WO2002087749A1 - Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof - Google Patents

Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof Download PDF

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Publication number
WO2002087749A1
WO2002087749A1 PCT/KR2002/000800 KR0200800W WO02087749A1 WO 2002087749 A1 WO2002087749 A1 WO 2002087749A1 KR 0200800 W KR0200800 W KR 0200800W WO 02087749 A1 WO02087749 A1 WO 02087749A1
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WIPO (PCT)
Prior art keywords
metal
silver
colloid solution
salt
water
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PCT/KR2002/000800
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French (fr)
Inventor
Mu-Sang Lee
Sang-Il Nam
Eun-Sun Min
Seung-Bin Kim
Hyun-Suk Shin
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Postech Foundation
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Priority claimed from KR10-2001-0023471A external-priority patent/KR100425976B1/en
Priority claimed from KR10-2002-0020593A external-priority patent/KR100484506B1/en
Priority claimed from KR10-2002-0020594A external-priority patent/KR100479847B1/en
Application filed by Postech Foundation filed Critical Postech Foundation
Priority to CA002445877A priority Critical patent/CA2445877C/en
Priority to US10/476,418 priority patent/US7348365B2/en
Priority to EP02730927A priority patent/EP1383597A4/en
Priority to JP2002585083A priority patent/JP4073788B2/en
Publication of WO2002087749A1 publication Critical patent/WO2002087749A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0039—Post treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0043—Preparation of sols containing elemental metal

Definitions

  • the present invention relates to a colloid solution of metal nanopartides, metal-polymer nanocomposites, and methods for preparing the same, and more particularly, to a metal colloid solution and metal-polymer nanocomposites prepared using a variety of polymeric stabilizers and having a uniform particle diameter, and methods for preparing the same.
  • the metal nanopartides prepared by those methods were known to have a size of from about 8 nm to tens of nanometers from the outstanding research reports. However, the metal nanopartides are prepared by these methods not so desirable in terms of particle diameter and shape uniformity.
  • ultrafine silver particles are essential materials in the electronics applications, for example, for conductive ink and paste and adhesive applied in the manufacture of a variety of electronic parts.
  • a silver salt is dissolved in water, mixed with acrylic amide as a water-soluble monomer, and subjected to gamma-rays irradiation to prepare the silver-polymer nanocomposites.
  • reduction of silver ions coincides with polymerization of the monomer, so that the metal nanopartides are comparatively uniformly dispersed in the polymerized medium.
  • the present invention provides a method for preparing a metal nanoparticle colloid solution, comprising: dissolving a metal salt and a water-soluble polymer in water, a non-aqueous solvent, or a solvent mixture of water and a non-aqueous solvent; purging a reaction container containing the solution with nitrogen or argon gas; and radiating radioactive rays onto the solution.
  • the water-soluble polymer includes polyvinyl pyrrolidone, a copolymer having vinyl pyrrolidone as a first polymerization unit, and a fatty acid-substituted or unsubstituted polyoxyethylene.
  • the copolymer having vinyl pyrrolidone as the first polymerization unit includes (1 -vinyl pyrrolidone)-acrylic acid copolymer, (1 -vinyl pyrrolidone)-vinyl acetic acid copolymer, (1 -vinyl pyrrolidone)-styrene copolymer, and (1 -vinyl pyrrolidone)-vinyl alcohol copolymer.
  • the fatty acid-substituted polyoxyethylene includes polyoxyethylene stearate and polyoxyethylene palmitate.
  • the present invention provides a metal nanoparticle colloid solution prepared by the preparation method described above.
  • the present invention provides a method for preparing metal-polymer nanocomposites, comprising: dissolving a metal salt and a polymeric stabilizer in a solvent mixture of water and a non-aqueous solvent; purging a reaction container containing the solution with nitrogen or argon gas; and radiating radioactive rays onto the solution to obtain precipitates.
  • the polymeric stabilizer is at least one polymer selected from the group consisting of polyethylene, polyacrylonitrile, poly(methyl (meth)acrylate), polyurethane, polyacrylamide, and polyethylene glycol.
  • the colloid solution of metal nanopartides and the metal-polymer nanocomposites have favorable stability, a uniform shape, and a small diameter within a narrow distribution range, so that the colloid solution of metal nanopartides and the metal-polymer nanocomposites have wide, effective applications, for example, as an antibacterial agent, a deodorizing agent, a conductive adhesive, conductive ink, and a electromagnetic wave shielder for an image display.
  • an antibacterial agent for example, a deodorizing agent, a conductive adhesive, conductive ink, and a electromagnetic wave shielder for an image display.
  • Electrons are generated in a solvent by gamma-rays irradiation and reduce silver ions in a solution. Reduced silver atoms agglomerate to form a silver cluster and become larger. In this case, when an appropriate polymeric stabilizer is added, the agglomeration of the silver atoms can be prevented to result in nano-sized silver particles. Polymeric stabilizers stabilize the nanopartides in a colloid state through steric repulsion as well as prevent the silver clustering. The gamma- rays irradiation produces radicals as well as the electrons in the solvent. To remove the radicals, a scavenger, such as alcohol, is used. Oxygen present in the solution is removed by nitrogen or argon purging before the gamma-rays irradiation, to prevent side reactions by the oxygen.
  • a scavenger such as alcohol
  • any metal salt capable of forming a general nanoparticle colloid solution can be used without limitations.
  • a salt of at least one metal selected from the group consisting of silver, copper, nickel, palladium, and platinum is preferable, with the silver salt being more preferable.
  • the metal salt is, for example, nitrate, sulfate, hydrochloride, perchlorate, or acetate.
  • a silver salt such as AgNO 3 , AgCIO4, Ag 2 SO 4 , or CH 3 COOAg is more preferred. These silver salts are well dissolved in water and thus form an aqueous colloid of silver nanopartides.
  • a water-soluble polymer preferably, having a weight average molecular weight of 2,000-2,000,000, is used as a stabilizer for improving dispersion of the metal nanopartides.
  • Suitable stabilizers include, for example, polyvinyl pyrrolidone, a copolymer including vinyl pyrrolidone as a first polymerization unit, and a fatty acid-substituted or unsubstituted polyoxyethylene.
  • the copolymer including vinyl pyrrolidone as a first polymerization unit may further include an acrylic acid, styrene, vinyl acetate, or vinyl alcohol as a second polymerization unit.
  • the copolymer examples include (1 -vinyl pyrrolidone)-acrylic acid copolymer and (1 -vinyl pyrrolidone)-vinyl acetic acid copolymer.
  • the copolymer includes the first and second polymerization units in a weight ratio of 1 :99-99:1 , and preferably, 20:80-80:20.
  • the (1 -vinyl pyrrolidone)-acrylic acid copolymer includes a 1-vinyl pyrrolidone repeating unit and an acrylic acid repeating unit in a weight ratio of 75:25.
  • the (1 - vinyl pyrrolidone)-vinyl acetic acid copolymer includes a 1 -vinyl pyrrolidone repeating unit and a vinyl acetic acid repeating unit in a weight ratio of 57:43.
  • the fatty acid-substituted polyoxyethylene which is a water- soluble polymer used as the stabilizer
  • the fatty acid is palmitic acid, oleic acid, linoleic acid, or stearic acid, with the stearic acid being more preferred.
  • any solvent capable of dissolving the water-soluble polymer and metal salt therein can be used without limitations.
  • water, a non-aqueous solvent, or a mixture of these solvents can be used.
  • Suitable non-aqueous solvents include alcoholic solvents, and typically, isopropyl alcohol, methanol, ethanol, ethylene glycol, or a mixture including at least two of the forgoing solvents.
  • the non-aqueous solvents also act as a scavenger for removing radicals during gamma-rays radiation as well as act as a solvent for the metal salt and water-soluble polymer.
  • the water-soluble polymer is used in an amount of 0.1-10 parts by weight based on 100 parts of the solvent by weight. If the water-soluble polymer is used in an amount of less than 0.1 parts by weight, it is difficult to provide the effect of the stabilizer. If the water-soluble polymer is used in an amount of greater than 10 parts by weight, the particle size undesirably increases.
  • the metal salt is used in an amount of 0.01 -5 parts by weight based on 100 parts of the solvent by weight. If the metal salt is used in an amount of less than 0.01 parts by weight, it is difficult to provide the effect of the metal salt. If the metal salt is used in an amount of greater than 5 parts by weight, the particle size increases, or the particles slightly precipitate.
  • a water-soluble polymer and a metal salt are dissolved in a solvent.
  • a reaction container containing the solution is purged with nitrogen (N 2 ) or argon (Ar) gas for 10 minutes to 10 hours and tightly sealed.
  • the resultant product is irradiated with radioactive rays, and preferably, gamma rays, to a radiation dosage of 10-50 KGy.
  • radioactive rays and preferably, gamma rays
  • a post-process of diluting the source solution and ultrasonic treatment may be performed to decompose the metal nanopartides further into much smaller metal particles.
  • the post-process supports the fact that the adsorption and steric repulsion mechanism of polymers enables the formation of the metal nanopartides and ensures dispersion stability.
  • very small metal nanopartides are surrounded and adsorbed by the polymeric stabilizer to form clusters of the polymeric stabilizer-adsorbed metal nanopartides. Since the clusters of the metal nanopartides agglomerate, the metal nanopartides forming the colloid appear to be much larger after the radioactive-rays irradiation.
  • the colloid of the metal nanopartides is diluted and subjected to the ultrasonic treatment, the clusters of the metal nanopartides are decomposed further into much smaller metal particles.
  • the much smaller particle diameter and narrower distribution of particle diameters are believed to be due to the use of the water-soluble polymeric stabilizer, such as polyvinyl pyrrolidone, (1 -vinyl pyrrolidone)-acrylic acid copolymer, polyoxyethylene stearate, and (1 -vinyl pyrrolidone)-vinyl acetic acid copolymer.
  • the metal nanopartides having a very small diameter prepared in the present invention have a very large surface area-to-volume ratio, and thus they provide good antibacterial activity and conductivity even when only a trace is used. Therefore, the colloid solution of the metal nanopartides according to the present invention can be used as an antibacterial agent, a sterilizer, a deodorizing agent, an electromagnetic wave shielder, and conductive adhesive and ink.
  • the metal nanopartides according to the present invention need to be miscible with a variety of organic solvents, plasticizers, and resins to prepare a non-aqueous colloid solution of the metal nanopartides.
  • a non-aqueous solvent which does not contain water, i.e., an alcoholic solvent
  • the alcoholic solvent acts as a scavenger as well as the solvent, and thus is favorable for economical reasons.
  • the ethylene glycol is more preferred as the solvent and scavenger.
  • isopropyl alcohol can be used as the solvent and scavenger.
  • the metal nanopartides are miscible with alcohol-soluble resins, alcohol-soluble plasticizers, such as dioctyl phthalate (DOP), and organic solvents.
  • DOP dioctyl phthalate
  • the present invention provides a solid paste of metal- polymer nanocomposites.
  • the solid paste of the metal-polymer nanocomposites is prepared by a similar method as that applied to prepare the colloid solution of the metal nanopartides as described above, except that polyacrylamide or polyethylene glycol is used as a polymeric stabilizer.
  • the polyacrylamide and polyethylene glycol are water-soluble polymers and precipitate the metal-polymer nanocomposites when dissolved in a solvent together with a metal salt, followed by radioactive-rays irradiation.
  • a water-insoluble stabilizer such as poly(methyl (meth)acrylate), polyacrylonitrile, or polyurethane
  • a surfactant for example, polyoxyethylene sorbitan mono-oleate, which is commercially available in the trade name of Span-80, Tween-81, or Tween-80, is added.
  • Span-80 polyoxyethylene sorbitan mono-oleate
  • Tween-81 polyacrylonitrile
  • Tween-80 polyoxyethylene sorbitan mono-oleate
  • the metal salt is added in an amount of 0.01-5 parts by weight based on 100 parts of the solvent by weight. If the metal salt is added in an amount of less than 0.01 parts by weight, the effect of adding the metal salt is negligible. If the metal salt is added in an amount of greater than 5 parts by weight, the particle size increases.
  • the polymeric stabilizer is added in an amount of about 0.1-10 parts by weight based on 100 parts of the solvent by weight. If the amount of the polymeric stabilizer is less than 0.1 parts by weight, the effect of adding the polymeric stabilizer is negligible. If the amount of the polymeric stabilizer exceeds 10 parts by weight, the particle size increases, and the addition of the polymeric stabilizer such an amount is uneconomical.
  • the polymeric stabilizer and metal salt are dissolved in a solvent, and a reaction container containing the solution is purged with nitrogen or argon gas for 30 minutes to 10 hours and completely tightened.
  • the solution is irradiated with gamma rays of a radiation dosage of about 10-50 KGy, followed by solvent removal and vacuum drying to attain the metal-polymer nanocomposites according to the present invention.
  • the metal-polymer nanocomposites according to the present invention have a uniform particle diameter at room temperature. Since greatly diversified kinds of polymers can be applied to the metal-polymer nanocomposites, unlike conventional methods using monomers to prepare metal-polymer nancomposites, it is easy to control the molecular weight. In addition, due to a great surface area-to-volume ratio of the metal-polymer nanocomposites, favorable effects, for example, in terms of antibacterial activity and conductivity, are provided with a trace of the metal-polymer nanocomposites.
  • the metal-polymer nanocomposites can be effectively used as an antibacterial agent, a sterilizer, a deodorizing agent, a conductive adhesive, and conductive ink.
  • FIG. 1 shows a transmission electron microscopic (TEM) photograph and particle diameter distribution of silver nanopartides prepared in Example 1 according to the present invention
  • FIG. 2 shows the UV/VIS absorption spectrum of the silver nanopartides prepared in Example 1 according to the present invention at 405 nm;
  • FIG. 3 is a TEM photograph after dilution with water and ultrasonic treatment of the silver nanopartides prepared in Example 2 according to the present invention
  • FIG. 4 shows a TEM photograph and particle diameter distribution of silver nanopartides prepared in Example 5 according to the present invention
  • FIG. 5 shows the UVA IS absorption spectrum of the silver nanopartides prepared in Example 5 according to the present invention at 405 nm;
  • FIG. 6 is a field emission scanning electron microscopic (FESEM) photograph of a paste of silver-polymer nanocomposites prepared in Example 6 according to the present invention
  • FIG. 7 shows a TEM photograph and particle diameter distribution of a dispersion of silver-polymer nanocomposites prepared in Example 7 according to the present invention in chloroform
  • FIG. 8 shows the UVA/IS absorption spectrum of the silver-polymer nanocomposites prepared in Example 7 according to the present invention at 405 nm;
  • FIG. 9 is a TEM photograph of a silver nanoparticle colloid solution prepared in Example 1 according to the present invention after being left for 10 months at room temperature;
  • FIG. 10 shows the infrared (IR) spectrum of a silver nanoparticle colloid solution prepared in Example 2 according to the present invention
  • FIG. 1 1 shows the surface enhanced Raman scattering spectrum of the silver nanopartides prepared in Example 2 according to the present invention with respect to pH of a 1 .0X10 "5 M thionin solution; and
  • FIG. 12 shows the result of an antibacterial activity test of a textile soaked with the silver nanoparticle colloid solution prepared in Example 2 according to the present invention;
  • FIG. 13 shows the result of an antibacterial activity test of a textile soaked with a solution containing no silver nanopartides according to the present invention.
  • Example 1 Silver nanoparticle colloid solution prepared by using (1- vinyl pyrrolidone)-acrylic acid copolymer as a stabilizer
  • the silver nanoparticle colloid solution had a very uniform particle diameter distribution and a uniform particle shape. Most of the particles had a diameter of 3.0 ⁇ 0.9 nm on average, which is the smallest among silver nanopartides prepared by gamma-rays irradiation, which have been reported to date.
  • the formation of the silver nanopartides was identified by UVA IS spectrometry. The result is shown in FIG. 2. As shown in FIG. 2, an absorption peak of the silver nanopartides appeared at 405 nm.
  • Example 2 Silver nanoparticle colloid solution prepared by using polyvinyl pyrrolidone as a stabilizer
  • a silver nanoparticle colloid solution was prepared in the same manner as in Example 1 , except that 11.137 g polyvinyl pyrrolidone having a MW of 55,000 was used as the stabilizer, instead of the (1-vinyl pyrrolidone)-acrylic acid copolymer.
  • the resultant silver nanoparticle colloid solution had a minimum particle diameter of 6.6 ⁇ 1.1 nm and an average particle diameter of about 10-12 nm.
  • Example 3 Silver nanoparticle colloid solution prepared by using polyoxyethylene stearate as a stabilizer
  • a silver nanoparticle colloid solution was prepared in the same manner as in Example 1 , except that 11.137 g polyoxyethylene stearate having a MW of ⁇
  • the resultant silver nanoparticle colloid solution had an average particle diameter of 7.5 ⁇ 1.8 nm.
  • Example 4 Particle diameter of silver nanoparticle colloid solution prepared by using polyvinyl pyrrolidone as a stabilizer after dilution and ultrasonic treatment
  • the silver nanoparticle colloid solution (having an average particle diameter of 12.1 ⁇ 1.6 nm) prepared in Example 2 was diluted 20 folds with water and subjected to ultrasonic treatment for 3 hours and particle diameter measurement. The result is shown in FIG. 3. As shown in FIG. 3, after the dilution and the ultrasonic treatment, particles of a diameter of ⁇ 2 nm and - 4 nm appeared. This result supports that the particle diameter can be further reduced by dilution and ultrasonic treatment. Apparently, a number of very small unit silver nanopartides on which polyvinyl pyrrolidone is adsorbed form the silver nanoparticle colloid solution.
  • Example 5 Silver nanoparticle colloid solution prepared by using ethylene glycol as a solvent and polyvinyl pyrrolidone as a stabilizer
  • a non-aqueous, yellow silver nanoparticle colloid solution was prepared in the same manner as in Example 1 , except that 987g ethylene glycol was used, instead of the isopropyl alcohol and water. Particle diameter and particle diameter distribution were observed for the prepared silver nanoparticle colloid solution by using a transmission electron microscope (TEM). The results are shown in FIG. 4. As shown in FIG. 4, the silver nanoparticle colloid solution had a very uniform particle diameter distribution and a small, uniform particle diameter of 6.02 ⁇ 0.8 nm on average. The formation of the silver nanopartides was identified by UVA/IS spectrometry. The result is shown in FIG. 5. As shown in FIG. 5, an absorption peak of the silver nanopartides appeared at 405 nm.
  • Example 6 Solid paste of silver-polyacrylamide nanocomposites prepared by using polyacrylamide as a stabilizer
  • the solid paste of the silver-polyacrylamide nanocomposites was observed by field emission scanning electron microscopy (FESEM). The result is shown in FIG. 6. As shown in FIG. 6, the silver-polyacrylamide nanocomposites had a particle diameter of 4-8 nm and a uniform particle shape.
  • Example 7 Solid paste of silver-poly(methyl methacrylate) nanocomposites prepared by using poly(methyl methacrylate) as a stabilizer
  • the dried silver-poly(methyl methacrylate) nanocomposites were dispersed in chloroform and subjected to TEM to observe the silver particle diameter and shape. The result is shown in FIG. 7. As is apparent from the particle distribution of FIG. 7, the silver particles had an average diameter of 6.55 ⁇ 1.27 nm and a uniform particle diameter and shape.
  • the formation of the silver-poly(methyl methacrylate) nanocomposites was identified by UV/VIS spectrometry. The result is shown in FIG. 8. As shown in FIG. 8, an absorption peak of the nanocomposites appeared at 405 nm.
  • silver nanopartides prepared by gamma-rays radiation as in the present invention, silver nanopartides prepared by using sodium dodecyl sulfate as a stabilizer were reported to have a smallest particle diameter of about 8 nm (Mater. Lett, 1993, 17, 314). In this article, the silver nanopartides had a considerably wide diameter distribution ranging from 5 nm to 37 nm, having an average particle diameter of 13 nm.
  • silver-poly(butyl acrylate-co- styrene) nanocomposites prepared by gamma-rays irradiation of a water-in-oil emulsion were reported to have an average particle diameter of 8.5 nm (Chem. Commun. 1998, 941 ). In this article, the particle diameter distribution was not apparent due to low magnification of the TEM photograph.
  • Example 1 the silver nanoparticle colloid solution was left for 10 months at room temperature and observed by TEM. The result is shown in FIG. 9. As shown in FIG. 9, the particle size was slightly increased, but the particle shape and the colloid state were stably maintained without precipitation.
  • Antibacterial activity was measured in a textile soaked with the silver nanoparticle colloid solution prepared in Example 2, according to the method of KS K 0693.
  • the silver nanoparticle colloid solution of Example 2 was diluted with water to 0.5%. 1.0%, and 1.5%, and textiles were immersed in each of the diluted sample solutions.
  • Staphylococcus aureus (ATCC 6538) strain was used for the antibacterial activity test.
  • Table 1 The results for each of the samples are shown in Table 1 below. As shown in Table 1 , the silver nanoparticle colloid solution according to the present invention showed a 99.9% antibacterial activity for all colloid dilutes. Table 1
  • a metal nanoparticle colloid solution and metal-polymer nancomposites having a uniform particle diameter and shape can be prepared at room temperature on a large scale.
  • Conventional methods using a reducing agent are ineffective to prepare uniform particles on a large scale.
  • the metal nanopartides according to the present invention have a more uniform, smaller particle diameter and shape, compared to metal nanopartides that have been reported to date, and thus a great surface area to volume ratio. Therefore, the metal nanoparticle colloid solution and metal-polymer nanocomposites according to the present invention have a high level of antibacterial activity even when only a trace is used.
  • the metal nanopartides according to the present invention have a nano-scaled particle size and are greatly adsorptive due to polymer surrounding individual particles, and thus shows an effect of shielding electromagnetic waves when applied to the field of thin film coating, in addition to antibacterial and sterilizing effects.

Abstract

A metal nanoparticle colloid solution, metal-polymer nanocomposites, and methods for preparing the same are provided. The metal nanoparticle colloid solution and the metal-polymer nanocomposites can be prepared with a variety of polymeric stabilizers and have uniform particle diameter and shape. The metal nanoparticle colloid solution and the metal-polymer nanocomposites have wide applications, for example, as an antibacterial agent, a sterilizer, a conductive adhesiv, conductive ink, or an electromagnetic wave shielder for an image display.

Description

COLLOID SOLUTION OF METAL NANOPARTICLES, METAL-POLYMER
NANOCOMPOSITES AND METHODS FOR PREPARATION THEREOF
Technical Field
The present invention relates to a colloid solution of metal nanopartides, metal-polymer nanocomposites, and methods for preparing the same, and more particularly, to a metal colloid solution and metal-polymer nanocomposites prepared using a variety of polymeric stabilizers and having a uniform particle diameter, and methods for preparing the same.
Background Art
Recently, a method for preparing a colloidal dispersion of silver nanopartides using gamma rays and appropriate stabilizers, such as polyvinyl alcohol and sodium dodecyl sulfate (SDS) was disclosed (Nature 1985, 317, 344;
Materials Letters 1993, 17, 314). The preparation method using gamma rays was reported to provide uniform diameter distribution of the silver nanopartides.
The metal nanopartides prepared by those methods were known to have a size of from about 8 nm to tens of nanometers from the outstanding research reports. However, the metal nanopartides are prepared by these methods not so desirable in terms of particle diameter and shape uniformity.
It is important to obtain pure silver particles having a uniform shape within a narrow distribution range of particle diameters for industrial applications. For example, ultrafine silver particles are essential materials in the electronics applications, for example, for conductive ink and paste and adhesive applied in the manufacture of a variety of electronic parts.
As described above, there is a need for a new method for preparing metal nanopartides having a uniform size and shape. In addition, good dispersion stability for preventing agglomeration of metal nanopartides in a dispersion medium is another consideration for industrial applications. For diversified industrial applications, miscibility with a variety of organic solvents, plasticizers, and resins is required to prepare a metal colloid solution in a non-aqueous medium.
A variety of methods for preparing a solid phase of polymer-metal nanocomposites were suggested (Polym. Composites 1996, 7, 125; J. Appl. Polym. Sci. 1995, 55, 371 ; J. Appl. Polym. Sci. 1996, 60, 323). These methods involve two steps: (1 ) polymerization of monomer particles and (2) reduction of metal ions in a polymerized medium. However, the separate polymerization and reduction processes cause non-uniform size distribution of the metal nanoparicles in the polymerized medium. To solve this problem, a method for preparing silver-polymer nanocomposites using gamma rays was developed [Chem. Commun. 1997, 1081 ). In the method, a silver salt is dissolved in water, mixed with acrylic amide as a water-soluble monomer, and subjected to gamma-rays irradiation to prepare the silver-polymer nanocomposites. Here, reduction of silver ions coincides with polymerization of the monomer, so that the metal nanopartides are comparatively uniformly dispersed in the polymerized medium.
However, this method also cannot be applied when using a variety of water-insoluble monomers. To overcome the limitation encountered when using an aqueous medium, the preparation of silver-polymer nanocomposites from a water-in-oil (W/O) emulsion was reported {Chem. Commun. 1998, 941 ), wherein toluene was used for the oil phase.
According to the method, since a variety of water-insoluble monomers can be applied, various kinds of metal-polymer nanopartides can be prepared. However, the use of excess toluene for the oily medium, up to about 5 times the amount of water, causes environmental concerns. In addition, a safe working environment is not guaranteed due to a high risk of explosion in its preparation.
Disclosure of the Invention
Accordingly, it is an object of the present invention to provide a colloid solution of metal nanopartides having a uniform particle characters and a method for preparing the same. It is another object of the present invention to provide metal-polymer nanocomposites having a uniform particle characters and a method for preparing the same.
In one aspect, the present invention provides a method for preparing a metal nanoparticle colloid solution, comprising: dissolving a metal salt and a water-soluble polymer in water, a non-aqueous solvent, or a solvent mixture of water and a non-aqueous solvent; purging a reaction container containing the solution with nitrogen or argon gas; and radiating radioactive rays onto the solution. In the preparation method, the water-soluble polymer includes polyvinyl pyrrolidone, a copolymer having vinyl pyrrolidone as a first polymerization unit, and a fatty acid-substituted or unsubstituted polyoxyethylene. The copolymer having vinyl pyrrolidone as the first polymerization unit includes (1 -vinyl pyrrolidone)-acrylic acid copolymer, (1 -vinyl pyrrolidone)-vinyl acetic acid copolymer, (1 -vinyl pyrrolidone)-styrene copolymer, and (1 -vinyl pyrrolidone)-vinyl alcohol copolymer. The fatty acid-substituted polyoxyethylene includes polyoxyethylene stearate and polyoxyethylene palmitate.
In another aspect, the present invention provides a metal nanoparticle colloid solution prepared by the preparation method described above. In another aspect, the present invention provides a method for preparing metal-polymer nanocomposites, comprising: dissolving a metal salt and a polymeric stabilizer in a solvent mixture of water and a non-aqueous solvent; purging a reaction container containing the solution with nitrogen or argon gas; and radiating radioactive rays onto the solution to obtain precipitates. In the preparation method of the metal-polymer nanocomposites, the polymeric stabilizer is at least one polymer selected from the group consisting of polyethylene, polyacrylonitrile, poly(methyl (meth)acrylate), polyurethane, polyacrylamide, and polyethylene glycol.
According to the present invention, the colloid solution of metal nanopartides and the metal-polymer nanocomposites have favorable stability, a uniform shape, and a small diameter within a narrow distribution range, so that the colloid solution of metal nanopartides and the metal-polymer nanocomposites have wide, effective applications, for example, as an antibacterial agent, a deodorizing agent, a conductive adhesive, conductive ink, and a electromagnetic wave shielder for an image display. The formation of the silver nanopartides will be described in greater detail.
Electrons are generated in a solvent by gamma-rays irradiation and reduce silver ions in a solution. Reduced silver atoms agglomerate to form a silver cluster and become larger. In this case, when an appropriate polymeric stabilizer is added, the agglomeration of the silver atoms can be prevented to result in nano-sized silver particles. Polymeric stabilizers stabilize the nanopartides in a colloid state through steric repulsion as well as prevent the silver clustering. The gamma- rays irradiation produces radicals as well as the electrons in the solvent. To remove the radicals, a scavenger, such as alcohol, is used. Oxygen present in the solution is removed by nitrogen or argon purging before the gamma-rays irradiation, to prevent side reactions by the oxygen.
To prepare the colloid solution of metal nanopartides according to the present invention, any metal salt capable of forming a general nanoparticle colloid solution can be used without limitations. However, in terms of conductivity and economical reasons, a salt of at least one metal selected from the group consisting of silver, copper, nickel, palladium, and platinum is preferable, with the silver salt being more preferable.
The metal salt is, for example, nitrate, sulfate, hydrochloride, perchlorate, or acetate. According to the present invention, a silver salt, such as AgNO3, AgCIO4, Ag2SO4, or CH3COOAg is more preferred. These silver salts are well dissolved in water and thus form an aqueous colloid of silver nanopartides.
In the preparation of the colloid solution of metal nanopartides according to the present invention, a water-soluble polymer, preferably, having a weight average molecular weight of 2,000-2,000,000, is used as a stabilizer for improving dispersion of the metal nanopartides. Suitable stabilizers include, for example, polyvinyl pyrrolidone, a copolymer including vinyl pyrrolidone as a first polymerization unit, and a fatty acid-substituted or unsubstituted polyoxyethylene. The copolymer including vinyl pyrrolidone as a first polymerization unit may further include an acrylic acid, styrene, vinyl acetate, or vinyl alcohol as a second polymerization unit. Examples of the copolymer include (1 -vinyl pyrrolidone)-acrylic acid copolymer and (1 -vinyl pyrrolidone)-vinyl acetic acid copolymer. The copolymer includes the first and second polymerization units in a weight ratio of 1 :99-99:1 , and preferably, 20:80-80:20. Preferably, the (1 -vinyl pyrrolidone)-acrylic acid copolymer includes a 1-vinyl pyrrolidone repeating unit and an acrylic acid repeating unit in a weight ratio of 75:25. Preferably, the (1 - vinyl pyrrolidone)-vinyl acetic acid copolymer includes a 1 -vinyl pyrrolidone repeating unit and a vinyl acetic acid repeating unit in a weight ratio of 57:43.
Regarding the fatty acid-substituted polyoxyethylene, which is a water- soluble polymer used as the stabilizer, the fatty acid is palmitic acid, oleic acid, linoleic acid, or stearic acid, with the stearic acid being more preferred.
Any solvent capable of dissolving the water-soluble polymer and metal salt therein can be used without limitations. For example, water, a non-aqueous solvent, or a mixture of these solvents can be used. Suitable non-aqueous solvents include alcoholic solvents, and typically, isopropyl alcohol, methanol, ethanol, ethylene glycol, or a mixture including at least two of the forgoing solvents. The non-aqueous solvents also act as a scavenger for removing radicals during gamma-rays radiation as well as act as a solvent for the metal salt and water-soluble polymer.
According to the present invention, the water-soluble polymer is used in an amount of 0.1-10 parts by weight based on 100 parts of the solvent by weight. If the water-soluble polymer is used in an amount of less than 0.1 parts by weight, it is difficult to provide the effect of the stabilizer. If the water-soluble polymer is used in an amount of greater than 10 parts by weight, the particle size undesirably increases.
According to the present invention, the metal salt is used in an amount of 0.01 -5 parts by weight based on 100 parts of the solvent by weight. If the metal salt is used in an amount of less than 0.01 parts by weight, it is difficult to provide the effect of the metal salt. If the metal salt is used in an amount of greater than 5 parts by weight, the particle size increases, or the particles slightly precipitate.
In the preparation of the colloid solution of metal nanopartides according to the present invention, a water-soluble polymer and a metal salt are dissolved in a solvent. A reaction container containing the solution is purged with nitrogen (N2) or argon (Ar) gas for 10 minutes to 10 hours and tightly sealed.
Next, the resultant product is irradiated with radioactive rays, and preferably, gamma rays, to a radiation dosage of 10-50 KGy. As a result, the colloid solution of metal nanopartides having a much smaller particle diameter of about 1 -5 nm than those prepared by conventional methods, within a narrow distribution of particle diameters, is obtained.
In the colloid solution of metal nanopartides prepared by the method according to the present invention, a post-process of diluting the source solution and ultrasonic treatment may be performed to decompose the metal nanopartides further into much smaller metal particles. The post-process supports the fact that the adsorption and steric repulsion mechanism of polymers enables the formation of the metal nanopartides and ensures dispersion stability. In particular, very small metal nanopartides are surrounded and adsorbed by the polymeric stabilizer to form clusters of the polymeric stabilizer-adsorbed metal nanopartides. Since the clusters of the metal nanopartides agglomerate, the metal nanopartides forming the colloid appear to be much larger after the radioactive-rays irradiation. Accordingly, when the colloid of the metal nanopartides is diluted and subjected to the ultrasonic treatment, the clusters of the metal nanopartides are decomposed further into much smaller metal particles. In the present invention, the much smaller particle diameter and narrower distribution of particle diameters, compared to when conventional methods are applied, are believed to be due to the use of the water-soluble polymeric stabilizer, such as polyvinyl pyrrolidone, (1 -vinyl pyrrolidone)-acrylic acid copolymer, polyoxyethylene stearate, and (1 -vinyl pyrrolidone)-vinyl acetic acid copolymer. The metal nanopartides having a very small diameter prepared in the present invention have a very large surface area-to-volume ratio, and thus they provide good antibacterial activity and conductivity even when only a trace is used. Therefore, the colloid solution of the metal nanopartides according to the present invention can be used as an antibacterial agent, a sterilizer, a deodorizing agent, an electromagnetic wave shielder, and conductive adhesive and ink. For diversified industrial applications, the metal nanopartides according to the present invention need to be miscible with a variety of organic solvents, plasticizers, and resins to prepare a non-aqueous colloid solution of the metal nanopartides. In this case, a non-aqueous solvent, which does not contain water, i.e., an alcoholic solvent, can be used alone as the solvent. The alcoholic solvent acts as a scavenger as well as the solvent, and thus is favorable for economical reasons. Among the above-listed kinds of alcoholic solvents, the ethylene glycol is more preferred as the solvent and scavenger.
For the miscibility with a variety of resins, plasticizers, and solvents, instead of the ethylene glycol used as a non-aqueous alcohol, isopropyl alcohol can be used as the solvent and scavenger. In this case, the metal nanopartides are miscible with alcohol-soluble resins, alcohol-soluble plasticizers, such as dioctyl phthalate (DOP), and organic solvents.
In another aspect, the present invention provides a solid paste of metal- polymer nanocomposites. The solid paste of the metal-polymer nanocomposites is prepared by a similar method as that applied to prepare the colloid solution of the metal nanopartides as described above, except that polyacrylamide or polyethylene glycol is used as a polymeric stabilizer. The polyacrylamide and polyethylene glycol are water-soluble polymers and precipitate the metal-polymer nanocomposites when dissolved in a solvent together with a metal salt, followed by radioactive-rays irradiation.
In the preparation of the solid paste of the metal-polymer nanocomposites, when a water-insoluble stabilizer, such as poly(methyl (meth)acrylate), polyacrylonitrile, or polyurethane, is used, a surfactant, for example, polyoxyethylene sorbitan mono-oleate, which is commercially available in the trade name of Span-80, Tween-81, or Tween-80, is added. In this case, it is preferable to initially form an emulsion with the addition of the surfactant. The surfactant is added little by little until the emulsion is formed.
As in the preparation of the colloid solution of the metal nanopartides, in the preparation of the solid paste of the metal-polymer nanocomposites, it is preferable to use a mixture of water and a non-aqueous solvent as the solvent, instead of using water or the non-aqueous solvent alone.
In the preparation of the solid paste of the metal-polymer nanocomposites, it is preferable that the metal salt is added in an amount of 0.01-5 parts by weight based on 100 parts of the solvent by weight. If the metal salt is added in an amount of less than 0.01 parts by weight, the effect of adding the metal salt is negligible. If the metal salt is added in an amount of greater than 5 parts by weight, the particle size increases.
In the preparation of the metal-polymer nanocomposites according to the present invention, the polymeric stabilizer is added in an amount of about 0.1-10 parts by weight based on 100 parts of the solvent by weight. If the amount of the polymeric stabilizer is less than 0.1 parts by weight, the effect of adding the polymeric stabilizer is negligible. If the amount of the polymeric stabilizer exceeds 10 parts by weight, the particle size increases, and the addition of the polymeric stabilizer such an amount is uneconomical.
In the preparation of the metal-polymer nanocomposites according to the present invention, the polymeric stabilizer and metal salt are dissolved in a solvent, and a reaction container containing the solution is purged with nitrogen or argon gas for 30 minutes to 10 hours and completely tightened. Next, the solution is irradiated with gamma rays of a radiation dosage of about 10-50 KGy, followed by solvent removal and vacuum drying to attain the metal-polymer nanocomposites according to the present invention.
The metal-polymer nanocomposites according to the present invention have a uniform particle diameter at room temperature. Since greatly diversified kinds of polymers can be applied to the metal-polymer nanocomposites, unlike conventional methods using monomers to prepare metal-polymer nancomposites, it is easy to control the molecular weight. In addition, due to a great surface area-to-volume ratio of the metal-polymer nanocomposites, favorable effects, for example, in terms of antibacterial activity and conductivity, are provided with a trace of the metal-polymer nanocomposites. The metal-polymer nanocomposites can be effectively used as an antibacterial agent, a sterilizer, a deodorizing agent, a conductive adhesive, and conductive ink.
Brief Description of the Drawings
FIG. 1 shows a transmission electron microscopic (TEM) photograph and particle diameter distribution of silver nanopartides prepared in Example 1 according to the present invention; FIG. 2 shows the UV/VIS absorption spectrum of the silver nanopartides prepared in Example 1 according to the present invention at 405 nm;
FIG. 3 is a TEM photograph after dilution with water and ultrasonic treatment of the silver nanopartides prepared in Example 2 according to the present invention; FIG. 4 shows a TEM photograph and particle diameter distribution of silver nanopartides prepared in Example 5 according to the present invention;
FIG. 5 shows the UVA IS absorption spectrum of the silver nanopartides prepared in Example 5 according to the present invention at 405 nm;
FIG. 6 is a field emission scanning electron microscopic (FESEM) photograph of a paste of silver-polymer nanocomposites prepared in Example 6 according to the present invention;
FIG. 7 shows a TEM photograph and particle diameter distribution of a dispersion of silver-polymer nanocomposites prepared in Example 7 according to the present invention in chloroform; FIG. 8 shows the UVA/IS absorption spectrum of the silver-polymer nanocomposites prepared in Example 7 according to the present invention at 405 nm;
FIG. 9 is a TEM photograph of a silver nanoparticle colloid solution prepared in Example 1 according to the present invention after being left for 10 months at room temperature;
FIG. 10 shows the infrared (IR) spectrum of a silver nanoparticle colloid solution prepared in Example 2 according to the present invention;
FIG. 1 1 shows the surface enhanced Raman scattering spectrum of the silver nanopartides prepared in Example 2 according to the present invention with respect to pH of a 1 .0X10"5 M thionin solution; and FIG. 12 shows the result of an antibacterial activity test of a textile soaked with the silver nanoparticle colloid solution prepared in Example 2 according to the present invention; and
FIG. 13 shows the result of an antibacterial activity test of a textile soaked with a solution containing no silver nanopartides according to the present invention.
Best mode for carrying out the Invention
The present invention will be described in greater detail with reference to the following examples. The following examples are for illustrative purposes and are not intended to limit the scope of the invention.
Example 1 : Silver nanoparticle colloid solution prepared by using (1- vinyl pyrrolidone)-acrylic acid copolymer as a stabilizer
1.863 g AgNO3, 395 g isopropyl alcohol, and 1 1.137g (1 -vinyl pyrrolidone)-acrylic acid copolymer in a weight ratio of 75:25, having a molecular weight (MW) of 96,000, were thoroughly dissolved in 592 g water. A reaction container containing the solution was purged with nitrogen gas for 1 hour and completely tightened, followed by gamma-rays radiation of a dosage of 30 KGy, thereby to prepare a yellow silver nanoparticle colloid solution. Particle diameter distribution and particle shape were observed for the prepared silver nanoparticle colloid solution by using a transmission electron microscope (TEM). The results are shown in FIG. 1.
As shown in FIG. 1 , the silver nanoparticle colloid solution had a very uniform particle diameter distribution and a uniform particle shape. Most of the particles had a diameter of 3.0±0.9 nm on average, which is the smallest among silver nanopartides prepared by gamma-rays irradiation, which have been reported to date.
The formation of the silver nanopartides was identified by UVA IS spectrometry. The result is shown in FIG. 2. As shown in FIG. 2, an absorption peak of the silver nanopartides appeared at 405 nm.
Example 2: Silver nanoparticle colloid solution prepared by using polyvinyl pyrrolidone as a stabilizer
A silver nanoparticle colloid solution was prepared in the same manner as in Example 1 , except that 11.137 g polyvinyl pyrrolidone having a MW of 55,000 was used as the stabilizer, instead of the (1-vinyl pyrrolidone)-acrylic acid copolymer. The resultant silver nanoparticle colloid solution had a minimum particle diameter of 6.6±1.1 nm and an average particle diameter of about 10-12 nm.
Example 3: Silver nanoparticle colloid solution prepared by using polyoxyethylene stearate as a stabilizer
A silver nanoparticle colloid solution was prepared in the same manner as in Example 1 , except that 11.137 g polyoxyethylene stearate having a MW of ~
2,000 was used as the stabilizer, instead of the (1-vinyl pyrrol idone)-acry lie acid copolymer. The resultant silver nanoparticle colloid solution had an average particle diameter of 7.5±1.8 nm.
Example 4: Particle diameter of silver nanoparticle colloid solution prepared by using polyvinyl pyrrolidone as a stabilizer after dilution and ultrasonic treatment
The silver nanoparticle colloid solution (having an average particle diameter of 12.1 ±1.6 nm) prepared in Example 2 was diluted 20 folds with water and subjected to ultrasonic treatment for 3 hours and particle diameter measurement. The result is shown in FIG. 3. As shown in FIG. 3, after the dilution and the ultrasonic treatment, particles of a diameter of ~2 nm and - 4 nm appeared. This result supports that the particle diameter can be further reduced by dilution and ultrasonic treatment. Apparently, a number of very small unit silver nanopartides on which polyvinyl pyrrolidone is adsorbed form the silver nanoparticle colloid solution.
Example 5: Silver nanoparticle colloid solution prepared by using ethylene glycol as a solvent and polyvinyl pyrrolidone as a stabilizer
A non-aqueous, yellow silver nanoparticle colloid solution was prepared in the same manner as in Example 1 , except that 987g ethylene glycol was used, instead of the isopropyl alcohol and water. Particle diameter and particle diameter distribution were observed for the prepared silver nanoparticle colloid solution by using a transmission electron microscope (TEM). The results are shown in FIG. 4. As shown in FIG. 4, the silver nanoparticle colloid solution had a very uniform particle diameter distribution and a small, uniform particle diameter of 6.02±0.8 nm on average. The formation of the silver nanopartides was identified by UVA/IS spectrometry. The result is shown in FIG. 5. As shown in FIG. 5, an absorption peak of the silver nanopartides appeared at 405 nm.
Example 6: Solid paste of silver-polyacrylamide nanocomposites prepared by using polyacrylamide as a stabilizer
592 g water, 1.863 g AgNO3, and 395 g isopropyl alcohol were mixed together, and 11.137 g polyacrylamide was added to the mixture and vigorously stirred. A reaction container containing the solution was purged with nitrogen gas for 1 hour and completely tightened, followed by gamma-rays radiation of a dosage of 30 KGy, thereby to attain a paste of precipitates. The solvent was removed from the paste, followed by vacuum drying. As a result, silver- polyacrylamide nanocomposites were obtained. The dried silver- polyacrylamide nanocomposites were dispersed in water.
The solid paste of the silver-polyacrylamide nanocomposites was observed by field emission scanning electron microscopy (FESEM). The result is shown in FIG. 6. As shown in FIG. 6, the silver-polyacrylamide nanocomposites had a particle diameter of 4-8 nm and a uniform particle shape.
Example 7: Solid paste of silver-poly(methyl methacrylate) nanocomposites prepared by using poly(methyl methacrylate) as a stabilizer
592 g water, 1.863 g AgNO3, and 395 g isopropyl alcohol were mixed together, and 1 1.137 g poly(methyl methacrylate) was added to the mixture and vigorously stirred. Twin-81 as a surfactant was added little by little to the mixture with stirring until a white emulsion is formed. A reaction container containing the emulsion was purged with nitrogen gas for 1 hour and completely tightened, followed by gamma-rays radiation of a dosage of 30 KGy, thereby to attain a solid paste of precipitates. The solvent was removed from the paste, followed by vacuum drying. As a result, silver-poly(methyl methacrylate) nanocomposites were obtained. The dried silver-poly(methyl methacrylate) nanocomposites were dispersed in chloroform and subjected to TEM to observe the silver particle diameter and shape. The result is shown in FIG. 7. As is apparent from the particle distribution of FIG. 7, the silver particles had an average diameter of 6.55±1.27 nm and a uniform particle diameter and shape.
The formation of the silver-poly(methyl methacrylate) nanocomposites was identified by UV/VIS spectrometry. The result is shown in FIG. 8. As shown in FIG. 8, an absorption peak of the nanocomposites appeared at 405 nm.
Comparative Example
Among conventional silver nanopartides prepared by gamma-rays radiation as in the present invention, silver nanopartides prepared by using sodium dodecyl sulfate as a stabilizer were reported to have a smallest particle diameter of about 8 nm (Mater. Lett, 1993, 17, 314). In this article, the silver nanopartides had a considerably wide diameter distribution ranging from 5 nm to 37 nm, having an average particle diameter of 13 nm. Regarding silver-polymer nanocomposites, silver-poly(butyl acrylate-co- styrene) nanocomposites prepared by gamma-rays irradiation of a water-in-oil emulsion were reported to have an average particle diameter of 8.5 nm (Chem. Commun. 1998, 941 ). In this article, the particle diameter distribution was not apparent due to low magnification of the TEM photograph.
Experimental Example 1 : Stability of silver nanoparticle colloid solution
To determine stability of the silver nanoparticle colloid solution prepared in
Example 1 , the silver nanoparticle colloid solution was left for 10 months at room temperature and observed by TEM. The result is shown in FIG. 9. As shown in FIG. 9, the particle size was slightly increased, but the particle shape and the colloid state were stably maintained without precipitation.
Experimental Example 2: Interaction between silver and polyvinyl pyrrolidone An Infrared (IR) spectrum was measured for the silver nanoparticle colloid solution prepared in Example 2 to determine whether the silver and the polyvinyl pyrrolidone interact. The result is shown in FIG. 10. In FIG. 10, (a) is the IR spectrum for polyvinyl pyrrolidone alone, and (b) is the IR spectrum for the silver nanopartides prepared in Example 2 by using the polyvinyl pyrrolidone as a stabilizer. It is evident from the results of FIG. 10 that the silver and the polyvinyl pyrrolidone interact in the colloid solution.
Experimental Example 3: Surface enhanced Raman scattering measurement Surface enhanced Raman scattering occurs in silver nanoparticle colloid solutions. The Raman scattering spectrum of the silver nanopartides prepared in Example 2 was measured with respect to pH of a 1 .0X10"5 M thionin solution. The results are shown in FIG. 11. The results of FIG. 11 show that the silver nanopartides can be applied to surface enhanced Raman spectroscopy for assaying a trace of organic substances, including bioorganic substances.
Figure imgf000017_0001
Thionin
Experimental Example 4: Antibacterial activity test in textile
Antibacterial activity was measured in a textile soaked with the silver nanoparticle colloid solution prepared in Example 2, according to the method of KS K 0693. The silver nanoparticle colloid solution of Example 2 was diluted with water to 0.5%. 1.0%, and 1.5%, and textiles were immersed in each of the diluted sample solutions. Staphylococcus aureus (ATCC 6538) strain was used for the antibacterial activity test. The results for each of the samples are shown in Table 1 below. As shown in Table 1 , the silver nanoparticle colloid solution according to the present invention showed a 99.9% antibacterial activity for all colloid dilutes. Table 1
Figure imgf000017_0002
In samples containing no silver nanoparticle colloid solution according to the present invention, white spots by the Staphylococcus aureus (ATCC 6538) strain were observed, as shown in FIG. 13. In contrast, in the samples containing the silver nanoparticle colloid solution according to the present invention, the Staphylococcus aureus (ATCC 6538) strain was hardly observed, as shown in FIG. 12.
Industrial Applicability
According to the present invention, a metal nanoparticle colloid solution and metal-polymer nancomposites having a uniform particle diameter and shape can be prepared at room temperature on a large scale. Conventional methods using a reducing agent are ineffective to prepare uniform particles on a large scale. As is apparent from the observation by TEM, the metal nanopartides according to the present invention have a more uniform, smaller particle diameter and shape, compared to metal nanopartides that have been reported to date, and thus a great surface area to volume ratio. Therefore, the metal nanoparticle colloid solution and metal-polymer nanocomposites according to the present invention have a high level of antibacterial activity even when only a trace is used. The metal nanopartides according to the present invention have a nano-scaled particle size and are greatly adsorptive due to polymer surrounding individual particles, and thus shows an effect of shielding electromagnetic waves when applied to the field of thin film coating, in addition to antibacterial and sterilizing effects.

Claims

What is claimed is:
1. A method for preparing a metal nanoparticle colloid solution, comprising: dissolving a metal salt and a water-soluble polymer in water, a non- aqueous solvent, or a solvent mixture of water and a non-aqueous solvent; purging a reaction container containing the solution with nitrogen or argon gas; and radiating radioactive rays onto the solution.
2. The method of claim 1 , further comprising dilution and ultrasonic treatment after radiating the radioactive rays onto the solution.
3. - The method of claim 1 , wherein the water-soluble polymer includes polyvinyl pyrrolidone, a copolymer having vinyl pyrrolidone as a first polymerization unit, and a fatty acid-substituted or unsubstituted polyoxyethylene.
4. The method of claim 1 , wherein the copolymer having vinyl pyrrolidone as the first polymerization unit includes (1-vinyl pyrrolidone)-acrylic acid copolymer, (1-vinyl pyrrolidone)-vinyl acetic acid copolymer, (1-vinyl pyrrolidone)-styrene copolymer, and (1-vinyl pyrrolidone)-vinyl alcohol copolymer.
5. The method of claim 3, wherein the fatty acid-substituted polyoxyethylene includes polyoxyethylene stearate and polyoxyethylene palmitate.
6. The method of claim 1 , wherein the metal salt is a salt of at least one metal selected from the group consisting of silver, copper, nickel, palladium, and platinum.
7. The method of claim 6, wherein the metal salt is a silver salt.
8. The method of claim 7, wherein the silver salt includes silver nitrate, silver perchlorate, silver sulfate, and silver acetate.
9. The method of claim 1 , wherein the non-aqueous solvent is an alcoholic solvent.
10. The method of claim 9, wherein the alcoholic solvent is at least one selected from the group consisting of isopropyl alcohol, methanol, ethanol, and ethylene glycol.
11. A metal nanoparticle colloid solution prepared by the method according to any one of claims 1 through 10.
12. The metal nanoparticle colloid solution of claim 11 for use as an antibacterial agent, a sterilizer, a conductive adhesive, conductive ink, or an electromagnetic wave shielder for an image display.
13. A method for preparing metal-polymer nanocomposites, comprising: dissolving a metal salt and a polymeric stabilizer in a solvent mixture of water and a non-aqueous solvent; purging a reaction container containing the solution with nitrogen or argon gas; and radiating radioactive rays onto the solution to obtain precipitates.
14. The method of claim 13, further comprising dilution and ultrasonic treatment after the formation of the precipitates.
15. The method of claim 13, wherein the polymeric stabilizer is at least one polymer selected from the group consisting of polyethylene, polyacrylonitrile, poly(methyl (meth)acrylate), polyurethane, polyacrylamide, and polyethylene glycol.
16. The method of claim 13, wherein a surfactant is added to the solvent mixture of water and the non-aqueous solvent together with the metal salt and the polymeric stabilizer to form an emulsion.
17. The method of claim 16, wherein the surfactant is polyoxyethylene sorbitan mono-oleate.
18. The method of claim 13, wherein the metal salt is a salt of at least one metal selected from the group consisting of silver, copper, nickel, palladium, and platinum.
19. The method of claim 18, wherein the metal salt is a silver salt.
20. The method of claim 19, wherein the silver salt includes silver nitrate, silver perchlorate, silver sulfate, and silver acetate.
21. The method of claim 13, wherein the non-aqueous solvent is an alcoholic solvent.
22. The method of claim 21 , wherein the alcoholic solvent is at least one selected from the group consisting of isopropyl alcohol, methanol, ethanol, and ethylene glycol.
23. Metal-polymer nanocomposites prepared by the method according to any one of claims 13 through 22.
24. The metal-polymer nanocomposites of claim 23 for use as an antibacterial agent, a sterilizer, a conductive adhesive, conductive ink, or an electromagnetic wave shielder for an image display.
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Publication number Priority date Publication date Assignee Title
FR2850661A1 (en) * 2003-02-04 2004-08-06 Atofina A method of preparing a composite material used for injection molded, extruded or press formed articles consisting of a matrix of a thermoplastic polymer, especially poly(methyl methacrylate) containing metallic nanoparticles
WO2004081111A1 (en) * 2003-03-11 2004-09-23 Dow Global Technologies Inc. High dielectric constant composites
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US7618560B2 (en) * 2004-10-21 2009-11-17 Pharma Diagnostics N.V. Stable metal/conductive polymer composite colloids and methods for making and using the same
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US7786049B2 (en) * 2003-04-10 2010-08-31 Halliburton Energy Services, Inc. Drilling fluids with improved shale inhibition and methods of drilling in subterranean formations
US7833945B2 (en) 2005-07-15 2010-11-16 Halliburton Energy Services Inc. Treatment fluids with improved shale inhibition and methods of use in subterranean operations
US7905287B2 (en) 2005-04-19 2011-03-15 Halliburton Energy Services Inc. Methods of using a polymeric precipitate to reduce the loss of fluid to a subterranean formation
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US8101680B1 (en) 2010-10-12 2012-01-24 Sabic Innovative Plastics Ip B.V. Methods of preparing polymer nanocomposites
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US20130122321A1 (en) * 2004-07-30 2013-05-16 Kimberly-Clark Worldwide, Inc. Methods and Compositions for Metal Nanoparticle Treated Surfaces
US8455404B2 (en) 2005-07-15 2013-06-04 Halliburton Energy Services, Inc. Treatment fluids with improved shale inhibition and methods of use in subterranean operations
US9109270B2 (en) 2006-02-01 2015-08-18 University Of Washington Methods for production of silver nanostructures
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US10384936B2 (en) 2002-12-09 2019-08-20 University Of Washington Methods of nanostructure formation and shape selection

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US6605751B1 (en) * 1997-11-14 2003-08-12 Acrymed Silver-containing compositions, devices and methods for making
EP1244476B1 (en) 1999-12-30 2006-05-31 Acrymed Methods and compositions for improved delivery devices
CN1678277B (en) 2002-07-29 2010-05-05 艾克里麦德公司 Methods and compositions for treatment of dermal conditions
KR100656169B1 (en) * 2002-12-23 2006-12-12 삼성전자주식회사 Method for Producing A Stuff Having Bacillus Resistance on The Surface Thereof by Nano Size Metal
EP1613787A4 (en) * 2003-04-02 2007-09-26 Univ Northwestern Methods of controlling nanoparticle growth
MXPA06012528A (en) 2004-04-28 2007-08-02 Headwaters Heavy Oil Llc Ebullated bed hydroprocessing methods and systems and methods of upgrading an existing ebullated bed system.
US10941353B2 (en) * 2004-04-28 2021-03-09 Hydrocarbon Technology & Innovation, Llc Methods and mixing systems for introducing catalyst precursor into heavy oil feedstock
EP1778010B1 (en) 2004-07-30 2014-06-04 Kimberly-Clark Worldwide, Inc. Antimicrobial silver compositions
US10251392B2 (en) * 2004-07-30 2019-04-09 Avent, Inc. Antimicrobial devices and compositions
EP1809264B1 (en) * 2004-09-20 2016-04-13 Avent, Inc. Antimicrobial amorphous compositions
EP1853673B1 (en) * 2005-01-10 2010-03-24 Yissum Research Development Company Of The Hebrew University Of Jerusalem Aqueous-based dispersions of metal nanoparticles
ATE434024T1 (en) 2005-02-28 2009-07-15 Samsung Sdi Germany Gmbh METALLIC INK AND SUBSTRATE FOR A DISPLAY AND THE PRODUCTION METHOD THEREOF
US7599828B2 (en) * 2005-03-01 2009-10-06 Microsoft Corporation Grammatically correct contraction spelling suggestions for french
KR100653251B1 (en) * 2005-03-18 2006-12-01 삼성전기주식회사 Mathod for Manufacturing Wiring Board Using Ag-Pd Alloy Nanoparticles
JP4207161B2 (en) * 2005-04-20 2009-01-14 セイコーエプソン株式会社 Microencapsulated metal particles and method for producing the same, aqueous dispersion, and ink jet ink
US20060258875A1 (en) * 2005-05-10 2006-11-16 Clementine Reyes Methods for manufacturing supported nanocatalysts and methods for using supported nanocatalysts
US7547347B2 (en) * 2005-05-13 2009-06-16 University Of Rochester Synthesis of nano-materials in ionic liquids
KR100620615B1 (en) * 2005-05-23 2006-09-06 한국생명공학연구원 Multicolor-encoded colloidal particles coated with metal nanoparticles mixture having colors in the visible region and preparing method thereof
US7892299B2 (en) 2005-09-15 2011-02-22 Headwaters Technology Innovation, Llc Methods of manufacturing fuel cell electrodes incorporating highly dispersed nanoparticle catalysts
DK1943016T3 (en) * 2005-10-14 2012-10-01 Vive Crop Prot Inc Composite nanoparticles, nanoparticles and processes for their preparation
KR100730414B1 (en) * 2005-12-29 2007-06-19 제일모직주식회사 Antibacterial and antistatic multifunctional hard coating composition, its coating method and hard coating transparent sheet using it
US7842635B2 (en) 2006-01-06 2010-11-30 Headwaters Technology Innovation, Llc Hydrocarbon-soluble, bimetallic catalyst precursors and methods for making same
US7670984B2 (en) 2006-01-06 2010-03-02 Headwaters Technology Innovation, Llc Hydrocarbon-soluble molybdenum catalyst precursors and methods for making same
US8097229B2 (en) 2006-01-17 2012-01-17 Headwaters Technology Innovation, Llc Methods for manufacturing functionalized inorganic oxides and polymers incorporating same
KR100754326B1 (en) * 2006-02-15 2007-09-03 삼성전기주식회사 Manufacturing Method of Metal Nanoparticle
US7514476B2 (en) * 2006-03-17 2009-04-07 Headwaters Technology Innovation, Llc Stable concentrated metal colloids and methods of making same
US7718710B2 (en) * 2006-03-17 2010-05-18 Headwaters Technology Innovation, Llc Stable concentrated metal colloids and methods of making same
US7632774B2 (en) * 2006-03-30 2009-12-15 Headwaters Technology Innovation, Llc Method for manufacturing supported nanocatalysts having an acid-functionalized support
CN100503744C (en) * 2006-04-07 2009-06-24 中国科学院上海应用物理研究所 Method for preparing nano silver grain, and prepared nano silver grain
EP2015722B1 (en) * 2006-04-28 2016-11-16 Avent, Inc. Antimicrobial site dressings
KR100790948B1 (en) 2006-05-25 2008-01-03 삼성전기주식회사 Method for preparing metal nanoparticles and metal nanoparticles prepared using the same
KR100836659B1 (en) 2006-07-06 2008-06-10 삼성전기주식회사 Method for manufacturing metal nanoparticles
DE102007037079A1 (en) * 2006-10-25 2008-04-30 Bayer Materialscience Ag Formulation for use in generation of electrical conductive or optical coatings, comprises silver metal particles, solvent, dispersion agent and additives
US10231344B2 (en) 2007-05-18 2019-03-12 Applied Nanotech Holdings, Inc. Metallic ink
US8404160B2 (en) 2007-05-18 2013-03-26 Applied Nanotech Holdings, Inc. Metallic ink
US8034232B2 (en) 2007-10-31 2011-10-11 Headwaters Technology Innovation, Llc Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker
US7951745B2 (en) * 2008-01-03 2011-05-31 Wilmington Trust Fsb Catalyst for hydrocracking hydrocarbons containing polynuclear aromatic compounds
US8142645B2 (en) 2008-01-03 2012-03-27 Headwaters Technology Innovation, Llc Process for increasing the mono-aromatic content of polynuclear-aromatic-containing feedstocks
US8506849B2 (en) * 2008-03-05 2013-08-13 Applied Nanotech Holdings, Inc. Additives and modifiers for solvent- and water-based metallic conductive inks
US9427297B2 (en) * 2008-05-09 2016-08-30 Boston Scientific Scimed, Inc. Surgical meshes with radiopaque coatings
US9333063B2 (en) * 2008-05-09 2016-05-10 Boston Scientific Scimed, Inc. Antimicrobial medical devices
US20090286383A1 (en) * 2008-05-15 2009-11-19 Applied Nanotech Holdings, Inc. Treatment of whiskers
US9730333B2 (en) 2008-05-15 2017-08-08 Applied Nanotech Holdings, Inc. Photo-curing process for metallic inks
US8372908B2 (en) * 2008-05-16 2013-02-12 The Regents Of The University Of California Method of fabrication of nanoparticulate composites using monomer stabilization
US8097149B2 (en) * 2008-06-17 2012-01-17 Headwaters Technology Innovation, Llc Catalyst and method for hydrodesulfurization of hydrocarbons
KR101021960B1 (en) * 2008-09-08 2011-03-16 한국생명공학연구원 Gold Nanoparticles of Various Sizes and Shapes Coated with Polymer and Method for Preparing Thereof
KR101066545B1 (en) * 2008-09-08 2011-09-22 한국생명공학연구원 Metal Nanoparticles of Various Sizes and Shapes Having Functional Groups and Method for Preparing the Same
JP5532199B2 (en) * 2008-11-07 2014-06-25 株式会社豊田中央研究所 Colloidal solution of metal compound and method for producing the same
CA2743774C (en) * 2008-11-24 2017-11-28 Kimberly-Clark Worldwide, Inc. Antimicrobial laminate constructs
WO2010077985A1 (en) * 2008-12-16 2010-07-08 Board Of Regents, The University Of Texas System In situ formation of nanoparticles in resins
KR101027239B1 (en) 2009-01-15 2011-04-06 부경대학교 산학협력단 Composition for EMI SHIELDING OR ABSOTPTION
US20090202444A1 (en) * 2009-01-21 2009-08-13 Karel Newman Treatment and prevention of systemic Xylella fastidiosa infections of plants using antimicrobial metal compositions
US20100183739A1 (en) * 2009-01-21 2010-07-22 Karel Newman Treatment and prevention of systemic bacterial infections in plants using antimicrobial metal compositions
WO2010085945A1 (en) * 2009-01-30 2010-08-05 Philipps-Universität Marburg Method for producing metal-containing nanoparticles enveloped with polymers and particles that can be obtained therefrom
DE102009006942A1 (en) * 2009-01-30 2010-08-05 Philipps-Universität Marburg Producing polymer coated metal containing nanoparticles, comprises forming anionic macroinitiators solution in solvent, adding polymerizable monomer, polymerizing, adding sulfide, metal salt and homogeneous reducing agent and precipitating
CN101497135B (en) * 2009-03-12 2010-09-22 宁波大学 Method for preparing spherical silver nano granule
KR101735710B1 (en) 2009-03-27 2017-05-15 어플라이드 나노테크 홀딩스, 인크. Buffer layer to enhance photo and/or laser sintering
US8029700B2 (en) * 2009-04-30 2011-10-04 Chung-Shan Institute of Science and Technology Armaments Bureau, Ministry of National Defense Compound of silver nanowire with polymer and compound of metal nanostructure with polymer
JP5679696B2 (en) * 2009-05-22 2015-03-04 日東電工株式会社 UV-curable adhesive composition, adhesive layer, adhesive sheet and method for producing the same
US8422197B2 (en) 2009-07-15 2013-04-16 Applied Nanotech Holdings, Inc. Applying optical energy to nanoparticles to produce a specified nanostructure
BR112012010962A2 (en) * 2009-11-09 2020-09-08 Carnegie Mellon University metallic paint compositions, conductor patterns, methods and devices.
JP5514561B2 (en) * 2010-01-14 2014-06-04 株式会社豊田中央研究所 Noble metal colloid solution and method for producing the same
KR101329081B1 (en) * 2011-04-12 2013-11-14 한국수력원자력 주식회사 Method for manufacturing metal nanoparticle of core-shell structure having excellent oxidation stability
RU2474471C2 (en) * 2011-05-12 2013-02-10 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) Colloidal solution of silver nanoparticles, metal-polymer nanocomposite film material, methods for production thereof, bactericidal composition based on colloidal solution and bactericidal film made from metal-polymer material
US8454737B2 (en) 2011-09-12 2013-06-04 Hewlett-Packard Development Company, L.P. Ink composition
US9790440B2 (en) 2011-09-23 2017-10-17 Headwaters Technology Innovation Group, Inc. Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker
US20130156971A1 (en) 2011-10-28 2013-06-20 Liquid X Printed Metals, Inc. Transparent conductive- and ito-replacement materials and structures
CN102371358A (en) * 2011-11-18 2012-03-14 复旦大学 Aqueous-phase preparation method for re-dispersible nano-copper particles
TWI696668B (en) 2012-02-27 2020-06-21 美商黎可德X印製金屬公司 Self-reducing metal complex inks soluble in polar protic solvents and improved curing methods
CN102601381B (en) * 2012-03-11 2014-01-29 郭雨 Preparation method of copper nano powder
US9403153B2 (en) 2012-03-26 2016-08-02 Headwaters Heavy Oil, Llc Highly stable hydrocarbon-soluble molybdenum catalyst precursors and methods for making same
US9598776B2 (en) 2012-07-09 2017-03-21 Pen Inc. Photosintering of micron-sized copper particles
US9644157B2 (en) 2012-07-30 2017-05-09 Headwaters Heavy Oil, Llc Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking
US9328253B2 (en) * 2013-01-22 2016-05-03 Eastman Kodak Company Method of making electrically conductive micro-wires
EP3110407B1 (en) * 2014-02-26 2021-12-01 The Trustees of Princeton University Metal-polymer composite nanoparticles
CN104588645B (en) * 2015-02-04 2016-08-24 山西大学 A kind of ag nano-cluster compound with antibacterial activity and preparation method thereof
US9557648B2 (en) 2015-03-18 2017-01-31 Eastman Kodak Company Articles with silver-containing polymeric complexes
US10745570B2 (en) 2015-05-18 2020-08-18 Eastman Rodack Company Copper-containing articles
US9963614B2 (en) 2015-05-18 2018-05-08 Eastman Kodak Company Copper-containing articles and methods for providing same
RU2610197C2 (en) * 2015-07-29 2017-02-08 Федеральное Государственное Унитарное Предприятие "Государственный Ордена Трудового Красного Знамени Научно-Исследовательский Институт Химических Реактивов И Особо Чистых Химических Веществ" Colloidal solution of nanosilver in ethylene-glycol and method of its production
CN105127441B (en) * 2015-08-18 2017-11-10 昆明理工大学 A kind of preparation method of platinum nano microcrystalline dispersion
US10040957B2 (en) 2015-09-17 2018-08-07 Eastman Kodak Company Ink jettable, UV-curable compositions
US9676950B2 (en) 2015-09-17 2017-06-13 Eastman Kodak Company Articles prepared using ink jettable, UV-curable compositions
US9731513B2 (en) 2015-09-17 2017-08-15 Eastman Kodak Company Methods for using ink jettable, UV-curable compositions
US11414608B2 (en) 2015-09-22 2022-08-16 Hydrocarbon Technology & Innovation, Llc Upgraded ebullated bed reactor used with opportunity feedstocks
US11414607B2 (en) 2015-09-22 2022-08-16 Hydrocarbon Technology & Innovation, Llc Upgraded ebullated bed reactor with increased production rate of converted products
CN105353127B (en) * 2015-11-16 2017-10-20 暨赛再生医学科技有限公司 A kind of composition that can detect kinds of tumors and its application
US11421164B2 (en) 2016-06-08 2022-08-23 Hydrocarbon Technology & Innovation, Llc Dual catalyst system for ebullated bed upgrading to produce improved quality vacuum residue product
US10468675B2 (en) * 2016-08-30 2019-11-05 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Method of making a concentrated metal salt solution in a non-aqueous solvent system
JP7336831B2 (en) 2017-03-02 2023-09-01 ハイドロカーボン テクノロジー アンド イノベーション、エルエルシー Improved ebullated bed reactor with low fouling deposits
US11732203B2 (en) 2017-03-02 2023-08-22 Hydrocarbon Technology & Innovation, Llc Ebullated bed reactor upgraded to produce sediment that causes less equipment fouling
CN106905543B (en) * 2017-03-15 2019-11-22 西安理工大学 A kind of preparation method of nano silver gel fluorescent solutions
US11214672B2 (en) 2018-01-19 2022-01-04 The Trustees Of Princeton University Hybrid polymer-inorganic nanocolloids and methods of making them
WO2019145409A1 (en) * 2018-01-24 2019-08-01 Nanogap Sub Nm Powder, S.A. Process for producing atomic quantum clusters
CA3057131A1 (en) 2018-10-17 2020-04-17 Hydrocarbon Technology And Innovation, Llc Upgraded ebullated bed reactor with no recycle buildup of asphaltenes in vacuum bottoms
GB2598249A (en) * 2019-06-20 2022-02-23 Univ South Africa Nanofluids
CN110947979B (en) * 2019-11-08 2021-10-15 上海交通大学 Method for synthesizing superfine single crystal nickel powder by solvothermal method
KR102410707B1 (en) * 2021-03-25 2022-06-22 서울방사선서비스주식회사 Method for manufacturing antiviral copper nanoparticles using radiation and antiviral copper nanoparticles manufactured thereby
CN113714508A (en) * 2021-08-12 2021-11-30 深圳大学 Nano silver and preparation method and application thereof
CN113603548B (en) * 2021-08-17 2022-11-04 华中农业大学 Manganese element foliar spray fertilizer and preparation method thereof
CN114101656B (en) * 2021-12-07 2022-09-27 浙江大学 Preparation method and application of silver nanoparticles with universal dispersion characteristics
CN115043690A (en) * 2022-05-09 2022-09-13 南京理工大学 Preparation method of silver ignition bridge based on ink-jet direct writing
CN115369391B (en) * 2022-07-20 2023-12-19 厦门大学 Silver colloid activating liquid composition with electroless copper plating metallization on polymer surface and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5431967A (en) * 1989-09-05 1995-07-11 Board Of Regents, The University Of Texas System Selective laser sintering using nanocomposite materials
US5560960A (en) * 1994-11-04 1996-10-01 The United States Of America As Represented By The Secretary Of The Navy Polymerized phospholipid membrane mediated synthesis of metal nanoparticles
DE19639632A1 (en) * 1996-09-26 1998-04-09 Zenneck Ulrich Prof Dr Ion-free nano-metal-polymer composites
US5912069A (en) * 1996-12-19 1999-06-15 Sigma Laboratories Of Arizona Metal nanolaminate composite
KR20020043363A (en) * 2000-12-04 2002-06-10 박호군 Composite Polymers Containing Nanometer-sized Metal Particles and Fabrication Method Thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2565844B1 (en) 1984-06-13 1988-10-28 Centre Nat Rech Scient NOVEL NON-NOBLE METAL MICROAGGREGATES, PROCESS FOR THEIR PREPARATION AND APPLICATION TO THE CATALYSIS OF PHOTOREDUCTION OF WATER
US5187209A (en) * 1986-07-01 1993-02-16 Hidefumi Hirai Colloidal metal dispersion, and a colloidal metal complex
DE19501802A1 (en) 1994-02-01 1995-08-03 Basf Ag Compsns. useful as non-linear optical materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5431967A (en) * 1989-09-05 1995-07-11 Board Of Regents, The University Of Texas System Selective laser sintering using nanocomposite materials
US5560960A (en) * 1994-11-04 1996-10-01 The United States Of America As Represented By The Secretary Of The Navy Polymerized phospholipid membrane mediated synthesis of metal nanoparticles
DE19639632A1 (en) * 1996-09-26 1998-04-09 Zenneck Ulrich Prof Dr Ion-free nano-metal-polymer composites
US5912069A (en) * 1996-12-19 1999-06-15 Sigma Laboratories Of Arizona Metal nanolaminate composite
KR20020043363A (en) * 2000-12-04 2002-06-10 박호군 Composite Polymers Containing Nanometer-sized Metal Particles and Fabrication Method Thereof

Cited By (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11471939B2 (en) 2002-12-09 2022-10-18 University Of Washington Methods of nanostructure formation and shape selection
US10384936B2 (en) 2002-12-09 2019-08-20 University Of Washington Methods of nanostructure formation and shape selection
WO2004078386A2 (en) * 2003-02-04 2004-09-16 Arkema Method for production of a composite material comprising a polymer and metallic nanoparticles
FR2850661A1 (en) * 2003-02-04 2004-08-06 Atofina A method of preparing a composite material used for injection molded, extruded or press formed articles consisting of a matrix of a thermoplastic polymer, especially poly(methyl methacrylate) containing metallic nanoparticles
WO2004078386A3 (en) * 2003-02-04 2004-11-25 Atofina Method for production of a composite material comprising a polymer and metallic nanoparticles
WO2004081111A1 (en) * 2003-03-11 2004-09-23 Dow Global Technologies Inc. High dielectric constant composites
US8263418B2 (en) 2003-03-28 2012-09-11 The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin Sensors for detecting an analyte using silver nanoparticles
WO2004086044A1 (en) * 2003-03-28 2004-10-07 The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin Sensor for detecting an analyte using silver nanoparticles
JP2006521556A (en) * 2003-03-28 2006-09-21 ザ・プロウボウスト・フェロウズ・アンド・スカラーズ・オブ・ザ・カレッジ・オブ・ザ・ホリー・アンド・アンデバイデッド・トリニティ・オブ・クイーン・エリザベス・ニア・ダブリン Detecting sensor using silver nanoparticles
US7786049B2 (en) * 2003-04-10 2010-08-31 Halliburton Energy Services, Inc. Drilling fluids with improved shale inhibition and methods of drilling in subterranean formations
US8283034B2 (en) 2003-05-29 2012-10-09 Orica Australia Pty Ltd Process for producing a nanoscale zero-valent metal
EP1641582A1 (en) * 2003-05-29 2006-04-05 Crc For Waste Management And Pollution Control Limited Process for producing a nanoscale zero-valent metal
EP1641582A4 (en) * 2003-05-29 2009-11-11 Environmental Biotechnology Cr Process for producing a nanoscale zero-valent metal
WO2005007328A1 (en) 2003-07-17 2005-01-27 Asahi Kasei Medical Co., Ltd. Metal colloid solution
EP1647345A1 (en) * 2003-07-17 2006-04-19 Asahi Kasei Medical Co., Ltd. Metal colloid solution
US7745499B2 (en) 2003-07-17 2010-06-29 Asahi Kasei Medical Co., Ltd Metal colloid solution
EP1647345A4 (en) * 2003-07-17 2009-03-25 Asahi Kasei Medical Co Ltd Metal colloid solution
WO2005070820A1 (en) * 2004-01-27 2005-08-04 Merck Patent Gmbh Nanoparticles
US20130122321A1 (en) * 2004-07-30 2013-05-16 Kimberly-Clark Worldwide, Inc. Methods and Compositions for Metal Nanoparticle Treated Surfaces
CN1322952C (en) * 2004-09-24 2007-06-27 昆明贵金属研究所 Indirecting light chemical preparation for gold nanometer material
US7686983B2 (en) * 2004-10-21 2010-03-30 Pharma Diagnostics N.V. Stable metal/conductive polymer composite colloids and methods for making and using the same
US7618560B2 (en) * 2004-10-21 2009-11-17 Pharma Diagnostics N.V. Stable metal/conductive polymer composite colloids and methods for making and using the same
JP2006124787A (en) * 2004-10-29 2006-05-18 Hideaki Maeda High crystallinity nano-silver particle slurry and its production method
WO2006049477A1 (en) * 2004-11-08 2006-05-11 Bio Dreams Co. Ltd. Antifungal pharmaceutical composition
WO2006049478A1 (en) * 2004-11-08 2006-05-11 Bio Dreams Co. Ltd. Anti-microbial fiber products
WO2006049479A1 (en) * 2004-11-08 2006-05-11 Bio Dreams Co. Ltd. Antimicrobial spray compositions
WO2006069696A1 (en) * 2004-12-24 2006-07-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for producing polymers that are interspersed with fines
US7824466B2 (en) 2005-01-14 2010-11-02 Cabot Corporation Production of metal nanoparticles
US7905287B2 (en) 2005-04-19 2011-03-15 Halliburton Energy Services Inc. Methods of using a polymeric precipitate to reduce the loss of fluid to a subterranean formation
US7943555B2 (en) 2005-04-19 2011-05-17 Halliburton Energy Services Inc. Wellbore treatment kits for forming a polymeric precipitate to reduce the loss of fluid to a subterranean formation
US7935540B2 (en) 2005-07-14 2011-05-03 3M Innovative Properties Company Water-soluble polymeric substrate having metallic nanoparticle coating
WO2007011331A2 (en) * 2005-07-14 2007-01-25 3M Innovative Properties Company Water-soluble polymeric substrate having metallic nanoparticle coating
WO2007011331A3 (en) * 2005-07-14 2007-04-12 3M Innovative Properties Co Water-soluble polymeric substrate having metallic nanoparticle coating
US7833945B2 (en) 2005-07-15 2010-11-16 Halliburton Energy Services Inc. Treatment fluids with improved shale inhibition and methods of use in subterranean operations
US8455404B2 (en) 2005-07-15 2013-06-04 Halliburton Energy Services, Inc. Treatment fluids with improved shale inhibition and methods of use in subterranean operations
US10981231B2 (en) 2006-02-01 2021-04-20 University Of Washington Methods for production of silver nanostructures
US9388480B2 (en) 2006-02-01 2016-07-12 University Of Washington Methods for production of silver nanostructures
US9109270B2 (en) 2006-02-01 2015-08-18 University Of Washington Methods for production of silver nanostructures
WO2007138345A1 (en) * 2006-05-26 2007-12-06 Johnson Matthey Public Limited Company Process for producing stabilised metal nanoparticles
US8105643B2 (en) 2006-05-31 2012-01-31 Cabot Corporation Process for printing features with smaller dimensions
WO2008151066A1 (en) * 2007-05-30 2008-12-11 Cabot Corporation Production of metal nanoparticles
US8058195B2 (en) 2007-06-19 2011-11-15 Cabot Corporation Nanoglass and flame spray processes for producing nanoglass
CN101821039B (en) * 2007-09-27 2013-07-17 巴斯夫欧洲公司 Preparation method of isolable and redispersable transition metal nanoparticles and use thereof as IR absorbers
WO2009056401A1 (en) * 2007-09-27 2009-05-07 Basf Se Isolable and redispersable transition metal nanoparticles their preparation and use as ir absorbers
US8841375B2 (en) 2007-09-27 2014-09-23 Basf Se Isolable and redispersable transition metal nanoparticles their preparation and use as IR absorbers
US8372472B2 (en) 2007-12-07 2013-02-12 Cabot Corporation Forming photovoltaic conductive features from multiple inks
US8101231B2 (en) 2007-12-07 2012-01-24 Cabot Corporation Processes for forming photovoltaic conductive features from multiple inks
DE102009015470A1 (en) 2008-12-12 2010-06-17 Byk-Chemie Gmbh Process for the preparation of metal nanoparticles and metal nanoparticles obtained in this way and their use
WO2010066335A1 (en) 2008-12-12 2010-06-17 Byk-Chemie Gmbh Method for producing metal nanoparticles and nanoparticles obtained in this way and use thereof
MD4075C1 (en) * 2009-12-31 2011-07-31 Анатолий ЭФКАРПИДИС Process for obtaining highly dispersed colloidal silver
US8101680B1 (en) 2010-10-12 2012-01-24 Sabic Innovative Plastics Ip B.V. Methods of preparing polymer nanocomposites
WO2017071949A1 (en) * 2015-10-30 2017-05-04 Clariant International Ltd Metal dispersion with increased stability

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