EP2358489A1 - Procédé de fabrication de nanoparticules métalliques, nanoparticules métalliques ainsi obtenues et leur utilisation - Google Patents

Procédé de fabrication de nanoparticules métalliques, nanoparticules métalliques ainsi obtenues et leur utilisation

Info

Publication number
EP2358489A1
EP2358489A1 EP09760108A EP09760108A EP2358489A1 EP 2358489 A1 EP2358489 A1 EP 2358489A1 EP 09760108 A EP09760108 A EP 09760108A EP 09760108 A EP09760108 A EP 09760108A EP 2358489 A1 EP2358489 A1 EP 2358489A1
Authority
EP
European Patent Office
Prior art keywords
metal nanoparticles
functionalized
metal
particularly preferably
weight
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.)
Withdrawn
Application number
EP09760108A
Other languages
German (de)
English (en)
Inventor
Ulrich Nolte
Michael Berkei
Thomas Sawitowski
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.)
BYK Chemie GmbH
Original Assignee
BYK Chemie GmbH
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 BYK Chemie GmbH filed Critical BYK Chemie GmbH
Publication of EP2358489A1 publication Critical patent/EP2358489A1/fr
Withdrawn legal-status Critical Current

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
    • B22F9/24—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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles
    • B22F2304/054—Particle size between 1 and 100 nm
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/84—Manufacture, treatment, or detection of nanostructure
    • Y10S977/895—Manufacture, treatment, or detection of nanostructure having step or means utilizing chemical property
    • Y10S977/896—Chemical synthesis, e.g. chemical bonding or breaking

Definitions

  • the present invention relates to the technical field of nanotechnology.
  • the present invention relates to a process for the preparation of metal nanoparticles and the metal nanoparticles obtainable in this way and to their use. Furthermore, the present invention relates to the invention containing metal nanoparticles dispersions. Finally, the present invention relates to coating materials and coating systems, glasses and glassy coatings, inks and printing inks, plastics, foams, cosmetics, cleaning agents and impregnating agents, adhesives, sealants and catalyst systems which contain the metal nanoparticles according to the invention or the dispersions of the invention.
  • the preparation of such metal nanoparticles can be carried out via the reduction of a metal salt (eg a silver salt) in a two-phase reaction with sodium borohydride as the reducing agent.
  • a metal salt eg a silver salt
  • the metal salt is first using z. B. of tetraoctylammonium bromide from the aqueous into the organic phase (eg., Toluene or chloroform) and then reduced by means of sodium borohydride.
  • the organic phase eg., Toluene or chloroform
  • a stabilizer such.
  • dodecanethiol almost monodisperse metal nanoparticles can be synthesized and dispersed in various media due to the surface modification. For use in water, it requires in most cases a phase transfer catalyst such.
  • Another alternative is the so-called polyol method (see, for example, US 2006/0090599 A1), according to which a reduction of a metal ion source in or by a polyol at elevated temperatures above 100 0 C, in general above 150 ° C, is performed.
  • the polyol also serves as a stabilizer and solvent, ie no additional solvent is required.
  • a disadvantage of this method is that the resulting metal nanoparticles as such are not or at most very expensive isolatable. In addition, the resulting metal nanoparticles are not or only with difficulty modifiable for non-polar systems.
  • Another disadvantage is the use of relatively expensive starting chemicals and the relatively high process temperatures.
  • metal nanoparticles in particular gold nanoparticles
  • sonolysis is possible, but generally only on an experimental scale.
  • This method is based on an energy input by means of ultrasound.
  • An aqueous solution of, for example, HAuCl 4 is reacted with glucose, the actual reducing agent being hydroxyl radicals and sugar pyrolysis radicals which form at the interface region between the collapsing cavities of the glucose and the water.
  • So-called nanoribbons with widths of 30 to 50 nm and lengths of a few micrometers are created, these bands are flexible and more than 90 ° flexible.
  • JP 2003-147418 A relates to the preparation of metal nanoparticles (for example Au or Pd) by reduction in micelles in aqueous media, the micelles being produced from amphiphilic block copolymers.
  • metal nanoparticles for example Au or Pd
  • the necessary for Micellbil- formation block copolymers are relatively expensive to produce and also act as a reducing agent.
  • US 2006/0266156 A1 relates to metal particles which comprise on their surface two mutually different wetting or dispersing agents with different evaporation temperatures, and a process for their preparation.
  • US 2006/0266157 A1 describes the preparation of metal nanoparticles by reduction of aqueous metal salt solutions in the presence of a wetting agent, such. Cetyltrimethylammonium bromide (CTAB).
  • CTCAB Cetyltrimethylammonium bromide
  • the particles obtained in this way can be dispersed with the addition of wetting or dispersing agents and combined for bindings with binders.
  • the preparation is not carried out in a purely aqueous medium.
  • the reaction is a combination of citrate method on the one hand and two-phase reaction on the other hand.
  • the coverage of the particle surfaces, for example with CTAB as wetting agent provides readily dispersible particles in nonpolar media, but CTAB is relatively expensive and must be used in significant excess.
  • the addition of further dispersants is required in order to achieve a certain coating compatibility at all.
  • WO 2006/053225 A2 relates to the preparation of metal nanoparticles / protein complexes.
  • the preparation is carried out in an aqueous medium below
  • WO 2006/072959 A1 relates to water-based dispersions of metal nanoparticles and to a process for their preparation in the presence of a reducing water-soluble polymer which allows metal formation to form metal cores.
  • US 2007/0034052 A1 and US 2006/0159603 A1 describe the preparation of metal nanoparticles, in particular silver nanoparticles, by reduction of metal ions by means of polyols.
  • No. 6,992,039 B2 relates to the preparation of supported monodisperse noble metal nanoparticles on oxidic substrates.
  • the in situ preparation of noble metal nanoparticles on porous ceramics is described.
  • the reduction of the noble metal salts occurs in the presence of metal alkoxides and wetting agents, followed by a subsequent step of calcining.
  • US 2003/0199653 A1 relates to the preparation of metal nanoparticles in an aqueous medium in the presence of sulfur-containing copolymers by reduction with NaBH 4 . Due to the use of sulfur-containing stabilizers, the particles obtained in this way can not be used for catalysis. Furthermore, the synthesis is relatively expensive. Also, the redispersibility of the particles thus obtained is not very large.
  • WO 02/087749 A1 CA 2 445 877 A1 and US 2004/0147618 A1 describe the preparation of silver nanoparticles in various media using gamma radiation or ultrasound in the presence of polymeric stabilizers.
  • the problem underlying the present invention is thus to provide a process for the production of metal nanoparticles, which at least largely avoids or at least mitigates the previously described disadvantages of the prior art processes.
  • the present invention proposes a method according to claim 1; Further, advantageous embodiments are the subject of the relevant sub-claims.
  • the subject of the present invention are dispersions of the metal nanoparticles according to the invention in a carrier or dispersion medium according to claim 44.
  • the invention further relates to coating materials and coating systems, in particular paints, paints and the like, glasses and glassy coatings, inks and printing inks, plastics, foams, cosmetics, in particular nail varnishes, cleaning agents and impregnating agents, adhesives, sealants and catalyst systems, which are known from US Pat Metal nanoparticles according to the invention or the dispersions according to the invention contain (claim 45).
  • coating materials and coating systems in particular paints, paints and the like, glasses and glassy coatings, inks and printing inks, plastics, foams, cosmetics, in particular nail varnishes, cleaning agents and impregnating agents, adhesives, sealants and catalyst systems, which are known from US Pat Metal nanoparticles according to the invention or the dispersions according to the invention contain (claim 45).
  • the subject matter of the present invention is a process for the preparation of metal nanoparticles in which metal ions are reduced by means of at least one reducing agent in the presence of at least one polymeric stabilizer and converted into metal nanoparticles. This results in dispersions of metal nanoparticles, which are modified or coated on their surface with the polymeric stabilizer.
  • the reducing agent effects the reduction to elemental metal in the oxidation state 0, while the polymeric stabilizer ensures that the metal particles formed are produced as so-called nanoparticles, in particular agglomerate or not as an amorphous precipitate can separate or the like.
  • the inventive method is carried out in a liquid, preferably an aqueous medium or medium.
  • a liquid preferably an aqueous medium or medium.
  • the metal ions are dissolved in the respective medium or finely distributed in the form of salts.
  • the process according to the invention is carried out as a liquid-phase process, in particular as a single-phase reaction. This is a significant advantage over the initially described in the prior art reactions with two liquid phases to see.
  • defoamers known per se to the person skilled in the art can be used for this purpose.
  • the amount of defoamer can vary within wide ranges; Usually, the defoamer in amounts of 0.0001 to 5 wt .-%, preferably 0.001 to 2 wt .-%, particularly preferably 0.01 to 1 wt .-%, based on the total reaction mixture used.
  • Additives suitable according to the invention are selected, for example, from the group of pH regulators, pH buffer substances, emulsifiers, rheology modifiers, preservatives, surfactants or the like.
  • co-solvent may also be added to the reaction mixture.
  • the amount of co-solvent (s) can likewise vary widely; Usually amounts of from 0.01 to 10% by weight, particularly preferably from 0.1 to 7% by weight, very particularly preferably from 0.5 to 5% by weight, of co-solvent (s) are used on the entire reaction.
  • the co-solvent may in particular be selected from organic, preferably polar solvents, such as alcohols, glycols (eg butylglycol etc.) or the like, or else from inorganic solvents, such as acids and bases.
  • inorganic acids or bases for metal salts can be used as co-solvents for starting materials.
  • NH 3 to achieve the solubility of AgCl in water, which leads to the formation of [Ag (NH 3 ) 2 ] Cl, or HCl for AuCl 3 as the starting material, which in turn leads to the formation of HAuCl 4 .
  • the process according to the invention can be carried out over a wide temperature range. Since the process is carried out as a liquid phase process, the temperature range is limited downwards by the melting point of the reaction milieu and upwards by its boiling point. In general, especially when using an aqueous medium, the process in the temperature range of> 0 0 C and ⁇ 100 0 C, in particular 5 to 90 0 C, preferably 10 to 80 0 C, particularly preferably 10 to 40 0 C, very particularly preferably 10 to 30 0 C, performed. Lower temperatures have the advantage that generally more stable dispersions are obtained and, in addition, the resulting nanoparticles generally show better redispersibility.
  • a further advantage of the method according to the invention can be seen in the relatively short process times, which is of great advantage, especially in the case of large-scale implementation or implementation on an industrial scale.
  • the process according to the invention is usually carried out with a reaction time of ⁇ 10 minutes, in particular ⁇ 5 minutes, preferably ⁇ 1 minute, more preferably ⁇ 0.5 minutes.
  • the process according to the present invention is carried out with a reaction time in the range of 0.0001 to 10 minutes, in particular 0.0001 to 5 minutes, preferably 0.0001 to 1 minute, particularly preferably 0.0001 to 0.5 minutes.
  • the actual implementation is completed within a few seconds in the context of the method according to the invention.
  • the process according to the invention can alternatively be operated either batchwise or batchwise or else continuously.
  • the inventive method can be carried out, for example, in a simple stirred tank.
  • a continuous procedure however, the process of the invention in a continuous stirred or tubular reactor, a continuous Rhakkesselkaskade or be carried out in a so-called spinning disk reactor.
  • the continuous implementation in a so-called spinning-disk reactor offers the additional advantage of extremely fast conversion due to a very rapid and intensive mixing; for further details of the procedure in a spinning disk reactor, reference may be made, for example, to WO 2006/018622 A1, WO 2006/040566 A1 and WO 2006/008500 A1, the entire disclosure of which is hereby incorporated by reference.
  • the method according to the invention can be carried out such that a temporal and / or local separation of the nucleation and growth processes is achieved by regulating temperature and / or volume flows;
  • the method according to the invention can be carried out in particular in a so-called microreaction technology system.
  • a particular advantage of this procedure is that a particularly uniform morphology and / or monodispersibility of the resulting metal nanoparticles is achieved.
  • the reducing agent should be selected such that it is capable of reducing the relevant metal ion to be reduced to elemental metal (i.e., oxidation state: 0).
  • the reducing agent in the electrochemical series has a lower normal potential than the metal of the metal ion to be reduced.
  • the reducing agent should be selected to be soluble or dispersible in the reaction medium.
  • Reducing agents which are suitable according to the invention are in particular selected from the group of inorganic hydrides, such as sodium borohydride or lithium aluminum hydride; inorganic thiosulfates or thiosulfuric acid; inorganic sulfides or hydrogen sulfide; inorganic sulfites; hydrazines; hydroxylamines; Hydrogen (eg gaseous or in situ generated hydrogen or nascent hydrogen); carbon monoxide; Acetylene; Oxalic acid or oxalates; Citric acid or citrates; Tartaric acid or tartrates; monohydric or polyhydric alcohols, e.g.
  • inorganic hydrides such as sodium borohydride or lithium aluminum hydride
  • inorganic thiosulfates or thiosulfuric acid inorganic sulfides or hydrogen sulfide
  • inorganic sulfites inorganic sulfites
  • hydrazines
  • glycol or else hydroxy-functional polyglycol ethers; Sugar; inorganic phosphides; and mixtures or combinations of at least two of the aforementioned reducing agents.
  • inorganic hydrides in particular of the aforementioned type.
  • the amount of reducing agent used can likewise vary widely.
  • the reducing agent in a ratio of reducing agent to metal ions, calculated as the amount of electrons required for the reduction in the range of 1.05: 1 to 200: 1, in particular 1.1: 1 to 100: 1, preferably 1 , 1: 1 to 50: 1, used.
  • the larger the aforementioned ratio the more nuclei are formed and the smaller the nanoparticles are formed.
  • the metal is selected from at least one metallic element of groups III A to VA and IB to VIII B of the periodic system of the elements.
  • the metal is selected from the group of Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Ru, Os, Se, Te, Cd, Bi, In, Ga, As, Ti, V, W , Mo, Si, Al and / or Sn and mixtures, alloys and mixed crystals of at least two of these elements.
  • the metal is selected from the group of Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Ru, Os, Se and / or Te and mixtures, alloys and mixed crystals of at least two of these elements .
  • the metal is selected from noble metals, in particular Cu, Ag, Au, Ni, Pd, Pt, Ru, Ir and / or Rh, most preferably Ag, Au, Pd and / or Pt.
  • the nanoparticles can be obtained based on at least two metals, in particular of the type CdSe, CdTe, BiTe, GaAs, InAs, AgPd, CoPt and / or AgAu. These are thus at least binary metal nanoparticles.
  • Such systems are of interest, for example, for the semiconductor technology and the catalyst technology.
  • the metal ions can basically be used in any desired forms. It is possible to use all metal ion sources which are compatible in the context of the process according to the invention, in particular in which the reaction medium is soluble or dispersible.
  • the metal ions may be present in particular in the form of metal salts (eg AgNO 3 , Na 2 PtCl 4 , NaAuCl 4 • 2H 2 O etc.), metal acids and their hydrates (eg HAuCl 4 • 3 H 2 O, H 2 PtCl 4 • 6H 2 O, H 2 PtCl 4 etc.), ionic or covalent metal compounds (eg AuCl 3 , PtCl 2 , AgCl etc.), complexed metal ions and / or metal electrodes (eg in electrolysis ), preferably in the form of metal salts.
  • metal salts eg AgNO 3 , Na 2 PtCl 4 , NaAuCl 4 • 2H 2 O etc.
  • metal acids and their hydrates e
  • the amount of metal ions used can likewise vary widely.
  • the metal ions based on the total reaction mixture and calculated as metal, in amounts of 0.0001 to 20 wt .-%, in particular 0.001 to 15 wt .-%, preferably 0.005 to 10 wt .-%, particularly preferably 0, 01 to 3 wt .-%, most preferably 0.1 to 2 wt .-%, used.
  • the metal nanoparticles obtained can have absolute particle sizes in the range from 0.3 to 1000 nm, in particular 0.5 to 750 nm, preferably 1 to 500 nm, particularly preferably 2 to 100 nm, very particularly preferably 3 to 50 nm.
  • the metal nanoparticles obtained have average particle sizes (determined as so-called D50 value) in the range from 1 to 500 nm, in particular 2 to 200 nm, particularly preferably 2 to 100 nm, very particularly preferably 5 to 40 nm.
  • the size and shape of the resulting metal nanoparticles can be varied by the corresponding variation of the reaction conditions. For example, by varying the type and / or quantity of the reduction by means of and / or the type and / or amount of the polymeric stabilizer and / or the reaction temperature and / or the addition mode (single addition, stepwise addition, etc.) or the like, the particle size targeted influence or adjust. This is known to the skilled person as such.
  • the metal nanoparticles obtained may have a bimodal particle size distribution.
  • the average particle diameter (D50) of the two fractions of metal nanoparticles can advantageously not differ by at least 10 nm, in particular at least 25 nm, preferably at least 50 nm, particularly preferably at least 75 nm, very particularly preferably at least 100 nm.
  • special effects, in particular surface effects can be achieved, in particular with regard to the mechanical properties, such as mechanical stability, abrasion resistance, surface properties, gloss etc.
  • a bimodal particle size distribution can be achieved by deliberate variation or adjustment of the reaction conditions, for example by selecting the ratio of reducing agent to metal ions to be reduced, by the amount of polymeric stabilizer (eg lower or substoichiometric amounts of polymeric Stabilizer), by stepwise and / or repeated addition of the individual reagents etc. This is familiar to the person skilled in the art as such.
  • the polymeric stabilizer As far as the polymeric stabilizer is concerned, it can equally be used in wide ranges.
  • the polymeric stabilizer may be used in amounts of 1 to 1000% by weight, preferably 5 to 500% by weight, more preferably 10 to 200% by weight, most preferably 20 to 100% by weight, based on the resulting metal nanoparticles are used.
  • the polymeric stabilizer As far as the chemical nature of the polymeric stabilizer is concerned, it is in particular a polymeric dispersant or a polymeric wetting agent and / or a surfactant.
  • the molecular weight of the polymeric stabilizer used can equally vary within wide ranges.
  • the polymeric stabilizer used usually has an average, in particular weight-average molecular weight of at least 1,000 g / mol, preferably at least 1,500 g / mol.
  • the polymeric stabilizer has an average, in particular weight-average molecular weight in the range from 1,000 to 1,000,000 g / mol, in particular from 1,250 to 100,000 g / mol, preferably from 1,500 to 75,000 g / mol, particularly preferably from 2,000 to 50,000 g / mol ,
  • the polymeric stabilizer is based on a functionalized, in particular acid and / or basic functionalized, polymer, in particular with polar functional groups formed.
  • the polymeric stabilizer can be selected from the group of functionalized polyamines, functionalized polyurethanes, functionalized poly (meth) acrylates, functionalized vinyl copolymers, functionalized polyether / polyester copolymers, functionalized polyethers, functionalized polyesters, functionalized fatty acid copolymers, functionalized block copolymers. copolymeric and / or functionalized polyalkoxy laten and mixtures or combinations of at least two of these compounds.
  • the polymeric stabilizer may usually be based on a functionalized, especially acid and / or basic functionalized polymer, the polymer containing at least one functional group, which may in particular be selected from the group of hydroxyl (-OH), thiol (-) SH), amine, ammonium, carboxyl, carbonyl, ester, ether, sulfonyl, phosphoric and / or phosphoric acid ester functions, preferably hydroxyl (-OH), thiol (-SH) and / or amine functions.
  • a functionalized, especially acid and / or basic functionalized polymer the polymer containing at least one functional group, which may in particular be selected from the group of hydroxyl (-OH), thiol (-) SH), amine, ammonium, carboxyl, carbonyl, ester, ether, sulfonyl, phosphoric and / or phosphoric acid ester functions, preferably hydroxyl (-OH), thiol (-SH) and / or
  • the base number of the polymer in question may be at least 10 mg KOH / g, in particular at least 20 mg KOH / g, preferably at least 25 mg KOH / g, and in the case of acidic functionalization, the acid number may be at least 10 mg KOH / g, preferably at least 25 mg KOH / g, more preferably at least 50 mg KOH / g.
  • the polymeric stabilizer can be selected from the dispersants and / or wetting agents mentioned below, as described in the publications listed below, whose respective disclosure content is hereby incorporated by reference:
  • modified polyurethanes and polyamines according to EP 1 593 700 A; salified polyamines according to EP 0 893 155 A; - Phosphoric acid ester according to EP 0 417 490 A;
  • a step of purification may follow the actual production of the metal nanoparticles.
  • the purification can be carried out in a manner known per se to those skilled in the art, so that no further relevant embodiment is required.
  • the resulting metal nanoparticles can be separated by methods known per se, to which may optionally follow a process step of redispersing (for example in another medium).
  • the metal nanoparticle dispersions obtained can also be used as such, ie as they are obtained immediately after the preparation, since the respective metal nanoparticles are present in stable, in particular long-term stable dispersion.
  • the process according to the invention for the preparation of metal nanoparticles is associated with a number of advantages, some of which are to be mentioned below in a nonlimiting manner:
  • the inventive method works cost-effectively and economically and is also readily Anlagenmotherbar on an industrial or industrial scale.
  • the method according to the invention can be configured extremely flexibly with regard to its process control.
  • the process of the invention can be operated continuously as a batch. In discontinuous procedure can be moved, for example, in a stirred tank. In a continuous procedure, the reaction can be carried out, for example, in a continuous stirred reactor or tubular reactor, a continuous stirred tank cascade or in a so-called spinning disk reactor.
  • the relatively low process temperatures also contribute to process efficiency and process economics and also meet today's environmental requirements.
  • the process according to the invention is carried out in purely aqueous media; it is, as it were, a "green process" which, moreover, is flexibly modifiable.
  • the process is thus simple, inexpensive and ecologically compatible and largely dispenses with organic solvents.
  • the metal nanoparticles obtained in the context of the process according to the invention can readily be isolated from the dispersion. Due to the stability of the dispersions, however, the dispersions can also be used as such without having to carry out a preceding isolation of the metal nanoparticles.
  • nanoparticles are achieved in a variety of media (such as water, organic solvents, polymers, waxes, oils, glycols, etc.).
  • dispersants or wetting agents used can readily be removed either partially or completely
  • the metal nanoparticles obtained by the process according to the invention allow a wide variety of uses, for example as paint and / or plastic additives, as pigments, as catalysts, etc. This is described in detail below.
  • the process according to the invention thus provides a purely aqueous synthesis of metal nanoparticles, more preferably noble metal nanoparticles, using suitable polymeric wetting or dispersing agents.
  • the synthesis can be flexibly applied to different metals (eg silver, gold, etc.).
  • suitable wetting or dispersing agents By using suitable wetting or dispersing agents, the subsequent dispersibility can be controlled in a wide variety of media.
  • By adapting the oxidation potential of the reducing agent and choosing a suitable stabilizer it is also possible to produce nanoparticles (oxidation) -sensitive metals.
  • the inventive method is also flexible transferable to a variety of metals. With the method according to the invention can be achieve significantly higher concentrations in dispersion of nanoparticles compared to the prior art. In addition, the process according to the invention uses exclusively favorable starting chemicals or educts. In addition, the method according to the invention can also be carried out on an industrial or industrial scale and thus upscalebar. Due to the removability of the wetting or dispersing agents used, no "dead" surfaces are formed on the resulting metal nanoparticles.
  • a further subject of the present invention - according to one aspect of the invention - are the metal nanoparticles obtainable by the process according to the invention.
  • the present invention relates to metal nanoparticles which comprise on their surface at least one polymeric stabilizer, in particular a polymeric wetting and dispersing agent, or on their surface with at least one polymeric stabilizer, in particular a polymeric wetting agent Dispersants, modified and / or coated.
  • the metal nanoparticles according to the invention have an excellent dispersing behavior and can be easily redispersed even after isolation from the reaction mixture.
  • the metal nanoparticles according to the invention are dispersible both in aqueous and in organic media.
  • the metal nanoparticles according to the invention are dispersible in both polar and non-polar solvents.
  • the dispersing properties of the metal nanoparticles according to the invention can be adjusted selectively by the surface modification with the polymeric stabilizer or, so to speak, tailor-made.
  • Another object of the present invention - according to a third aspect of the invention - is the inventive use of the metal nanoparticles according to the present invention.
  • the metal nanoparticles according to the invention can be used, for example, as additives, pigments or fillers, in particular for paints, coatings and plastics.
  • metal nanoparticles according to the invention can be used as or in catalysts or catalyst systems.
  • the metal nanoparticles according to the invention can also be used in coating materials and coating systems, in particular paints, inks and the like, in glasses and glassy coatings, in inks and printing inks, in dispersions of all kinds, in plastics, in foams, in cosmetics, in particular nail varnishes , in detergents and impregnating agents, in adhesives, in sealants and in catalysts or catalyst systems, in particular as additives, pigments or fillers.
  • coating materials and coating systems in particular paints, inks and the like, in glasses and glassy coatings, in inks and printing inks, in dispersions of all kinds, in plastics, in foams, in cosmetics, in particular nail varnishes , in detergents and impregnating agents, in adhesives, in sealants and in catalysts or catalyst systems, in particular as additives, pigments or fillers.
  • the nanoparticles according to the invention can be used in optics and optoelectronics as well as in electronics, electrical engineering and semiconductor technology.
  • the metal nanoparticles according to the invention can be used to increase conductivities, in particular of plastics, or else for the production of printable circuits.
  • metal nanoparticles according to the invention can also be used in spectroscopy, in particular in Raman spectroscopy, for example for purposes of signal amplification.
  • metal nanoparticles of the invention in the glass, ceramic and enamel manufacture, for. As in the manufacture of windows (for example, church windows), in particular as pigments or dyes. Furthermore, it is possible to use the metal nanoparticles according to the invention in textile production, for example, equally as pigments and / or dyes.
  • a further subject matter of the present invention - according to one aspect of the invention - are dispersions which contain the metal nanoparticles according to the invention in a carrier or dispersion medium.
  • further object of the present invention are coating materials and coating systems, in particular paints, inks and the like, plastics, foams, cosmetics, in particular nail varnishes, adhesives, sealants and catalyst systems comprising the metal nanoparticles according to the invention or the comprising dispersions containing them.
  • Gold nanoparticles are prepared according to the method described by Turkevich et al. developed method by citrate synthesis as follows. 10 ml of an aqueous solution of 2.5 - 10 '4 mol / 1 HAuCl 4 • 3 H 2 O are heated to 95 0 C. Subsequently, 417 ⁇ l of a 20 mmol / l trisodium citrate solution are added with vigorous stirring, whereupon the solution slowly changes its color to red. The Au / citrate ratio is 0.3. The solution is left for 15 minutes near the boiling point, then allowed to cool the whole.
  • the example is repeated except that 312 ⁇ l of a 20 mmol / l trisodium citrate solution are added, which corresponds to an Au / citrate ratio of 0.4.
  • the aforementioned Au / citrate ratios influence the resulting sizes of the Au nanoparticles obtained.
  • Example 2 Preparation of Silver Nanoparticles by Two-Phase Synthesis in the Presence of NaBH 4 as Reducing Agent (Comparative, Prior Art) 9 mmol (1.53 g) of silver nitrate are dissolved in 300 ml of water in a 1-liter three-necked flask. 40 mmol (21.86 g) of tetra-n-octylammonium bromide are dissolved in 204 ml of CHCl 3 in a beaker.
  • the CHCl 3 solution is added to the silver nitrate solution. After about 1 minute, the N 2 stream is issued. The CHCl 3 phase turns green and becomes cloudy. The water phase becomes milky, but contains no target product.
  • the resulting powder must still be washed with ethanol to remove impurities and then be dispersed in nonpolar solvents up to 0.2%.
  • the particle size is 10 nm, but has a coarse fraction (10%) of> 100 nm. The reaction is very sensitive and not always reproducible.
  • EXAMPLE 3A Preparation of Silver Nanoparticles by the Process According to the Invention (Invention) First, a solution of 3.5 parts by weight of AgNO 3 , 100 parts by weight of water, 7.2 parts by weight of a polymeric wetting or dispersing agent ( z. B. Disperbyk ® 2001, BYK-Chemie GmbH, Wesel, Germany) and optionally 0.6 parts by weight of a defoamer (z. B. BYK028 BYK-Chemie GmbH, Wesel, Germany) ( "solution a”) prepared and stirred at room temperature. The approach is a cloudy mixture.
  • a polymeric wetting or dispersing agent z. B. Disperbyk ® 2001, BYK-Chemie GmbH, Wesel, Germany
  • a defoamer z. B. BYK028 BYK-Chemie GmbH, Wesel, Germany
  • solution B is prepared from 3 parts by weight of NaBH 4 and 50 parts by weight of water. Solution B is slowly added to solution A at room temperature. It creates strong foam and blackening. This results in a dispersion of Ag nanoparticles in water.
  • z. B. be extracted with PMA (methoxypropyl acetate), which leads to nanoparticles of high purity, which z. B. can be used for catalytic purposes, or centrifuged, dried and redispersed (eg in PMA).
  • PMA methoxypropyl acetate
  • the preceding experiment is repeated, but with the difference that the solution B is rapidly added to the solution A. Rapid addition of solution B to solution A produces smaller nanoparticles. As a result of the rate of addition, the particle size of the resulting nanoparticles can thus be controlled in a targeted manner.
  • Example 3B is used: Preparation of silver nanoparticles by the inventive process (invention) Example 3A but with the difference that another wetting agent (Disperbyk ® 194 from BYK-Chemie GmbH, Wesel, Germany concrete) is repeated.
  • the resulting Ag nanoparticles are redispersible both in water and in PMA. This dispersion of Ag nanoparticles can thus be used directly as an additive, if appropriate after a corresponding treatment and / or concentration step.
  • HAuCl 4 is used instead of AgNO 3 . This results in the corresponding Au nanoparticles.
  • Example 3D Reduction of AgNO 3 in Water Without the Presence of a Dispersing Agent (Comparison)
  • Example 3A is repeated, but with the difference that no wetting or dispersing agent is used as stabilizer. There is no formation of Ag nanoparticles, but a through-reaction to an Ag sludge.
  • the silver particles produced at temperatures up to 40 ° C have much better redispersibilities in polar solvents, such as water and 1,3-propanediol.
  • polar solvents such as water and 1,3-propanediol.
  • the dispersing behavior in ethyl acetate is initially good in all experiments, but the dispersions of the nanoparticles From 60 0 C lower stability in ethyl acetate, as evidenced by the formation of a silver level on the glass wall. Redispersibility in PMA is equally good at all temperatures.
  • the formation of a silver mirror can also be used to advantage for the mirroring or formation of conductive layers.
  • the destabilization causes the particles to approach each other and optionally a plasmon transition.

Abstract

L'invention concerne un procédé de fabrication de nanoparticules métalliques, des ions métalliques étant réduits au moyen d'au moins un agent de réduction en présence d'au moins un stabilisateur polymère et convertis en nanoparticules métalliques. L'invention concerne également les nanoparticules métalliques ainsi obtenues ainsi que leur utilisation.
EP09760108A 2008-12-12 2009-11-20 Procédé de fabrication de nanoparticules métalliques, nanoparticules métalliques ainsi obtenues et leur utilisation Withdrawn EP2358489A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102008061703 2008-12-12
DE102009015470A DE102009015470A1 (de) 2008-12-12 2009-03-28 Verfahren zur Herstellung von Metallnanopartikeln und auf diese Weise erhaltene Metallnanopartikel und ihre Verwendung
PCT/EP2009/008289 WO2010066335A1 (fr) 2008-12-12 2009-11-20 Procédé de fabrication de nanoparticules métalliques, nanoparticules métalliques ainsi obtenues et leur utilisation

Publications (1)

Publication Number Publication Date
EP2358489A1 true EP2358489A1 (fr) 2011-08-24

Family

ID=42168810

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09760108A Withdrawn EP2358489A1 (fr) 2008-12-12 2009-11-20 Procédé de fabrication de nanoparticules métalliques, nanoparticules métalliques ainsi obtenues et leur utilisation

Country Status (8)

Country Link
US (1) US8870998B2 (fr)
EP (1) EP2358489A1 (fr)
JP (1) JP5833447B2 (fr)
KR (1) KR101278939B1 (fr)
CN (1) CN102245333B (fr)
BR (1) BRPI0923509A2 (fr)
DE (1) DE102009015470A1 (fr)
WO (1) WO2010066335A1 (fr)

Families Citing this family (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8894760B2 (en) * 2009-11-20 2014-11-25 Rohm And Haas Electronic Materials Llc Group 3a ink and methods of making and using same
DE102010033924A1 (de) * 2010-08-03 2012-02-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von Nanopartikeln aus einem Edelmetall und die Verwendung der so hergestellten Nanopartikel
TW201219470A (en) * 2010-11-12 2012-05-16 Univ Nat Taiwan Oil dispersible composite of metallic nanoparticle and method for synthesizing the same
US8308842B2 (en) * 2010-12-08 2012-11-13 Xerox Corporation Pyrophoric iron nanoparticles and continuous processes for production thereof
CN102179525B (zh) * 2011-04-15 2013-05-08 北京航空航天大学 一种室温条件制备镍铂双层纳米碗的可控合成方法
CN103582500A (zh) * 2011-06-06 2014-02-12 俄勒冈州，由高等教育州委员会代表俄勒冈州立大学 铋粒子x-射线造影剂
JP5140187B1 (ja) * 2011-09-27 2013-02-06 田中貴金属工業株式会社 導電粒子及び金属ペースト並びに電極
CN102528070B (zh) * 2012-01-09 2014-01-01 苏州银瑞光电材料科技有限公司 利用高速射流生产纳米银粉的方法和装置
CN102554219B (zh) * 2012-01-31 2014-03-26 云南云天化股份有限公司 铜锡核壳结构的纳米粒子及其制备方法
CN102649035A (zh) * 2012-02-06 2012-08-29 京东方科技集团股份有限公司 一种电泳粒子及其制作方法、电泳微胶囊
KR101279459B1 (ko) * 2012-04-19 2013-06-26 서울과학기술대학교 산학협력단 화학적 환원 합성법을 이용한 주석계 솔더 페이스트 제조 방법
CN103624265A (zh) * 2012-08-21 2014-03-12 国家纳米科学中心 一种纳米金颗粒及其制备方法
CN103658672B (zh) * 2012-09-11 2015-10-21 中国科学院大连化学物理研究所 一种金属纳米粒子的水相制备方法
CN104797363B (zh) 2012-09-27 2018-09-07 罗地亚经营管理公司 制造银纳米结构的方法和可用于此方法的共聚物
FR2997101B1 (fr) * 2012-10-18 2015-01-02 Holding Textile Hermes Procede de fabrication d'un textile a effet de coloration variable contenant de l'or ou au moins un alliage contenant de l'or sous forme de particules et textile a effet de coloration variable.
CN104736483A (zh) * 2012-10-29 2015-06-24 阿尔法金属公司 烧结粉末
CN103056388B (zh) * 2013-01-22 2015-07-22 西南科技大学 液相化学还原法制备包覆有分散稳定剂的铝纳米粒子的方法
CN103970375A (zh) * 2013-01-29 2014-08-06 华为终端有限公司 指甲油、指甲装饰物及触控屏幕的操作方法
CN103157808B (zh) * 2013-02-01 2015-04-01 天津商业大学 一种金铂钌合金纳米粒子及其胶体分散体系的制备方法
CN103149194B (zh) * 2013-02-28 2015-08-26 西安交通大学 一种表面增强拉曼散射基体的制备方法
EP2781562B1 (fr) * 2013-03-20 2016-01-20 Agfa-Gevaert Procédé pour préparer une dispersion de nanoparticules métalliques
US10543536B2 (en) 2013-06-07 2020-01-28 Lg Chem, Ltd. Method for fabricating metal nanoparticles
CN105324851B (zh) * 2013-08-01 2017-03-22 株式会社Lg化学 用于制造太阳能电池光吸收层的聚集前驱体及其制造方法
CN103433044B (zh) * 2013-08-27 2015-05-13 安徽大学 一种钴-镍双金属氢氧化物纳米复合物的制备方法
EP3062945B1 (fr) * 2013-11-01 2019-12-04 Council of Scientific and Industrial Research;an Indian Reg. body incorporated under Reg. of Societies Act (Act XXI of 1860) Procédé de préparation de nanoparticules métalliques
CN103752846A (zh) * 2014-01-17 2014-04-30 昆明理工大学 一种微通道连续快速制备纳米铜的方法
CN103990810A (zh) * 2014-05-30 2014-08-20 洛阳理工学院 一种纳米铟粉的制备工艺
CN106413951B (zh) * 2014-05-30 2019-05-03 韩国化学研究院 金属纳米颗粒及其制备方法
CN104130629B (zh) * 2014-07-30 2016-01-20 深圳市宇顺电子股份有限公司 导电墨水及其制备方法
CN104128616B (zh) * 2014-08-12 2016-03-23 苏州思美特表面材料科技有限公司 一种金属粉末的制备方法
CZ307129B6 (cs) * 2014-09-24 2017-12-27 Univerzita Pardubice Způsob přípravy bimodální směsi nanočástic a mikročástic mědi s polymerní ochrannou vrstvou
CN104475751A (zh) * 2014-12-05 2015-04-01 山东理工大学 一种制备两亲性纳米银粒子的新方法
CN105732918A (zh) * 2014-12-12 2016-07-06 中国石油天然气股份有限公司 一种有机硅改性的丙烯酸酯/银纳米复合材料及其制备方法
CN105798320B (zh) * 2014-12-31 2018-05-04 中国科学院化学研究所 一种低温制备纳米铜粉的方法
CN104624204B (zh) * 2015-02-06 2017-02-01 中国科学院上海高等研究院 用于co选择性加氢的催化剂及其制法和应用
CN104841932A (zh) * 2015-06-04 2015-08-19 山东理工大学 制备核壳型聚苯乙烯包覆纳米银复合粒子的新方法
CN105056996B (zh) * 2015-08-20 2017-05-17 郑州大学 对苯二甲酸二甲酯选择性加氢制1,4‑环己烷二甲酸二甲酯用催化剂及其制备方法、使用方法
CN105056997B (zh) * 2015-08-20 2017-08-11 郑州大学 一种对苯二甲酸选择性加氢制1,4‑环己烷二甲酸用催化剂及其制备方法、使用方法
CN105080603B (zh) * 2015-08-20 2017-05-17 郑州大学 一种硝基苯选择性加氢制苯胺用催化剂及其制备方法、使用方法
CN105149609A (zh) * 2015-09-07 2015-12-16 昆明仁旺科技有限公司 一种制备贵金属粉体的方法
CN105127413B (zh) * 2015-09-18 2017-07-21 温州大学 贵金属纳米环及其制备方法
CN105153401B (zh) * 2015-10-13 2017-11-17 厦门大学 荧光金纳米团簇及其水性聚氨酯模板法制备方法
DE102015221529A1 (de) 2015-11-03 2017-05-04 Cht R. Beitlich Gmbh Kontinuierliches Verfahren für Reaktionen mit feinteiligen Alkalimetall-Dispersionen
CN106807952B (zh) * 2015-12-01 2019-05-07 中国科学院大连化学物理研究所 一种合成Au25纳米球的方法及Au25纳米球
US11162161B2 (en) * 2015-12-21 2021-11-02 Sandvik Intellectual Property Ab Cutting tool
CL2015003794A1 (es) * 2015-12-30 2016-07-29 Univ Chile Método de obtención de nano partículas de cobre y uso de dichas partículas
JP6255635B1 (ja) * 2016-04-22 2018-01-10 Dic株式会社 金属ナノ粒子水分散液
CN105834450B (zh) * 2016-05-13 2019-03-19 浙江光达电子科技有限公司 银粉的制备方法
CN107520459A (zh) * 2016-06-21 2017-12-29 张家港市山牧新材料技术开发有限公司 铜纳米颗粒的制备方法和抗菌塑料
EP3519510A4 (fr) * 2016-09-30 2019-09-11 Nanyang Technological University Composition d'encre, procédé de formation d'un élément conducteur et dispositif conducteur
JP6849374B2 (ja) * 2016-10-06 2021-03-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ 接合用の導電性ペースト
US9975110B1 (en) 2016-11-23 2018-05-22 Honda Motor Co., Ltd. Method for producing metal catalyst nanoparticles
KR101874623B1 (ko) * 2016-11-29 2018-08-02 주식회사 나노뉴텍 우수한 항균 효과를 갖는 고급 함침재 및 이를 구비한 화장품
CN108161020A (zh) * 2016-12-13 2018-06-15 中国科学院光电技术研究所 一种金纳米八面体的制备方法
JP7132695B2 (ja) * 2016-12-20 2022-09-07 Ｔｏｍａｔｅｃ株式会社 金属微粒子、金属微粒子含有分散液及びその製造方法
CN106984804A (zh) * 2017-05-10 2017-07-28 哈尔滨工程大学 一种纳米铝粉包覆方法
KR102497069B1 (ko) * 2017-09-06 2023-02-06 카운슬 오브 사이언티픽 앤드 인더스트리얼 리서치 금속 나노와이어의 연속 흐름 제조
KR102067819B1 (ko) * 2017-10-31 2020-02-11 영남대학교 산학협력단 나노 구조체의 안정화 방법
CN108284232B (zh) * 2018-01-26 2021-07-20 上海应用技术大学 一种银纳米粒子的制备方法
EP3656825B1 (fr) 2018-11-22 2021-04-28 Société BIC Procédé de préparation d'encres de gel aqueuses à couleur variable et encres de gel aqueuses correspondantes
CN109746457A (zh) * 2018-11-28 2019-05-14 石河子大学 一种纳米金的制备方法
CN109848438B (zh) * 2019-03-25 2022-02-25 珠海纳金科技有限公司 一种双模粒径纳米银颗粒及其制备方法
KR20220053593A (ko) 2019-08-29 2022-04-29 소시에떼 빅 은 또는 금 나노입자를 포함하는 고정 색을 갖는 수성 겔 잉크의 제조 방법
CN110480004B (zh) * 2019-08-29 2021-11-09 南京理工大学 水热法制备碳包覆纳米铝粉的方法
US11802214B2 (en) * 2019-08-29 2023-10-31 Societe Bic Process of preparation of an aqueous gel ink with variable color comprising silver nanoparticles
US11820905B2 (en) 2019-08-29 2023-11-21 Societe Bic Process of preparation of an aqueous gel ink with fixed color comprising gold nanoparticles
CN111592788B (zh) * 2020-05-29 2022-09-16 合肥福纳科技有限公司 量子点发光二极管、量子点墨水及其制作方法
CN111975011B (zh) * 2020-07-20 2022-01-18 华南理工大学 一种芯片无压烧结互连用纳米铜浆及其制备方法与应用
CN114316666A (zh) * 2022-01-06 2022-04-12 渭南市瑞梦印务有限责任公司 一种专色油墨配方及其加工工艺
CN114833334B (zh) * 2022-04-02 2023-08-15 有研工程技术研究院有限公司 可连续制备微米级球形金粉的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006072959A1 (fr) * 2005-01-10 2006-07-13 Yissum Research Development Company Of The Hebrew University Of Jerusalem Dispersions aqueuses de nanoparticules de metal
US20070190323A1 (en) * 2006-02-15 2007-08-16 Samsung Electro-Mechanics Co., Ltd. Method of producing metal nanoparticles
US20070207335A1 (en) * 2004-07-30 2007-09-06 Karandikar Bhalchandra M Methods and compositions for metal nanoparticle treated surfaces

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0154678B2 (fr) 1984-01-27 1998-12-09 Byk-Chemie GmbH Composés d'addition utilisables comme agents de dispersion, procédé de leur préparation, leur utilisation et matériaux solides revêtus par ceux-ci
DE3641581C3 (de) 1986-12-05 1996-08-01 Byk Chemie Gmbh Verfahren zur Herstellung von Dispergiermitteln und deren Salzen und ihre Verwendung
US4942213A (en) 1987-12-04 1990-07-17 Byk-Chemie Gmbh Addition compounds useful as dispersing agents and dispersion stabilizers, process for producing them, their use and solids coated therewith
DE3930687A1 (de) 1989-09-14 1991-04-11 Byk Chemie Gmbh Phosphorsaeureester, verfahren zu deren herstellung und deren verwendung als dispergiermittel
DE19721728C2 (de) 1997-05-24 2001-07-12 Byk Chemie Gmbh Dispergiermittel für Pigmente oder Füllstoffe auf der Basis von Acrylsäurealkylester-Polymeren, Verwendung und Verfahren zur Herstellung
JP3594803B2 (ja) * 1997-07-17 2004-12-02 日本ペイント株式会社 貴金属又は銅のコロイド溶液及びその製造方法並びに塗料組成物及び樹脂成型物
DE19732251B4 (de) 1997-07-26 2004-07-29 Byk-Chemie Gmbh Versalzungsprodukte von Polyaminen und deren Einsatz als Dispergiermittel für Pigmente und Füllstoffe
DE19745904A1 (de) * 1997-10-17 1999-04-22 Hoechst Ag Polymerstabilisierte Metallkolloid-Lösungen, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren für Brennstoffzellen
EP1135682B1 (fr) * 1998-11-30 2007-07-11 Nanosphere, Inc. Nanoparticules a enveloppes polymeres
DE19941031A1 (de) 1999-08-28 2001-03-01 Byk Chemie Gmbh Verzweigte, Imidazolgruppen enthaltende Polymere, sowie deren Herstellung und Verwendung
JP2002285207A (ja) * 2001-03-23 2002-10-03 Nippon Paint Co Ltd 白金コロイド水溶液、その製造方法及び白金の担持方法
WO2002087749A1 (fr) 2001-04-30 2002-11-07 Postech Foundation Solution colloidale de nanoparticules metalliques, nanocomposites metal-polymere et procedes de preparation associes
JP4094277B2 (ja) * 2001-11-09 2008-06-04 独立行政法人科学技術振興機構 シェル架橋型ミセルを鋳型とする金属ナノ粒子の調製
US7138468B2 (en) 2002-03-27 2006-11-21 University Of Southern Mississippi Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT
JP2004033901A (ja) * 2002-07-03 2004-02-05 Nippon Paint Co Ltd 金属コロイド溶液の製造方法
DE10236133A1 (de) 2002-08-07 2004-02-26 Byk-Chemie Gmbh Verwendung von Gradientencopolymeren als Dispergiermittel zur Behandlung von Pigmenten und Feststoffen
JP4448962B2 (ja) * 2003-01-14 2010-04-14 Ｄｏｗａエレクトロニクス株式会社 ニッケル被覆微粒子銅粉の製法
US20040180988A1 (en) * 2003-03-11 2004-09-16 Bernius Mark T. High dielectric constant composites
US6992039B2 (en) 2003-03-13 2006-01-31 General Motors Corporation Method for making monodispersed noble metal nanoparticles supported on oxide substrates
DE10326147A1 (de) 2003-06-06 2005-03-03 Byk-Chemie Gmbh Epoxid-Addukte und deren Salze als Dispergiermittel
US20060266157A1 (en) 2003-09-05 2006-11-30 Dai Nippon Toryo Co., Ltd. Metal fine particles, composition containing the same, and production method for producing metal fine particles
DE602005025454D1 (de) 2004-03-10 2011-02-03 Asahi Glass Co Ltd Metallhaltiger feinpartikel, flüssigdispersion eines metallhaltigen feinpartikels und leitfähiges metallhaltiges material
DE102004016479B4 (de) 2004-03-31 2007-03-15 Byk-Chemie Gmbh Verwendung von Polyestern als Dispergiermittel und Polyester enthaltende Masterbatches
DE102004022753B3 (de) 2004-05-07 2006-02-16 Byk-Chemie Gmbh Als Dispergiermittel und Dispersionsstabilisatoren geeignete Additionsverbindungen
US7718094B2 (en) * 2004-06-18 2010-05-18 The Research Foundation Of State University Of New York Preparation of metallic nanoparticles
GB2416316A (en) 2004-07-20 2006-01-25 Protensive Ltd Spinning disc reactor with spiral passageway for heat transfer fluid
GB2417215B (en) 2004-08-18 2009-06-10 Protensive Ltd Spinning disc reactor with enhanced spreader plate features
DE102004044879A1 (de) 2004-09-14 2006-03-30 Byk-Chemie Gmbh Copolymerisate, deren Herstellung und Verwendung als Netz- und Dispergiermittel
GB2419100A (en) 2004-10-15 2006-04-19 Protensive Ltd Spinning disc reactor with cross-flow filtration or solvation
DE102004050955A1 (de) 2004-10-20 2006-04-27 Byk-Chemie Gmbh Alkoxylierte Epoxyd-Amin-Addukte und deren Verwendung
WO2006050251A2 (fr) * 2004-10-29 2006-05-11 Nanodynamics, Inc. Procede a base de polyol permettant de produire des poudres metalliques ultra-fines
US20060090597A1 (en) 2004-10-29 2006-05-04 Goia Dan V Polyol-based method for producing ultra-fine metal powders
CA2587376A1 (fr) 2004-11-12 2006-05-18 Board Of Regents, The University Of Texas System Nanoparticules metalliques riches en proteines
US7575621B2 (en) 2005-01-14 2009-08-18 Cabot Corporation Separation of metal nanoparticles
US7824466B2 (en) * 2005-01-14 2010-11-02 Cabot Corporation Production of metal nanoparticles
DE102005006870A1 (de) 2005-02-14 2006-08-24 Byk-Chemie Gmbh Oberflächenmodifizierte Nanopartikel, Verfahren zu ihrer Herstellung und ihre Verwendung
JP2006252976A (ja) * 2005-03-11 2006-09-21 Nippon Paint Co Ltd 金属ナノ粒子ペーストおよびその製造方法
US7291292B2 (en) 2005-08-26 2007-11-06 E.I. Du Pont De Nemours And Company Preparation of silver particles using thermomorphic polymers
KR20080047545A (ko) 2005-09-16 2008-05-29 후지필름 가부시키가이샤 착색 조성물 및 감광성 전사재료
WO2007043664A1 (fr) * 2005-10-14 2007-04-19 Toyo Ink Mfg. Co., Ltd. Procédé de production de dispersion de particules métalliques, encre conductrice utilisant ladite dispersion et pellicule de revêtement conductrice
JP2007301461A (ja) * 2006-05-10 2007-11-22 Nippon Paint Co Ltd 金属コロイド溶液の製造方法及び金属コロイド溶液
KR100790948B1 (ko) * 2006-05-25 2008-01-03 삼성전기주식회사 금속 나노입자의 제조방법 및 이에 의해 제조되는 금속나노입자
TW200806408A (en) * 2006-06-27 2008-02-01 Ishihara Sangyo Kaisha Nickel fine particles, method for preparing the same and fluid composition comprising the same
GB0621050D0 (en) * 2006-10-23 2006-11-29 Univ Strathclyde Functionalised polymers for labelling metal surfaces
DE102006055218A1 (de) 2006-11-21 2008-05-29 Bayer Technology Services Gmbh Kontinuierliches Verfahren zur Synthese von nanoskaligen metallhaltigen Nanopartikel und Nanopartikeldispersion
US20080272344A1 (en) * 2007-03-23 2008-11-06 Georgia Tech Research Corporation Conductive polymer composites
JP5026303B2 (ja) * 2007-03-30 2012-09-12 Ｄｏｗａエレクトロニクス株式会社 銀粉の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070207335A1 (en) * 2004-07-30 2007-09-06 Karandikar Bhalchandra M Methods and compositions for metal nanoparticle treated surfaces
WO2006072959A1 (fr) * 2005-01-10 2006-07-13 Yissum Research Development Company Of The Hebrew University Of Jerusalem Dispersions aqueuses de nanoparticules de metal
US20070190323A1 (en) * 2006-02-15 2007-08-16 Samsung Electro-Mechanics Co., Ltd. Method of producing metal nanoparticles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2010066335A1 *

Also Published As

Publication number Publication date
KR20110099731A (ko) 2011-09-08
CN102245333B (zh) 2013-10-09
JP2012511627A (ja) 2012-05-24
BRPI0923509A2 (pt) 2019-09-24
US8870998B2 (en) 2014-10-28
KR101278939B1 (ko) 2013-06-28
CN102245333A (zh) 2011-11-16
US20120037041A1 (en) 2012-02-16
JP5833447B2 (ja) 2015-12-16
WO2010066335A1 (fr) 2010-06-17
DE102009015470A1 (de) 2010-06-17

Similar Documents

Publication Publication Date Title
WO2010066335A1 (fr) Procédé de fabrication de nanoparticules métalliques, nanoparticules métalliques ainsi obtenues et leur utilisation
KR100754326B1 (ko) 금속 나노입자의 제조방법
US20070275259A1 (en) Method of producing metal nanoparticles and metal nanoparticles produced thereby
CN101357403B (zh) 用于制造金属纳米颗粒的方法
CN101161380B (zh) 用于制备铜纳米颗粒的方法
KR100716201B1 (ko) 금속 나노 입자 및 이의 제조방법
DE112011103233T5 (de) Feine, beschichtete Kupferpartikeln und Verfahren zur Herstellung derselben
KR100790457B1 (ko) 금속 나노입자의 제조방법
US20080207934A1 (en) Method for producing metal nanoparticles and metal nanoparticles produced thereby
DE102006017696A1 (de) Verfahren zur Herstellung von Metallpartikeln, hieraus hergestellte Metallpartikel und deren Verwendung
EP1133447B1 (fr) Colloides d'oxyde metallique nanostructures solubles dans l'eau et procede permettant de les produire
JP2007031835A (ja) 金属ナノ粒子およびその製造方法並びに導電性インク
DE102010062093A1 (de) Ultra niedrig schmelzende Metallnanopartikelzusammensetzung für Dickfilm-Anwendungen
JP2008013798A (ja) ナノワイヤ状金属物質の製造方法及びナノワイヤ状金属物質並びにナノワイヤ状金属物質含有組成物
US20160121402A1 (en) Method for preparing metal nanoparticles using a multi-functional polymer and a reducing agent
DE102011076792A1 (de) ERHÖHTER DURCHSATZ FÜR EINE PRODUKTION IN GROßTECHNISCHEM MAßSTAB VON MIT NIEDRIGSCHMELZENDEN ORGANOAMIN STABILISIERTEN SILBERNANOPARTIKELN
WO2018206645A1 (fr) Procédé et composition pour fabriquer des objets tridimensionnels contenant du carbure de silicium
Kumar et al. Phase transfer of platinum nanoparticles from aqueous to organic solutions using fatty amine molecules
Orel et al. Conversion of uniform colloidal Cu2O spheres to copper in polyols
JP2011195951A (ja) 金属ナノ粒子の製造方法、これを用いたインク組成物及びその製造方法
WO2015018897A1 (fr) Colloïdes métalliques modifiés en surface et leur préparation
JP5210467B2 (ja) 金属微粒子分散液の製造方法
DE102010034293A1 (de) Verfahren zur Herstellung einer Dispersion von Nanopartikeln

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110526

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

17Q First examination report despatched

Effective date: 20140321

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20170601