CN102069193B - Method for preparing granularity-controllable narrow-distribution spherical easily-dispersible silver powder through radiation reduction - Google Patents
Method for preparing granularity-controllable narrow-distribution spherical easily-dispersible silver powder through radiation reduction Download PDFInfo
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- CN102069193B CN102069193B CN201110008831XA CN201110008831A CN102069193B CN 102069193 B CN102069193 B CN 102069193B CN 201110008831X A CN201110008831X A CN 201110008831XA CN 201110008831 A CN201110008831 A CN 201110008831A CN 102069193 B CN102069193 B CN 102069193B
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Abstract
The invention relates to the technical field of preparing powder materials through nuclear radiation technology, in particular to a method for preparing granularity-controllable narrow-distribution spherical easily-dispersible silver powder through radiation reduction. Chemically reduced small-granularity monodisperse silver powder is taken as a seed, silver ions are reduced under the gamma-ray radiation generated by radioactive substances, and the narrow-distribution, granularity-controllable, spherical and smooth-surface silver powder is obtained. The method comprises the following steps of: (1) preparing seed silver powder; (2) preparing raw materials for preparing the silver powder, and stirring and mixing; and (3) performing radiation reduction reaction by using cobalt-60 with stirring to obtain the narrow-distribution, granularity-controllable, spherical and smooth-surface silver powder, wherein the granularity is controlled to be 0.5-5mu m. The method has the advantages that: the seed silver powder is taken as a template, the narrow-distribution, granularity-controllable and spherical silver powder is generated through radiation reduction, the design and arbitrary mixing of electronic paste are facilitated, and the silver powder can meet various application requirements and has great promotion effect on development of electronic devices and products.
Description
Technical field
The present invention relates to utilize nuclear radiation tech to prepare the technical field of powder body material, concrete is a kind of through the controlled narrow spherical method that is prone to disperse silver powder that distributes of radiation reduction prepared sizes.
Background technology
At present, silver powder adopts chemical reduction method to make more.Chinese patent (publication number CN 1227148A) discloses " a kind of method of utilizing formates to be mixed with silver powder for reducing agent and special nozzle ", but it needs special shower nozzle equipment, is unfavorable for large-scale production.Chinese patent (publication number CN 101462164A) discloses " a kind of electronation prepares the method for high tap density silver powder ", but its size distribution broad still.Chinese patent (publication number CN 1709618A) discloses " a kind of method for preparing nanometer, sub-micron and silver powder ", but its particle diameter is mainly at Nano grade, and particle diameter is less.Chinese patent (publication number CN 101347841A) discloses " a kind of preparation method who utilizes tipping prepared sizes high tap density silver powder with controllable ", and it causes the adhesion between particulate possibly when producing.Chinese patent (publication number CN 101569937A) discloses " a kind of method that liquor argenti nitratis ophthalmicus and reducing agent is added simultaneously hyper-dispersant formulations prepared from solutions silver powder "; Chinese patent (publication number CN 1387968A) discloses " a kind of method for preparing silver powder through adjusting liquor argenti nitratis ophthalmicus pH value "; But; From they concrete contents of introducing, the distribution of the silver powder particle diameter of these methods preparations is all than broad.Chinese patent (publication number CN 101612670A) discloses and " a kind ofly in the aqueous solution, has utilized
60Co-gamma-ray irradiation reduction prepare the method for nano-scale silver powder ", the method is easy to operate, and is with short production cycle and do not produce any environmental pollution, and still, all in 10～50 nanometers, particle diameter is less for its particle diameter, is not suitable for application.In addition, and " radiation research and radiation process journal " (2001,02:118) published the report of " a kind of irradiation template prepares the method for Nano Silver band ".But the technology of existing irradiation reduction preparation of silver powder can only prepare nano level silver powder, has influenced its scope of application.
Can find out that from disclosed document present silver powder technology of preparing is chemical reduction method mostly, the deficiency that they exist is: the silver powder particle diameter wider distribution of preparation, and rough, be prone to bonding between the particle, dispersed relatively poor, it is complicated to operate relative irradiation method.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of in the presence of seed silver powder, through
60The method of the narrow distribution of Co-gamma-ray irradiation reduction preparation, particle diameter controlled (between 0.5～5 μ m), sphere, compact structure, ganoid silver powder, the silver powder of its preparation is convenient to the design of electric slurry, can satisfy multiple different application requirements.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
A kind of through the controlled narrow spherical method that is prone to disperse silver powder that distributes of radiation reduction prepared sizes; Utilize the single silver powder that disperses of small particle diameter of electronation to be seed; Under the gamma-ray irradiation condition that radioactive substance produced, reduce silver ion; Obtain controlled, the spherical and ganoid silver powder of narrow distribution, particle diameter, its concrete preparation process comprises:
(1) preparation of seed silver powder: at first in silver nitrate aqueous solution (weight fraction 1～25%), add dispersant (weight fraction 0.1～5%) and ammoniacal liquor; Then the reducing agent aqueous solution (weight fraction 0.1～10%) is added drop-wise in the silver ammino solution, 35 ℃ were reacted 1 hour; The silver powder of gained is used washed with de-ionized water, obtain the silver powder seed of monodisperse spherical, its particle diameter is between 150～400nm;
(2) mark disposes the raw material for preparing silver powder by weight: seed silver powder 1～35%, dispersant 0.1～5%, silver nitrate 1～50%, active ion agent for capturing 0.5～10%, deionized water 45～90%;
The seed silver powder that step (1) is obtained joins in the deionized water that contains dispersant, stirs down to add liquor argenti nitratis ophthalmicus, active ion agent for capturing, feeds inert gas and deoxygenation 5 minutes;
(3) put into radiation source; Under stirring condition, carry out the radiation reduction reaction; The close rate of irradiation is 0.8～6.0 kGy/h, and absorbed dose of radiation is 10～30kGy, and the silver powder after the radiation reduction reaction is used washed with de-ionized water; Obtain controlled, the spherical and ganoid silver powder of narrow distribution, particle diameter, its particle diameter is between 0.5～5 μ m.
Described dispersant comprises a kind of in polyvinylpyrrolidone (PVP), gelatin, the polyvinyl alcohol (PVA).
Described reducing agent comprises a kind of in hydrazine hydrate, formaldehyde, ascorbic acid and the glucose.
Described active ion agent for capturing comprises a kind of in isopropyl alcohol, n-butanol and the isoamyl alcohol.
Described radiation source be cobalt-60 (
60Co).
Good effect of the present invention is:
(1) in the presence of seed silver powder, through the radiation reduction, be template with seed silver powder, generate narrow distribution and size-controllable spherical silver powder;
(2) because
60The gamma-ray penetrability of Co-is high, and is more even when making the generation of system silver crystal grain when irradiation than electronation, so the silver powder surface that makes is more smooth; In addition, the particle diameter of final silver powder can be controlled through the amount that adds silver ion solution;
(3) the narrow spherical dispersion silver powder that is prone to that distributes of the controllable granularity of the present invention's preparation is convenient to the design of electric slurry and collocation arbitrarily, can satisfy multiple demands of applications, and its application will have bigger impetus to the development of electronic device and product.
The specific embodiment
Below introduce the present invention through the controlled narrow spherical practical implementation process that is prone to disperse the method for silver powder that distributes of radiation reduction prepared sizes through specific embodiment, 3 embodiment are provided.But it may be noted that enforcement of the present invention is not limited to following embodiment.
Embodiment 1Radiation reduction preparation 1.0 μ m monodisperse spherical silver powder
(1) preparation of 200nm seed silver powder: at first with adding dispersant PVP (weight fraction 0.1%) and ammoniacal liquor among silver nitrate aqueous solution (weight fraction 5%) 50L, the amount of ammoniacal liquor is suitable so that system is dissolved as; Then 50L hydrazine hydrate aqueous solution (weight fraction is 0.1%) is added drop-wise in the silver ammino solution, 35 ℃ were reacted 1 hour; The silver powder of gained is repeatedly cleaned with the deionized water warp, in the aqueous solution, do not contain till organic impurity, obtain the seed silver powder of clean monodisperse spherical, its particle diameter is 200nm;
(2) get the 200nm seed silver powder 1Kg that step (1) obtains and join in the 10L deionized water that contains dispersant PVP (weight fraction 0.5%) and active particle agent for capturing (weight fraction is 0.5%) dispersed with stirring; Add liquor argenti nitratis ophthalmicus (weight fraction 5%) 10L again, fed nitrogen and deoxygenation 5 minutes;
(3) put into radiation source cobalt-60, under stirring condition, carry out the radiation reduction reaction, the close rate of irradiation is 1.0 kGy/h, and absorbed dose of radiation is 3 kGy; Silver powder after the radiation reduction reaction with washed with de-ionized water repeatedly obtains the monodisperse spherical silver powder of 1.0 μ m.
Embodiment 2Radiation reduction preparation 2.0 μ m monodisperse spherical silver powder
(1) (with embodiment 1);
(2) get the seed silver powder 1Kg that step (1) obtains and join in the 10L deionized water that contains gelatin (weight fraction 1%) and active particle agent for capturing (weight fraction 0.5%) dispersed with stirring; Add liquor argenti nitratis ophthalmicus (weight fraction 10%) 10L again, logical nitrogen and deoxygenation 5 minutes;
(3) put into radiation source cobalt-60, under stirring condition, carry out the radiation reduction reaction, the close rate of irradiation is 0.5 kGy/h, and absorbed dose of radiation is 5 kGy; Silver powder after the radiation reduction reaction with washed with de-ionized water does not repeatedly contain till organic impurity in the aqueous solution, obtains the monodisperse spherical silver powder of 2.0 μ m.
Embodiment 3Radiation reduction preparation 5.0 μ m monodisperse spherical silver powder
(1) preparation of 400nm seed silver powder: at first with adding dispersant PVP (weight fraction is 0.5%) and ammoniacal liquor among silver nitrate (weight fraction 10%) aqueous solution 10L, the amount of ammoniacal liquor is suitable so that system is dissolved as; Then 5L hydrazine hydrate aqueous solution (weight fraction is 1%) is added drop-wise in the silver ammino solution, 35 ℃ were reacted 1 hour; The silver powder of gained is repeatedly cleaned with the deionized water warp, in the aqueous solution, do not contain till organic impurity, obtain the seed silver powder of clean monodisperse spherical, its particle diameter is 400nm;
(2) getting the 400nm seed silver powder 0.5Kg that step (1) obtains joins in the 20L deionized water solution that contains dispersant polyethylene glycol (weight fraction 2%) and active particle agent for capturing (weight fraction 0.5%); Dispersed with stirring; Add liquor argenti nitratis ophthalmicus (weight fraction 10%) 20L again, logical nitrogen and deoxygenation 5 minutes;
(3) put into radiation source cobalt-60, under stirring condition, carry out the radiation reduction reaction, the close rate of irradiation is 0.5 kGy/h, and absorbed dose of radiation is 8 kGy; Silver powder after the radiation reduction reaction with washed with de-ionized water does not repeatedly contain till organic impurity in the aqueous solution, obtains the monodisperse spherical silver powder of 5.0 μ m.
The narrow spherical silver powder that is prone to disperse that distributes of the controllable granularity of embodiment 1～3 preparation is analyzed with ESEM (SEM), and the silver powder particle diameter that obtains, shape and dispersed index are: (seeing the following form)
Claims (4)
1. one kind through the controlled narrow spherical method that is prone to disperse silver powder that distributes of radiation reduction prepared sizes; Utilize the single silver powder that disperses of small particle diameter of electronation to be seed; Under the gamma-ray irradiation condition that radioactive substance produced, reduce silver ion; Obtain controlled, the spherical and ganoid silver powder of narrow distribution, particle diameter, it is characterized in that its concrete preparation process comprises:
(1) preparation of seed silver powder: be that to add weight fraction in 1～25% the silver nitrate aqueous solution be 0.1～5% dispersant and ammoniacal liquor at first at weight fraction; Be that 0.1～10% the reducing agent aqueous solution is added drop-wise in the silver ammino solution with weight fraction then, 35 ℃ of reactions 1 hour; The silver powder of gained is used washed with de-ionized water, obtain the seed silver powder of monodisperse spherical, its particle diameter is between 150～400nm;
(2) mark disposes the raw material for preparing silver powder by weight: seed silver powder 1～35%, dispersant 0.1～5%, silver nitrate 1～50%, active ion agent for capturing 0.5～10%, deionized water 45～90%;
The seed silver powder that step (1) is obtained joins in the deionized water that contains dispersant, stirs down to add liquor argenti nitratis ophthalmicus, active ion agent for capturing, feeds inert gas and deoxygenation 5 minutes;
(3) put into radiation source; Under stirring condition, carry out the radiation reduction reaction; The close rate of irradiation is 0.8～6.0 kGy/h, and absorbed dose of radiation is 10～30kGy, and the silver powder after the radiation reduction reaction is used washed with de-ionized water; Obtain controlled, the spherical and ganoid silver powder of narrow distribution, particle diameter, its particle diameter is between 0.5～5 μ m;
Described radiation source is a cobalt-60.
2. according to claim 1ly it is characterized in that described dispersant comprises a kind of in polyvinylpyrrolidone, gelatin, the polyvinyl alcohol through the controlled narrow spherical method that is prone to disperse silver powder that distributes of radiation reduction prepared sizes.
3. according to claim 1ly it is characterized in that described reducing agent comprises a kind of in hydrazine hydrate, formaldehyde, ascorbic acid and the glucose through the controlled narrow spherical method that is prone to disperse silver powder that distributes of radiation reduction prepared sizes.
4. according to claim 1ly it is characterized in that described active ion agent for capturing comprises a kind of in isopropyl alcohol, n-butanol and the isoamyl alcohol through the controlled narrow spherical method that is prone to disperse silver powder that distributes of radiation reduction prepared sizes.
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| CN201110008831XA CN102069193B (en) | 2011-01-17 | 2011-01-17 | Method for preparing granularity-controllable narrow-distribution spherical easily-dispersible silver powder through radiation reduction |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102248177B (en) * | 2011-07-29 | 2012-12-12 | 上海龙翔新材料科技有限公司 | Laser-induced method for preparing spherical silver powder |
| CN103203468B (en) * | 2013-04-17 | 2016-05-25 | 苏州冷石纳米材料科技有限公司 | A kind of preparation method of nano silver wire |
| CN105364082B (en) * | 2014-08-18 | 2018-01-19 | 上海理凯材料科技有限公司 | The method that radiation reduction prepares silver powder |
| CN114007783A (en) * | 2019-06-20 | 2022-02-01 | 南非大学 | Nanofluid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127177A (en) * | 1995-01-16 | 1996-07-24 | 中国科学技术大学 | Ionization radiation chemistry redox preparation method for nm metal powder |
| CN1557588A (en) * | 2004-01-13 | 2004-12-29 | 上海大学 | Method for manufacturing nano-silver |
| JP2009256776A (en) * | 2008-03-27 | 2009-11-05 | Tokyo Printing Ink Mfg Co Ltd | Method for producing silver fine particle |
| CN101612670A (en) * | 2009-07-13 | 2009-12-30 | 浙江省技术物理应用研究所 | A kind ofly in the aqueous solution, use 60The Co-gamma-rays prepares the method for nano-silver powder |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127177A (en) * | 1995-01-16 | 1996-07-24 | 中国科学技术大学 | Ionization radiation chemistry redox preparation method for nm metal powder |
| CN1557588A (en) * | 2004-01-13 | 2004-12-29 | 上海大学 | Method for manufacturing nano-silver |
| JP2009256776A (en) * | 2008-03-27 | 2009-11-05 | Tokyo Printing Ink Mfg Co Ltd | Method for producing silver fine particle |
| CN101612670A (en) * | 2009-07-13 | 2009-12-30 | 浙江省技术物理应用研究所 | A kind ofly in the aqueous solution, use 60The Co-gamma-rays prepares the method for nano-silver powder |
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