CN104646683B - Controllable ball shape silver powder of a kind of granularity and preparation method thereof - Google Patents
Controllable ball shape silver powder of a kind of granularity and preparation method thereof Download PDFInfo
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- CN104646683B CN104646683B CN201510090655.7A CN201510090655A CN104646683B CN 104646683 B CN104646683 B CN 104646683B CN 201510090655 A CN201510090655 A CN 201510090655A CN 104646683 B CN104646683 B CN 104646683B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 238000001556 precipitation Methods 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 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
- 230000008859 change Effects 0.000 claims abstract description 5
- 210000003722 extracellular fluid Anatomy 0.000 claims description 41
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 24
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 230000004044 response Effects 0.000 claims description 9
- 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
- 239000002738 chelating agent Substances 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001509 sodium citrate Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-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
- 239000008103 glucose Substances 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 ketopyrrolidines Polymers 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 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
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-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
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 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
- 238000002156 mixing Methods 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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000009472 formulation Methods 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
- 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
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 claims 1
- 230000006698 induction Effects 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003643 water by type Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 235000011083 sodium citrates Nutrition 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000004062 sedimentation Methods 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
- 238000001035 drying Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen 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
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
Abstract
A kind of controllable ball shape silver powder of granularity, more than 99.9%, its tap density is in 4.2g/cm for its purity3More than, granularity D of ball shape silver powder90It is that to be maintained at 0.2～0.65 μm of interval based on reaction system formula during its preparation method with the change of reaction condition adjustable.The preparation method of the ball shape silver powder includes：With soluble silver salt as raw material, first pass through hydro-thermal method and prepare nano-level sphere argentum powder；Then using aforesaid nano-level sphere argentum powder as silver-colored crystal seed, induce silver-colored crystal seed uniformly to grow up using precipitation, and the degree that silver-colored crystal seed is grown up is adjusted by controlling the reaction system formula of precipitation with reaction condition, and then obtain the controllable ball shape silver powder of granularity.The product pattern rule of the present invention, product granularity are uniform, and it is controllable to can achieve granularity by technological operation.
Description
Technical field
The present invention relates to used in electronic industry precious metal raw material powder body and its preparation technology, more particularly to a kind of ball shape silver powder and
Its preparation method.
Background technology
Argentum powder has excellent electric conductivity and chemical stability, be in electronics industry most widely used noble metal powder it
One.In recent years, with the fast development of electronics industry, the demand with electric slurry that argentum powder is main function phase is quickly increased
Long.Argentum powder is the raw material for preparing electric slurry most critical, and the performance of argentum powder directly or indirectly affects slurry and ultimately form to lead
The performance of body, such as film-forming process, the change of thickness, the change of electrical property, solderability, adhesion etc..Therefore high-quality argentum powder
The key technology for having become electric slurry development is developed, is at home and abroad increasingly taken seriously.
It is a kind of most widely used method that at present chemical reduction method prepares argentum powder, the method using reducing agent from silver salt,
Argent grain is restored in the complex system of silver, and electronation is included silver-colored nucleation and the process that grows up, typically reacted by regulation
Temperature, pH value, reactant concentration, reducing agent species etc. control nucleation with the speed that grows up and then adjust the pattern of argentum powder, granularity.
But in silver ion with reducing agent course of reaction, nucleation and growth is carried out, and a part of particle growth time can be caused long simultaneously
And the short problem of another part growth time, make powder size skewness.And traditional handicraft prepares the course of reaction of argentum powder
In there is heat effect, unavoidably there is thermograde in reaction solution, due to heat transfer, mass transfer velocity with generate argentum powder reaction
Speed is inconsistent so that reaction solution local response condition is variant, causes the argentum powder granularity heterogeneity for generating, pattern not to be advised
Then.Reducing agent mixed solution is directly fallen by such as preparation method disclosed in the Chinese patent literature of Publication No. CN1387968A
Enter silver nitrate mixed solution to be reacted, it is difficult to realize nucleation and the control that grows up to silver-colored crystal grain.Publication No. CN
In the Chinese patent literature of 103273082A, reductant solution and silver nitrate solution are directly mixed generation reduction reaction, reacted
Liquid internal temperature can be affected by reaction heat, make local temperature difference in solution, cause the argentum powder granularity for ultimately generating uneven
One.
Hydro-thermal method is another kind of method for preparing micro aluminum powder, the method be in autoclave, using aqueous solution as
Reaction system, carries out liquid phase reactor in certain pressure with a temperature of, can homogeneous, soilless sticking the micro aluminum powder of prepared sizes.Single
One hydro-thermal method is typically only capable to prepare nano level argentum powder, it is difficult to obtain micron order argentum powder.For example, Publication No. CN
Simple use hydro-thermal method in preparation method disclosed in 102205421 Chinese patent literature prepares argentum powder, can only prepare 50 and receive
Nanometer silver powder below rice.
Content of the invention
The technical problem to be solved is to overcome the shortcomings of to mention and defect in background above technology, there is provided one
Plant the pattern rule of product, product granularity is uniform and the controllable ball shape silver powder of granularity is can achieve by technological operation, also accordingly carry
Preparation method for a kind of controllable ball shape silver powder of granularity.
For solving above-mentioned technical problem, technical scheme proposed by the present invention is a kind of controllable ball shape silver powder of granularity, described
, more than 99.9%, the tap density of the ball shape silver powder is in 4.2g/cm for the purity of ball shape silver powder3More than, the ball shape silver powder
Granularity D90It is change based on reaction system formula during its preparation method and reaction condition and is maintained at 0.2～0.65 μm
Between adjustable.
Above-mentioned ball shape silver powder, preferably：Granularity D of the ball shape silver powder10Control is adjustable in 0.08～0.3 μm of interval,
Granularity D50Control is adjustable in 0.1～0.5 μm of interval.
Used as a total technology design, the present invention also provides a kind of preparation method of above-mentioned ball shape silver powder, including with
Lower step：With soluble silver salt as raw material, first pass through hydro-thermal method and prepare nano-level sphere argentum powder；Then with aforesaid nanometer
Level ball shape silver powder induces silver-colored crystal seed uniformly to grow up as silver-colored crystal seed using precipitation, and by controlling the reaction of precipitation
System formulation adjusts the degree that silver-colored crystal seed is grown up with reaction condition, and then obtains the controllable ball shape silver powder of granularity (in macroscopically general
Silver-colored crystal seed nucleation and granular grows separate operation).
Above-mentioned preparation method, it is preferred that the hydro-thermal method specifically includes following steps：By soluble silver salt and dispersant
Mol ratio according to 1: 0.02～1 is dissolved in deionized water, and the pH value for adjusting mixed liquor is close to neutral (preferably regulation with alkali liquor
PH value to 6～8), in then being obtained containing the nano-level sphere argentum powder by the reduction of reducing agent under hydrothermal conditions
Interstitial fluid A.The dispersant is preferably Oleic acid, polyvinylpyrrolidone (PVP), N- methyl polyethylene ketopyrrolidines, Arabic tree
One or more in glue, citric acid, sodium citrate, dodecylbenzene sodium sulfonate.
Above-mentioned preparation method, it is preferred that the reducing agent be glucose, hydrogen peroxide, formaldehyde, hydrazine hydrate, ferrous sulfate,
The combination of one or more in ascorbic acid；Temperature control under the hydrothermal condition at 120 DEG C～180 DEG C, hydrothermal condition
Under the reduction response time control in 5min～5h.
Above-mentioned preparation method, it is preferred that the reaction raw materials of the precipitation include the middle interstitial fluid A and slow liquid feeding C,
Containing soluble silver salt and chelating agent in the slow liquid feeding C, the precipitant of the precipitation is added in the middle interstitial fluid A,
The mode of the precipitation be slow liquid feeding C is added slowly under conditions of interstitial fluid A in high-speed stirred in interstitial fluid A luring
Lead silver-colored crystal seed uniformly to grow up.
Above-mentioned preparation method, it is preferred that the temperature control of the precipitation at 0 DEG C～40 DEG C, the precipitation time
Control is in 10min～30min.It is centrifuged after precipitation again, wash, is drying to obtain finished product.
Above-mentioned preparation method, it is preferred that be also added with thickening agent and/or dispersant in the middle interstitial fluid A；The thickening
Agent is water-soluble acrylic polymer, sodium polyacrylate, polyacrylamide, one or more in methylcellulose of combination；
The dispersant be polyvinylpyrrolidone, Radix Acaciae senegalis, Polyethylene Glycol, citric acid, one or more in sodium citrate
Combination.Can be directly precipitant, dispersant, thickening agent etc. are added in reacted in interstitial fluid A, or in hydro-thermal method
Cheng Houjing once filters to isolate nano-level sphere argentum powder, then during to be mixed in proportion which with precipitant, dispersant etc.
Interstitial fluid A, such operation do not have essential distinction.
Above-mentioned preparation method, it is preferred that the precipitant is ascorbic acid, triethanolamine, glucose, hydrazine hydrate, double
The combination of one or more in oxygen water, concentration of the precipitant in middle interstitial fluid A are controlled to 0.05～2.00mol/L.
Above-mentioned preparation method, it is preferred that the soluble silver salt be silver nitrate, the slow liquid feeding C be by silver nitrate with
Chelating agent is dissolved in the mixed liquor that the silver nitrate concentration that formed in deionized water is 0.05～2.00mol/L；In the slow liquid feeding C
Chelating agent is 0.5～2: 1 with the mol ratio of silver nitrate, and the chelating agent is ammonia, polyvinylpyrrolidone, ethylenediaminetetraacetic acid
(EDTA), one or more in sodium citrate.
In the technical scheme of the invention described above, realize that the controllable concrete mode of ball shape silver powder granularity includes：Pass through water first
In full-boiled process, reactant concentration and reducing agent, the collocation of dispersant can prepare the different silver-colored crystal seed of particle diameter；Control granularity is big
Little key be then after precipitation in, by control soluble silver salt, the consumption of precipitant, type and concentration and
Sedimentation time can control argentum powder granularity (reactant concentration increases, and the sedimentation time extends, and silver-colored crystal seed has time enough to grow up,
Then granularity becomes big).
Compared with prior art, it is an advantage of the current invention that：
Hydro-thermal method is combined by the present invention with the sedimentation method, can by silver-colored nucleation and the process that grows up macroscopically separating,
Preparation process is simple.Due to the presence of High Temperature High Pressure in hydrothermal system, reaction system internal heat transfer mass transfer velocity is fast, does not have substantially
Thermograde, reaction environment residing for silver atoms are identical, and the silver-colored crystal seed sphericity for therefore preparing is high, pattern is homogeneous, particle size distribution is equal
Even.With this silver-colored crystal seed as raw material, by controlling the technological parameter of post precipitation reaction, silver-colored crystal seed is made uniformly to grow up to micron order,
Epigranular, the argentum powder of pattern rule is obtained, and can realize that argentum powder granularity is adjustable between 0.2～0.65 μm.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can be with basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is microscopic appearance figure of the ball shape silver powder under scanning electron microscope in the embodiment of the present invention 1.
Specific embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
Identical.Technical term used herein is intended merely to the purpose for describing specific embodiment, is not intended to limit the present invention
Protection domain.
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of controllable ball shape silver powder of granularity of the present invention, 99.97%, the tap density of the ball shape silver powder exists its purity
4.22g/cm3, granularity D of the ball shape silver powder10、D50、D90Respectively 0.09 μm, 0.13 μm and 0.28 μm, the granularity is based on which
During preparation method, reaction system formula is realized with the control of reaction condition.
The preparation method of the above-mentioned ball shape silver powder of the present embodiment, specifically includes following steps：
(1) weigh 1g silver nitrate first to be dissolved in 100ml deionized waters, add 0.7g dodecylbenzene sodium sulfonate, stir
The two mix homogeneously is made under the conditions of mixing；Sodium hydroxide is added to adjust the pH to 8 of mixed liquor；3ml mass fraction is separately weighed for 37%
Formalin, add in aforesaid mixed liquor；Immediately reactant liquor is transferred in hydrothermal reaction kettle (200ml), at 180 DEG C
By reduction airtight heating 1h of reducing agent, reactor is taken out after the completion of question response, naturally cool to room temperature and contained
The middle interstitial fluid A of nano-level sphere argentum powder (as silver-colored crystal seed), and be transferred in 500ml there-necked flasks；The silver-colored crystal seed for obtaining is average
Particle diameter is about 70nm.
(2) 0.5g thickening agent polyacrylic acid (water-soluble acrylic polymer) is added in above-mentioned middle interstitial fluid A；Separately weigh
3g ascorbic acid is dissolved in above-mentioned middle interstitial fluid A；Weigh 3g silver nitrate and be dissolved in obtain in 50ml deionized waters with 0.8g PVP and add slowly
Liquid C；Interstitial fluid A in high-speed stirred, while slow liquid feeding C is added drop-wise in middle interstitial fluid A, continues stirring reaction 10min, obtains at room temperature
Arrive final solution；Separate through centrifugal filtration again, and be respectively washed three times using deionized water and ethanol solution, the argentum powder for obtaining
Solution dries 12h in 70 DEG C of vacuum drying ovens, obtains the micron grade ball shape silver powder product of the present embodiment, and its microscopic appearance is as schemed
Shown in 1.
As seen from Figure 1, the ball shape silver powder product of the present embodiment has preferable sphericity, and narrow diameter distribution, purity are high, point
Scattered property is good, and concrete physical and chemical parameter is referring to table 1 below.
Embodiment 2：
A kind of controllable ball shape silver powder of granularity of the present invention, 99.98%, the tap density of the ball shape silver powder exists its purity
4.35g/cm3, granularity D of the ball shape silver powder10、D50、D90Respectively 0.16 μm, 0.25 μm and 0.38 μm, the granularity is based on which
During preparation method, reaction system formula is realized with the control of reaction condition.
The preparation method of the above-mentioned ball shape silver powder of the present embodiment, specifically includes following steps：
(1) weigh 1g silver nitrate first to be dissolved in 100ml deionized waters, add 0.6g PVP, under stirring condition, make two
Person's mix homogeneously；Sodium hydroxide is added to adjust the pH to 8 of mixed liquor；Formalin that 3ml mass fraction be 37% is separately weighed, plus
Enter in aforesaid mixed liquor；Immediately reactant liquor is transferred in hydrothermal reaction kettle (200ml), by reducing agent at 170 DEG C
Reduction airtight heating 1h, takes out reactor after the completion of question response, naturally cools to room temperature and obtains containing nano-level sphere silver
The middle interstitial fluid A of powder (as silver-colored crystal seed), and be transferred in 500ml there-necked flasks；The silver-colored crystal seed mean diameter for obtaining is about 75nm.
(2) 0.5g thickening agent polyacrylic acid (water-soluble acrylic polymer) is added in above-mentioned middle interstitial fluid A；Separately weigh
In the above-mentioned middle interstitial fluid A of 6.0g ascorbic acid；Weigh 6.0g silver nitrate and be dissolved in obtain in 50ml deionized waters with 1.6g PVP and add slowly
Liquid C；Interstitial fluid A in high-speed stirred, while slow liquid feeding C is added drop-wise in middle interstitial fluid A, continues stirring reaction 15min, obtains at room temperature
Arrive final solution；Separate through centrifugal filtration again, and be respectively washed three times using deionized water and ethanol solution, the argentum powder for obtaining
Solution dries 12h in 70 DEG C of vacuum drying ovens, and (physical and chemical parameter is shown in Table to obtain the micron grade ball shape silver powder product of the present embodiment
1).
Compared with Example 1, the granularity of (1st) the step gained silver crystal seed of embodiment 2 is close, except for the difference that in embodiment 2
The reactant consumption of precipitation is big, concentration is high, and the response time is long, and therefore silver-colored crystal seed has the more sufficient time to grow up, product grain
Degree becomes big.
Embodiment 3：
A kind of controllable ball shape silver powder of granularity of the present invention, 99.98%, the tap density of the ball shape silver powder exists its purity
4.46g/cm3, granularity D of the ball shape silver powder10、D50、D90Respectively 0.26 μm, 0.37 μm and 0.49 μm, the granularity is based on which
During preparation method, reaction system formula is realized with the control of reaction condition.
The preparation method of the above-mentioned ball shape silver powder of the present embodiment, specifically includes following steps：
(1) weigh 0.6g silver nitrate first to be dissolved in 50ml deionized waters, add 0.5g dodecylbenzene sodium sulfonate, stir
The two mix homogeneously is made under the conditions of mixing；Sodium hydroxide is added to adjust the pH to 7 of mixed liquor；1.3g reducing agent ferrous sulfate is separately weighed
It is dissolved in 50ml deionized waters, in the aforesaid mixed liquor of addition afterwards to be dissolved；Reactant liquor is transferred to hydrothermal reaction kettle immediately
(200ml) in, by reduction airtight heating 2h of reducing agent at 150 DEG C, reactor is taken out after the completion of question response, natural
It is cooled to room temperature and obtains the middle interstitial fluid A containing nano-level sphere argentum powder (as silver-colored crystal seed), and is transferred to 500ml there-necked flasks
In；Obtain the silver-colored crystal seed that mean diameter is 90nm.
(2) 0.3g thickening agent methylcellulose is added in above-mentioned middle interstitial fluid A；Separately weigh 4.8g ascorbic acid to be dissolved in
State in interstitial fluid A；Weigh 4.8g silver nitrate and 1.2g PVP are dissolved in 50ml deionized waters and obtain slow liquid feeding C；High at room temperature
Interstitial fluid A in speed stirring, while slow liquid feeding C is added drop-wise in middle interstitial fluid A, continues stirring reaction 20min, obtains final solution；Again
Separate through centrifugal filtration, and be respectively washed three times using deionized water and ethanol solution, the argentum powder solution for obtaining is true at 70 DEG C
12h is dried in empty drying baker, the micron grade ball shape silver powder product (physical and chemical parameter is shown in Table 1) of the present embodiment is obtained.
Embodiment 4：
A kind of controllable ball shape silver powder of granularity of the present invention, 99.97%, the tap density of the ball shape silver powder exists its purity
4.52g/cm3, granularity D of the ball shape silver powder10、D50、D90Respectively 0.21 μm, 0.39 μm and 0.59 μm, the granularity is based on which
During preparation method, reaction system formula is realized with the control of reaction condition.
The preparation method of the above-mentioned ball shape silver powder of the present embodiment, specifically includes following steps：
(1) weigh 1g silver nitrate first to be dissolved in 50ml deionized waters, add 0.4g N- methyl polyethylene pyrrolidines
The two mix homogeneously is made under ketone, stirring condition；Sodium hydroxide is added to adjust the pH to 7 of mixed liquor；1.2g reducing agent Portugal is separately weighed
Grape sugar is dissolved in 50ml deionized waters, in the aforesaid mixed liquor of addition afterwards to be dissolved, obtains the reactant liquor of grey black；Immediately will be anti-
Liquid is answered to be transferred in hydrothermal reaction kettle (200ml), by reduction airtight heating 3h of reducing agent, question response at 140 DEG C
After the completion of take out reactor, naturally cool to room temperature and obtain the middle interstitial fluid A containing nano-level sphere argentum powder (as silver-colored crystal seed), and
It is transferred in 500ml there-necked flasks；The mean diameter for obtaining silver-colored crystal seed is about 145nm.
(2) 0.4g thickening agent sodium polyacrylate is added in above-mentioned middle interstitial fluid A；Separately weigh 18.0g ascorbic acid to be dissolved in
In above-mentioned middle interstitial fluid A；Weigh 18.0g silver nitrate and 8.0g sodium citrates are dissolved in 100ml deionized waters and obtain slow liquid feeding C；?
Interstitial fluid A in high-speed stirred under room temperature, while slow liquid feeding C is added drop-wise in middle interstitial fluid A, continues stirring reaction 30min, obtains final
Solution；Separate through centrifugal filtration again, and be respectively washed three times using deionized water and ethanol solution, the argentum powder solution for obtaining exists
12h is dried in 70 DEG C of vacuum drying ovens, the micron grade ball shape silver powder product (physical and chemical parameter is shown in Table 1) of the present embodiment is obtained.
Embodiment 5：
A kind of controllable ball shape silver powder of granularity of the present invention, 99.98%, the tap density of the ball shape silver powder exists its purity
4.36g/cm3, granularity D of the ball shape silver powder10、D50、D90Respectively 0.28 μm, 0.43 μm and 0.62 μm, the granularity is based on which
During preparation method, reaction system formula is realized with the control of reaction condition.
The preparation method of the above-mentioned ball shape silver powder of the present embodiment, specifically includes following steps：
(1) weigh 1.0g silver nitrate first to be dissolved in 50ml deionized waters, add 0.3g N- methyl polyethylene pyrrolidines
The two mix homogeneously is made under ketone, stirring condition；Sodium hydroxide is added to adjust the pH to 7 of mixed liquor；1.2g reducing agent Portugal is separately weighed
Grape sugar is dissolved in 50ml deionized waters, in the aforesaid mixed liquor of addition afterwards to be dissolved, obtains the reactant liquor of grey black；Immediately will be anti-
Answer liquid to be transferred in hydrothermal reaction kettle (300ml), by reduction airtight heating 3h of reducing agent formaldehyde at 130 DEG C, treat
Reactor is taken out after the completion of reaction, room temperature is naturally cooled to and is obtained the middle interstitial fluid containing nano-level sphere argentum powder (as silver-colored crystal seed)
A, and be transferred in the precipitation kettle of 500ml；The mean diameter for obtaining silver-colored crystal seed is about 155nm.
(2) 0.4g thickening agent sodium polyacrylate is added in above-mentioned middle interstitial fluid A；Separately weigh 15.0g triethanolamine to be dissolved in
In above-mentioned middle interstitial fluid A；Weigh 18.0g silver nitrate and 8.0g sodium citrates are dissolved in 100ml deionized waters and obtain slow liquid feeding C；?
Interstitial fluid A in high-speed stirred under room temperature, while slow liquid feeding C is added slowly in middle interstitial fluid A, continues stirring reaction 30min, obtains most
Whole solution；Separate through centrifugal filtration again, and be respectively washed three times using deionized water and ethanol solution, the argentum powder solution for obtaining
10h is dried in 70 DEG C of vacuum drying ovens, the micron grade ball shape silver powder product (physical and chemical parameter is shown in Table 1) of the present embodiment is obtained.This
The particle mean size of the argentum powder product of embodiment is 0.43 μm, tap density 4.36g/cm3, with good dispersibility.
Compared with Example 4, the precipitation of the present embodiment employs the relatively low triethanolamine of reproducibility, while reducing
Reactant concentration, the carrying out for making reaction more gentle, the silver atoms that precipitation is generated more are consumed in growing up for silver-colored crystal seed,
Rather than form new nucleus.
Obtained in various embodiments above, the performance parameter of argentum powder product is as shown in table 1 below.
Table 1：Argentum powder product contrast obtained in each embodiment
Particle size distribution numbers in upper table 1 are determined by Malvern laser particle size analyzer, and the scanning electron microscope of embodiment 1 shines
Piece by scanning electron microscope amplify 6000 times afterwards observation obtain.From upper table 1, with the growth in response time, product
The granularity of grain substantially increases, but after precipitation is more than 30min, little of forming core can have been seen partly again by gained argentum powder
Grain, the i.e. granularity of argentum powder are not further added by.The argentum powder product pattern rule of each embodiment, purity is high, good dispersion, tap density compared with
High.
Claims (9)
1. a kind of preparation method of ball shape silver powder, it is characterised in that the purity of the ball shape silver powder more than 99.9%, the ball
The tap density of shape argentum powder is in 4.2g/cm3More than, it is characterised in that：Granularity D of the ball shape silver powder90It is based on its preparation side
During method, to be maintained at 0.2～0.65 μm of interval with the change of reaction condition adjustable for reaction system formula；The preparation method
Comprise the following steps：With soluble silver salt as raw material, first pass through hydro-thermal method and prepare nano-level sphere argentum powder；Then with aforementioned
Nano-level sphere argentum powder as silver-colored crystal seed, induce silver-colored crystal seed uniformly to grow up using precipitation, and by controlling precipitation
Reaction system formula and reaction condition adjust the degree that silver-colored crystal seed is grown up, and then obtain the controllable ball shape silver powder of granularity.
2. preparation method according to claim 1, it is characterised in that：Granularity D of the ball shape silver powder10Control 0.08
～0.3 μm of interval is adjustable, granularity D50Control is adjustable in 0.1～0.5 μm of interval.
3. preparation method according to claim 1 and 2, it is characterised in that the hydro-thermal method specifically includes following steps：Will
Soluble silver salt is dissolved in deionized water according to 1: 0.02～1 mol ratio with dispersant, and the pH value for adjusting mixed liquor is close to
Neutrality, then obtains the middle interstitial fluid A containing the nano-level sphere argentum powder by the reduction of reducing agent under hydrothermal conditions.
4. preparation method according to claim 3, it is characterised in that the reducing agent be glucose, hydrogen peroxide, formaldehyde,
The combination of one or more in hydrazine hydrate, ferrous sulfate, ascorbic acid；Temperature control under the hydrothermal condition is at 120 DEG C
～180 DEG C, the reduction response time under hydrothermal condition is controlled in 5min～5h.
5. preparation method according to claim 3, it is characterised in that the reaction raw materials of the precipitation include described in
Interstitial fluid A and slow liquid feeding C, containing soluble silver salt and chelating agent in the slow liquid feeding C, the precipitant of the precipitation is added to
In the middle interstitial fluid A, the mode of the precipitation under conditions of interstitial fluid A is slowly added slow liquid feeding C in high-speed stirred
Uniformly grown up with the silver-colored crystal seed of induction in middle interstitial fluid A.
6. preparation method according to claim 5, it is characterised in that the temperature control of the precipitation is 0 DEG C～40
DEG C, precipitation time control is in 10min～30min.
7. preparation method according to claim 5, it is characterised in that be also added with the middle interstitial fluid A thickening agent and/or
Dispersant；The thickening agent be water-soluble acrylic polymer, sodium polyacrylate, polyacrylamide, in methylcellulose one
Plant or multiple combinations；The dispersant is polyvinylpyrrolidone, Radix Acaciae senegalis, Polyethylene Glycol, citric acid, citric acid
The combination of one or more in sodium, Oleic acid, N- methyl polyethylene ketopyrrolidines, dodecylbenzene sodium sulfonate.
8. preparation method according to claim 5, it is characterised in that the precipitant be ascorbic acid, triethanolamine,
The combination of one or more in glucose, hydrazine hydrate, hydrogen peroxide, concentration of the precipitant in middle interstitial fluid A are controlled to
0.05～2.00 mol/L.
9. preparation method according to claim 5, it is characterised in that the soluble silver salt is silver nitrate, described slow plus
Liquid C is that silver nitrate and chelating agent are dissolved in the mixing that the silver nitrate concentration that formed in deionized water is 0.05～2.00 mol/L
Liquid；The slow liquid feeding C complexing agents are 0.5～2: 1 with the mol ratio of silver nitrate, and the chelating agent is ammonia, polyvinyl pyrrole
One or more in alkanone, ethylenediaminetetraacetic acid, sodium citrate.
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| JP2005240092A (en) * | 2004-02-26 | 2005-09-08 | Dowa Mining Co Ltd | Silver powder and its production method |
| JP2005330529A (en) * | 2004-05-19 | 2005-12-02 | Dowa Mining Co Ltd | Spherical silver powder and its production method |
| CN102554265B (en) * | 2012-03-16 | 2014-01-01 | 上海交通大学 | Preparation method of mono-dispersed highly crystalline silver powder with adjustable particle size |
| CN102632248B (en) * | 2012-05-03 | 2014-01-08 | 中国人民解放军国防科学技术大学 | Spherical silver powder and preparation method thereof |
| CN103100722B (en) * | 2013-01-30 | 2015-03-04 | 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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