Method for preparing oxide material

• US 8,597,610 B2
• Filed: 06/09/2008
• Issued: 12/03/2013
• Est. Priority Date: 06/07/2007
• Status: Expired due to Fees

• Current Assignee: Estonian Nanotechnology Competence Centre
• Original Assignee: Estonian Nanotechnology Competence Centre, University of Tartu
• Inventors: Kink, Ilmar, Jrveklg, Martin, Reedo, Valter, Meorg, Uno, Lhmus, Ants
• Primary Examiner(s): Li, Jun
• Application Number:
  US12/663,179
• Publication Number:
  US 20100183829A1
• Time in Patent Office: 2,003 Days
• Field of Search: 428/34.1, 264/134, 423/608
• US Class Current: 423/608
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 13/32 by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
• CPC Class Codes: C01G 23/053 Producing by wet processes, e.g. hydrolysing titanium salts
• CPC Class Codes: C01G 25/02 Oxides
• CPC Class Codes: C01G 27/02 Oxides
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/12 with a cylindrical shape
• CPC Class Codes: C01P 2004/13 Nanotubes
• CPC Class Codes: C01P 2004/136 Nanoscrolls, i.e. tubes having a spiral section
• CPC Class Codes: Y10T 428/13 Hollow or container type article [e.g., tube, vase, etc.]

Abstract

In the current invention a method for the preparation of an oxide material was described that involves bringing the sol onto the substrate, the gelation of the solution and thermal treatment of the gel. Alkoxides are used as precursor materials for the sol preparation and substrate free structures are employed for the manufacturing of the oxide material. A gel film with thickness ranging from 5 nm to 1 μm is created onto the sol layer. The gelled film is separated into pieces by self organizing and the gelled part is disconnected from the substrate. Substrate free tubular structures with diameters ranging from 0.01-100 μm are formed of the gel film which are then heated at temperature range of 200-1600 C during a period of 5 minutes to 10 hours. The manufactured oxide materials are employed as catalysts, gas sensors, stationary phases of chromatographic columns, composite materials, thermal isolation materials and micro- or nano electronic mechanical systems (MEMS or NEMS) components.

Claims

1. A method for preparing tubular oxide material structures, comprising the steps of:

bringing a sol onto a substrate, wherein alkoxide precursors are used for the source of the sol;

gelation of a surface of the sol by forming a gel film of 5 nm to 1 μ

m on the surface of the sol during the gelation, wherein the gel film formed onto the sol contracts, fractures, and separates to pieces with a controlled surface area by self-organizing;

adding a solvent to dissolve a sol layer between the gel film and the substrate, removing the gel film pieces from the substrate, and bringing the gel film pieces into a solution, whereby by releasing the gel film pieces from the substrate, freestanding tubular oxide material structures with diameters ranging from 0.01-100 μ

m are formed; and

oxidizing the tubular oxide material structures by heating;

wherein cracking and formation of slits in the gel film cause the self-organizing separation into pieces.

2. The method according to claim 1, wherein the gel film is formed by partial gelation of the surface of the sol by exposing it to humid gas 0.0001-900 g/m³ during a period of 1 second to 10 days.

3. The method according to claim 1, wherein a pure alkoxide or an alkoxide that is hydrolyzed up to 50% is used for preparing of the sol.

4. The method according to claim 3, wherein a pure alkoxide is dissolved in an organic solvent with 1:

50 mass ratio for preparing of the sol.

5. The method according to claim 4, wherein ethoxide, methoxide, propoxide, or butoxide are used for preparing of the sol.

6. The method according to claim 3, wherein ethoxide, methoxide, propoxide, butoxide or various mixtures thereof are used.

7. The method according to claim 1, wherein Hafnium, zirconium, tin, aluminium, silicon, nickel, manganese, yttrium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, ytterbium or various mixtures of metal alkoxides are used as the metal of the alkoxide.

8. The method according to claim 3, wherein Hafnium, zirconium, tin, aluminium, silicon, nickel, manganese, yttrium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, ytterbium or various mixtures of metal alkoxides are used as the metal of the alkoxide.

9. The method according to claim 2, wherein the relative humidity of the used gas is between 5-100%.

10. The method according to claim 9, wherein the relative humidity of the used gas is between 80-95%.

11. The method according to claim 1, wherein an organic solvent or mixture of organic solvents is added to the gel in an amount ratio that exceeds 2:

1.

12. The method according to claim 2, wherein the surface of the sol is flushed with a humid gas during a period of 1 to 60 minutes.

13. The method according to claim 12, wherein the surface of the sol is flushed with humid air preferably during a period of 5 minutes.

14. The method according to claim 11, wherein the surface of the sol is flushed with humid air in an amount of 10-20 g/m³.

15. The method according to claim 4, wherein the organic solvent is hexane or butanol.