CN101784342A - 具有可调节涂层的SiO2涂覆的二氧化钛颗粒的制备 - Google Patents

具有可调节涂层的SiO2涂覆的二氧化钛颗粒的制备 Download PDF

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CN101784342A
CN101784342A CN200880103772A CN200880103772A CN101784342A CN 101784342 A CN101784342 A CN 101784342A CN 200880103772 A CN200880103772 A CN 200880103772A CN 200880103772 A CN200880103772 A CN 200880103772A CN 101784342 A CN101784342 A CN 101784342A
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nano particle
core
shell
aerosol
present
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A·西伯尔
G-P·申德勒
K·弗赖塔格
F·克莱内耶格尔
D·克林勒
F·博格迈尔
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BASF SE
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/26Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2/00Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/003Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic followed by coating of the granules
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/04Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08Silica
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    • B01J35/45Nanoparticles
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    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
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    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/04Oxides; Hydroxides
    • C01G23/047Titanium dioxide
    • C01G23/07Producing by vapour phase processes, e.g. halide oxidation
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    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36Compounds of titanium
    • C09C1/3607Titanium dioxide
    • C09C1/3653Treatment with inorganic compounds
    • C09C1/3661Coating
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    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36Compounds of titanium
    • C09C1/3607Titanium dioxide
    • C09C1/3684Treatment with organo-silicon compounds
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    • C01P2004/84Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C01P2004/86Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
    • YGENERAL 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
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
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    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • Y10T428/2993Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

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CN200880103772A 2007-08-28 2008-08-27 具有可调节涂层的SiO2涂覆的二氧化钛颗粒的制备 Pending CN101784342A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07115104 2007-08-28
EP07115104.7 2007-08-28
PCT/EP2008/061221 WO2009027433A2 (de) 2007-08-28 2008-08-27 HERSTELLUNG VON SiO2-BESCHICHTETEN TITANDIOXIDPARTIKELN MIT EINSTELLBARER BESCHICHTUNG

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CN101784342A true CN101784342A (zh) 2010-07-21

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US (1) US20100304143A1 (https=)
EP (1) EP2185656A2 (https=)
JP (1) JP2010536709A (https=)
CN (1) CN101784342A (https=)
WO (1) WO2009027433A2 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120205077A (zh) * 2025-05-27 2025-06-27 苏州大学 一种零羟基、微米级二氧化硅颗粒火焰合成方法及装置

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102196997A (zh) * 2008-10-27 2011-09-21 巴斯夫欧洲公司 制备纳米颗粒状金属硼化物悬浮液的方法
KR20110120910A (ko) 2009-02-26 2011-11-04 바스프 에스이 자가-세정 중합체
US8545796B2 (en) 2009-07-31 2013-10-01 Cristal Usa Inc. Silica-stabilized ultrafine anatase titania, vanadia catalysts, and methods of production thereof
US9365939B2 (en) * 2011-05-31 2016-06-14 Wisconsin Alumni Research Foundation Nanoporous materials for reducing the overpotential of creating hydrogen by water electrolysis
US9004293B2 (en) * 2011-12-16 2015-04-14 Samsung Electronics Co., Ltd. Semi-permeable film and separation membrane including nanoporous material, and method of manufacturing the same
KR101282142B1 (ko) * 2012-02-15 2013-07-04 한국과학기술연구원 복합 나노입자의 제조장치 및 제조방법
CN103464220B (zh) * 2013-09-13 2015-01-14 太原理工大学 一种超声雾化改性催化剂的方法
WO2017037599A1 (en) * 2015-08-28 2017-03-09 Sabic Global Technologies B.V. Hydrogen production using hybrid photonic-electronic materials
DE102016001349A1 (de) * 2016-02-08 2017-08-24 Horst Büchner Verfahren zur thermischen Materialbehandlung
CN105755227A (zh) * 2016-05-24 2016-07-13 江苏金基特钢有限公司 低碳合金钢专用淬火剂
DE102017204488A1 (de) * 2017-03-17 2018-09-20 Technische Universität Berlin Verfahren zur Herstellung von monodispersen Nanopartikeln aus einer flüssigen Mischung
LU100335B1 (en) * 2017-07-18 2019-01-28 Luxembourg Inst Science & Tech List Plasma device for depositing functional composite film comprising crystallized particles embedded in a matrix and method of deposition thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6250196A (en) * 1995-05-17 1996-11-29 Kemira Pigments, Inc. Coating of tio2 pigment by gas-phase and surface reactions
EP1089093B1 (en) * 1999-09-28 2008-04-02 FUJIFILM Corporation Anti-reflection film, polarizing plate comprising the same, and image display device using the anti-reflection film or the polarizing plate
JP2001316115A (ja) * 2000-03-28 2001-11-13 Degussa Ag ドーピングされた二酸化チタン
ATE445568T1 (de) * 2000-03-29 2009-10-15 Evonik Degussa Gmbh Dotiertes titandioxid
DE10260718A1 (de) * 2002-12-23 2004-07-08 Degussa Ag Mit Siliziumdioxid umhülltes Titandioxid
WO2004062799A1 (ja) * 2003-01-09 2004-07-29 Showa Denko K.K. 複合粒子およびその製造方法と用途
US7214363B2 (en) * 2004-10-28 2007-05-08 Seoul National University Industry Foundation Method for preparing composite microparticles
FR2884111B1 (fr) * 2005-04-07 2007-05-18 Saint Gobain Mat Constr Sas Granule biocide, notamment pour la fabrication de bardeau d'asphalte

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120205077A (zh) * 2025-05-27 2025-06-27 苏州大学 一种零羟基、微米级二氧化硅颗粒火焰合成方法及装置

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JP2010536709A (ja) 2010-12-02
US20100304143A1 (en) 2010-12-02
WO2009027433A2 (de) 2009-03-05
EP2185656A2 (de) 2010-05-19

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