CN102407342B - Preparation method of nano silver powder with accurately controllable particle size - Google Patents
Preparation method of nano silver powder with accurately controllable particle size Download PDFInfo
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- CN102407342B CN102407342B CN201110336268.9A CN201110336268A CN102407342B CN 102407342 B CN102407342 B CN 102407342B CN 201110336268 A CN201110336268 A CN 201110336268A CN 102407342 B CN102407342 B CN 102407342B
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Abstract
The invention relates to a preparation method of nano silver powder with accurately controllable particle size. Silver nitrate is used as a starting raw material, and reacts with a precipitator to form uniform silver-containing precursor precipitate, and then a reducing agent is added to reduce the silver-containing precursor precipitate under the condition of adding silver seed crystals to obtain simple substance silver. The obtained silver powder particles are polyhedral or approximately spherical, the powder has good dispersibility and uniform particle size distribution, and the particle size of the silver powder can be accurately controlled within the range of 20-300 nm by controlling the size and the adding amount of the seed crystal. The invention is a method for preparing the aqueous solution system of the nano silver powder, which can accurately control the grain diameter of the silver powder under the reaction condition of normal temperature and pressure and is suitable for large-scale production. The preparation method has the advantages of mild reaction conditions, simplicity, convenience, low cost and stable quality.
Description
Technical field
The present invention relates to the preparation method of the nano-silver powder that a kind of particle diameter can accurately control, belong to field of inorganic chemical engineering.
Background technology
Argent has excellent physicochemical characteristics, as normal temperature electric conductivity, the thermal conductivity of optimum, and the strongest reflection characteristic, the photosensitive imaging characteristic, anti-inflammation characteristics etc. make it be widely used in the modern industry field.Silver is also the noble metal of the most cheap resistance to high temperature oxidation, utilizes its electrical and thermal conductivity performance, and silver powder is applied to electrocondution slurry, makes it become the indispensable functional material of electronics industry.Because the particle diameter of nano-silver powder is little, active high, can effectively regulate and improve the parameters such as viscosity, rheological characteristic, thixotropy and sintering activity of conductive silver slurry, along with light, little, the thin trend of electric development, make nano-silver powder become one of main application direction in the microelectronics industry field; In addition, utilize the anti-inflammation characteristic of Nano Silver, use it for the fields such as antibacterial fabric, plastics, pottery, coating, Medical dressing, also present tempting prospect.
The production method of silver powder can be divided into Physical and chemical method simply, and Physical comprises plasma gas phase condensation method, atomization (water atomization, aerosolization) etc., and chemical method comprises thermal decomposition method, liquid phase reduction etc.The characteristics of Physical are that output is large, product degree of crystallinity is high, but still there is a difficult problem at aspects such as production equipment design, technology controlling and process, more crucial is that the silver powder that Physical is produced substantially all arrives tens of microns at several microns, and the particle diameter of silver powder distributes wide, yield is low, has therefore limited its application (referring to CN1164452A).Chemical reduction method is to study at present more thorough, most widely used silver powder preparation method, its production equipment is simple, technological process is simple and easy to control, especially for the preparation of nano-silver powder, utilize the nucleation of crystal in solution phase and the stable and dispersion theory of growth control and nano-colloid particle, be expected to realize that the control of particle morphology and size is synthetic.Over past ten years, the standby nano-silver powder of liquid phase chemical reduction legal system has been obtained plentiful and substantial achievement in research, add the conditions such as speed, whipped form by regulator solution concentration, pH value, reaction temperature, reducing agent kind, reducing agent, the size Control that has realized silver nano material is synthetic (referring to Angew.Chem.Int.Ed.2009,48,60).But liquid phase is controlled preparation silver nanoparticle powder and is still had some defectives at present.At first, most method need adopt the control devices such as organic solvent, pyroreaction or microwave, ultraviolet lighting, in water solution system, the nano-silver powder that the preparation different size is controlled in the normal temperature and pressure reaction is still a challenge (referring to Chem.Eur.J.2005,11,454); Secondly, size Control for silver powder, before obtaining experimental result, can only do qualitative estimation (become large or diminish as size) to the product size, can't design in advance and realize that by the regulation and control response parameter accurate and quantitative control is synthetic (referring to Acc.Chem.Res.2007 the product size, 40,1067); In addition, for obtaining nano-silver powder, control growing up of silver-colored particle in solution phase, often adopt the silver ion solution of low concentration, production efficiency obviously descend (referring to CN1653907A).Therefore, adopt the liquid-phase reduction technology to prepare the silver nanoparticle powder, countries in the world also are difficult to accomplish scale production at present.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the nano-silver powder that a kind of particle diameter can accurately control.
The present invention is under the normal temperature and pressure reaction condition, can accurately control the water solution system preparation method of the nano-silver powder of silver powder particle diameter, suitable large-scale production.Take silver nitrate as initiation material, first form uniform argentiferous presoma precipitation with the precipitating reagent reaction, then adding under the condition of silver-colored crystal seed, add reducing agent reduction argentiferous presoma precipitation to obtain simple substance silver.Can accurately control the particle diameter of silver powder by controlling crystal seed size and addition in 20～300nm scope.
Technical scheme of the present invention is as follows:
The preparation method of the silver powder that a kind of particle diameter can accurately be controlled comprises the following steps:
(1) preparation of crystal seed
Polymer calculates with monomer, first with dispersant I and silver nitrate in molar ratio 1～100: 1 is dissolved in the water, forming silver nitrate concentration is 0.01～20.0mmol/L mixed solution I, adds the solution of reducing agent I under then stirring, and continues stirring reaction and forms the Nano Silver crystal seed; Wherein, dispersant I is one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, enuatrol, neopelex or combination; Reducing agent is one of sodium borohydride, hydrazine hydrate, ascorbic acid or hydrogen peroxide or combination; The mol ratio of reducing agent I and silver nitrate is 0.2～3: 1.
(2) preparation of argentiferous presoma precipitation
1. first complexing agent and silver nitrate are dissolved in the water, forming silver nitrate concentration is the mixed solution I I of 0.1～2.0mol/L; Wherein, described complexing agent is one of citric acid, trisodium citrate, enuatrol, ammoniacal liquor, polyvinylpyrrolidone, formamide, polyacrylic acid or combination; Wherein polymer calculates with monomer, and the mol ratio of complexing agent and silver nitrate is 0.1～10: 1;
2. the crystal seed that again dispersant II, precipitating reagent and step (1) is prepared is scattered in and forms mixed solution I II in water;
Described dispersant II is one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, enuatrol, neopelex or combination; Described precipitating reagent is one of oxalic acid, sodium oxalate, carbonic hydroammonium, sodium carbonate, phosphoric acid, sodium phosphate, hydrochloric acid, sodium chloride, NaOH, sulfuric acid, ammonium sulfate or combination;
3. under agitation, mixed solution I I is added in mixed solution I II, stirring reaction forms uniform argentiferous presoma precipitation;
(3) redox of Nano Silver micelle preparation
1. polymer calculates with monomer, is to be added to the water dissolving and to form mixed solution I V at 0.1～10: 1 in molar ratio with dispersant III and reducing agent II; Described dispersant III is one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, enuatrol, neopelex or combination, and reducing agent II is sodium borohydride, hydrazine hydrate, ascorbic acid or hydrogen peroxide;
2. dispersant IV, reaction speed controlling agent are added to the water dissolving and form mixed solution V; Described dispersant IV is one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, enuatrol, neopelex or combination; The reaction speed controlling agent is ammoniacal liquor, nitric acid or NaOH; Wherein polymer calculates with monomer, and in described dispersant IV consumption and mixed solution I V, the mol ratio of reducing agent II is 0.1～10: 1; In reaction speed controlling agent consumption and mixed solution I V, the mol ratio of reducing agent II is 0.1～10: 1; In mixed solution V, the concentration of reaction speed controlling agent is 0.05～3.0mol/L;
3. mixed solution I V and mixed solution V constant speed are added in the argentiferous presoma precipitation that step (2) makes, stirring reaction generates the Nano Silver micelle.
(4) separation of Nano Silver micelle, washing, drying and pulverizing
The middle Nano Silver micelle that generates of step (3) through Separation of Solid and Liquid, washing, drying and pulverizing, is obtained nano-silver powder.
According to the present invention, be preferably as follows:
In step (1), in mixed solution I, the concentration of silver nitrate is preferably 0.1～2.0mmol/L, and the concentration of reducing agent I solution is 0.1～200.0mmol/L, more preferably 1～20.0mmol/L; Polymer calculates with monomer, and the mol ratio of dispersant I and silver nitrate is preferably 5～50: 1; Reducing agent I is 0.5～1.5: 1 to the preferred molar ratio of silver nitrate; Reaction temperature is room temperature～100 ℃, is preferably room temperature～60 ℃; The stirring reaction time is 1～120 minute, is preferably 5～30 minutes.
Step (2) 1. in, polymer calculates with monomer, complexing agent is preferably 0.1～3 to the mol ratio of silver nitrate: 1; In mixed solution I I, the concentration of silver nitrate is preferably 0.2～1.0mol/L.
Step (2) 2. in the addition of dispersant II and mixed solution I I the mol ratio of silver nitrate be 0.1～10: 1 (polymer calculates with monomer), be preferably 0.4～3: 1; The addition of precipitating reagent is 0.5～5: 1 to the mol ratio of silver nitrate in mixed solution I I, is preferably 1～3: 1; The consumption of crystal seed is in silver nitrate, is 0.001～5% to the ratio of silver nitrate in mixed solution I I, is preferably 0.002～2%; In the consumption contrast mixed solution I I of water, the amount ratio of water is 0～5: 1, is preferably 0～3: 1.
Step (2) 3. in, reaction temperature is room temperature～100 ℃, is preferably room temperature～60 ℃; Reaction time is 1～120 minute, is preferably 5～30 minutes; Mixing speed is 25～1200 rev/mins, is preferably 120～600 rev/mins.
Step (3) 1. in, polymer calculates with monomer, dispersant III is preferably 0.1～3 to the mol ratio of reducing agent II: 1; Reducing agent II consumption is 0.5～3: 1 to the mol ratio of silver nitrate in mixed solution I I, is preferably 1～2: 1; In mixed solution I V, the concentration of reducing agent is 0.05～3.0mol/L, is preferably 0.1～1.0mol/L.
Step (3) 2. in dispersant IV consumption the mol ratio of reducing agent II in mixed solution I V is preferably 0.1～3: 1 (polymer calculates with monomer); In mixed solution V, the concentration of reaction speed controlling agent is preferably 0.1～1.0mol/L; In reaction speed controlling agent consumption and mixed solution I V, the mol ratio of reducing agent II is preferably 0.5～3: 1.
Step (3) 3. in, reaction temperature is room temperature～100 ℃, is preferably room temperature～60 ℃; Feed time is 30～600 minutes, is preferably 120～300 minutes; Reaction time is 30～300 minutes, is preferably 60～180 minutes.
Preferably, the nanometer elargol described in step (4) adopts the Separation of Solid and Liquid of suction filtration, press filtration or centrifugation, more preferably decanter type centrifugation.
Preferably, the Nano Silver micelle that Separation of Solid and Liquid obtains in step (4) adopts water, absolute ethyl alcohol, acetone washing, and further preferred embodiment is for first washing with deionized water, then uses absolute ethanol washing.
Preferably, the Nano Silver micelle in step (4) after washing adopts micro-wave oven, electric dry oven or vacuum drying chamber dry, and further preferred embodiment is vacuum drying chamber.Baking temperature described in step (4) is 30～120 ℃, more preferably 40～80 ℃.
Preferably, the pulverizing described in step (4) adopts air-flow crushing, jaw formula to pulverize or hammer type crushing, and further preferred grinding mode is air-flow crushing.
Technical characterstic of the present invention and principle are described as follows:
In step (1), silver nitrate is reduced the agent fast restore, forms rapidly the silver nanoparticle nucleus.Due to the stable and protective effect of adopting low concentration of silver ions and dispersant, can avoid growing up and assembling of nucleus, the nanometre glue silver that obtain evenly, stablize, disperses, freshly prepd nanometre glue silver is as the crystal seed of next step reaction.In step (2), silver nitrate forms the presoma precipitation of argentiferous and mixes with crystal seed with the precipitating reagent reaction.Adopt complexing agent can control the speed of micelle formation, adopt dispersant can stablize and protect newly-generated micelle, therefore, the argentiferous presoma precipitation that can obtain disperseing also forms uniform the mixing with crystal seed.In step (3), argentiferous presoma precipitation is reduced and forms the Nano Silver micelle.The argentiferous presoma is precipitated as slightly soluble compound, dissolves ionization equilibrium by it, can control discharge and continue to provide silver ion, and can keep concentration of silver ions low in reaction system, grows up rapidly to avoid nano-Ag particles; Dispersant can stablize with the protective reaction system in silver-colored particle, avoid particle aggregation to grow the Nano Silver micelle that obtains disperseing; The reaction speed controlling agent can be controlled the formation speed of redox reaction speed and simple substance silver, avoids homogeneous nucleation in reaction system and forms new silver-colored nucleus, with the simple substance silver evenly growth on the crystal seed that provides in advance that impels reduction to form.Due to the gathering of the generation of having avoided new nucleus and particle growth, so the consumption of particle diameter, consumption and argentiferous presoma that can be by crystal seed is accurately controlled the particle diameter of product, realize that the particle diameter of Nano Silver micelle is accurately controlled preparation.In step (4), in the situation that guarantee powder recovery rate and silver powder dispersiveness, the mode of selecting the separation of Nano Silver micelle, washing, drying and pulverizing obtains the nano-silver powder that particle diameter can accurately be controlled.
Compared with prior art, excellent results of the present invention is as follows:
1. the present invention is in 20～300nm scope, can accurately control the particle diameter of silver powder synthetic, the product good dispersion, particle diameter is evenly distributed;
2. the present invention adopts the slightly soluble compound of argentiferous to replace silver nitrate as precursors, under the prerequisite of having controlled the concentration of silver ions that dissociates in the system, can effectively increase total concentration of silver ions, guarantees higher production efficiency;
3. water solution system of the present invention, the normal temperature and pressure reaction condition, process is easy, with low cost, steady quality, is suitable for industrial applications.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the embodiment of the present invention 1 gained silver powder.
Fig. 2 is field emission scanning electron microscope (FE-SEM) photo of the embodiment of the present invention 1 gained silver powder.
Fig. 3 is the FE-SEM photo of the embodiment of the present invention 2 gained silver powder.
Fig. 4 is the FE-SEM photo of the embodiment of the present invention 3 gained silver powder.
Fig. 5 is the FE-SEM photo of the embodiment of the present invention 4 gained silver powder.
Fig. 6 is the FE-SEM photo of the embodiment of the present invention 5 gained silver powder.
Fig. 7 is the FE-SEM photo of the embodiment of the present invention 6 gained silver powder.
Fig. 8 is the FE-SEM photo of the embodiment of the present invention 7 gained silver powder.
Fig. 9 is the FE-SEM photo of the embodiment of the present invention 8 gained silver powder.
Figure 10 is the FE-SEM photo of the embodiment of the present invention 9 gained silver powder.
Figure 11 is the FE-SEM photo of the embodiment of the present invention 10 gained silver powder.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, further illustrate the present invention, but be not limited to this.
Embodiment 1
(1) preparation of crystal seed
The component of dispersant I: 5.0g trisodium citrate (17.0mmol)+6.7g polyvinylpyrrolidone (PVP K-30 counts 60.4mmol with monomer)+18.0g enuatrol (59.1mmol);
Reducing agent I solution: be the fresh solution of 225mg sodium borohydride (5.9mmol) and the preparation of 330mL water, the about 17.9mmol/L of sodium borohydride concentration wherein, in sodium borohydride and mixed solution I, the mol ratio of silver nitrate is 1: 1.
Described dispersant I and 1.0g silver nitrate (5.9mmol) are dissolved in form mixed solution I in 25.0L water (wherein the mol ratio of dispersant I and silver nitrate is 23.1: 1, the concentration of silver nitrate is about 0.2mmol/L), under rapid stirring, add rapidly again reducing agent I solution, under normal temperature, stirring reaction is 10 minutes, and is standby as crystal seed.
(2) preparation of argentiferous presoma
1. complexing agent is 165g polyvinylpyrrolidone (PVP K-30 is in monomer 1.49mol) and 110g enuatrol (0.36mol);
Described complexing agent and 500g silver nitrate (2.94mol) are dissolved in formation mixed solution I I in 10.0L water;
The mol ratio of complexing agent and silver nitrate is 0.63: 1; In mixed solution I I, the concentration of silver nitrate is about 0.29mol/L.
2. the composition of dispersant II: 330g polyvinylpyrrolidone (PVP K-30 counts 2.97mol with monomer)+220g enuatrol (0.72mol);
Be that 25% ammoniacal liquor (approximately contains 6.5molNH with described dispersant II and 500mL concentration
3) add in the seed-solution of step (1) preparation, stirring and dissolving forms mixed solution I II;
Wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 1.25: 1; Precipitating reagent is 2.2: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.2% to the ratio of silver nitrate in mixed solution I I;
3. under 500 rev/mins of stirrings, mixed solution I I is added in mixed solution I II, under normal temperature, stirring reaction is 10 minutes, forms uniform argentiferous presoma precipitation.
(3) preparation of Nano Silver micelle
1. the composition of dispersant III: identical with above-mentioned dispersant II.
With dispersant III and reducing agent II ascorbic acid 530g (3.0mol)) add and dissolve formation mixed solution I V in 16.0L water;
Wherein dispersant III is 1.23: 1 to the mol ratio of reducing agent II; In ascorbic acid and mixed solution I I, the mol ratio of silver nitrate is 1.02: 1; In mixed solution I V, ascorbic acid concentrations is 0.19mol/L.
2. with the composition of dispersant IV: identical with above-mentioned dispersant II.
With dispersant IV and reaction speed controlling agent 300g NaOH (7.5mol)) add and dissolve formation mixed solution V in 30.0L water; Wherein dispersant IV is 1.23: 1 to the mol ratio of reducing agent II in mixed solution I V; In reaction speed controlling agent and mixed solution I V, the mol ratio of reducing agent II is 2.5: 1; In mixed solution V, the concentration of reaction speed controlling agent is 0.25mol/L.
3. mixed solution I V and mixed solution V are added in the argentiferous presoma precipitation that step (2) forms (during reinforced sharing approximately 180 minutes) with the speed of 10.0L/h, stirring reaction is 120 minutes at normal temperatures, generates the Nano Silver micelle.
(4) separation of Nano Silver micelle, washing, drying and pulverizing
The Nano Silver micelle that generates in step (3) is separated with high speed rotary drum sedimentation centrifuge, then water and ethanol washing 2 times respectively, then 50 ℃ of lower vacuum drying, last air-flow crushing obtains approximately 300g nano-silver powder.The XRD diffracting spectrum of gained silver powder is face-centred cubic structure simple substance silver (referring to Fig. 1), and particle is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 20nm (referring to Fig. 2) approximately.
Embodiment 2
(1) preparation of crystal seed
The composition of dispersant I: 2.5g trisodium citrate (8.5mmol)+3.3g polyvinylpyrrolidone (PVP K-30 counts 29.7mmol with monomer)+9.0g enuatrol (29.6mmol);
Reducing agent I solution is: the fresh solution of 115mg sodium borohydride (3.0mmol) and 165mL water preparation, and the about 18.4mmol/L of sodium borohydride concentration wherein, in sodium borohydride and mixed solution I, the mol ratio of silver nitrate is approximately 1: 1;
Described dispersant I and 500mg silver nitrate (2.94mmol) are dissolved in form mixed solution I in 12.5L water (wherein the mol ratio of dispersant I and silver nitrate is 23: 1, the concentration of silver nitrate is about 0.2mmol/L), under rapid stirring, add rapidly again reducing agent I solution, under normal temperature, stirring reaction is 10 minutes, and is standby as crystal seed.
(2) preparation of argentiferous presoma
1. prepare mixed solution I I, with embodiment 1.
2. dispersant II's consists of 330g polyvinylpyrrolidone (PVP K-30 counts 2.97mol with monomer) and 220g enuatrol (0.72mol); Be that 25% ammoniacal liquor (approximately contains 6.5molNH with dispersant II and 500mL concentration
3) add in the seed-solution of step (1) preparation, then adding 12.5L water, stirring and dissolving forms mixed solution I II, and (wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 1.25: 1; Precipitating reagent is 2.2: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.1% to the ratio of silver nitrate in mixed solution I I; In the consumption contrast mixed solution I I of water, the consumption of water is 1.25: 1).
3. form uniform argentiferous presoma precipitation, with embodiment 1.
The preparation of step (3) Nano Silver micelle is with the separation of (4) Nano Silver micelle, washing, drying and pulverize all identical with embodiment 1.The gained nano-silver powder is 300g approximately, and silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 35nm (referring to Fig. 3) approximately.
Embodiment 3
(1) preparation of crystal seed
The composition of dispersant I: 1.25g trisodium citrate (4.2mmol)+1.67g polyvinylpyrrolidone (PVP K-30 counts 15.0mmol with monomer)+4.5g enuatrol (14.8mmol);
Reducing agent I solution: the fresh solution of 56mg sodium borohydride (1.48mmol) and 82.0mL water preparation, the about 18.0mmol/L of sodium borohydride concentration wherein, in sodium borohydride and mixed solution I, the mol ratio of silver nitrate is approximately 1: 1.
Dispersant I and 250mg silver nitrate (1.47mmol) are dissolved in form mixed solution I in 6.25L water (wherein the mol ratio of dispersant I and silver nitrate is 23: 1, the concentration of silver nitrate is about 0.2mmol/L), under rapid stirring, add rapidly again reducing agent I solution, under normal temperature, stirring reaction is 10 minutes, and is standby as crystal seed.
(2) preparation of argentiferous presoma
1. prepare mixed solution I I, with embodiment 1.
2. the ammoniacal liquor as 25% (approximately contains 6.5molNH with dispersant II (330g polyvinylpyrrolidone (PVP K-30 counts 2.97mol take monomer)+220g enuatrol (0.72mol)) and 500mL concentration
3) add in the seed-solution of step (1) preparation, then adding 19.0L water, stirring and dissolving forms mixed solution I II, and (wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 1.25: 1; Precipitating reagent is 2.2: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.05% to the ratio of silver nitrate in mixed solution I I; In the consumption contrast mixed solution I I of water, the consumption of water is 1.9: 1).
3. form uniform argentiferous presoma precipitation, with embodiment 1.
The preparation of step (3) Nano Silver micelle is with the separation of (4) Nano Silver micelle, washing, drying and pulverize all identical with embodiment 1.The gained nano-silver powder is 300g approximately, and silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 50nm (referring to Fig. 4) approximately.
Embodiment 4
(1) preparation of crystal seed
The composition of dispersant I: 625mg trisodium citrate (2.1mmol)+837mg polyvinylpyrrolidone (PVP K-30 counts 7.5mmol with monomer)+2.25g enuatrol (7.4mmol);
Reducing agent I solution is: the fresh solution of 28mg sodium borohydride (0.74mmol) and 40mL water preparation, and the about 18.5mmol/L of sodium borohydride concentration wherein, in sodium borohydride and mixed solution I, the mol ratio of silver nitrate is 1: 1;
Dispersant I and 125mg silver nitrate (0.74mmol) are dissolved in form mixed solution I in 3.1L water (wherein the mol ratio of dispersant I and silver nitrate is 23: 1, the concentration of silver nitrate is about 0.2mmol/L), under rapid stirring, add rapidly again reducing agent I solution, under normal temperature, stirring reaction is 10 minutes, and is standby as crystal seed.
(2) preparation of argentiferous presoma
1. prepare mixed solution I I, with embodiment 1.
2. the composition of dispersant II: 330g polyvinylpyrrolidone (PVP K-30 counts 2.97mol with monomer)+220g enuatrol (0.72mol); Be that 25% ammoniacal liquor (approximately contains 6.5molNH with dispersant II and 500mL concentration
3) add in the seed-solution of step (1) preparation, then adding 22.0L water, stirring and dissolving forms mixed solution I II; Wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 1.25: 1; Precipitating reagent is 2.2: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.025% to the ratio of silver nitrate in mixed solution I I; In the consumption contrast mixed solution I I of water, the consumption of water is 2.2: 1.
3. form uniform argentiferous presoma precipitation, with embodiment 1.
The preparation of step (3) Nano Silver micelle is with the separation of (4) Nano Silver micelle, washing, drying and pulverize all identical with embodiment 1.The gained nano-silver powder is 300g approximately, and silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 65nm (referring to Fig. 5) approximately.
Embodiment 5
(1) preparation of crystal seed
The composition of dispersant I: 250mg trisodium citrate (0.85mmol)+335mg polyvinylpyrrolidone (PVP K-30 counts 3.0mmol with monomer)+900mg enuatrol (3.0mmol);
Reducing agent I solution: the fresh solution of 11mg sodium borohydride (0.29mmol) and 20.0mL water preparation, the about 14.5mmol/L of sodium borohydride concentration wherein, in sodium borohydride and mixed solution I, the mol ratio of silver nitrate is 1.1: 1.
Described dispersant I and 50mg silver nitrate (0.29mmol) are dissolved in form mixed solution I in 1.25L water (wherein the mol ratio of dispersant I and silver nitrate is 23: 1, the concentration of silver nitrate is about 0.2mmol/L), under rapid stirring, add rapidly more described reducing agent I solution, under normal temperature, stirring reaction is 10 minutes, and is standby as crystal seed.
(2) preparation of argentiferous presoma
1. prepare mixed solution I I, with embodiment 1.
2. the composition of dispersant II: 330g polyvinylpyrrolidone (PVP K-30 counts 2.97mol with monomer)+220g enuatrol (0.72mol); Be that 25% ammoniacal liquor (approximately contains 6.5molNH with dispersant II and 500mL concentration
3) add in the seed-solution of step (1) preparation, then adding 24L water, stirring and dissolving forms mixed solution I II; Wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 1.25: 1; Precipitating reagent is 2.2: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.01% to the ratio of silver nitrate in mixed solution I I; In the consumption contrast mixed solution I I of water, the consumption of water is 2.4: 1.
3. form uniform argentiferous presoma precipitation, with embodiment 1.
The preparation of step (3) Nano Silver micelle is with the separation of (4) Nano Silver micelle, washing, drying and pulverize all identical with embodiment 1.The gained nano-silver powder is 300g approximately, and silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 80nm (referring to Fig. 6) approximately.
Embodiment 6
(1) preparation of crystal seed
with dispersant I (5.0g trisodium citrate (17.0mmol)+6.7g polyvinylpyrrolidone (PVP K-30, take monomer 60.4mmol)) and 560mg silver nitrate (3.3mmol) be dissolved in and form mixed solution I in 13.5.0L water (wherein the mol ratio of dispersant I and silver nitrate is 23.5: 1, the concentration of silver nitrate is about 0.24mmol/L), under rapid stirring, (reducing agent I solution is the fresh solution of 580mg ascorbic acid (3.3mmol) and the preparation of 330mL water to add rapidly reducing agent I solution again, the about 10mmol/L of ascorbic acid concentrations wherein, in ascorbic acid and mixed solution I, the mol ratio of silver nitrate is 1: 1), under normal temperature, stirring reaction is 10 minutes, standby as crystal seed.
(2) preparation of argentiferous presoma
1. with complexing agent 165g polyvinylpyrrolidone (PVP K-30 is take monomer 1.49mol)) and 1000g silver nitrate (5.9mol) be dissolved in 10.0L water and form mixed solution I I (wherein the mol ratio of complexing agent and silver nitrate is 0.25: 1; In mixed solution I I, the concentration of silver nitrate is about 0.59mol/L).
2. with dispersant II 330g polyvinylpyrrolidone (PVP K-30, in monomer 2.97mol)) and precipitating reagent (1.0L hydrochloric acid, concentration is 36.5%, approximately contains 6.0molHCl) add in the seed-solution of step (1) preparation, stirring and dissolving forms mixed solution I II;
Wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 0.5: 1; Precipitating reagent is 1.02: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.056% to the ratio of silver nitrate in mixed solution I I.
3. under 500 rev/mins of stirrings, mixed solution I I is added in mixed solution I II, under normal temperature, stirring reaction is 10 minutes, forms uniform argentiferous presoma precipitation.
(3) preparation of Nano Silver micelle
1. with dispersant III polyvinylpyrrolidone (PVP K-30) 330g (take monomer 2.97mol)) and reducing agent II ascorbic acid 1065g (6.05mo1) adds in 16.5L water dissolving to form mixed solution I V, and (wherein dispersant III is 0.49: 1 to the mol ratio of reducing agent II; In ascorbic acid and mixed solution I I, the mol ratio of silver nitrate is 1.02: 1; In mixed solution I V, ascorbic acid concentrations is 0.36mol/L).
2. (wherein dispersant IV is 1.23: 1 to the mol ratio of reducing agent II in mixed solution I V dispersant IV polyvinylpyrrolidone (PVP K-30) 330g and reaction speed controlling agent (440g NaOH (11.0mol)) to be added in 30.0L water dissolving to form mixed solution V; In reaction speed controlling agent and mixed solution I V, the mol ratio of reducing agent II is 2.5: 1; In mixed solution V, the concentration of reaction speed controlling agent is 0.36mol/L).
3. mixed solution I V and mixed solution V are added in the argentiferous presoma precipitation that step (2) forms (during reinforced sharing approximately 180 minutes) with the speed of 10.0L/h, stirring reaction is 120 minutes at normal temperatures, generates the Nano Silver micelle.
(4) separation of Nano Silver micelle, washing, drying and pulverizing
The Nano Silver micelle that generates in step (3) is separated with high speed rotary drum sedimentation centrifuge, then water and ethanol washing 2 times respectively, then 50 ℃ of lower vacuum drying, use at last air-flow crushing, obtain approximately 600g nano-silver powder.The gained silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 100nm (referring to Fig. 7) approximately.
Embodiment 7
(1) preparation of crystal seed
with dispersant I (1.5g trisodium citrate (5.1mmol)+2.0g polyvinylpyrrolidone (PVP K-30, take monomer 18mmol)) and 166mg silver nitrate (0.98mmol) be dissolved in and form mixed solution I in 4.0L water (wherein the mol ratio of dispersant I and silver nitrate is 21.5: 1, the concentration of silver nitrate is about 0.24mmol/L), under rapid stirring, (reducing agent I solution is the fresh solution of 170mg ascorbic acid (0.97mmol) and the preparation of 100.0mL water to add rapidly reducing agent I solution again, the about 9.7mmol/L of ascorbic acid concentrations wherein, in ascorbic acid and mixed solution I, the mol ratio of silver nitrate is 1: 1), under normal temperature, stirring reaction is 10 minutes, standby as crystal seed.
(2) preparation of argentiferous presoma
1. prepare mixed solution I I, with embodiment 6.
2. with dispersant II (330g polyvinylpyrrolidone (PVP K-30, in monomer 2.97mol)) and precipitating reagent (1.0L hydrochloric acid, concentration is 36.5%, approximately contain 6.0molHCl) add in the seed-solution of step (1) preparation, add 10.0L water, stirring and dissolving forms mixed solution I II, and (wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 0.5: 1 again; Precipitating reagent is 1.02: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.017% to the ratio of silver nitrate in mixed solution I I; In the consumption contrast mixed solution I I of water, the consumption of water is 1: 1).
3. form uniform argentiferous presoma precipitation, with embodiment 6.
The preparation of step (3) Nano Silver micelle is with the separation of (4) Nano Silver micelle, washing, drying and pulverize all identical with embodiment 6.The gained nano-silver powder is 600g approximately, and silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 150nm (referring to Fig. 8) approximately.
Embodiment 8
(1) preparation of crystal seed
with dispersant I (625mg trisodium citrate (2.1mmol)+840mg polyvinylpyrrolidone (PVP K-30, take monomer 7.6mmol)) and 70mg silver nitrate (0.41mmol) be dissolved in and form mixed solution I in 1.7L water (wherein the mol ratio of dispersant I and silver nitrate is 23.6: 1, the concentration of silver nitrate is about 0.24mmol/L), under rapid stirring, (reducing agent I solution is the fresh solution of 72mg ascorbic acid (0.41mmol) and the preparation of 42.0mL water to add rapidly reducing agent I solution again, the about 9.8mmol/L of ascorbic acid concentrations wherein, in ascorbic acid and mixed solution I, the mol ratio of silver nitrate is 1: 1), under normal temperature, stirring reaction is 10 minutes, standby as crystal seed.
(2) preparation of argentiferous presoma
1. prepare mixed solution I I, with embodiment 6.
2. with dispersant II (330g polyvinylpyrrolidone (PVP K-30, in monomer 2.97mol)) and precipitating reagent (1.0L hydrochloric acid, concentration is 36.5%, approximately contain 6.0molHCl) add in the seed-solution of step (1) preparation, add 12.0L water, stirring and dissolving forms mixed solution I II, and (wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 0.5: 1 again; Precipitating reagent is 1.02: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.007% to the ratio of silver nitrate in mixed solution I I; In the consumption contrast mixed solution I I of water, the consumption of water is 1.2: 1).
3. form uniform argentiferous presoma precipitation, with embodiment 6.
The preparation of step (3) Nano Silver micelle is with the separation of (4) Nano Silver micelle, washing, drying and pulverize all identical with embodiment 6.The gained nano-silver powder is 600g approximately, and silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 200nm (referring to Fig. 9) approximately.
Embodiment 9
(1) preparation of crystal seed
with dispersant I (320mg trisodium citrate (1.1mmol)+430mg polyvinylpyrrolidone (PVP K-30, count 3.9mmol take monomer)) and 36mg silver nitrate (0.21mmol) be dissolved in and form mixed solution I in 860mL water (wherein the mol ratio of dispersant I and silver nitrate is 23.8: 1, the concentration of silver nitrate is about 0.24mmol/L), under rapid stirring, (reducing agent I solution is the fresh solution of 37mg ascorbic acid (0.2lmmol) and the preparation of 22.0mL water to add rapidly reducing agent I solution again, the about 9.5mmol/L of ascorbic acid concentrations wherein, in ascorbic acid and mixed solution I, the mol ratio of silver nitrate is 1: 1), under normal temperature, stirring reaction is 10 minutes, standby as crystal seed.
(2) 1. the preparation of argentiferous presoma prepares mixed solution I I, with embodiment 6.
2. with dispersant II (330g polyvinylpyrrolidone (PVP K-30, count 2.97mol with monomer)) and precipitating reagent (1.0L hydrochloric acid, concentration is 36.5%, approximately contain 6.0molHCl) add in the seed-solution of step (1) preparation, add 12.5L water, stirring and dissolving forms mixed solution I II, and (wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 0.5: 1 again; Precipitating reagent is 1.02: 1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.0036% to the ratio of silver nitrate in mixed solution I I; In the consumption contrast mixed solution I I of water, the consumption of water is 1.25: 1).
3. form uniform argentiferous presoma precipitation, with embodiment 6.
The preparation of step (3) Nano Silver micelle is with the separation of (4) Nano Silver micelle, washing, drying and pulverize all identical with embodiment 6.The gained nano-silver powder is 600g approximately, and silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 250nm (referring to Figure 10) approximately.
(1) preparation of crystal seed
with dispersant I (185mg trisodium citrate (0.63mmol)+250mg polyvinylpyrrolidone (PVP K-30, count 2.25mmol take monomer)) and 20mg silver nitrate (0.12mmol) be dissolved in and form mixed solution I in 500mL water (wherein the mol ratio of dispersant I and silver nitrate is 24: 1, the concentration of silver nitrate is about 0.24mmol/L), under rapid stirring, (reducing agent I solution is the fresh solution of 22mg ascorbic acid (0.12mmol) and the preparation of 12mL water to add rapidly reducing agent I solution again, the about 10mmol/L of ascorbic acid concentrations wherein, in ascorbic acid and mixed solution I, the mol ratio of silver nitrate is 1: 1), under normal temperature, stirring reaction is 10 minutes, standby as crystal seed.
(2) preparation of argentiferous presoma
1. prepare mixed solution I I, with embodiment 6.
2. with dispersant II (330g polyvinylpyrrolidone (PVP K-30, count 2.97mol with monomer)) and precipitating reagent (1.0L hydrochloric acid, concentration is 36.5%, approximately contain 6.0molHCl) add in the seed-solution of step (1) preparation, add 13.0L water, stirring and dissolving forms mixed solution I II, and (wherein in dispersant II and mixed solution I I, the mol ratio of silver nitrate is 0.5: 1 again; Precipitating reagent is 1.02: 1 to the mol ratio of silver nitrate in mixed solution I I; In the consumption of crystal seed (take silver nitrate) and mixed solution I I, the ratio of silver nitrate is 0.002%; In the consumption of water and mixed solution I I, the consumption of water is 1.3: 1).
3. form uniform argentiferous presoma precipitation, with embodiment 6.
The preparation of step (3) Nano Silver micelle is with the separation of (4) Nano Silver micelle, washing, drying and pulverize all identical with embodiment 6.The gained nano-silver powder is 600g approximately, and silver powder particles is polyhedron or almost spherical, and powder dispersity is good, particle diameter is evenly distributed, and average grain diameter is 300nm (referring to Figure 11) approximately.
Those skilled in the art can do other and change in the present invention enlightens, change crystal seed size and type as the preparation condition by the change crystal seed, thereby change size and the pattern of silver powder; The chemical composition that precipitates by changing crystal seed and presoma, thereby the chemical composition of change product; By the temperature of change crystal seed preparation feedback or silver powder reduction reaction, thus the size of change silver powder and pattern etc.Certainly, the variation that these are done according to spirit of the present invention is within all should being included in the present invention's scope required for protection.
Claims (10)
1. the preparation method of the silver powder that can accurately control of a particle diameter comprises the following steps:
⑴ the preparation of crystal seed
Polymer calculates with monomer, first with dispersant I and silver nitrate in molar ratio 1 ~ 100:1 be dissolved in the water, forming silver nitrate concentration is 0.01 ~ 20.0mmol/L mixed solution I, adds the solution of reducing agent I under then stirring, and continues stirring reaction and forms the Nano Silver crystal seed;
Wherein, dispersant I is one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, enuatrol, neopelex or combination; Reducing agent I is one of sodium borohydride, hydrazine hydrate, ascorbic acid or hydrogen peroxide or combination; The mol ratio of reducing agent I and silver nitrate is 0.2 ~ 3:1;
⑵ the preparation of argentiferous presoma precipitation
1. first complexing agent and silver nitrate are dissolved in the water, forming silver nitrate concentration is the mixed solution I I of 0.1 ~ 2.0mol/L; Wherein, described complexing agent is one of citric acid, trisodium citrate, enuatrol, ammoniacal liquor, polyvinylpyrrolidone, formamide, polyacrylic acid or combination; Wherein polymer calculates with monomer, and the mol ratio of complexing agent and silver nitrate is 0.1 ~ 10:1;
2. the crystal seed that again dispersant II, precipitating reagent and step ⑴ is prepared forms mixed solution I II in water;
Described dispersant II is one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, enuatrol, neopelex or combination; Described precipitating reagent is one of oxalic acid, sodium oxalate, carbonic hydroammonium, sodium carbonate, phosphoric acid, sodium phosphate, hydrochloric acid, sodium chloride, NaOH, sulfuric acid, ammonium sulfate or combination;
3. under agitation, mixed solution I I is added in mixed solution I II, stirring reaction forms uniform argentiferous presoma precipitation;
⑶ the redox preparation of Nano Silver micelle
1. polymer calculates with monomer, is that 0.1 ~ 10:1 is added to the water dissolving formation mixed solution I V in molar ratio with dispersant III and reducing agent II; Described dispersant III is one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, enuatrol, neopelex or combination, and reducing agent II is sodium borohydride, hydrazine hydrate, ascorbic acid or hydrogen peroxide;
2. dispersant IV, reaction speed controlling agent are added to the water dissolving and form mixed solution V; Described dispersant IV is one of gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, citric acid, trisodium citrate, enuatrol, neopelex or combination; The reaction speed controlling agent is ammoniacal liquor, nitric acid or NaOH; Wherein polymer calculates with monomer, and in described dispersant IV consumption and mixed solution I V, the mol ratio of reducing agent II is 0.1 ~ 10:1; In reaction speed controlling agent consumption and mixed solution I V, the mol ratio of reducing agent II is 0.1 ~ 10:1; In mixed solution V, the concentration of reaction speed controlling agent is 0.05 ~ 3.0mol/L;
3. mixed solution I V and mixed solution V constant speed are added in the argentiferous presoma precipitation that step ⑵ makes, stirring reaction generates the Nano Silver micelle;
⑷ the separation of Nano Silver micelle, washing, drying and pulverizing
The Nano Silver micelle that generates in step ⑶ through Separation of Solid and Liquid, washing, drying with pulverize, is obtained nano-silver powder.
2. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, in step ⑴, in mixed solution I, the concentration of silver nitrate is 0.1 ~ 2.0mmol/L, and the concentration of reducing agent I solution is 0.1 ~ 200.0mmol/L; Polymer calculates with monomer, and the mol ratio of dispersant I and silver nitrate is 5 ~ 50:1; Reducing agent I is 0.5 ~ 1.5:1 to the mol ratio of silver nitrate; Reaction temperature is room temperature ~ 100 ° C; The stirring reaction time is 1 ~ 120 minute.
3. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, step ⑵ 1. in, polymer calculates with monomer, complexing agent is 0.1 ~ 3:1 to the mol ratio of silver nitrate; In mixed solution I I, the concentration of silver nitrate is 0.2 ~ 1.0mol/L.
4. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, step ⑵ 2. in the addition of dispersant II and mixed solution I I the mol ratio of silver nitrate be 0.1 ~ 10:1, polymer calculates with monomer; The addition of precipitating reagent is 0.5 ~ 5:1 to the mol ratio of silver nitrate in mixed solution I I; The consumption of crystal seed is in silver nitrate, is 0.001 ~ 5% to the ratio of silver nitrate in mixed solution I I; In the consumption contrast mixed solution I I of water, the amount ratio of water is 0 ~ 5:1.
5. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, step ⑵ 3. in, reaction temperature is room temperature ~ 100 ° C; Reaction time is 1 ~ 120 minute; Mixing speed is 25 ~ 1200 rev/mins.
6. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, step ⑶ 1. in, polymer calculates with monomer, dispersant III is 0.1 ~ 3:1 to the mol ratio of reducing agent II; Reducing agent II consumption is 0.5 ~ 3:1 to the mol ratio of silver nitrate in mixed solution I I; In mixed solution I V, the concentration of reducing agent is 0.05 ~ 3.0mol/L.
7. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, step ⑶ 2. in dispersant IV consumption be 0.1 ~ 3:1 to the mol ratio of reducing agent II in mixed solution I V, polymer calculates with monomer; In mixed solution V, the concentration of reaction speed controlling agent is 0.1 ~ 1.0mol/L; In reaction speed controlling agent consumption and mixed solution I V, the mol ratio of reducing agent II is 0.5 ~ 3:1.
8. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, step ⑶ 3. in, reaction temperature is room temperature ~ 100 ° C; Feed time is 30 ~ 600 minutes; Reaction time is 30 ~ 300 minutes.
9. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, the nanometer elargol described in step ⑷ adopts the Separation of Solid and Liquid of suction filtration, press filtration or centrifugation.
10. the preparation method of the silver powder that can accurately control of particle diameter as claimed in claim 1, is characterized in that, the Nano Silver micelle that in step ⑷, Separation of Solid and Liquid obtains adopts water, absolute ethyl alcohol, acetone washing; Baking temperature described in step ⑷ is 30 ~ 120 ° of C; Pulverizing described in step ⑷ adopts air-flow crushing, jaw formula to pulverize or hammer type crushing.
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| JP5047864B2 (en) * | 2008-04-04 | 2012-10-10 | Ｄｏｗａエレクトロニクス株式会社 | Conductive paste and cured film containing fine silver particles |
| CN102009185B (en) * | 2010-12-09 | 2013-01-30 | 中山火炬职业技术学院 | Preparation method of silver nanobelts |
| CN102145389B (en) * | 2011-04-15 | 2012-07-04 | 华北水利水电学院 | Method for preparing nano silver powder |
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2011
- 2011-10-31 CN CN201110336268.9A patent/CN102407342B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9982322B2 (en) | 2012-08-30 | 2018-05-29 | Corning Incorporated | Solvent-free syntheses of silver products produced thereby |
| US9670564B2 (en) | 2012-08-31 | 2017-06-06 | Corning Incorporated | Low-temperature dispersion-based syntheses of silver and silver products produced thereby |
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