano silver powder;
6. the black nano silver powder that obtains is sealed and packed, place low tempertaure storage standby.
2, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder the silver nitrate concentration scope is between 0.75mol/L-1.0mol/L; The concentration of reducing agent sodium hypophosphite between 0.05mol/L-0.1mol/L, its used amount of substance be with silver nitrate reduction completely theoretical consumption 2-4 doubly; The quality of used protective agent polyvinylpyrrolidone equates with the silver nitrate quality; The quality of used sodium hexametaphosphate dispersant is the 10%-13% of silver nitrate quality.
3, conducting resinl as claimed in claim 2 is characterized in that with preparation, the storage procedures of nano-silver powder silver nitrate concentration is 1.0mol/L; The optimum concentration of reducing agent sodium hypophosphite is 0.1mol/L, and its used amount of substance is with silver nitrate reduction 4 times of theoretical consumption completely; Protective agent polyvinylpyrrolidone optimum amount equates with the silver nitrate quality; The optimum amount of sodium hexametaphosphate dispersant is 12.5% of a silver nitrate quality.
4, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder the liquor argenti nitratis ophthalmicus rate of addition is 20/min.
5, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder the centrifugation rotating speed of employing is 7000r/min.
6, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder used passivator is 1,2 of w=1.0%, the 3-BTA.
7, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder drying condition is 50 ℃-60 ℃.
8, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder, and silver nitrate oxidation liquid is constant temperature in 35 ℃-45 ℃ water-soluble.
9, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder, after liquor argenti nitratis ophthalmicus drips fully, continues to stir 30min.
10, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder, silver sol is left standstill carry out centrifugation after 1 hour.
11, conducting resinl as claimed in claim 1 is characterized in that with preparation, the storage procedures of nano-silver powder the nano-silver powder storage temperature for preparing is controlled at 1 ℃-10 ℃.
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| CN101450386B (en) * | 2008-12-30 | 2010-10-13 | 天津大学 | Nano silver or gold material preparation method using inorganic polyphosphate as protectant |
| CN102189270A (en) * | 2011-05-04 | 2011-09-21 | 上海大学 | Method for chemically synthesizing nano lead-free solder particles with low melting point |
| CN103128298A (en) * | 2011-11-28 | 2013-06-05 | 重庆华浩冶炼有限公司 | Metal powder production method |
| CN103331454A (en) * | 2013-07-02 | 2013-10-02 | 南京大学 | Nano-silver manufacturing technology |
| CN103894625A (en) * | 2014-04-21 | 2014-07-02 | 中国医学科学院生物医学工程研究所 | Preparation method for bionic nano-silver |
| CN104174864A (en) * | 2013-05-21 | 2014-12-03 | 中国科学院理化技术研究所 | Preparation method of nano or sub-micron silver particle powder |
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| CN101450386B (en) * | 2008-12-30 | 2010-10-13 | 天津大学 | Nano silver or gold material preparation method using inorganic polyphosphate as protectant |
| CN102189270A (en) * | 2011-05-04 | 2011-09-21 | 上海大学 | Method for chemically synthesizing nano lead-free solder particles with low melting point |
| CN103128298B (en) * | 2011-11-28 | 2016-02-10 | 重庆华浩冶炼有限公司 | A kind of production method of metal dust |
| CN103128298A (en) * | 2011-11-28 | 2013-06-05 | 重庆华浩冶炼有限公司 | Metal powder production method |
| CN104174864B (en) * | 2013-05-21 | 2016-06-01 | 中国科学院理化技术研究所 | The preparation method of a kind of nanometer or submicron order Argent grain powder |
| CN104174864A (en) * | 2013-05-21 | 2014-12-03 | 中国科学院理化技术研究所 | Preparation method of nano or sub-micron silver particle powder |
| CN103331454A (en) * | 2013-07-02 | 2013-10-02 | 南京大学 | Nano-silver manufacturing technology |
| CN103894625A (en) * | 2014-04-21 | 2014-07-02 | 中国医学科学院生物医学工程研究所 | Preparation method for bionic nano-silver |
| CN103894625B (en) * | 2014-04-21 | 2016-09-21 | 中国医学科学院生物医学工程研究所 | A kind of preparation method of bionic nano silver |
| CN107000050A (en) * | 2014-09-29 | 2017-08-01 | 同和电子科技有限公司 | Silver powder and preparation method thereof and conductive hydrophilic slurry |
| CN107000050B (en) * | 2014-09-29 | 2019-11-26 | 同和电子科技有限公司 | Silver powder and preparation method thereof and conductive hydrophilic slurry |
| CN104353843B (en) * | 2014-10-29 | 2017-04-19 | 长沙理工大学 | Method for preparing high-purity superfine silver powder from copper or lead anodic slimes |
| CN104353843A (en) * | 2014-10-29 | 2015-02-18 | 长沙理工大学 | Method for preparing high-purity superfine silver powder from copper or lead anodic slimes |
| CN104772471A (en) * | 2015-04-24 | 2015-07-15 | 北京化工大学 | Preparation method of nano-silver colloid with preservation performance |
| CN104741621A (en) * | 2015-04-24 | 2015-07-01 | 北京化工大学 | Preparation method of nano-silver colloid with antibacterial property |
| CN106180746A (en) * | 2016-07-06 | 2016-12-07 | 江苏理工学院 | A kind of preparation method of electrical alloy copper silver powder |
| CN107570912A (en) * | 2017-08-30 | 2018-01-12 | 桂林电子科技大学 | A kind of preparation method of the nano mattisolda with high wettability energy |
| CN107858039A (en) * | 2017-11-13 | 2018-03-30 | 天津宝兴威科技股份有限公司 | A kind of preparation method of water-based UV conductive oils ink film |
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