CN109848438B - Double-mode particle size nano silver particle and preparation method thereof - Google Patents
Double-mode particle size nano silver particle and preparation method thereof Download PDFInfo
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Abstract
The invention provides a double-mode particle size nano silver particle and a preparation method thereof, the method provided by the invention can directly react to generate the nano silver particle containing two particle sizes, the process avoids the steps of ammonia water addition, pH adjustment, centrifugal separation and the like, the whole production process is simple, the requirements on reaction conditions and reaction equipment are low, the reaction can be completed at normal temperature, and the method has the advantages of low cost, high yield, large-scale production and the like. In addition, compared with the conventional single-size nano silver particles, the nano silver particles prepared by the method have the characteristics of higher compaction density, lower sheet resistance and better conductivity.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of nano materials, in particular to a nano silver particle with a dual-mode particle size and a preparation method thereof.
[ background of the invention ]
With the continuous development of modern science and technology, the application field of nano materials is more and more extensive, so that the development of nano silver particles has important practical significance. The nano silver particles have small particle size, low sintering temperature, good uniformity and large surface area, and the contact area of the silver particles is increased, so the nano silver conductive slurry has good conductivity, and the nano silver particles are widely applied to the fields of biological pharmacy, light emitting diodes, labels, solar energy, computer chips, coatings, aerospace, daily necessities, catalysts and the like.
The preparation of the nano silver particles is generally prepared by a chemical method, such as the research on solid-liquid separation of nano silver particles prepared by a liquid-phase reduction method of grandma and the like (grandma, Liuheng, Yiguanfu, and the like; research on solid-liquid separation of nano silver particles prepared by a liquid-phase reduction method [ J ]. rare metals 2006,30(2):153-157), the research on the preparation of nano silver particles and influence factors thereof of Zhuyuping and the like (Zhuyuping, Wanxiquan, Zhouweilin, and the like; research on the preparation of nano silver particles and influence factors thereof [ J ]. Chinese powder technology 2009,15(6):1008-5548), the research on two preparation methods of nano silver particles of Xiaohong and the like (Jixian, Liujian, Jiantangguo. two preparation methods of nano silver particles [ J ]. Shandong industrial technology, 2016, (9):74), the research on preparation of nano silver particles prepared by a liquid-phase reduction method of Wanxia and the like (Kishin Chun-silver particles), li Yinlin, Xulie, etc. research on preparing nano silver particles by a liquid phase chemical reduction method [ J ] chemical technology and development, 2014,6(43):25-27), Xiaoyong ' composite nano silver particle low-temperature sintering mechanism and performance research ' (Xiaoyong ' composite nano silver particle low-temperature sintering mechanism and performance research [ D ] Shenyang: Harbin industrial university, 2016), etc. the technology prepares the silver particle average grain diameter of the stock solution is about 20nm, the brownish red transparent liquid has the solid content of the stock solution of about 1.5%, and ammonia water is added to adjust the pH value, so that the silver particles are agglomerated into black precipitates. The nano silver crystal grains in the stock solution prepared by the method have single grain diameter and smaller size, and are difficult to concentrate by using conventional centrifugal filtration and other methods, so the stock solution is precipitated by adding ammonia water and other methods, and the average grain diameter of the precipitated nano silver aggregate grains is 3-5 mu m. In general, the disadvantages of the existing preparation of nano silver particles can be summarized as follows: (1) the prepared nano silver particles are generally single-size nano silver particles, and can not directly generate a nano silver powder material with two particle sizes in one step; (2) the single small-size nano silver particles have the characteristics of low sintering temperature, short baking time and the like, but the conductive performance is influenced due to low compaction density, for example, 50nm silver particles are sintered at 180 ℃ for 30min, but the average sheet resistance is as high as 71.4m omega/□; (3) the subsequent ammonia water addition can realize the agglomeration and precipitation of the small-particle-size nano particles, but the size of the agglomerates reaches the micron level, and the process generates pollution, thus not conforming to the current environmental protection trend; (4) the preparation process has the advantages of multiple steps, low yield, strict requirements on equipment and strict requirements on preparation environment, thereby increasing the cost and influencing the scale application.
[ summary of the invention ]
Aiming at the technical problems in the prior art, the invention provides a double-mode particle size nano silver particle and a preparation method thereof, the method can directly prepare the nano silver particle containing two particle sizes simultaneously, and the average particle size ratio is about 1: and 5, the pore size and the diameter of the packed spheres in the close-to-ideal spherical close-packed model are in proportion (shown in a schematic diagram in figure 2). In addition, the preparation process does not need to be subjected to post-treatment steps such as centrifugation or ammonia water regulation, the prepared nano silver particles can be naturally settled, the preparation process is simple, the equipment requirement is low, and the industrial implementation is easy. In order to achieve the purpose, the main technical scheme of the invention is as follows:
a preparation method of nano silver particles with double-mode particle sizes comprises the following steps:
s1: mixing a reducing agent and a protective agent, dissolving the mixture in a first solvent, adjusting the pH value to be acidic, adding a first stabilizing agent, and uniformly mixing to prepare a solution A;
s2: dissolving silver salt in a second solvent to prepare a solution B, and dividing the solution B into two parts;
s3: adding the first solution B in the S2 into the solution A positively, reacting for 10-60min, and adding a second stabilizer;
s4: dropwise adding the second part of solution B into S3, and standing for 5-24h after the reaction is finished to form a mixed solution with a precipitate;
s5: taking the precipitate in the mixed solution, washing and drying to prepare the nano silver particles with double-mode particle size;
wherein the solution B in the S2 is divided into two parts according to the proportion of 1: 1; the molecular weight of the first stabilizer is 40000-50000, and the molecular weight of the second stabilizer is 20000-30000.
The first solvent is any one or a mixture of more than two of water, ethanol, glycol and glycerol.
The second solvent is any one or a mixture of more than two of water, ethanol, glycol and glycerol.
Further, the method further comprises the following steps after the step of S1 and before the step of S2: the solution A was heated to 60-100 ℃.
Further, the contents of the reducing agent, the silver salt, the protective agent, the first stabilizer, the second stabilizer, the inorganic acid solution, the first solvent and the second solvent are respectively as follows in parts by weight:
further, the silver salt is any one or a mixture of more than two of silver nitrate, silver sulfate, silver carbonate, silver chloride and silver complex.
Further, the reducing agent is any one or a mixture of more than two of citric acid, sodium hypophosphite and sodium hexametaphosphate; more preferably, the purity of the reducing agent is not lower than industrial grade.
Further, the protective agent comprises any one or a mixture of two of polyvinylpyrrolidone and lauric acid.
Further, the first stabilizing agent and the second stabilizing agent are respectively selected from any one or a mixture of more than two of silane coupling agent, Tween-65 and gelatin.
Further, the inorganic acid is any one or a mixture of more than two of nitric acid, sulfuric acid and hydrochloric acid.
The invention also provides a double-mode particle size nano silver particle, which is prepared by the preparation method; more specifically, the silver particles with large particle size are intensively distributed in the region of 350-450nm, and the silver particles with small particle size are intensively distributed in the region of 60-80 nm.
Compared with the prior art, the invention has the following beneficial effects:
the technical principle of the invention is as follows: completely dissolving a reducing agent, a protective agent and a stabilizing agent with larger molecular weight in a first solvent, wherein the reducing agent mainly acts to reduce silver salt into silver simple substance, the protective agent can protect the generated silver seed crystal, the stabilizing agent mainly wraps the generated silver particles to prevent the generated silver particles from agglomeration, the silver particles wrapped by the stabilizing agent can naturally settle under the condition of no external force, the reducing agent, the protective agent and the stabilizing agent have the defects of incapability, and the silver particles naturally settle under the combined action without subsequent addition of ammonia water or other processes for extraction; adding a part of silver salt to a solution containing a reducing agent, a protective agent and a stabilizer with a larger molecular weight (namely a first stabilizer) to directly generate silver particles with larger particle size, wherein the protective agent can play a role in protecting when a silver simple substance is formed, and the stabilizer with the larger molecular weight can wrap the generated silver particles with larger particle size; after the silver salt completely reacts, adding a stabilizer with smaller molecular weight (namely a second stabilizer), then dropwise adding another part of silver salt to uniformly form silver particles with larger particle size, and simultaneously wrapping the silver particles with smaller particle size by the stabilizer with smaller molecular weight and naturally settling in a reaction container.
The method can directly react to generate the nano silver particles with two particle sizes (the silver particles with the particle sizes are respectively and intensively distributed in the 350-450nm region and the 60-80nm region), can extract the nano silver particles without subsequent treatment processes such as dropwise adding ammonia water, adjusting pH or centrifuging and the like, has simple production process, low requirements on reaction conditions and reaction equipment, can complete the reaction at normal temperature, has low cost and high yield (more than 90 percent and up to 97 percent), and can realize large-scale production.
By using the preparation method provided by the invention, the nano silver particles with double-mode particle size can be prepared, namely the nano silver particles simultaneously comprise two characteristic sizes, and as the ratio of the two particle sizes is close to the theoretical optimal value of 1: 5, the prepared nano silver particles have high compaction density and better conductivity, and under the same sintering temperature and sintering time, the average sheet resistance of the product sintered body is lower than that of single-size nano silver particles prepared by the prior art, and can reach 4.6m omega/□ at least.
[ description of the drawings ]
Fig. 1 is a distribution diagram of the particle size of nano silver particles prepared in example 1;
FIG. 2 is a scanning electron microscope image of the nano-silver particles prepared in example 1;
fig. 3 is a schematic diagram of a compacted density structure of nano silver particles.
[ detailed description ] embodiments
The invention aims to provide a preparation method of nano silver particles with double-mode particle sizes, the method can be used for directly preparing the nano silver particles with double-mode particle sizes, namely preparing the nano silver particles with two sizes, can finish the extraction of the nano silver particles without a centrifugal process, has simple preparation process and high conversion rate, and can realize the batch production of the nano silver particles. In addition, the prepared nano silver particles have high compaction density, low sheet resistance and good conductivity. In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of nano silver particles with double-mode particle sizes comprises the following steps:
s1: mixing a reducing agent and a protective agent, dissolving the mixture in a first solvent, adjusting the pH value to be acidic, adding a first stabilizing agent, and uniformly mixing to prepare a solution A;
s2: dissolving silver salt in a second solvent to prepare a solution B, and dividing the solution B into two parts;
s3: adding the first solution B in the S2 into the solution A positively, reacting for 10-60min, and adding a second stabilizer;
s4: dropwise adding the second part of solution B into S3, and standing for 5-24h after the reaction is finished to form a mixed solution with a precipitate;
s5: taking the precipitate in the mixed solution, washing and drying to prepare the nano silver particles with double-mode particle size;
wherein the solution B in the S2 is divided into two parts according to the proportion of 1: 1; the molecular weight of the first stabilizer is 40000-50000, and the molecular weight of the second stabilizer is 20000-30000.
The first solvent is any one or a mixture of more than two of water, ethanol, glycol and glycerol.
The second solvent is any one or a mixture of more than two of water, ethanol, glycol and glycerol.
The method for preparing the nano silver particles has the following advantages: directly reacting to generate nano silver particles with double-mode particle sizes (namely, simultaneously containing two particle sizes), wherein the nano silver particles with small particle sizes are intensively distributed in a 60-80nm area and the nano silver particles with large particle sizes are intensively distributed in a 350-plus-450 nm area, the double-mode defining mode is that the prepared nano silver particle product has a sharp peak value measured by using a laser particle size analyzer, the two peak values are respectively regarded as a triangle-like shape, the contents of the two particle sizes are respectively calculated according to a triangle calculation formula, and as shown in figure 1, most of the particle sizes are almost distributed in the two areas (the 60-80nm area and the 350-plus-450 nm area); secondly, the surface layers of the silver particles are wrapped by adding stabilizers with different molecular weights, so that a plurality of particles are integrated into a whole, have a protective layer and can be directly precipitated, the post-treatments of centrifugation, filtration, pH adjustment and the like are not needed, small particles in the precipitated silver particles can be stably attached to the surface of large particles under the condition of not increasing external force, and the small particles can be dispersed into independent individuals after being washed for multiple times and stirred for 10-20min by shearing force; the method has low requirements on reaction environment and equipment, can be finished at room temperature, and has high yield (the yield can reach over 90 percent).
In addition, the nano silver particles prepared by the method have high compaction density. According to the "percolation theory" in the 70's of the 20 th century, when the filling amount of the conductive phase in the conductive paste reaches a certain degree (i.e., "percolation threshold"), the conductive phases contact with each other to form a good percolation network, and have the most initial conductive path, that is, the more complete and connected the particles in the conductive paste, the better the conductivity. However, a certain gap always exists between the particles, and if the contact area of the particles is too small, a larger 'concentrated resistance' is generated, so that the contact area of the particles is increased, the compaction density of the conductive phase is increased, and the contact resistance is reduced, as shown in fig. 3, the contact resistance is large because the gap between the particles is large and the compaction density is relatively small due to the hierarchical structure of the nano silver particles with the single particle size; the silver particles with two sizes fill gaps among large particles, the small particles fill gaps among the large particles, contact points among the particles are more, the contact area is increased, the compaction density is high, and the contact resistance is small. The high and low compaction density is visually shown in the advantages and disadvantages of the conductivity, the characterization of the conductivity is based on the square resistance, according to the test, the prepared nano silver particles with double-mode particle size have low square resistance and good conductivity, and under the same sintering temperature and sintering time, the average square resistance of the prepared nano silver particles is only 4.60m omega/□.
As a preferred embodiment, said step after S1 and before S2 further comprises the steps of: the step of S1 before S2 further comprises the steps of: heating the solution A to 60-100 ℃ can increase the solubility of the reducing agent, the protective agent and the stabilizing agent on the one hand, and can fully react the silver ions on the other hand, thereby increasing the conversion rate and further increasing the yield (the yield can reach 97 percent at most).
Further, the contents of the reducing agent, the silver salt, the protective agent, the first stabilizing agent, the second stabilizing agent, the inorganic acid solution, the first solvent and the second solvent are respectively as follows in parts by weight:
further, the silver salt is any one or a mixture of more than two of silver nitrate, silver sulfate, silver carbonate, silver chloride and silver complex.
Further, the reducing agent is any one or a mixture of more than two of citric acid, sodium hypophosphite and sodium hexametaphosphate; more preferably, the purity of the reducing agent is not lower than industrial grade.
Further, the protective agent comprises any one or a mixture of two of polyvinylpyrrolidone and lauric acid.
Further, the first stabilizing agent and the second stabilizing agent are respectively selected from any one or a mixture of more than two of silane coupling agent, Tween-65 and gelatin.
Further, the inorganic acid is any one or a mixture of more than two of nitric acid, sulfuric acid and hydrochloric acid.
The invention also provides a double-mode particle size nano silver particle which is prepared by the preparation method, and the nano silver particle has two characteristic sizes, higher compaction density, lower sheet resistance and better conductivity; more specifically, the silver particles with large particle size are intensively distributed in the region of 350-450nm, and the silver particles with small particle size are intensively distributed in the region of 60-80 nm.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The double-mode particle size nano silver particles comprise the following components in parts by weight:
the preparation method of the nano silver particles with the double-mode particle size comprises the following steps:
s1: weighing a reducing agent and a protective agent according to the proportion, mixing, dissolving in a first solvent, adjusting the pH value to be acidic, adding a first stabilizing agent, and mixing uniformly to prepare a solution A;
s2: heating solution A to 60 ℃;
s3: dissolving silver salt in a second solvent to prepare a solution B, and dividing the solution B into two parts;
s4: adding the first solution B in the S3 into the heated solution A in the S2 in a positive mode, stirring for 10-20min, and then adding a second stabilizing agent;
s5: dropwise adding the second part of solution B into S4 at a speed of 20-50 drops/min, continuously stirring for 15-20min, and standing for 12h after the reaction is finished to form a mixed solution with a precipitate;
s6: filtering the liquid by using filter paper, taking precipitate, repeatedly washing the precipitate for 2 to 5 times by using deionized water, and then placing the precipitate in a forced air drying oven for drying to obtain the nano silver particles with the double-mode particle size.
In the embodiment, the reducing agent is sodium citrate produced by Tianjin Damao chemical reagent factory, and the purity is more than industrial grade; the silver salt is silver nitrate produced by Guangdong Guanghua science and technology limited company, and the purity is more than industrial grade; the protective agent is polyvinyl pyridine alkanone produced by Guangdong Xiong chemical industry Co Ltd, and the purity is more than industrial grade; the first stabilizer and the second stabilizer are both Tween T-65 and gelatin produced by Guangzhou double chemical engineering and technology Limited, and the purities of the Tween T-65 and the gelatin are both above industrial grade, wherein the Tween T-65 content used by the first stabilizer is 6 parts, the gelatin content is 10 parts, and the molecular weight is 40000-; the content of Tween T-65 used by the second stabilizing agent is 5 parts, the content of gelatin is 5 parts, and the molecular weights are 20000-one 30000; the inorganic acid is nitric acid produced by Guangdong Xiong chemical Limited, and the purity of the nitric acid is more than industrial grade.
The nano silver particles prepared in this example were subjected to the following performance tests:
analysis of particle size
The nano silver particles prepared in this example were subjected to particle size analysis using a laser particle size analyzer (model LT3600), and the detection results are shown in fig. 1: has two peaks and small dispersion degree, and the particle size of the nano silver particles is mostly concentrated in a 60-80nm region and a 350-450nm region.
② analysis by scanning Electron microscope
The results of analysis and observation by scanning electron microscope are shown in FIG. 2: the silver particles have two characteristic sizes, and the small-sized silver particles are attached to the surface of the large-sized silver particles.
③ Square resistance test
Preparing a thin layer square: two identical PET substrates were prepared, one of the substrates was coated with the silver nanoparticles prepared in this example, and the other was coated with silver nanoparticles having a single particle size, an average particle size of 50nm and coating thicknesses of 10 μm, respectively, and the sheet resistances of the silver nanoparticle coating layers were measured after drying in an air-blast drying oven, respectively, and the measurement results are shown in tables 1 and 2:
table 1 sheet resistance test and results for PET substrates coated with single particle size nano-silver particles
Table 2 sheet resistance test and results of PET substrate coated with nano silver particles prepared in this example
According to the test results in tables 1 and 2, the nano silver particles prepared by the preparation method provided by the invention have the characteristics of low sheet resistance (the average sheet resistance can reach 4.6m omega/□) and good conductivity compared with the nano silver particles with uniform particle size.
Yield test
Taking three glass culture dishes, and sequentially weighing the three glass culture dishes by using a one-ten-thousandth balance: m1，M2，M3(ii) a Then 2ml of nano silver particle sample solution is taken by using a pipette and is dripped into a culture dish, and the mass is weighed again: m4，M5，M6(ii) a Placing the three culture dishes into an oven, drying at 130 ℃ for 10min, cooling to normal temperature, and sequentially measuring the mass: m7，M8，M9；MConcentration(mg/g)＝[(M7-M1)/(M4-M1)+(M8-M2)/(M5-M2)+(M9-M3)/(M6-M3)]/3；
Weighing the mass M of the productProduct produced by birth(g) According to the concentration MConcentration(mg/g) the actual amount M of silver particles can be determinedFruit of Chinese wolfberry：
MFruit of Chinese wolfberry＝MProduct produced by birth(g)*MAre all made of(mg/g)
MOriginal source(mg) as the amount of raw material charged, then α% yield:
ɑ％＝[Mfruit of Chinese wolfberry(mg)/MOriginal source(mg)]*100％
The specific calculation results are as follows:
example 2
The double-mode particle size nano silver particles comprise the following components in parts by weight:
wherein, the molecular weight of the Tween T-65 is 40000-50000, and the molecular weight of the gelatin is 250000-30000.
The preparation method of the nano silver particles with the double-mode particle size comprises the following steps:
s1: weighing citric acid and polyvinylpyrrolidone according to the proportion, mixing, dissolving in ethanol 1, adjusting pH to acidity, adding Tween T-65, and mixing to obtain solution A;
s2: dissolving silver nitrate in ethanol 2 to prepare solution B, and dividing the solution B into two parts according to the proportion of 1: 1;
s3: positively adding the first solution B in S2 into the solution A in S1, stirring for 10-20min, and adding gelatin;
s4: dropwise adding the second part of solution B into S3, continuously stirring for 15-20min, and standing for 12h after the reaction is finished to form a mixed solution with a precipitate;
s5: filtering the liquid by using filter paper, taking precipitate, repeatedly washing the precipitate for 2 to 5 times by using deionized water, and then placing the precipitate in a forced air drying oven for drying to obtain the nano silver particles with the double-mode particle size. The yield of this example was 90%.
Example 3
Wherein the first stabilizer is a mixture consisting of 7 parts of silane coupling agent and 10 parts of Tween T-65, and the molecular weights of the silane coupling agent and the Tween T-65 are 40000; the second stabilizer is Tween-65 with molecular weight of 20000.
The preparation method of the nano silver particles with the double-mode particle size comprises the following steps:
s1: weighing sodium hypophosphite and lauric acid according to the proportion, mixing, dissolving in ethylene glycol 1, adjusting the pH value to be acidic, adding a first stabilizer, and mixing uniformly to prepare a solution A;
s2: heating solution A to 80 ℃;
s3: dissolving silver sulfate in ethylene glycol 2 to prepare a solution B, and averagely dividing the solution B into two parts;
s4: adding the first solution B in the S3 into the heated solution A in the S2 in a positive mode, stirring for 10-20min, and then adding a second stabilizing agent;
s5: dropwise adding the second part of solution B into S4, continuously stirring for 15-20min, and standing for 12h after the reaction is finished to form a mixed solution with a precipitate;
s6: and removing liquid in the mixed solution by using a suction filtration mode, taking precipitate, repeatedly washing the precipitate for 2 to 5 times by using deionized water, and then placing the precipitate in an air-blast drying box for drying to obtain the nano silver particles with the double-mode particle size. The yield of this example was 93%.
Example 4
Wherein the molecular weight of gelatin 1 is 50000, and the molecular weight of gelatin 2 is 20000.
The preparation method of the nano silver particles with the double-mode particle size comprises the following steps:
s1: weighing sodium hypophosphite and lauric acid according to the proportion, mixing, dissolving in glycerol 1, adjusting the pH value to be acidic, adding gelatin 1, and mixing uniformly to prepare a solution A;
s2: heating solution A to 70 ℃;
s3: dissolving silver chloride in glycerol 2 to prepare a solution B, and averagely dividing the solution B into two parts;
s4: adding the first solution B in S3 into the heated solution A in S2, stirring for 10-20min, and adding gelatin 2;
s5: dropwise adding the second part of solution B into S4, continuously stirring for 15-20min, and standing for 12h after the reaction is finished to form a mixed solution with a precipitate;
s6: filtering the liquid by using a suction filtration mode, taking the precipitate, repeatedly washing the precipitate for 2 to 5 times by using deionized water, and then placing the precipitate in a forced air drying oven for drying to obtain the nano silver particles with the double-mode particle size. The yield of this example was 95%.
Example 5
The preparation method of the nano silver particles with the double-mode particle size comprises the following steps:
s1: weighing citric acid and polyvinylpyrrolidone according to the proportion, mixing, dissolving in ethylene glycol 1, adjusting pH value to be acidic, adding gelatin, and mixing uniformly to prepare a solution A;
s2: heating solution A to 100 ℃;
s3: dissolving silver carbonate in ethylene glycol 2 to prepare a solution B, and averagely dividing the solution B into two parts;
s4: positively adding the first solution B in S3 into the heated solution A in S2, stirring for 10-20min, and then adding Tween T-65;
s5: dropwise adding the second part of solution B into S4, continuously stirring for 15-20min, and standing for 12h after the reaction is finished to form a mixed solution with a precipitate;
s6: filtering the liquid by using filter paper, taking precipitate, repeatedly washing the precipitate for 2 to 5 times by using deionized water, and then placing the precipitate in a forced air drying oven for drying to obtain the nano silver particles with the double-mode particle size. The yield of this example was 91%.
Example 6
Wherein, the molecular weight of the silane coupling agent is 45000, and the molecular weight of the gelatin is 25000.
The preparation method of the nano silver particles with the double-mode particle size comprises the following steps:
s1: weighing citric acid and polyvinylpyrrolidone according to the proportion, mixing, dissolving in ethanol 1, adjusting the pH value to be acidic, adding a silane coupling agent, and uniformly mixing to prepare a solution A;
s2: heating solution A to 90 ℃;
s3: dissolving silver salt in ethanol 2 to prepare solution B, and dividing the solution B into two parts;
s4: adding the first solution B in S3 into the heated solution A in S2, stirring for 10-20min, and adding gelatin;
s5: dropwise adding the second part of solution B into S4, continuously stirring for 15-20min, and standing for 12h after the reaction is finished to form a mixed solution with a precipitate;
s6: and (3) extracting the precipitate in a centrifugal mode, repeatedly washing the precipitate for 2 to 5 times by using deionized water, and then placing the precipitate in a forced air drying box for drying to obtain the nano silver particles with the double-mode particle size. The yield of this example was 91%.
The foregoing is a more detailed description of the present invention in connection with specific preferred embodiments and is not intended to limit the practice of the invention to these embodiments. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of nano silver particles with double-mode particle sizes is characterized by comprising the following steps:
s1: mixing a reducing agent and a protective agent, dissolving the mixture in a first solvent, adjusting the pH value to be acidic, adding a first stabilizing agent, and uniformly mixing to prepare a solution A;
s2: dissolving silver salt in a second solvent to prepare a solution B, and dividing the solution B into two parts;
s3: adding the first solution B in the S2 into the solution A positively, reacting for 10-60min, and adding a second stabilizer;
s4: dropwise adding the second part of solution B into S3, and standing for 5-24h after the reaction is finished to form a mixed solution with a precipitate;
s5: taking the precipitate in the mixed solution, washing and drying to prepare the nano silver particles with double-mode particle size;
wherein the solution B in the S2 is divided into two parts according to the proportion of 1: 1; the molecular weight of the first stabilizer is 40000-50000, and the molecular weight of the second stabilizer is 20000-30000.
2. The method for preparing nano silver particles with dual grain sizes as claimed in claim 1, wherein the step of S1 and the step of S2 are further included as follows: the solution A was heated to 60-100 ℃.
3. The method for preparing silver nanoparticles with bimodal particle size according to claim 1 or 2, wherein the reducing agent, the silver salt, the protective agent, the first stabilizer, the second stabilizer, the inorganic acid solution, the first solvent and the second solvent respectively comprise the following components in parts by weight:
35-55 parts of reducing agent
Silver salt 10-26 parts
10-21 parts of protective agent
5-17 parts of first stabilizer
5-20 parts of second stabilizer
0.2 to 0.4 portion of inorganic acid solution
100 portions of first solvent
100 portions and 200 portions of second solvent.
4. The method for preparing silver nanoparticles with bimodal particle size according to claim 1 or 2, wherein the silver salt is any one or a mixture of more than two of silver nitrate, silver sulfate, silver carbonate, silver chloride and silver complex.
5. The method for preparing nano silver particles with dual-mode particle size according to claim 1 or 2, wherein the reducing agent is any one or a mixture of more than two of citric acid, sodium hypophosphite and sodium hexametaphosphate.
6. The method for preparing nano silver particles with bimodal particle size as claimed in claim 1 or 2, wherein the protective agent comprises one or a mixture of two of polyvinylpyrrolidone and lauric acid.
7. The method for preparing silver nanoparticles with bimodal particle size according to claim 1 or 2, wherein the first stabilizer and the second stabilizer are respectively selected from any one or a mixture of more than two of silane coupling agent, tween-T-65 and gelatin.
8. The method for preparing silver nanoparticles with bimodal particle size according to claim 3, wherein the inorganic acid solution is any one or a mixture of more than two of nitric acid, sulfuric acid and hydrochloric acid.
9. A nano silver particle with a bimodal particle size, which is prepared by the preparation method of any one of claims 1 to 8.
10. The bi-modal silver nanoparticle as claimed in claim 9, wherein the bi-modal silver nanoparticle, the large silver nanoparticle, and the small silver nanoparticle are distributed in a concentrated manner in the region of 350-450nm, and in a concentrated manner in the region of 60-80 nm.
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