CN105522165B - Preparation method for nano-silver particles - Google Patents

Preparation method for nano-silver particles Download PDF

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CN105522165B
CN105522165B CN201510948285.6A CN201510948285A CN105522165B CN 105522165 B CN105522165 B CN 105522165B CN 201510948285 A CN201510948285 A CN 201510948285A CN 105522165 B CN105522165 B CN 105522165B
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CN105522165A (en
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安春
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Anhua New Materials Technology (Beijing) Co.,Ltd.
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Huaxing & New Materials (jiangsu) Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/054Nanosized particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures

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Abstract

The invention discloses a preparation method for nano-silver particles, and belongs to the field of preparation of the nano-silver particles. The preparation method includes the steps that rice is washed, water is added for stewing the rice, yeast powder and amylase are added to be stirred, and a reaction under the heat preservation condition is made; then glucose class matter is added to be mixed, and centrifugal separation is carried out after standing to obtain a supernatant for standby application; an ultrasonic container is opened, the infrared wave length is controlled, an ammonium chloride solution is added, the pH of the solution is adjusted to be alkaline through sodium hydroxide, and the solution, ethyl acetate and the like are mixed; carbon dioxide is led in from the bottom of the container for aeration, and silver nitrate and the supernatant for standby application are dropwise added while aeration is carried out; and standing filtering is carried out to obtain filtration matter, and warming evaporation is carried out after freezing to prepare the nano-silver particles. The preparation method has the beneficial effects that the preparing method is simple, the nano-silver particles are evenly scattered in the preparing process, solid-liquid separating is easy, and by-products are fewer; and obtained products are regular in shape and broad and even in size distribution, and the purity of the obtained product is more than 6% higher than those obtained through other methods.

Description

A kind of preparation method of nano silver particles
Technical field
The present invention relates to a kind of preparation method of nano silver particles, belong to nano silver particles preparation field.
Background technology
Nano material refers to that nanostructured is piled up by certain way or disperses the macroscopic material to be formed nanometer in certain matrix Material has quantum size effect, small-size effect, skin effect and macro quanta tunnel effect and shows different from common The unusual performance of the aspects such as the light of material, electricity, magnetic, thermodynamics and chemical reaction, is a kind of important functional material.Nanometer silver granuel Significant properties of the son with nanostructured, can be widely applied to the multiple fields such as catalyst, medicine, antibacterial, composite.In recent years Come, the technology of preparing of nano silver particles is developed rapidly, and domestic and international preparation method is varied.Because some of nano silver particles are special Different property:Such as good electric conductivity, superpower sterilizing ability, laser excitation efficiency higher and extremely strong third-order non-linear system The properties such as number so that nano silver particles or using the prepared composite of nano silver particles doping be widely used in superconduction, The industries such as chemical industry, medical science, optics, electronics, electrical equipment.Because nano silver particles have very big Raman active, with surface enhanced The development of Raman technology, the preparation of nano silver particles also obtains great development.
The method for preparing nano silver particles at present has solution phase chemical reduction, physical crushing method, vacuum condensation method and precipitation Method, solution phase chemical reduction is that silver is sunk in powder form from its salt or the complex aqueous solution or organic system with reducing agent Product is out.Conventional reducing agent has compound of ascorbic acid, unsaturated alcohol, sodium citrate, hydrazine and hydrazine etc..The advantage of the method is Apparatus and process is simple, yield is high, be easy to industrialized production, and obtained silver powder granularity is small, favorable reproducibility, be current laboratory and Industrial widely used method.But obtained nano-Ag particles have that separation of solid and liquid is difficult, size distribution is wide, easy group Poly- the shortcomings of.Physical crushing method is to crush raw material by methods such as mechanical crushing, ultrasonic wave, electric spark blasts to obtain Nano Silver Particle.By in inert gas, on the substrate of low temperature, being sputtered using high-pressure magnetic, containing nano silver particles two have been made Silicon oxide film.The characteristics of the method is that operation is simple, low cost, but product purity is low, and distribution of particles is uneven, and not It is readily available the product compared with small particle.Vacuum condensation method be in vacuum or atmosphere of inert gases, it is high with heating, laser, electric arc The methods such as frequency sensing produce high temperature, silver material is gasified or form plasma, and then quenching is allowed to condensation and obtains a nanometer silver granuel Son.In atmosphere of inert gases, nano silver particles are prepared by the method for condensing.The method has that purity is high, crystallization group Weave, the advantage that granularity is controllable, but technical equipment requirement is high, typically requires purity silver material very high, and there is Nano Silver The shortcoming of particle coalescence.The precipitation method are that precipitating reagent is added in salting liquid, and the active ingredient of raw material is given birth to by chemical reaction Into precipitation, then nano silver particles are obtained through filtering, washing, dry, drying.In the condition that PVP is present Under, reduce silver ionized water solution, the nano silver particles for having obtained with urotropine.The method is at present using widely A kind of method, its advantage is that technological process is short, easy to operate, raw material is readily available, but is easily introduced impurity, and purity is low, particle diameter Greatly, it is difficult to prepare the nano silver particles for comparing small particle.
The content of the invention
The technical problems to be solved by the invention:Easily reunite for nano silver particles in current method preparation process, consolidate Liquid separates difficult, and accessory substance is more, cause that products obtained therefrom pattern is irregular, particle diameter distribution it is wide in range it is uneven, the drawbacks of purity is low, carry Supply one kind to clean the boiling that adds water by by rice, added insulation reaction after starter powder and amylase stirring, add glucose Material mixing, to obtain supernatant standby for centrifugation after standing, then opens ultrasonic container, controls infrared wavelength, adds chlorination Ammonium salt solution, it is alkalescence to adjust its pH with NaOH, mix with ethyl acetate etc., and being passed through carbon dioxide from container bottom is aerated, Silver nitrate and standby supernatant is added dropwise in aeration, then stands and filters to obtain filtrate, the prepared Nano Silver of evaporation is heated after freezing The method of particle.Preparation process solid-liquid of the present invention is easily separated, and products obtained therefrom particle diameter distribution is uniform, and purity is high.
In order to solve the above technical problems, the present invention is using technical scheme as described below:
(1) 1~2kg rice is taken, 30~40min of immersion in clear water is put into, circular bottom pot is put into after rinsing 1~2 time with current In, water is added thereto to, make it not have 7~8cm of rice to be advisable, 50~60 DEG C, boiling are warming up to the speed program of 5 DEG C/min After 20~30min, stir-fried 3~4 times with iron spoon bottom from pot, then heat to 100~105 DEG C, 1~2h of insulation boiling;
(2) treat it is secondary boiled after the completion of, the starch of 20~30g starter powders and gross mass 0.3~0.5% is separately added into thereto Enzyme, controls temperature for 40~50 DEG C, controls rotating speed for 200~300r/min, stirs 20~30min, it is sufficiently mixed uniformly, 1~2h of insulation reaction, after the completion for the treatment of insulation reaction, then is added thereto to 20~22mL kiwi-fruit juices, keeps rotating speed, temperature not Become, stir 50~60min;
(3) while stirring with the speed of 2~3mL/min to the grape juice that 8~10mL is added in said mixture, stirring 20 ~30min, it is 60~80r/min then to reduce rotating speed, stirs 20~25min, stands 1~2h, after standing is finished, is put into rotating speed For 10~15min is centrifuged in the centrifuge of 2000~3000r/min, supernatant is obtained standby;
(4) ultrasonic response container is opened, 25~35kHz of supersonic frequency is set, control infrared wavelength for 200~300 μm, The ammonium chloride solution that 20~30mL mass fractions are 60~80% is added thereto to, while adding 15~20mL NaOH molten Liquid, it is 11.2~12.2 to adjust its pH value, then is added to 10~15mL diethanol amine and 10~15mL ethyl acetate respectively, Control rotating speed for 500~700r/min, 50~60min of magnetic agitation is well mixed;
(5) after after above-mentioned being well mixed, it is passed through carbon dioxide from ultrasonic response container bottom and is aerated, controls dioxy Change carbon and be passed through speed for 10~15mL/s, 30~40mL mass point is added dropwise with the speed of 10~12mL/min thereto in aeration Number is 20~30% silver nitrate solution, while 180~360mL steps (3) are added dropwise thereto with the speed of 60~100mL/min Standby supernatant;
(6) after after above-mentioned completion of dropping, continuing to be aerated 40~50min, 1~2h is stood, then carries out filtering to obtain filtrate, At being placed in -20~-18 DEG C freeze 5~7h, it is to be frozen finish after, be heated up to 100~105 DEG C, 2~3h of rotary evaporation makes Obtain a kind of nano silver particles.
Application process of the invention:Obtained nano silver particles are added in the coating such as paint, pigment, addition be 5~ 7g/kg, is coated on sheet material after stirring, and can effectively kill the germ that is attached on sheet material and the duration is long, so as to drop The probability of low people's bacteria infection, is worthy to be popularized and uses.
Compared with other method, Advantageous Effects are the present invention:
(1) preparation method of the present invention is simple, in preparation process nano silver particles be uniformly dispersed, solid-liquid it is easily separated, accessory substance It is few;
(2) the wide in range uniform, purity of products obtained therefrom pattern rule, particle diameter distribution is higher than other method more than 6%.
Specific embodiment
1~2kg rice is taken first, 30~40min of immersion in clear water is put into, and circular bottom pot is put into after rinsing 1~2 time with current In, water is added thereto to, make it not have 7~8cm of rice to be advisable, 50~60 DEG C, boiling are warming up to the speed program of 5 DEG C/min After 20~30min, stir-fried 3~4 times with iron spoon bottom from pot, then heat to 100~105 DEG C, 1~2h of insulation boiling;Treat After the completion of secondary boiled, the amylase of 20~30g starter powders and gross mass 0.3~0.5% is separately added into thereto, control the temperature to be 40~50 DEG C, control rotating speed for 200~300r/min, stir 20~30min, it is sufficiently mixed uniformly, insulation reaction 1~ 2h, after the completion for the treatment of insulation reaction, then is added thereto to 20~22mL kiwi-fruit juices, keeps rotating speed, temperature-resistant, and stirring 50~ 60min;While stirring with the speed of 2~3mL/min in said mixture add 8~10mL grape juice, stirring 20~ 30min, it is 60~80r/min then to reduce rotating speed, stirs 20~25min, stands 1~2h, and after standing is finished, being put into rotating speed is 10~15min is centrifuged in the centrifuge of 2000~3000r/min, supernatant is obtained standby;Then ultrasonic response container is opened, if Put 25~35kHz of supersonic frequency, control infrared wavelength for 200~300 μm, be added thereto to 20~30mL mass fractions for 60~ 80% ammonium chloride solution, while adding 15~20mL sodium hydroxide solutions, adjusts its pH value for 11.2~12.2, then respectively to 10~15mL diethanol amine and 10~15mL ethyl acetate are wherein added, rotating speed is controlled for 500~700r/min, magnetic agitation 50 ~60min is well mixed;After after above-mentioned being well mixed, it is passed through carbon dioxide from ultrasonic response container bottom and is aerated, controls Carbon dioxide processed is passed through speed for 10~15mL/s, and 30~40mL is added dropwise thereto with the speed of 10~12mL/min in aeration Mass fraction is 20~30% silver nitrate solution, while 180~360mL is added dropwise thereto with the speed of 60~100mL/min Standby supernatant;Finally after after above-mentioned completion of dropping, continuing to be aerated 40~50min, 1~2h is stood, then carry out filtering Filtrate, freezes 5~7h at being placed in -20~-18 DEG C, it is to be frozen finish after, be heated up to 100~105 DEG C, rotary evaporation 2~ 3h, that is, be obtained a kind of nano silver particles.
Example 1
1kg rice is taken first, is put into clear water and is soaked 30min, be put into circular bottom pot after rinsing 1 time with current, thereto Add water, make it not have rice 7cm to be advisable, be warming up to 50 DEG C, after boiling 20min with the speed program of 5 DEG C/min, with iron spoon from Bottom stir-fries 3 times in pot, then heats to 100 DEG C, insulation boiling 1h;Treat it is secondary boiled after the completion of, 20g is separately added into thereto The amylase of starter powder and gross mass 0.3%, controls temperature for 40 DEG C, controls rotating speed for 200r/min, stirs 20min, fills it Point well mixed, insulation reaction 1h, after the completion for the treatment of insulation reaction, then is added thereto to 20mL kiwi-fruit juices, keeps rotating speed, temperature It is constant, stir 50min;While stirring with the speed of 2mL/min to the grape juice that 8mL is added in said mixture, stirring 20min, it is 60r/min then to reduce rotating speed, stirs 20min, stands 1h, and after standing is finished, it is 2000r/min's to be put into rotating speed 10min is centrifuged in centrifuge, supernatant is obtained standby;Then ultrasonic response container is opened, supersonic frequency 25kHz, control is set Infrared wavelength is 200 μm, is added thereto to the ammonium chloride solution that 20mL mass fractions are 60%, while adding 15mL NaOH Solution, adjusts its pH value for 11.2, then is added to 10mL diethanol amine and 10mL ethyl acetate respectively, controls the rotating speed to be 500r/min, magnetic agitation 50min are well mixed;After after above-mentioned being well mixed, dioxy is passed through from ultrasonic response container bottom Change carbon to be aerated, control carbon dioxide to be passed through speed for 10mL/s, be added dropwise thereto with the speed of 10mL/min in aeration 30mL mass fractions are 20% silver nitrate solution, while the standby supernatants of 180mL are added dropwise thereto with the speed of 60mL/min Liquid;Finally after after above-mentioned completion of dropping, continuing to be aerated 40min, 1h is stood, then carry out filtering to obtain filtrate, be placed in -20 DEG C Lower freezing 5h, it is to be frozen finish after, be heated up to 100 DEG C, rotary evaporation 2h is obtained a kind of nano silver particles.
Obtained nano silver particles are added in the coating such as paint, pigment, addition is 5g/kg, are coated after stirring In on sheet material, can effectively killing the germ that is attached on sheet material and the duration is long, so that the probability of people's bacteria infection is reduced, It is worthy to be popularized and uses.
Example 2
1.5kg rice is taken first, is put into clear water and is soaked 35min, be put into circular bottom pot after rinsing 2 times with current, Xiang Qi Middle addition water, makes it not have rice 7.5cm to be advisable, and 55 DEG C are warming up to the speed program of 5 DEG C/min, after boiling 25min, uses iron Spoon bottom from pot stir-fries 4 times, then heats to 103 DEG C, insulation boiling 1.5h;Treat it is secondary boiled after the completion of, distinguish thereto The amylase of 25g starter powders and gross mass 0.4% is added, temperature is controlled for 45 DEG C, controls rotating speed for 250r/min, stir 25min, It is set to be sufficiently mixed uniformly, insulation reaction 1.5h after the completion for the treatment of insulation reaction, then is added thereto to 21mL kiwi-fruit juices, keeps Rotating speed, temperature-resistant, stirring 55min;While stirring with the speed of 3mL/min to the grape juice that 9mL is added in said mixture, Stirring 25min, it is 70r/min then to reduce rotating speed, stirs 23min, stands 1.5h, and after standing is finished, being put into rotating speed is 13min is centrifuged in the centrifuge of 2500r/min, supernatant is obtained standby;Then ultrasonic response container is opened, supersonic frequency is set 30kHz, controls infrared wavelength for 250 μm, is added thereto to the ammonium chloride solution that 25mL mass fractions are 70%, while adding 18mL sodium hydroxide solutions, it is 11.7 to adjust its pH value, then is added to 13mL diethanol amine and 13mL ethyl acetate respectively, Control rotating speed for 600r/min, magnetic agitation 55min is well mixed;After after above-mentioned being well mixed, from ultrasonic response container bottom Portion is passed through carbon dioxide and is aerated, and controls carbon dioxide to be passed through speed for 13mL/s, in aeration with the speed of 11mL/min 35mL mass fractions are added dropwise thereto and are 25% silver nitrate solution, while 270mL is added dropwise thereto with the speed of 80mL/min Standby supernatant;Finally after after above-mentioned completion of dropping, continuing to be aerated 45min, 1.5h is stood, then carry out filtering and must filtering Thing, freezes 6h at being placed in -19 DEG C, it is to be frozen finish after, be heated up to 103 DEG C, rotary evaporation 2.5h is obtained a kind of Nano Silver Particle.
Obtained nano silver particles are added in the coating such as paint, pigment, addition is 6g/kg, are coated after stirring In on sheet material, can effectively killing the germ that is attached on sheet material and the duration is long, so that the probability of people's bacteria infection is reduced, It is worthy to be popularized and uses.
Example 3
2kg rice is taken first, is put into clear water and is soaked 40min, be put into circular bottom pot after rinsing 2 times with current, thereto Add water, make it not have rice 8cm to be advisable, be warming up to 60 DEG C, after boiling 30min with the speed program of 5 DEG C/min, with iron spoon from Bottom stir-fries 4 times in pot, then heats to 105 DEG C, insulation boiling 2h;Treat it is secondary boiled after the completion of, 30g is separately added into thereto The amylase of starter powder and gross mass 0.5%, controls temperature for 50 DEG C, controls rotating speed for 300r/min, stirs 30min, fills it Point well mixed, insulation reaction 2h, after the completion for the treatment of insulation reaction, then is added thereto to 22mL kiwi-fruit juices, keeps rotating speed, temperature It is constant, stir 60min;While stirring with the speed of 3mL/min to the grape juice that 10mL is added in said mixture, stirring 30min, it is 80r/min then to reduce rotating speed, stirs 25min, stands 2h, and after standing is finished, it is 3000r/min's to be put into rotating speed 15min is centrifuged in centrifuge, supernatant is obtained standby;Then ultrasonic response container is opened, supersonic frequency 35kHz, control is set Infrared wavelength is 300 μm, is added thereto to the ammonium chloride solution that 30mL mass fractions are 80%, while adding 20mL NaOH Solution, adjusts its pH value for 12.2, then is added to 15mL diethanol amine and 15mL ethyl acetate respectively, controls the rotating speed to be 700r/min, magnetic agitation 60min are well mixed;After after above-mentioned being well mixed, dioxy is passed through from ultrasonic response container bottom Change carbon to be aerated, control carbon dioxide to be passed through speed for 15mL/s, be added dropwise thereto with the speed of 12mL/min in aeration 40mL mass fractions are 30% silver nitrate solution, while the standby supernatants of 360mL are added dropwise thereto with the speed of 100mL/min Liquid;Finally after after above-mentioned completion of dropping, continuing to be aerated 50min, 2h is stood, then carry out filtering to obtain filtrate, be placed in -18 DEG C Lower freezing 7h, it is to be frozen finish after, be heated up to 105 DEG C, rotary evaporation 3h is obtained a kind of nano silver particles.
Obtained nano silver particles are added in the coating such as paint, pigment, addition is 7g/kg, are coated after stirring In on sheet material, can effectively killing the germ that is attached on sheet material and the duration is long, so that the probability of people's bacteria infection is reduced, It is worthy to be popularized and uses.

Claims (1)

1. a kind of preparation method of nano silver particles, it is characterised in that specific preparation process is:
(1) 1~2kg rice is taken, 30~40min of immersion in clear water is put into, is put into circular bottom pot after rinsing 1~2 time with current, to Water is wherein added, makes it not have 7~8cm of rice to be advisable, 50~60 DEG C are warming up to the speed program of 5 DEG C/min, boiling 20~ After 30min, stir-fried 3~4 times with iron spoon bottom from pot, then heat to 100~105 DEG C, 1~2h of insulation boiling;
(2) treat it is secondary boiled after the completion of, the amylase of 20~30g starter powders and gross mass 0.3~0.5% is separately added into thereto, Temperature is controlled for 40~50 DEG C, controls rotating speed for 200~300r/min, stir 20~30min, it is sufficiently mixed uniformly, protected Temperature 1~2h of reaction, after the completion for the treatment of insulation reaction, then is added thereto to 20~22mL kiwi-fruit juices, keeps rotating speed, temperature-resistant, 50~60min of stirring;
(3) while stirring with the speed of 2~3mL/min in said mixture add 8~10mL grape juice, stirring 20~ 30min, it is 60~80r/min then to reduce rotating speed, stirs 20~25min, stands 1~2h, and after standing is finished, being put into rotating speed is 10~15min is centrifuged in the centrifuge of 2000~3000r/min, supernatant is obtained standby;
(4) ultrasonic response container is opened, 25~35kHz of supersonic frequency is set, it is 200~300 μm, Xiang Qi to control infrared wavelength Middle addition 20~30mL mass fractions are 60~80% ammonium chloride solution, while adding 15~20mL sodium hydroxide solutions, are adjusted It is 11.2~12.2 to save its pH value, then is added to 10~15mL diethanol amine and 10~15mL ethyl acetate respectively, is controlled Rotating speed is 500~700r/min, and 50~60min of magnetic agitation is well mixed;
(5) after after above-mentioned being well mixed, it is passed through carbon dioxide from ultrasonic response container bottom and is aerated, controls carbon dioxide Speed is passed through for 10~15mL/s, 30~40mL mass fractions are added dropwise thereto with the speed of 10~12mL/min in aeration is 20~30% silver nitrate solution, while it is standby that 180~360mL steps (3) are added dropwise thereto with the speed of 60~100mL/min Supernatant;
(6) after after above-mentioned completion of dropping, continuing to be aerated 40~50min, 1~2h is stood, then carries out filtering to obtain filtrate, juxtaposition In freezing 5~7h at -20~-18 DEG C, it is to be frozen finish after, be heated up to 100~105 DEG C, 2~3h of rotary evaporation is obtained one Plant nano silver particles.
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CN106238748A (en) * 2016-08-31 2016-12-21 华南理工大学 The synthetic method of ball shaped nano Argent grain and ball shaped nano Argent grain
CN115090893B (en) * 2022-06-06 2024-06-25 爱科美材料科技(南通)有限公司 Method for preparing nano silver with controllable size

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CN102343440A (en) * 2010-07-29 2012-02-08 同济大学 Method for preparing water-soluble nano silver by using actinidia as template
CN105057690A (en) * 2015-07-20 2015-11-18 昆明理工大学 Preparation method of high-dispersibility superfine spherical silver powder
CN105142829A (en) * 2013-04-26 2015-12-09 同和电子科技有限公司 Metal nanoparticle dispersion, process for producing metal nanoparticle dispersion, and bonding method

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Publication number Priority date Publication date Assignee Title
JP2007039718A (en) * 2005-08-01 2007-02-15 Dowa Holdings Co Ltd Method for producing silver powder
JP2008214691A (en) * 2007-03-02 2008-09-18 Ishihara Sangyo Kaisha Ltd Metal particulate, metal colloid solution obtained by dispersing the same into solvent, and method for producing them
CN102343440A (en) * 2010-07-29 2012-02-08 同济大学 Method for preparing water-soluble nano silver by using actinidia as template
CN105142829A (en) * 2013-04-26 2015-12-09 同和电子科技有限公司 Metal nanoparticle dispersion, process for producing metal nanoparticle dispersion, and bonding method
CN105057690A (en) * 2015-07-20 2015-11-18 昆明理工大学 Preparation method of high-dispersibility superfine spherical silver powder

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