CN107127353A - A kind of nano silver colloidal sol and preparation method thereof - Google Patents
A kind of nano silver colloidal sol and preparation method thereof Download PDFInfo
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- CN107127353A CN107127353A CN201710359697.5A CN201710359697A CN107127353A CN 107127353 A CN107127353 A CN 107127353A CN 201710359697 A CN201710359697 A CN 201710359697A CN 107127353 A CN107127353 A CN 107127353A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides a kind of preparation method of nano silver colloidal sol, the protective agent aqueous solution and reducing agent aqueous solution are mixed, then mixed with silver nitrate aqueous solution, obtain just mixed material；The just mixed material is subjected to first 30~35min of reduction reaction at 35~45 DEG C, nano silver colloidal sol presoma is obtained；The nano silver colloidal sol presoma is mixed with polyatomic alcohol water solution, mixed material is obtained；The mixed material is carried out to second 10~30s of reduction reaction at 35~45 DEG C, nano silver colloidal sol is obtained.Preparation method step that the present invention is provided is simple, safety and environmental protection, production cost are low；The particle diameter of nano silver particles is small in the nano silver colloidal sol prepared and is evenly distributed (10~20nm), and stability is high, is kept in dark place at room temperature in brown bottle 6 months, does not occur flocculating and precipitating.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of nano silver colloidal sol and preparation method thereof.
Background technology
Nano Silver is often shown notable and only compared with corresponding macroscopical silver metal in terms of physics, chemistry and biology
Special performance, such as SERS, catalysis, data storage, biology and medical sensor and strong broad-spectrum antiseptic
Activity, to human cell's nonhazardous etc..Nano Silver is in anti-biotic material, effective catalyst, lubricant, light absorbing material, coating, biography
The fields such as sensor, electrocondution slurry, high performance electrode material all have broad application prospects, as new function material field
Study hotspot.
The performance of Nano Silver is strongly depend on the physical features such as pattern, size and the stability of nano silver particles.It is literary at present
Offering the preparation method of the Nano Silver of report mainly includes chemical method and the major class of physical method two, wherein, chemical method is mainly wrapped
Include chemical reduction method, electrochemical reducing and photochemical reduction.But all there is certain deficiency in these methods, such as to some extent
Electrochemical reducing prepares speed slowly, and the protective agent of necessary high concentration, the silver granuel for having more big particle diameter in preparation process
Son is in negative electrode deposition, and this causes the cost for preparing Nano Silver to greatly improve, and the particle diameter distribution of the nano silver particles prepared
Wide, stability is poor, seriously constrains it and promotes the use of；The reaction rate of photochemical reduction is slower, the product amount prepared every time
It is few, be not suitable for industrialized production；And the reducing agent used in chemical reduction method, such as sodium borohydride, hydrazine hydrate, formaldehyde, toxicity is big,
And the nano silver particles prepared using these reducing agents particle diameter is larger and skewness, greatly limit Nano Silver
The performance of energy.
The content of the invention
It is an object of the invention to provide a kind of nano silver colloidal sol and preparation method thereof, the preparation method step that the present invention is provided
Rapid simple, safety and environmental protection, production cost are low；The particle diameter of nano silver particles is small in the nano silver colloidal sol prepared and is evenly distributed
(10~20nm), stability is high, is kept in dark place at room temperature in brown bottle 6 months, does not occur flocculating and precipitating.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of nano silver colloidal sol, comprise the following steps：
(1) the protective agent aqueous solution and reducing agent aqueous solution are mixed, then mixed with silver nitrate aqueous solution, obtain just mixed thing
Material；
(2) material will be just mixed in the step (1) and first 30~35min of reduction reaction is carried out at 35~45 DEG C, obtained
Nano silver colloidal sol presoma；
(3) nano silver colloidal sol presoma in the step (2) is mixed with polyatomic alcohol water solution, obtains mixed material；
(4) mixed material in the step (3) is subjected to second 10~30s of reduction reaction at 35~45 DEG C, received
Rice silver sol.
It is preferred that, the mass concentration that silver nitrate in material is just mixed in the step (1) is 0.08~0.12mg/mL.
It is preferred that, the mass ratio that silver nitrate, protective agent and reducing agent in material are just mixed in the step (1) is 1：(4.5~
5.5)：(0.45~0.55).
It is preferred that, the protective agent includes polyvinylpyrrolidone or polyethylene glycol.
It is preferred that, the number-average molecular weight of the polyvinylpyrrolidone is 25000~35000.
It is preferred that, the number-average molecular weight of the polyethylene glycol is 5500~7500.
It is preferred that, the reducing agent includes N, N- dimethylethanolamines, triethanolamine or methyl diethanolamine.
It is preferred that, the mass concentration of polyalcohol is 0.013~0.017mg/mL in mixed material in the step (3).
It is preferred that, the polyalcohol includes mannitol, glycerine or pentaerythrite.
The invention provides the nano silver colloidal sol that preparation method described in above-mentioned technical proposal is prepared, the Nano Silver is molten
The particle diameter of nano silver particles is 10~20nm in glue.
The invention provides a kind of preparation method of nano silver colloidal sol, the protective agent aqueous solution and reducing agent aqueous solution are mixed
Close, then mixed with silver nitrate aqueous solution, obtain just mixed material；The just mixed material is subjected to the first reduction at 35~45 DEG C
30~35min is reacted, nano silver colloidal sol presoma is obtained；The nano silver colloidal sol presoma is mixed with polyatomic alcohol water solution,
Obtain mixed material；The mixed material is carried out to second 10~30s of reduction reaction at 35~45 DEG C, Nano Silver is obtained molten
Glue.Preparation method step that the present invention is provided is simple, safety and environmental protection, production cost are low, can prepare at a lower temperature
Nano silver colloidal sol；The second reduction reaction is carried out by using polyalcohol, there can be higher reaction rate at a lower temperature,
Effectively shorten the reaction time；In the nano silver colloidal sol prepared the particle diameter of nano silver particles it is small and be evenly distributed (10~
20nm), stability is high, is kept in dark place at room temperature in brown bottle 6 months, does not occur flocculating and precipitating.
Brief description of the drawings
Fig. 1 is the UV-visible spectrum of nano silver colloidal sol prepared by the embodiment of the present invention 1 and comparative example 1；Wherein, (1)
The ultraviolet-visible light spectral curve of the nano silver colloidal sol prepared for the embodiment of the present invention 1, (2) are receiving for comparative example 1 of the present invention preparation
The ultraviolet-visible light spectral curve of rice silver sol；
Fig. 2 is the transmission electron microscope picture of nano silver colloidal sol prepared by the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope picture of nano silver colloidal sol prepared by comparative example 1 of the present invention.
Embodiment
The invention provides a kind of preparation method of nano silver colloidal sol, comprise the following steps：
(1) the protective agent aqueous solution and reducing agent aqueous solution are mixed, then mixed with silver nitrate aqueous solution, obtain just mixed thing
Material；
(2) material will be just mixed in the step (1) and first 30~35min of reduction reaction is carried out at 35~45 DEG C, obtained
Nano silver colloidal sol presoma；
(3) nano silver colloidal sol presoma in the step (2) is mixed with polyatomic alcohol water solution, obtains mixed material；
(4) mixed material in the step (3) is subjected to second 10~30s of reduction reaction at 35~45 DEG C, received
Rice silver sol.
The present invention mixes the protective agent aqueous solution and reducing agent aqueous solution, is then mixed with silver nitrate aqueous solution, obtains just
Mixed material.In the present invention, protective agent, reducing agent and silver nitrate are used as an aqueous solution, is conducive to preparing stabilization
The good nano silver colloidal sol of property.In the present invention, the water in the protective agent aqueous solution, reducing agent aqueous solution and silver nitrate aqueous solution
Preferably deionized water.
In the present invention, the mixing of the protective agent aqueous solution and reducing agent aqueous solution, and gained mixture with it is described
The mixing of silver nitrate aqueous solution is preferably carried out under agitation.In the present invention, the stirring is preferably magnetic agitation；It is described
The speed of magnetic agitation is preferably independently 300~400rpm, most preferably more preferably 330~370rpm, 350rpm.
In the present invention, the mass concentration of silver nitrate is preferably 0.08~0.12mg/mL in the just mixed material, more preferably
For 0.09~0.11mg/mL, most preferably 0.10mg/mL.In the present invention, silver nitrate in the just mixed material, protective agent and
The mass ratio of reducing agent is preferably 1：(4.5~5.5)：(0.45~0.55), more preferably 1：(4.8~5.2)：(0.48~
0.52), most preferably 1：5：0.5.
In the present invention, the protective agent preferably includes polyvinylpyrrolidone or polyethylene glycol, more preferably polyethylene
Pyrrolidones.In the present invention, the number-average molecular weight of the polyvinylpyrrolidone is preferably 25000~35000, more preferably
27000~33000, most preferably 29000~31000.In the present invention, the number-average molecular weight of the polyethylene glycol is preferably
5500~7500, more preferably 6000~7000.In the present invention, the protective agent can reduce the nano silver particles of generation
Surface energy, prevents its from occurring to reunite, precipitate.
In the present invention, the reducing agent preferably includes N, N- dimethylethanolamines, triethanolamine or methyl diethanolamine,
More preferably N, N- dimethylethanolamine.In the present invention, on the one hand silver ion reduction can be atomic state by the reducing agent
Silver；On the other hand the surface of nano silver particles can be also coated on, prevents it from occurring to reunite, precipitate, and reducing agent molecular structure
Symmetry is better, cladding it is tighter, this be conducive to increase nano silver particles reunite resistance.
In the present invention, the just mixed material is preferably obtained by following steps：
Under agitation, original reducing agent aqueous solution, the original protective agent aqueous solution and water are mixed, then with original nitre
Sour silver aqueous solution mixing, obtains just mixed material.
In the present invention, the mass concentration of the original reducing agent aqueous solution is preferably 1.8~2.2mg/mL, more preferably
1.9~2.1mg/mL, most preferably 2.0mg/mL.In the present invention, the mass concentration of the original protective agent aqueous solution is preferred
For 18.0~22.0mg/mL, most preferably more preferably 19.0~21.0mg/mL, 20.0mg/mL.In the present invention, the original
The mass concentration of beginning silver nitrate aqueous solution is preferably 1.8~2.2mg/mL, more preferably 1.9~2.1mg/mL, is most preferably
2.0mg/mL。
In an embodiment of the present invention, be specifically according to the original reducing agent aqueous solution, the original protective agent aqueous solution and
The mass concentration of reducing agent, protective agent and silver nitrate in the mass concentration of original silver nitrate aqueous solution and the just mixed material,
Select the addition of suitable water.
In an embodiment of the present invention, the original reducing agent aqueous solution, the original protective agent aqueous solution and original silver nitrate
Water in the aqueous solution is preferably deionized water；The water is preferably deionized water.
Obtain after just mixed material, the present invention by the just mixed material carried out at 35~45 DEG C the first reduction reaction 30~
35min, obtains nano silver colloidal sol presoma.In the present invention, first reduction reaction is preferably carried out under agitation；It is described to stir
Mix preferably magnetic agitation；The speed of the magnetic agitation is preferably 300~400rpm, more preferably 330~370rpm, optimal
Elect 350rpm as.In the present invention, the temperature of first reduction reaction be 35~45 DEG C, preferably 38~43 DEG C, more preferably
For 40~42 DEG C.In the present invention, the time of first reduction reaction be 30~35min, preferably 31~34min, it is more excellent
Elect 32~33min as.
Complete after the first reduction reaction, the present invention mixes obtained nano silver colloidal sol presoma with polyatomic alcohol water solution,
Obtain mixed material.In the present invention, the mixing is preferably carried out under agitation, and the stirring is preferably magnetic agitation；
The speed of the magnetic agitation is preferably 300~400rpm, more preferably 330~370rpm, most preferably 350rpm.In this hair
In bright, the mass concentration of polyalcohol is preferably 0.013~0.017mg/mL in the mixed material, more preferably 0.014~
0.016mg/mL, most preferably 0.015mg/mL.In the present invention, the mass concentration of the polyatomic alcohol water solution is preferably 1.8
~2.2mg/mL, more preferably 1.9~2.1mg/mL, most preferably 2.0mg/mL.In an embodiment of the present invention, specifically root
According to polynary in the mass concentration of the polyatomic alcohol water solution, the volume of the nano silver colloidal sol presoma and the mixed material
The mass concentration of alcohol, selects the addition of suitable polyatomic alcohol water solution.In an embodiment of the present invention, the polyalcohol is water-soluble
Water in liquid is preferred to use deionized water.
In the present invention, the polyalcohol preferably includes mannitol, glycerine or pentaerythrite, more preferably mannitol.
Obtain after mixed material, the present invention mixed material is carried out at 35~45 DEG C the second reduction reaction 10~
30s, obtains nano silver colloidal sol.In the present invention, second reduction reaction is preferably carried out under agitation；The stirring is preferably
Magnetic agitation；The speed of the magnetic agitation is preferably 300~400rpm, more preferably 330~370rpm, is most preferably
350rpm.In the present invention, the temperature of second reduction reaction is 35~45 DEG C, preferably 38~43 DEG C, more preferably 40
~42 DEG C.In the present invention, the time of second reduction reaction be 10~30s, preferably 15~25s, more preferably 18~
22s。
In the present invention, the polyalcohol is due to containing multiple hydroxyls, with reproducibility, can be cooperateed with reducing agent formation
Effect, while reduction reaction rate is accelerated, the particle diameter for being also beneficial to make the nano silver particles to be formed evenly, improves nanometer
The content of nano silver particles and the stability of nano silver colloidal sol in silver sol.
The invention provides the nano silver colloidal sol that preparation method described in above-mentioned technical proposal is prepared, the Nano Silver is molten
The particle diameter of nano silver particles is 10~20nm in glue.In the present invention, the nano silver colloidal sol is golden transparent colloidal sol.At this
In invention, the nano silver colloidal sol is preferably sealed to be kept in dark place in brown reagent bottle.
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described.It is aobvious
So, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made all belongs to
In the scope of protection of the invention.
Embodiment 1
(1) under conditions of magnetic agitation speed is 350rpm, by 36mL deionized waters, 1mLN, N- dimethylethanolamines
The aqueous solution (mass concentration is 2mg/mL) and 1mL aqueous povidone solutions (mass concentration is 20mg/mL) mixing, then
Mixed with 2mL silver nitrate aqueous solutions (mass concentration is 2mg/mL), obtain just mixed material；
(2) under conditions of magnetic agitation speed is 350rpm, by just mixed material is carried out at 35 DEG C in the step (1)
First reduction reaction 30min, obtains nano silver colloidal sol presoma；
(3) magnetic agitation speed be 350rpm under conditions of, by nano silver colloidal sol presoma in the step (2) with
300 μ L Osmitrols (mass concentration is 2mg/mL) are mixed, and obtain mixed material；
(4) under conditions of magnetic agitation speed is 350rpm, mixed material in the step (3) is carried out at 35 DEG C
Second reduction reaction 30s, obtains nano silver colloidal sol, is sealed in brown reagent bottle and is kept in dark place.
Comparative example 1
Without Osmitrol, nano silver colloidal sol is prepared according to the raw material proportioning and method of embodiment 1.
Nano silver colloidal sol prepared by embodiment 1 and comparative example 1 carries out ultraviolet-visible light analysis of spectrum, as a result such as Fig. 1 institutes
Show；In Fig. 1, (1) is the ultraviolet-visible light spectral curve of nano silver colloidal sol prepared by embodiment 1, and (2) are receiving for the preparation of comparative example 1
The ultraviolet-visible light spectral curve of rice silver sol.The content of nano silver particles can be according to ultraviolet-visible in usual nano silver colloidal sol
The absorbance and maximum absorption wavelength of spectrum are judged that maximum absorption wavelength is smaller, and absorbance is bigger, then in nano silver colloidal sol
The content of nano silver particles is higher.As shown in Figure 1, the maximum absorption wavelength of curve (1) and curve (2) is essentially identical, but bent
The absorbance of line (1) is much larger than curve (2), illustrate that addition mannitol can improve containing for nano silver particles in nano silver colloidal sol
Amount.Meanwhile, the peak shape symmetry of curve (1) is more preferable, half-peak breadth is narrower, illustrates to add in the nano silver colloidal sol obtained after mannitol
The particle diameter distribution of nano silver particles is evenly.
Nano silver colloidal sol prepared by embodiment 1 and comparative example 1 carries out transmission electron microscope analysis, as a result sees Fig. 2 and Fig. 3；Fig. 2
The transmission electron microscope picture of the nano silver colloidal sol prepared for embodiment 1, Fig. 3 is the transmission electron microscope of nano silver colloidal sol prepared by comparative example 1
Figure.Evenly, the particle diameter of nano silver particles is for the shape of nano silver particles, particle size distribution in Fig. 2 and Fig. 3, Fig. 2
10~20nm, show plus mannitol after nano silver particles in nano silver colloidal sol particle diameter distribution evenly, this is widened significantly
The application of nano silver colloidal sol.
Embodiment 2
(1) under conditions of magnetic agitation speed is 300rpm, by 36mL deionized waters, 1mLN, N- dimethylethanolamines
The aqueous solution (mass concentration is 2mg/mL) and 1mL aqueous povidone solutions (mass concentration is 20mg/mL) mixing, then
Mixed with 2mL silver nitrate aqueous solutions (mass concentration is 2mg/mL), obtain just mixed material；
(2) under conditions of magnetic agitation speed is 300rpm, by just mixed material is carried out at 40 DEG C in the step (1)
First reduction reaction 35min, obtains nano silver colloidal sol presoma；
(3) magnetic agitation speed be 300rpm under conditions of, by nano silver colloidal sol presoma in the step (2) with
300 μ L Osmitrols (mass concentration is 2mg/mL) are mixed, and obtain mixed material；
(4) under conditions of magnetic agitation speed is 300rpm, mixed material in the step (3) is carried out at 40 DEG C
Second reduction reaction 20s, obtains nano silver colloidal sol, is sealed in brown reagent bottle and is kept in dark place.
Embodiment 3
(1) under conditions of magnetic agitation speed is 400rpm, by 36mL deionized waters, 1mLN, N- dimethylethanolamines
The aqueous solution (mass concentration is 2mg/mL) and 1mL aqueous povidone solutions (mass concentration is 20mg/mL) mixing, then
Mixed with 2mL silver nitrate aqueous solutions (mass concentration is 2mg/mL), obtain just mixed material；
(2) under conditions of magnetic agitation speed is 400rpm, by just mixed material is carried out at 45 DEG C in the step (1)
First reduction reaction 30min, obtains nano silver colloidal sol presoma；
(3) magnetic agitation speed be 400rpm under conditions of, by nano silver colloidal sol presoma in the step (2) with
300 μ L Osmitrols (mass concentration is 2mg/mL) are mixed, and obtain mixed material；
(4) under conditions of magnetic agitation speed is 400rpm, mixed material in the step (3) is carried out at 45 DEG C
Second reduction reaction 10s, obtains nano silver colloidal sol, is sealed in brown reagent bottle and is kept in dark place.
As seen from the above embodiment, the preparation method step that provides of the present invention is simple, safety and environmental protection, production cost are low；System
The particle diameter of nano silver particles is small in standby obtained nano silver colloidal sol and is evenly distributed (10~20nm), and stability is high, at room temperature
It is kept in dark place in brown bottle 6 months, does not occur flocculating and precipitate.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nano silver colloidal sol, comprises the following steps：
(1) the protective agent aqueous solution and reducing agent aqueous solution are mixed, then mixed with silver nitrate aqueous solution, obtain just mixed material；
(2) material will be just mixed in the step (1) and first 30~35min of reduction reaction is carried out at 35~45 DEG C, obtain nanometer
Silver sol presoma；
(3) nano silver colloidal sol presoma in the step (2) is mixed with polyatomic alcohol water solution, obtains mixed material；
(4) mixed material in the step (3) is subjected to second 10~30s of reduction reaction at 35~45 DEG C, obtains Nano Silver
Colloidal sol.
2. preparation method according to claim 1, it is characterised in that silver nitrate in material is just mixed in the step (1)
Mass concentration is 0.08~0.12mg/mL.
3. preparation method according to claim 1 or 2, it is characterised in that nitric acid in material is just mixed in the step (1)
The mass ratio of silver, protective agent and reducing agent is 1：(4.5~5.5)：(0.45~0.55).
4. preparation method according to claim 3, it is characterised in that the protective agent includes polyvinylpyrrolidone or poly-
Ethylene glycol.
5. preparation method according to claim 4, it is characterised in that the number-average molecular weight of the polyvinylpyrrolidone is
25000~35000.
6. preparation method according to claim 4, it is characterised in that the number-average molecular weight of the polyethylene glycol is 5500~
7500。
7. preparation method according to claim 3, it is characterised in that the reducing agent includes N, N- dimethylethanolamines,
Triethanolamine or methyl diethanolamine.
8. preparation method according to claim 1, it is characterised in that polyalcohol in mixed material in the step (3)
Mass concentration is 0.013~0.017mg/mL.
9. preparation method according to claim 8, it is characterised in that the polyalcohol includes mannitol, glycerine or season
Penta tetrol.
10. received in the nano silver colloidal sol that any one of claim 1~9 preparation method is prepared, the nano silver colloidal sol
The particle diameter of rice silver particles is 10~20nm.
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| CN111572151A (en) * | 2020-04-09 | 2020-08-25 | 广盟（广州）包装有限公司 | Antibacterial heat-insulating material composite film and preparation method thereof |
| CN111992734A (en) * | 2020-08-21 | 2020-11-27 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
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| CN111572151A (en) * | 2020-04-09 | 2020-08-25 | 广盟（广州）包装有限公司 | Antibacterial heat-insulating material composite film and preparation method thereof |
| CN111992734A (en) * | 2020-08-21 | 2020-11-27 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
| CN111992734B (en) * | 2020-08-21 | 2022-02-22 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
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