EP2477942A2 - Procédé de préparation de dispersions contenant des nanoparticules d'oxyde métallique et dispersion obtenue - Google Patents

Procédé de préparation de dispersions contenant des nanoparticules d'oxyde métallique et dispersion obtenue

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Publication number
EP2477942A2
EP2477942A2 EP10742442A EP10742442A EP2477942A2 EP 2477942 A2 EP2477942 A2 EP 2477942A2 EP 10742442 A EP10742442 A EP 10742442A EP 10742442 A EP10742442 A EP 10742442A EP 2477942 A2 EP2477942 A2 EP 2477942A2
Authority
EP
European Patent Office
Prior art keywords
metal oxide
metal
particles
dispersion
powder
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Withdrawn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
EP10742442A
Other languages
German (de)
English (en)
Inventor
Christian Wolfrum
Stefan Trummer
Marco Greb
Michael GRÜNER
Dieter Prölss
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.)
Eckart GmbH
Original Assignee
Eckart 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 Eckart GmbH filed Critical Eckart GmbH
Publication of EP2477942A2 publication Critical patent/EP2477942A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C01B13/326—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process of elements or compounds in the liquid state
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
    • C01F7/428—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation by oxidation in an aqueous solution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • 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
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • 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
    • 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
    • C09C1/64—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to a process for producing a dispersion containing metal oxide nanoparticles in a liquid phase.
  • Dispersions are mixtures of at least two substances which are not soluble in each other and in which one substance, the disperse phase, is finely dispersed in the other substance, the dispersing agent. Both disperse phase and dispersant may be solid, liquid or gaseous. In the case of mixtures of solids and liquids one also speaks of
  • colloids When the solid is present as particles of a diameter on the order of 1 nm to 10,000 nanometers (10 microns), such suspensions are also referred to as colloids.
  • colloids is particularly used when the particle diameter of the solid particles is less than 200 nm, i. when the solid particles are present as nanoparticles.
  • a stable dispersion is a dispersion which, over a relatively long period of time, in particular days, weeks or months, retains a particle diameter in the stated range.
  • unstable Dispersions lead to the aggregation of solid particles, so that particle aggregates with a larger diameter arise.
  • Agglomeration also called aggregation
  • Possible causes include interactions between particles such as van der Waals forces, dipole-dipole interactions, hydrogen bonds, and hydrophobic interactions. Due to the high specific surface area of the colloidal solid particles, the tendency for aggregation is very high. Furthermore, colloidal particles are often moved by Brownian molecular motion in the liquid, causing the
  • the dispersion of the solid or particle particles is electrostatically stabilized.
  • targeted modification of the particle surface for example by addition of molecules, by setting a certain pH of the dispersion or by loading the
  • Particle surface with ions or electrons can be arranged on the surface or in the immediate vicinity of an electrical charge.
  • This charge may e.g. are expressed and also measured by the zeta potential of the particles or particles.
  • the like-charged particles then repel, so that aggregation is avoided.
  • bulky molecules for example polymers, long-chain alkanes, surfactants, etc.
  • these bulky molecules prevent the particles from approaching each other and thus aggregating.
  • the dispersion is stabilized by electrosteric stabilization.
  • molecules are used which on the one hand cause a steric shielding and on the other hand also an electrostatic shielding by means of charge carriers.
  • charge carriers usually used for this purpose polyelectrolytes.
  • nanoparticles are first produced and then dispersed in a liquid.
  • the preparation of the nanoparticles can be carried out via a variety of methods.
  • WO 2006/071199 A1 discloses a method for the production of
  • Nanoparticles in which zinc is converted into the vapor phase and the zinc vapor is oxidized upon reaction with an oxidizing gas when supplied with heat to nanoparticulate zinc oxide.
  • WO 03/080515 A1 likewise discloses a process for the preparation of nanoparticulate zinc oxide.
  • zinc powder is first evaporated without oxidation and the resulting zinc vapor then by
  • the product obtained is a powder of aggregated nanoparticles.
  • a disadvantage of the aforementioned methods and further gas-phase syntheses of nanoparticles is that these methods have a high energy requirement, sometimes require expensive starting materials and sometimes only a low
  • Agglomerates or aggregates of the solid particles or particles are introduced into a liquid and simultaneously or subsequently the aggregates are comminuted.
  • the primary particle sizes of the introduced solid particles are not changed. In the dispersion, therefore, only the particles are separated, there is no comminution.
  • the dispersion the e.g. measured by a laser scattering method
  • Particle size distribution however, the size of the primary particles as such, which can be determined for example by means of electron microscopic methods, remains unchanged.
  • one or more of the dispersion stabilization methods mentioned above are used to protect the particles from re-aggregation during and after dispersion.
  • DE 102006025848 A1 describes a method for
  • Dispersion of agglomerates in which pulverulent aggregates are first comminuted in a gas phase with introduction of energy and then into
  • organically-based matrix particles are dispersed.
  • US 2003/0032679 A1 discloses the dispersion of aggregates of nanoscale individual particles, which were prepared by gas phase synthesis, in non-aqueous liquids, with energy input and with the addition of polymeric dispersants.
  • DE 102004048230 A1 discloses a method for dispersing nanoscale particles or particles with temperature treatment of the particles or particles and subsequent dispersion by means of energy input in the presence of a dispersant and a particle surface modifying
  • WO 2008/035996 A2 discloses the production of nanoparticles by decomposition of an electrically conductive material by introduction of electric current. Such a method is particularly in view of the low
  • Nanoparticles were synthesized directly in a liquid. Since the nanoparticles in these processes are each produced by synthesis from smaller starting materials, such as steam, salts, etc., these processes are also referred to as "bottom-up" processes.
  • top-down processes Processes in which the production of nanoparticles takes place by comminution of larger solids are therefore referred to as "top-down" processes.
  • the comminution of the larger solids is usually carried out in mills, very often in so-called stirred ball mills.
  • DE 10304849 A1 discloses a process for the preparation of a colloid in which particles are prepared by comminution in the presence of a modifier which reacts chemically with the surface of the particle.
  • stirred ball mills are preferably used. In these mills loose Mahlköper, usually grinding balls of a hard metal oxide, used for comminution. Because of the underlying
  • Size ratio between the grinding balls and the material to be crushed can not be arbitrarily large.
  • Primary particle size less than 100 nm are preferably spheres with a
  • the diameter of the starting material must not be greater than 0.5 millimeters. Typically, the diameter is less than 0.1 millimeter.
  • the preparation of such a fine starting material is expensive. Frequently, aggregated nanomaterials produced by one of the described bottom-up methods are used, which have the described disadvantages. Materials are also used which have been precomminuted in a first comminution step. However, this first step is time-consuming and energy-intensive. Partly also materials are used, which in their natural form in a suitable size
  • End product also contains these impurities, or they need to be removed consuming before the final crushing.
  • the object of the invention is to provide a simple method by which dispersions of nanoparticles can be produced industrially. This method is intended in particular in the prior art
  • the object underlying the invention was achieved by providing a process for producing a dispersion which contains metal oxide nanoparticles in a liquid phase, the process comprising the following steps:
  • step (b) optionally deforming the metallic powder obtained in step (a),
  • step (c) oxidizing the metallic powder obtained in step (a) or (b) to obtain a metal oxide powder, (d) comminuting the metal oxide powder obtained in step (c) in the presence of a liquid phase to obtain a dispersion whose metal oxide particles have a particle size dgo.oxi d of less than 300 nm.
  • the dispersion obtainable by the process according to the invention can also be referred to as colloid.
  • the shape of the metal oxide particles or the metal oxide powder is irrelevant. It can be more or less spherical, rectangular, square, rod-shaped, platelet-shaped or unshaped metal oxide particles. Due to the small diameter of the metal oxide particles, they have a very large surface area in relation to their volume. For this reason, has the over the metal oxide particles.
  • metal oxide nanoparticles can be produced.
  • inventive method in contrast to the prior art, essentially no, preferably no, in particular bridged via sintered bridges, metal oxide aggregates arise. Furthermore, the inventive method allows a surprisingly high
  • the metallic starting material all metals and alloys thereof can be used.
  • the metals aluminum, iron, copper, magnesium, zinc, tin, zirconium, hafnium, titanium or alloys or mixtures thereof have proven to be.
  • the alloys of 2, 3, 4 or more metals.
  • the starting materials used are preferably the metals aluminum, zinc, tin, titanium, iron, copper or alloys or mixtures thereof. According to a variant of the method according to the invention, aluminum, zinc, iron or alloys or mixtures thereof are particularly preferred.
  • the degree of purity of the metals is preferably more than 70 wt .-%, more preferably more than 90 wt .-%, particularly preferably more than 95 wt .-%, each based on the total weight of the metal, the alloy or
  • the metal, the metal mixture or metal alloy is first melted under heat.
  • the preparation of the melt of the metal, the metal mixture or metal alloy can according to the methods known to those skilled in the
  • Melting of metal (s) take place.
  • the production of the molten metal can be carried out by melting a metal in a melting furnace or crucible with heat supply.
  • the heat can be made using a
  • a metallic powder or metal powder is produced by atomizing the molten metal.
  • the metallic powder can be generated from the liquid molten metal, in which, for example, the molten metal is abruptly atomized by high-pressure gas expansion into a space and thus atomized. Atomization of the molten metal may also be accomplished by applying the molten metal to a rotating disk or disk, whereupon the deposited molten metal is deposited as droplets having diameters in the molten metal
  • Nanometer to micrometer range throwing away (Rotating Disc Method).
  • the molten metal can also be applied to rotating rollers or rollers and squirted by them as droplets.
  • the liquid metal which is thrown as a droplet in the nanometer to micrometer range, cools down during the skidding flight and solidifies.
  • the particle size distribution of the resulting metallic powder may be e.g. be determined by laser diffraction method.
  • the particle size of the resulting metallic powder may be controlled via the temperature of the molten metal, the energy input applied to atomize the molten metal, the amount of gas, the gas pressure and / or the gas flow of gas introduced into the atomised molten metal.
  • Suitable gases are used for the atomization of the respective metal suitable gases.
  • the selection of the gas takes place in such a way that
  • the process parameters are optimized, the particle size distribution is optimized and / or chemical reactions of the metal with the gas are reduced or increased.
  • the gas can
  • the metal powder obtained after the sputtering can be classified with respect to the particle size. Size classification can be done for example by means of cyclone, sieving, etc.
  • the atomization of the molten metal is carried out so that a particle size classification is no longer required.
  • the metallic powder or metal powder produced has a particle size distribution with an average size (D 5 o value) in the range from 5 to 100 ⁇ m, preferably from 10 to 80 ⁇ m, more preferably from 15 to 50 ⁇ m, even more preferably from 20 up to 40 ⁇ m, on.
  • D 5 o value average size
  • the metallic powder or metal powder produced has a particle size distribution in which the particles obtained are approximately more preferably of a particle size having a D 99 of at most 100 ⁇ m, more preferably of not more than 80 ⁇ m, even more preferably of not more than 50 ⁇ m of a maximum of 40 ⁇ m.
  • a D 9 g of a maximum of 30 ⁇ m has proven to be very suitable.
  • a Dso value means that 50% of all particles have a particle size equal to or less than the specified value.
  • a D 99 value means that 99% of all particles have a particle size equal to or less than the specified value.
  • the particle or particle shape of the generated metallic powder is preferably approximately spherical. However, the powder may also have particles which are irregularly shaped and / or in the form of needles, rods, cylinders or platelets.
  • the resulting metallic powder can be deformed in the process according to the invention, for example by introduction of mechanical energy, in a step (b).
  • the aspect ratio is defined as the
  • the particles advantageously have an aspect ratio ranging from 3: 1 to 2000: 1, preferably from 5 to 1000, more preferably from 10 to 500.
  • the particles after the deformation in at least one dimension particularly preferably have a size of less than 25 ⁇ m, more preferably less than 20 ⁇ m, even more preferably less than 10 ⁇ m.
  • Deformation is advantageously carried out by grinding the metallic powder in mills. Attritors, ball mills, stirred ball mills, etc. can be used as mills.
  • the metallic powder can together with
  • Grinding aids and preferably a liquid, for a suitable period of, for example, more than 10 minutes to 100 hours, preferably from 30 minutes to 50 hours, more preferably from 1 hour to 25 hours in a ball mill with grinding media, preferably grinding balls ,
  • the milling time is chosen according to the desired degree of deformation and / or depending on the ductility of the metal to be deformed. Such a deformation is for example in the document DE 102007062942
  • Particle size D 50 from a range of 1 micron and 100 microns are known in the art and are used on a large scale. Therefore, the processes for the production of metallic powders or metal powders are so far technically mature and optimized in economic and energy terms.
  • the melting temperature of aluminum is about 660 C 0, while the boiling point of aluminum about 2460 0 C.
  • the heat of fusion is 10.79 kJ / mol, whereas the heat of vaporization is 293.4 kJ / mol.
  • a large amount of energy is saved when the metal is transferred only in the liquid, but not in the vapor state.
  • metal oxide particles whose particle diameters are wholly or predominantly in the nanometer range, in particular whose D 90 , o ⁇ i d -vVert is less than 300 nm.
  • step (c) of the process according to the invention the metallic particles are first oxidized. This oxidation can be carried out by all methods known to the person skilled in the art.
  • the metallic particles are oxidized by gas phase oxidation and / or by liquid phase oxidation.
  • the oxidation is carried out in a liquid or by combustion in a gas stream.
  • the oxidation is carried out in a liquid phase or liquid
  • this is preferably done by first distributing the powder in the liquid phase or liquid. This can be done with or without addition of excipients and with or without the input of energy.
  • the dispersion takes place without the addition of auxiliaries and with stirring.
  • the liquid may be an inert liquid that does not oxidize, or it may be a reactive liquid that acts as an oxidizer and reacts with the metallic particles. After the dispersion, therefore, the oxidation either begins immediately or by the addition of an oxidizing agent and / or
  • Oxidation catalyst and / or started by increasing the temperature If the liquid is reactive and reacts with the metal, the oxidation may already begin during the dispersion. Whether the oxidation reaction starts immediately depends in each case on the chosen combination of liquid / metallic powder.
  • the oxidation is preferably started by adding an oxidizing agent and / or oxidation catalyst. Preferably, to accelerate the oxidation reaction, the reaction mixture is heated during the oxidation.
  • oxidizing agents are sulfuric acid, potassium permanganate,
  • oxidation catalysts are metals, metal salts, acids and bases.
  • the addition is preferably carried out so that a pH value suitable for the oxidation reaction is set in the reaction mixture. After the reaction is started, it is preferably maintained until the metal is at least 90% by weight, more preferably at least 95% by weight, even more preferably at least 99% by weight, based on the total weight the metallic particle is present in a non-zero oxidation state.
  • the metal is at least 90% by weight, more preferably at least 95% by weight, even more preferably at least 99% by weight, based on the total weight the metallic particle is present in a non-zero oxidation state.
  • Embodiment particles are completely present as metal oxide after the oxidation treatment.
  • the metal oxide fraction can be determined experimentally by methods known to the person skilled in the art. During the oxidation reaction, the temperature can be raised, lowered or kept constant. In addition, a further addition of one or more oxidizing agents and / or oxidation catalysts can take place, whereby the oxidation process can be controlled. During the oxidation, optionally with the addition of further reaction components, additional chemical reactions may be initiated and / or further
  • Components for example metals or metal oxides, are incorporated into the resulting metal oxide particles, for example as doping.
  • Reaction parameters are adjusted so that the oxidation product has properties that facilitate the final comminution and / or are advantageous for a desired application. Particularly preferred are the
  • the resulting metal oxide particles have a porous or layered structure.
  • a porous or layered structure of the metal oxide particles obtained may be advantageous in the other
  • Powder lead are:
  • the metal oxide particles can be crushed in a process variant directly in the liquid in which the oxidation was carried out.
  • other components or additives may be added prior to comminution to facilitate, for example, comminution or, for example, the surfaces of the
  • the metal oxide particles can be separated from the liquid in which the oxidation has been carried out.
  • the separation can be carried out by directly removing the liquid from the reaction mixture. This can be done by methods known in the art such as thermal drying, preferably in a reduced pressure atmosphere.
  • the separation of the liquid takes place after a first concentration of the solid by a simple
  • the metal oxide particles may optionally be subjected to annealing, i. be supplied to an additional temperature treatment.
  • annealing i. be supplied to an additional temperature treatment.
  • the chemical composition and / or the crystal structure of the metal oxide particles can be changed by the tempering or this temperature treatment. The temperatures of such
  • Temperature treatment is typically above 200 ° C., but below the melting or decomposition temperature. The duration is
  • aluminum hydroxide prepared by reacting aluminum metal powder in water by heating
  • Alumina are converted. Upon further heat treatment in the range between 800 0 C and 1300 0 C, the crystal structure of the Alumina can be adjusted specifically. Thus, for example, converts v- AI 2 O 3 to when heated to temperatures greater than 800 0 C in Q-Al 2 O 3.
  • the oxidation can also be carried out by gas phase oxidation, for example by direct burning of the metallic powder or metal powder.
  • the metallic powder or metal powder is burned by supplying energy and oxidizing gas.
  • This can be done by conveying the metallic powder or metal powder into a reactor in which the metallic powder or metal powder is mixed with an oxidizing gas, e.g. Air or oxygen, mixed and oxidized by energy input.
  • the conveying can be carried out mechanically, by means of a powder metering device, manually or preferably by means of a gas stream, which can be produced, for example, using a gas such as nitrogen, argon,
  • the energy input in the form of heat can be effected in particular by a burner, for example a gas-fuel burner or a pure gas burner, by a hot-wall reactor, by a plasma source or by an arc.
  • a burner for example a gas-fuel burner or a pure gas burner
  • the entry is made by a burner, more preferably by a burner that uses hydrogen as an energy supplier.
  • the temperature during the oxidation may be between 500 ° C. and 5,000 ° C., preferably between 1,000 and 2,500 ° C.
  • the respective temperature is in
  • the metal oxide powder can be collected. This collection can be carried out using all methods known to the person skilled in the art. The collection preferably takes place by means of filtering. Before the collection, the metal oxide powder can optionally be cooled, which can be done, for example, in a gas supplied.
  • a powder of a metal oxide or a suspension of the metal oxide powder in a liquid can be obtained.
  • Metal oxide powder has a number of advantages.
  • metal oxide powders with metal oxide particles which have a precisely defined composition, as a mixture of at least two, three, four or more different metal oxide powders or particles.
  • metal oxide particles which have a precisely defined composition, as a mixture of at least two, three, four or more different metal oxide powders or particles.
  • metal oxide particles which have a precisely defined composition, as a mixture of at least two, three, four or more different metal oxide powders or particles.
  • metal oxide particles which have a precisely defined composition, as a mixture of at least two, three, four or more different metal oxide powders or particles.
  • the after step (c) of the inventive metal oxide powder has a particle diameter D 50 between 1 and 200 microns.
  • Metal oxide powder with such Particle size distribution are particularly suitable for comminution in step (d) of the method according to the invention.
  • step (d) of the process according to the invention the metal oxide powder is comminuted.
  • the comminution of the particles takes place in a selected liquid.
  • Comminution takes place in a particularly preferred form by grinding in mills.
  • mills with loose grinding media preferably grinding balls
  • agitator ball mills In comminution in such mills, grinding media are used to comminute the metal oxide particles. This energy is through a
  • the grinding media preferably grinding balls.
  • the energy of the grinding media preferably grinding balls, transferred to a certain proportion of the metal oxide particles. If the transmitted energy is sufficient, it will happen
  • a difficulty in the construction of such mills is the separation of the grinding media, preferably grinding balls, from the material to be ground. This becomes
  • the grinding chamber of the mill is designed such that only the material to be ground, but not the grinding media can get out of the grinding chamber. This is usually done by a mechanical separation system in the grinding chamber is present, which only for the ground material, but not for the
  • the diameter of the grinding media preferably grinding balls, not more than a thousand times the desired
  • Particle diameter amount particles with a diameter of 50 nm can be produced with grinding bodies, preferably grinding balls, with a diameter of 50 ⁇ m. Since it is only an empirically derived rule, deviations upwards and downwards are possible.
  • This maximum size of grinding media determines in two ways the maximum particle size of the powder to be comminuted. On the one hand, the maximum grinding media size determines a characteristic size of the separation system necessary for the separation of the grinding media. As a separation system, for example, so-called screen cartridges can be used. These have a characteristic gap size. Material with one
  • Particle size below this gap size can pass through the sieve cartridge, while material with a larger particle size can not pass through the sieve cartridge.
  • the gap size must be according to a specialist
  • the powder to be crushed may also have this maximum
  • the stress energy is a function of
  • the maximum particle size of the metal oxide particles to be crushed is determined, if these except for a certain
  • dispersions of the invention are particularly suitable metal oxide particles having a particle size between 1 .mu.m and 200 .mu.m, preferably 5 to 100 .mu.m, wherein at least one dimension of the metal oxide particles is present in this order of magnitude.
  • metal oxide nanoparticles by the process surprisingly energy and cost extremely advantageous.
  • metallic powder or metal powder having an average particle size D 50 between 1 .mu.m and 100 .mu.m can be produced with low energy.
  • subsequent oxidation step (c) also requires little energy because it is an exothermic reaction.
  • Oxygen increases the mass of the particles, so that the supplied energy can be neglected when it is related to a certain mass of oxidized metal powder.
  • metal oxides are also first prepared. However, since the metal must be evaporated during the process, much more energy is needed than in the atomization, such as atomization, a molten metal. Since the resulting metal oxide powder can not be directly converted into a dispersion, a subsequent dispersion with energy input must also be carried out in these processes. Although the methods also metal oxide powders with particles in the order of less than 200 microns, but these are aggregated, so that in addition considerable energy must be introduced for the dispersion.
  • the inventive method Compared to liquid phase syntheses from the prior art, the inventive method has the advantages that the starting materials are significantly cheaper, the achievable concentration is much higher and the inventive method can be much easier converted to an industrial scale.
  • pure metal salts usually have to be used, which are then mixed with a corresponding one
  • Precipitant are mixed, resulting in the precipitation of nanoparticles.
  • These metal salts are significantly more expensive compared to the pure metals, since they are regularly produced by chemical transformation of metals.
  • the aluminum chloride necessary for the precipitation of aluminum hydroxide nanoparticles is obtained by the reaction of aluminum with hydrochloric acid.
  • concentration achievable by precipitation processes is obtained by the reaction of aluminum with hydrochloric acid.
  • Nanoparticles based on the total mass of the reaction product, is limited because on the one hand the solubility of the starting materials is limited in liquids, and on the other hand too high
  • the concentration of aluminum chloride in the precipitation of aluminum hydroxide is typically 1 mol / L or less, which corresponds to a solid content of 13 wt% or less. Furthermore, it is very important for the production of nanoparticles by precipitation reactions to precisely define the fluid dynamic parameters. In particular, the stirring speed or the
  • Liquid speed can be set specifically. By this movement of the liquid a nearly same spatial distribution of the chemical becomes
  • the energy used in a stirred ball mill is transferred by means of a mechanical structure to the metal oxide particles to be comminuted. Most of this energy transfer takes place by a motor is driven by energy, which transmits energy via a shaft, which is also referred to as a rotor to components, which by direct or indirect
  • the geometry of the rotor may also have different configurations known to the person skilled in the art. Preferably, this geometry is optimized in such a way that on the one hand it promotes the transfer of energy and on the other hand the separation of the grinding media.
  • the grinding chamber which is also referred to as a stator, may also have different geometries, which may also be optimized for the functions described.
  • Rotor and stator i.
  • the rotor-stator system can in principle be made of any material.
  • the stator is at least in the areas where it with the metal oxide particles and the stator
  • Mahl stresses comes in contact, made of aluminum oxide, silicon carbide or zirconium oxide or lined with these materials.
  • the rotor is preferably also made of one of these materials or of polyurethane, polyamide or polyethylene or lined with these materials. It is
  • the rotor and stator are made of the same material as the metal oxide particles to be milled, since in this case any possible abrasion does not contaminate the product, the metal oxide nanoparticles.
  • the stator and / or the rotor is actively cooled in a particularly preferred variant of the method in order to remove the heat generated by the friction from the rotor-stator system.
  • the cooling can be done for example by the use of a stator with double-shell construction, wherein cooling water is passed through the double jacket. The heat absorbed by the cooling water can this in turn be withdrawn by a circulation cooler (eg Fa. Lauda, Germany).
  • the speed at which the rotor rotates is indicated regularly relative to the outer diameter of the energy-transmitting component, for example a disk. This speed is also called
  • the grinding media used are preferably balls made of ceramic, metal or a metal oxide.
  • the balls are made of stainless steel, zirconium oxide, glass or alumina.
  • the balls are made of a doped material, e.g. yttrium doped zirconia ball.
  • the balls are made of the same material as the metal oxide particles to be milled, since in this case any possible abrasion does not contaminate the metal oxide particles.
  • the metal oxide particles are particularly preferably circulated through the mill (circulation mode).
  • a master container in which the metal oxide particles can be stirred, be integrated into the circuit.
  • this document container is also actively cooled to improve the heat dissipation.
  • the Mahlrauminhalt the ball mill used can be between 0.5 liters and 10,000 liters. Such mills are commercially available from various suppliers. During milling, the primary particle diameter of the metal oxide particles decreases. Therefore, the number of metal oxide particles and the specific surface area that can be given in [m 2 / g] increase. To prevent the formation of agglomerates, it is preferable to add additives which prevent agglomeration. These additives can stabilize the dispersion via electrostatic, steric or electrosteric mechanisms.
  • additive it is meant according to the invention at least one additive and the additive may be an additive mixture The addition of the additive or the additive mixture may take place before or during the grinding in one or more portions.
  • the amount of additive based on the weight of the total dispersion, can be from 0.1% by weight to 60% by weight.
  • the amount may also be based on the amount of metal oxide particles, in which case the amount of additive is preferably 2% by weight to 500% by weight, preferably 3% by weight to 400% by weight .-%.
  • the additives may be substances which interact with the
  • the additive or the additives may be attached to the metal oxide particle surface via chemical or physical bonds.
  • chemical bonds can form between the metal oxide particle surface or active groups on the surface of the metal oxide particles.
  • the additive or additives may also be bound by physical bonds such as physisorption or be absorptively bound in possibly present pores of the metal oxide particles.
  • the attachment of the additive or the additives can also be done via van der Waals or electrostatic forces.
  • the additive or additives consist of a main body and active groups.
  • the active groups can be arranged terminally distributed on the additive or over the entire main body.
  • the number of active groups is preferably at least one. But it can also two, three or more active groups may be present.
  • the active groups can on the one hand serve for a good binding of the additive to the metal oxide surface and on the other hand ensure a good compatibility of the additive with the surrounding liquid.
  • active groups are acid groups, amine groups, hydroxyl groups, sulfur groups, amide groups, imide groups or phosphorus groups.
  • the basic body of the additive can either be without function, ensure good compatibility with the metal oxide particles, a good
  • the backbone may also be a backbone of alkyl chains or siloxane chains
  • the additive may have any chemical structure.
  • the additive can be
  • the additive has a molecular weight between 501 and 100,000 g / mol and more preferably between 700 and 90,000 g / mol.
  • the additive may be salts, surfactants, oligomers or polymers in which the backbone preferably has alkyl chains or siloxane chains. They are preferably polymers or block polymers with solids-affine groups.
  • Particle diameter D 90 of the metal oxide particles or of the metal oxide powder in the dispersion prepared by the process according to the invention in a range from 1 nm to 300 nm, preferably from 5 nm to 250 nm, more preferably from 10 nm to 200 nm, even more preferably from 20 nm to 150 nm, even more preferably from 30 nm to 100 nm.
  • a particle diameter Dgo from a range of 40 nm to 80 nm has proven to be very suitable.
  • the dispersion is optionally concentrated to the desired solids content. This concentration can be after each
  • Substantially non-aggregated form Preferably, at least 95%, more preferably at least 98%, even more preferably 99%, even more preferably at least 99.5%, by weight of the metal oxide particles are present in unaggregated form.
  • the dispersion of the invention is further preferably characterized in that the degree of aggregation by not more than 2 wt .-% / month storage time at 20 0 C, preferably not more than 1 wt .-% / month storage time at 20 0 C, more preferably by not more than 0.5 wt .-% / month storage time at 20 0 C, increases. According to a highly preferred variant of the degree of aggregation increases by not more than 0.1 wt .-% / month storage period at 20 0 C to.
  • the amount of zeta potential is below 30 mV and more preferably below 15 mV.
  • the metal oxide particles are largely stabilized by the electrostatic and / or electrosteric stabilization mechanism in the dispersion.
  • Dispersion is particularly suitable for use as an adjuvant for scratch-resistant coatings, as a UV absorber in paints, cosmetics, plastics or printing inks.
  • Aluminum oxide dispersions in particular ⁇ -Al 2 O 3 (corundum), can as
  • Abrasives are used.
  • ZnO dispersions can be used as transparent, conductive coatings.
  • Fig. 1 shows a schematic representation of the sequence of the process according to the invention for the preparation of a dispersion.
  • Fig. 2 shows the particle size and the zeta potential of a deformed and oxidized aluminum powder as a function of the pH, measured with
  • Fig. 3 shows an XRD spectrum of a deformed and oxidized
  • FIG. 4 shows the particle size and the zeta potential of a deformed, oxidized and subsequently temperature-treated aluminum powder as a function of the pH measured by ultrasound spectroscopy.
  • Fig. 5 shows an XRD spectrum of a deformed, oxidized and subsequently temperature-treated aluminum powder.
  • Fig. 6 shows the course of the particle size and the zeta potential in the
  • FIG. 8 shows the XRD spectrum of the zinc oxide powder obtained in the inventive example 2 after the oxidation.
  • FIG. 9 shows the UV / Vis spectrum of the dispersion obtained in Example 2 according to the invention after comminution with additive.
  • the aluminum grit produced after atomization / atomization solidifies and cools down in the air.
  • the induction furnace is integrated in a closed system.
  • the atomization takes place under inert gas (nitrogen).
  • the deposition of the aluminum grit (A) takes place first in a cyclone, the powdery aluminum grit deposited there having a D 50 of 14-17 ⁇ m.
  • a multicyclone is used in succession, the pulverulent aluminum powder deposited in this powder having a D 50 of 2.3-2.8 ⁇ m.
  • the gas-solid separation takes place in a filter (Fa. Alpine, Thailand)
  • Metal elements PaII
  • the finest fraction is an aluminum grit with a d10 of 0.7 ⁇ m, a d50 of 1.9 ⁇ m and a d90 of 3.8 ⁇ m.
  • the fine grain is largely freed of white spirit via a suction filter (about 80% solids).
  • the particle diameter is slightly larger and the
  • Zinc ingot metal continuously introduced and melted. in the
  • the molten zinc was liquid at a temperature of about 790 0 C.
  • the liquid zinc exited a nozzle from the oven and impacted a rotating copper disk which was cooled.
  • the incident zinc stream cools and forms zinc grit.
  • the induction furnace was integrated in a closed system.
  • the atomization was carried out under inert gas (nitrogen).
  • Precipitation of the zinc grit (A) was first carried out in a cyclone, with the powdered zinc grit deposited there having a d.sub.50 of 25-38 .mu.m.
  • a multicyclone was used in succession, wherein the powdery semolina deposited in this had a d 5 o of 17-22 microns.
  • the gas-solid separation was carried out in a filter (Fa. Alpine) with metal elements (Fa. PaII).
  • a gray-white powder was obtained (B). This powder was then characterized by XRD analysis. Figure 8 shows that the zinc powder was converted during the reaction to zinc oxide. The reflections known from the zinc oxide literature are clearly visible.
  • a sample of the obtained dispersion was examined by electron microscopy (SEM). The investigations were carried out on a device Leo Supra 35 device of Company Zeiss performed. It turns out that the particle size of the zinc oxide nanoparticles was less than 100 nm. The dispersion was storage stable for several months. A sample of the dispersion was analyzed in a UV / Vis spectrometer (Lambda 25, Perkin Elmer). The solids content of the sample was 0.01%. The spectrum shown in Figure 9 clearly shows the good transparency in the range of visual light (400 nm to 800 nm) and the good absorption of UV light less than 400 nm.

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Abstract

L'invention concerne un procédé de préparation d'une dispersion contenant des nanoparticules d'oxyde métallique dans une phase liquide. Le procédé comporte les étapes suivantes: (a) pulvérisation d'une matière en fusion métallique de manière à obtenir une poudre métallique; (b) éventuellement mise en forme de la poudre métallique obtenue à l'étape (a); (c) oxydation de la poudre métallique obtenue à l'étape (a) ou (b) de manière à obtenir une poudre d'oxyde métallique; et (d) fractionnement de la poudre d'oxyde métallique obtenue à l'étape (c) en présence d'une phase liquide de manière à obtenir une dispersion dont les particules d'oxyde métallique présentent une taille d90.oxyde inférieure à 300 nm. L'invention concerne également une dispersion pouvant être obtenue au moyen du procédé.
EP10742442A 2009-08-20 2010-08-10 Procédé de préparation de dispersions contenant des nanoparticules d'oxyde métallique et dispersion obtenue Withdrawn EP2477942A2 (fr)

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DE102009037992A DE102009037992A1 (de) 2009-08-20 2009-08-20 Verfahren zur Herstellung von Dispersionen mit metalloxidischen Nanopartikeln und Dispersion
PCT/EP2010/004874 WO2011020573A2 (fr) 2009-08-20 2010-08-10 Procédé de préparation de dispersions contenant des nanoparticules d'oxyde métallique et dispersion

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JP6939025B2 (ja) * 2017-03-31 2021-09-22 東洋インキＳｃホールディングス株式会社 光輝性呈色樹脂組成物、光輝性呈色物品およびその製造方法
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WO2021049154A1 (fr) * 2019-09-11 2021-03-18 株式会社フジミインコーポレーテッド Composition de polissage et procédé de polissage l'utilisant
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