CN115740478A - Preparation method of nano gold particle sol and composite optical film thereof - Google Patents
Preparation method of nano gold particle sol and composite optical film thereof Download PDFInfo
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- CN115740478A CN115740478A CN202211027345.7A CN202211027345A CN115740478A CN 115740478 A CN115740478 A CN 115740478A CN 202211027345 A CN202211027345 A CN 202211027345A CN 115740478 A CN115740478 A CN 115740478A
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Abstract
The invention discloses a preparation method of nano gold particle sol, which comprises the following steps: mixing a gold compound with an organic solvent to obtain a first mixture; adding a stabilizer into the first mixture to obtain a second mixture; heating the second mixed mixture in water bath, and cooling to room temperature after reaction to obtain a third mixture; and adjusting the pH value of the third mixture, adding a reducing agent into the third mixture, and reacting to obtain the nano gold particle sol. The metal sol obtained by the preparation method of the nano gold particle sol has smaller particle size, high dispersion degree and good stability.
Description
Technical Field
The invention relates to the field of nano-particle materials, in particular to a preparation method of nano-gold particle sol.
Background
In recent years, a composite film of a nano metal particle dispersed oxide has been highly regarded, in which an interface interaction between a metal particle and an oxide can well disperse a nano metal. Meanwhile, the metal particles generate electrons and holes through the excitation of light, so that surface plasma resonance and a local field enhancement effect are triggered, the film can generate stronger absorption in a specific wavelength range, extremely fast response time and extremely high nonlinear coefficient, and the nonlinear optical material is a nonlinear optical material with good application prospect. Therefore, the special optical film can be well developed and applied in the field of the non-linear optical material as the base material, such as: in the electronics industry, optical switches, optical communications, optical information processing, optical computers, laser technology, for example, are used.
Au, ag, cu, pt and other elements can be used as metal nanoparticles to be doped into a thin film medium to improve the nonlinearity of the material. Among them, the nano Au particle mosaic dielectric thin film is widely studied due to its excellent nonlinear enhancement effect. Researches find that the preparation technology of the composite film comprises ion implantation, a vacuum evaporation method, a sputtering method, a sol-gel method, a pulse laser deposition method and the like. The sol-gel method can achieve molecular level dispersion, can disperse a plurality of metals in different medium matrixes, has the advantages of easily controlled film components, simple process equipment, short preparation period, energy conservation, low cost, relatively low heat treatment temperature and the like, and is considered to be one of the most effective film preparation technologies at present.
The patent application No. 200710100037.1 discloses a nano metal particle dispersed nickel oxide optical film and its preparation method, which refers to the utilization of nickel nitrate solution (Ni (NO) 3 ) 2 •6H 2 O) and chloroauric acid solution (HAuCl) 4 •4H 2 O) forming a precursor by a sol-gel method to prepare the Au/NiO composite film. A composite optical film of nm-class metal particles dispersed cobalt oxide (Co (NO) solution) and its preparing process from the patent No. 200910078279.4 3 ) 2 •6H 2 O) and chloroauric acid solution (HAuCl) 4 •4H 2 O) forming a precursor by a sol-gel method to prepare the Au/CoO composite film. Gold and silver nanoparticle dispersed oxide non-linear line with patent application number of 201110227386.6Optical film and method of making using cobalt nitrate solution (Co (NO) 3 ) 2 •6H 2 O), silver nitrate (AgNO) 3 ) And chloroauric acid solution (HAuCl) 4 •4H 2 O) preparation of Ag by sol-gel method forming precursor x Au y /(Co 3 O 4 ) 1-x-y And (3) compounding the film. The composite film prepared by the sol-gel method has good absorption peak at 350-650nm due to the plasma resonance effect, and shows nonlinear optical performance. However, the size and dispersion degree of the nano metal particle sol are difficult to control by mixing the chloroauric acid solution and the metal oxide precursor, so that the utilization rate of the prepared sol on the gold nanoparticles is not high.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of nano gold particle sol, which can effectively relieve the problem of poor dispersion effect of metal nano particles in the sol.
In order to achieve the above object, an embodiment of the present invention provides a method for preparing a gold nanoparticle sol, including the following steps:
mixing a gold compound with an organic solvent to obtain a first mixture;
adding a stabilizer into the first mixture to obtain a second mixture;
heating the second mixed mixture in water bath, and cooling to room temperature after reaction to obtain a third mixture;
and adjusting the pH value of the third mixture, adding a reducing agent into the third mixture, and reacting to obtain the nano gold particle sol.
In one or more embodiments of the invention, the adjusting the pH of the third mixture and the adding the reducing agent to the third mixture comprises:
adding an alkaline substance to the third mixture, adjusting the pH value to be 7-8, then adding a reducing agent to the mixture after the pH value is adjusted, and stirring for 1-5h at 20-25 ℃ to obtain the nano metal particle sol.
In one or more embodiments of the invention, the water bath heating time is 2-8h; the temperature of the water bath heating is 60-70 ℃.
In one or more embodiments of the present invention, the gold compound includes chloroauric acid.
In one or more embodiments of the present invention, the organic solvent includes dimethylacetamide, dimethylformamide, dimethylsulfoxide, ethyl acetate, or methyl isobutyl ketone.
In one or more embodiments of the present invention, the stabilizer includes one or more of tetrakis hydroxymethyl phosphonium chloride, polydiallyldimethylammonium chloride, polyvinyl alcohol, polyvinylidene fluoride, and lysine.
In one or more embodiments of the present invention, the reducing agent includes one or more of sodium borohydride, potassium borohydride, formaldehyde, sodium hypophosphite, glucose, and ascorbic acid.
In one or more embodiments of the present invention, the mixing of the gold compound with the organic solvent further comprises:
stirring the gold compound and the organic solvent for 0.5-2h at the stirring temperature of 20-25 ℃; and/or; the adding a stabilizer to the first mixture and mixing further comprises:
and stirring the first mixture and the stabilizer for 0.5-2h at 20-25 ℃.
In one or more embodiments of the present invention, the gold compound is 0.1 to 10wt% by mass.
The invention also provides a composite optical film which comprises the nano-gold particle sol, wherein the nano-gold particle sol is prepared by adopting the preparation method of the nano-gold particle sol.
Compared with the prior art, the preparation method of the nano gold particle sol has the following advantages: preferably, dimethylacetamide or dimethylformamide is used as an organic solvent, polydiallyldimethylammonium chloride or tetramethylolphosphonium chloride is used as a stabilizer, sodium borohydride is used as a reducing agent to easily prepare metal particle sol, and a liquid-phase chemical reduction method is utilized to firstly prepare metal nanoparticles with uniform relative sizes and concentrated dispersion.
Drawings
FIG. 1 is a plot of the fraction of different particle sizes according to example 1 of the present invention;
FIG. 2 is a plot of the fraction of different particle sizes according to example 2 of the present invention;
FIG. 3 is a plot of the fraction of different particle sizes according to example 3 of the present invention;
FIG. 4 is a plot of the fraction of different particle sizes according to example 4 of the present invention;
FIG. 5 is a plot of the fraction of different particle sizes according to example 5 of the present invention;
FIG. 6 is a plot of the fraction of different particle sizes of comparative example 1 according to the present invention;
FIG. 7 is a plot of the fractional particle sizes of comparative example 2 according to the present invention;
FIG. 8 is a plot of the fraction of different particle sizes for comparative example 3 according to the present invention;
FIG. 9 is a reaction chart of absorbance at different wavelengths according to example 1 and comparative example 1 of the present invention;
fig. 10 is a flowchart of a method for preparing a gold nanoparticle sol according to the present invention.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations such as "comprises" or "comprising", etc., will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
A method for preparing a gold nanoparticle sol according to a preferred embodiment of the present invention includes the steps of:
mixing a gold compound with an organic solvent to obtain a first mixture;
adding a stabilizer into the first mixture to obtain a second mixture;
heating the second mixed mixture in water bath, and cooling to room temperature after reaction to obtain a third mixture;
and adjusting the pH value of the third mixture, adding a reducing agent into the third mixture, and reacting to obtain the nano gold particle sol.
Specifically, the preparation method of the nano gold particle sol comprises the following steps:
adding 25-100mg of gold compound with the mass percent of 0.1-10wt% into a beaker filled with 50-100g of organic solvent, and stirring for 0.5-2h to obtain a first mixture;
adding 50-100mg of stabilizer into the first mixture, and stirring for 0.5-2h to obtain a second mixture;
placing the beaker with the second mixture into a water bath kettle, carrying out water bath reaction for 2-8h, and cooling to room temperature after the reaction is finished to obtain a third mixture;
adding an alkaline substance to the third mixture, adjusting the pH value to be 7-8, then adding 50-100mg of a reducing agent to the mixture after the pH value is adjusted, and stirring for 1-5h at 20-25 ℃ to obtain the nano metal particle sol.
Specifically, the gold compound includes chloroauric acid. The organic solvent includes dimethylacetamide, dimethylformamide, dimethylsulfoxide, ethyl acetate or methyl isobutyl ketone. The stabilizer comprises one or more of tetrakis (hydroxymethyl) phosphonium chloride, polydiallyldimethylammonium chloride, polyvinyl alcohol, polyvinylidene fluoride and lysine. The reducing agent comprises one or more of sodium borohydride, potassium borohydride, formaldehyde, sodium hypophosphite, glucose and ascorbic acid.
Specifically, the stirring temperature of the gold compound and the organic solvent is 20-25 ℃. The stirring temperature of the first mixture and the stabilizer is 20-25 ℃. The water bath temperature of the water bath kettle is 60-70 ℃.
The mass percent of the gold compound is 0.1-10wt%.
The invention also provides a composite optical film which comprises the nano-gold particle sol, wherein the nano-gold particle sol is prepared by adopting the preparation method of the nano-gold particle sol.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
25mg of chloroauric acid (HAuCl) with the mass percent of 0.1wt percent 4 ) Was added to a beaker containing 75g of dimethylacetamide by mass, and stirred continuously at 20 ℃ for 0.5h to obtain a first mixture.
Then, 50mg of polydiallyldimethylammonium chloride and 50mg of tetrakis hydroxymethyl phosphonium chloride were added to the first mixture, followed by sufficient stirring at 20 ℃ for 0.5 hour to obtain a second mixture. And transferring the beaker filled with the second mixture into a water bath kettle, carrying out water bath reaction for 4 hours at the temperature of 60 ℃, and cooling to 20 ℃ after the water bath reaction is finished to obtain a third mixture.
Then, na was added to the beaker containing the third mixture 2 CO 3 The third mixture pH was adjusted and tested with a pH meter until pH =7. And finally, adding 50mg of sodium borohydride, and fully stirring for 2 hours at 20 ℃ to finally obtain the nano metal particle sol.
Example 2
25mg of chloroauric acid (HAuCl) with a mass percentage of 5wt% are added 4 ) Was added to a beaker containing 50g of dimethylformamide by mass, and stirred continuously at 23 ℃ for 1 hour to obtain a first mixture.
60mg of tetrakis (hydroxymethyl) phosphonium chloride was further added to the first mixture, followed by sufficient stirring at 23 ℃ for 1 hour to obtain a second mixture. And transferring the beaker filled with the second mixture into a water bath kettle, carrying out water bath reaction for 6 hours at the temperature of 65 ℃, and cooling to room temperature of 23 ℃ after the water bath reaction is finished to obtain a third mixture.
Ammonia was then added to the beaker with the third mixture to adjust the pH of the third mixture, which was measured with a pH meter until pH =8. And finally, adding 40mg of sodium borohydride and 40mg of potassium borohydride, and fully stirring for 4 hours at 23 ℃ to finally obtain the nano metal particle sol.
Example 3
50mg of 10wt% chloroauric acid (HAuCl) 4 ) Adding into a beaker filled with 100g of dimethyl sulfoxide, and continuously stirring at 23 DEG CStirring for 1h to obtain a first mixture.
Then, 50mg of polyvinyl alcohol and 50mg of polyvinylidene fluoride were added to the first mixture, followed by stirring thoroughly at 25 ℃ for 2 hours to obtain a second mixture. And transferring the beaker filled with the second mixture into a water bath kettle, carrying out water bath reaction for 10 hours at 68 ℃, and cooling to 25 ℃ after the water bath reaction is finished to obtain a third mixture.
Ammonia was then added to the beaker with the third mixture to adjust the pH of the third mixture, which was tested with a pH meter until pH =7. And finally, adding 40mg of sodium borohydride and 40mg of potassium borohydride, and fully stirring for 5 hours at 25 ℃ to finally obtain the nano metal particle sol.
Example 4
100mg of chloroauric acid with a mass percentage of 6wt% was added to a beaker containing 100g of ethyl acetate and stirred continuously at 25 ℃ for 2 hours to obtain a first mixture.
50mg of polyvinyl alcohol and 50mg of polyvinylidene fluoride were added to the first mixture, and then, the mixture was sufficiently stirred at 25 ℃ for 2 hours to obtain a second mixture. And transferring the beaker filled with the second mixture into a water bath kettle, carrying out water bath reaction for 10 hours at the temperature of 70 ℃, and cooling to 25 ℃ after the water bath reaction is finished to obtain a third mixture.
Ammonia was then added to the beaker with the third mixture to adjust the pH of the third mixture, which was measured with a pH meter until pH =8. And finally, adding 30mg of sodium hypophosphite, 30mg of glucose and 40mg of ascorbic acid, and fully stirring for 5 hours at 25 ℃ to finally obtain the nano metal particle sol.
Example 5
100mg of 2wt% chloroauric acid was added to a beaker containing 90g of methyl isobutyl ketone by mass, and continuously stirred at 25 ℃ for 2 hours to obtain a first mixture.
Then, 20mg of tetrakis (hydroxymethyl) phosphonium chloride, 20mg of polydiallyldimethylammonium chloride, 20mg of polyvinyl alcohol, 20mg of polyvinylidene fluoride and 20mg of lysine were added to the first mixture, and then, the mixture was sufficiently stirred at 25 ℃ for 2 hours to obtain a second mixture. And transferring the beaker filled with the second mixture into a water bath kettle, carrying out water bath reaction for 10 hours at the temperature of 70 ℃, and cooling to 25 ℃ after the water bath reaction to obtain a third mixture.
Then to the beaker with the third mixture, ammonia was added to adjust the pH of the third mixture, which was measured with a pH meter until pH =7. And finally, adding 20mg of sodium borohydride, 20mg of potassium borohydride, 20mg of sodium hypophosphite, 20mg of glucose and 20mg of ascorbic acid, and fully stirring for 5 hours at 25 ℃ to finally obtain the nano metal particle sol.
Comparative example 1
25mg of chloroauric acid (HAuCl) 4 ) Was added to a beaker containing 75g of dimethylacetamide by mass, and stirred continuously at 25 ℃ for 1h to obtain a first mixture.
To the first mixture were further added 50mg of Sodium Dodecylbenzenesulfonate (SDBS) and 50mg of cetyltrimethylammonium bromide (CTAB), followed by thoroughly stirring at 25 ℃ for 1 hour to obtain a second mixture.
And transferring the beaker filled with the second mixture into a water bath kettle, reacting for 8 hours at 60 ℃, and cooling to 25 ℃ after the reaction is finished to obtain a third mixture.
Adding an appropriate amount of Na to the third mixture 2 CO 3 The pH was adjusted to around pH =7. And finally, adding 50mg of sodium borohydride, and fully stirring for 3 hours at 25 ℃ to finally obtain the nano metal particle sol.
Comparative example 2
25mg of chloroauric acid (HAuCl) 4 ) Was added to a beaker containing 75g of dimethylacetamide by mass, and stirred continuously at 25 ℃ for 1h to obtain a first mixture.
To the first mixture were added 50mg of polydiallyldimethylammonium chloride (PDDA) and 50mg of tetrakis (hydroxymethyl) phosphonium chloride (THPC), followed by stirring thoroughly at 25 ℃ for 1 hour to obtain a second mixture.
And transferring the beaker filled with the second mixture into a water bath kettle, reacting for 8 hours at 60 ℃, and cooling to 25 ℃ after the reaction is finished to obtain a third mixture.
Adding an appropriate amount of Na to the third mixture 2 CO 3 The pH was adjusted to around pH =7. Finally 21.5mg of hydrazine hydrate and 64.5mg of formaldehyde are added, followed by 25 deg.CStirring for 3h to obtain the final product.
Comparative example 3
25mg of chloroauric acid (HAuCl) 4 ) Added to a beaker containing 75g of ethanol by mass and stirred continuously at 25 ℃ for 1 hour to obtain a first mixture.
To the first mixture were added 50mg of polydiallyldimethylammonium chloride (PDDA) and 50mg of tetrakis (hydroxymethyl) phosphonium chloride (THPC), followed by stirring thoroughly at 25 ℃ for 1 hour to obtain a second mixture.
And transferring the beaker filled with the second mixture into a water bath kettle, reacting for 8 hours at the temperature of 60 ℃, and cooling to 25 ℃ after the reaction is finished to obtain a third mixture.
Adding an appropriate amount of Na to the third mixture 2 CO 3 The pH was adjusted to around pH =7. And finally, adding 50mg of sodium borohydride, and fully stirring for 3 hours at 25 ℃ to finally obtain the nano metal particle sol.
The following particle size distribution tests were conducted for each of the examples and comparative examples, and the results are shown in FIGS. 1 to 8:
as can be seen from the examples and comparative examples, metal particle sols which are easily prepared by selecting Dimethylacetamide (DMAC) or Dimethylformamide (DMF) as an organic solvent, polydiallyldimethylammonium chloride (PDDA) or tetrakis (hydroxymethyl) phosphonium chloride (THPC) as a stabilizer, and sodium borohydride or potassium borohydride as a reducing agent are substantially 6-20nm and have uniform sizes. Meanwhile, the size of the gold particle sol is small, which shows that the nano gold particles are well dispersed.
The technical nanoparticles prepared by the stabilizer and the reducing agent used in the comparative example have the size of 10-100nm, nonuniform size distribution and poor stability.
As shown in fig. 9, unlike comparative example 1, example 1 has a higher absorption at 550nm, because the gold particles are well dispersed in a small particle size and the gold particles are highly available, resulting in a good SPR effect. Thus, example 1 is the most preferred embodiment of the present invention.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A preparation method of nano gold particle sol is characterized by comprising the following steps:
mixing a gold compound with an organic solvent to obtain a first mixture;
adding a stabilizer into the first mixture to obtain a second mixture;
heating the second mixed mixture in water bath, and cooling to room temperature after reaction to obtain a third mixture;
and adjusting the pH value of the third mixture, adding a reducing agent into the third mixture, and reacting to obtain the nano gold particle sol.
2. The method of preparing the gold nanoparticle sol of claim 1, wherein the adjusting the pH of the third mixture and the adding the reducing agent to the third mixture comprises:
adding an alkaline substance to the third mixture, adjusting the pH value to be 7-8, then adding a reducing agent to the mixture after the pH value is adjusted, and stirring for 1-5h at 20-25 ℃ to obtain the nano metal particle sol.
3. The method for preparing the gold nanoparticle sol of claim 1, wherein the heating in the water bath is carried out for 2 to 8 hours; the temperature of the water bath heating is 60-70 ℃.
4. The method of preparing a nano-gold particle sol of claim 1, wherein the gold compound comprises chloroauric acid.
5. The method for preparing a gold nanoparticle sol of claim 1, wherein the organic solvent comprises dimethylacetamide, dimethylformamide, dimethylsulfoxide, ethyl acetate or methyl isobutyl ketone.
6. The method of preparing the gold nanoparticle sol of claim 1, wherein the stabilizer comprises one or more of tetrakis hydroxymethyl phosphonium chloride, polydiallyldimethylammonium chloride, polyvinyl alcohol, polyvinylidene fluoride, and lysine.
7. The method of preparing the gold nanoparticle sol of claim 1, wherein the reducing agent comprises one or more of sodium borohydride, potassium borohydride, formaldehyde, sodium hypophosphite, glucose, and ascorbic acid.
8. The method of preparing a nanogold particle sol of claim 1, wherein the mixing of the gold compound with the organic solvent further comprises:
stirring the gold compound and the organic solvent for 0.5-2h at 20-25 ℃; and/or; the adding a stabilizer to the first mixture further comprises:
and stirring the first mixture and the stabilizer for 0.5-2h at 20-25 ℃.
9. The method for preparing the nano gold particle sol of claim 1, wherein the mass percentage of the gold compound is 0.1 to 10wt%.
10. A composite optical film comprising a gold nanoparticle sol, wherein the gold nanoparticle sol is prepared by the method for preparing the gold nanoparticle sol according to any one of claims 1 to 9.
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