Process for the manufacture of a mesoporous product

Patent metadata

Field	Value
Publication number	US-10071502-B2
Application number	US-201214368044-A
Country	US
Kind code	B2
Filing date	Dec 20, 2012
Priority date	Dec 23, 2011
Publication date	Sep 11, 2018
Grant date	Sep 11, 2018

Abstract

Process for the manufacture of a mesoporous product comprising the following successive steps:
a) preparation of a slip comprising:
a solvent, an additive, more than 4%, as percentage by volume based on the slip, of a powder formed of ceramic particles,
b) oriented freezing of the slip, so as to form a block comprising ice crystals separated by walls, c) removal of the ice crystals from said frozen slip block, optionally removed from the mold, so as to obtain a porous preform, d) removal of the additive, so as to obtain a preformed mesoporous product, the additive and the amount of additive being chosen so that the additive is present in a mesopore-forming micellar phase in said walls, more than 25% by volume of said ceramic particles exhibiting a size less than twice the size of the micelles of said mesopore-forming micellar phase.

First claim

The invention claimed is:

1. A process for the manufacture of a mesoporous product comprising the following successive steps:
a) preparation of a slip comprising:
a solvent,
an additive,
more than 4%, as percentage by volume based on the slip, of a powder formed of ceramic particles,

d) oriented freezing of the slip, so as to form a block comprising ice crystals separated by walls,
f) removal of the ice crystals from said frozen slip block so as to obtain a porous green part,
g) removal of the additive, so as to obtain a preformed mesoporous product comprising a mesoporosity consisting of mesopores being accessible pores having an equivalent diameter of between 2 and 50 nm, the mesopore volume being greater than 0.9/w v and less than 9/w v , w v denoting the absolute density of the mesoporous product, the mesopore volume being the volume of the combined mesopores, divided by the absolute density of the mesoporous product, wherein the amount of additive in the slip at step a) is adapted such that the additive is present in a mesopore-forming micellar phase in said walls at step d) and such that more than 25% by volume of said ceramic particles exhibit a size less than twice the size of the micelles of said mesopore-forming micellar phase.

2. The process as claimed in claim 1 , in which at step d) the amount of additive is adapted such that the additive exists in an organized mesopore-forming micellar phase in said walls.

3. The process as claimed in claim 1 , in which at step a) the amounts of additive and solvent are adapted such that the additive does not exist in an organized mesopore-forming phase in the unfrozen slip.

4. The process as claimed in claim 1 , in which, in step g), the additive is removed by heat treatment at a temperature less than the sintering temperature or by extraction using a product which can dissolve said additive.

5. The process as claimed in claim 1 , in which the solvent comprises more than 50% of water, and/or the amount of solvent is greater than 60%, as percentage by volume of the slip.

6. The process as claimed in claim 1 , in which the slip comprises more than 10% and less than 40% of ceramic particles, as percentage by volume of the slip.

7. The process as claimed in claim 1 , in which more than 50% by volume of the ceramic particles exhibit a size smaller than the size of the micelles of the additive.

8. The process as claimed in claim 1 , in which more than 90%, as percentage by volume, of the particles exhibit a size of less than 10 μm.

9. The process as claimed in claim 1 , in which the fraction by volume of additive in said walls is greater than 10% and less than 95%.

10. The process as claimed in claim 1 , in which the additive is chosen in order to exhibit, in the mesopore-forming micellar phase, micelles exhibiting a size of greater than 2 nm and less than 50 nm.

11. The process as claimed in claim 1 , in which the powder formed of particles comprises at least one oxide chosen from
the group A consisting of unstabilized zirconium oxide, partially stabilized zirconium oxide, stabilized zirconium oxide, undoped yttrium oxide, doped yttrium oxide, titanium oxide, aluminosilicates, unhydrated alumina, hydrated aluminas, magnesium oxide, talc, nickel oxide, iron oxides, undoped cerium oxide, doped cerium oxide, solid solutions of cerium oxides, undoped oxides of perovskite structure, oxides of perovskite structure doped with a dopant chosen in the group consisting in platinum, palladium, rhodium, gold, silver and their mixtures, compounds comprising titanium of La 4 Sr 8 Ti 11 Mn 1-x Ga x O 38 type with 0≤x≤1 and La 4 Sr 8 Ti 12-n Mn n O 38 type with 0≤n≤1, compounds with a structure of bimevox type, compounds with a structure of lamox type, compounds with an apatite structure, or
the group B formed by carbides, nitrides, borides, disilicides, oxynitrides, oxycarbides and their mixtures.

12. The process as claimed in claim 1 , in which more than 25% by volume of the ceramic particles have a size of less than the correlation distance of the organized mesoporosity generated by the additive, and/or in which, in step a), more than 25% by volume of the ceramic particles exhibit a size less than twice the median equivalent diameter of the mesopores of the mesoporous product obtained in step g).

13. The process as claimed in claim 1 , in which the powder formed of particles comprises more than 10% by volume of ceramic particles exhibiting an organized microporosity.

14. The process according to claim 1 , further comprising a step b) performed after step a) and before step d), consisting in observing a waiting time greater than 0.5 hour.

15. The process according to claim 1 , further comprising a step c) performed after step a) and before step d), consisting in pouring the slip into a mold.

16. The process according to claim 1 , further comprising a step c) performed after step a) and before step d), consisting in removing the air bubbles present in the slip.

17. A process according to claim 14 , further comprising a step c) performed after step b) and before step d), consisting in pouring the slip into a mold.

18. A process according to claim 14 , further comprising a step c) performed after step b) and before step d), consisting in removing of air bubbles present in the slip.

19. A process according to claim 17 , further comprising a step e) performed after step d) and before step f), consisting in removal of said frozen slip block from the mold.

20. A process according to claim 1 , wherein at step f) removal of the ice crystals from said frozen slip block is performed by sublimation.

21. A process according to claim 1 , further comprising a step h) performed after step g), consisting in sintering of the porous green part obtained at the end of step f) so as to obtain a sintered mesoporous product.

22. A process according to claim 21 , further comprising a step i) performed after step h), consisting in machining said sintered mesoporous product.

23. A process according to claim 21 , further comprising a step i) performed after step h), consisting in impregnating said sintered mesoporous product with an impregnating material.

24. A process according to claim 1 , further comprising a step h) performed after step g), consisting in sintering the preformed mesoporous product obtained at the end of step g), so as to obtain a sintered mesoporous product.

25. A process according to claim 24 , further comprising a step i) performed after step h), consisting in machining said sintered mesoporous product.

26. A process according to claim 24 , further comprising a step i) performed after step h), consisting in impregnating said sintered mesoporous product with an impregnating material.

27. A process according to step 1 , wherein the amount of additive in the slip at step a) is adapted such that the additive is present in an organized mesopore-forming micellar phase in said walls at step d).

28. A process according to claim 1 , wherein at step a) the ceramic particles are partially or completely replaced by equivalent amounts of precursors of particles, said precursors of particles being converted into ceramic particles before step g).

29. A process according to claim 1 , wherein the additive is a nonionic surfactant of formula (EO) m (PO) n (EO) m′ , which comprise a hydrophobic core made of polyoxypropylene (PO)

Assignees

• Saint Gobain Centre D Rech Et Detudes Europeen
• Saint Gobain Ct Recherches
• Centre Nat Rech Scient

Inventors

• Klotz Michaela
• Amirouche Idris
• Deville Sylvain
• Guizard Christian Gilbert

Classifications

• C04B35/10

  based on aluminium oxide · CPC title

• H01M8/124

  characterised by the process of manufacturing or by the material of the electrolyte · CPC title

• C04B35/26 Primary

  based on ferrites · CPC title

• B01D71/02

  Inorganic material · CPC title

• C04B35/515

  based on non-oxide ceramics · CPC title