Hybrid Materials

Inorganic-Organic
Hybrid Materials
Bressanone Sept. 2006
Hybrid Materials
Hybrid Materials
Composites Hybrid Materials
cm
nm
CLASSICAL COMPOSITES
Property Improvement:
mechanical stability
thermal stability
photochemical stability
Hybrid Materials
From Molecules to Nanobuilding Blocks
Various properties possible depending on precursors and processing
Hybrid Materials
Hybrid Materials
Composite Material
Compound 1
Macroscopic
phases
Compound 2
Hybrid Material
Molecular or
nanoscale
building blocks
The goal is to create materials with specific combinations of properties by

combining different molecular building blocks in various ratios and by controlling
their mutual arrangement
Control at the nanolevel
Hybrid Materials
Homogeneity
vs.
Problems: scatters light,

mechanical properties, etc
Control over homogeneity:
precursor selection (functional group)
reaction conditions: kinetics, solvent, etc.
interactions between the components
Hybrid Materials
Typical Properties of Organic and Inorganic Materials
Properties
Organic materials
(polymers)
Inorganic materials
(glass, ceramics)
Nature of bonds
covalent [CC], van der

Waals, H-bonding
low
low (except polyimides)
low
low
elastic
flexible
rubbery (depending on Tg)
hydrophilic or hydrophobic
ionic or covalent
high
high
high
high
hard
strong
brittle
hydrophilic
insulating to conductive
non-magnetic
at low temperatures and
pressures (molding, casting,
etc.)
insulating to semiconductors
magnetic
at high temperatures and/or
pressures (sintering, glass
forming)
Tg
Thermal stability
Density
Refractive index
Mechanical properties
Hydrophobicity
Electronic and
magnetic properties
Processability
Hybrid Materials
Nanolego
Form
Function
Geometry of the linkage
Connectivity
Kind of linkage
Hybrid Materials
Nanolego: Building Blocks

Inorganic Building Blocks
O
O
O
Si
O
Ti
Mechanical, optical, electrical,

magnetical properties
O
O
Connecting Blocks
H2C
Si
O
O
X
Ti
Y
O
Reduction of the crosslinking density,

coupling sites between inorganic /
organic components
Organic Building Blocks

Functional groups, crosslinking,
polymerizability
Flexibility, elasticity, processability

H2
C
H2
C
C
H2
C
H2
Hybrid Materials
Nanolego: Linking the Building Blocks

Polymerization / Polycondensation
CH3
COOR
CH3
COOR
CH3
COOR
HO
OR
+
O
H2N
HN
HN
NH2
OH
NH
Sol-Gel-Process
RO
Si
OR
OR
HO
+ H2O
Si
OH
OH
OH
OR
HO
- H2O
+ H+
HO
Si
OH
OH
OH
Na4SiO4
Si
HO
Si
OH
OH
OH
OH
Self-Organization
Zn(NO3)2 +
HO
O
Zn4O(terephthalate)6
OH
Hybrid Materials
Nanolego: Critical Issues
Homogeneous distribution of the building blocks in the material

Stable distribution: no microphase separation
Interaction between the two components
Structure-property relationships
Inclusion of functionalities
Tailoring of
molecular structure nanostructure microstructure
(= hierarchical structure design)
Hybrid Materials
10
Precursors
Molecular precursors
Clusters (nano-building blocks, NBB)
Alkoxysilyl-substituted organic polymers
Pre-formed nanostructures
Classes of sol-gel hybrid materials

Physically entrapped components
Functionalized inorganic networks
Interpenetrating networks
Dual networks
Hybrid Materials
11
Molecular Precursors
Network Modifiers (non-reactive organic groups)
(RO)3Si CH3
(RO)3Si
(RO)3Si
Precursors with Functional Organic Groups

(RO)3Si
(RO)3Si
O
O
+ HS-Si(OR)3
(RO)3Si
(RO)3Si
O
RO
(EtO)3Si
O
Ti
H
N
O
O
N
R
OR
OR
(RO)3TiSO3(Co-phthalocyanine)
polymerizable organic groups

inorganic-organic hybrid polymers
NO2
NH2
N
H
groups with other organic functions
Hybrid Materials
12
Nano Building Blocks: Polyhedral Oligomeric Silsesquioxanes (POSS)
Hybrid Materials
13
Nano Building Blocks: Functionalized Metal Oxide Clusters
Ti16O16(OEt)24(OPr)8
(same with
OCH2CH2OC(O)C(Me)=CH2)
Zr6O4(OH)4(methacrylate)12
covalent interaction
[(BuSn)12O14(OH)6]2+2 methacrylate[SiW11O39(OSi2(C6H4CH=CH2)2)]4-
Hybrid Materials
electrostatic interaction
14
Bridged Alkoxysilanes
(RO)3Si
(RO)3Si-(CH2)n-Si(OR)3
Si(OR)3
H
N
(RO)3Si-(CH2)m
H
(CH2)n N
H
N (CH2)n
H
N
H
N (CH2)m-Si(OR)3
O
(EtO)3Si
O
O
N
N
H
(EtO)3Si
H
N
SO2(CH2)2O
O
O
Si(OEt)3
2+
NH
(RO)3Si
H2N
NH2
Ni
NH
Si(OR)3
Hybrid Materials
15
Alkoxysilyl-Substituted Organic Polymers
CH3
(EtO)3SiO
Si
Si(OEt)3
n
CH3
(EtO)3Si-(CH2)3 O
CH3
H2
C
n
C
(CH2)4-O
Si(OMe)3
(CH2)3-Si(OEt)3
Hybrid Materials
16
Pre-formed Nanostructures
(Nano)Particles
Preformed Oligomers
and Polymers
Clays / Layered Materials
Porous Materials
(Nano)Fibres, Nanotubes
Hybrid Materials
17
Consequences of Introducing Organic Substituents
Reduced degree of crosslinking of the inorganic network

Polarity changes (changes in hydrogen bonding)
Reactivity change of the remaining alkoxide groups
(electronic and steric effect of the organic substituents)
These effects are an inevitable consequence

of the organic modification
Hybrid Materials
18
Degree of Crosslinking
Si(OR)4-nRn
n = 1-3
Si(OR)2R2
Si(OR)3R
R
Si
Si
Si
O
O
R
Si
Si
O
O
Si
Si
Si
Si
Silsesquioxanes
R
R
O Si O
Si
O
R
R
O
n
Si(OR)R3
R
Si O
Si R
R'
Oligo- and Polysiloxanes
Dimers
R
Si
O
O
R
O
Si
Si
OR
Si
O
O
Si
Si O
O
R
R
Polyhedral Oligomeric
Silsesquioxanes
Hybrid Materials
19
Influence on Reaction Rates

Example:
(RO)3Si
Si(OR)3
0.6 M in methanol, 25C

The dashed line is pH vs. gel time for
Si(OMe)4 (2.0 M in methanol, 60C).
Hybrid Materials
20
10
Influence on Reaction Rates
(acac = acetylacetonate, ftac =trifluoroacetylacetonate, dbzm = dibenzoylmethanide)
Hybrid Materials
21
Precursors

Interpenetrating structures
Dual networks
Hybrid Materials
22
11
Types of Inorganic-Organic Hybrid Materials by Sol-Gel Processing

Physically entrapped
molecules, particles, etc.
Interpenetrating inorganic
and organic networks
Class I materials:
weak interactions
R R
RR
R
Class II materials:
strong interactions
RR
R R
R R
RR
RR
R R
RR
R
R
R R
R
R RR
RR
R
R
R
R
RRR
R
R
Modification of the gel

network by organic groups
Dual inorganic and organic networks

connected by covalent bonds
Hybrid Materials
23
Entrapped Biomolecules
Hybrid Materials
24
12
Entrapped Biomolecules: Glucose Sensor

NO-releasing glucose biosensor
(cleaved NO suppresses degradation by bacteria)
Glucose oxidase in MeSi(OEt)3 Gel
SiO2
Si
CH3
OH
N NO
H
O Si (CH2)3 N (CH2)6 N
H
in polyurethan
M.H.Schoenfisch et al., 2004
Hybrid Materials
25
Entrapped Inorganic Particles: Dental Filling

abrasion 9 m
shrinkage 1,97 vol%

adhesion 25,8 / 27,6 MPa
pyrogenic
silica
( 40 nm)
+
standard
dental glass
particles
( 0,7 m)
Hybrid Materials
26
13
Entrapped Inorganic Particles: Controlled Release
in SiO2
Hybrid Materials
27
Precursors

Dual networks
Hybrid Materials
28
14
Heterogenization of Homogeneous Catalysts

Classical approach
RO
RO
RO
Si
RO
Sol-gel approach
+ MLn
RO
Si
RO
MLn
+ MLn
O
Si
Si
MLn
MLn
+ MLn
+ MLn
Si
RO
Si
Si
E(OR) n
RO
RO
RO
RO
Si
MLn
+ E(OR) n
RO
RO
Si
RO
RO
RO
RO
RO
Si
Hybrid Materials
29
Heterogenization of Catalysts by Sol-Gel Processing

RO
Si
RO
MLn
Examples:
+ Si(OR)4
RO
Si
Ph
C
O
Ph
P
Si(OR)3
Ph
MLn
(EtO)3Si
Poren
pores
(EtO)3Si
sol-gel
Sol-GelProze
processing
Ph Cl
P
Ru
P
Ph Cl
Ph
P
P
Ph
Si(OEt)3
Si(OEt)3
Synthesis of N,N-diethylformamide from CO2, H2

and diethylamine
A. Baiker et al., 1999
K
K
Cl
Rh
More active in the hydrosilation of 1-hexene than

Rh(CO)Cl(PR3)2
U. Schubert et al., 1989
SiO2 /
Ph
(RO)3Si
K
K
(RO)3Si
K
K
aktive
Spezies
= katalytisch
catalytically
active
species
N
H
NH2 N
Cu2+
NH
2
Catalyst for the oxidation of 3,5-di-tert.butylcatechol

to the quinone
M. Louloudi et al., 1998
Hybrid Materials
30
15
Coatings with Optical Properties

Photochromism: fast for optical switches, for eye protection, privacy shields
slow for optical data storage, energy conserving coatings, etc...
Example: Spirooxazine derivative
h1
N
N
or h2
N
N
Embedding in sol-gel coatings:

For sufficient photochromism: dye concentration > 25 wt% mechanical stability of
sol-gel film is deteriorated.
Grafting of the dye to the
sol-gel matrix higher chromophore
concentrations can be achieved
without affecting the mechanical integrity
of the sol-gel matrix
Si(OEt)3
HN
O
N
N
Photochromic coating on paper
Hybrid Materials
31
Precursors

Dual networks
Hybrid Materials
32
16
Interpenetrating Networks
Sequential
Sequentialtwo-step
two-stepprocess:
process:
Second
Secondnetwork
networkis
is
formed
formedin
inthe
thefirst
first
IPN
Examples:
Generation of the organic polymer in the pores of an inorganic porous material
(in channels of zeolites or mesoporous materials, between sheets of a layered
lattice, such as a clay mineral) rigid inorganic moiety with a regular pore or
channel structure in the nanoscale
Inorganic structures form and interpenetrate an organic polymer (difficulties:
incompatibility between the moieties phase separation)
Hybrid Materials
33
Interaction via hydrogen bonds to silanol groups of the forming silica
Organic polymers with hydrogen bonding ability:
n
NMe2
OH
OMe
n
O
OH
poly(VP)
poly(DMAA)
poly(VA)
poly(VAc)
poly(MMA)
poly(HEMA)
Si(OR)4 and/or RSi(OR)3

H2O, [Kat]
No macro phase separation

Resulting materials: high degree of homogeneity
and optical transparency
Important reaction parameter: pH

Change of crosslinking density and interaction with polymer using RSi(OR)3/Si(OR)4 mixtures
Hybrid Materials
34
17
+
Sol from GLYMO and Al(OsBu)3 (H2O/HCl)
Poly(isopren-block-ethylenoxide)
swollen in THF/CH3Cl
(RO)3Si
O
O
Nanostructured hybrid polymer

U.Wiesner et al., 2004
Hybrid Materials
35
Organic
Monomer
Inorganic Monomer
Catalyst
Solvent
AIBN
TEOS
HF
Water
OH
C. L. Jackson et al. Chem. Mater. 1996, 8, 727
Initiator
Addition of tetrakis(2-(acryloxy)ethoxy)silane
improves homogenity
TEM images of the nanocomposites:
Increasing Sol-Gel Catalyst Concentration => Faster Reaction
Hybrid Materials
36
18
Nanocomposites: Polymer-Clay
Layered solid
Layered solid
+ Monomer
(Polymerization)
Exfoliated layers
+ Polymer
+ Monomer
(Polymerization)
or
+ Polymer
Hybrid Materials
37
Hybrid Materials
38
19
15 m glass fibre in polyolefin
1 nm thick montmorillonite
sheet in epoxy resin
Hybrid Materials
39
Nanocomposites: Intercalation of Polymers in Pores
Direct Intercalation
Polymer
Porous Host
Problems:
Pore diameter size of Polymer
Diffusion of polymer
Usually only end of polymer sits in pore but not the whole chain
Hybrid Materials
40
20
Nanocomposites: Polymerization in Pores
Monomer
Intercalation
Monomer
Polymerization
Porous Host
Monomer is interacalated into the pores

(vapor, liquid), then polymerization
T. Aida et al. 2000
Hybrid Materials
41
Nanocomposites: Polymerization in Pores
T. Aida et al. 2000
T. Bein et al. 1992
Hybrid Materials
42
21
Precursors

Dual networks
Hybrid Materials
43
Dual Network Structures

Preparation strategies
Concomitant formation of the inorganic and organic structures
Stepwise formation of the organic and inorganic networks
from pre-formed organic structures
from pre-formed inorganic structures
Options
Chemical composition of the inorganic component(s)

Chemical composition of the organic component(s)
Proportion of the inorganic/organic components
Curing method (thermal / photochemical)
Dimension of the inorganic / organic components (molecular, nanometer,
extended)
Hybrid Materials
44
22
Concomitant Formation of Inorganic and Organic Network

Typical procedure
Metal Alkoxides
Metal Salts
+ water (ev. catalyst or additives)
- alcohol
Precursors
Hydrolysis
Condensation
Sol
Gelation
formation of inorganic network
Gel
formation of organic network
Hardening
(thermal or uv)
Many Examples:
Coatings Section
Hybrid Polymer
Hybrid Materials
45

Often used precursors
O
(RO)3Si
(RO)3Si
(RO)3Si
O
O
or
O
OH
+ Zr(OR)4
+ Si(OR)4, Zr(OR)4, Al(OR)3,

etc.
+ acrylate, epoxide
monomers, etc.
increase of inorganic /
organic ratio
decrease of inorganic /
organic ratio
Hybrid Materials
46
23

O
O
O
O
Sequential
formation of
the organic
network
UV-polymerization
of methacryl groups
photo-initiator, h
O
O
O
O
O
O
O
O
O
O
thermal polymerization
of epoxy groups
T
O
O
O
O
O
O
O
O
O
O
O
O
O
Hybrid Materials
47
*) SBU: Sequentially Built-up

O
H2O / NaF
Si
CH2O
SiO2
CH2OH n
H2O / NaF
O(CH2)2O Si
4
aq. ROMP
O
+
Free Radical
Polymerization
SiO2 +
Hybrid Materials
O(CH2)2OH 4
48
24
Photochemical Crosslinking (3D Laser Lithography)

Coating or forming of
ORMOCER
(with chromophor as UV initiator)
Direct 3D-laser writing

(2-photon polymerisation with
femtosecond laser pulses)
Requirements for hardening:
Development of the structure
(removal of uncured
ORMOCER)
precise focussing
2-photon process
polymerisation in Ormocer layer

(O2 protection)
chromophor as initiator
Ormocer = Organically modified Ceramics
Hybrid Materials
49

CAD File
Layer model
Venus of Milo in
ORMOCER (REM)
I am made
from
ORMOCER!
Hybrid Materials
50
25
Hybrid Materials
51
Hybrid Polymers from Pre-Formed Organic Polymers

CH3
Low shrinkage by the use of

prepolymerized materials
CH3
acrylic component
silane component
(MeO)3Si(H2C)3O
y
MeO
1. inorganic condensation
2. organic polymerization
acrylic monomer + polymer

(incomplete polymerization)
inorganic condensation
between fully
polymerized polyacrylate
Hybrid Materials
52
26
Hybrid Polymers from Pre-Formed Organic Polymers

A.-M. Caminade, J.-P. Majoral, J. Mater. Chem., 2005, 15, 3643-3649
Hybrid Materials applying Dendrimers
Porous Materials using Dendrimers as Templates
Hybrid Materials
53
Hybrid Polymers from Pre-Formed Inorganic Structures
Hybrid Materials
54
27

Improved Properties through Controlled
Reinforcement of Polymer Chains at the Molecular Level
R
O
Si
Si
Si
O
Si
O R
Si
O
Si
R'
O
O
O
RO
O
Si
Si O
R
www.hybridplastics.com
Property enhancements via POSS

observed in POSS-copolymers and blends
Increased Tdec
Increased Tg
Reduced Flammability
Reduced Heat Evolution
Lower Density
Disposal as Silica
Extended Temperature Range
Increased Oxygen Permeability
Lower Thermal Conductivity
Thermoplastic or Curable
Enhanced Blend Miscibility
Oxidation Resistance
Altered Mechanicals
Reduced Viscosity
Hybrid Materials
55

POSS for fire retardant materials
Hybrid Materials
56
28

Polymerizable Metal Oxo Clusters
X
X
X
X
X
X
X
Polymerizable groups X
Zr6O4(OH)4(methacrylate)12
for free radical polymerization
Zr6O4(OH)4(5-norbornene-2-carboxylate)12 for ROMP
Hybrid Materials
57

Metal Oxo Clusters as Initiators for ATRP
multifunctional initiator + monomer
X
catalyst
X
X
X
X
X
X
+ solvent
= PMMA, PS, PtBuA
catalyst = pmdeta / CuBr or CuCl
e.g. Ti6O4(OOCCBrMe2)(OiPr)8
0.9
100
0.7
ln (M0/M)
G.Kickelbick et al.
80
Y=0,0058*X
R=0,997
70
60
0.5
50
0.4
40
0.3
Polydispersities <1.5. 0.2

90% of the chain ends 0.1
still active after isolation 0.0 0
Hybrid Materials
30
Conversion [%]
0.6
90
ln (M 0/M)
linear Fit for ln (M 0/M)
0.8
20
10
0
20
40
60
80
100 120 140 160
Time [min]
58
29

Combination of polyoxometallates (electrochromism, photochromism,
conductivity, redox activitities) + conjugated molecules and polymers
electrically active organic materials (light emitting diodes, field-effect
transistors, solid-state lasers)
Monofunctionalization of Mo6O192-
Examples:
Z. Peng et al. 2004
Hybrid Materials
59
Z. Peng et al. 2004
Hybrid Materials
60
30

Magnetic Polymers
Mn12O12(OOC-CH=CH2)16
Radical polymerization
+ CH2=CMe-COOMe
PMMA crosslinked by Mn12

Mn12
total cluster spin S = 10
(4 MnIV, S = 3/2 + 8 MnIII, S = 2)
Superparamagnetic
Hybrid Materials
61
Preparation of nanoparticles
Stber-Process
Si(OEt)4 + NH4OH
FG
Surface modification
O
N
NC
CH3
CH3
CH3
CN
SiO
FG
Si
Si
FG
O O O OO O
O
Si
O
O
O
O
O
O
Si O
2
O
O
O Si
O
O
FG
O
O O OO
Si
FG
FG
Si
Initiators at the surface, e.g.

(EtO)3Si(H2C)3O
HO HO OH OH
HO
OH
HO
HO
OH
HO
OH
2
HO
OH
HO
OH
HO
OH
HO
HO HO OHOH
FG
O
CH3
(EtO)3Si(H2C)3O
Br
CH3
SiO
(RO) 3 Si
FG
FG
Polymerization from the functionalised surface
AFM
G.Kickelbick et al.
Hybrid Materials
62
31

Hybrid Materials

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Inorganic-Organic

Bressanone Sept. 2006

Bressanone Sept. 2006

Composites Hybrid Materials

From Molecules to Nanobuilding Blocks

Various properties possible depending on precursors and processing

Bressanone Sept. 2006

The goal is to create materials with specific combinations of properties by

Bressanone Sept. 2006

Problems: scatters light,

Bressanone Sept. 2006

Typical Properties of Organic and Inorganic Materials

covalent [CC], van der

Bressanone Sept. 2006

Bressanone Sept. 2006

Nanolego: Building Blocks

Mechanical, optical, electrical,

Reduction of the crosslinking density,

Organic Building Blocks

Flexibility, elasticity, processability

Bressanone Sept. 2006

Nanolego: Linking the Building Blocks

Bressanone Sept. 2006

Nanolego: Critical Issues

Homogeneous distribution of the building blocks in the material

Bressanone Sept. 2006

Classes of sol-gel hybrid materials

Bressanone Sept. 2006

Precursors with Functional Organic Groups

polymerizable organic groups

Bressanone Sept. 2006

groups with other organic functions

Nano Building Blocks: Polyhedral Oligomeric Silsesquioxanes (POSS)

Bressanone Sept. 2006

Nano Building Blocks: Functionalized Metal Oxide Clusters

Bressanone Sept. 2006

Bressanone Sept. 2006

Alkoxysilyl-Substituted Organic Polymers

Bressanone Sept. 2006

Clays / Layered Materials

Bressanone Sept. 2006

Consequences of Introducing Organic Substituents

Reduced degree of crosslinking of the inorganic network

These effects are an inevitable consequence

Bressanone Sept. 2006

Oligo- and Polysiloxanes

Bressanone Sept. 2006

Influence on Reaction Rates

0.6 M in methanol, 25C

Bressanone Sept. 2006

Influence on Reaction Rates

(acac = acetylacetonate, ftac =trifluoroacetylacetonate, dbzm = dibenzoylmethanide)

Bressanone Sept. 2006

Classes of sol-gel hybrid materials

Bressanone Sept. 2006

Types of Inorganic-Organic Hybrid Materials by Sol-Gel Processing

Modification of the gel

Bressanone Sept. 2006

Dual inorganic and organic networks

Bressanone Sept. 2006

Entrapped Biomolecules: Glucose Sensor

Glucose oxidase in MeSi(OEt)3 Gel

M.H.Schoenfisch et al., 2004

Bressanone Sept. 2006