WO2012067590A1 - Revêtement de nanoparticules de rutile de type tio2 en suspension avec des oxydes de sio2 et d'al2o3 hydratés - Google Patents

Revêtement de nanoparticules de rutile de type tio2 en suspension avec des oxydes de sio2 et d'al2o3 hydratés Download PDF

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Publication number
WO2012067590A1
WO2012067590A1 PCT/SI2011/000064 SI2011000064W WO2012067590A1 WO 2012067590 A1 WO2012067590 A1 WO 2012067590A1 SI 2011000064 W SI2011000064 W SI 2011000064W WO 2012067590 A1 WO2012067590 A1 WO 2012067590A1
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WO
WIPO (PCT)
Prior art keywords
nanoparticles
coating
suspension
acid
mineral acid
Prior art date
Application number
PCT/SI2011/000064
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English (en)
Inventor
Nika Veronovski
Dejan VERHOVŠEK
Aljaž SELIŠNIK
Original Assignee
Cinkarna, Metalurško Kemična Industrija Celje, D.D.
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 Cinkarna, Metalurško Kemična Industrija Celje, D.D. filed Critical Cinkarna, Metalurško Kemična Industrija Celje, D.D.
Publication of WO2012067590A1 publication Critical patent/WO2012067590A1/fr

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Classifications

    • 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
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C09C1/3661—Coating
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • 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
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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

Definitions

  • the present invention belongs to the field of colloidal chemistry and more precisely it comprises suspensions of Ti0 2 nanoparticles in a crystal rutile structure with the stress being on their surface treatment by using sodium silicate and sodium aluminate as reagents for the coating of nanoparticles with thin layers of hydrated silica or alumina (Si0 2 and A1 2 0 3 ).
  • the invention provides for a controlled coating of nanoparticles in the form of Ti0 2 suspension with thin layers of hydrated alumina and silica (Si0 2 and Al 2 0 3 ).
  • a decision about a production of Ti0 2 nanoparticles, in which products are exclusively produced in the form of a suspension, is based on a care for healthy conditions of workers in production, use and prevention of negative effects on the environment (emission of nanoparticles).
  • Coating is based on the principle of hydrolysis of sodium silicate (Na 2 Si0 3 ) and sodium aluminate (NaA10 2 ).
  • Ti0 2 nanoparticles are coated with inorganic oxides in order to limit formation of free radicals on the surface of Ti0 2 and in order to change electrokinetic properties.
  • Literature contains no data about a modification mode of non-powder Ti0 2 nanoparticles. There is further no explanation about the stability of Na 2 Si0 3 and NaA10 2 precursors in various pH conditions by using a titration approach and explaining electrokinetic properties of Ti0 2 nanoparticles that have influence on the selection of process conditions and finally on the result of coating. Moreover, no data can be found about the influence of washing of surface treated Ti0 2 nanoparticles.
  • the described mode of modification is different than the remaining coating processes in that the method does not include a drying phase and consequently powder particles that have a negative effect on industrial workers, users and on the environment. Coated Ti0 2 nanoparticles will be available for various applications in the form of a suspension not powder. The costs of heating in calcination and the agglomeration of coated nanoparticles that appears in calcination are thus avoided.
  • An average size of an individual Ti0 2 nanoparticle in a suspension is 80x20 nm.
  • Specific surface area of Ti0 2 nanoparticles is 130 m /g.
  • An analysis of electrokinetic properties determined the isoelectric point (IEP) of Ti0 2 nanoparticles, which is at pH value ⁇ 6.5.
  • An increase in pH value of a suspension of Ti0 2 nanoparticles from a very acidic pH to a pH 10.5 is achieved by an addition of a base.
  • a base for adjusting the pH of the medium 10 - 60 wt. % of sodium hydroxide is used.
  • the particles While passing the isoelectric point during the process of surface treatment, the particles can get heavily agglomerated and are as such unsuitable for coating with Si0 2 .
  • agglomeration of particles needs to be avoided, which means that a stable suspension in water needs to be prepared.
  • Agglomeration can be avoided by binding citric acid to the surface. The acid bound to the surface sterically prevents the nanoparticles from agglomerating and simultaneously creates a high charge on their surface, which contributes to electrostatic stabilisation of the suspension (electrosteric stabilisation).
  • the mixture was heated to 40 - 100 °C and stirred at 150 - 400 rev/min for 0.5 - 2 hours.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Cette invention décrit une approche rapide, adaptable, contrôlable et reproductible de la synthèse de nanoparticules de TiO2 revêtues d'oxydes de silicium et d'aluminium hydratés faisant appel à des agents chimiques inoffensifs. Le procédé selon l'invention comprend la préparation d'un système parfaitement dispersé de nanoparticules de TiO2 et l'hydrolyse contrôlée du SiO2 à partir du précurseur alcalin Na2SiO3, en présence de l'acide minéral H2SO4, ou l'hydrolyse de l'Al2O3 à partir du précurseur alcalin NaAlO2, en présence de l'acide minéral H2SO4. Les analyses ont prouvé que plus les temps de revêtement sont longs, plus la quantité de SiO2 est élevée, et de là, l'épaisseur du revêtement. Des conditions de synthèse contrôlées ont été utilisées pour revêtir des nanoparticules de TiO2 individuelles. Le mécanisme régissant le revêtement inorganique de nanoparticules de TiO2 peut s'apparenter à la catégorie des mécanismes opérant par précipitation d'oxydes hydratés sous la forme d'un film mince sur des particules déjà présentes (nucléation hétérogène). L'avantage de ce procédé est sa simplicité et le fait qu'une suspension stable de nanoparticules de TiO2 est présente du début à la fin du procédé, ce qui crée des conditions de travail saines pour les ouvriers de l'industrie et les utilisateurs et prévient également les conséquences négatives sur l'environnement (émission de nanoparticules).
PCT/SI2011/000064 2010-11-19 2011-11-18 Revêtement de nanoparticules de rutile de type tio2 en suspension avec des oxydes de sio2 et d'al2o3 hydratés WO2012067590A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SIP-201000397 2010-11-19
SI201000397A SI23547A (sl) 2010-11-19 2010-11-19 OPLAŠČEVANJE RUTILNIH NANODELCEV TIO V SUSPENZIJI S HIDRATIZIRANIM SiO IN Al O

Publications (1)

Publication Number Publication Date
WO2012067590A1 true WO2012067590A1 (fr) 2012-05-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SI2011/000064 WO2012067590A1 (fr) 2010-11-19 2011-11-18 Revêtement de nanoparticules de rutile de type tio2 en suspension avec des oxydes de sio2 et d'al2o3 hydratés

Country Status (2)

Country Link
SI (1) SI23547A (fr)
WO (1) WO2012067590A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111484756A (zh) * 2020-05-22 2020-08-04 中信钛业股份有限公司 一种提高氧化铝包覆钛白粉分散稳定性的方法
CN113234336A (zh) * 2021-05-18 2021-08-10 浙江天女集团制漆有限公司 一种无机复合紫外线吸收剂的制备方法
CN111234567B (zh) * 2020-03-18 2021-11-05 中南大学 一种制备高耐候钛白粉的无机包膜工艺
CN116285425A (zh) * 2022-12-15 2023-06-23 宜宾天原海丰和泰有限公司 一种钛白粉硅铝包膜方法
CN116285425B (zh) * 2022-12-15 2024-05-31 宜宾天原海丰和泰有限公司 一种钛白粉硅铝包膜方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104877393B (zh) * 2015-04-08 2018-03-30 攀钢集团攀枝花钢铁研究院有限公司 一种低吸油量钛白粉及其制备方法
CN105293505A (zh) * 2015-12-10 2016-02-03 周坤友 一种新型结构的纳米二氧化硅溶胶体

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040259997A1 (en) * 1998-08-20 2004-12-23 Catherine Enjalbert Use of titanium dioxide as anti-UV agent in a rubber composition
US20050222297A1 (en) * 2001-11-01 2005-10-06 Bettler Charles R Easy to disperse, high durability TiO2 pigment and method of making same
US20080299056A1 (en) * 2003-12-16 2008-12-04 Scott Rickbeil Frerichs Passivated nano-titanium dioxide particles and methods of making the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040259997A1 (en) * 1998-08-20 2004-12-23 Catherine Enjalbert Use of titanium dioxide as anti-UV agent in a rubber composition
US20050222297A1 (en) * 2001-11-01 2005-10-06 Bettler Charles R Easy to disperse, high durability TiO2 pigment and method of making same
US20080299056A1 (en) * 2003-12-16 2008-12-04 Scott Rickbeil Frerichs Passivated nano-titanium dioxide particles and methods of making the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111234567B (zh) * 2020-03-18 2021-11-05 中南大学 一种制备高耐候钛白粉的无机包膜工艺
CN111484756A (zh) * 2020-05-22 2020-08-04 中信钛业股份有限公司 一种提高氧化铝包覆钛白粉分散稳定性的方法
CN111484756B (zh) * 2020-05-22 2022-02-08 中信钛业股份有限公司 一种提高氧化铝包覆钛白粉分散稳定性的方法
CN113234336A (zh) * 2021-05-18 2021-08-10 浙江天女集团制漆有限公司 一种无机复合紫外线吸收剂的制备方法
CN116285425A (zh) * 2022-12-15 2023-06-23 宜宾天原海丰和泰有限公司 一种钛白粉硅铝包膜方法
CN116285425B (zh) * 2022-12-15 2024-05-31 宜宾天原海丰和泰有限公司 一种钛白粉硅铝包膜方法

Also Published As

Publication number Publication date
SI23547A (sl) 2012-05-31

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