CN104646683A - Spherical silver powder with controllable granularity and preparation method thereof - Google Patents
Spherical silver powder with controllable granularity and preparation method thereof Download PDFInfo
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- CN104646683A CN104646683A CN201510090655.7A CN201510090655A CN104646683A CN 104646683 A CN104646683 A CN 104646683A CN 201510090655 A CN201510090655 A CN 201510090655A CN 104646683 A CN104646683 A CN 104646683A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000009472 formulation Methods 0.000 claims abstract description 11
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 61
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 19
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 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 16
- 238000000034 method Methods 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 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 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- -1 polyethylene pyrrolidones Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000084 Gum arabic Polymers 0.000 claims description 3
- 241000978776 Senegalia senegal Species 0.000 claims description 3
- 239000000205 acacia gum Substances 0.000 claims description 3
- 235000010489 acacia gum Nutrition 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 239000013049 sediment Substances 0.000 abstract 2
- 238000011112 process operation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 239000000376 reactant Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Abstract
The invention relates to spherical silver powder with controllable granularity. The spherical silver powder has more than 99.9 percent of purity and more than 4.2g/cm<3> of tap density, and the granularity D90 of the spherical silver powder keeps being adjustable within an interval ranged from 0.2 mu m to 0.65 mu m based on a reaction system formula and reaction condition changes during a preparation method thereof. The preparation method of the spherical silver powder comprises the following steps of adopting soluble silver salt as raw materials, and preparing to obtain the nanoscale spherical silver powder through a hydrothermal method; adopting the nanoscale spherical silver powder as silver seed crystal, utilizing sediment reaction to induce the silver seed crystal to grow up uniformly, adjusting the growth degree of the silver seed crystal through controlling a reaction system formula and reaction conditions of the sediment reaction, and further obtaining the spherical silver powder with controllable granularity. The spherical silver powder is regular in shape, uniform in granularity, and can realize controllable granularity through process operation.
Description
Technical field
The present invention relates to used in electronic industry precious metal raw material powder and preparation technology thereof, particularly relate to a kind of ball shape silver powder and preparation method thereof.
Background technology
Silver powder has excellent electric conductivity and chemical stability, is one of most widely used noble metal powder in electronics industry.In recent years, along with the fast development of electronics industry, the demand of the electric slurry taking silver powder as major function phase is increased fast.Silver powder is the raw material preparing electric slurry most critical, and the performance of silver powder directly or indirectly affects slurry and the final performance forming conductor, as the change of film-forming process, thickness, the change, solderability, adhesion etc. of electrical property.Therefore the development of high-quality silver powder has become the key technology of electric slurry development, at home and abroad more and more comes into one's own.
Current chemical preparation silver powder is a kind of most widely used method, the method utilizes reducing agent to restore Argent grain from the complex system of silver salt, silver, electronation comprises the process of silver-colored nucleation and growing, general by regulating reaction temperature, pH value, reactant concentration, reducing agent kind etc. control the speed of nucleation and growing and then regulate pattern, the granularity of silver powder.But in silver ion and reducing agent course of reaction, nucleation and growth carries out simultaneously, the problem that a part of granule growth time is long and another part growth time is short can be caused, make powder size skewness.And traditional handicraft is prepared in the course of reaction of silver powder and be there is fuel factor, unavoidably thermograde is there is in reaction solution, because the reaction speed of heat transfer, mass transfer velocity and generation silver powder is inconsistent, make reaction solution local reaction condition variant, cause the silver powder granularity heterogeneity of generation, pattern irregular.Such as publication number reacts for the preparation method disclosed in the Chinese patent literature of CN1387968A directly pours reducing agent mixed solution into silver nitrate mixed solution, is difficult to realize the control to the nucleation and growing of silver-colored crystal grain.Publication number is in the Chinese patent literature of CN 103273082A, reductant solution is directly mixed generation reduction reaction with liquor argenti nitratis ophthalmicus, reactant liquor internal temperature can be subject to the impact of reaction heat, makes local temperature in solution different, causes the final silver powder granularity heterogeneity generated.
Hydro-thermal method prepares the another kind of method of micro aluminum powder, and the method is in autoclave, using the aqueous solution as reaction system, under certain pressure and temperature, carries out liquid phase reactor, can the micro aluminum powder of homogeneous, the soilless sticking of prepared sizes.Single hydro-thermal method can only prepare nano level silver powder usually, is difficult to obtain micron order silver powder.Such as, in publication number preparation method disclosed in the Chinese patent literature of CN 102205421, simple use hydro-thermal method prepares silver powder, can only prepare the nano-silver powder of below 50 nanometers.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, there is provided a kind of pattern of product rule, product granularity evenly and the controlled ball shape silver powder of granularity can be realized by technological operation, the also preparation method of the corresponding ball shape silver powder providing this granularity a kind of controlled.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is the controlled ball shape silver powder of a kind of granularity, and the purity of described ball shape silver powder is more than 99.9%, and the tap density of described ball shape silver powder is at 4.2g/cm
3above, the granularity D of described ball shape silver powder
90be change based on reaction system formula and reaction condition in its preparation method process and remain between 0.2 ~ 0.65 μm adjustable.
Above-mentioned ball shape silver powder, preferred: the granularity D of described ball shape silver powder
10control adjustable in 0.08 ~ 0.3 μm of interval, granularity D
50control adjustable in 0.1 ~ 0.5 μm of interval.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned ball shape silver powder, comprises the following steps: take soluble silver salt as raw material, first prepare nano-level sphere silver powder by hydro-thermal method; Then using aforesaid nano-level sphere silver powder as silver-colored crystal seed, precipitation reaction is utilized to induce silver-colored crystal seed evenly to grow up, and by the degree that the reaction system formula and reaction condition controlling precipitation reaction regulates silver-colored crystal seed to grow up, and then obtain the controlled ball shape silver powder of granularity (macroscopically by silver-colored crystal seed nucleation and germination separate operation).
Above-mentioned preparation method, preferably, described hydro-thermal method specifically comprises the following steps: by soluble silver salt and dispersant according to 1: 0.02 ~ 1 mol ratio be dissolved in deionized water, regulate the pH value of mixed liquor close to neutral (preferably using alkali lye adjust ph to 6 ~ 8), then obtain the intermediate liquid A containing described nano-level sphere silver powder by the reduction of reducing agent under hydrothermal conditions.Described dispersant to be preferably in oleic acid, polyvinylpyrrolidone (PVP), N-methyl polyethylene pyrrolidones, gum arabic, citric acid, natrium citricum, neopelex one or more.
Above-mentioned preparation method, preferably, described reducing agent is one or more the combination in glucose, hydrogen peroxide, formaldehyde, hydrazine hydrate, ferrous sulfate, ascorbic acid; Temperature under described hydrothermal condition controls at 120 DEG C ~ 180 DEG C, and the reduction reaction time under hydrothermal condition controls at 5min ~ 5h.
Above-mentioned preparation method, preferably, the reaction raw materials of described precipitation reaction comprises described intermediate liquid A and slow liquid feeding C, containing soluble silver salt and complexing agent in described slow liquid feeding C, the precipitating reagent of described precipitation reaction adds in described intermediate liquid A, and the mode of described precipitation reaction is slowly added to by slow liquid feeding C in intermediate liquid A to induce silver-colored crystal seed evenly to grow up under the condition of high-speed stirred intermediate liquid A.
Above-mentioned preparation method, preferably, the temperature of described precipitation reaction controls at 0 DEG C ~ 40 DEG C, and precipitation reaction time controling is at 10min ~ 30min.After precipitation reaction again through centrifugation, wash, be drying to obtain finished product.
Above-mentioned preparation method, preferably, is also added with thickener and/or dispersant in described intermediate liquid A; Described thickener is one or more the combination in water-soluble acrylic polymer, Sodium Polyacrylate, polyacrylamide, methylcellulose; Described dispersant is one or more the combination in polyvinylpyrrolidone, gum arabic, polyethylene glycol, citric acid, natrium citricum.Can be directly precipitating reagent, dispersant, thickener etc. are added in intermediate liquid A, also can be through once filtering to isolate nano-level sphere silver powder after hydro-thermal method has been reacted, again itself and precipitating reagent, dispersant etc. are mixedly configured into intermediate liquid A in proportion, such operation does not have essential distinction.
Above-mentioned preparation method, preferably, described precipitating reagent is one or more the combination in ascorbic acid, triethanolamine, glucose, hydrazine hydrate, hydrogen peroxide, and the concentration of described precipitating reagent in intermediate liquid A controls to be 0.05 ~ 2.00mol/L.
Above-mentioned preparation method, preferably, described soluble silver salt is silver nitrate, and described slow liquid feeding C is that silver nitrate and complexing agent to be dissolved in the silver nitrate concentration formed in deionized water be the mixed liquor of 0.05 ~ 2.00mol/L; The mol ratio of described slow liquid feeding C complexing agent and silver nitrate is 0.5 ~ 2: 1, and described complexing agent is one or more in ammoniacal liquor, polyvinylpyrrolidone, ethylenediamine tetra-acetic acid (EDTA), natrium citricum.
In the technical scheme of the invention described above, the concrete mode realizing ball shape silver powder granularity controlled comprises: first can prepare the different silver-colored crystal seed of particle diameter by the collocation of reactant concentration in hydro-thermal method and reducing agent, dispersant; In precipitation reaction after the key of Control granularity size is then, silver powder granularity can be controlled by controlling soluble silver salt, the consumption of precipitating reagent, type and concentration and sedimentation time (reactant concentration increases, sedimentation time extends, silver crystal seed has time enough to grow up, then granularity becomes large).
Compared with prior art, the invention has the advantages that:
Hydro-thermal method combines with the precipitation method by the present invention, and silver-colored nucleation and the process of growing up macroscopically can separated, preparation technology is simple.Due to the existence of HTHP in hydrothermal system, reaction system internal heat transfer mass transfer velocity is fast, and substantially do not have thermograde, residing for silver atoms, reaction environment is identical, and the silver-colored crystal seed sphericity therefore prepared is high, pattern is homogeneous, even particle size distribution.With this silver-colored crystal seed for raw material, by controlling the technological parameter of post precipitation reaction, silver-colored crystal seed evenly being grown up to micron order, obtain the silver powder of epigranular, pattern rule, and it is adjustable between 0.2 ~ 0.65 μm to realize silver powder granularity.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the microscopic appearance figure of ball shape silver powder under ESEM in the embodiment of the present invention 1.
Detailed description of the invention
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various raw material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
The ball shape silver powder that granularity of the present invention is controlled, its purity is 99.97%, and the tap density of this ball shape silver powder is at 4.22g/cm
3, the granularity D of this ball shape silver powder
10, D
50, D
90be respectively 0.09 μm, 0.13 μm and 0.28 μm, this granularity is control based on reaction system formula and reaction condition in its preparation method process and realizes.
The preparation method of the ball shape silver powder that the present embodiment is above-mentioned, specifically comprises the following steps:
(1) first take 1g silver nitrate to be dissolved in 100ml deionized water, add 0.7g neopelex, under stirring condition, make the two mix; Add the pH to 8 that NaOH regulates mixed liquor; Separately take the formalin that 3ml mass fraction is 37%, add in aforesaid mixed liquor; Immediately reactant liquor is transferred in hydrothermal reaction kettle (200ml), by the reduction airtight heating 1h of reducing agent at 180 DEG C, taking-up reactor after question response completes, naturally cool to the intermediate liquid A that room temperature obtains containing nano-level sphere silver powder (as silver-colored crystal seed), and be transferred in 500ml there-necked flask; The silver-colored crystal seed average grain diameter obtained is about 70nm.
(2) 0.5g thickener polyacrylic acid (water-soluble acrylic polymer) is joined in above-mentioned intermediate liquid A; Separately taking 3g ascorbic acid is dissolved in above-mentioned intermediate liquid A; Take 3g silver nitrate and 0.8g PVP and to be dissolved in 50ml deionized water to obtain slow liquid feeding C; At room temperature high-speed stirred intermediate liquid A, is added drop-wise in intermediate liquid A by slow liquid feeding C simultaneously, continues stirring reaction 10min, obtains final solution; Be separated through centrifugal filtration, and use deionized water and ethanolic solution to clean three times respectively, the silver powder solution obtained is at 70 DEG C of vacuum drying chamber inner drying 12h, and obtain the micron grade ball shape silver powder product of the present embodiment, its microscopic appearance as shown in Figure 1.
As seen from Figure 1, the ball shape silver powder product of the present embodiment has good sphericity, narrow diameter distribution, and purity is high, favorable dispersibility, and concrete physical and chemical parameter sees table 1.
Embodiment 2:
The ball shape silver powder that granularity of the present invention is controlled, its purity is 99.98%, and the tap density of this ball shape silver powder is at 4.35g/cm
3, the granularity D of this ball shape silver powder
10, D
50, D
90be respectively 0.16 μm, 0.25 μm and 0.38 μm, this granularity is control based on reaction system formula and reaction condition in its preparation method process and realizes.
The preparation method of the ball shape silver powder that the present embodiment is above-mentioned, specifically comprises the following steps:
(1) first take 1g silver nitrate to be dissolved in 100ml deionized water, add 0.6g PVP, under stirring condition, make the two mix; Add the pH to 8 that NaOH regulates mixed liquor; Separately take the formalin that 3ml mass fraction is 37%, add in aforesaid mixed liquor; Immediately reactant liquor is transferred in hydrothermal reaction kettle (200ml), by the reduction airtight heating 1h of reducing agent at 170 DEG C, taking-up reactor after question response completes, naturally cool to the intermediate liquid A that room temperature obtains containing nano-level sphere silver powder (as silver-colored crystal seed), and be transferred in 500ml there-necked flask; The silver-colored crystal seed average grain diameter obtained is about 75nm.
(2) 0.5g thickener polyacrylic acid (water-soluble acrylic polymer) is joined in above-mentioned intermediate liquid A; Separately take in the above-mentioned intermediate liquid A of 6.0g ascorbic acid; Take 6.0g silver nitrate and 1.6g PVP and to be dissolved in 50ml deionized water to obtain slow liquid feeding C; At room temperature high-speed stirred intermediate liquid A, is added drop-wise in intermediate liquid A by slow liquid feeding C simultaneously, continues stirring reaction 15min, obtains final solution; Be separated through centrifugal filtration, and use deionized water and ethanolic solution to clean three times respectively, the silver powder solution obtained, at 70 DEG C of vacuum drying chamber inner drying 12h, obtains the micron grade ball shape silver powder product (physical and chemical parameter is in table 1) of the present embodiment.
Compared with embodiment 1, the granularity of (1) step gained silver crystal seed of embodiment 2 is close, and the reactant consumption unlike precipitation reaction in embodiment 2 is large, concentration is high, and the reaction time is long, therefore silver-colored crystal seed has the more sufficient time to grow up, and product granularity becomes large.
Embodiment 3:
The ball shape silver powder that granularity of the present invention is controlled, its purity is 99.98%, and the tap density of this ball shape silver powder is at 4.46g/cm
3, the granularity D of this ball shape silver powder
10, D
50, D
90be respectively 0.26 μm, 0.37 μm and 0.49 μm, this granularity is control based on reaction system formula and reaction condition in its preparation method process and realizes.
The preparation method of the ball shape silver powder that the present embodiment is above-mentioned, specifically comprises the following steps:
(1) first take 0.6g silver nitrate to be dissolved in 50ml deionized water, add 0.5g neopelex, under stirring condition, make the two mix; Add the pH to 7 that NaOH regulates mixed liquor; Separately taking 1.3g reducing agent ferrous sulfate is dissolved in 50ml deionized water, adds in aforesaid mixed liquor after to be dissolved; Immediately reactant liquor is transferred in hydrothermal reaction kettle (200ml), by the reduction airtight heating 2h of reducing agent at 150 DEG C, taking-up reactor after question response completes, naturally cool to the intermediate liquid A that room temperature obtains containing nano-level sphere silver powder (as silver-colored crystal seed), and be transferred in 500ml there-necked flask; Obtain the silver-colored crystal seed that average grain diameter is 90nm.
(2) 0.3g thickener methylcellulose is joined in above-mentioned intermediate liquid A; Separately taking 4.8g ascorbic acid is dissolved in above-mentioned intermediate liquid A; Take 4.8g silver nitrate and 1.2g PVP and to be dissolved in 50ml deionized water to obtain slow liquid feeding C; At room temperature high-speed stirred intermediate liquid A, is added drop-wise in intermediate liquid A by slow liquid feeding C simultaneously, continues stirring reaction 20min, obtains final solution; Be separated through centrifugal filtration, and use deionized water and ethanolic solution to clean three times respectively, the silver powder solution obtained, at 70 DEG C of vacuum drying chamber inner drying 12h, obtains the micron grade ball shape silver powder product (physical and chemical parameter is in table 1) of the present embodiment.
Embodiment 4:
The ball shape silver powder that granularity of the present invention is controlled, its purity is 99.97%, and the tap density of this ball shape silver powder is at 4.52g/cm
3, the granularity D of this ball shape silver powder
10, D
50, D
90be respectively 0.21 μm, 0.39 μm and 0.59 μm, this granularity is control based on reaction system formula and reaction condition in its preparation method process and realizes.
The preparation method of the ball shape silver powder that the present embodiment is above-mentioned, specifically comprises the following steps:
(1) first take 1g silver nitrate to be dissolved in 50ml deionized water, add 0.4g N-methyl polyethylene pyrrolidones, under stirring condition, make the two mix; Add the pH to 7 that NaOH regulates mixed liquor; Separately taking 1.2g reducing agent glucose is dissolved in 50ml deionized water, adds in aforesaid mixed liquor, obtain the reactant liquor of grey black after to be dissolved; Immediately reactant liquor is transferred in hydrothermal reaction kettle (200ml), by the reduction airtight heating 3h of reducing agent at 140 DEG C, taking-up reactor after question response completes, naturally cool to the intermediate liquid A that room temperature obtains containing nano-level sphere silver powder (as silver-colored crystal seed), and be transferred in 500ml there-necked flask; The average grain diameter obtaining silver-colored crystal seed is about 145nm.
(2) 0.4g thickener Sodium Polyacrylate is joined in above-mentioned intermediate liquid A; Separately taking 18.0g ascorbic acid is dissolved in above-mentioned intermediate liquid A; Take 18.0g silver nitrate and 8.0g natrium citricum and to be dissolved in 100ml deionized water to obtain slow liquid feeding C; At room temperature high-speed stirred intermediate liquid A, is added drop-wise in intermediate liquid A by slow liquid feeding C simultaneously, continues stirring reaction 30min, obtains final solution; Be separated through centrifugal filtration, and use deionized water and ethanolic solution to clean three times respectively, the silver powder solution obtained, at 70 DEG C of vacuum drying chamber inner drying 12h, obtains the micron grade ball shape silver powder product (physical and chemical parameter is in table 1) of the present embodiment.
Embodiment 5:
The ball shape silver powder that granularity of the present invention is controlled, its purity is 99.98%, and the tap density of this ball shape silver powder is at 4.36g/cm
3, the granularity D of this ball shape silver powder
10, D
50, D
90be respectively 0.28 μm, 0.43 μm and 0.62 μm, this granularity is control based on reaction system formula and reaction condition in its preparation method process and realizes.
The preparation method of the ball shape silver powder that the present embodiment is above-mentioned, specifically comprises the following steps:
(1) first take 1.0g silver nitrate to be dissolved in 50ml deionized water, add 0.3g N-methyl polyethylene pyrrolidones, under stirring condition, make the two mix; Add the pH to 7 that NaOH regulates mixed liquor; Separately taking 1.2g reducing agent glucose is dissolved in 50ml deionized water, adds in aforesaid mixed liquor, obtain the reactant liquor of grey black after to be dissolved; Immediately reactant liquor is transferred in hydrothermal reaction kettle (300ml), by the reduction airtight heating 3h of reducing agent formaldehyde at 130 DEG C, taking-up reactor after question response completes, naturally cool to the intermediate liquid A that room temperature obtains containing nano-level sphere silver powder (as silver-colored crystal seed), and be transferred in the precipitation reaction still of 500ml; The average grain diameter obtaining silver-colored crystal seed is about 155nm.
(2) 0.4g thickener Sodium Polyacrylate is joined in above-mentioned intermediate liquid A; Separately taking 15.0g triethanolamine is dissolved in above-mentioned intermediate liquid A; Take 18.0g silver nitrate and 8.0g natrium citricum and to be dissolved in 100ml deionized water to obtain slow liquid feeding C; At room temperature high-speed stirred intermediate liquid A, is slowly added in intermediate liquid A by slow liquid feeding C simultaneously, continues stirring reaction 30min, obtains final solution; Be separated through centrifugal filtration, and use deionized water and ethanolic solution to clean three times respectively, the silver powder solution obtained, at 70 DEG C of vacuum drying chamber inner drying 10h, obtains the micron grade ball shape silver powder product (physical and chemical parameter is in table 1) of the present embodiment.The particle mean size of the silver powder product of the present embodiment is 0.43 μm, tap density 4.36g/cm
3, there is good dispersiveness.
Compared with embodiment 4, the precipitation reaction of the present embodiment have employed the lower triethanolamine of reproducibility, reduces reactant concentration simultaneously, makes the carrying out that reaction is more gentle, the silver atoms that precipitation reaction generates more is consumed in growing up of silver-colored crystal seed, instead of forms new nucleus.
The performance parameter of silver powder product that obtains of each embodiment is as shown in table 1 below above.
Table 1: the silver powder product contrast that each embodiment is obtained
Particle size distribution numbers in upper table 1 is measured by Malvern laser particle size analyzer, and the stereoscan photograph of embodiment 1 amplifies 6000 times by SEM to be observed afterwards and obtain.From upper table 1, along with the growth in reaction time, the granularity of product particle obviously increases, but precipitation reaction is more than after 30min, and gained silver powder can see partly again the granule of forming core, and namely the granularity of silver powder no longer increases.The silver powder product pattern rule of each embodiment, purity is high, good dispersion, and tap density is higher.
Claims (10)
1. the ball shape silver powder that granularity is controlled, the purity of described ball shape silver powder is more than 99.9%, and the tap density of described ball shape silver powder is at 4.2g/cm
3above, it is characterized in that: the granularity D of described ball shape silver powder
90be change based on reaction system formula and reaction condition in its preparation method process and to remain on 0.2 ~ 0.65 μm of interval adjustable.
2. ball shape silver powder according to claim 1, is characterized in that: the granularity D of described ball shape silver powder
10control adjustable in 0.08 ~ 0.3 μm of interval, granularity D
50control adjustable in 0.1 ~ 0.5 μm of interval.
3. a preparation method for ball shape silver powder as claimed in claim 1 or 2, comprises the following steps: take soluble silver salt as raw material, first prepare nano-level sphere silver powder by hydro-thermal method; Then using aforesaid nano-level sphere silver powder as silver-colored crystal seed, precipitation reaction is utilized to induce silver-colored crystal seed evenly to grow up, and by the degree that the reaction system formula and reaction condition controlling precipitation reaction regulates silver-colored crystal seed to grow up, and then obtain the controlled ball shape silver powder of granularity.
4. preparation method according to claim 3, it is characterized in that, described hydro-thermal method specifically comprises the following steps: by soluble silver salt and dispersant according to 1: 0.02 ~ 1 mol ratio be dissolved in deionized water, regulate the pH value of mixed liquor close to neutral, then obtain the intermediate liquid A containing described nano-level sphere silver powder by the reduction of reducing agent under hydrothermal conditions.
5. preparation method according to claim 4, is characterized in that, described reducing agent is one or more the combination in glucose, hydrogen peroxide, formaldehyde, hydrazine hydrate, ferrous sulfate, ascorbic acid; Temperature under described hydrothermal condition controls at 120 DEG C ~ 180 DEG C, and the reduction reaction time under hydrothermal condition controls at 5min ~ 5h.
6. preparation method according to claim 4, it is characterized in that, the reaction raw materials of described precipitation reaction comprises described intermediate liquid A and slow liquid feeding C, containing soluble silver salt and complexing agent in described slow liquid feeding C, the precipitating reagent of described precipitation reaction adds in described intermediate liquid A, and the mode of described precipitation reaction is slowly added to by slow liquid feeding C in intermediate liquid A to induce silver-colored crystal seed evenly to grow up under the condition of high-speed stirred intermediate liquid A.
7. preparation method according to claim 6, is characterized in that, the temperature of described precipitation reaction controls at 0 DEG C ~ 40 DEG C, and precipitation reaction time controling is at 10min ~ 30min.
8. preparation method according to claim 6, is characterized in that, is also added with thickener and/or dispersant in described intermediate liquid A; Described thickener is one or more the combination in water-soluble acrylic polymer, Sodium Polyacrylate, polyacrylamide, methylcellulose; Described dispersant is one or more the combination in polyvinylpyrrolidone, gum arabic, polyethylene glycol, citric acid, natrium citricum, oleic acid, N-methyl polyethylene pyrrolidones, neopelex.
9. preparation method according to claim 6, it is characterized in that, described precipitating reagent is one or more the combination in ascorbic acid, triethanolamine, glucose, hydrazine hydrate, hydrogen peroxide, and the concentration of described precipitating reagent in intermediate liquid A controls to be 0.05 ~ 2.00mol/L.
10. preparation method according to claim 6, is characterized in that, described soluble silver salt is silver nitrate, and described slow liquid feeding C is that silver nitrate and complexing agent to be dissolved in the silver nitrate concentration formed in deionized water be the mixed liquor of 0.05 ~ 2.00mol/L; The mol ratio of described slow liquid feeding C complexing agent and silver nitrate is 0.5 ~ 2: 1, and described complexing agent is one or more in ammoniacal liquor, polyvinylpyrrolidone, ethylenediamine tetra-acetic acid, natrium citricum.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660529A (en) * | 2004-02-26 | 2005-08-31 | 同和矿业株式会社 | Silver powder and its mfg.process |
| JP2005330529A (en) * | 2004-05-19 | 2005-12-02 | Dowa Mining Co Ltd | Spherical silver powder and its production method |
| CN102554265A (en) * | 2012-03-16 | 2012-07-11 | 上海交通大学 | Preparation method of mono-dispersed highly crystalline silver powder with adjustable particle size |
| CN102632248A (en) * | 2012-05-03 | 2012-08-15 | 中国人民解放军国防科学技术大学 | Spherical silver powder and preparation method thereof |
| CN103100722A (en) * | 2013-01-30 | 2013-05-15 | 广东羚光新材料股份有限公司 | Preparation method of high tap density monodisperse silver powder |
-
2015
- 2015-02-28 CN CN201510090655.7A patent/CN104646683B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660529A (en) * | 2004-02-26 | 2005-08-31 | 同和矿业株式会社 | Silver powder and its mfg.process |
| JP2005330529A (en) * | 2004-05-19 | 2005-12-02 | Dowa Mining Co Ltd | Spherical silver powder and its production method |
| CN102554265A (en) * | 2012-03-16 | 2012-07-11 | 上海交通大学 | Preparation method of mono-dispersed highly crystalline silver powder with adjustable particle size |
| CN102632248A (en) * | 2012-05-03 | 2012-08-15 | 中国人民解放军国防科学技术大学 | Spherical silver powder and preparation method thereof |
| CN103100722A (en) * | 2013-01-30 | 2013-05-15 | 广东羚光新材料股份有限公司 | Preparation method of high tap density monodisperse silver powder |
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