The glass transition temperature (Tg) of layers of stereoregular poly(methyl methacrylate) (PMMA) spin-cast on silicon and aluminum surfaces has been investigated by ellipsometry. The interfacial specific interactions were highlighted and quantified by infrared reflection absorption spectroscopy. It was found that depending on PMMA tacticity, a strong correlation exists between the density of the polymer/surface interactions and the Tg of that polymer at the interface. Indeed, i-PMMA with a large density of interfacial interactions increases its Tg at the interface whereas s-PMMA with a lower value of bonded segments exhibits a Tg depression. It is suggested that a certain level of interfacial interactions associated with an increase of density of the layer will compensate for the increase of mobility resulting from a reduction of the entanglement density or a segregation of chain ends at an interface.
Thermal characteristics of ethylene-vinylacetate (EVA) copolymers having vinylacetate contents ranging from 5 to 40 w/w % are studied by differential scanning calorimetry. It is first shown that EVA copolymers having a vinylacetate content lower than 30 w/w % obey the Flory and Burfield theories of copolymer crystallisation. The minimum sequence length of CH 2 ethylenic entities required to participate in a crystalline lamella is also deduced. One can conclude that EVA copolymers represent cases of ''total exclusion'' of the noncrystallizable comonomer. Moreover, it is observed that when the vinylacetate content is increased, the relative quantity of polyethylene amorphous phase increases and the degree of crystallinity decreases; whereas the b transition temperature of a characteristic-oriented amorphous phase is kept constant. A phase model of ethylene-vinylacetate copolymers, based on an enrichment process of the interlamellar amorphous phase by polyethylene segments originating from the crystalline phase, at increasing vinylacetate content, is proposed.
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