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Thus, MMT causes a retardation of the crystal growth front, and results in crystal morphologies which are characterized by non-spherical shapes with jagged edges. Thedependence of the enthalpy fractions on the MMT suggests that the inorganicsurface promotes a new, higher Tm crystal form, at the expense of the bulkcrystalline material. Mechanical variations across polymer surfaces as those between amorphous and crystalline regions are manifested in various AFM imaging modes, including contact, intermittent contact, and two force modes. Since in most cases the mechanical variations are superimposed on surface topographical features, sometimes comparative imaging with various modes is needed to unambiguously resolve polymer crystal, amorphous polymer, and filler particles. When inorganic layers (MMT) are added to the PVA polymer, crystallites are initiated and grown in the immediate vicinity of the inorganic surface. We believe that this is due to the strong specific interactions between the inorganic surfaces and the polymer. The crystallites found near the inorganic fillers are about 2 microns in size, smaller than the crystallites found in the neat PVA film, which are 5 microns or larger. Moreover, the melting temperature of these crystals was found to be higher than the bulk Tm. At the same time, XRD also shows differences in the PVA crystalline structure when crystallized in the presence of MMT, suggesting that the inorganic fillers change also the crystal structure. The structure is explored over the full range of silicate compositions. These include DSC and thermal gravimetric analysis. DSC and XRD analysis of PVA crystallites in the nanocomposite Thermal characterization Bulk PVA has a glass transition at Tg 70C and a melting transition atTm 225C. Although the physical origins of this behavior are still under debate,30,31 this absence of thermal events is in agreement with the general behavior of polymers intercalated in clays and synthetic silicates. In a plethora of systems studied: nylon-6,2 PEO,9,10 PMPS,30 PS,31 PCL,32 PMMA33 intercalated in naturally occurring silicates (MMT) and in synthetic layered alumino-silicates (fluorohectorite), there exist no detectable thermal transitions for the intercalated polymers, over a wide temperature range below the Tg and above the Tm. On a local scale, intercalated polymers exhibit simultaneously fastand slow modes of segmental relaxations for a wide range of tempera- tures,10,30,31 but again with a marked suppression (or even absence) of cooperative dynamics typically associated with the glass transition. For higher polymer concentrations (e. . 20wt. MMT) there appear two distinct and overlapping melting peaks, one around the bulk Tm and another one at higher melting temperature. PVA crystallinity The PVA melting was studied by performing DSC on several high PVA concentration nanocomposites (2 the neat PVA, in the nanocomposites appears also a new higher-Tm crystal phase.

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