CN109848438A - A kind of bimodal grain size nano-Ag particles and preparation method thereof - Google Patents
A kind of bimodal grain size nano-Ag particles and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of bimodal grain size nano-Ag particles and preparation method thereof; method provided by the present invention can directly react the nano-Ag particles for generating while containing two kinds of partial sizes; technical process is because avoiding the links such as ammonium hydroxide addition, pH adjusting and centrifuge separation; whole simple production process; requirement to reaction condition and consersion unit is low, and reaction can be completed under room temperature, has at low cost; yield is high, the advantages that being produced on a large scale.In addition, the nano-Ag particles prepared using this method have the characteristics that compacted density is higher, sheet resistance is lower, electric conductivity is more preferable compared to the nano-Ag particles of conventional single size.
Description
[technical field]
The present invention relates to nano material correlative technology fields, and in particular to a kind of bimodal grain size nano-Ag particles and its preparation
Method.
[background technique]
With the continuous development of modern science and technology, applications to nanostructures field is more and more extensive, so that nano-Ag particles
Development has important practical significance.Nano-Ag particles partial size is small, sintering temperature is low and has good uniformity, and surface area
Greatly, the contact area of Argent grain is increased, therefore the electrocondution slurry of nano silver system has good conductivity type, nano-Ag particles are wide
It is general to be applied to bio-pharmaceuticals, light emitting diode, label, solar energy, computer chip, coating, space flight, daily necessities, catalyst etc.
Field.
The preparation of nano-Ag particles generally uses chemical method to prepare, such as " the liquid phase reduction preparation nanometer of Sun Honggang
(Sun Honggang, Liu Heng, Yin Guangfu wait liquid phase reduction to prepare the solid-liquid point of nano-Ag particles for the separation of solid and liquid research of Argent grain "
From research [J] rare metal, 2006,30 (2): 153-157), Zhu Yuping etc. " preparations of nano-Ag particles and its influence because
(Zhu Yuping, Wang Xikui, Zhou Weilin wait preparation and its Study on influencing factors [J] the China powder of nano-Ag particles for element research "
Technology, 2009,15 (6): 1008-5548), record small red " two kinds of preparation methods of nano-Ag particles " (Ji little Hong, Liu Ji waited
Constitution, the two kinds of Shandong preparation method [J] industrial technologies of Tang Jianguo nano-Ag particles, 2016, (9): 74), " liquid of Chunxia WANG etc.
(Chunxia WANG, Li Yinglin, Xu Lei wait solution phase chemical reduction to prepare nano silver for the research of phase reduction method for preparing nanometer Argent grain "
Research [J] the Chemical Engineering Technology of particle and exploitation, 2014,6 (43): 25-27), " the composite Nano Argent grain low-temperature sintering of Xiao Yong
Mechanism and its performance study " (Xiao Yong composite Nano Argent grain Sintering Mechanism and its Shenyang performance study [D]: Harbin
Polytechnical university, 2016) etc., the Argent grain average crystal grain partial size that these technologies prepare stoste is about 20nm, brownish red transparent liquid
Body, stoste solid content are about 1.5%, then ammonium hydroxide is added dropwise and adjusts pH, and so that Argent grain is reunited is black precipitate.Above method is prepared
Stoste in nano silver size of microcrystal it is single, and size is smaller, it is difficult to the methods of be filtered with conventional centrifugal and realize and be concentrated, therefore also
It is 3-5 μm that the nano silver aggregate particle average grain diameter that stoste is precipitated, and is settled out by the means such as ammonium hydroxide, which need in addition be added,.It is overall
For, the preparations of existing nano-Ag particles there are the shortcomings that can conclude are as follows: (1) the generally single size nano silver prepared by
Particle, cannot a direct step to generate include two kinds of particle size of nanometer silver powder body materials；(2) single small-size nano-silver particle, which has, burns
The features such as junction temperature is low, baking time is short, but since compacted density is low, electric conductivity is influenced, by taking 50nm Argent grain as an example, sintering
180 DEG C of temperature, baking time 30min, but average sheet resistance is up to 71.4m Ω/；(3) subsequent ammonium hydroxide, which adds, can be achieved small particle
Nanoparticle agglomerates precipitating, but the Water-borne paint reaches micron level, and process generates pollution, and the environmental protection not met now becomes
Gesture；(4) preparation process flow step is more, low yield, stringent to equipment requirement, harsh to preparation environmental requirement, thus improve at
This simultaneously influences sizable application.
[summary of the invention]
For the above-mentioned technical problems in the prior art, the present invention provides a kind of bimodal grain size nano-Ag particles and
Preparation method, this method can be prepared directly while containing there are two types of the nano-Ag particles of partial size, and average grain diameter is approached than about 1:5
The proportionate relationship of pore-size and accumulation bulb diameter in perfect sphere closs packing model (schematic diagram is shown in Fig. 2).In addition, preparation process
In need not move through centrifugation or using ammonium hydroxide adjust etc. post-processing steps, prepared nano-Ag particles can natural subsidence, prepare work
Skill is simple, and equipment requirement is low, is easy to industrializing implementation.To achieve the goals above, main technical schemes of the invention are as follows:
A kind of preparation method of bimodal grain size nano-Ag particles, comprising the following steps:
S1: being dissolved in the first solvent after reducing agent and protective agent are mixed, and adjusts pH in acidity, adds first and stablize
Solution A is made in agent after mixing；
S2: silver salt is dissolved in the second solvent, solution B is made, solution B is divided into two parts；
S3: first part of solution B front in S2 is added in the solution A, after reacting 10-60min, is added second and is stablized
Agent；
S4: second part of solution B being added dropwise into S3, after the reaction was completed, stands 5-24h, that is, forms the mixed liquor with precipitating；
S5: taking the sediment in the mixed liquor, washs, dry, that is, bimodal grain size nano-Ag particles are made；
Wherein, solution B is divided into two parts in the ratio of 1:1 in the S2；The molecular weight of first stabilizer is 40000-
50000, the molecular weight of second stabilizer is 20000-30000.
First solvent is any one or two or more mixtures in water, ethyl alcohol, ethylene glycol and glycerol.
Second solvent is any one or two or more mixtures in water, ethyl alcohol, ethylene glycol and glycerol.
Further, further comprising the steps of before S2 after the S1: the solution A is heated to 60-100 DEG C.
Further, by weight, by weight, the reducing agent, silver salt, protective agent, the first stabilizer, second
Stabilizer, inorganic acid solution, the first solvent and the second solvent content be respectively as follows:
Further, the silver salt is any one in silver nitrate, silver sulfate, silver carbonate, silver chlorate and silver complex
Kind or two or more mixtures.
Further, the reducing agent be any one or two kinds in citric acid, sodium hypophosphite and calgon with
On mixture；More preferably, the purity of the reducing agent is not less than technical grade.
Further, the protective agent includes the mixing of any one or two kinds in polyvinyl pyridine alkanone and lauric acid
Object.
Further, first stabilizer and the second stabilizer are respectively selected from silane coupling agent, tween T-65 and gelatin
In any one or two or more mixtures.
Further, the inorganic acid is any one in nitric acid, sulfuric acid and hydrochloric acid or two or more mixtures.
The present invention also provides a kind of bimodal grain size nano-Ag particles, are prepared by preparation method as described above；
More specifically, large-sized Argent grain integrated distribution is in the region 350-450nm, the Argent grain integrated distribution of small particle is in 60-
The region 80nm.
Compared to the prior art, beneficial effects of the present invention are as follows:
Technical principle of the invention is: reducing agent, protective agent, the biggish stabilizer of molecular weight being first dissolved completely in
In one solvent, reducing agent main function is that restoring silver salt becomes silver-colored simple substance, and protective agent can protect the silver-colored crystal seed of generation, stabilizer
In mainly the Argent grain of generation is wrapped in, make the Argent grain generated not there is a phenomenon where reuniting, the case where not applying external force
Under, the Argent grain that there is stabilizer to wrap up can natural subsidence, reducing agent, protective agent and stabilizer three there are indispensable, altogether
Same-action extracts Argent grain natural subsidence without subsequent addition ammonium hydroxide or other processes；A silver salt front is added and is contained
In the solution for having reducing agent, protective agent and the biggish stabilizer of molecular weight (i.e. the first stabilizer), greater particle size is directly generated
Argent grain, protective agent can play the role of in time protection when the formation of silver-colored simple substance, and the biggish stabilizer of molecular weight can be by life
At the Argent grain of greater particle size wrap；After the fully reacting of silver salt, the lesser stabilizer of molecular weight (i.e. second is added
Stabilizer), another silver salt is then added dropwise, makes the Argent grain for being formed uniformly greater particle size, while the lesser stabilizer of molecular weight
Small particle Argent grain is wrapped, natural subsidence is in reaction vessel.
The present invention can directly react generation while (the Argent grain difference integrated distribution of big small particle is in 350- containing two kinds of partial sizes
The region 450nm and the region 60-80nm) nano-Ag particles, and without be added dropwise ammonium hydroxide, adjust the subsequent treatment process such as pH or centrifugation
I.e. extractable nano-Ag particles, simple production process, the requirement to reaction condition and consersion unit is low, can be completed under room temperature anti-
It answers, it is at low cost, and yield height (90% or more, it reaches as high as 97%), being produced on a large scale.
Bimodal grain size nano-Ag particles can be prepared using preparation method provided by the present invention, i.e., simultaneously include two kinds of features
The nano-Ag particles of size, since two kinds of particle size ratios are close to theoretical optimal value 1:5, so that prepared nano-Ag particles pressure
Real density is high, and electric conductivity is more preferable, and under identical sintering temperature and sintering time, this product sintered body is averaged the more existing skill of sheet resistance
The average sheet resistance of single size nano-Ag particles prepared by art is lower, minimum to can reach 4.6m Ω/.
[Detailed description of the invention]
Fig. 1 is the grain size distribution of nano-Ag particles prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of nano-Ag particles prepared by embodiment 1；
Fig. 3 is the compacted density structure principle chart of nano-Ag particles.
[specific embodiment]
The present invention is intended to provide a kind of preparation method of bimodal grain size nano-Ag particles, this method can directly prepare bimodulus grain
The nano-Ag particles of diameter, can preparing tool, there are two types of the nano-Ag particles of size, and can be completed without centrifuged technique
The extraction of nano-Ag particles, preparation process is simple and high conversion rate, it can be achieved that nano-Ag particles mass production.In addition, institute
The nano-Ag particles compacted density of preparation is high, sheet resistance is low, electric conductivity is good.In order to achieve the above purpose, skill of the invention
Art scheme is as follows:
A kind of preparation method of bimodal grain size nano-Ag particles, comprising the following steps:
S1: being dissolved in the first solvent after reducing agent and protective agent are mixed, and adjusts pH in acidity, adds first and stablize
Solution A is made in agent after mixing；
S2: silver salt is dissolved in the second solvent, solution B is made, solution B is divided into two parts；
S3: first part of solution B front in S2 is added in the solution A, after reacting 10-60min, is added second and is stablized
Agent；
S4: second part of solution B being added dropwise into S3, after the reaction was completed, stands 5-24h, that is, forms the mixed liquor with precipitating；
S5: taking the sediment in the mixed liquor, washs, dry, that is, bimodal grain size nano-Ag particles are made；
Wherein, solution B is divided into two parts in the ratio of 1:1 in the S2；The molecular weight of first stabilizer is 40000-
50000, the molecular weight of second stabilizer is 20000-30000.
First solvent is any one or two or more mixtures in water, ethyl alcohol, ethylene glycol and glycerol.
Second solvent is any one or two or more mixtures in water, ethyl alcohol, ethylene glycol and glycerol.
Nano-Ag particles are prepared using the above method, have the advantage that 1. directly reaction generates bimodal grain size (i.e. simultaneously
Containing two kinds of sizes) nano-Ag particles, wherein the nano-Ag particles integrated distribution of small particle is in the region 60-80nm and big grain
For the nano-Ag particles integrated distribution of diameter in the region 350-450nm, the mode that defines of " bimodulus " is to produce nano-Ag particles obtained
Product are sharp using laser particle size analyzer measurement peak value, and there are two peak values for discovery, regard two peak values as class triangle respectively, press
Triangle calculation formula calculates separately out the content of two kinds of partial sizes, as shown in Figure 1, partial size is largely almost distributed in two regions
(region 60-80nm and the region 350-450nm)；2. the present invention stabilizer different by addition molecular weight, by Argent grain surface layer
Package, make multiple particles be integrally formed rich in protective layer and can Direct precipitation, without centrifugation, filtering and adjust the post-processing such as pH,
In the case where no increase external force, the Argent grain small particles of sedimentation, which can also be stablized, is attached to large particle surface, is repeatedly washed
It washs, and clipped power stirs 10-20min, also little particle can be dispersed into independent individual；3. the present invention is to reaction environment and equipment
It is required that it is low, it can be completed at room temperature, and yield is high (yield is up to 90% or more).
In addition, using nano-Ag particles prepared by the present invention, compacted density is high.According to " the seepage flow of the 1970s
It is theoretical ", after the loading of the conductive phase in electrocondution slurry reaches a certain level (i.e. " percolation threshold "), conductive phase contacts with each other
Form good conductive percolating network, the conductive channel with most initial, that is to say, that particle contact is more complete in electrocondution slurry
It more connects, electric conductivity is better.But certain gap is constantly present between particle, if the contact area of particle can be generated when too small it is larger
" lumped resistance ", therefore increase particle contact area, improve conductive phase compacted density, facilitate reduce contact resistance,
As shown in figure 3, the hierarchical structure of single particle size nano-Ag particles, gap is larger between particle and particle, and compacted density is relatively
It is small, therefore contact resistance is big；And the Argent grain of two kinds of partial sizes containing size, little particle fill out the gap between bulky grain, particle with
Intergranular contact point is more, and contact area increases, and compacted density is high, and contact resistance is small.The height of compacted density, it is intuitive to show
In the superiority and inferiority of electric conductivity, the characterization present invention of electric conductivity is subject to sheet resistance value, according to test, bimodulus prepared by the present invention
Grain diameter nano Argent grain, sheet resistance is low, electric conductivity is good, under identical sintering temperature and sintering time, prepared by the present invention
The average sheet resistance of nano-Ag particles is only 4.60m Ω/.
It is further comprising the steps of before S2 after the S1 as preferred embodiment: after the S1 before S2 also
The following steps are included: the solution A is heated to 60-100 DEG C, the molten of reducing agent, protective agent and stabilizer on the one hand can be increased
On the other hand Xie Du can be such that silver ion sufficiently reacts, increase conversion ratio, to increase yield (yield reaches as high as 97%).
Further, by weight, the reducing agent, silver salt, protective agent, the first stabilizer, the second stabilizer, inorganic
The content of acid solution, the first solvent and the second solvent is respectively as follows:
Further, the silver salt is any one in silver nitrate, silver sulfate, silver carbonate, silver chlorate and silver complex
Kind or two or more mixtures.
Further, the reducing agent be any one or two kinds in citric acid, sodium hypophosphite and calgon with
On mixture；More preferably, the purity of the reducing agent is not less than technical grade.
Further, the protective agent includes the mixing of any one or two kinds in polyvinyl pyridine alkanone and lauric acid
Object.
Further, first stabilizer and the second stabilizer are respectively selected from silane coupling agent, tween T-65 and gelatin
In any one or two or more mixtures.
Further, the inorganic acid is any one in nitric acid, sulfuric acid and hydrochloric acid or two or more mixtures.
The present invention also provides a kind of bimodal grain size nano-Ag particles, are prepared by preparation method as described above,
There are two types of characteristic sizes for nano-Ag particles tool, and compacted density is higher, sheet resistance is lower, electric conductivity is more preferable；More specifically, big
The Argent grain integrated distribution of partial size is in the region 350-450nm, and the Argent grain integrated distribution of small particle is in the region 60-80nm.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
Embodiment 1
A kind of bimodal grain size nano-Ag particles, by weight, component and content are as follows:
The preparation methods of the bimodal grain size nano-Ag particles the following steps are included:
S1: being dissolved in the first solvent after weighing reducing agent and protective agent mixing by said ratio, and adjusting pH value is in acidity,
The first stabilizer is added, after mixing, solution A is made；
S2: solution A is heated to 60 DEG C；
S3: silver salt is dissolved in the second solvent, solution B is made, solution B is divided into two parts；
S4: first part of solution B front in S3 is added in the solution A after S2 heating, 10-20min is stirred, is then added
Second stabilizer；
S5: into S4 with 20-50 drop/point speed be added dropwise second part of solution B, continue stir 15-20min, wait react
Cheng Hou stands 12h, forms the mixed liquor with precipitating；
S6: liquid is filtered out using the mode that filter paper filters, taking precipitate, after being washed 2-5 times repeatedly with deionized water
It is placed in drying in air dry oven, that is, bimodal grain size nano-Ag particles are made.
In the present embodiment, reducing agent used is Tianjin great Mao chemical reagent factory sodium citrate produced, and purity is industry
Grade or more；Silver salt is the silver nitrate of Guangdong brilliance Science and Technology Ltd. production, and purity is technical grade or more；Protective agent is Guang Dongxi
The polyvinyl pyridine alkanone of Gansu Province Chemical Co., Ltd. production, purity are technical grade or more；First stabilizer and the second stabilizer are equal
For the tween T-65 and gelatin of the production of Guangzhou Jian Shuan Chemical Industry Science Co., Ltd, and the purity of tween T-65 and gelatin is work
More than industry grade, wherein tween T-65 content used in the first stabilizer is 6 parts, and gelatine content is 10 parts, and molecular weight is
40000-50000；Tween T-65 content used in second stabilizer is 5 parts, and gelatine content is 5 parts, and molecular weight is
20000-30000；Inorganic acid is the nitric acid of Guangdong Xilong Chemical Co., Ltd's production, and purity is technical grade or more.
Nano-Ag particles prepared by the present embodiment are subjected to following performance test:
1. granularmetric analysis
Nano-Ag particles prepared by the present embodiment are subjected to granularity point using laser particle size analyzer (model LT3600)
Analysis, there are two peak values as shown in Figure 1: for testing result, and degree of scatter is small, and nano-Ag particles partial size is largely focused on 60-
The region 80nm and the region 350-450nm.
2. scanning electron microscope analysis
It is observed using scanning electron microscope analysis, as a result as shown in Figure 2: there are two types of characteristic sizes for Argent grain tool, and small size is silver-colored
Particle is attached to large scale Argent grain surface.
3. sheet resistance is tested
It prepares thin layer square: preparing two pieces of identical PET base materials, one piece of surface is coated with nanometer prepared by the present embodiment
Argent grain, the nano-Ag particles of another piece of surface coating single particle size, average grain diameter 50nm, coating thickness is respectively 10 μm,
It is placed in air dry oven and tests the sheet resistance of nano-Ag particles coating layer after drying respectively, test result is as shown in Table 1 and Table 2:
Table 1 is coated with the test of PET base material sheet resistance and result of single particle size nano-Ag particles
Table 2 is coated with the test of PET base material sheet resistance and result of nano-Ag particles prepared by the present embodiment
It is shown according to the test result of Tables 1 and 2, the nano silver being prepared using preparation method provided by the present invention
Particle has sheet resistance low (mean square resistance value is up to 4.6m Ω/), electric conductivity compared to the nano-Ag particles of uniform particle size
Good feature.
4. yield is tested
Glass culture dish three are taken, successively carries out weighing quality: M using a ten thousandth balance1, M2, M3；Then using shifting
Liquid rifle takes 2ml nano-Ag particles sample solution to be added drop-wise in culture dish, weighs quality again: M4, M5, M6；Three culture dishes are put
Enter in baking oven, dry 10min, after being cooled to room temperature, successively measures quality: M at 130 DEG C7, M8, M9；MIt is dense(mg/g)=[(M7-
M1)/(M4-M1)+(M8-M2)/(M5-M2)+(M9-M3)/(M6-M3)]/3；
Weigh the mass M of productIt produces(g), according to concentration MIt is dense(mg/g) the actual amount M of Argent grain can be found outIt is real:
MIt is real=MIt produces(g)*M?(mg/g)
MIt is formerIt (mg) was originally the amount for putting into raw material, then ɑ % yield:
ɑ %=[MIt is real(mg)/MIt is former(mg)] * 100%
Specific calculated result is as follows:
Embodiment 2
A kind of bimodal grain size nano-Ag particles, by weight, component and content are as follows:
Wherein, the molecular weight of tween T-65 is 40000-50000, and the molecular weight of gelatin is 250000-30000.
The preparation methods of the bimodal grain size nano-Ag particles the following steps are included:
S1: being dissolved in ethyl alcohol 1 after weighing citric acid and polyvinylpyrrolidone mixing by said ratio, and adjusting pH value is in
Acidity adds tween T-65, after mixing, solution A is made；
S2: silver nitrate being dissolved in ethyl alcohol 2, solution B is made, and solution B is divided into two parts in the ratio of 1:1；
S3: first part of solution B front in S2 being added in the solution A of S1, stirs 10-20min, gelatin is then added；
S4: second part of solution B being added dropwise into S3, continues to stir 15-20min, to after the reaction was completed, stand 12h, forms tool
There is the mixed liquor of precipitating；
S5: liquid is filtered out using the mode that filter paper filters, taking precipitate, after being washed 2-5 times repeatedly with deionized water
It is placed in drying in air dry oven, that is, bimodal grain size nano-Ag particles are made.The yield of the present embodiment is 90%.
Embodiment 3
Wherein, the mixture of the first stabilizer is 7 parts silane coupling agent and 10 parts of tween T-65 composition, it is silane coupled
The molecular weight of agent and tween T-65 are 40000；Second stabilizer is tween T-65, molecular weight 20000.
The preparation methods of the bimodal grain size nano-Ag particles the following steps are included:
S1: it is dissolved in ethylene glycol 1 after weighing sodium hypophosphite and lauric acid mixing by said ratio, adjusts pH value in acid
Property, the first stabilizer is added, after mixing, solution A is made；
S2: solution A is heated to 80 DEG C；
S3: silver sulfate being dissolved in ethylene glycol 2, solution B is made, and solution B is divided into two parts；
S4: first part of solution B front in S3 is added in the solution A after S2 heating, 10-20min is stirred, is then added
Second stabilizer；
S5: second part of solution B being added dropwise into S4, continues to stir 15-20min, to after the reaction was completed, stand 12h, forms tool
There is the mixed liquor of precipitating；
S6: remove the liquid in mixed liquor using the mode of suction filtration, taking precipitate is washed 2-5 times repeatedly with deionized water
After be placed in air dry oven dry, that is, bimodal grain size nano-Ag particles are made.The yield of the present embodiment is 93%.
Embodiment 4
Wherein, the molecular weight of gelatin 1 is 50000, and the molecular weight of gelatin 2 is 20000.
The preparation methods of the bimodal grain size nano-Ag particles the following steps are included:
S1: being dissolved in glycerol 1 after weighing sodium hypophosphite and lauric acid mixing by said ratio, and adjusting pH value is in acidity,
Gelatin 1 is added, after mixing, solution A is made；
S2: solution A is heated to 70 DEG C；
S3: silver chlorate being dissolved in glycerol 2, solution B is made, and solution B is divided into two parts；
S4: first part of solution B front in S3 is added in the solution A after S2 heating, 10-20min is stirred, is then added
Gelatin 2；
S5: second part of solution B being added dropwise into S4, continues to stir 15-20min, to after the reaction was completed, stand 12h, forms tool
There is the mixed liquor of precipitating；
S6: being filtered out liquid using the mode of suction filtration, taking precipitate, is placed after being washed repeatedly with deionized water 2-5 times
It is dry in air dry oven, that is, bimodal grain size nano-Ag particles are made.The yield of the present embodiment is 95%.
Embodiment 5
The preparation methods of the bimodal grain size nano-Ag particles the following steps are included:
S1: it is dissolved in ethylene glycol 1 after weighing citric acid and the mixing of polyethylene pyrrole network alkanone by said ratio, adjusts pH value
In acidity, gelatin is added, after mixing, solution A is made；
S2: solution A is heated to 100 DEG C；
S3: silver carbonate being dissolved in ethylene glycol 2, solution B is made, and solution B is divided into two parts；
S4: first part of solution B front in S3 is added in the solution A after S2 heating, 10-20min is stirred, is then added
Tween T-65；
S5: second part of solution B being added dropwise into S4, continues to stir 15-20min, to after the reaction was completed, stand 12h, forms tool
There is the mixed liquor of precipitating；
S6: liquid is filtered out using the mode that filter paper filters, taking precipitate, after being washed 2-5 times repeatedly with deionized water
It is placed in drying in air dry oven, that is, bimodal grain size nano-Ag particles are made.The yield of the present embodiment is 91%.
Embodiment 6
Wherein, the molecular weight of silane coupling agent is 45000, and the molecular weight of gelatin is 25000.
The preparation methods of the bimodal grain size nano-Ag particles the following steps are included:
S1: being dissolved in ethyl alcohol 1 after weighing citric acid and polyvinylpyrrolidone mixing by said ratio, and adjusting pH value is in
Acidity adds silane coupling agent, after mixing, solution A is made；
S2: solution A is heated to 90 DEG C；
S3: silver salt is dissolved in ethyl alcohol 2, solution B is made, solution B is divided into two parts；
S4: first part of solution B front in S3 is added in the solution A after S2 heating, 10-20min is stirred, is then added
Gelatin；
S5: second part of solution B being added dropwise into S4, continues to stir 15-20min, to after the reaction was completed, stand 12h, forms tool
There is the mixed liquor of precipitating；
S6: sediment is extracted using the mode of centrifugation, is placed in air dry oven after being washed 2-5 times repeatedly with deionized water
Bimodal grain size nano-Ag particles are made in middle drying.The yield of the present embodiment is 91%.
The above content is combine specific optimal technical scheme further detailed description of the invention, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For the professional technician of the technical field of the invention,
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (10)
1. a kind of preparation method of bimodal grain size nano-Ag particles, which comprises the following steps:
S1: being dissolved in the first solvent after reducing agent and protective agent are mixed, and adjusts pH in acidity, adds the first stabilizer,
Solution A is made after mixing；
S2: silver salt is dissolved in the second solvent, solution B is made, solution B is divided into two parts；
S3: first part of solution B front in S2 is added in the solution A, and after reacting 10-60min, the second stabilizer is added；
S4: second part of solution B being added dropwise into S3, after the reaction was completed, stands 5-24h, that is, forms the mixed liquor with precipitating；
S5: taking the sediment in the mixed liquor, washs, dry, that is, bimodal grain size nano-Ag particles are made；
Wherein, solution B is divided into two parts in the ratio of 1:1 in the S2；The molecular weight of first stabilizer is 40000-
50000, the molecular weight of second stabilizer is 20000-30000.
2. the preparation method of bimodal grain size nano-Ag particles according to claim 1, which is characterized in that S2 after the S1
It is before further comprising the steps of: the solution A is heated to 60-100 DEG C.
3. the preparation method of bimodal grain size nano-Ag particles according to claim 1 or 2, which is characterized in that by weight
Meter, the reducing agent, silver salt, protective agent, the first stabilizer, the second stabilizer, inorganic acid solution, the first solvent and the second solvent
Content be respectively as follows:
4. according to claim 1 or 2 or the bimodal grain size nano-Ag particles preparation method, which is characterized in that the silver
Salt is any one or two or more mixtures in silver nitrate, silver sulfate, silver carbonate, silver chlorate and silver complex.
5. the preparation method of bimodal grain size nano-Ag particles according to claim 1 or 2, which is characterized in that the reduction
Agent is any one or two or more mixtures in citric acid, sodium hypophosphite and calgon.
6. the preparation method of bimodal grain size nano-Ag particles according to claim 1 or 2, which is characterized in that the protection
Agent includes the mixture of any one or two kinds in polyvinyl pyridine alkanone and lauric acid.
7. the preparation method of bimodal grain size nano-Ag particles according to claim 1 or 2, which is characterized in that described first
Stabilizer and the second stabilizer be respectively selected from silane coupling agent, tween T-65 and gelatin any one or it is two or more mixed
Close object.
8. the preparation method of bimodal grain size nano-Ag particles according to claim 1 or 2, which is characterized in that described inorganic
Acid is any one or two or more mixtures in nitric acid, sulfuric acid and hydrochloric acid.
9. a kind of bimodal grain size nano-Ag particles, which is characterized in that prepared by the described in any item preparation methods of claim 1-8
It forms.
10. bimodal grain size nano-Ag particles according to claim 9, which is characterized in that the bimodal grain size nano silver
Grain, large-sized Argent grain integrated distribution is in the region 350-450nm, and the Argent grain integrated distribution of small particle is in the region 60-80nm.
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