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

AND
SO

I and O components can not be prepared separately

before assembling
! simultaneous syntheses in the same batch
! successive syntheses
O components are "fragile" (< 250C)
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

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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
"

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

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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
%
ol .
g v nt
s in p o n e
rea
inc I c o m
of

ceramics
doped
xerogels
filled
xerogels

decreasing dimensional
organization
of one component
towards the other one

entangled
alternated core-shell
3D-networks 2D-layers particles

inc
r
o f eas i
O
n
c o g vo
mp
l
on . %
en
t

microcomposites materials
reinforced and/or crosslinked
O polymers
O polymers

! 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

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

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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

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

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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

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

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