hybrid organic-inorganic glasses inorganic chemistry = organic chemistry room temperature...
TRANSCRIPT
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Hybrid organic-inorganic glasses
inorganic chemistry = organic chemistry
room temperature
metal-organic precursors in organic solvents
a whole range of new materials from brittle glasses to plastic polymers
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Hybrid organic-inorganic materials
Classification
based on the nature of interactions between organic and inorganic components
Class I
No chemical bond between components
only weak interactions
(van der Waals, hydrogen, electrostatic)
Class IIChemical bonds between components
strong interactions(covalent bonds)
Entrapping Grafting
NH SiO2N
NO2
O
O
O
Si
Si
Si
OO
O
O
O
OO
O O
NH2O2N
NO2
Si
O
O
O
Si
Si
Si
OO
O
O
O
O
O O
HO
O
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Class I the organic molecule is trapped within the silica network
Si(OR)4
ROH
Si(OR)4
Si(OR)4
Si(OR)4
ROH
ROH
H2O
sol-gel precursorSi(OR)4
organic molecule
Solution(common solvent)
organic moleculetrapped in thesilica matrix
Hydrolysis-condensation
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Class II : network modifier
OR
RO - Si - CH3
OR
Si-O-Si network + pending organic groups
-Si-CH3
OR
H3COR
Si-O-Si chains + side organic groups
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Synthesis of hybrid organic-inorganic materials
R-Si-(OR)x + M(OR)n
metal alkoxideorgano-functionalalkoxide
Oxo-polymers
conventionalsol-gel route
organic templatesinorganic
building blocks
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Class II : network formers
Si-CH=CH2
OR
OR
RO
Double polymerization process
[SiOx(OH)y]n
-[SiMe2O]-
inorganic
organic
Si > R Si < R
The size of both phases depends on the Si/R ratio
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coordination saturation
slowly hydrolyzable complexing ligands
iOPrOPriH C3OPri OOCH CCH C3TiOPriPriOOPriOPriTiOOC3OOCOPriOPriPriOPriOPriOTiTiPriO3CHCHacetic acidacetylacetone
acetic acidacetylacetone
Chemically Controlled Condensation
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Ti(OR)4 + x AcacH
Ti(OR)4-x(acac)x + x ROH
M
OH2
M
AcacH
molecularclusters
Stable sols
Gels
Precipitates
Complexation ratio x = acacH/Tiprevents condensation
Hydrolysis ratio h = H2O/Ti
favors condensation
Chemically Controlled Condensation
2 parameters
x
h
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Ti12O16(OPri)16 Ti17O24(OPri)20Ti18O22(OBun)26(Acac)2
Ti(OR)4-x(acac)x
Molecular clusters Organic bridges
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K.J. Shea, D.A. Loy, Acc. Chem. Res. 34 (2001) 707
Bridged Polysilsesquioxanes3(RO)-Si Si(OR)3
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xerogel
aerogel
rigid bridge flexibe bridge
SSi(OCH3)3(H3CO)3Si
(H3CO)3Si Si(OCH3)3
Si(OCH3)3(H3CO)3Si ( )n
(n = 1-3)
triple bridge
Si(OCH3)3
Si(OCH3)3(H3CO)3Si
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The pore size depends on the length of the bridge
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Anisotropic silica
polarized light
Bruno Boury (ICG - Montpellier)
π-π stacking leads to anisotropic materials
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ORMOCER
ORMOSIL
ORganically MOdified SILicate
ORganically MOdified CERamic
CERAMER
CERAmic polyMER
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Hybrid Sol-Gel Coatings
Le dôme du
grand théâtre national chinois
est recouvert d’un revêtement auto-nettoyant
Beijing Zhongke Saina Glass Technology
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Sol-gel coating
magnifying lens coated with an abrasion resistant hybrid coatingScratch resistant coatings on plastics
ABRASIL
Si - ORR
OR
OR
SiO2polymer
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Modification of the glass surface tension
glass underatmosphericconditions
glass modifiedwith a
hydrophobiccoating
glass modifiedwith a
hydrophiliccoating
Antisoilingproperties
Antifoggingproperties
© INM - Saarbrücken - Germany
Antifogging and antisoiling glass coatings
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hydrophobic coatings on windshields
Hybride PDMS + TEOS : « sliding effect »
Hybride PDMS + TEOS + FAS : against rainFAS = CF3-(CF2)7-CH2-CH2-Si-(OCH3)3
HO-Si OR
R-(CH2)n-Si-OR OR
R = hydrophobic group : CF3, CH3, …
Central Glass Japon
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Stainless steel without coating
Stainless steel with an
abrasion resistant
fluorinated hybrid coating
Sol-gel hydrophobic coatings
G. Schottner, Chem. Mater. 13 (2001) 3422
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Hhydrophilic and photocatalytic coatings
Two layers :
SiO2 : hydrophilic, scratching resistant
TiO2 : photocatalytic effect under UV irradiation
Thermal treatment at 600°C
© CGC Ltd.© CGC Ltd.
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‘anti-mist’ coatings
Central Glass - Japon
To avoid moisture condensation on a cold surface
SiO2-ZrO2
SiO2 / ZrO2 colloïdal + top-layer SiO2 ou
Gel = isocyanate + ethylene oxide/propylene oxide + PEG + PC polyol
dépôt par spin-coating + traitement thermique (@150°C); ép. 20µm
© CGC Ltd.
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before after
Getty Museum - Los Angeles
Cathedral of Pragua Protection of the mosaic by an hybrid coating
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Nanopatterning via
sol-gel embossing
soft hybrid sol-gel films
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Nano-patterned films
produced by embossing a hybrid coating
Hybrid coating
Periodic microstructure leading to a gradient in the refractive index
coated
non-coated
‘ lotus ’ effect
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Filling composites for dental applications
Definite & Admira resins(Fraunhofer ISC - VOCO GmbH)
Reduction of polymerization shrinkage
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sol-gel optics
bulk pieces
no crack or shrinkage upon drying (hydrophobic organics)
easily shaped materials (molding, polishing)
nano-composite = transparency
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Matech
sol-gel optics
Organic dyes in a silica matrix
fluorescence - laser - NLO - photochromism
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Crystal glasses with
colored hybrid coatings
Fraunhofer Würzburg
Coating on glasses
hybrid coating + organic dyes
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Easily recyclable colored bottles
• Organic dyes large choice of colors (marketing !) pigments can be burned off before recycling
• Hybrid coatings improved mechanical properties of bottles© Asahi-Kirin
Si(OCH3)4 + Ti(OC3H7)4
CH2=CH-Si(OC2H5)3
methacrylate-Si(OC2H5)3
UV and curing
organic dyes
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Sol-gel dye lasers
Organic dyes are trapped
within sol-gel silica matrices
(solid ≠ solution)
Organic dyes cover the whole visible range
Tunable lasers
N O N
CO2H
Rhodamine 640
O O
CH3
HOCoumarine 4
LASER dyes
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singlet triplet
electronic energy levels of fullerene
C60
Reverse Saturable Absorption
the excited state absorption is stronger than the ground state absorption
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C60
Reverse Saturable Absorption
the excited state absorption is stronger than the ground state absorption
Input energy (J)
tran
smis
ssio
n
absorption increases with the input power
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Fullerene C60
Sol-gel devices
C60 fullerenes are not soluble
small amount of C60
aggregation
Functionalization of C60 grafted onto silica
P. Innocenzi et al. Carbon 38 (2000) 1653
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nonlinear hybrid C60-silica coated lenses
Optical limiters
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E
Non linear optic
alignment of NLO molecules by a external field
Second Order NLO
Induced polarisation : P = P0 + (1)E + (2)E2 + (3)E3 + …
electro-optic modulation
frequency doubling
frequency mixing
Non centro-symmetric materials
electrons AD
Non symmetric moleculesNO2H2N
H3C
heating plate
10 kV
corona poling
methyl nitro aniline
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Sol-gel entrapment poling relaxation
relaxation short lifetime
Covalent grafting increases dye concentration
prevents relaxation
NH Si(OEt)3
NO2
O2NN
N
OHN
O
OHN
O
O2N
Si(OEt)3
Si(OEt)3
d33 = 150-200 pm/V
High non resonant Second Harmonic Generation
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Photochromic glasses
switching time ≈ 1 hourHydrophilic silica
Spiro oxazinecolorless blue
hydrophilichydrophobic
N O
N
N+
N
O-
UV
, visible
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hydrophilic/hydrophobic walls of the nanopores
RO ORSi
OR
OR
RO CH3Si
OR
OR
+
Hybrid precursors
Switching time from 1 second to 1 hour Protavic - France
Si Si Si SiSi
SiSiSiSi
Si
Si
SiSi
Si Si Si Si SiSi
Si
Si
Si
CH3 H H
HH
HHHHHHH
HHH
HH
Si
HH
CH3
CH3CH3
CH3N
O
N
NO
N
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Microencapsulation of liquid crystal droplets dispersed in sol-gel films
Glass plate transparent electrode (ITO)
LC droplet (neff)
Silica gel film
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OFF : light scattering (opaque)ON : applied voltage - alignement of LC (transparent)
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Merck - Germany
safe and inert UV-filters that do not penetrate the skin
Organics undergo photodegradation
free radicals
1
Encapsulated UV-Filters
encapsulation of organic filters in hollow silica spheres
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Merck
aqueous suspension containing ≈ 40% nanoparticles