CN100420528C - Method for preparing redispersible Ag nanoparticle by using silver halide precrystallization reduction process - Google Patents
Method for preparing redispersible Ag nanoparticle by using silver halide precrystallization reduction process Download PDFInfo
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- CN100420528C CN100420528C CNB2005101355115A CN200510135511A CN100420528C CN 100420528 C CN100420528 C CN 100420528C CN B2005101355115 A CNB2005101355115 A CN B2005101355115A CN 200510135511 A CN200510135511 A CN 200510135511A CN 100420528 C CN100420528 C CN 100420528C
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 113
- 239000004332 silver Substances 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 65
- -1 silver halide Chemical class 0.000 title claims abstract description 39
- 239000002105 nanoparticle Substances 0.000 title 1
- 238000011946 reduction process Methods 0.000 title 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 23
- 238000013019 agitation Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- 238000002390 rotary evaporation Methods 0.000 claims description 18
- 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 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000000502 dialysis Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000012190 activator Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 73
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- 230000031709 bromination Effects 0.000 description 5
- 238000005893 bromination reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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Abstract
The invention relates to a method for using silver halide pre-crystallization reduction to prepare silver nanometer particles which can be dispersed again, wherein said method uses silver halide pre-crystallization reduction method to obtain uniform silver nanometer particles. The invention uses water as disperse medium; in the system with polymer surface activator, using organic solvent to reduce prepared silver halide pre-crystallized silver nanometer particles gel; then separating silver nanometer particles which can be dispersed into solvent to form gel again.
Description
Technical field
The invention belongs to technical field of nano material, the method that the pre-crystallization reducing process preparation of particularly a series of silver halide can disperse silver nano-grain again.
Background technology
Since nineteen seventies, the research of relevant nano metal, alloy becomes focus gradually.Particularly synthetic, the performance characterization technology of nano metallic colloid particle, powder are developed rapidly.Existing tens kinds of methods can be used for preparing nano level metal colloidal particle or powder.As gas evaporation method, sputtering method, arc process, blasting, cosedimentation method, electrochemical reducing, chemical reduction method, photoreduction met hod, sol-gal process, hydro-thermal method, micro emulsion method, or the like, the report of this respect can be referring to " nano material and nanostructured ", Zhang Lide, Mu Jimei, Science Press, 2000,2.Generally, physical method prepares metal nano powder and needs special equipment, and the distribution of particles that obtains is broad also, and price and cost is not suitable for large-scale industrial production generally than chemical method height.Chemical method is convenient, relatively inexpensive, but particle aggregation that brings and stability problem are the key issues that nano metal synthesizes needs solution always, also is the problem that the nano material synthetic technology needs emphasis to solve.Up to now, we also do not see with the report that can again be dispersed in the water silver nano-grain of formation colloidal sol of chemical method preparation less than 100nm.
Summary of the invention
The objective of the invention is to overcome the easy reunion of existing silver nano-grain, redispersible not, provide a kind of and can be dispersed to the method that forms the silver nano-grain of colloidal sol in the solvent again with a large amount of preparations of chemical method, the about 5～30nm of particle diameter by the silver nano-grain of this method preparation, and particle size distribution is even, product purity is high, and can be dispersed to easily and form colloidal sol in the solvent.
It is to adopt the pre-crystallization reducing process of silver halide that the pre-crystallization reducing process preparation of silver halide of the present invention can disperse the method for silver nano-grain again, for obtaining the uniform silver nano-grain of particle diameter, the present invention is decentralized medium with water, reduces the pre-crystallization of freshly prepd silver halide with organic solvent and prepare silver nano-grain high concentration colloidal sol in containing the system of polymeric surfactant; Can further from solution, separate and obtain to be dispersed to again the silver nano-grain solid that forms colloidal sol in the solvent.
The method that the pre-crystallization reducing process preparation of silver halide of the present invention can disperse silver nano-grain again may further comprise the steps:
(1). getting weight portion and be reducing agent that 1.2～2.3 parts surfactant and weight portion be 1.7～2.8 parts, to be dissolved in weight portion be in 25.5～29.6 parts the water, to make solution A;
(2). getting weight portion and be 3.2～3.7 parts silver nitrate, to be dissolved in weight portion be in 21.7～26.0 parts the water, to make solution B;
(3). getting weight portion and be 1.4～3.1 parts halide salts, to be dissolved in weight portion be in 21.7～26.0 parts the water, to make solution C;
(4). getting weight portion and be 1.0～1.4 parts pH conditioning agent, to be dissolved in weight portion be in 12.7～14.8 parts the water, to make solution D;
(5). in the solution A of the solution B and the solution C of step (2) and step (3) preparation is infused in 70 ± 5 ℃ of water-baths heating simultaneously with the speed that equates step (1), form the pre-crystallization of silver halide, after 1～2 minute the solution D of step (4) is slowly injected above-mentioned system, reinforced finishing continues reaction 0.5～2 hour; Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol; Gained colloidal sol is placed the pellicle dialysis,, obtain clean silver nano-grain colloidal sol to dialysate not till the Halogen ion;
(6). the silver nano-grain colloidal sol freeze drying that step (5) gained is clean can obtain being dispersed to again the silver nano-grain powder in the solvent; Or use the rotary evaporation method under 40 ± 5 ℃, water in the rotary evaporation gained colloidal sol, colloidal sol is concentrated into is about 1/10 of original volume, adding absolute ethyl alcohol washs product get off and transfers in the container (as polytetrafluoroethylene beaker), dry or in the baking oven below 50 ℃, dry with infrared lamp, obtain to be dispersed to again the silver nano-grain solid in the solvent.
Change surfactant/silver nitrate weight ratio, reactant concentration, can effectively control the size of silver nano-grain, its particle diameter is between 5～30 nanometers.
Described silver nano-grain is a spheric granules, and the average grain diameter of described silver nano-grain is between 5～30 nanometers.Described silver nano-grain can be dispersed in the solvent again, forms colloidal sol.
Described surfactant is polyvinylpyrrolidone K30 (molecular weight of polyvinylpyrrolidone K30 is 30000, commercial PVP by name).
Described reducing agent is glucose or the glucose that contains a crystallization water.
Described halide salts is potassium chloride or KBr.
Described pH conditioning agent is a NaOH.
The solvent that described dispersion is once more used is the mixture of water or water and ethanol.
The method that the pre-crystallization reducing process preparation of silver halide of the present invention can disperse silver nano-grain again can be used for preparing the silver nano-grain that can be dispersed to solvent again.The gained metal nanoparticle is easy to disperse again, particle diameter is little, monodispersity good, particle diameter is easy to control.
Advantage of the present invention and good effect:
Adopt the preparation of the pre-crystallization reducing process of silver halide of the present invention can disperse silver nano-grain to compare again to have the following advantages with conventional nano silver powder:
1. the gained silver nano-grain is easy to disperse again
Owing to adopt the silver nano-grain of technology preparation of the present invention in course of reaction, to be wrapped up by surfactant, and the gentle dry run of employing, make product avoid reunion, product can be scattered in water or water and the ethanol mixed solvent once more, form faint yellow vitreosol.
2. the size of gained silver nano-grain is little
That adopts the inventive method preparation can be dispersed to silver nano-grain particle diameter in the solvent again between 5～30nm.
3. the purity height of gained silver nano-grain
Adopt the silver nano-grain that can be dispersed to again in the solvent of the inventive method preparation to prove its high-purity with powder x-ray diffraction mensuration.See accompanying drawing 3.
4. the even particle size distribution of gained silver nano-grain
Statistics shows the even particle size distribution that can be dispersed to the silver nano-grain in the solvent again that adopts the inventive method preparation, and the particle diameter of 95% particle is between average grain diameter ± 10 nanometers.Particle diameter distributes and sees accompanying drawing 4.
5. the good stability of gained silver nano-grain
Stable existence is in decentralized medium for a long time to adopt the silver nano-grain in the solvent of can being dispersed to again of the inventive method preparation, and after the drying, the shape of particle size still can be distributed in the solvent again without any variation.
6. the controllability of particle diameter is good
The particle diameter that can be dispersed to the silver nano-grain in the solvent again that adopts the inventive method preparation can effectively be controlled by adjustment form surface-active agent/silver nitrate weight ratio, reactant concentration between 5～30 nanometers.And, avoided the shortcoming of product monodispersity difference in the existing technology because surfactant and preparation technology's joint effect is evenly distributed product cut size.
7. silver nano-grain preparation technology is simple
The present invention adopts the pre-crystallization reducing process of silver halide to prepare the silver nano-grain that can be dispersed to again in the solvent, and temperature is moderate, and employed equipment all is the standard devices that use in industries such as existing chemical industry.Material is disposable adding, and can utilize microcomputer control reinforced, easy and simple to handle, is easy to control.
8. material is obtained easily
The material that uses in the metal nano powder preparation of the present invention is conventional industrial chemicals, obtains easily.Do not use the material of relative price costliness, with low cost.
9. gained silver nano-grain productive rate height
Use technology of the present invention to prepare metal nano powder productive rate height, each prescription all can reach more than 95%, and loss is low.
Description of drawings
Fig. 1. double-jet method of the present invention prepares the nanometer metal powder process flow diagram.
Fig. 2. the particle diameter distribution map of the cube silver nano-grain that the embodiment of the invention 1 obtains.
Fig. 3. the embodiment of the invention 5 preparation can be dispersed to silver nano-grain transmission electron microscope photo in the solvent again, scale is 200 nanometers among the figure.
Fig. 4. the embodiment of the invention 6 preparation can be dispersed to silver nano-grain powder X-ray-diffracting spectrum in the solvent again.
The specific embodiment
Further describe the present invention below in conjunction with example.
Embodiment 1
Getting weight portion and be the glucose that contains a crystallization water that 2.22 parts polyvinylpyrrolidone (molecular weight is 30000) and weight portion be 2.29 parts, to be dissolved in weight portion be in 29.59 parts the water, make solution A, getting weight portion and be 3.70 parts silver nitrate, to be dissolved in weight portion be in 22.19 parts the water, make solution B, getting weight portion and be 1.70 parts potassium chloride, to be dissolved in weight portion be in 22.19 parts the water, make solution C, getting weight portion and be 1.33 parts NaOH, to be dissolved in weight portion be in 14.79 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 1 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the chloride ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol that gained is clean uses the rotary evaporation method under 40 ± 5 ℃, in the rotary evaporation gained colloidal sol water arranged, colloidal sol is concentrated into is about 1/10 of original volume, add absolute ethyl alcohol product is washed and transfers in the polytetrafluoroethylene beaker, dry with infrared lamp.Obtain to be dispersed to again the silver nano-grain solid of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Embodiment 2
Getting weight portion and be glucose that 1.29 parts polyvinylpyrrolidone (molecular weight is 30000) and weight portion be 2.07 parts, to be dissolved in weight portion be in 25.90 parts the water, make solution A, getting weight portion and be 3.24 parts silver nitrate, to be dissolved in weight portion be in 25.90 parts the water, make solution B, getting weight portion and be 1.55 parts potassium chloride salt, to be dissolved in weight portion be in 25.90 parts the water, make solution C, getting weight portion and be 1.20 parts NaOH, to be dissolved in weight portion be in 12.95 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 0.5 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the chloride ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol freeze drying that gained is clean can obtain being dispersed to again the silver nano-grain powder of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Embodiment 3
Getting weight portion and be glucose that 2.22 parts polyvinylpyrrolidone (molecular weight is 30000) and weight portion be 2.37 parts, to be dissolved in weight portion be in 29.60 parts the water, make solution A, getting weight portion and be 3.70 parts silver nitrate, to be dissolved in weight portion be in 22.21 parts the water, make solution B, getting weight portion and be 1.63 parts potassium chloride salt, to be dissolved in weight portion be in 22.21 parts the water, make solution C, getting weight portion and be 1.26 parts NaOH, to be dissolved in weight portion be in 14.80 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 0.5 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the chloride ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol that gained is clean uses the rotary evaporation method under 40 ± 5 ℃, in the rotary evaporation gained colloidal sol water arranged, colloidal sol is concentrated into is about 1/10 of original volume, add absolute ethyl alcohol and product is washed and transfers in the polytetrafluoroethylene beaker, dry in the baking oven under 50 ℃.Obtain to be dispersed to again the silver nano-grain solid of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Getting weight portion and be glucose that 1.30 parts polyvinylpyrrolidone (molecular weight is 300000) and weight portion be 2.01 parts, to be dissolved in weight portion be in 25.96 parts the water, make solution A, getting weight portion and be 3.24 parts silver nitrate, to be dissolved in weight portion be in 25.96 parts the water, make solution B, getting weight portion and be 1.49 parts potassium chloride salt, to be dissolved in weight portion be in 25.96 parts the water, make solution C, getting weight portion and be 1.10 parts NaOH, to be dissolved in weight portion be in 12.98 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 0.5～2 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the chloride ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol that gained is clean uses the rotary evaporation method under 40 ± 5 ℃, in the rotary evaporation gained colloidal sol water arranged, colloidal sol is concentrated into is about 1/10 of original volume, add absolute ethyl alcohol product is washed and transfers in the polytetrafluoroethylene beaker, dry with infrared lamp.Obtain to be dispersed to again the silver nano-grain solid of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Getting weight portion and be the glucose that contains a crystallization water that 1.92 parts polyvinylpyrrolidone (molecular weight is 30000) and weight portion be 2.05 parts, to be dissolved in weight portion be in 25.57 parts the water, make solution A, getting weight portion and be 3.20 parts silver nitrate, to be dissolved in weight portion be in 25.57 parts the water, make solution B, getting weight portion and be 2.24 parts bromination sylvite, to be dissolved in weight portion be in 25.57 parts the water, make solution C, getting weight portion and be 1.09 parts NaOH, to be dissolved in weight portion be in 12.79 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 0.5～2 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the bromine ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol that gained is clean uses the rotary evaporation method under 40 ± 5 ℃, in the rotary evaporation gained colloidal sol water arranged, colloidal sol is concentrated into is about 1/10 of original volume, add absolute ethyl alcohol and product is washed and transfers in the polytetrafluoroethylene beaker, dry in the baking oven under 50 ℃.Obtain to be dispersed to again the silver nano-grain solid of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Getting weight portion and be glucose that 1.29 parts polyvinylpyrrolidone (molecular weight is 30000) and weight portion be 1.79 parts, to be dissolved in weight portion be in 25.78 parts the water, make solution A, getting weight portion and be 3.21 parts silver nitrate, to be dissolved in weight portion be in 25.78 parts the water, make solution B, getting weight portion and be 2.37 parts bromination sylvite, to be dissolved in weight portion be in 25.78 parts the water, make solution C, getting weight portion and be 1.16 parts NaOH, to be dissolved in weight portion be in 12.84 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 0.5～2 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the bromine ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol that gained is clean uses the rotary evaporation method under 40 ± 5 ℃, in the rotary evaporation gained colloidal sol water arranged, colloidal sol is concentrated into is about 1/10 of original volume, add absolute ethyl alcohol product is washed and transfers in the polytetrafluoroethylene beaker, dry with infrared lamp.Obtain to be dispersed to again the silver nano-grain solid of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Embodiment 7
Getting weight portion and be glucose that 2.20 parts polyvinylpyrrolidone (molecular weight is 30000) and weight portion be 2.20 parts, to be dissolved in weight portion be in 29.33 parts the water, make solution A, getting weight portion and be 3.67 parts silver nitrate, to be dissolved in weight portion be in 22.00 parts the water, make solution B, getting weight portion and be 2.57 parts bromination sylvite, to be dissolved in weight portion be in 22.00 parts the water, make solution C, getting weight portion and be 1.36 parts NaOH, to be dissolved in weight portion be in 14.67 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 0.5～2 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the bromine ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol freeze drying that gained is clean can obtain being dispersed to again the silver nano-grain powder of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Getting weight portion and be glucose that 2.18 parts polyvinylpyrrolidone (molecular weight is 30000) and weight portion be 2.75 parts, to be dissolved in weight portion be in 29.05 parts the water, make solution A, getting weight portion and be 3.63 parts silver nitrate, to be dissolved in weight portion be in 21.79 parts the water, make solution B, getting weight portion and be 3.05 parts bromination sylvite, to be dissolved in weight portion be in 21.79 parts the water, make solution C, getting weight portion and be 1.23 parts NaOH, to be dissolved in weight portion be in 14.53 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 0.5～2 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the bromine ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol that gained is clean uses the rotary evaporation method under 40 ± 5 ℃, in the rotary evaporation gained colloidal sol water arranged, colloidal sol is concentrated into is about 1/10 of original volume, add absolute ethyl alcohol product is washed and transfers in the polytetrafluoroethylene beaker, dry with infrared lamp.Obtain to be dispersed to again the silver nano-grain solid of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Embodiment 9
Getting weight portion and be glucose that 1.28 parts polyvinylpyrrolidone (molecular weight is 30000) and weight portion be 2.24 parts, to be dissolved in weight portion be in 25.60 parts the water, make solution A, getting weight portion and be 3.20 parts silver nitrate, to be dissolved in weight portion be in 25.60 parts the water, make solution B, getting weight portion and be 2.56 parts bromination sylvite, to be dissolved in weight portion be in 25.60 parts the water, make solution C, getting weight portion and be 1.12 parts NaOH, to be dissolved in weight portion be in 12.80 parts the water, to make solution D.
The solution B, the C that are prepared are infused in the solution A of 70 ℃ of water-bath heating simultaneously with the speed that equates, form the pre-crystallization of silver halide, with in the slow injection system of solution D, reinforced finishing continues reaction 0.5～2 hour after one minute.Whole process is all carried out under magnetic agitation.Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol.Gained colloidal sol is placed the pellicle dialysis, to dialysate not till the bromine ion-containing.Obtain clean silver nano-grain colloidal sol.
The silver nano-grain colloidal sol that gained is clean uses the rotary evaporation method under 40 ± 5 ℃, in the rotary evaporation gained colloidal sol water arranged, colloidal sol is concentrated into is about 1/10 of original volume, add absolute ethyl alcohol and product is washed and transfers in the polytetrafluoroethylene beaker, dry in the baking oven under 50 ℃.Obtain to be dispersed to again the silver nano-grain solid of average grain diameter between 5～30 nanometers in water or water and the alcohol mixture.
Claims (7)
1. the pre-crystallization reducing process of silver halide prepares the method that can disperse silver nano-grain again, it is characterized in that this method may further comprise the steps:
(1). getting weight portion and be reducing agent that 1.2～2.3 parts surfactant and weight portion be 1.7～2.8 parts, to be dissolved in weight portion be in 25.5～29.6 parts the water, to make solution A;
(2). getting weight portion and be 3.2～3.7 parts silver nitrate, to be dissolved in weight portion be in 21.7～26.0 parts the water, to make solution B;
(3). getting weight portion and be 1.4～3.1 parts halide salts, to be dissolved in weight portion be in 21.7～26.0 parts the water, to make solution C;
(4). getting weight portion and be 1.0～1.4 parts pH conditioning agent, to be dissolved in weight portion be in 12.7～14.8 parts the water, to make solution D;
(5). in the solution A of the solution B and the solution C of step (2) and step (3) preparation is infused in 70 ± 5 ℃ of water-baths heating simultaneously with the speed that equates step (1), form the pre-crystallizing system of silver halide, after 1～2 minute the solution D of step (4) is slowly injected above-mentioned system, reinforced finishing continues reaction; Whole process is all under agitation carried out; Under agitation slowly cool to room temperature then, obtain homogeneous, dark red brown silver nano-grain colloidal sol; Gained colloidal sol is placed the pellicle dialysis,, obtain clean silver nano-grain colloidal sol to dialysate not till the Halogen ion;
(6). the silver nano-grain colloidal sol freeze drying that step (5) gained is clean obtains being dispersed to again the silver nano-grain powder-product in the solvent; Or use the rotary evaporation method under 40 ± 5 ℃, water in the rotary evaporation gained colloidal sol, make colloidal sol be concentrated into 1/10 of original volume, the silver nano-grain colloidal sol product that obtains concentrating, adding absolute ethyl alcohol washs and transfers to product in the container, dry or in the baking oven below 50 ℃, dry with infrared lamp, obtain to be dispersed to again the silver nano-grain solid in the solvent;
Described surfactant is a polyvinylpyrrolidone;
Described reducing agent is a glucose.
2. method according to claim 1 is characterized in that: the particle diameter of described silver nano-grain is between 5～30 nanometers.
3. method according to claim 1 is characterized in that: described halide salts is potassium chloride or KBr.
4. method according to claim 1 is characterized in that: described pH conditioning agent is a NaOH.
5. method according to claim 1 is characterized in that: the solvent that described dispersion is again used is the mixture of water or water and ethanol.
6. method according to claim 1 is characterized in that: it is 0.5～2 hour that described step (5) continues the reaction time.
7. method according to claim 1 is characterized in that: described glucose is the glucose that contains a crystallization water.
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| CN102039422A (en) * | 2010-11-03 | 2011-05-04 | 上海中科同力化工材料有限公司 | Neutral nano-silver aqueous solution as well as preparation method and application thereof |
| CN102366838A (en) * | 2011-09-16 | 2012-03-07 | 王利兵 | Preparation method of silver nano-particle with uniformity in particle size and favorable monodisperse stability |
| CN109570522A (en) * | 2017-09-29 | 2019-04-05 | 东北农业大学 | A kind of novel preparation method of nano silver freeze-dried powder |
| CN107755711B (en) * | 2017-10-20 | 2019-07-05 | 昆明理工大学 | A kind of pros' micro-nano silver powder, preparation method thereof |
| CN108283936A (en) * | 2018-01-11 | 2018-07-17 | 安徽大学 | A kind of preparation method and applications of the recyclable palladium catalyst of water soluble polymer load |
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| KR20040081215A (en) * | 2003-03-14 | 2004-09-21 | 한국화학연구원 | Method for making super-fine metal particle solution with high concentration |
| CN1586774A (en) * | 2004-07-06 | 2005-03-02 | 中国乐凯胶片集团公司 | Process for preparing nano silver colloidal water solution |
| CN1600477A (en) * | 2003-09-28 | 2005-03-30 | 中国印钞造币总公司 | Method for preparing nano silver powder |
| US20050257643A1 (en) * | 2004-05-19 | 2005-11-24 | Dowa Mining Co., Ltd. | Spherical silver powder and method for producing same |
| CN1709618A (en) * | 2005-07-08 | 2005-12-21 | 昆明理工大学 | Method for preparing nano or submicron silver powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20040081215A (en) * | 2003-03-14 | 2004-09-21 | 한국화학연구원 | Method for making super-fine metal particle solution with high concentration |
| CN1600477A (en) * | 2003-09-28 | 2005-03-30 | 中国印钞造币总公司 | Method for preparing nano silver powder |
| US20050257643A1 (en) * | 2004-05-19 | 2005-11-24 | Dowa Mining Co., Ltd. | Spherical silver powder and method for producing same |
| CN1586774A (en) * | 2004-07-06 | 2005-03-02 | 中国乐凯胶片集团公司 | Process for preparing nano silver colloidal water solution |
| CN1709618A (en) * | 2005-07-08 | 2005-12-21 | 昆明理工大学 | Method for preparing nano or submicron silver powder |
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