SOL-GEL METHOD

AND DIP-COATING TECHNIQUE

Qumica
2014
 What does mean sol and gel?
Colloid: is a suspension in which the
dispersed phase is so small (1-1000 nm)
that gravitational are negligible and
interactions are dominated by van Der LIQUID
Waals forces and surface charges.
AEROSOL(Neblina)
SOLID AEROSOL (Humo)
FOAM (Afeitar)
EMULSION (Leche)
SOLID FOAM (Piedra
Pmez)
SOLID SOL(Cristal de rub)
SOL (Pinturas)
GEL (Gelatina)
Dispersing
phase
 What does mean sol and gel?
Sol: is a colloidal suspension
of solid particles in a liquid.

Gel: is a substance that contains

a continuous solid skeleton
enclosing a continuous liquid
phase.
Gels can also be formed from
particles sols, when attractive
dispersion forces them to stick
together in such a way as to form
a network.
Sol-gel processing options
 How to get a sol and a gel?
A commonly studied approach for synthesizing oxides
has been to hydrolyze the appropriate METAL ALKOXIDES.

M= Metal
Precursor M(OR)n (Ti4+, Si4+, Al3+, Zr4+, etc)
O=Oxygen
R=Organic group

eg. = Ti(i-OPr)4 Ti(O-CH(CH3)2)4

 How to get a sol and a gel?
PROPERTIES OF METAL ALKOXIDES

The properties depend on the electronegativity of the

metal.
Metal alkoxides are stronger Lewis acids and will
promote nucleophilic attack.
Most metals have several stable coordination numbers.
Alkoxides dissolved in the solvent, usually an alcohol.
Metal alkoxides react with WATER.
 How to get a sol and a gel?
Reactions:
HYDROLYSIS AND CONDENSATION
Hydrolysis
H H R
(a) (b) (c)
O+ M OR O M OR HO M O HO M + R OH
H H H

Variables
When reacting
-Nature of the alkoxide group with water many
-Nature of the solvent metal alcoxides
-Species concentration in the solvent
-Molar ratio water:alkoxide form precipitates!!
-Temperature
 How to get a sol and a gel?
Hydrolysis
Hydrolysis, reactivity:
Si(OiPr)4 <<< Sn(OiPr)4, Ti(OiPr)4 < Zr(OiPr)4 < Ce(OiPr)4
Carga parcial positiva (M) para metales en varios alcxidos
Alcxido Zr(OEt)4 Ti(OEt)4 Nb(OEt)5 Ta(OEt)5 VO(OEt)3 W(OEt)6 Si(OEt)4
(M) + 0.65 + 0.63 + 0.53 + 0.49 + 0.46 +0.43 + 0.32
Tomado de Livage y col.

Cargas parciales del titanio y silicio con diferentes sustituyentes

R Si(OR)4 Ti(OR)4
CH3 +0,36 +0,66

C2H5 +0,32 +0,63

n-C4H9 +0,30 +0,61

n-C6H13 +0,29 +0,60

n-C9H19 +0,28 +0,59

 How to get a sol and a gel?
Condensation

alcoxolation
M M R
(a) (b) (c)
O+ M OR O M OR M O M O M O M + R OH
H H H

oxolation
M M H
(a) (b) (c)
O+ M OH O M OH M O M O M O M + H2O
H H H
 How to get a sol and a gel?
H2O:metalic precursor (substoichiometric ) H2O:metalic precursor (Stoichiometric excess)
Complete hydrolysis Linear oligomers Complete hydrolysis Branched polymers

Small ligands result in faster reaction than large ligands.

Bidentate ligands also slow down the hydrolysis.
 How to get a sol and a gel?
To consider
To reduce the rate of hydrolysis has the acac
M(OR)z + x acac M(OR)z-x (acac)x + xROH
 How to get a sol and a gel?
Condensation reactions... Clusters formation

100

Higher clusters Collisions between clusters

GEL
How to get a film?

-Spin coating
-spray coating
 How to get a film?
Temperature
Chemical changes
Transition to a crystalline phase

Between 100-300C crystallographic structure is equal to dry gel

Brookita ~ 300 C

TiO2 Anatasa ~ 350 C

Rutilo ~ 500 C
 BIBLIOGRAFA
-For coverage of current sol-gel research, the most widely used journals are J. Non-Cryst. Solids,
J. Mater. Res., J. Am. Ceram. Soc., J Sol-Gel Sci. Techn., and J. Mater. Sci.
-The Materials Research Society has sponsored meetings since 1984 under the title Better
Ceramics Through Chemistry and has published proceedings.
-Ebelman, J.J. and Bouquet, M. (1846) Ann. Chem. Phys. 17, 54. Ebelman was the first person to
describe alkoxide synthesis. This paper reported the synthesis of boron methoxide, ethoxide,
and pentoxide by the reaction of boron trichloride with the appropriate alcohol. These alkoxides
can be used in the synthesis of borosilicate glasses.
-Piau, J.M., Bremond, M., Couette, J.M., and Piau, M. (1994) Maurice Couette, one of the
founders of rheology, Rheol. Acta 33(5), 357.
-Roy, D.M. and Roy, R. (1955) Synthesis and stability of minerals in the system MgO-Al2O3-SiO2-
H2O, Am. Min. 40, 147. For studying phase equilibria in minerals homogeneous samples are
essential. Hydrolysis of alkoxides was used to synthesize the powders. Rustum Roy of
Pennsylvania State University was one of the pioneers in using sol-gel techniques for preparing
ceramics.
-Preparacin de materiales por sol-gel y su aplicacion en fotocatalisis y fotoelectrocatlisis,
dictado por (Dr. Roberto J. Candal); Piedecuesta, Santander