Experimental Report 18/06/2010

Proposal: 6-04-257 Council: 10/2008

Title: The Dynamics of Nanoconfined Polymers within Spherical Nanoparticles

This proposal is continuation of: 6-04-252

Researh Area: Soft condensed matter
Main proposer: RHARBI Yahya

Experimental Team: YOUSFI Mohamed

RHARBI Yahya
Local Contact: PORCAR LIONEL
Samples: deuterated polystyrene (D8) and hydrogeneated polybultyl methacrylate
Instrument Req. Days All. Days From To
D11 4 2 27/05/2009 29/05/2009
Abstract:
The glass transition (Tg) of nanoconfined polymers has been extensively studied throughout the last decade. The majority
of this research has focused on thin film geometry and was carried out on supported and free-standing films using various
experimental techniques; Brillouin light scattering, ellipsometry, dielectric relaxation and fluorescence. These reports
substantially agreed that the Tg of polystyrene (PS) decreases drastically with decreasing film thickness for h < 50 nm. In
contact, only two studies reported on chain diffusion in thin films. These studies suggested that the rate of diffusion
decreases with decreasing film thickness, which is in contradiction with the reduction of Tg with reducing film thicknesses.
Although polymers are often nanoconfined in spherical geometries (nanoparticles), little effort has been dedicated to the
study of their properties. This information could be useful in many industrial and environmental applications: nanoblends,
nanocomposites, coatings. There is an urgent need for developing novel experiments to study the dynamics and the
nanomechanical properties of nanoconfined polymers in spherical geometries.
Experiment report 6-04-257
Dynamics of Nanoonfined Polymers within Spherical Nanoparticles
Mohamed Yousfi, Yahya Rharbi
Laboratoire de Rheologie, UJF/INPG/CNRS, BP 53, Domaine universitaire 38041, Grenoble, France.

Local contact : Lionel Porcard

Introduction. The glass transition (Tg) of confined polymers has been extensively studied
throughout the last decade [for review see 1]. The majority of this research has focused on thin film
geometry and was carried out on supported and free-standing films using Brillouin light scattering,2
ellipsometry, fluorescence… These reports substantially agreed that the Tg of polystyrene (PS)
decreases drastically with decreasing film thickness in both supported and free standing films. For
instance Tg was reported to be 70 lower than bulk Tg (Tgbulk) for 20 nm free standing thin film. 2 On the
other hand there is no consensus on the behavior of the polymer dynamic in confined situation. For
example dielectric relaxation on PS thin films yielded an activation of the segmental dynamic in one
study3 and a bulk-like behavior in another one.4 Franck et al. using fluorescence recovery after photo-
bleaching suggested that chain diffusion slows down with decreasing film thickness, which is in
contradiction with the Tg reduction.5 Forrest et al. 6 using surface healing dynamic concluded that the
PS free surface exhibit a bulk relaxation close Tgbulk and deviates from the bulk behavior below Tgbulk.
These controversies were attributed by several groups4 to the film processing method (spin coating)
which generates an excessive residual stress in the films. Therefore there is a need to study the Tg and
the dynamic of polymers confined in other geometries such as nanoparticles.
Although polymers are often found confined in spherical particles, little effort has been dedicated
to the study of their glass transition and their dynamic. This information could be useful in many
industrial and environmental applications; blends, copolymers, nanocomposites, colloids, coatings…
One example is in nano-blends, where hard polymer nanoparticles are used to reinforce soft matrices.7
Reducing particle size would be counterproductive in this application if it causes the reduction of their
Tg. In this work we study the dynamic of polystyrene (PS) nanoparticles when dispersed in soft
matrices. First we present a new method to probe the long range dynamic of a single polymer
nanoparticle by small angle neutron scattering.8,9 We then address the question of how confinement in
nanoparticles and proximity to soft matrices would affect the dynamic and glass transition of
polystyrene.
Result and discussion. We developed a novel method to study the chain dynamic of nanoconfined
polymer in nanoparticles.8-9 We prepared dispersions of deuterated linear polystyrene nanoparticles
with various sizes between 30 nm and 80 nm and highly crossslinked PBMA particles (50 nm). We
made PBMA films containing individual dPS particles (2%) via evaporation of a mixture of the two
suspensions (Schema1). These films are made at temperatures well below the Tg of PS (TgPS) and
above the Tg of crosslinked PBMA TgPBMA. In these conditions the PBMA particles deform under
capillary pressure to fill the void between them, whereas the glassy PS particles remain spherical (G
~GPas). Therefore the elastic energy is stored within the deformed crosslinked PBMA particles. Upon
annealing the nanoblends above Tg PS, the PBMA particles regain their spherical shape and release the
stored elastic energy, which results in the deformation of neighboring PS particles (Schema 1). We
used SANS to follow the shape of the PS particle during annealing. The dynamic of particle
deformation is then used to estimate the relaxation time of confined polystyrene.
We started by investigating the conditions for making nanoblends of highly dispersed dPS particles
in crosslinked PBMA matrices.9 For that we controlled the surface chemistry of the particles during
polymer synthesis and throughout the evaporation process. The SANS spectra of the freshly
prepared films (Figure 1) suggest that dPS particles are spherical and dispersed individually in
the PBMA matrices. These spectra change drastically after annealing above TgPS (figure1), which
infers that the spherical dPS particles deform into an elongated form. From the simulation of the
SANS spectra we concluded that the particles most likely deform into a star-like shape with 12
branches.
PBMA
PS 1000
before a

I(q) (Arb. Unit)

100
after
10
1
0.1
0.01
Water evaporation at Annealing at 1E-3
TgPBMA <T<TgPS T >TgPS 10
-3 -2
10 10
-1

-1
q(A ) .
Figure 1 SANS spectra of 80 nm polystyrene nanoparticles (2
Schema 1: Description of the experimental wt %) in a 10 % crosslinked PBMA matrix before annealing (●)
procedure. and after annealing at 140°C for 1h (○)
We annealed the films in an online oven (ILL equipement) during SANS measurements. The oven
is able to perform temperaure jumps between room temperature and 150°C within 2 minutes, which
anabled us to follow relaxation kinetics slower than 1 min. The spectra were then collected every 0.5
min or 1 min throughout the annealing process.The form factor of dPS particles continuously changes
during annealing: the intensity decreases at low q and increases at large q (Figure 2). The evolution of
the spectra with time reflects the change in the particles’ shape during their deformation. This shows
that this procedure can be used to quantify the dynamic of a single polystyrene particle in
nanoblends for particles as small as 30 nm.
Time, min
Annealing time
1000
1000 b Figure 2. a) The scattering spectra plotted for
various annealing times for 77 nm dPS
I(q) (Arb. unit)

nanoparticles in a 10% crosslinked PBMA matrix

I(q) (Arb. Unit)

100
100
(□) before annealing; (■) 4 min, (∆) 17 min and
10 (▲) 37 min.. b) The scattering spectra plotted for
various annealing times for 30 nm dPS
1
-3 -2
nanoparticles in a 10% crosslinked PBMA matrix.
10 10 The films were annealed at 140 °C.
10
q (A-1) 0,001 0,01
-1
q (A )

We quantify the dynamic by probing the evolution of the scattering intensity at various q values
I(q, t) or the variation of the gyration radius Rg(t) with time. In Figure 3 we show the I(q, t) and Rg(t)
for 77 nm dPS particles in 10 % crosslinked PBMA matrix annealed at 140°C. Both the plots of I(q, t)
and Rg (t) fit perfectly to a stretched exponential equation (exp(-(t/τ)β)) with an exponent β
independent of q ( β = 0.72). The average relaxation time <τ(q)> for dPS particles was found to
increase with decreasing q and to converge towards <τ>Rg from Rg(t) curve.
8000
650
a
Intensity (Arb.Unit)

b
600 12
6000
550 τ(Rg)
10 a
Rg (nm)

4000
τ(q) ( minutes)

500

450 8
2000 q
400 6
0
0 20 40 60 80 100 120 140 350
0 20 40 60 80 100 120 140 4
Annealing time (min)
Annealing time (minutes)
0.002 0.003 0.004 0.005 0.006

Figure 3. a) The evolution of the scattering intensity I(q,t) various q

-1
q( A )

values, as a function of the annealing time for blends made from 77 nm Figure 4. Average relaxation time
dPS nanoparticles in 10% crosslinked PBMA annealed at 140 °C. b) Rg(t) <τ(q)> plotted against q for blends of 80 nm
vs. the annealing time. Rg is calculated using the Guinier representation. dPS particles in 10 % crosslinked PBMA
matrix.
 These experiments were repeated for various temperatures between 100°C and 150 °C (figure 5a).
We found the particle dynamic to be activated by the temperature as predicted by the time temperature
superposition. We calculated the shift factor aT using the average relaxation time <τ> (Figure5b) and we
plotted it in the Angel representation (log(aT) vs. Tg/T) (Figure 5b). The relaxation of dPS in 80 nm,
77nm and 30nm particles was then compared to the behaviour of bulk PS and bulk PBMA (Figure 5b).
Figure 5b suggests that the dynamic of PS particles deviates remarkably from the bulk behaviour of PS.
Because crosslinking of PBMA inhibits the mixing of PS/PBMA, we can exclude the interfacial
miscibility as the cause for the change of dPS dynamic. The fragility factor of PS particles is found to be
80-88, which is lower than the bulk value (139) and higher than that of PBMA (45). These results show
that the fragility factor of polystyrene nanoparticles is affected by confinement and by the proximity to
the PBMA matrix.
This work was published in Macromolecules8 and Canadian Journal of Chemistry9
Perspectives. The deviation of PS dynamic in nanoparticles from bulk behaviour could results from
the reduction of the glass transition and/or from the change of the activation energy. To give a
conclusive answer to this question we will investigate the glass transition of PS in particles by other
means such as the time of flight and fluorescence. Furthermore, we will investigate whether all the
aspects of the polymer dynamic are affected by confinement. For that we will carry out Neutron Spin-
Echo experiments to probe the modification of the small movement of the confined chains.

Figure 5. a) The I(q,t) at q = 0.0054 Å-1 as a function

1
3500 of the annealing time for 77 nm dPS in PBMA matrix
Intensity (Arb. Unit)

for various temperature between 100°C and 150°C.

0
PnBMA-BULK
105 °C
2500
100 °C -1
m=45 b) The shift factor aT calculated from the relaxation
-2
time for 80 nm, 77nm and 30nm particles plotted in
T
Loga

1500
115 °C 110 °C -3
the Angel representation and compared to the bulk aT
125 °C
-4
PS-BULK
for PS and PBMA.
120 °C m=80-88
130 °C -5
500 140 °C
150 °C -6 m=139
0 100 200
-7
Annealing time ( min ) 0.86 0.88 0.9 0.92 0.94 0.96 0.98 1 1.02
Tg/T

References.
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3) C. Rotella, S. Napolitano, M. Wübbenhorst, Macromolecules 42, 1415 (2009).
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9) Y. Rharbi, M. Yousfi, Lionel Porcar, Q. Nawaz ; Canadian Journal of Chemistry , 88, 288 (2010).