Role and properties of the confined amorphous phase of polymers

• Main Author: Walczak, Malgorzata
• Language: ENG
• Published: 2012
• Subjects: [SPI:OTHER] Engineering Sciences/Other; [SPI:OTHER] Sciences de l'ingénieur/Autre; Confined amorphous phase; Glass transition; Dynamics at the interface; Multilayered films; Viscoelasticity
• Online Access: http://pastel.archives-ouvertes.fr/pastel-00839174; http://pastel.archives-ouvertes.fr/docs/00/83/91/74/PDF/WALCZAK_-_Malgorzata.pdf

The aim of the thesis was to elucidate the effect of confinement of amorphous phase of apolymer above its glass transition temperature being in contact with another polymer in a rigid state.Confinement is unavoidably connected with surfaces enforcing confinement. It is very difficult to separate theeffect of confinement from the effect of interfaces because both effects arise parallel and coincide. Multilayeredfilms were chosen as the base material for the studies because they contain multifold number of confined layerand response from confinement and interfaces is multifold increased. Hoping that some of experimentaltechniques are more sensitive to interfaces while others to confinement we selected the following:microcalorimetry, SSNMR, direlectrical spectroscopy and dynamic shear rheology. We have searched for theinfluence of PS on dynamics of phenyl rings of PC for PC/PS film with ratio 70/30 in the temperature rangefrom 296 K to 393 K employing PILGRIM pulse sequence. .We show that above the glass transition temperatureof PS, the PC component became more flexible. It is at the first glance the effect of the interface because there isno significant confinement of thicker PC layers. Dielectric relaxation spectroscopy measurements in our studyclearly provide evidence for deviations from a simple 2-phase structure in multilayered films PC/PS that is worthto be analyzed more in the future. The dielectric response of the multilayer samples was also modeled andcompared with experimental results. We obtained again discrepancies between the simulated spectra and themeasured spectra for multilayer films. Knowing the exact composition and viscoelastic behaviour of eachcomponent, the theoretical viscoelastic behavior of composites has been predicted numerically. Then,rheological tests have been made, and confronted with numerical predictions, to detect the confinement effect.The upper limit of thickness beyond which PS in confined layers at rubbery state becomes stiffer than in bulk isabout 150/200 nm. It appeared that the shear modulus of the thinnest PS layers (10 nm) is nearly 2.5 times largerthan that for bulk PS sample. We can note that Tg of PS layers also begins to increase beyond this upper limit ofthickness.. None of the experiment could clearly deliver the information about the effect of confinement orinterface on the behavior of PS layers alone. The results obtained here point out that separation of the effects ofconfinement and interfaces remains very difficult.