Binder 1

General introduction
HOIM = Hybrid Organic-Inorganic Materials acronym
1 – The HOIM concept

a) HOIM definition
Traditional composite materials : multiphase material

brought about by combining materials that differ in composition
or form in order to obtain specific characteristics and properties.
! retain their identities and properties
! act in concert to achieve improved synergistic properties
These traditional composite materials, and in particular
materials with I fillers in O matrix, have macroscale domain size
of micrometer and even millimeter scale.
HOIM or nanocomposites or molecular composites : a

new class of composite materials with the physical constraint of
few nanometers as the maximum size of the I and/or O
component.
! I/O interface tends towards infinite.
! original properties, such as optical transparency.
BUT I and O components can not be prepared separately
before assembling
! simultaneous syntheses in the same batch
! successive syntheses
AND O components are "fragile" (< 250°C)
SO I component processing and/or modification at
temperatures substantially lower than those of
conventional ceramic processing conditions :
! sol-gel process
! intercalation chemistry
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 1-1

b) why such materials ?
When intimately associated

" I component acts as network former : chemical resistance,
mechanical resistance, optical transparency…
" O component acts as network former or network modifier :
processability, hydrophobic/hydrophilic balance, specific
property as NLO response, biological activity…
! synthesis and application of HOIM have attracted

" polymer scientists and " physicists
" solid state chemists " biologists
" ceramists
" inorganic chemists
" organ(ometall)ic chemists
Today the cooperation between them is very important to
understand the basic chemistry in conjunction with structure in
order to speed up the applications
! among present applications of HOIM :

" abrasion resistant coating on plastics
" decorative and functional coating on glasses
" coatings and adhesives for glass fibers
" NLO devices
" contact lenses
"…

2 – Classification attempt
HOIM could be classified according to

" the vol. % of the I (or O) component and the size of the
dispersed phase
" dimensional organization types of one component towards
the other one
inc I c o m
ceramics
of
rea
s in p o n e
g v nt
doped
ol .
xerogels decreasing dimensional

%
organization
filled
of one component
xerogels
towards the other one
entangled alternated core-shell

3D-networks 2D-layers particles
microcomposites materials
on . %
t
en
l
c o g vo
reinforced and/or crosslinked

O polymers
mp
n
o f eas i
O polymers
r
O
inc
! simplifying and non-exhaustive classification

! some of these classes do not fulfil the requirements of
nanoscale component size
BUT shared feature : the controlled association of I and O
components through the chemical design of inner
interfaces

3 – Class objectives
! just an introduction to HOIM

! rather from the polymer chemist point of view
! description of the chemical tools :
" polymer chemistry
" sol-gel process
" intercalation chemistry
" chemical modification of I surfaces
! HOIM examples with their versatile properties and
main applications
4 – Contents
1 " General introduction
2 " Macromolecular synthesis background

$ Basic definitions
$ Classification of polymerization reactions
$ Step polymerization
$ Chain polymerization : free-radical polymerization
3 " Sol-gel chemistry and engineering background

$ General mechanisms in the metal-organic route
$ Chemical reactivity of metal alkoxides
$ Gelation, aging, drying and firing
$ Applications and limitations of sol-gel techniques

4 " Sol-gel-derived hybrid organic-inorganic materials
$ Incorporation of small organic molecules or organic
groups/functions in inorganic networks
$ Sol-gel process in combination with organic polymers
and/or free-radical polymerization reactions
$ Incorporation of micrometric size "objects" in
inorganic networks
5 " Intercalation chemistry background

$ General considerations
$ The kinetics and mechanism of intercalation
$ Synthetic methods
6 " 2-D hybrid organic-inorganic materials based on

organic polymers intercalated in layered inorganic
solids
$ Intercalation of a preformed polymer
$ Monomer intercalation and in situ polymerization
7 " Core-shell hybrid organic-inorganic particles

$ Filling up techniques of polymer shells
$ Encapsulation processes of inorganic particles

Macromolecular synthesis background
1 – Basic definitions
polymer : substance composed of macromolecules which

have long sequences of one or more species of atoms or
groups of atoms linked to each other by primary, usually
covalent, bonds.
polymer and macromolecules are used interchangeably,
but the latter strictly defines the molecules of which the former is
composed.
macromolecules : formed by linking together monomer
molecules through chemical reactions, the process by which
this is achieved being known as polymerization.
a) skeletal structure
linear : a chain with two ends
non-linear :
! branched polymers : with side
chains or branches of significant length
which are bonded to the main chain at
branch points (or junction points)
! network polymers : with three-
dimensional structures in which each
chain is connected to all others by a
sequence of junction points and other
chains :
" said to be crosslinked
" characterized by their crosslink density or degree
of crosslinking (number of junction points per unit
volume)
" formed by polymerization or by linking together
pre-existing linear chains (i.e. crosslinking)
b) homopolymer and copolymer
homopolymer : polymer derived from one species of

monomer :
-A-A-A-A-A-A- or -[A]n-
where n is the number of repeat units (or monomer units)
linked together
copolymer : polymer derived from more than one species

of monomer :
! statistical copolymers : in which the sequential
distribution of the repeat units obeys known statistical laws
! random copolymers : a special type of statistical
copolymer in which the distribution of repeat units is truly
random
! alternating copolymers : only two different types of
repeat unit arranged alternately along the polymer chain
! block copolymers : linear copolymers in which the
repeat units exist only in long sequences, or blocks, of the
same type :
-A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-B- : AB di-block copolymer
-A-A-A-A-A-B-B-B-B-B-B-B-A-A-A-A- : ABA tri-block copolymer
! graft copolymers : branched polymers in which the
branches have a different chemical structure to that of the main
chain
" statistical, random and alternating copolymers :
properties intermediate to those of the corresponding
homopolymers
" block and graft copolymers : properties characteristic of
each of the constituent homopolymers

c) thermoplastics, elastomers and thermosets
Thermoplastics (or "plastics") : linear or branched polymers

which can be melted upon the application of heat :
" can be molded (and remolded) into virtually any shape
using processing techniques (injection molding or
extrusion)
" constitute by far the largest proportion of the polymers
used in industry
" semi-crystalline materials with both crystalline and
amorphous regions, characterized by their degree of
crystallinity
" crystalline phase with melting temperature Tm

" amorphous phase (bowl of spaghetti) with glass
transition temperature Tg : abrupt transformation from
glassy state (hard) to rubbery state (soft)
corresponding to the onset of chain motion
Elastomers : rubbery polymers of low crosslink density

" easily stretched to high extension (e.g. 3x to 10x their
original dimensions)
" rapidly recover their original dimensions
Thermosets : rigid network polymers in which chain motion is

greatly restricted by a high degree of crosslinking
d) molar mass and degree of polymerization
molar mass M : mass of 1 mole of the polymer (g.mol-1)

" for network polymers the molar mass is infinite
degree of polymerization x : number of repeat units in the
polymer chain
"M = x M0 where M0 is the molar mass of the repeat unit
polydispersity : polymers consist of macromolecules with
a range of molar masses and for long chains, the molar mass
distribution can be assumed to be continuous and is
characterized in terms of molar mass averages
Mn
weight
fraction
Mw
Mi / g.mol-1
∑ niMi
" number-average molar mass : Mn = i
∑ ni
i
∑ niMi 2
" weight-average molar mass : Mw = i
∑ niMi
i
by considering the discontinuous nature of the distribution in
which the macromolecules exist in discrete fractions i (in
intervals of M0) containing ni molecules of molar mass Mi
Mw
" polydispersity index : I = ≥1
Mn
and I = 1.00 in the case of a perfectly monodisperse polymer
Mn
" number-average degree of polymerization : x n =
M0
Mw
" weight-average degree of polymerization : x w =
M0
2 – Classification of polymerization reactions
the most basic requirement : each monomer must be

capable of being linked to two (or more) other monomer by
chemical reaction, i.e. monomers must have a functionality of
two (or higher)
" a multitude of chemical reactions and associated
monomer types can be used to effect polymerization
classification : based on the polymerization mechanisms :

! step polymerization (or step-growth polymerization) in
which the polymer chains grow step-wise by reactions that can
occur between any two molecular species
! chain polymerization (or chain-growth polymerization)
in which a polymer chain grows only by reaction of monomer
with a reactive end-group on the growing chain. They usually
require an initial reaction between the monomer and an initiator
to start the growth of the chain

step polymerization chain polymerization
first step none initiation : I + o → I-o*
initiator active
centre
steadily throughout the polymerization
dimer o + o → o-o I-o* + o → I-o-o*
formation
trimer o + o-o → o-o-o I-o-o* + o → I-o-o-o*
formation
tetramer o + o-o-o → o-o-o-o I-o-o-o* + o → I-o-o-o-o*
formation o-o + o-o → o-o-o-o
pentamer o + o-o-o-o → o-o-o-o-o I-o-o-o-o* + o → I-o-o-o-o-o*
formation o-o-o + o-o → o-o-o-o-o
growing reactions can occur between any consequent upon every addition of
chain two molecular species monomer, the active centre is transferred
principle to the newly-created chain end
monomer rapidly in the early stages (e.g. steadily throughout the reaction
consumption when x n = 10, less than 1% of the
monomer remains unreacted)

step polymerization chain polymerization
polymer the degree of polymerization high degrees of polymerization are
formation increases steadily throughout the attained at low monomer conversion,
reaction, but large macromolecules because at any moment the number of
are obtained for very high extents of growing macromolecules is low, but as
reaction soon as the active centre is created, it
reacts in few minutes with several
thousands of monomer molecules before it
dies through a termination reaction.
polymer
molar mass
molar mass
molar mass
evolution as
a function of
reaction
extent
0 50 100 0 50 100
extent of reaction (%) extent of reaction (%)
Table : Fundamental differences in reaction mechanism between step polymerization

and chain polymerization
3 – Step polymerization
" involve successive reactions between pairs of mutually-

reactive functional groups which initially are provided by
the monomer(s).
" consider the reaction between terephthalic acid and
ethylene glycol, both of which are difunctional :
O O O O
C C + HOCH2CH2OH C C + H 2O
HO OH HO OCH2CH2OH
dimer
and later :
O O
n C C + n HOCH2CH2OH
HO OH
HO C C OCH2CH2O H + (2n-1) H2O

O O n
poly(ethylene terephthalate) or PET
" polymerizations involving monomers of functionality

greater than two produce non-linear polymers : if a
trifunctional monomer was included, reaction at each of
the three functional groups would lead initially to the
formation of a branched polymer but ultimately to the
formation of a network (three-dimensional
macromolecules) :
O O
C C + HOCH2CHOHCH2OH
HO OH
terephthalic acid glycerol
O O
C C C C
O O O
O
CH2 CH2
CH
O C C
O O

a) polycondensation and polyaddition
Polycondensation : step polymerization involving reactions in

which small molecules are eliminated (ex : polyamides,
polyesters…).
" 3 types of monomer system exist, where R and R' are
divalent groups and A and B represent the mutually-
reactive functional groups :
! RA2 + R'B2 step polymerization :
A-R-A + B-R’-B → A-R-AB-R’-B → .... → A-(R-AB-R’)n-B
ex : n H2N (CH2)6 NH2 + n HOOC (CH2 )4 COOH
hexamethylene diamine adipic acid
H NH (CH2 )6 NH C (CH2)4 C OH + (2n-1) H 2 O

n
O O
polyamide-6,6 or nylon-6,6
" drawback : very slight excesses of one monomer

significantly reduce the attainable degree of
polymerization because the polymer chains become
terminated with functional groups derived from the
monomer present in excess (e.g. both end-groups are
ultimately of type B if RB2 is in excess). Since these
functional groups are unreactive towards each other,
further growth of the chains is not possible.
! ARB step polymerization :
A-R-B + A-R-B → A-R-BA-R-B → .... → A-(R-BA)n-R-B
ex : n H2N (CH2)5 COOH H NH (CH2)5 C OH + (n-1) H2O
n
O
6-amino hexanoic acid polyamide-6 or nylon-6
" advantage : with each condensation reaction the

polymer chain grows but remains an ω-amino carboxylic
acid and so can react further. So an exact stoichiometric
equivalence of the two functional groups is guaranteed.

! RA2 step polymerization :
A-R-A + A-R-A → A-R-A-R-A → .... → A-(R-A)n-R-A
" few examples :
n HO-R-OH → H-[O-R]n-OH + (n-1) H2O
n Cl-Si(CH3)2-Cl + (n+1) H2O → H-[O-Si(CH3)2]n-OH + 2n HCl
Polyadditions : step polymerizations in which the monomers

react together without the elimination of other molecules
" few important examples (RA2 + R'B2 reaction) :
n O=C=N-R-N=C=O + n HO-R'-OH → -[C(O)-NH-R-NH-C(O)-O-R'-O]n-
polyurethane
n O=C=N-R-N=C=O + n H2N-R'-NH2 → -[C(O)-NH-R-NH-C(O)-NH-R'-NH]n-

polyurea
b) molar mass control for linear step polymerization

Theory based on : principle of equal reactivity of functional
groups whatever the size of the reacting molecules
" prediction of the molar mass of macromolecules at time t
as a function of the extent of reaction p in the case of
an exact stoichiometric balance in the numbers of
mutually-reactive functional groups :
1 M
xn = and I = w = 1 + p
1− p Mn
number of functional groups that have reacted
where p =
number of functional groups present initially
" very high extents are needed for producing high
polymers
" necessity for using monomers of high purity and
reactions which are either highly efficient or can be
forced towards completion
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2 - 10
" in practice, slight stoichiometric imbalances are used to
control x n
" another way for limiting molar masses : the addition of
very low quantities of a monofunctional monomer, which
will prematurely stop the growth of macromolecules by
creating some unreacting chain ends
Important drawback : the intramolecular reaction of terminal
functional groups on the same molecule leading to ring
formation (i.e. cyclic molecules)
" disturbs the form of the molar mass distribution and
reduces the ultimate molar mass attainable
" polymerization in bulk (i.e. using only monomer(s) plus
catalysts)
c) gelation during non-linear step polymerization
The inclusion of a monomer with a functionality greater than

2 has a dramatic effect upon the structure and molar mass of
the polymer formed
" in the early stages : branched macromolecules and
much more rapid increase of molar mass
" as the reaction proceeds, further branching reactions
lead to the first network molecule : the gel-point
manifested by gelation
" critical extent of reaction pC for gelation always in the
case of a stoichiometric balance in the numbers of
mutually-reactive functional groups :
2
∑ nifi
pC = with f= i
f ∑ ni
i
where f is the number-average functionality (ni is the
initial number of molecules of monomer i which has
functionality fi)
4 – Chain polymerization : free-radical polymerization
Free-radicals : independently-existing species which

possess an unpaired electron and normally are highly reactive
with short life times
Free-radical polymerization : chain polymerization in
which each polymer molecule grows by addition of monomer to
a terminal free-radical reactive site (active centre).
a) initiation, propagation and termination
Initiation stage :
! the formation of free radicals from an initiator (e.g. by
homolysis of a single bond) :
∆
ex : C O O C 2 C O
O O O
benzoyl peroxide benzoyloxy radicals
! the addition of one of these free radicals to a molecule of

monomer. For vinyl monomers, the active centre is created
when the free radical attacks the π-bond :
kd
A R
R CH2 CH
Y
or
R + H2C CH
R CH CH2
Y
Y
Propagation stage : growth of the polymer chain by rapid

sequential addition of monomer to the active centre (1
millisecond for each monomer addition)
kp R CH2 CH CH2 CH head-to-tail addition
Y Y
R CH2 CH + H2C CH or
Y Y R CH2 CH CH CH2 head-to-head addition

Y Y

Termination stage : two common mechanisms taking place
simultaneously, but to different extents depending upon the
monomer and the polymerization conditions :
! combination :
k tc
CH2 CH + HC CH2 CH2 CH CH CH2
Y Y Y Y
! disproportionation :
ktd
CH2 CH + HC CH CH2 CH2 + HC CH
Y Y H Y Y
b) rate and degree of polymerization
! steady-state conditions : rapidly, the rate of radical loss

exactly equals the rate of radical formation
fk d
! rate of polymerization Rp : Rp = k p [M][I]½
kt
where kp, kd and kt are the rate constants for propagation,
initiator dissociation and termination respectively and f is the
initiator efficiency (i.e. the fraction of primary free radicals that
successfully initiate polymerization)
! number-average degree of polymerization of the
polymer produced at time t :
moles of monomer consumed in unit time k p [M]
xn = =
moles of polymer formed in unit time (1 + q) fk dk t [I]½
where q is the fraction of termination reactions proceeding by
disproportionation
" by increasing [M] : x n and Rp increase
" increasing [I] gives rise to a reduction in x n whilst
causing an increase in Rp

c) chain transfer reactions
ktr
+ T-A -T + A
where T and A are fragments linked in a single bond in a
hypothetical molecule T-A (monomer, initiator, solvent and/or
macromolecules)
" if re-initiation is rapid the rate of polymerization is not
affected and under steady-state conditions :
1
1 (1 + q) fk dk t [I] 2 k tr [T - A]
= +
xn k p [M] k p [M]
" chain transfer agents : compounds with high chain
transfer constants (e.g. carbon tetrabromide, dodecyl
mercaptan…) may be employed at low concentrations to
control (reduce) molar mass
chain transfer to polymer : no effect upon x n but results in the

formation of branched polymer molecules
" intramolecular reactions : short-chain branches :
H + n H2C=CH2 n-butyl
CH CH2 CH CH3 branch
H2C CH2 H2C CH2
CH2 CH2
+ H2C=CH2
CH2 ethyl
CH2 H
branches
CH CH CH2 CH3
CH2
+ n H2C=CH2
CH3
CH2
CH CH CH2 CH3
CH2

" intermolecular reactions : long-chain branches :
H
CH2 CH + CH2 C
COOCH3 COOCH3
CH2 CH2 + CH2 C CH2 CH

COOCH3 COOCH3 COOCH3
+ n
CH 2=CHCOOCH 3
CH2 C
COOCH3
d) bulk polymerization and its alternatives
Bulk polymerization is the simplest and involves only the

monomer and a monomer-soluble initiator
" advantages : high rates of polymerization, high degrees
of polymerization and polymer of high purity
" drawbacks : rapid increase of viscosity, inefficient
stirring, difficult removing of the heat evolved upon
polymerization
" autoacceleration or Tromsdorf-Norrish effect :
increasing of Rp and molar mass due to the reduction of
the long-chain radical mobility and therefore to their
termination probability ; the initiation and propagation
reactions are not affected because the monomer
molecules are small and more mobile
Solution polymerization in a solvent

" advantages : low viscosity, good heat transfer and low
likelihood of autoacceleration
" drawbacks : laborious isolation of the polymer
(evaporation or precipitation), solvent toxicity and hazard
" commercial use restricted for applications which require
the polymer to be used in solution
Suspension polymerization : the reaction mixture is
suspended as droplets in water (where it is insoluble)
" necessitates (i) vigorous agitation throughout the
reaction and (ii) dispersion stabilizers dissolved in the
aqueous phase [typically low molar polymers such as
poly(vinyl alcohol)].
" advantages : low viscosity and good heat transfer
" each droplets acts as a small bulk polymerization reactor
for which the normal kinetics apply
" polymer in the form of beads (typically 0.1-2 mm
diameter) easily isolated by filtration
" widely used on an industrial scale
e) emulsion polymerization
Second heterogeneous process where surfactants are used

and initiator must not be soluble in monomer but soluble only in
the aqueous dispersion medium
" reaction product : colloidally-stable dispersion of
particulate polymer (0.05-1 µm) in water known as latex
" anionic surfactants : molecules with hydrophobic
hydrocarbon chains at one end of which is a hydrophilic
anionic head group and its associated counter-ion (e.g.
sodium lauryl sulfate : CH3-(CH2)-SO4-,Na+)
" critical micelle concentration CMC : above which
surfactant molecules form into spherical aggregates (5
nm) known as micelles which contain of the order of 100
molecules
" when a water-insoluble monomer is added to an
aqueous solution containing a surfactant well above its
CMC three phases are established :

monomer
molecularly
dissolved large droplet
of monomer
surfactant
as reservoir
molecule
monomer-
swollen
micelle
dissolved
R
free radical
" initiation : in the aqueous phase, the initiator molecules

∆
(e.g. persulfate : S 2O 82 − → 2 SO •4 ) react with monomer to
produce oligomeric radical species which then diffuse
into monomer-swollen micelles to initiate polymerization
" propagation within the micelles is supported by
absorption of monomer from the aqueous phase, there
being concurrent diffusion of monomer droplets into the
aqueous phase to maintain equilibrium
" interval $ : particle nucleation with the consumption of
micelles ; the number Np of latex particles per unit
volume of latex then remains constant
conversion (%)
100
&
$
0
time
" interval % : the rate of monomer diffusion exceeds the
rate of polymerization so that the concentration [M]p of
monomer within a particle remains constant. Since Np is
constant, the rate of polymerization also is constant.
Because the particles are very small, termination can be
considered to occur immediately upon entry of a second
radical species into a particle containing a single
propagating chain radical. The particle then remains
dormant until entry of another radical initiates the
propagation of a new chain radical :
k p [M]p Np Np
Rp = and x n = k p [M]p
2Na ρiNa
where Na is the Avogadro constant and ρi is the molar
rate of formation of radical species from the initiator
" interval & : [M]p and the rate of polymerization decrease
continuously as the remaining monomer present in the
particles is polymerized
" advantages : good heat transfer, low viscosity of the
product latexes at high polymer concentrations and the
ability to control particle morphology (e.g. formation of
core-shell particle structures by successive additions of
different monomers)
" drawback : contamination by the surfactant
" polymers used either directly in the latex form (e.g.
emulsion paints, adhesives, foamed carpet-backings) or
after isolation by coagulation or spray-drying of the
latex (e.g. synthetic rubber and thermoplastics)
! bibliography
' Introduction to Polymers by R.J. Young and P.A. Lovell –
Chapman & Hall (1991)

Sol-gel chemistry and engineering background
Solid state reactions : precursors are thoroughly ground,

mixed together and heated at high temperature. This procedure
has to be repeated several times until an homogeneous product
is obtained. Then, the materials have to be transformed into the
desired shape : single crystal, film, fiber, fine powder…
Sol-gel synthesis : a new approach to the preparation of

glasses and ceramics :
! the metal-organic route with metal alkoxides in organic
solvent
! the inorganic route with metal salts in aqueous solution
(chloride, oxychloride, nitrate..) : much cheaper and easier to
handle than metal alkoxides, but their reactions are more
difficult to control
1 – General mechanisms in the metal-organic route
Based on the growth of metal oxo polymers in a solvent

" inorganic step polymerization reactions through
hydrolysis and condensation of metal alkoxides M(OR)Z,
where M = Si, Ti, Zr, Al, Sn, Ce…, OR is an alkoxy group
and Z is the valence or the oxidation state of the metal
" first step : hydroxylation upon the hydrolysis of alkoxy
groups :
M-OR + H2O # M-OH + ROH
" second step : polycondensation process leading to the
formation of branched oligomers and polymers with a
metal oxo based skeleton and reactive residual hydroxo
and alkoxy groups ; 2 competitive mechanisms :

! oxolation : formation of oxygen bridges :
M-OH + XO-M # M-O-M + XOH
where X = H, generally when hydrolysis ratio h = H2O/M >> 2
or X = R, when h = H2O/M < 2
! olation : formation of hydroxo bridges when the coordi-
nation of the metallic center is not fully satisfied (N - Z > 0) :
M-OH + HO-M # M-(OH)2-M where X = H or R
The kinetics of olation are usually faster than those of oxolation
" formation of a metal oxo macromolecular network :
! a sol where the polymerized structures do not reach
macroscopic sizes
! a gel when the recombination of the metal oxo polymers
can produce bushy structures which invade the whole volume
inside which the solvent, reaction by-products and free
polymers are trapped
! a precipitate when the reactions produce dense rather
than bushy structures
Depending on the control of the structures of these oxo
polymers through
! the hydrolysis ratio h
! the use of catalysts, complexing ligands or nucleophilic
reagents
! the steric hindrance of the alkoxy groups
! the nature of solvents
! the temperature

2 – Chemical reactivity of metal alkoxides
M(OR)n + m XOH # [M(OR)n-m(OX)m] + m ROH

where X stands for H (hydrolysis), M (condensation) or L
(complexation by an organic ligand L)
X X + R
O + M OR O M OR XO M + O
H H H
oxidation state : Z Z-1 Z

coordination number : N N+1 N
Consequently, the chemical reactivity of metal alkoxides toward

nucleophilic reactions mainly depends on :
! the strength of the nucleophile
! the electrophilic character of the metal atom (an
electronegativity-related property characterized by the positive
charge on the metal atom)
! its ability to increase its coordination number N : the
degree of unsaturation of the metal coordination can be simply
expressed by the difference N - Z, where N is the coordination
number usually found in the oxide and Z is the oxidation state
alkoxides χ partial ionic oxide N N-Z

charge δ radius (Ă)
Si(OPri)4 1.74 + 0.32 0.40 SiO2 4 0
Sn(OPri)4 1.89 0.60 SnO2 6 2
Ti(OPri)4 1.32 + 0.60 0.64 TiO2 6 2
Zr(OPri)4 1.29 + 0.64 0.87 ZrO2 7 3
Ce(OPri)4 1.17 + 0.75 1.02 CeO2 8 4
For similar alkoxy groups OR :
Si(OR)4 <<< Sn(OR)4
and Ti(OR)4 < Zr(OR)4 < Ce(OR)4
" silicon : relatively low electrophilicity and N - Z = 0 ;
thus, silicon alkoxides are not very reactive : hydrolysis-
condensation reaction rates must be increased by
catalysts
" tin : higher electrophilic power and higher degree of
unsaturation N – Z
" titanium, zirconium and cerium : lower electronega-
tivity, but very high degree of unsaturation N – Z
Hydrolysis and condensation reactions of non-silicate metal
alkoxides must be controlled by using chemical additives
a) reactivity of silicon alkoxides (N = Z = 4)
SN2 mechanism : involving a hypervalent silicon transition state

(penta- or hexacoordinated metallic center)
" the rates of hydrolysis and condensation increase under
pressure without affecting the distribution of hydrolyzed
or condensed species
" the reactivity of silicon alkoxides decreases when the
size of the alkoxy group increases because of steric
hindrance factors
Under acidic conditions (e.g. with mineral acids), the

hydrolysis reaction is speeded up more efficiently than the
condensation reaction :
RO RO
RO RO H OR
RO + H+ RO + + H2O + + OR
Si OR Si OR Si OR HO Si + ROH
RO RO H RO H OR
protonation of the alkoxo group, making alcohol a better leaving group
Condensation involves the attack of silicon atoms carrying

protonated silanol species by neutral ≡Si-OH nucleophiles
" acidic conditions further the formation of protonated
silanol species, but inhibit some nucleophiles

" the most basic silanol species (the most likely to be
protonated) are those contained in monomers or weakly
branched oligomers :
+ +
Si OH + Si OH Si O Si + H3O
H
preferentially a monomer
or the end-group of a macromolecule
So a bushy network of weakly branched polymers is obtained
Under basic conditions (e.g. with ammonia), hydroxyl anions

(OH-) and deprotonated silanol (≡Si-O-) are better nucleophiles
than water and silanol species
" a fast attack at the silicon atom and both hydrolysis and
condensation reactions occur simultaneously
The condensation involves the attack of a deprotonated silanol
(≡Si-O-) on a neutral siloxane species
" the acidity of silanol increases when -OH or -OR groups
are replaced with -O-Si≡ groups because of the reduced
electron density on Si atom
- -
Si OH + OH Si O + H2O
- -
Si O + Si OH Si O Si + OH
preferentially preferentially
a highly a weakly
condensed branched
species species
The result of basic catalysis is an aggregation (monomer-

cluster) that leads to more compact highly branched silica
networks, that are not interpenetrable before drying and thus
behave as discrete species

The nucleophilic activation by Lewis bases (dimethylamino-
pyridine, n-Bu4NF, NaF…) is also efficient for both hydrolysis
and condensation reactions, which occur simultaneously as for
basic catalysis
" reversible formation of a pentavalent intermediate with F-
that stretches and weakens the surrounding ≡Si-OR
bonds
" the positive charge of the silicon atom increases,
rendering the silicon atom more prone to nucleophilic
attack
Highly branched silica networks are obtained.
b) reactivity of non-silicate tetravalent alkoxides (Z = 4)
Very sensitive to moisture, they must handled with care under a

dry atmosphere otherwise precipitation occurs
Coordination expansion : self regulation of their reactivity by
increasing the number of coordinating molecules using their
vacant orbitals to accept electrons from nucleophilic ligands
" occurs by alkoxy bridging or solvation :
R R H
OR OR O
RO O OR R OR
OR RO O OR
RO Ti Ti OR
RO Ti OR RO Ti Ti OR
RO RO O
R O
Ti OR R
RO OR O H
OR R
trimer dimer
monomer in pure benzene in alcohol
" the molecular complexity depends on concentration,
temperature, solvent, oxidation state of the metal, steric
hindrance of the alkoxy groups

" it increases with the atomic size of the metal atom and
decreases with increasing bulkiness of the OR groups
" in non-polar solvents, the molecular complexity of
alkoxides is higher than in their parent alcohol, and
therefore their hydrolysis reaction is slower and leads to
the formation of clear gels
Control of the reactivity with inhibitors : inorganic acids, β-

diketones, carboxylic acids or other complexing ligands which
inhibit condensation reactions and therefore prevent
precipitation, force the growth to a gel state or stop growth
ex : acetylacetone (AcacH) leads to less hydrolyzable M-Acac
bonds : molecular clusters, chain polymers or colloidal particles
depending on
! the hydrolysis ratio h = H2O/M
! the complexation ratio x = Acac/M
Figure 1 : State
diagram describing
the hydrolysis-
condensation
behavior of
complexed
tetravalent metal
alkoxides

c) reactivity of different metal alkoxide combinations
Phase separation : ex : Ti(OBu)4 generally reacts rapidly with

water and precipitates out of the reaction mixture before it can
react with Si(OEt)4 network
" allowing Si(OEt)4 species to prehydrolyse in the
presence of water and an acid catalyst. Then, fast-
reacting Ti(OBu)4 is added ; it quickly hydrolyzes and at
least partially condenses into the preexisting immature
Si(OEt)4-based network

3 – Gelation, aging, drying and firing
We focus on the mechanisms in silicate systems

a) gelation
Under acid catalyzed conditions : « polymeric » gel
Figure 2 : Polymer growth and gel formation in acid-catalyzed

systems (polymeric gel)
Under basic conditions and/or with higher additions of water
(e.g. h ≥ 7) : more highly branched clusters which do not
interpenetrate prior to gelation and thus behave as discrete
species.
If the total concentration of alkoxysilane is low (< ~0.3 M)
gelation leads to the formation of colloidal silica (Stöber
process).
Figure 3 : TEM imaging of colloidal silica obtained through

Stöber process

But for higher alkoxysilane concentrations : « colloidal » gel
Figure 4 : Polymer growth and gel formation in base-catalyzed

systems (colloidal gel)
b) aging
Gelation : freezing in a particular structure (i.e. may be

considered as a rapid solidification process)
Aging : structure modifications with time depending on
temperature, solvent and pH conditions
" gel separation into regions of high and low polymer
density because it is expected that as the critical point is
approached (e.g. during a change in concentration),
fluctuations in polymer density grow larger in amplitude
(than those resulting merely from thermal motions)
" promotion of additional crosslinking as unreacted
terminal groups (OH and OR) come in contact in regions
of higher polymer density
" acceleration of the phase separation process and
creation of liquid-solid interfaces
" further structural changes attributed primarily to surface
energy effects : it is well known that surfaces exhibiting
positive radii of curvature dissolve more readily than
surfaces exhibiting negative radii of curvature. Therefore
as the dissolution rate is increased (e.g. by increased
temperature or pH) dissolution-redeposition results in
neck formation causing the gel structure to become
fibrillar and the pore formation. Of course, when
dissolution is extensive, the gel network would break
down and ripen to form a colloidal sol.
c) drying (or desiccation)
Drying : removing of the solvent phase

Method influenced by the intended use of the dried material :
! if powdered ceramics are desired, no special care
need be exercised to prevent fragmentation

! if monoliths from colloidal gels are desired, the
drying procedures are largely determined by the need to
minimize internal stresses associated with the volume changes
on drying and the capillary forces in the gel pores :
" during the initial stages of drying, the volume change of
the gel is equal to the volume of evaporated liquid. The
gel network is still flexible and can rearrange to
accommodate the decreasing volume. All pores are filled
with solvent and liquid-air interfaces are not present
" as drying proceeds, the gel network becomes more
restricted and the removal of liquid leads to the formation
of such interfaces and the development of capillary
stresses : the capillary pressure ∆P developed in a
cylindrical capillary of radius r partially filled with a liquid
of wetting angle θ, can be expressed by :
∆P = 2γcosθ/r
where γ is the surface tension. The development of
cracks in a drying gel is shown on figure 5 :
(a) (b)
∆ P1 < ∆ P2
crack
crack
Figure 5 : Formation of differential strains at the pores during

drying : (a) before and (b) after the onset of capillary forces.
When evaporation leads to the formation of menisci, the
different radii of the pores cause unequal capillary
pressures to generate differential stresses σ1 < σ2. If the
stress difference σ2 - σ1 locally exceeds the strength of
the gel network, a crack will result. The tendency toward
fragmentation is thus determined by both the average
pore size and the pore size distribution.
" generally, fractures associated with excessive
capillary forces can be reduced or eliminated by :
! strengthening the gel by reinforcement
! enlarging the pores
! reducing the surface tension of the liquid with
the use of surfactants
! making the interior surfaces hydrophobic
! evacuating the solvent by freeze-drying
! operating under hypercritical conditions :
effected by heating the gel with methanol in an
autoclave to temperatures and pressures
exceeding the critical point of methanol
(240°C/8.1MPa). A slow evacuation (3-4 hr) was
followed by flushings with dry argon to eliminate the
last traces of alcohol. This method produces dried
gels with much larger pore volumes (aerogels :
porosity of ~85 %, specific surface area of 250-600
m2.g-1 and pore size of 250-1250 Å) than
conventional evaporative drying (xerogels : pore
size ≤ 20 Å). Because of the absence of the liquid-
vapor interfaces, no capillary forces arise to cause
network collapse and shrinkage during drying
! if monoliths from polymeric gels (such as those

obtained by the acid catalysis of silicon alkoxide at low water
contents) are desired : the polymeric species are weakly
crosslinked and as solvent is removed, they can deform readily
and form a dense gel structure while polymer itself shrinks and
forms more crosslinks
" dense dried gel with no large voids

d) firing
Firing : heating to convert the dried gel to a dense ceramic. For

silica gels, the following reactions occur :
" desorption of physically adsorbed solvent and water from
the walls of micropores (100-200°C)
" decomposition of residual organic groups into CO2 (300-
500°C)
" collapse of small pores (400-500°C)
" collapse of larger pores (700-900°C)
" continued polycondensation (100-700°C)
! if powdered ceramics are desired, no special care

need be exercised to prevent fragmentation. Attention must,
however, be directed to the removal of organics to avoid
undesirable bloating, foaming or blackening
! if monolithic ceramics are desired, special care must

be taken to ensure complete removal of water, organic groups
or decomposition products, prior to micropore collapse to avoid
the development of stresses leading to fragmentation
" for the production of large monoliths of SiO2, poly-
condensation has to be completed prior to pore collapse
" with non-optimized firing schedules, residual organic
groups and H2O can lead to blackening and fragmenta-
tion, as well as to the formation of bloated and foamed
samples (in cases where foams are desired, specific
agents such as urea can be used in forming the gel)
Sintering and densification phenomena also take place, via

typical sintering mechanisms such as evaporation
condensation, surface diffusion, grain boundary and bulk
diffusion. The small particle size of the powders lead to high
reactivities and enhanced sintering and/or coarsening rates (the
principal process involved in densification is often viscous
sintering)
4 – Applications and limitations of sol-gel techniques
a) advantages
Sol-gel processes allow the synthesis of ceramics of

! high purity, because organometallic alkoxy precursors
can be purified by distillation or recrystallisation
! high degree of homogeneity, because reagents are
mixed at the molecular level
! low or high porosity, by using appropriate heat
treatment and firing times
The veritable explosion of interest in this area seems to

result in large measure from the perceived technological
opportunities :
! the ability to prepare glasses of materials which cannot
be obtained as amorphous solids by cooling from the liquid
state
! the capability of obtaining fully-dense amorphous solids
at temperatures lower by hundreds of centigrade degrees than
those required for conventional compaction/densification or for
melting
! the possibility of obtaining fully-dense crystalline
ceramics which cannot be prepared by conventional powder
processing
! the ability to obtain materials with novel distributions of
phases contained therein...
b) drawbacks
! high cost for the majority of alkoxide precursors

! long processing times
! volatiles production
! shrinkage
! development of stresses leading to fragmentation
c) applications
! novel glasses produced from gel precursors in three

ways :
% melting gel-derived powders : gel-derived powders
are used as batch ingredients for glass melting primarily
because of the high degree of chemical homogeneity which
they offer. This leads to shorter melting times and lower
melting temperature as well as compositional uniformity
% sintering or hot pressing gel derived powders :
the key to glass formation is the development of an
appropriate heat treatment schedule to remove the residual
organic groups and achieve pore collapse without inducing
crystallization in the sample
% heat treating gels to produce monoliths (already
described)
The physical properties of gel-derived glasses are usually
closely similar to those of glasses obtained from the melt. The
most attractive feature is the development of novel glass
compositions : CaO-SiO2 or Na2O-ZrO2-SiO2 with high ZrO2
content, which simply cannot be obtained from the melt
because the cooling rate must be very high to avoid detectable
crystallization.
! fibers : using appropriate hydrolysis conditions,

continuous fibers may be drawn from solutions of metal
alkoxides and converted to glass fibers by heating (ex : ZrO2-
SiO2 or Na2O-ZrO2-SiO2). Fibers can also be prepared by
extruding gelled solutions (colloidal as well as polymeric gels)
through dies of appropriate diameter (ex : polycrystalline
alumina, microcrystalline Al2O3-Cr2O3-SiO2, mullite 3Al2O3&
2SiO2, aluminum borosilicate 3Al2O3&B2O3&3SiO2)
! abrasives : after gelation and drying, the material is

crushed (a simple process with frangible dried gel) and sized.
The sized powders are then fired. In this way, Al2O3 abrasive
particles with uniformly dispersed ZrO2 particles and a very fine
grain size (< 300 nm) can be obtained. Such abrasive particles
have superior grinding performance compared with fused or
sintered Al2O3-based abrasives in a number of applications
! thin films and coating : the permissible drying rates,

consistent with the avoidance of fracture, were evaluated and
found to vary inversely with the thickness of the body being
dried. This limitation leads naturally to the main use of gels in
coating applications, where the thickness are small and the
drying rates can be correspondingly high. Four techniques are
mainly used for film deposition onto substrates :
% dipping (the most widely used), where the part to be
coated is withdrawn from a solution. The faster the
substrate is withdrawn, the thicker the deposited film

Figure 6 : Industrial dip-coating system
% lowering, where the object remains at rest and the
liquid level is lowered
% spinning, where the liquid film is spread out by
spinning the wetted surface. Advantages : the uniform
thickness of the film due to the spin-off stage and the
deposition onto small substrate from a small quantity of sol

% spraying, where the surfaces are sprayed with fine
disperse solutions. This process has difficulty in
maintaining strict tolerances and is thus used mostly for
protective coatings.
Some of the coating-type applications which seem well-

suited for sol-gel techniques include :
! antireflection coatings (single layer or multilayer films)
! absorbing coatings
! filters for lighting and optical purposes
! semiconducting coatings
! protective layers (both chemical and thermal)
! independent films, prepared by
" pouring alkoxide solutions onto liquids which do not
mix with the solution and allowing the film to hydrolyze
" pouring the solution onto non-wetting surfaces such as
Teflon
" forming films using wire rings with solutions of
appropriate viscosity
d) conclusion
Sol-gel chemistry is still in its infancy and a better

understanding of the basic inorganic polymerization chemistry
has still to be reached before a real mastery of the process can
be obtained.
Nevertheless this low temperature processing may be
exploited. As a result, the incorporation of organic materials
into sol-gel-derived oxides becomes possible

summary of sol-gel process, techniques and products
hydrolysis/condensation aging/drying
∆
wet fiber fiber
e
ia ut
ar
ec ho
drawing
lc
powder
sp wit
extruding
out
alkoxide slow sintering
precursors
∆
water sol gel xerogel dense
ceramic
hy on
catalyst
pe dit
c
rc ion
rit s
dip-
ica
l
spray- coating
aerogel
spin-
∆
or radiation
wet film coating
! bibliography
' Gel technology in ceramics by B.J.J. Zelinski and D.R.

Uhlmann, J. Phys. Chem. Solids, 45, 1069-1090 (1984)
' Sol-gel synthesis of solids by J. Livage, Encyclopedia of
Inorganic Chemistry, edited by R. Bruce King, John Wiley
edition, New-York, pp. 3836-3851 (1994)
' Sol # gel # glass : I Gelation and gel structure by C.J.
Brinker and G.W. Scherer, J. Non-Crystalline Solids, 70, 301-
322 (1985)
' Design of hybrid organic-inorganic materials synthesized via
sol-gel chemistry by C. Sanchez and F. Ribot, New J. Chem.,
18, 1007-1047 (1994)
' Introduction aux procédés sol-gel by A.C. Pierre, Forceram
collection, Septima edition, Paris (1992)
' Supercritical drying in structural and microstructural evolution
of gels : a critical review by S.P. Murkherjee, Ultrastructure
processing of advanced ceramics, edited by Mackenzie and
Ulrich, John Wiley edition, New-York, pp. 747-759 (1988)

Sol-gel derived hybrid organic-inorganic materials
One of the major challenges of sol-gel synthesis :

preparation of new HOIM made of a combination of inorganic
and organic components on a molecular scale
1 – Incorporation of small organic molecules or organic

groups/functions in inorganic networks
! doped xerogels and functional coatings

! named ORMOCERs (Organically Modified CERamics)
or ORMOSILs (ORganically MOdified SILicates)
a) organic molecules embedded within xerogel pores
The main synthesis routes are :
# impregnation of the xerogel with organic molecules (10 Ă

< pore size < 100 Ă) :
! open porosity can be filled by immersing the bulk xerogel

in a solution of organic molecules or biomolecules upon
capillarity phenomenon. The carrier fluid has to be
removed by repeating the drying step
! for avoiding a possible leakage of the guest molecules,
the filling up of the pores must be completed by
incorporating a second sol for sealing the residual open
porosity
# incorporation of organic molecules during the sol-gel

process :
! the organic molecules get trapped within the oxide gel

network during the hydrolysis and polycondensation
reactions

Among the applications of such materials :
# optical applications :
example of dye lasers
absorption emission
non-radiative
transition (relaxation
or energy transfer)
! advantages of organic fluorescent dye : high
fluorescence quantum yield (95 %) and low excited-state
absorption. So they are highly efficient for both pulsed
and continuous-wave laser action
H H
N O N+ C2H5 rhodamine 6G
H5C2
H3C CH3
COOC2H5
coumarin 4
HO O O
! current dye lasers : based on liquid dye solutions, they

have valuable properties because of their continuous
and wide range tunability (with different dyes) from the
near-UV to the near-IR regions of the spectrum.
However, because of dye degradation, heating and
triplet-state formation, solutions have to be flowed
through the laser cavity to maintain constant gain and
beam quality. This requires bulky dye-flow system
systems and reservoirs, with large quantities of dye
dissolved in often flammable and toxic solvents
! advantages of inorganic matrix : inorganic glasses are
excellent photonic media (in the spectral region of
interest) because of their low optical losses, good
mechanical properties (high strength, stiffness, hardness

and abrasion resistance) and long-term environmental
stability
! solid state dye laser : dye-matrix interactions
(hydrogen bonds between the dye and hydroxyls) allow
the adsorption of the dye on the micropores surface,
prevent the dye dimerisation, and enhance the dye
thermal and environmental stability
! other optical applications with the same strategy :

non-linear optical filters, wave guides, optical sensors,
optical limiters…
# materials of controlled pore size :

! xerogels are prepared in the presence of template
molecule and the HOIM is calcined at a temperature
below the fusion temperature (400-500°C)
! pore size is controlled by the structure of the template
molecule
! applications : gas and liquid adsorbents, membranes,
carriers for catalysts and enzymes, sensors, ion
exchangers, enantiomer purification (molecular
impression)…

b) use of heterofunctional metal alkoxides R'M(OR)x
In silicate systems, R'Si(OR)3 are usual precursors to introduce

organic groups within the inorganic network
Reactivity of R'Si(OR)3 towards sol-gel reactions :

! in acid-catalyzed conditions : similar to Si(OR)4
! in base-catalyzed conditions : hydrolysis rate :
Si(OR)4 > R'Si(OR)3 > R"Si(OR)3
where R" is larger than R', because the higher the steric
hindrance and the electron-donor effect, the more destabilized
the hypervalent silicon transition state : so R'/R" groups are
found onto the surface of micropores
Among the applications of such materials :
# dye lasers : the presence of R' groups allow to control the

dye-matrix interactions
# hydrophobic aerogels : with R' = methyl, phenyl, isobutyl,

isopropyl…
# abrasion resistant coating on plastics :

! plastic substrate are highly sensitive to mechanical
abrasion
! pure sol-gel coating made from metal alkoxides have
commercial applications for glass and metal substrates,
but they are often incompatible with polymeric substrates
(poor adhesion)
! application fields : automotive headlights and glazing,
compact discs and data discs for optical information
storage, where polycarbonate (PC) and PMMA present
high optical transparency, light weight, well-established
processing and shaping technology compared to
inorganic silicate glass
! example of protective coating on PC for automotive
applications :
M(OR) x + (MeO)3Si O O
highly crosslinked inorganic network organic network

upon hydrolysis/condensation upon thermally or photochemically
induced polymerization
Ti not stable to UV
(photoreduction)
the most interesting

system
( )
Figure 1 : abrasion resistance of three types of coating containing

equimolar amounts of metal alkoxides. The spin coating parameters
(rpm) are given in brackets
! example of protective coating on PC for compact

discs (spin coating because of round substrates) :
O
Zr(OPr)4 + (MeO)3Si O
UV-induced
prehydrolyzed polymerization
! example of protective coating on PMMA glazing :

(EtO)3Si + (EtO)3Si SH in equimolar amounts
highly crosslinked inorganic network highly crosslinked organic network

upon hydrolysis/condensation upon UV-induced thiol/ene addition

Figure 2 : performance of a coated
acrylic sheet in comparison to an
uncoated sheet after treatment with
steel wool (thickness coating
around 5 µm). The color is due to
an incorporated fluorescent dye in
the substrate
! example of hydrophobic/hydrophilic coating on

glasses : for buildings, cars and other transport vehicles
coating coating
under
modified with modified with
pristine glass atmospheric
hydrophobic hydrophilic
conditions
groups groups
(EtO)3 Si (EtO)3 Si
HN
(C F2 ) n
NH2
F3 C
θwater < 5° θwater = 20-70° θwater > 90° θwater < 5°
γs = 70 mJ.m-2 γs = 30-40 mJ.m-2 γs < 20 mJ.m-2 γs = 70 mJ.m-2
antisoiling antifogging
properties properties
! example of decorative coating on glasses :

incorporation of organic dye molecules to the coating

Figure 3 : lead crystal glass ware
with decorative hybrid coatings
(spray-coating)

! example of hard contact lens materials : they require :
$ high O2-permeability to maintain the O2-supply of the
cornea
$ good wettability to preserve the lachrymal film
between the cornea and the contact lens
$ density 1.1-1.2 g.cm-3, sufficient flexibility, high
hardness and good scratch resistance
$ refractive index > 1.43 and transmission > 98 %
$ water absorbing capacity < 10 wt.%, chemical stability
(no unlinked components) and resistance to
microorganisms and UV-light
Silicone rubber has high O2-permeability but is very
hydrophobic. So :
Ti(OR)4 + (RO)3Si O O
crosslinked inorganic network glycol group upon acid or

upon hydrolysis/condensation base-catalyzed hydrolysis
! others examples : coatings and adhesives for glass

fibers, barrier coating…

c) use of polyfunctional metal alkoxides
! application : materials of controlled-pore size

! use of silsesquioxanes :
O O Si O
O plasma
(MeO)3Si Si(OMe)3 O Si Si O O Si
oxidation meso-
O OH HO porous
O silica
Si(OMe)3 HO Si O HO
OH Si Si
O Si O
O
silsesquioxane O
500-1000 m2.g-1 300 m2.g-1
! use of precursors with Si-Csp labile bond :

(MeO)3Si Si(OMe)3
& % '
Si(OMe)3
Si(OMe)3 MeOH/H2O 600-680°C
2 mol. % NH4F under air
& 656 / 50 657 / 46
% 441 / 70 407 / 70
' 736 / 60 706 / 65
Si(OMe)3 Si(OMe)3 Si(OMe)3 m2.g-1 nm
The resulting microstructure of the materials is governed

by the structure of the template polyfunctional alkoxides,
the catalyst, the solvent and the precursor
concentrations, which influence the kinetics of the
hydrolysis/condensation reactions

2 – Sol-gel process in combination with organic polymers
and/or free-radical polymerization reactions
! named CERAMERs (CERAmics and polyMERs)

! numerous studies during the last 15 years
a) many synthesis routes : silica/PMMA system
Si(OEt)4 sol-gel
TEOS chemistry
xerogel
O free-radical
O polymerization n
MMA PMMA
O O

# impregnation of the pre-formed xerogel with MMA and in
situ free-radical polymerization :
+ 2 wt.% of benzoyl peroxide

60°C / 1 week
! PMMA amount may be adjusted by varying the xerogel

porosity prior to impregnation by heat treating
n at 600°C
and higher temperatures O O
! macromolecules are longer components
hydrogen
bond
than in traditional bulk andH PMMA
O
carboxyl
polymerization probably
because of the lower probability O
groups
Si
O
O
of termination reactions
! hydrogen bonding between the
residual hydroxyls onto silica
# sol-gel processing in the presence of PMMA :
H2O / H+
! restricted to polymers which are soluble in the alkoxide

precursors solutions (use of co-solvent)
! sol-gel chemistry has to be thoroughly controlled to avoid
phase separation (in particular pH regimes)
! under acidic conditions, small SiO2 domains (< 100 Ă)
are well dispersed in the PMMA matrix
! drying time and gel shrinkage are lower than for pure
silica xerogel synthesis
! but the traditional sol-gel drawbacks of solvents and by-
products elimination remain…

# sol-gel processing with alkoxysilane Si(OR)4 where R is
a polymerizable group :
SiCl4 + 4 HO O
Si O O
4
O
H2O/H+
! since both the co-solvent and the liberated alcohol

polymerize, gel drying is unnecessary and no gel
shrinkage occurs (non-shrinking materials)
! but resulting polymer is not PMMA
but poly(2-hydroxyéthyl methacry-
n
late), with lower mechanical HO
O
O
properties than PMMA
! so this original route is restricted to few macromolecule
types (polyalcohols)

# sol-gel processing with trialkoxysilyl-functionnalized
PMMA :
! synthesis of PMMA with trialkoxysilyle side-groups by

copolymerization of MMA with γ-methacryloyloxypropyl-
trimethoxysilane (γ-MPS)
R
n + m
O O n m
O O
O O
O O
Si(OCH3)3 poly(MMA-co-γγ-MPS)
(CH3O)3 Si
! synthesis of PMMA with trialkoxysilyle terminal group by

using γ-mercaptopropyltrimethoxysilane (γ-M'PS) as
chain transfer agent during MMA polymerization
SH
+ H
Si(OCH3)3
+
S
+ MMA
S Si(OCH3)3 Si(OCH3)3
! sol-gel processing leading to covalent bonding between

the both components ; the higher the γ-MPS amount, the
clearer the xerogel

# simultaneous syntheses of silica and acrylic networks :
O + O + Si(OEt)4
O O
γ-MPS
(MeO)3 Si
! TEOS, γ-MPS, appropriate amounts of water and HCl

are mixed together
! separately, benzoyl peroxide is dissolved in MMA
! the both mixtures are blended and let react at 50°C for
few days
! a careful control of the kinetics of each polymerization

reaction allows to avoid the phase separation process

b) tunable mechanical properties :
example of the silica/PDMS system :
CH3
HO-(Si-O)n-H + Si(OEt)4
CH3
hydroxy-functionalized
polydimethylsiloxane
120
100
stress MPa
80
60
40
20 elastomer
0
0 10 20 30 40 50
strain %
Figure 4 : compressive stress-strain behavior of ORMOSILs for various
PDMS (550 g.mol-1) theoretical contents

c) some applications :
# dye lasers : after the xerogel impregnation with an organic

dye or the sol-gel processing in presence of this organic dye,
the residual porosity is closed by a second impregnation with
MMA and its in situ polymerization
! the transparency is preserved because their respective
refraction indexes are similar and the dimensions of
the silica and PMMA components (~ 15 nm) are lower
than the wavelength of the visible light of the spectral
region of interest
! drastic improvement of mechanical properties and
polishing properties (essential for optical applications)
# packing glass (returnable bottles…) : hybrid coatings

made of TEOS, MMA and γ-MPS allows the healing of surface
defects and the rupture pressure is improved from 28 to 42
kg.cm-2.

3 – Incorporation of micrometric size "objects" in
inorganic networks
! filled xerogels
a) encapsulation of biomolecules and micro-organisms :
! biological species are not able to withstand ethanol and

acids. So sol-gel processing has to be modified :
hydrolysis pH is gelation
Si(OMe)4 + H2O/H+
under ultrasound adjusted to 7 and aging
biological
species
! examples with enzymes :

$ encapsulation of glucose oxidase for the detection
and titration of glucose (biosensor)
$ encapsulation of Thiobacilus thioxidans for the H2S
oxidation (bioreactor)
! examples with microorganisms :

$ encapsulation of plant cells for the production of
alkaloids and coumarins (bioreactor)
$ encapsulation of leishmania cell as antigene source
(ELISA test for parasitology)

! biological response and
biological activity are
preserved for several
months because the guest
species are protected from
environmental attack : pH,
temperature..

b) encapsulation of liquid crystal droplets :
! application for electrooptical devices :
! encapsulation of microdroplets of nematogenic organic

compounds in a thin film of silica-gel based matrix. The
molecules are oriented in microdomains according to the
pore innersurface anchoring via Si-Et groups :

# bibliography
( Matériaux hybrides, coll. Arago, éd. OFTA/Masson, 17 (1996)

( Design of hybrid organic-inorganic materials synthesized via
sol-gel chemistry by C. Sanchez and F. Ribot, New J. Chem.,
18, 1007-1047 (1994)
( Hybrid organic-inorganic materials : The sol-gel approach by
J. D. Mackenzie, in Hybrid Organic-Inorganic Composites, pp.
226-236 (1995)
( Organic/inorganic composites materials by J. M. O'Reilly and
B. K. Coltrain, in Polymeric Materials Encyclopedia, ed. by J. C.
Salamone, CRC Press London, 4772-4781 (1996)
( Organic/inorganic composites by G. L. Wilkes and J. Wen, in
Polymeric Materials Encyclopedia, ed. by J. C. Salamone, CRC
Press London, 4782-4792 (1996)
( Organic/inorganic polymer hybrids by Y. Chujo, in Polymeric
Materials Encyclopedia, ed. by J. C. Salamone, CRC Press
London, 4793-4798 (1996)
( Des gels pour l'optique by F. Chaput, J. P. Boilot, F. Devreux,
M.Canva, A. Brun and P. Georges, Pour la science, 191 (1993)
( Polydimethylsiloxane-based ORMOSIL microstructure :
correlation with compressive behavior by O. Fouassier, M.
Menetrier, J. J. Videau and E. Duguet, Mater. Lett., 42, 305-310
(2000)

Intercalation chemistry background
In China circa 600-700 AD : production of porcelain from the

intercalation of alkali metal ions into commonly found naturally
occurring minerals such as quartz, feldspar and kaolin
Since, intercalation reactions have attracted attention (over
several thousands of scientific papers) for several reasons :
! they provide routes for the synthesis of new solids with
kinetic rather than thermodynamic stability
! they permit controlled systemic changes in physical
properties, particularly the electronic, magnetic and optical
properties of the host lattice
! they allow the fine tuning of the chemical properties by
incremental changes in composition through ion exchange
reactions
Application fields : catalysts, sorbents, solid electrolytes,
sensors, electrochromic displays and batteries
1 – General considerations
Literally, intercalation : act of inserting into a calendar some

extra interval of time
Today, according to chemists, intercalation : insertion of
mobile guest species (atoms, molecules or ions) into a
crystalline host lattice that contains an interconnected system of
empty lattice sites (") of appropriate size :
x guest + "x [host] ⇔ [guest]x [host]
# usually reversible, they are topochemical processes :

the structural integrity of the host lattice is formally
conserved in the course of the forward and reverse
reactions

# therefore different from normal solid state reactions that
involve extensive bond breaking and structural
reorganization and require temperatures in excess of
600°C
# typically intercalation reactions occur near room
temperature and many intercalation compounds are
metastable because of the inherent anisotropy in the
chemical bonding
# remarkably, a wide range of host lattices have been
found to undergo these low temperature reactions,
including : framework (3-D), layer (2-D) and linear
chain (1-D) lattices. Recent studies of alkali metal
reactions with C60 molecules (fullerenes) have been
discussed in terms of intercalation in a host lattice of
effectively zero dimensionality
# in 3-D systems : the size of the guest species which

can access the host lattice is constrained
# in lower dimensional systems : the strongly bonded
components can adjust their separation freely to
accommodate guest species of different sizes. With
increasing guest size, the structural correlation between
layers or chains is diminished. In the limiting case,
complete separation of single layers or chains occurs
(exfoliation)
Layered host lattices have been much more extensively
investigated than the others
# because of the structural flexibility of the layer structures,
with their ability to adapt to the geometry of the inserted
guest species by free adjustment of the interlayer
separation
# all these layer phases are characterized by strong
intralayer iono-covalent bonding and weak interlayer
interactions
# the layers may be electrically neutral or possess an
overall charge which may be either positive or negative
(table) :
% in compounds with neutral layers, the interlayer
bonding is often described as Van der Waals' and the
interlayer space is a connected network of empty
lattice sites
% in the charged layered systems, the layers are held
together by weak electrostatic forces and the
interlayer sites are partially or completely filled by
ions or by combination of ions and solvent molecules.
# layered host lattices and their intercalates span the
entire spectrum of electronic behavior from insulators
(such as clays) through semiconductors and
semimetals (graphite and dichalcogenides) to
superconducting metals (some dichalcogenides) see
table
# insulating lattices undergo reactions which involve ion-
exchange, acid-base chemistry and solvent
exchange and the concentration of ionic guests is fixed
by the chemical composition and remains unchanged
throughout subsequent reactions
# the chemistry of conducting host lattices involves
reduction reactions and cation insertions, except for
graphite, which can be both reductively intercalated with
cations or oxidized with anion insertion. The
concentration of ionic guest species can be altered by
oxidation or reduction of the host lattice

lattice type illustrative examples layer charge
elemental graphite 0
black-phosphorus 0
metal MX2 / M = Ti, Zr, Hf, V, Nb, Ta, Mo, W and X = S, Se 0
chalcogenides MPX3 / M = Mg, V, Mn, Fe, Co, Ni, Zn, Cd, In and X = S, Se 0
AMS2 / A = alkaline metal and M = Ti, V, Cr, Mn, Fe, Co, Ni 0
metal oxides MxOy : MoO3, Mo18O52, V2O5, LiNbO2, LixV3O8 0
MOXO4 / M = Ti, V, Cr, Mn, Fe and X = P, As 0
metal oxy-halides MOX / M = Ti, V, Cr, Fe and X = Cl, Br 0
titanates : K2Ti4O9 -
niobates : K[Ca2Nan-3Nb2O2n+1] with 3 ≤ n < 7 -
metal halides α-RuCl3 0
β-ZrNCl 0
Table : examples of layered host structures that exhibit intercalation reactions (1st part)

lattice type illustrative examples layer charge
hydrous metal uranium micas : (Az+)1/z(H2O)y[UO2XO4]z- / X = P, As, V -
oxides tarankite : (A+)3+x(H2O)y[Al5(PO4)2+x(HPO4)6-x](3+x)- -
double hydroxides : X-(H2O)n[Zn2Cr(OH)6]+ -
M(HPO4)2 / M = Ti, Zr, Hf, Ce, Sn -
metal phosphates Zr(RPO3)2 R = Ph, Me, Et, CH2COOH -
and Zr(ROPO3)2 -
phosphonates
smectite clays kaolinites : Al4Si4O10(OH)8 -
and silicates hectorites : Na0.6[Li0.6Mg5.4](Si8.0)O20(X)4 / X = OH, F -
montmorillonite : Ca0.35[Mg0.7Al3.3](Si8)O20(OH)4 -
hydrotalcite-types LiAl2(OH)6OH, 2H2O +
Zn2Cr(OH)6Cl, 2H2O +
coordination Ni(CN)2 0
compounds
silicides CaSi2 -
Table : examples of layered host structures that exhibit intercalation reactions (2nd part)

2 – The kinetics and mechanism of intercalation
Intercalation reactions typically involve breaking bonds in the

host and the formation of new interactions between the guest
and host
# the increase in the basal spacing of the unit cell of the
layer host lattice upon intercalation imposes one of the
most significant energy penalties
# layered host lattices which have stronger interlayer
bonding appear to be most difficult to intercalate
ex : metal dichalcogenides MX2 :
MS2 > MSe2 >>>> MTe2
because of the increased covalent bonding between
the dichalcogenide layers
a) staging
This interlayer bond breaking penalty can be minimized by the

phenomenon of staging : the intercalation proceeds in discreet
stages, in which occupation of every nth interlayer occurs prior to
further filling of the lattice (figure). In that case, the intercalates
can be prepared with specific stoichiometry, each one
associated with a specific nth order stage
ex : potassium intercalates of graphite, (An+)x/n[MS2]x-(H2O)y

The most simple model explains staging in terms of a smaller
loss of energy lattice at low guest concentrations, if the guest
species are concentrated in a limited number of van der Waals'
gaps rather than being homogeneously distributed over all
interlayer sites
A more realistic model involves staging in all van der Waals'
gaps but with local concentrations of the guest species across
the basal plane in certain regions (domain model). This
phenomenon is most commonly observed for flexible layers
But staging is not systematically observed : for LixTiS2 (0≤x≤1),

a single stage phase is formed over the entire composition
range. At intermediate compositions each interlayer has the
same concentration of guest species distributed randomly over
the available interlayer sites
b) kinetics
Complex phenomenon : the reaction seems to be initiated at

defects on the host surface and therefore variations in reactivity
often arise from one batch to another of the same host due to
microcrystalline or particle size differences of the solid
During the chemical lithiation of TaS2 with LiBun, strong
evidence was found for a kinetics dominated by nucleation
processes, leading to the coexistence of three homogeneous
phases differing in lithium contents. The kinetic model involves
concentric cylindrical phase boundaries moving towards the
crystal centre (following figure)

Figure : schematic for the proposed kinetic
Additional kinetic scheme for the chemical lithiation of TaS2
considerations are the
increased activation 3 – Synthetic methods
energy for stage
a) direct reaction
formation with increasing
stiffness (elasticity) of the
layers or increasing layer
thickness
The simplest and most widely used method for preparing large
amounts of an intercalation compound :
G + MXn → Gg MXn
involving oxidation of the guest and electron transfer to the
conduction band of the host lattice (M reduction)
the most
oxidising
the most
reducing

# a major consideration in the choice of an intercalation
reagent is the ease of reduction of the host (previous
scheme)
so : V2O5 + x LiI → LixV2O5 (intercalation compound)
but the more reactive LiBun reacts with V2O5 to give

products which are not intercalation compounds (the
reagent must be just on the reducing side of the host)
# experimental conditions : under anhydrous conditions,
at temperatures up to 200°C, with guests :
% as neat reagents if they are either liquids or low
melting solids
% in solution in polar organic solvents (for solid organic
or organometallic guests)
# choice of the solvent : solvents such as toluene,
acetonitrile, dimethoxyethane and DMF are generally
used. Highly polar solvents often accelerate the
intercalation process but also co-intercalate with the
guest molecules
# organometallic guests must be good reducing agents
and form stable cations, as measured by their first
ionisation potential or electrochemical oxidation potential
ex : cobaltocene [Co(η-C5H5)2] : 1st I.P. : 5.5 eV
ferrocene [Fe(η-C5H5)2] : 1st I.P. : 6.9 eV (less reducing)
so cobaltocene will intercalate into both TaS2 and FeOCl,
but ferrocene will only intercalate into the more oxidising
host lattice FeOCl

reagents products reaction
conditions
0.5 C5H5N + TaS2 → TaS2(C5H5N)0.5 50 µm, 200°C, 1 d
0.25 [Co(Cp)2] + VSe2 → VSe2{Co(Cp)2}0.25 130°C, 3d

OsF6 + C(graphite) → C8(OsF6) 20°C
Na(naphthalide) + TiS2 → NaTiS2 naphthalene, r.t.
LiBun + V6O13 → LixV6O13 hexane, 20°C
HCl/Zn + WO3 → HxWO3 H2O, 25°C
Table : examples of intercalation compounds formed by direct

reaction of the host lattice with the appropriate guest molecules
b) ion exchange
Once an intercalation compound has been formed the

intercalated guest ions can often be replaced by immersing the
material in a concentrated solution containing another potential
guest ion
ex : NaxTiS2 + LiPF6 → LixTiS2
# driving force : the great excess of the replacement ion
# useful strategy for intercalating large guest cations that
do not intercalate by direct reaction (pre-intercalation +
ion exchange)
# particularly used in zeolithes, pyrochlores, silicates and
clay hosts

c) swelling, flocculation and reflocculation
swelling : expansion of the host lattice by pre-intercalation of a

small molecule or ion to the point where the interlayer spacing is
comparable to the diameter of the reactant molecule
exfoliation : if swelling is taken to its extreme then the host
structure is completely delaminated and leads to the formation
of colloidal solutions (or gels at higher solid concentration).
Then reflocculation by addition of electrolyte solutions of other
cations is possible
ex : smectic clays completely exfoliate in water and undergo
rapid ion exchange with large cations such as
polyoxometallates and metal chelates
d) electrointercalation methods
Host lattices serve as the cathode of an electrochemical cell :
# simple method, ease of control of stoichiometry and fast

rate of reaction at room temperature
# convenient method to carry out detailed thermodynamic
measurements (free energy of the cell reaction) and
elegant means of studying the staging phenomenon
# but not ideal for preparation of bulk samples and
unusable to intercalate insulating hosts or for the
intercalation of neutral species
! bibliography
& Inorganic intercalation compounds by D. O'Hare, in Inorganic
Materials, ed. by D. W. Bruce and D. O'Hare, John Wiley
edition, pp. 165-235 (1992)
& Intercalation chemistry by A. J. Jacobson, in Encyclopedia of
Inorganic Chemistry, edited by R. Bruce King, John Wiley
edition, New-York, pp. 1556-1582 (1994)

2-D Hybrid Organic-Inorganic Materials based on
Organic Polymers Intercalated in Layered Inorganic Solids
A new strategy to prepare materials with synergetic or

complementary behavior between the polymer and the
inorganic solids interacting at the molecular scale
Ø the constrained environment is expected to lead to
higher degree of polymer ordering
Ø promising applications : optics, electronics, ionics,
mechanics and biology
Ø 3 main synthesis strategies :
§ direct intercalation of a preformed polymer into the
host lattice
§ simultaneous intercalation and polymerization of
monomer molecules which can be induced by redox
properties of the layered host : redox intercalative
polymerization (RIP)
§ intercalation of monomer molecules with subsequent
chemical, thermal or photo-induced in situ
polymerization

1 - Intercalation of a preformed polymer
into the host lattice
a) direct intercalation of PEO into phyllosilicates
Ø poly(ethylene oxide) –(CH2-CH2-O)n- : the simplest

water-soluble polymer. As an infinite crown-ether, its salt
complexes are promising solid electrolytes for
applications in solid-state batteries and electrochromic
devices
Ø phyllosilicates : layers built up by two tetrahedral silica
sheets and a central octahedral sheet of magnesia or
alumina. Isomorphous substitutions, mainly in the
octahedral sheets, give a negative charge located in the
layers which is compensated by exchangeable cations
in the interlayer space
Na-montmorillonite : Nax(Al2-xMgx)(Si4O10)(OH)2.mH2O
Na-hectorite : Nax(Mg3-xLix)(Si4O10)(OH)2.mH2O

Ø driving force of the polymer insertion process : the
solvation of the alkali guest ions by the oxygen atoms of
the polyether :
POE/H2O
Tamb
Na+-montmorillonite 6 < ∆d < 8 Å

Ø the longer the macromolecules, the slower the reaction
Ø helical conformation as in crystalline PEO
Ø intercalated PEO amount is proportional to PEO
concentration in aqueous solution
Ø ∆d depends only on the cation size
Ø ionic conductivity close to that determined for
conventional PEO-salt complexes, but better thermal
stability
b) intercalation of water-soluble polymers in V2O5

after previous swelling in water
OMe polyvinylpyrrolidone
MeO n (PVP)
O
MeO O n N O HO O H
MeO O O n
OMe MeO
Ø
méthylcellulose (MeCel) poly(propylene glycol) (PPG)
Ø V2O5.nH2O (xero)gels : prepared by polycondensation

of decavanadic acid. Orientated films present a layered
structure with an interlayer spacing of 11.5 and n
∼1.6. It is proposed that V2O5 layers are composed of
corrugated ribbons with a step of 2.8 with the
intraribbon structure close to the layers of orthorhombic
V2O5 : layers of vanadium-oxygen square pyramids are
connected by dπ-pπ covalent V=O…V=O bonds :

V2O5.1.6H2O gel structure orthorhombic V2O5 structure
Ø driving force of the polymer insertion process : it would

be the entropy stabilization by adsorption into the solid
Ø experimental conditions : aqueous polymer solutions
are mixed with V2O5 solution and stirred at room
temperature for several hours, prior to film casting. After
slow water evaporation, a red film is formed
Ø the crystallinity decreases as the polymer loading
increases
Ø in (PVP)xV2O5.nH2O : as x increases, the interlayer dis-
tance increases continuously and linearly up to x = 3
with an increment of 7 per PVP mole. The deviation at
x > 3 values is attributed to the saturation of V2O5
galleries and the polymer deposition outside the host
Ø polymer/V2O5 films become flexible with MeCel, but

brittle with PPG and PVP
c) intercalation through complete exfoliation/
reflocculation of the MoS2 host
Non-topotactic method where the inorganic layered host is

completely exfoliated (colloidal dispersion) : then, the
separated layers interact with organic macromolecules and
precipitate from the solution, by re-stacking the single-layers
and trapping the macromolecules in the interlayer galleries
General method (except for smectic clays as Na+-

montmorillonite, which exfoliate by simple dissolution in water) :
§ the reduction of layered compounds
§ the destroying re-oxidation by hydrolysis
Ø metal dichalcogenide lattices consist of two
hexagonally close-packed chalcogen layers between
which reside the metal ions, which are found in sites of
either octahedral or trigonal prismatic symmetry
Ø direct intercalation in MoS2 is possible only with highly

reducing agent such as alcali metals :
MoS2 + BuLi LiMoS2 + ½ Bu-Bu reduction

LiMoS2 + x H2O (MoS2)single-layer + x LiOH + x/2 H2 exfoliation
(MoS2)single-layer + x polymer (polymer)xMoS2 flocculation

Ø so the MoS2 layers sandwich the polymer chains in a
remarkably well-ordered way to produce a single-phase
product (here : intercalation of polyamide-6)
Ø among the intercalated polymers through this route :

MeCel, PEO, PPG, PVP and :
O
NH N
N n n
n
H
nylon-6 H polyaniline (PANI) poly(ethylene imine) (PEI)
Ø the electrical conductivity of (PEO)xMoS2 and

(PPG)xMoS2 with respective room temperature of 0.1
and 0.2 S.cm-1 are among the highest reported for
polymer/host nanocomposites
Ø potential cathodes in solid state high energy lithium

batteries, because the encapsulated polymers when
complexed with Li would provide the desired solid
electrolyte and because the high conductivity of the
layers should not necessitate the addition of conductive
additives (e.g. graphite, carbon black…)

d) nucleation and growth of a lamellar mineral
in presence of macromolecules
General method : nucleation and growth of inorganic crystals

from homogeneous solutions containing the polymer chains as
co-solutes
ex : organoceramics synthesized by growing calcium
aluminate crystals (double hydroxides) Ca2Al(OH)6[X].nH2O
where X-= OH- or CO32- from a supersaturated calcium
aluminate solution and a saturated calcium hydroxide solution
in the presence of poly(vinyl alcohol) (PVA)
Ø this route allows to overcome large entropic barriers and

incorporate significant amounts of polymer, in some
cases up to 38 wt.%
Ø the layered structure of the organoceramic was found to
be stable up to a temperature of 400°C, whereas the
pure layered double hydroxide lacking organic material
decomposed at 125°C ; this phenomenon may be due
to an extensive and strongly bonded interface between
organic and inorganic components
Ø compacted into a cylinder the organoceramic has more
than twice the compressive strength than the pure
calcium aluminate
e) polymer "melt" intercalation
General method : annealing a mixture of polymer and layered

silicate powders above Tg or Tf in order to further the diffusion
of the macromolecules from the bulk polymer melt into the van
der Waals galleries between the silicate layers
Ø Li-fluorohectorite : Lix(Mg3-xLix)(Si4O10)F2.mH2O
Ø polystyrene -(CH2-CHΦ)n- : Tg ∼ 100°C
Li+-fluorohectorite + H2N-(CH2)17-CH3
cationic exchange
(octadecylammonium)+-fluorohectorite + polystyrene
mixing
formed into a pellet
at 70 MPa
annealing at 150°C
Figure : high-resolution bright-field TEM image of an intercalated

primary particle near the polystyrene matrix (ultra-thin section)
+ polymer
intercalated material
delaminated
material
Ø original properties of such materials when compared

to their pure polymer constituent or their
"microcomposites" counterparts :
§ compatibility with current polymer processing
techniques (injection, extrusion…)
§ higher modulus
§ lower thermal expansion coefficient
§ reduced gas permeability
§ increased solvent resistance
§ enhanced ionic conductivity

2 - Monomer intercalation and in situ polymerization
a) redox intercalative polymerization (RIP)
General principle : oxidative intercalation/polymerization of

organic monomers with concomitant reduction of the inorganic
lattice
Ø oxidatively polymerizable monomers :
NH2 NH NH2
aniline 4-anilinoaniline
Me
S S S S
thiophene 2,2’-bithiophene 3-methylthiophene
Me Me Me
NH N NH NH
Me
pyrrole 3-methylpyrrole 3,4-dimethylpyrrole
N-methylpyrrole
O
O O terfurane
The oxidative polycondensation leads to electrically

conductive polymers, whose structure is 3-dimensional
and remains poorly understood :
oxidant
n
n
+ 2n e- + 2n H+
S S
thiophene polythiophene
Ø electron-acceptor inorganic hosts : they contain

transition metals, which may be reduced : V2O5.nH2O,
FeOCl, VOPO4 or some montmorillonites with pre-
intercalated Fe3+ or Cu2+ cations

Ø experimental conditions : a mixture of inorganic host
and a solution of monomer in acetonitrile (neat
monomer may also be used) is stirred at ∼50°C for
several days under N2. A black solid is obtained and
collected by filtration. It consists in oriented electroactive
polymer chains between the layers of the inorganic host
(2-dimensional organization)
Ø the necessary and sufficient condition for RIP :
Epa the anodic potential of the
monomer must be less positive
2,06 V
S than the redox potential of the
1,86 V
S
inorganic host. Here the RIP of
thiophene and 3-methylthiophene
in FeOCl failed contrarily to 2,2'-
FeOCl
bithiophene. So upper and lower
bounds can be placed on the redox
S
1,32 V
S
potential of FeOCl at 1.32 < E <
1.86 V
FeOCl structure is
orthorhombic, characte-
rized by double sheets of
distorted octahedra which
share edges : each iron
atom is coordinated to
four oxide anions and two
chloride anions
Ø electronic conductivity : (C4H2S)0.28FeOCl : 5 S.cm-1

b) intercalation/polymerization of MMA
in Na-montmorillonite
Ø experimental conditions : the clay is saturated with

MMA guest molecules, followed by desorption of the
excess monomer by means of repeated washings. No
spontaneous polymerization is observed. The
polymerization is initiated with γ-ray irradiation or by co-
intercalated benzoyl peroxide
Ø observed results :
§ ∆d = 7.6 Å
§ polymer yield is below 50 %
§ the PMMA/montmorillonite nanocomposite has a
greater thermal stability than conventional PMMA
because of steric factors hindering the thermal
motion of the polymer segments sandwiched
between the inorganic sheet
§ NMR spectroscopy shows short stereo-sequences
with a predominant isotactic component, due to
strong dipole-ion interactions between MMA and Na+

c) intercalation/polymerization of ε-caprolactone
in CrIII-fluorohectorite
Ø ε-caprolactone : cyclic monomer leading to

biodegradable poly(ε-caprolactone) :
O
-[(CH2)5-CO-O]n- O
Ø experimental conditions : mixing at 25°C for 12 h

followed by heating at 100°C for an additional 48 h
§ the polymerization reaction appears to proceed
through cleavage of the acyl-oxygen bond catalyzed
by the interlayer Cr3+ ions
§ intercalated polymer is strongly adsorbed onto the
silicate layers and shows no melting transition
d) intercalation/polymerization of aniline
in hydrogen uranyl phosphate
Ø HUO2PO4.4H2O : the layers consist of dumbbell-shaped

UO2+ ions with the uranium further coordinated by four
equatorial oxygen atoms of four PO43- tetrahedra
forming two-dimensional sheets ; the galleries contain
two water layers and H+ ions with can be exchanged
with cations or neutralized with bases :
130°C/air
HUO2 PO4.nH2O + C6 H5NH2 (C6 H5NH3)UO2 PO4.0.5H2O (PANI)0.94 UO2 PO4.0.4H2O
3 weeks
excess pale-yellow solid black solid
§ IR analysis of extracted polymer shows a small
degree of cross-linking with 2-dimensional structure
§ air oxygen is uniquely responsible for polymerization
of intercalated anilinium ions
§ on the contrary, solvated oxidants such (NH4)2S2O8,
FeCl3,… lead to the release of anilinium ions (by ion-
exchange with NH4+, H3O+…) which are polymerized
in solution outside of the host
n bibliography
w Poly(ethylene oxide)-silicate intercalation materials by P.
Aranda and E. Ruiz-Hitzky, Chem. Mater., 4, 1395-403 (1992)
w Intercalation of water-soluble polymers in V2O5 xerogel by
Y.J. Liu et al., Adv. Mater., 5, 369-72 (1993)
w Encapsulation of polymers into MoS2 and metal to insulator
transition in metastable MoS2 by M.G. Kanatzidis and coll., J.
Chem. Soc., Commun., 1582-5 (1993)
w Synthesis of nanocomposites : organoceramics by P.B.
Messersmith and S.I. Stupp, J. Mater. Res., 7, 2599-611 (1992)
w Microstructural evolution of melt intercalated polymer-
organically modified layered silicate nanocomposites by E.P.
Giannelis and coll., Chem. Mater., 8, 2628-35 (1996)
w In situ intercalative polymerization chemistry of FeOCl.
Generation and properties of novel, highly conductive
inorganic/organic polymer microlaminates by M.G. Kanatzidis
et al., Solid State Ionics, 32/33, 594-608 (1989)
w Polymerization of monolayers. V - Tacticity of the insertion
poly(methyl methacrylate) by A. Blumstein and coll., J. Polym.
Sci. : part A2, 8, 1599-1615 (1970)
w Polymer-layered silicate nanocomposites : in situ intercalative
polymerization of ε-caprolactone in layered silicate by E.P.
Giannelis and coll., Chem. Mater., 5, 1064-66 (1993)
w Topotactic polymerization of aniline in layered uranyl
phosphate by M.G. Kanatzidis et al., Inorg. Chem., 32, 2989-91
(1993)
w Acrylate intercalation and in situ polymerization in iron
substituted nickel hydroxides by E. Duguet and coll., Polym.
Int., 48, 277-282 (1999).

Core-Shell Hybrid Organic-Inorganic Particles
Core-shell HOI particles : mainly consist of an inorganic core

and a polymer shell
! interest of the polymer shell towards the inorganic
core :
# protection : anticorrosion barrier…
# wettability improvement towards organic liquids
# dispersibility improvement in organic medium
# interface tailoring in composite materials
# possibility of functionalization by anchoring active
molecules and biomolecules
! interest of the inorganic core :
! offer interesting prospects in various applications :
# composite materials
# elastomers
# adhesives
# cosmetics
# inks and paints
# catalysis
# magnetic recording media
# biotechnology : biomolecule and cell sorting
# medicine : drug targeting
! 2 main synthesis strategies :
# filling up of polymer shell with inorganic particles
# encapsulation of inorganic particles by polymer shell

1 - Filling up techniques of polymer shells
This technique is possible with rapid inorganic reactions, such

as oxide precipitation
pH $
ex : Fe2+ + Fe3+ Fe3O4
a) precipitation from soluble precursors

in macromolecular solution
! particle growth is controlled by solution viscosity
+ precursors
ex : synthesis of superparamagnetic
Fe3O4 in dextran solution
O
HO
O HO
O HO
HO
O HO
OH O
dextran HO
O HO
O
HO
O HO
O
HO
HO
O HO
O
HO
HO
O HO
HO

! functional molecules may be grafted on adsorbed
polymer, but due to weak interactions it may also easily
released
ex : grafting of fluorescent dye TRITC onto Fe3O4/dextran :
N O N+
dextran
COO -
OH
S C N TRITC
+ NaIO4
NH-(CH2)6-NH-C-NH- O
S
+ S=C=N- + H2N-(CH2)6-NH2
NH-(CH2)6-NH2 N-(CH2)6-NH2
+ KBH4
b) precipitation from soluble precursors

in polymer particles
solvent
+ precursors
! nucleation in pores of the swollen particles of partially

cross-linked polymer
! inorganic particle growth is limited by the pore size
2 - Encapsulation processes of inorganic particles
! presentation restricted to oxide particles

! inorganic particles obtained by grinding, precipitation,
sol-gel technique…
! advantages :
# a priori conceivable with every inorganic phase
# with every polymer at the expense of a possible
inorganic surface treatment
! main drawback : avoiding of the aggregation
phenomenon of inorganic particles
a) surface modification
with heterofunctional metal alkoxides
General principle : condensation of metal alkoxides onto oxide

surface via hydroxyl surface groups
H H H H H H
O O O physisorbed
H H H H H H water
O O O
H H H H H H H H H H H H H
O chimisorbed
O O O O O O O O O O O water :
O O
hydroxyl groups
M M M M M M M M M M M M M M M
water chimisorption
ex : grafting of γ-MPS onto alumina particles :

O
OH + (CH3O)3Si O
Al2O3 γ -MPS
O
anhydrous solvent
O Si O
HOI macromonomer

grafted γ-MPS greffé µmol.m-2
14
(TGA) ! surface saturation
12 due to the steric
10 hindrance of non-
8 hydrolyzable group
6
! multilayer surface
arrangement (29Si
4
2
NMR analysis)
0
0 10 20
used γ-MPS µmol.m-2
hydrogen
bonds organophilic
surface
O
O O O
O O
O
O H O O
O O O O
OH O O
O Si O O
O Si O Si O
OH HO
O O O OH Si
O Si H O Si H Si O OH H
H Si
Si OH O O
Si O O O
OH
O
O O O O O
Al Al Al Al Al Al Al Al Al Al
alumina
! so R'Si(OR)3 grafting leads to the formation of a

polysiloxane film of few Å thick with pendant γ-
methacryloyloxypropyl groups
! with H2N-(CH2)3-Si(OMe)3 -modified Y3Fe5O12 garnet
particles, TRITC fluorescent molecules may be grafted :
Figure : epifluorescence microscopy

b) adsorption of macromolecules
% inert macromolecule precipitation (old method allowing the

preparation of Egyptian inks from carbon particles stabilized
with gum Arabic) : inorganic particles are dispersed in
macromolecular solution and the quality of the solvent is
reduced by decreasing temperature or adding a non-solvent :
! main drawback : adsorption/depletion equilibrium due

to weak interfacial interactions
% functional macromolecule grafting :
ex : synthesis and grafting of PMMA macromolecules with

pendant trialkoxysilyle groups :
R
n + m
O O n m
O O
O O
O O
Si(OCH3)3 poly(MMA-co-γγ-MPS)
(CH3O)3 Si

ex : synthesis and grafting of PMMA macromolecules with
pendant trialkoxysilyl groups :
SH
+ H
Si(OCH3)3
+
S
+ MMA
S Si(OCH3)3 Si(OCH3)3
! main limit : macromolecule surface density is restricted

by steric hindrance, therefore by macromolecule molar
masses
% growing macromolecule grafting : solution polymerization
in presence of inorganic particles which participate to the free-
radical polymerization reaction :
R + n R
+ n
+
SH + H
+
+ MMA
S S

! main limit : grafting surface density < 30 µmol.m-2
polysiloxane grafted
film chains
entangled
chains
! polymerization through heterogeneous processes

c) encapsulation through suspension polymerization
% traditional suspension polymerization process : the

reaction mixture (monomer + initiator + polymer) is suspended
as droplets in water (where it is insoluble)
! necessitates (i) vigorous agitation throughout the
reaction and (ii) dispersion stabilizers dissolved in the
aqueous phase [typically low molar polymers such as
poly(vinyl alcohol)]
! each droplets acts as a small bulk polymerization reactor
for which the normal kinetics apply
! polymer in the form of beads (typically 0.1-2 mm
diameter) easily isolated by filtration
! widely used on an industrial scale : PMMA, PS, PVC…
water
R
R

% encapsulation : through double dispersion system with
organophilic inorganic particles such as γ-MPS/alumina
preferentially dispersed in monomer droplets
water
R
R
Figure : SEM image and aluminum X-ray map of alumina/PMMA beads
% "static" process using a

water-agarose gel as suspen-
ding phase : dispersion is
prepared under vigorous stirring
at 41°C in agarose solution (10
g.L-1). The stirrer is switched off
when the gelling point is reached
(42°C). The polymerization is
performed at 70°C and when it is
completed, the gelled phase is
reverted to an aqueous solution
by warming up to 90°C
d) encapsulation through emulsion polymerization
Second heterogeneous process where surfactants are used

and initiator must not be soluble in monomer but soluble only in
the aqueous dispersion medium
eau
hydrophobic
inorganic
particles
hydrophilic
water inorganic
particles
Figure : SEM image of 0.2 µm γ-MPS TiO2

encapsulated in 0.4 µm PMMA latex particles
% bibliography
& Polymers at the surface of oxide nanoparticles by C.H.M.
Hofman-Caris, New J. Chem., 18, 1087 (1994)
& Formation of chemically bond polymer layers on oxide
surfaces and their role in colloidal stability by R. Laible and K.
Hamann, Adv. Colloid Interface Sci., 13, 65 (1980)
& PMMA-based composite materials with reactive ceramic fillers
– Part 1. Chemical modification and characterization of ceramic
particles by E. Duguet and coll., J. Mater. Chem., 7, 1527
(1997)
& PMMA encapsulation of alumina particles through aqueous
suspension polymerization processes by E. Duguet et al.,
Macromol. Symp., 151, 365-70 (2000)

% acknowledgments
& Post-graduate students :

# Stanislas VOL
# Eric AMEDRO
# Stéphanie REY
# Olivier FOUASSIER
# Pierre MAHEU
# Benoît BOUE
# Fabrice MORVAN
# Jean-François LAHITTE
# Stéphane MORNET
# Laeticia PETIT
# Flavien DELRIEU
# Clément NGUYEN VAN THAN
# Nicolas JAUSSAUD
& Ph.D. students

# Maher ABBOUD
# Fabrice MORVAN
# Stéphane MORNET
# Christophe VAYSSE
# Jérôme ROUBIN
& Post-docs
# Michelle R. TURNER - university of California (USA)
# Josepha MERIDA-ROBLES – university of Málaga (Spain)
# Fabien GRASSET – university of Bordeaux-1 (France)

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General introduction

HOIM = Hybrid Organic-Inorganic Materials acronym

1 – The HOIM concept

Traditional composite materials : multiphase material

HOIM or nanocomposites or molecular composites : a

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 1-1

When intimately associated

! synthesis and application of HOIM have attracted

! among present applications of HOIM :

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 1-2

HOIM could be classified according to

xerogels decreasing dimensional

entangled alternated core-shell

reinforced and/or crosslinked

! simplifying and non-exhaustive classification

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 1-3

! just an introduction to HOIM

1 " General introduction

2 " Macromolecular synthesis background

3 " Sol-gel chemistry and engineering background

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 1-4

5 " Intercalation chemistry background

6 " 2-D hybrid organic-inorganic materials based on

7 " Core-shell hybrid organic-inorganic particles

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 1-5

polymer : substance composed of macromolecules which

homopolymer : polymer derived from one species of

copolymer : polymer derived from more than one species

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2-2

Thermoplastics (or "plastics") : linear or branched polymers

" crystalline phase with melting temperature Tm

Elastomers : rubbery polymers of low crosslink density

Thermosets : rigid network polymers in which chain motion is

molar mass M : mass of 1 mole of the polymer (g.mol-1)

2 – Classification of polymerization reactions

the most basic requirement : each monomer must be

classification : based on the polymerization mechanisms :

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2-5

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2-6

Table : Fundamental differences in reaction mechanism between step polymerization

" involve successive reactions between pairs of mutually-

HO C C OCH2CH2O H + (2n-1) H2O

" polymerizations involving monomers of functionality

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2-8

Polycondensation : step polymerization involving reactions in

H NH (CH2 )6 NH C (CH2)4 C OH + (2n-1) H 2 O

" drawback : very slight excesses of one monomer

" advantage : with each condensation reaction the

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2-9

n Cl-Si(CH3)2-Cl + (n+1) H2O → H-[O-Si(CH3)2]n-OH + 2n HCl

Polyadditions : step polymerizations in which the monomers

n O=C=N-R-N=C=O + n H2N-R'-NH2 → -[C(O)-NH-R-NH-C(O)-NH-R'-NH]n-

b) molar mass control for linear step polymerization

c) gelation during non-linear step polymerization

The inclusion of a monomer with a functionality greater than

Free-radicals : independently-existing species which

a) initiation, propagation and termination

! the addition of one of these free radicals to a molecule of

Propagation stage : growth of the polymer chain by rapid

Y Y R CH2 CH CH CH2 head-to-head addition

Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2 - 12

b) rate and degree of polymerization

! steady-state conditions : rapidly, the rate of radical loss