WO2006049831A1 - Method of production of high purity silver particles - Google Patents

Method of production of high purity silver particles Download PDF

Info

Publication number
WO2006049831A1
WO2006049831A1 PCT/US2005/036727 US2005036727W WO2006049831A1 WO 2006049831 A1 WO2006049831 A1 WO 2006049831A1 US 2005036727 W US2005036727 W US 2005036727W WO 2006049831 A1 WO2006049831 A1 WO 2006049831A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
surfactants
surfactant
oxalate
group
Prior art date
Application number
PCT/US2005/036727
Other languages
French (fr)
Inventor
Insoo Kim
Chang Gun Lee
Sang Ho Kim
Charles E. Smith, Jr.
Young Jin Kim
Original Assignee
Tokusen U.S.A., Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokusen U.S.A., Inc. filed Critical Tokusen U.S.A., Inc.
Priority to KR1020077008295A priority Critical patent/KR100888559B1/en
Priority to EP05851218A priority patent/EP1819467A4/en
Priority to US11/664,640 priority patent/US20080105085A1/en
Priority to CNA2005800348201A priority patent/CN101065205A/en
Priority to JP2007536851A priority patent/JP2008517153A/en
Publication of WO2006049831A1 publication Critical patent/WO2006049831A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the object of the present invention is to synthesize high purity silver particles and colloids in a process that does not require either surfactants or reducing agents, or only a minimal amount of a surfactant.
  • this object is achieved by dispersing silver oxalates into an appropriate carrier and then thermally decomposing the silver oxalates at a
  • the process of synthesizing silver particles and colloids by the method of the present invention comprises: (i) a silver oxalate synthesizing process; (ii) a process of dispersing silver oxalates into an appropriate carrier, for example, water, alcohol or the like, including a combination of more than one carrier; and (iii) a process of heating said silver oxalates
  • Fig. 1 is a microphotograph of silver particles obtained under the conditions described in Example " ! .
  • Fig. 2 is a microphotograph of silver particles obtained under the conditions described in Example 2.
  • Fig. 3 is a microphotograph of silver particles obtained under the conditions described in Example 3.
  • Fig. 4 is a microphotograph of silver particles obtained under the conditions described in Example 4.
  • Fig. 5 is a microphotograph of silver particles obtained under the conditions described in Example 5.
  • Fig. 6 is a microphotograph of silver particles obtained under the conditions described in Example 6.
  • a method for the production of silver particles and colloids comprises three processes as follows: (i) a silver oxalate (Ag 2 C 2 O 4 ) synthesizing process; (ii) a process of dispersing silver oxalate into an appropriate carrier, for example, water, alcohol or the like, including a combination of more than one carrier; and (iii) a process of heating said
  • a silver oxalate Ag 2 C 2 O 4
  • a first solution of a water soluble silver compound and a second solution of an oxalate compound are mixed together to precipitate silver oxalates.
  • the silver compound may be AgNO 3 .
  • the oxalate compound may be sodium oxalate or oxalic acid.
  • the present invention is not, however, limited to these specific compounds but may include any two solutions of compounds that form silver oxalates upon mixing. After water cleaning processes, preferably two or more rounds of water cleaning processes, are performed to remove impure ions from the precipitated silver oxalate, the silver oxalate is used as the starting material for synthesizing silver powder or colloids.
  • the synthesized silver oxalate is dispersed into an appropriate carrier.
  • the silver oxalate is not dissolved to any substantial extent in the carrier, but is dispersed as solid particles by using ultrasonic treatment.
  • the appropriate carrier may include all types of carriers which can disperse silver oxalate to effectively deliver heat.
  • the carrier is selected to have properties that allow it to behave similarly to a surfactant so as to prevent agglomeration of the silver particles formed from the thermal decomposition of the silver oxalate.
  • alcohols consist of alkyl and hydroxyl groups. Generally, alkyl groups have hydrophobic properties and hydroxyl groups have hydrophilic properties. Organic materials having both hydrophobic and hydrophilic properties can play a role as a surfactant.
  • organic materials having higher carbon numbers tend to be dominantly hydrophobic and may therefore tend to lose the ability to act as a surfactant in the process of the present invention.
  • organic materials having higher numbers of carbon atoms have superior surfactant properties.
  • organic materials with a higher number of carbon atoms is observed to agglomerate silver particles.
  • organic materials with a higher number of carbon atoms do not mix well with water. Therefore, the present invention is limited to methyl, ethyl and propyl alcohols, which have a low number of carbon atoms. Water is also effective in the practice of the present invention.
  • the appropriate carrier may therefore consist of ethyl alcohol, methyl alcohol, propyl alcohol, water or a combination of more than one of the preceding.
  • the carriers selected for the practice of the present invention all have low boiling points: water (10O 0 C), methyl alcohol (64.65°C), ethyl alcohol (78.3°C), and propyl alcohol (82°C). Accordingly, when the carrier with the dispersed silver oxalate is heated in a container at or above 100 0 C, the pressure is always above atmospheric pressure. Typical reaction pressures are about 1.86 * 10 5 N/m 2 when using water as the carrier and about 5.31 * 10 5 N/m 2 when using ethyl alcohol as the carrier.
  • the carbon dioxide gas evolved during the thermal decomposition of the silver oxalate and the carrier vapor may be evacuated as necessary but pressure drops of less than about 6.89 * 10 4 N/m 2 do not affect the quality of the silver particles.
  • the dispersed silver oxalate in the carrier is placed into a closed reactor to heat the dispersed silver oxalate and carrier up to at least 100 0 C to synthesize silver powder or colloids of various form factors.
  • This method may optionally use surfactants in order to prevent coagulation or agglomeration of the silver particles.
  • Surfactants may be added to the water soluble silver or oxalate solutions used to produce silver oxalate, or may be added after the silver oxalate is produced by mixing the two solutions.
  • Surfactants used in this method may include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorochemical surfactants, and polymerizable surfactants, or combinations of the preceding, which may be added to aid in forming silver particles and to break down silver plates or prevent silver plates from coagulation.
  • Surfactants suitable for use in the present invention include PVP (polyvinyl pyrrolidone) and gelatine.
  • silver particles or colloids can be obtained by the method of the present invention, however, it is desirable to limit the amount of surfactant to no more than 80% of the weight of the silver. For example, if 10 grams of silver is placed into the reactor, the weight of the surfactant, such as PVP or gelatin, should be no more than 8 grams.
  • the weight of the surfactant such as PVP or gelatin
  • Example 2 After 2.8 grams of silver oxalate was placed into 300cc of distilled water, ten minutes of ultrasonic treatment was performed to disperse the particles. The dispersed silver oxalate was reacted for 15 minutes at 130 0 C to obtain a solution containing silver particles as shown in Fig. 1.
  • Example 2 After 2.8 grams of silver oxalate was placed into 300cc of distilled water, ten minutes of ultrasonic treatment was performed to disperse the particles. The dispersed silver oxalate was reacted for 15 minutes at 130 0 C to obtain a solution containing silver particles as shown in Fig. 1. Example 2

Abstract

A method for synthesizing high purity silver particles and colloids without requiring the addition of either surfactants or reducing agents thereto, or requiring only a minimal amount thereof. The synthesizing process comprises: (i) a silver oxalate synthesizing process; (ii) a process of dispersing silver oxalate into an appropriate carrier; and {iii) a process of heating said silver oxalate dispersed into said carrier at a temperature of at least 100°C. Silver particles and colloids of various form factor and size may be synthesized depending upon the reaction conditions, the carrier, and the type of surfactant.

Description

Description
Method Of Production Of High Purity Silver Particles
This application claims the benefit of U.S. Provisional Application No.
60/618,876, filed October 14, 2004 and entitled "Method for Production of Fine Silver Particles," which is incorporated herein by reference.
Technical Field The present invention relates to a method of forming silver particles by dispersing silver oxalate into an appropriate carrier and then applying
heat at a temperature of 1000C or higher to decompose the silver oxalate.
Background Art A number of methods have been developed to synthesize silver particles including, but not limited to, chemical reduction, photochemical, sonochemical and gas evaporation methods. Of these methods, the chemical reduction method is widely used due to the ease of production. However, silver powder produced using the chemical reduction method pan be contaminated by the reducing agent, the surfactant and impurity ions used during the reaction process, which can serve as a limiting factor in the field of electronics requiring high conductivity or in the field of bacteria resistance requiring high purity.
In order to resolve these problems, it is desirable to have a method of producing high purity silver powder and silver colloids that does not require either surfactants or reducing agents, or only a minimal amount of a surfactant.
Disclosure of the Invention The object of the present invention is to synthesize high purity silver particles and colloids in a process that does not require either surfactants or reducing agents, or only a minimal amount of a surfactant. In the present invention, this object is achieved by dispersing silver oxalates into an appropriate carrier and then thermally decomposing the silver oxalates at a
temperature of 1000C or higher to synthesize high purity silver particles and
colloids.
The process of synthesizing silver particles and colloids by the method of the present invention comprises: (i) a silver oxalate synthesizing process; (ii) a process of dispersing silver oxalates into an appropriate carrier, for example, water, alcohol or the like, including a combination of more than one carrier; and (iii) a process of heating said silver oxalates
dispersed into said carrier at a temperature of 100°C or higher under a
pressure greater than atmospheric pressure.
These and other features, objects and advantages of the present invention will become better understood from a consideration of the following detailed description of the preferred embodiments and appended claims in conjunction with the drawings as described following. Brief Description Of The Drawings
Fig. 1 is a microphotograph of silver particles obtained under the conditions described in Example"! .
Fig. 2 is a microphotograph of silver particles obtained under the conditions described in Example 2.
Fig. 3 is a microphotograph of silver particles obtained under the conditions described in Example 3.
Fig. 4 is a microphotograph of silver particles obtained under the conditions described in Example 4. Fig. 5 is a microphotograph of silver particles obtained under the conditions described in Example 5.
Fig. 6 is a microphotograph of silver particles obtained under the conditions described in Example 6.
Best Mode for Carrying Out the Invention
With reference to Figs. 1-6, the preferred embodiments of the present invention may be described as follows.
In the present invention, a method for the production of silver particles and colloids comprises three processes as follows: (i) a silver oxalate (Ag2C2O4) synthesizing process; (ii) a process of dispersing silver oxalate into an appropriate carrier, for example, water, alcohol or the like, including a combination of more than one carrier; and (iii) a process of heating said
silver oxalate dispersed into said carrier at a temperature of 1-000C or higher
under a pressure greater than atmospheric pressure to form silver particle or colloids from the decomposition of the silver oxalate. A first solution of a water soluble silver compound and a second solution of an oxalate compound are mixed together to precipitate silver oxalates. The silver compound may be AgNO3. The oxalate compound may be sodium oxalate or oxalic acid. The present invention is not, however, limited to these specific compounds but may include any two solutions of compounds that form silver oxalates upon mixing. After water cleaning processes, preferably two or more rounds of water cleaning processes, are performed to remove impure ions from the precipitated silver oxalate, the silver oxalate is used as the starting material for synthesizing silver powder or colloids.
The synthesized silver oxalate is dispersed into an appropriate carrier. The silver oxalate is not dissolved to any substantial extent in the carrier, but is dispersed as solid particles by using ultrasonic treatment. The appropriate carrier may include all types of carriers which can disperse silver oxalate to effectively deliver heat. The carrier is selected to have properties that allow it to behave similarly to a surfactant so as to prevent agglomeration of the silver particles formed from the thermal decomposition of the silver oxalate. For example, alcohols consist of alkyl and hydroxyl groups. Generally, alkyl groups have hydrophobic properties and hydroxyl groups have hydrophilic properties. Organic materials having both hydrophobic and hydrophilic properties can play a role as a surfactant. However, organic materials having higher carbon numbers tend to be dominantly hydrophobic and may therefore tend to lose the ability to act as a surfactant in the process of the present invention. Generally, organic materials having higher numbers of carbon atoms have superior surfactant properties. However, in the present invention, organic materials with a higher number of carbon atoms is observed to agglomerate silver particles. Furthermore, organic materials with a higher number of carbon atoms do not mix well with water. Therefore, the present invention is limited to methyl, ethyl and propyl alcohols, which have a low number of carbon atoms. Water is also effective in the practice of the present invention. The appropriate carrier may therefore consist of ethyl alcohol, methyl alcohol, propyl alcohol, water or a combination of more than one of the preceding.
The carriers selected for the practice of the present invention all have low boiling points: water (10O0C), methyl alcohol (64.65°C), ethyl alcohol (78.3°C), and propyl alcohol (82°C). Accordingly, when the carrier with the dispersed silver oxalate is heated in a container at or above 1000C, the pressure is always above atmospheric pressure. Typical reaction pressures are about 1.86 * 105 N/m2 when using water as the carrier and about 5.31 * 105 N/m2 when using ethyl alcohol as the carrier. During thermal decomposition of silver oxalate, the silver oxalate (Ag2C2O4) decomposes into silver (Ag) and carbon dioxide (CO2) according to the formula Ag2C2O4 = 2Ag + 2CO2. The carbon dioxide gas evolved during the thermal decomposition of the silver oxalate and the carrier vapor may be evacuated as necessary but pressure drops of less than about 6.89 * 104 N/m2 do not affect the quality of the silver particles.
The dispersed silver oxalate in the carrier is placed into a closed reactor to heat the dispersed silver oxalate and carrier up to at least 100 0C to synthesize silver powder or colloids of various form factors. This method may optionally use surfactants in order to prevent coagulation or agglomeration of the silver particles. Surfactants may be added to the water soluble silver or oxalate solutions used to produce silver oxalate, or may be added after the silver oxalate is produced by mixing the two solutions. Surfactants used in this method may include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorochemical surfactants, and polymerizable surfactants, or combinations of the preceding, which may be added to aid in forming silver particles and to break down silver plates or prevent silver plates from coagulation. Surfactants suitable for use in the present invention include PVP (polyvinyl pyrrolidone) and gelatine.
Irrespective of the amount of surfactant added, silver particles or colloids can be obtained by the method of the present invention, however, it is desirable to limit the amount of surfactant to no more than 80% of the weight of the silver. For example, if 10 grams of silver is placed into the reactor, the weight of the surfactant, such as PVP or gelatin, should be no more than 8 grams. Example 1
After 2.8 grams of silver oxalate was placed into 300cc of distilled water, ten minutes of ultrasonic treatment was performed to disperse the particles. The dispersed silver oxalate was reacted for 15 minutes at 130 0C to obtain a solution containing silver particles as shown in Fig. 1. Example 2
After 28 grams of silver oxalate was placed into IOOOcc of ethyl alcohol, ten minutes of ultrasonic treatment was performed to disperse the particles. The dispersed silver oxalate was reacted for 15 minutes at 134 0C to obtain silver powder as shown in Fig. 2. Example 3
After 70mg of silver oxalate was placed into IOOOcc of ethyl alcohol, ten minutes of ultrasonic treatment was performed to disperse the particles. The dispersed particles were reacted for 25 minutes at 135 0C to obtain nano-sized silver particles as shown in Fig. 3. Example 4
After 4.2 grams of silver oxalate was placed into a mixed solution of water (vol. 50%) and ethyl alcohol (vol. 50%), the solution was reacted for 15 minutes at 130 0C to synthesize 0.5μm silver particles as shown in Fig. 4. Example 5
30 wt% of PVP (polyvinyl pyrrolidone) was placed into 4.2 grams of silver oxalate in 1 Liter of water and ultrasonic treatment was performed to disperse the particles thereof. The dispersed particles were reacted for 20 minutes at 135 0C to synthesize silver particles of 0.5μm or smaller in size as shown in Fig. 5. Example 6
10 grams of gelatin was placed into 28 grams of silver oxalate in 1 Liter of water and ultrasonic treatment was performed to disperse the particles thereof. The dispersed particles were reacted for 15 minutes at 135 0C to synthesize silver particles of 50nm or smaller in size as shown in Fig. 6. Industrial Applicability
Due to its inherent characteristics of high conductivity and bacteria resistance, silver particles are widely used in the electronics industry as well as in other industries requiring bacteria resistance. The present invention has been described with reference to certain preferred and alternative embodiments that are intended to be exemplary only and not limiting to the full scope of the present invention as set forth in the appended claims.

Claims

Claims
1. A method for production of silver particles, comprising the steps of:
(a) dispersing solid silver oxalate particles in a carrier; and (b) heating said dispersed silver oxalate to a temperature of at least 100 0C under a pressure that is greater than atmospheric pressure to decompose said silver oxalate into silver particles.
2. The method of claim 1 , further comprising the step before step (a) of producing said silver oxalate by mixing a first solution of a silver compound and a second solution of an oxalate compound to form silver oxalate.
3. The method of claims 1 or 2, further comprising the step of adding a surfactant to said dispersed silver oxalate before the heating of step (b).
4. The method of claim 3 wherein said surfactant is selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorochemical surfactants, polymerizable surfactants, and any combination of the preceding surfactants.
5. The method of claim 2, further comprising the step of adding a surfactant to said first solution before said mixing step.
6. The method of claim 5 wherein said surfactant is selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorochemical surfactants, polymerizable surfactants, and any combination of the preceeding surfactants.
7. The method of claim 2 further comprising the step of adding a surfactant to said second solution before said mixing step.
8. The method of claim 7 wherein said surfactant is selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorochemical surfactants, polymerizable surfactants, and any combination of the preceeding surfactants.
9. The method of claims 1 or 2, wherein the dispersing of step (a) comprises adding silver oxalate to said carrier and subjecting the mixture of silver oxalate and carrier to ultrasonic treatment.
10. The method of claims 1 or 2, wherein said carrier is selected from the group comprising water, methyl alcohol, ethyl alcohol, propyl alcohol, and a mixture of any of the preceding.
11. The method of claim 2, wherein said silver compound is
AgNO3.
12. The method of claim 2, wherein said oxalate compound is selected from the group comprising sodium oxalate and oxalic acid.
13. The method of claim 2, further comprising the step following the production of silver oxalate of washing said silver oxalate with water to remove impurities.
14. The method of claim 4, wherein said surfactant is selected from the group comprising PVP (polyvinyl pyrrolidone) and gelatin.
15. The method of claim 6, wherein said surfactant is selected from the group comprising PVP (polyvinyl pyrrolidone) and gelatin.
16. The method of claim 8, wherein said surfactant is selected from the group comprising PVP (polyvinyl pyrrolidone) and gelatin.
17. The method of claim 3, wherein said surfactant is no greater than 80% by weight of the silver in step (b).
18. The method of claim 5, wherein said surfactant is no greater than 80% by weight of the silver in step (b).
19. The method of claim 7, wherein said surfactant is no greater than 80% by weight of the silver in step (b).
PCT/US2005/036727 2004-10-14 2005-10-13 Method of production of high purity silver particles WO2006049831A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020077008295A KR100888559B1 (en) 2004-10-14 2005-10-13 Method of production of high purity silver particles
EP05851218A EP1819467A4 (en) 2004-10-14 2005-10-13 Method of production of high purity silver particles
US11/664,640 US20080105085A1 (en) 2004-10-14 2005-10-13 Method Of Production Of High Purity Silver Particles
CNA2005800348201A CN101065205A (en) 2004-10-14 2005-10-13 Method of production of high purity silver particles
JP2007536851A JP2008517153A (en) 2004-10-14 2005-10-13 Method for producing high purity silver particles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US61887604P 2004-10-14 2004-10-14
US60/618,876 2004-10-14

Publications (1)

Publication Number Publication Date
WO2006049831A1 true WO2006049831A1 (en) 2006-05-11

Family

ID=36319502

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/036727 WO2006049831A1 (en) 2004-10-14 2005-10-13 Method of production of high purity silver particles

Country Status (6)

Country Link
US (1) US20080105085A1 (en)
EP (1) EP1819467A4 (en)
JP (1) JP2008517153A (en)
KR (1) KR100888559B1 (en)
CN (1) CN101065205A (en)
WO (1) WO2006049831A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008214695A (en) * 2007-03-05 2008-09-18 Shoei Chem Ind Co Method for producing ultra-fine particle of silver

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100869666B1 (en) * 2004-10-14 2008-11-21 토쿠센, 유.에스.에이. 인코포레이티드 Method for synthesizing nano-sized titanium dioxide particles
JP2010504272A (en) * 2006-09-21 2010-02-12 トクセン ユー．エス．エー．、インコーポレイテッド Low temperature method for the production of nano-sized titanium dioxide particles
US8231704B2 (en) * 2009-05-01 2012-07-31 E I Du Pont De Nemours And Company Silver particles and processes for making them
WO2011013542A1 (en) * 2009-07-30 2011-02-03 国立大学法人京都大学 Metal nanoparticles, dispersion containing same, and process for production of same
WO2011065135A1 (en) * 2009-11-27 2011-06-03 トクセン工業株式会社 Composition containing metal microparticles
KR20110113877A (en) * 2010-04-12 2011-10-19 서울대학교산학협력단 Process for large-scale production of uniform silver nanoparticle
US20110088593A1 (en) * 2010-12-23 2011-04-21 Mansour Hemmati Silver dz nano-fluid composition for nano-fin formation and a method of producing the same
JP6182294B2 (en) * 2011-01-28 2017-08-16 宣政 奥田 Bactericidal composition and medicine
FR2977178B1 (en) * 2011-06-30 2014-05-16 Thales Sa METHOD FOR MANUFACTURING A DEVICE COMPRISING BRASURES REALIZED FROM METAL OXALATE
JP5872440B2 (en) * 2012-02-13 2016-03-01 Ｄｏｗａエレクトロニクス株式会社 Spherical silver powder and method for producing the same
KR20150081253A (en) 2012-08-30 2015-07-13 코닝 인코포레이티드 Solvent-free syntheses of silver and silver products produced thereby
JP2015531432A (en) 2012-08-31 2015-11-02 コーニング インコーポレイテッド Low temperature dispersion synthesis of silver and silver products produced thereby
DE112013004232T5 (en) 2012-08-31 2015-08-20 Corning Incorporated Silver recovery process and silver products produced thereby
TWI508799B (en) * 2012-12-06 2015-11-21 China Steel Corp A Method for Synthesis of Silver Powder with Adjustable Particle Size
JP6157104B2 (en) * 2012-12-14 2017-07-05 田中貴金属工業株式会社 Silver precursor for producing silver compound, method for producing the same, and method for producing silver compound
CN103602019B (en) * 2013-11-15 2015-12-02 三河市京纳环保技术有限公司 A kind of novel method preparing high transparency plastics silver-containing inorganic antibacterial matrices on a large scale

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426761A (en) 1943-08-28 1947-09-02 Honorary Advisory Council Sci Preparation of silver catalysts
US4463030A (en) * 1979-07-30 1984-07-31 Graham Magnetics Incorporated Process for forming novel silver powder composition
US5250101A (en) * 1991-04-08 1993-10-05 Mitsubishi Gas Chemical Company, Inc. Process for the production of fine powder
EP1201301A1 (en) 2000-10-25 2002-05-02 Mitsubishi Chemical Corporation Olefin oxidation catalyst comprising silver and alkali metal(s) and process for its production
US20050217429A1 (en) * 2004-04-01 2005-10-06 Dong-A University Synthesis of nanosized metal particles

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3377160A (en) * 1964-12-31 1968-04-09 Allis Chalmers Mfg Co Process of making a high surface area silver catalyst
JPS491153B1 (en) * 1970-07-31 1974-01-11
US3702259A (en) * 1970-12-02 1972-11-07 Shell Oil Co Chemical production of metallic silver deposits
US4186244A (en) * 1977-05-03 1980-01-29 Graham Magnetics Inc. Novel silver powder composition
JPH02275718A (en) * 1988-11-30 1990-11-09 Ceskoslovenska Akad Ved Production of precursor for high-temperature superconducting material
AU638832B2 (en) * 1990-05-18 1993-07-08 Mitsubishi Materials Corporation Precious metal article, method for manufacturing same, moldable mixture for use in manufacture of same and method for producing moldable mixture
US5369429A (en) * 1993-10-20 1994-11-29 Lasermaster Corporation Continuous ink refill system for disposable ink jet cartridges having a predetermined ink capacity
KR0139437B1 (en) * 1995-06-19 1998-06-01 윤덕용 A process for preparine crystalling titania powder from a solution of titanium salt in mixde solvent of water and alcohol
JP2822317B2 (en) * 1996-04-15 1998-11-11 日鉄鉱業株式会社 Antibacterial titania and method for producing the same
US5973175A (en) * 1997-08-22 1999-10-26 E. I. Du Pont De Nemours And Company Hydrothermal process for making ultrafine metal oxide powders
TW408034B (en) * 1997-12-16 2000-10-11 Nippon Catalytic Chem Ind Silver catalyst for production of ethylene oxide, method for production thereof, and method for production of ethylene oxide
US6444189B1 (en) * 1998-05-18 2002-09-03 E. I. Du Pont De Nemours And Company Process for making and using titanium oxide particles
KR100277164B1 (en) * 1998-07-16 2001-01-15 장인순 A preparing method for crystalline micropowder of Titania from aqueous Titanium(Ⅳ) chloride by homogeneous precipitation process at low temperature
EP1167296A4 (en) * 1999-02-04 2005-03-16 Kawasaki Heavy Ind Ltd Method for producing anatase type titanium dioxide and titanium dioxide coating material
US6440383B1 (en) * 1999-06-24 2002-08-27 Altair Nanomaterials Inc. Processing aqueous titanium chloride solutions to ultrafine titanium dioxide
KR100350226B1 (en) * 2000-02-29 2002-08-27 나노케미칼 주식회사 Photocatalytic TiO2 powder with large specific surface area by homogeneous precipitation process at low temperature and method for manufacturing
TWI230689B (en) * 2000-07-31 2005-04-11 Sumitomo Chemical Co Titanium oxide production process
US6660058B1 (en) * 2000-08-22 2003-12-09 Nanopros, Inc. Preparation of silver and silver alloyed nanoparticles in surfactant solutions
DE10107777A1 (en) * 2001-02-16 2002-09-05 Bayer Ag Continuous process for the synthesis of nanoscale precious metal particles
ATE399740T1 (en) * 2001-03-24 2008-07-15 Evonik Degussa Gmbh DOPPED OXIDE PARTICLES SURROUNDED WITH A SHELL
TWI240700B (en) * 2001-07-19 2005-10-01 Sumitomo Chemical Co Ceramics dispersion liquid, method for producing the same, and hydrophilic coating agent using the same
US20030185889A1 (en) * 2002-03-27 2003-10-02 Jixiong Yan Colloidal nanosilver solution and method for making the same
US20040055420A1 (en) * 2002-05-30 2004-03-25 Arkady Garbar Method for enhancing surface area of bulk metals
JP2004196626A (en) * 2002-12-20 2004-07-15 Sumitomo Chem Co Ltd Method for producing titanium oxide
TW200420499A (en) * 2003-01-31 2004-10-16 Sumitomo Chemical Co A method for producing titanium oxide
US6969690B2 (en) * 2003-03-21 2005-11-29 The University Of North Carolina At Chapel Hill Methods and apparatus for patterned deposition of nanostructure-containing materials by self-assembly and related articles
US7208126B2 (en) * 2004-03-19 2007-04-24 E. I. Du Pont De Nemours And Company Titanium dioxide nanopowder manufacturing process
US7205049B2 (en) * 2004-04-16 2007-04-17 Tioxoclean Inc. Metal peroxide films
US20050265918A1 (en) * 2004-06-01 2005-12-01 Wen-Chuan Liu Method for manufacturing nanometer scale crystal titanium dioxide photo-catalyst sol-gel
KR100869666B1 (en) * 2004-10-14 2008-11-21 토쿠센, 유.에스.에이. 인코포레이티드 Method for synthesizing nano-sized titanium dioxide particles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426761A (en) 1943-08-28 1947-09-02 Honorary Advisory Council Sci Preparation of silver catalysts
US4463030A (en) * 1979-07-30 1984-07-31 Graham Magnetics Incorporated Process for forming novel silver powder composition
US5250101A (en) * 1991-04-08 1993-10-05 Mitsubishi Gas Chemical Company, Inc. Process for the production of fine powder
EP1201301A1 (en) 2000-10-25 2002-05-02 Mitsubishi Chemical Corporation Olefin oxidation catalyst comprising silver and alkali metal(s) and process for its production
US20050217429A1 (en) * 2004-04-01 2005-10-06 Dong-A University Synthesis of nanosized metal particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1819467A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008214695A (en) * 2007-03-05 2008-09-18 Shoei Chem Ind Co Method for producing ultra-fine particle of silver

Also Published As

Publication number Publication date
JP2008517153A (en) 2008-05-22
EP1819467A1 (en) 2007-08-22
EP1819467A4 (en) 2010-01-20
KR20070073775A (en) 2007-07-10
KR100888559B1 (en) 2009-03-16
CN101065205A (en) 2007-10-31
US20080105085A1 (en) 2008-05-08

Similar Documents

Publication Publication Date Title
US20080105085A1 (en) Method Of Production Of High Purity Silver Particles
US5861136A (en) Method for making copper I oxide powders by aerosol decomposition
US20080064767A1 (en) High-concentration nanoscale silver colloidal solution and preparing process thereof
KR20080000658A (en) Production of fine particle copper powders
KR100221181B1 (en) Method for making gold powder by aerosol decomposition
CA2392031C (en) Production method of ultrafine gold particle-dissolved water and device therefor
EP1422302B1 (en) Foaming agent for manufacturing a foamed metal
KR20150110458A (en) Low-temperature dispersion-based syntheses of silver and silver products produced thereby
KR100890632B1 (en) Preparation of silver colloid from impure silver salt
KR101798776B1 (en) The manufacturing methods of the hybrid composite ZnO/Graphene oxide for antibacterial activity
WO1990009963A1 (en) Production of spherical particulate titanium oxide
JPS6017431B2 (en) Manufacturing method of ultrafine silver-silica composite powder
JPH03215399A (en) Method for preparing fibrous aluminum nitride
JPH05156326A (en) Production of fine silver powder
JP2005161238A (en) Production method of nanoparticle or nanostructure
CN112091233B (en) Synthesis method of silver nanoparticles
JPH0249364B2 (en)
EP0721919A1 (en) Method for making copper (I) oxide powders by aerosol decomposition
JP2000281797A (en) Preparation of fine particle
TW200523054A (en) Nickel powder coated with titanium compound and conductive paste containing the nickel powder
JP3509939B2 (en) Exhaust gas treatment agent
US5707420A (en) Process for the production of a copper powder containing dispersoids
JPH07241473A (en) Production of hydrogen peroxide
Wang et al. Effect of Electric Field on the Morphology of Silver Nanocrystals Prepared by. GAMMA.-Irradiation.
EP3348325A1 (en) Catalyst for synthesis of hydrogen peroxide

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 11664640

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 200580034820.1

Country of ref document: CN

Ref document number: 1020077008295

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2007536851

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2005851218

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2005851218

Country of ref document: EP