CN101972855A - Method for preparing silver micro-powder for high-temperature sintering silver pastes - Google Patents
Method for preparing silver micro-powder for high-temperature sintering silver pastes Download PDFInfo
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- CN101972855A CN101972855A CN 201010542552 CN201010542552A CN101972855A CN 101972855 A CN101972855 A CN 101972855A CN 201010542552 CN201010542552 CN 201010542552 CN 201010542552 A CN201010542552 A CN 201010542552A CN 101972855 A CN101972855 A CN 101972855A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 37
- 239000004332 silver Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 title abstract description 6
- 238000005245 sintering Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 238000012805 post-processing Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 53
- 238000002360 preparation method Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- 229920002521 macromolecule Polymers 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 13
- 239000002562 thickening agent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 239000007787 solid Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 229920000447 polyanionic polymer Polymers 0.000 claims description 5
- 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 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 235000010489 acacia gum Nutrition 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 230000029087 digestion Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000003311 flocculating effect Effects 0.000 abstract 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000005303 weighing Methods 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007603 infrared drying Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920006321 anionic cellulose Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940053080 isosol Drugs 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing silver micro-powder for high-temperature sintering silver pastes, which comprises the following steps: preparing a colloidal liquid silver system, a colloidal reduction system and protection solution firstly; then mixing the three. In the invention, a sol gel process and a solution chemical reduction method are used to effectively control the reaction process, so that the industrialized production can be performed stably, and the uniform reaction under the condition of production enlarging still can be ensured, thereby greatly improving the uniformities of shapes and other superficial characteristics of silver particles generated by reaction, and eventually generating flocculating soft silver powder wodges which are easy to carry out post-processing such as collecting and washing, and the like.
Description
Technical field
The present invention relates to a kind of preparation of functional micro silver powder, its preparation method is suitable for industrial large-scale production micro silver powder.The use of can arranging in pairs or groups in proportion of preparation gained micro silver powder is to satisfy the preparation of electric slurry.
Background technology
Metal ultrafine powder itself possesses superior catalytic performance, magnetic property, electrical property etc., thereby in the application that has aspect industry such as aerospace, atomic energy, electronics, powder metallurgy, chemistry and medical science, the bioengineering more and more widely.
Wherein micro silver powder is owing to have good electric conductivity and application performance, and application is very extensive in fields such as electronics and electronic materials, has the status that can not be substituted in electronics industry.Micro silver powder is mainly used in the preparation conductive silver paste, and electronics silver slurry series of products are a kind of noble metal slurries that are most widely used in the electronics industry with the consumption maximum, are the critical materials of producing various electronic devices and components.Micro silver powder also in physical property, all has strict demand as granule-morphology, dispersiveness, diameter of particle, size distribution, surface property, crystallinity, tap density etc. except that chemical composition, impurity content etc. has higher requirements.The performance of micro silver powder directly determines key technologies such as conductance after the conductive silver paste film forming and compactness.
The preparation method of micro silver powder has a variety of, mainly contains vapor phase method, liquid phase method and solid phase method.The vapor phase method investment is big, energy consumption is high, productive rate is low; The micro silver powder particle diameter of solid phase method preparation is bigger than normal and particle size distribution range is wide; Liquid phase method is the method that the most general being used at present prepares micro silver powder.And liquid phase method divides chemical reducing process, electrochemical deposition method, electrolysis, sputtering method, sol-gal process etc.Industrial production micro silver powder adopts the liquid phase chemical reduction method mostly.
The principle that the liquid phase chemical reduction legal system is equipped with micro silver powder is with reducing agent silver to be deposited out with powder type from its salt or the complex aqueous solution or organic system.Chemical reduction method prepares the key of micro silver powder, to search out a suitable chemical reaction condition exactly: one, select corresponding reaction material to come the nucleation and the nucleus growth speed of powder are controlled, reducing agent commonly used has formaldehyde, ascorbic acid, glycerine, organic amine, unsaturated alcohol, natrium citricum, hydrazine and hydrazine derivative etc., the general hydrazine hydrates that adopt more.Two, select effective dispersant can eliminate multiple nucleation and increase the merging speed of nucleus before reaching critical radius, thereby reduce the reunion between powder granule.Generally select long-chain protective agents such as gelatin, gum arabic, polyvinyl alcohol, PVP, Sodium Polyacrylate for use.
Electronation silver powder belongs to a silver-colored solids precipitation process, its process comprises reaction nucleation and two processes of crystalline growth, owing to be reacted into nuclear process is quick moment reaction (Millisecond), must make reactant moment in reactor reach molecular level and else realize promptly evenly that microcosmic mixes, just can make the final silver powder pattern may be consistent.
How controlling its particle size, size distribution and pattern when producing in batches is even more important for producing micro silver powder.Patent about the micro silver powder preparation has much both at home and abroad; but less to silver powder particles pattern and uniformity control set forth; and most of silver powder preparations are not tight to the technology controlling and process of course of reaction and selection all from selecting suitable dispersant, protective agent to start with, and are difficult to be amplified to industrial process.Publication number CN1266761A preparation method makes silver ammino solution with silver nitrate, slowly adds in the reducing solution that is made into by reducing agent and protective agent then, prepares nano silver colloidal sol, and high speed centrifugation separates, and leaches silver powder, washs, drying again.This method is unfavorable for the control of silver powder granularity, and the high speed centrifugation separating energy consumption is big, and equipment is required height, and Separation of Solid and Liquid is collected difficulty, is difficult to satisfy industrialization and produces for large quantities of times; Publication number CN1785558 preparation method adopts and in oxidation-reduction process liquor argenti nitratis ophthalmicus is added drop-wise in reducing agent and the dispersant, pH value with the ammoniacal liquor regulator solution prepares micron order silver powder simultaneously, makes the micron grade ball shape silver powder of the different-grain diameter of 0.1～3.0 μ m.This method has been strengthened the stable control of pH value in the course of reaction, make whole process of preparation in more stable controlled range, help amplifying and produce, but amplification along with batch output, this method exists local reaction concentration and W-response concentration difference constantly to widen, owing to be reacted into nuclear process is quick moment reaction (Millisecond), and amplifying the concentration difference of producing and producing will directly influence the uniformity of silver powder.
Summary of the invention
For addressing the above problem, the object of the invention is exactly the deficiency at prior art, a kind of high-temperature sintered silver paste micro silver powder preparation method is provided, its technological process is simple, technology amplify stable, controllability is strong, be easy to suitability for industrialized production, the micro silver powder of preparing simultaneously is applicable to the conductive filler of piezoelectricity, high temperature sintering slurry such as pressure-sensitive.
The present invention is achieved in that a kind of high-temperature sintered silver paste micro silver powder preparation method, it is characterized in that may further comprise the steps:
(1) the preparation silver ammino solution adds macromolecule thickener solution, and fully stirring and dissolving forms the silvering solution system of colloidal sol shape;
(2) preparation is fully stirred the reduction system that forms the colloidal sol shape by the reduction system of reducing agent, NaOH and macromolecule thickener solution composition;
(3) preparation contains the protection solution of macromolecule space obstacle agent;
(4) the silvering solution system of step (1) gained is mixed in the protection solution that directly is added to step (3) gained with the reduction system of step (2) gained, constantly stir in the adition process;
(5) stop to stir and ageing behind reinforced the finishing, obtain flocculence micro silver powder slurries;
(6) Separation of Solid and Liquid, washing, post processing are separated soft-agglomerated, dry.
In the described step (1), the content range of silver ion is 10-50g/L in the silvering solution system, more preferably is selected as 20-30g/L.
In described step (1) and the step (2), macromolecule thickener solution is selected from a kind of or mixed solution in Arabic gum, gelatin, polyanion cellulose, methylcellulose, the sodium carboxymethylcellulose.
In described step (1) and the step (2), the mass ratio of macromolecule thickener and silver ion is 0.1～10: 100, more preferably is selected as 2～5: 100.
Described step (2), in whole reduction system, reducing agent is selected from one or more mixing of vitamin C, formaldehyde, hydrazine hydrate, formic acid, sodium borohydride, and in whole reduction system, reducing agent is 1: 1～20 with the mass ratio of silver; The mass ratio of silver ion and NaOH is 4～6: 1.
The macromolecule space obstacle agent of described step (3) is selected from polyvinyl alcohol or polyvinylpyrrolidone.
In the described step (4), the silvering solution system is mixed by pressurization and stream with reduction system.Pressure limit is preferably 0.03-0.05Mpa in 0.01-0.1Mpa
In the described step (4), silvering solution system, reduction system, protection solution three's reaction ratio is 3.5～4.5: 3.5～4.5: 2.
In the described step (4), the rotating speed of stirring is 60-100r/min.
In the described step (5), digestion time is 20-40min.
The present invention is used by adopting sol-gal process and liquid phase chemical reduction method, course of reaction has been carried out effective control, can be stable carry out suitability for industrialized production, but and guarantee to amplify and produce still homogeneous reaction, improve the silver-colored granule-morphology of reaction generation and the homogeneity of other signs greatly, the final soft-agglomerated silver powder of flocculence that generates is easy to collect washing and waits post processing.
Description of drawings
Fig. 1 is the Electronic Speculum figure of the embodiment of the invention 1 obtained silver powder;
Fig. 2 is the Electronic Speculum figure of the embodiment of the invention 2 obtained silver powder;
Fig. 3 is the Electronic Speculum figure of the embodiment of the invention 3 obtained silver powder.
The specific embodiment
The present invention is a kind of high-temperature sintered silver paste micro silver powder preparation method, may further comprise the steps:
(1) the preparation silver ammino solution adds macromolecule thickener solution, and fully stirring and dissolving forms the silvering solution system of colloidal sol shape.Wherein, macromolecule thickener solution is selected from a kind of or mixed solution in Arabic gum, gelatin, polyanion cellulose, methylcellulose, the sodium carboxymethylcellulose.
(2) preparation is fully stirred the reduction system that forms the colloidal sol shape by the reduction system of reducing agent, NaOH and macromolecule thickener solution composition.In the system, reducing agent can be selected one or more of vitamin C, formaldehyde, hydrazine hydrate, formic acid, sodium borohydride for use, and reducing agent is 1: 1～20 with the mass ratio of silver; The mass ratio of silver ion and NaOH is 4～6: 1.Best, reducing agent is 1: 1.2～15 with the mass ratio of silver; The mass ratio of silver ion and NaOH is 5: 1.
(3) preparation contains the protection solution of macromolecule space obstacle agent.The agent of macromolecule space obstacle is optional from polyvinyl alcohol or polyvinylpyrrolidone.
(4) the silvering solution system of step (1) gained is mixed in the protection solution that directly is added to step (3) gained with the reduction system of step (2) gained, constantly stir in the adition process.The rotating speed that stirs is preferably 60-100r/min.Silvering solution system, reduction system, protection solution three's reaction ratio is 3.5～4.5: 3.5～4.5: 2, and the best is 4: 4: 2.
(5) stop to stir and ageing behind reinforced the finishing, the preferred 20-40min of digestion time obtains flocculence micro silver powder slurries;
(6) soft-agglomerated, drying etc. is separated in Separation of Solid and Liquid, washing, post processing.
The present invention is used by adopting sol-gal process and liquid phase chemical reduction method, and course of reaction has been carried out effective control, can be stable carry out suitability for industrialized production.The present invention is used by agent of anionic cellulose isosol and polyvinylpyrrolidone dispersant, uses the generation of flocculant stopping reaction silver particle, uses dispersant that the silver-colored particle that generates is disperseed protection simultaneously, prevents the silver powder reunion.React with stable control by the consumption and the mixing speed of regulating flocculant, making silver ion mix, react nucleation with reduction system slows down, the flocculant that is adopted simultaneously has parcel and space obstacle effect to generating silver-colored particle, thus the silver-colored granule-morphology that better control reaction generates and the homogeneity of other signs.Simultaneously, the present invention can change reaction solution viscosity generates silver-colored particle with the control reaction granularity and reunion degree by regulating flocculant addition.The present invention can make the uniformity that can guarantee reaction in the reaction system that is reflected at different scales by the cocurrent adding material mode.Quantity that can corresponding adjusting charge door is to satisfy industrial amplification.
(1) take by weighing the 50g polyanion cellulose and be dissolved in the 1000ml deionized water, fully stirring and dissolving becomes the colloidal sol body A of 5% mass ratio.
(2) take by weighing 40g and analyze pure AgNO
3Be dissolved in the 200ml deionized water, be made into liquor argenti nitratis ophthalmicus; The ammoniacal liquor 30-40ml that adds 25-28% obtains silver ammino solution till making to the liquor argenti nitratis ophthalmicus solution change clarification by muddiness.Add 20ml again and joined Sol A, fully mix the silver sol system that obtains after the adding deionized water is diluted to 400ml.
(3) taking by weighing the analytically pure NaOH of 5g is dissolved in the 200ml deionized water, stir and to add 80% the pure hydrazine hydrate 5ml of analysis after the fully dissolving respectively, add 20ml and joined colloidal sol body A, add deionized water at last and be diluted to fully to mix behind the 400ml and obtain reducing sol system.
(4) take by weighing 1.5g polyvinylpyrrolidone PVP heating and be dissolved in the 200ml deionized water, be made into protection solution.
(5) the silvering solution system for preparing is added in the protection solution that contains polyvinylpyrrolidone PVP by also flowing to mix under 0.1Mpa pressure with reduction system, and mixes in the 80r/min rotating speed.Stopping to stir also behind reinforced the finishing, ageing 30min obtains polymolecularity, evengranular flocculence micro silver powder slurries.Whole reaction system can be finished under 25-30 ℃.
(6) after reaction finishes, the micro silver powder slurries are filtered Separation of Solid and Liquid use deionized water cleaning silver powder, use soaked in absolute ethyl alcohol again 2 times, filter and drain to electrical conductivity≤20us/cm.
(7) silver powder that will wet obtains the micro silver powder product through 75 ℃ of infra-red dryings after 30 hours.Product carries out SEM, granularity and specific area measuring, silver powder Electronic Speculum uniform particles, and grain diameter is (as shown in Figure 1) between 0.1-0.3um; Products obtained therefrom particle mean size 0.3-0.5um, narrow distribution range; Specific area 7.0-7.5m
2/ g.
Embodiment 2
(1) take by weighing the 50g polyanion cellulose and be dissolved in the 1000ml deionized water, fully stirring and dissolving becomes the colloidal sol body A of 5% mass ratio.
(2) take by weighing 40g and analyze pure AgNO
3Be dissolved in the 200ml deionized water, be made into liquor argenti nitratis ophthalmicus; The ammoniacal liquor 30-40ml that adds 25-28% obtains silver ammino solution till making to the liquor argenti nitratis ophthalmicus solution change clarification by muddiness.Add 10ml again and joined Sol A, fully mix the silver sol system that obtains after the adding deionized water is diluted to 400ml.
(3) taking by weighing the analytically pure NaOH of 5g is dissolved in the 200ml deionized water, stir to add respectively after the fully dissolving and analyze pure formaldehyde 5g, add 10ml and joined colloidal sol body A, add deionized water at last and be diluted to fully to mix behind the 400ml and obtain reducing sol system.
(4) take by weighing 1.5g polyvinylpyrrolidone PVP heating and be dissolved in the 200ml deionized water, be made into protection solution.
(5) the silvering solution system for preparing is added in the protection solution that contains polyvinylpyrrolidone PVP by also flowing to mix under 0.05Mpa pressure with reduction system, and mixes in the 80r/min rotating speed.Stopping to stir also behind reinforced the finishing, ageing 30min obtains polymolecularity, evengranular flocculence micro silver powder slurries.Whole reaction system can be finished under 25-30 ℃.
(6) after reaction finishes, the micro silver powder slurries are filtered Separation of Solid and Liquid use deionized water cleaning silver powder, use soaked in absolute ethyl alcohol again 2 times, filter and drain to electrical conductivity≤20us/cm.
(7) silver powder that will wet obtains the micro silver powder product through 75 ℃ of infra-red dryings after 30 hours.Product carries out SEM, granularity and specific area measuring, silver powder Electronic Speculum uniform particles, and grain diameter is (as shown in Figure 2) between 0.2-0.3um; Products obtained therefrom particle mean size 0.6-1.5um, narrow distribution range; Specific area 6.0-6.5m
2/ g.
Embodiment 3:
(1) take by weighing the 50g arabia gum and be dissolved in the 1000ml deionized water, fully stirring and dissolving becomes the colloidal sol body B of 5% mass ratio.
(2) take by weighing 40g and analyze pure AgNO
3Be dissolved in the 200ml deionized water, be made into liquor argenti nitratis ophthalmicus; The ammoniacal liquor 30-40ml that adds 25-28% obtains silver ammino solution till making to the liquor argenti nitratis ophthalmicus solution change clarification by muddiness.Add 5ml again and joined sol B, fully mix the silver sol system that obtains after the adding deionized water is diluted to 400ml.
(3) take by weighing the analytically pure NaOH of 5g and be dissolved in the 200ml deionized water, stir to add respectively after the fully dissolving and analyze pure Vc25g, add 5ml and joined colloidal sol body B, add deionized water at last and be diluted to fully to mix behind the 400ml and obtain reducing sol system.
(4) take by weighing 1.5g polyvinylpyrrolidone PVP heating and be dissolved in the 200ml deionized water, be made into protection solution.
(5) with the silvering solution system for preparing and reduction system under 0.03Mpa pressure and stream mix and be added in the protection solution that contains polyvinylpyrrolidone PVP, and mix in the 100r/min rotating speed.Stopping to stir also behind reinforced the finishing, ageing 30min obtains lead fine-powdered silver powder.Whole reaction system can be finished under 25-30 ℃.
(6) after reaction finishes, the micro silver powder slurries are filtered Separation of Solid and Liquid use deionized water cleaning silver powder, use soaked in absolute ethyl alcohol again 2 times, filter and drain to electrical conductivity≤20us/cm.
(7) silver powder that will wet obtains the micro silver powder product through 75 ℃ of infra-red dryings after 30 hours.Product carries out SEM, granularity and specific area measuring, silver powder Electronic Speculum uniform particles, and grain diameter is (as shown in Figure 3) between 0.4-0.6um; Products obtained therefrom particle mean size 3-5um, narrow distribution range; Specific area 2.0-3.0m
2/ g.
Above-mentioned three embodiment are easy to industrialization and amplify owing to by the cocurrent adding material mode, can make the uniformity that can guarantee reaction in the reaction system that is reflected at different scales.Quantity that can corresponding adjusting charge door is to satisfy industrial amplification.The silver powder that makes above three kinds of specifications can be satisfied with the conductive filler as high temperature sintering type conductor paste, is applicable to the piezoelectricity of high temperature sintering, pressure-sensitive silver slurry.Different matched combined by three kinds of silver powder are used, and can realize the sintering result of different target.
Claims (10)
1. high-temperature sintered silver paste micro silver powder preparation method is characterized in that may further comprise the steps:
(1) the preparation silver ammino solution adds macromolecule thickener solution, and fully stirring and dissolving forms the silvering solution system of colloidal sol shape;
(2) preparation is fully stirred the reduction system that forms the colloidal sol shape by the reduction system of reducing agent, NaOH and macromolecule thickener solution composition;
(3) preparation contains the protection solution of macromolecule space obstacle agent;
(4) the silvering solution system of step (1) gained is mixed in the protection solution that directly is added to step (3) gained with the reduction system of step (2) gained, constantly stir in the adition process;
(5) stop to stir and ageing behind reinforced the finishing, obtain flocculence micro silver powder slurries;
(6) Separation of Solid and Liquid, washing, post processing are separated soft-agglomerated, dry.
2. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1 is characterized in that: in the described step (1), the content range of silver ion is 10-50g/L in the silvering solution system.
3. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1, it is characterized in that: in described step (1) and the step (2), macromolecule thickener solution is selected from a kind of or mixed solution in Arabic gum, gelatin, polyanion cellulose, methylcellulose, the sodium carboxymethylcellulose.
4. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1 is characterized in that: in described step (1) and the step (2), the mass ratio of macromolecule thickener and silver ion is 0.1～10: 100.
5. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1, it is characterized in that: described step (2), reducing agent is selected from one or more mixing of vitamin C, formaldehyde, hydrazine hydrate, formic acid, sodium borohydride, in whole reduction system, reducing agent is 1: 1～20 with the mass ratio of silver; The mass ratio of silver ion and NaOH is 4～6: 1.
6. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1 is characterized in that: the macromolecule space obstacle agent of described step (3) is selected from polyvinyl alcohol or polyvinylpyrrolidone.
7. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1 is characterized in that: in the described step (4), the silvering solution system is mixed by pressurization and stream with reduction system, and pressure limit is 0.01-0.1Mpa.
8. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1 is characterized in that: in the described step (4), silvering solution system, reduction system, protection solution three's reaction ratio is 3.5～4.5: 3.5～4.5: 2.
9. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1 is characterized in that: in the described step (4), the rotating speed of stirring is 60-100r/min.
10. a kind of high-temperature sintered silver paste micro silver powder preparation method according to claim 1 is characterized in that: in the described step (5), digestion time is 20-40min.
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