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ceramics
of
rea
s in p o n e
g v nt
doped
ol .
organization
filled
of one component
xerogels
towards the other one
O polymers
r
O
inc
4 – Contents
1 – Basic definitions
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
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2-4
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
molar mass
evolution as
a function of
reaction
extent
0 50 100 0 50 100
extent of reaction (%) extent of reaction (%)
and later :
O O
n C C + n HOCH2CH2OH
HO OH
O O
C C C C
O O O
O
CH2 CH2
CH
O C C
O O
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)
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2 - 11
4 – Chain polymerization : free-radical polymerization
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
! disproportionation :
ktd
CH2 CH + HC CH CH2 CH2 + HC CH
Y Y H Y Y
CH2 ethyl
CH2 H
branches
CH CH CH2 CH3
CH2
+ n H2C=CH2
CH3
CH2
CH CH CH2 CH3
CH2
e) emulsion polymerization
monomer-
swollen
micelle
dissolved
R
free radical
$
0
time
" interval % : the rate of monomer diffusion exceeds the
rate of polymerization so that the concentration [M]p of
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 2 - 17
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)
+ +
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
- -
Si OH + OH Si O + H2O
- -
Si O + Si OH Si O Si + OH
preferentially preferentially
a highly a weakly
condensed branched
species species
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
Figure 1 : State
diagram describing
the hydrolysis-
condensation
behavior of
complexed
tetravalent metal
alkoxides
crack
crack
a) advantages
b) drawbacks
d) conclusion
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
# 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
Ti not stable to UV
(photoreduction)
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
& % '
Si(OMe)3
Si(OMe)3 MeOH/H2O 600-680°C
2 mol. % NH4F under air
& 656 / 50 657 / 46
% 441 / 70 407 / 70
Si(OEt)4 sol-gel
TEOS chemistry
xerogel
O free-radical
O polymerization n
MMA PMMA
O O
SiCl4 + 4 HO O
Si O O
4
O
H2O/H+
O + O + Si(OEt)4
O O
γ-MPS
(MeO)3 Si
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
! filled xerogels
1 – General considerations
Table : examples of layered host structures that exhibit intercalation reactions (1st part)
a) staging
b) kinetics
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
b) ion exchange
d) electrointercalation methods
POE/H2O
Tamb
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)
delaminated
material
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
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+
Ø observed results :
§ 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
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 6 - 13
d) intercalation/polymerization of aniline
in hydrogen uranyl phosphate
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
Ø observed results :
§ 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
Introduction to Hybrid Organic-Inorganic Materials / Etienne Duguet / university Bordeaux-1 6 - 14
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).
+ 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
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
solvent
+ precursors
a) surface modification
with heterofunctional metal alkoxides
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
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
+ n
+
SH + H
+
+ MMA
S S
entangled
chains
water
R
R
R
R
eau
hydrophobic
inorganic
particles
hydrophilic
water inorganic
particles
& Post-docs
# Michelle R. TURNER - university of California (USA)
# Josepha MERIDA-ROBLES – university of Málaga (Spain)
# Fabien GRASSET – university of Bordeaux-1 (France)