EP2030706B1 - Procédé de préparation de nanoparticules d'argent - Google Patents

Procédé de préparation de nanoparticules d'argent Download PDF

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Publication number
EP2030706B1
EP2030706B1 EP07115455A EP07115455A EP2030706B1 EP 2030706 B1 EP2030706 B1 EP 2030706B1 EP 07115455 A EP07115455 A EP 07115455A EP 07115455 A EP07115455 A EP 07115455A EP 2030706 B1 EP2030706 B1 EP 2030706B1
Authority
EP
European Patent Office
Prior art keywords
silver
nanoparticles
silver nanoparticles
concentration
dispersed
Prior art date
Legal status (The legal status 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 status listed.)
Not-in-force
Application number
EP07115455A
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German (de)
English (en)
French (fr)
Other versions
EP2030706A1 (fr
Inventor
Gérard Klein
Edouard Marc Meyer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Metalor Technologies International SA
Original Assignee
Metalor Technologies International SA
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
Priority to EP07115455A priority Critical patent/EP2030706B1/fr
Application filed by Metalor Technologies International SA filed Critical Metalor Technologies International SA
Priority to DE602007010457T priority patent/DE602007010457D1/de
Priority to PL07115455T priority patent/PL2030706T3/pl
Priority to ES07115455T priority patent/ES2355376T3/es
Priority to AT07115455T priority patent/ATE487554T1/de
Priority to PCT/EP2008/061142 priority patent/WO2009027396A2/fr
Priority to CA2696588A priority patent/CA2696588A1/fr
Priority to US12/675,894 priority patent/US20100303876A1/en
Priority to JP2010522346A priority patent/JP2010537057A/ja
Priority to KR1020107005565A priority patent/KR101526335B1/ko
Publication of EP2030706A1 publication Critical patent/EP2030706A1/fr
Priority to IL204075A priority patent/IL204075A/he
Application granted granted Critical
Publication of EP2030706B1 publication Critical patent/EP2030706B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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

Definitions

  • the present invention relates to the field of nanotechnology. It relates, more particularly, to a process for preparing silver nanoparticles.
  • Metal nanoparticles are widely studied for their optical, electrical, catalytic or biological properties. The size and shape of these particles greatly influence their characteristics. Numerous studies have been carried out in order to define processes that make it possible precisely to control the shape and the size of these different metallic nanoparticles. Various preparation routes have been tested for this purpose, such as chemical reduction, gas condensation, laser irradiation ...
  • silver particles are of great interest. Firstly, their antimicrobial properties resulting from their interaction with thiol, amine, imidazole, carboxyl or phosphate functional groups of living organisms proteins make them suitable for a large number of applications in the medical field.
  • the silver particles when they are dispersed in polymeric organic matrices, they can serve as conductors in electronic and electrotechnical applications.
  • This use is doubly interesting, on the one hand because the resulting conductive formulations can be partially transparent and, on the other hand, because it is possible to induce sintering between the particles to create a crosslinked metal assembly of which the conductive properties are greatly improved.
  • S. Mukherjee proposes the production of an Ag-PAM nanocomposite.
  • a silver salt is mixed with a polymeric agent ( S. Mukherjee: "Nitrogen-mediated interaction in polyacrylamide-silver nanocomposites", Journal of Physics, Condensed Matter 18 2006, 11233-11242 ).
  • the object of the present invention is therefore to propose an easily industrializable silver nanoparticle synthesis route which makes it possible to obtain these particles with good control of their size and shape.
  • the above process is particularly advantageous when the organic silver salt used is selected from silver acetate, silver acetylacetonate, silver citrate, silver lactate or silver pentafluoropropionate.
  • the method according to the invention does not involve toxic product or dangerous for the environment.
  • the reaction conditions are mild and minimize the risks inherent in the reaction.
  • the process for the preparation of silver nanoparticles comprises a first step of mixing 5 g of silver acetate with a solution of 5 g of polyvinylpyrrolidone (PVP) of molecular mass 10000 in 200 ml of water at a temperature of temperature between 40 and 60 ° C, typically at 50 ° C.
  • PVP serves as a nucleating agent and stabilizer, to allow the formation of silver nanoparticles, while avoiding that they agglomerate.
  • a rise in temperature is carried out in 5 minutes to reach a temperature between 60 and 90 ° C, typically 75 ° C.
  • the solution white at the beginning of the reaction, then evolves towards a burne color.
  • the reaction mixture is then left stirring for 45 minutes at 95 ° C.
  • the solution then evolves slowly from a brown color to a green color.
  • the heating is then stopped and the solution is left stirring to reach 35 ° C.
  • the reaction medium is then mixed with a solution of ascorbic acid at 20 mM.
  • Ascorbic acid serves as a reducing agent. It has a coordination affinity with the Ag + ions, while having a limited reduction potential, so as not to agglomerate the reduced silver.
  • the ascorbic acid can initially bind with the Ag + ions stably, allowing the electron transfer to be done in a second time, without agglomeration of silver particles.
  • the reduction potential of ascorbic acid is -0.41V.
  • Other reducing agents with a reduction potential typically less than + 0.2V, preferably less than -0.2V, but greater than -1.5V, preferably greater than -1.2V, preferably greater than -1V may be envisaged.
  • glucose -1.87V reduction potential
  • glucose is a too strong reducing agent and reduces Ag + ions but forming agglomerates.
  • the potentials above are given according to the usual norm in Europe and extracted from: CRC Handbook Series in Organic Electrochemistry, Vol 1, 1976 .
  • the solution is centrifuged to concentrate the polymer matrix containing the silver nanoparticles. It will be noted that the evolution of the reduction reaction can be followed by UV / visible spectroscopy.
  • the analyzes carried out on the final product make it possible to determine that 80% of the silver introduced in the form of silver acetate is converted into metallic silver (Ag 0 ).
  • the figures 1 and 2 are images obtained by transmission electron microscopy (TEM) that measure the size of nanoparticles and their distribution. The size of the nanoparticles obtained is between 3 and 50 nm.
  • PVP polyethylene Glycol
  • PEG polypropylene glycol
  • the term PVP, PEG or polypropylene glycol polymer includes copolymers having one of these monomers as a unit.
  • the silver nanoparticles obtained have a diameter of less than 100 nm, more particularly less than 80 nm, more particularly less than 50 nm. Particles with a diameter of around 2 nm could be detected. These particles are dispersed in the polymer matrix at a concentration greater than 1 M, particularly greater than 2M, more particularly greater than 3M.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
EP07115455A 2007-08-31 2007-08-31 Procédé de préparation de nanoparticules d'argent Not-in-force EP2030706B1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
DE602007010457T DE602007010457D1 (de) 2007-08-31 2007-08-31 Verfahren zur Herstellung von Silbernanoteilchen
PL07115455T PL2030706T3 (pl) 2007-08-31 2007-08-31 Sposób wytwarzania nanocząstek srebra
ES07115455T ES2355376T3 (es) 2007-08-31 2007-08-31 Procedimiento para preparar nanopartículas de plata.
AT07115455T ATE487554T1 (de) 2007-08-31 2007-08-31 Verfahren zur herstellung von silbernanoteilchen
EP07115455A EP2030706B1 (fr) 2007-08-31 2007-08-31 Procédé de préparation de nanoparticules d'argent
CA2696588A CA2696588A1 (fr) 2007-08-31 2008-08-26 Procede de preparation de nanoparticules d'argent
PCT/EP2008/061142 WO2009027396A2 (fr) 2007-08-31 2008-08-26 Procede de preparation de nanoparticules d'argent
US12/675,894 US20100303876A1 (en) 2007-08-31 2008-08-26 Method for preparing silver nanoparticles
JP2010522346A JP2010537057A (ja) 2007-08-31 2008-08-26 銀ナノ粒子の製造方法
KR1020107005565A KR101526335B1 (ko) 2007-08-31 2008-08-26 은 나노입자의 제조 방법
IL204075A IL204075A (he) 2007-08-31 2010-02-21 שיטה להכנת ננוחלקיקים של כסף

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07115455A EP2030706B1 (fr) 2007-08-31 2007-08-31 Procédé de préparation de nanoparticules d'argent

Publications (2)

Publication Number Publication Date
EP2030706A1 EP2030706A1 (fr) 2009-03-04
EP2030706B1 true EP2030706B1 (fr) 2010-11-10

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP07115455A Not-in-force EP2030706B1 (fr) 2007-08-31 2007-08-31 Procédé de préparation de nanoparticules d'argent

Country Status (11)

Country Link
US (1) US20100303876A1 (he)
EP (1) EP2030706B1 (he)
JP (1) JP2010537057A (he)
KR (1) KR101526335B1 (he)
AT (1) ATE487554T1 (he)
CA (1) CA2696588A1 (he)
DE (1) DE602007010457D1 (he)
ES (1) ES2355376T3 (he)
IL (1) IL204075A (he)
PL (1) PL2030706T3 (he)
WO (1) WO2009027396A2 (he)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD4075C1 (ro) * 2009-12-31 2011-07-31 Анатолий ЭФКАРПИДИС Procedeu de obţinere a argintului coloidal de înaltă dispersie
AR080385A1 (es) * 2010-03-09 2012-04-04 Polymers Crc Ltd Procedimiento para la preparacion de un articulo antimicrobiano
CN102212806B (zh) * 2010-04-07 2013-03-13 南京理工大学 细菌纤维素-纳米银复合材料的制备方法
EP2468827B1 (en) 2010-12-21 2014-03-12 Agfa-Gevaert A dispersion comprising metallic, metal oxide or metal precursor nanoparticles
WO2012169628A1 (ja) * 2011-06-08 2012-12-13 住友金属鉱山株式会社 銀粉及びその製造方法
EP2608218B1 (en) 2011-12-21 2014-07-30 Agfa-Gevaert A dispersion comprising metallic, metal oxide or metal precursor nanoparticles, a polymeric dispersant and a thermally cleavable agent
ES2485308T3 (es) 2011-12-21 2014-08-13 Agfa-Gevaert Dispersión que contiene nanopartículas metálicas, de óxido de metal o de precursor de metal, un dispersante polimérico y un aditivo de sinterización
EP2671927B1 (en) 2012-06-05 2021-06-02 Agfa-Gevaert Nv A metallic nanoparticle dispersion
CN102828176A (zh) * 2012-07-31 2012-12-19 东南大学 一种制备均匀金纳米颗粒薄膜的方法
JP5500237B1 (ja) * 2012-12-05 2014-05-21 住友金属鉱山株式会社 銀粉
CN102935520B (zh) * 2012-12-05 2015-10-28 苏州大学 一种用改性葡萄糖制备纳米银水溶液的方法
US20140239504A1 (en) * 2013-02-28 2014-08-28 Hwei-Ling Yau Multi-layer micro-wire structure
EP2781562B1 (en) 2013-03-20 2016-01-20 Agfa-Gevaert A method to prepare a metallic nanoparticle dispersion
US20160083594A1 (en) 2013-07-04 2016-03-24 Agfa Gevaert A method of preparing a conductive metallic layer or pattern
JP6176809B2 (ja) 2013-07-04 2017-08-09 アグフア−ゲヴエルト 金属ナノ粒子分散物
KR101533565B1 (ko) * 2013-07-04 2015-07-09 한국화학연구원 종횡비 조절이 가능한 고수율의 판상형 Ag 미세입자의 합성 방법
EP2821164A1 (en) 2013-07-04 2015-01-07 Agfa-Gevaert A metallic nanoparticle dispersion
CN103785852B (zh) * 2014-01-25 2016-08-17 华南理工大学 一种纳米银-纳米微晶纤维素复合物及其制备方法与应用
WO2016077936A1 (es) * 2014-11-18 2016-05-26 Nano Innova Spa. Método para la formación de nano-partículas de un metal, no-metal y/o un organo-metal; nanoparticulas derivadas del proceso; y su uso industrial
EP3037161B1 (en) 2014-12-22 2021-05-26 Agfa-Gevaert Nv A metallic nanoparticle dispersion
EP3099146B1 (en) 2015-05-27 2020-11-04 Agfa-Gevaert Method of preparing a silver layer or pattern comprising a step of applying a silver nanoparticle dispersion
EP3099145B1 (en) 2015-05-27 2020-11-18 Agfa-Gevaert Method of preparing a silver layer or pattern comprising a step of applying a silver nanoparticle dispersion
EP3287499B1 (en) 2016-08-26 2021-04-07 Agfa-Gevaert Nv A metallic nanoparticle dispersion
CN106637356B (zh) * 2016-12-22 2018-08-21 东南大学 一种三维黑色纳米金属宽光谱吸光薄膜的制备方法
WO2019113059A1 (en) * 2017-12-04 2019-06-13 Greene Lyon Group, Inc. Silver recovery
WO2019215068A1 (en) 2018-05-08 2019-11-14 Agfa-Gevaert Nv Conductive inks
CN112059205B (zh) * 2020-09-18 2022-08-16 东北大学 一种稳定粒径纳米银的制备方法
EP4163343A1 (en) 2021-10-05 2023-04-12 Agfa-Gevaert Nv Conductive inks
CN115156550A (zh) * 2022-07-26 2022-10-11 深圳先进电子材料国际创新研究院 一种中空银纳米颗粒的制备方法
CN115777725B (zh) * 2022-12-02 2024-01-26 山西益鑫泰生物科技有限公司 一种纳米银消毒剂及其制备方法

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JP4413095B2 (ja) * 2004-07-07 2010-02-10 財団法人川村理化学研究所 金属多孔体の製造方法
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Also Published As

Publication number Publication date
ES2355376T3 (es) 2011-03-25
IL204075A (he) 2013-08-29
CA2696588A1 (fr) 2009-03-05
PL2030706T3 (pl) 2011-04-29
WO2009027396A3 (fr) 2009-07-23
EP2030706A1 (fr) 2009-03-04
DE602007010457D1 (de) 2010-12-23
KR101526335B1 (ko) 2015-06-08
WO2009027396A2 (fr) 2009-03-05
ATE487554T1 (de) 2010-11-15
JP2010537057A (ja) 2010-12-02
KR20100066511A (ko) 2010-06-17
US20100303876A1 (en) 2010-12-02

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