Experimental Report 16/09/2008

Proposal: 6-04-252 Council: 10/2007

Title: Chain Diffusion of Confined Polymers within Spherical Nanoparticles

This proposal is a new proposal
Researh Area: Soft condensed matter
Main proposer: RHARBI Yahya

Experimental Team: NAWAZ Qamar

RHARBI Yahya
YOUSFI Mohamed
Local Contact: PORCAR LIONEL
Samples: Polystyrene, polybuthyl methacrylate
Instrument Req. Days All. Days From To
D22 4 2 14/06/2008 16/06/2008
Abstract:
It is most likely that the polymer chain environment modifies their dynamics, their rheological properties and more
particularly their glass transition temperature (Tg). This idea is backed up by "Brillouin Light scattering", and ellipsometry
results on ultrathin films. They suggest that the Tg of polystyrene is reduced below the bulk values with decreasing film
thickness (h) for h< 50 nm. For free standing film, where thickness h ~ 20 nm, the Tg is reduced by about 60°C below the
bulk value. On the other hand, polymer chain diffusion in the confined situation has not been extensively studied. Only two
studies have been reported on chain diffusion in thin films; one using fluorescence recovery after photo-bleaching and the
other using mass spectroscopy The two studies showed that the in plane and out of plane diffusion rates decrease with
decreasing film thickness, which is in contradiction with the reduction of Tg with reducing film thicknesses. However, the
situation of a polymer confined within another polymer has not been thoroughly investigated. In this work we propose to
study the influence of nanoconfinement in polymer environments on polymer chain diffusion.
Experiment 6-04-252

The Dynamics of Nanoconfined Polymers within Spherical

Nanoparticles
Mohamed Yousfi, Yahya Rharbi
Laboratoire de Rheologie, UJF/INPG/CNRS, BP 53, Domaine universitaire 38041, Grenoble, France

Local contact : Lionel Porcar

Introduction. The glass transition (Tg) of nanoconfined 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 various experimental
techniques; Brillouin light scattering,2 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 and for h = 20 nm Tg has been reported to decrease by 70 °C. 2 MacKeena et
al.3 carried out mechanical tests using the “bubble inflation” technique on ultra-thin films and
suggested that film stiffness increases with decreasing film thickness. These results are in
contradiction with theoretical predictions and with the results on the reduction of glass transition with
film thickness. On the other hand, only two studies have been reported on chain diffusion in thin
films; one using fluorescence recovery after photo-bleaching4 and the other using mass spectroscopy. 5
The two studies showed that the in plane and out of plane diffusion rates decrease with decreasing film
thickness, which is in contradiction with the reduction of Tg with reducing film thicknesses.1
Although polymers are often found nanoconfined in geometries such as spheres, little effort has been
dedicated to the study of their glass transition. This information could be useful in many industrial and
environmental applications; blends, copolymers, nanocomposites, colloids or coatings. Another
example is in nano-blends, where hard polymer nanoparticles are used to reinforce soft matrices.5
Reducing nanoparticle size would be counterproductive in this application if it causes the reduction of
their Tg. It is therefore of utmost importance to tune in to the study of nanoconfined glass transition of
polymers in spherical geometries. There is an urgent need for developing novel experiments to study
the nanomechanical properties of nanoconfined polymers: glass transition, relaxation and creep
compliance experiments.
Context. We developed a novel method to study the chain dynamics of nanoconfined polymers in
nanoparticles.6-7 We prepared dispersions of deuterated linear polystyrene nanoparticles with various
sizes 20 nm to 200 nm and highly crossslinked PBMA nanoparticles (50 nm). We made PBMA films
containing individual PS nanoparticles via evaporation of the dispersion mixture (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 ~GPa). The elastic energy is hence
stored within the deformed crosslinked PBMA nanoparticles. Upon annealing the nanoblends above Tg
PS
, the PBMA nanoparticles 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 nanoparticle during annealing. The transformation of the PS particles in time is used to
estimate the relaxation time of the polystyrene nanoconfined in nanoparticles.
In the last experiment on D22, we carried out in-situ kinetic experiments using an oven (ILL
equipement) to anneal the samples during measurements. The oven is equipped with 4 compertements
and 2 independent temperture controls. The oven is able to perform temperaure jumps between room
teperture and 140°C within 2 minutes. This allowed us to carry out rapid in-situ relaxation kinetics.
The spectra of the spherical PS particles observed before annealing change drastically during
annealing above TgPS (figure 1). This change infers that the spherical dPS particles deform into star-
like shapes with 12 branches. The change in the particle shape is used to extract useful information on
the dynamics of the nanoconfined polystyrene in nanoparticles. The relaxation time τ is calculated by
fitting the evolution kinetics of the radius of gyration or the intensity at various q values to either the
exponential expression or to a stretched exponential (Figure 1). In figure 2 we show the time
dependence of the intensity at various annealing temperatures. The dynamics of particle deformation
is activated by increasing the temperature. The time-temperature shift factor aT calculated from the
decays at different temperatures using 140°C as the reference temperature is plotted vs. the
temperature (figure 3). The general tendency of aT is found to be different from the bulk behaviour.
Time, min

1000
PBMA

I(q) (Arb. unit)

PS
100

10

1
-3 -2
10 10
Water evaporation at Annealing at
q (A-1)
TgPBMA <T<TgPS T >TgPS

Schema 1: Description of the experimental procedure. Figure1. Evolution of the scattering intensity at different
annealing times of 80 nm dPS in 10% crosslinled PBMA
(□) before annealing; (■) 4 min, (∆) 17 min and (▲) 37
min. The films were annealed at 140 °C.

900 4

3
Intensity (arb. unit)

Log(aT)

600 2

1
300
0

0 10 20 30 40 -1
0.9 0.92 0.94 0.96 0.98
time (min)
Tg/T
Figure 2. The evolution of the scattering intensity at q = 0.0054 Å-1 as a Figure 3. The time-temperature shift factor aT
function of the annealing time for 80 nm dPS in PBMA matrix. The plot calculated from the decays at different temperatures
is fitted to a single exponential (continuous line) with a τ = 5.4 minutes using 140°C as the reference temperature, plotted vs.
the temperature.

References
1) M. Alcoutlabi, and G.B. McKenna, J. Phys.: Condens. Matter 17, 461 (2005).
2) J.A. Forrest, K Dalnoki-Veress, J.R. Stevens and J.R. Dutcher, Phys. rev. Lett. 77, 2002-2005 (1996); 77, 4108 (1996).
3) P.A.O'Connell, G.B.McKenna, Science, 307, 1760-1766 (2005).
4) B. Frank, AP Gast, TP. Russel,,HR. Brown, C. Hawker, Macromolecules, 29 (1996) 6531
5 ) X. Zheng, MH Rafailovich, J. Sokolov, Phys. Rev. Lett, 79 (1997) 241
6) Reduction of the Glass Transition Temperature of Confined Polystyrene Nanoparticles in Nanoblends, Yahya Rharbi*,
Phys review E, 2008, 77; 3; 031806.
7) A Novel Method for Sstudying the dynamics of Confined Polymers in Nanoparticles in Nanoblends. M Yousfi, L.
Porcar, P. Lindner, F. Boué, Y Rharbi, in prepration.