Blends of poly(vinylacetate) (PVAc) and poly(cyclohexylmethacrylate) (PCHMA) labeled by copolymerization with 4-methacryloylamine-4Ј-nitrostilbene (Sb), with (1-pyrenylmethyl)methacrylate (Py), or with 3-(methacryloylamine)propyl-N-carbazole (Cbz) were prepared by casting dilute solutions in tetrahydrofurane (THF) or chloroform. Films about 10 m thick were formed. Phase separation in two types of domains is observed by transmission optical microscopy (TOM) and epifluorescence microscopy (EFM): small craters of 1 to 10 m placed at the polymer-air interface and larger domains, on the scale of 100 m. The morphology of samples depends on the composition of the polymer blend and on solvent. The green fluorescence of Sb, the violet of Py, or the blue of Cbz provides imaging of the distribution of PCHMA in the different domains and in the matrix. It is thus observed that (i) superficial craters and large domains are formed mainly by PCHMA and (ii) the matrix is composed of PVAc in films cast from THF and it is a blend of the two polymers, homogeneous at the submicrometric scale, for chloroform. The emission intensity of Py, recorded by microfluorescence spectroscopy (MFS), yields a mapping similar to imaging detection. It is remarkable that in films cast from chloroform, the smaller domains are distributed with a 2D hexatic order disrupted by dislocations and disclinations, whereas in films cast from THF, a larger heterogeneity is found, denoting different mechanisms of solvent evaporation.
ABSTRACT:Blends of poly(vinyl acetate) (PVAc) and poly(cyclohexyl methacrylate) (PCHMA) labeled by copoly-merization with 4-methacryloylamine-4�-nitrostilbene (Sb), with (1-pyrenylmethyl)methacrylate (Py) or with 3-(methacryloylamine)propyl-N-carbazole (Cbz), were prepared by casting dilute solutions in tetrahydrofurane (THF) or chloroform onto silanized glass plates. The resulting films were studied by epifluorescence microscopy, microfluorescence spectroscopy, DSC and optical microscopy. Epifluorescence micrography probes the chemical composition of the different regions in phase separated blends, with black areas corresponding to PVAc rich regions and colored areas corresponding to labeled PCHMA rich regions. The technique also visualizes primary and secondary morphologies, which depend on the composition of the polymer blend and on the casting solvent. Mixtures containing 80 wt % PCHMA show, in general, a bicontinuous primary morphology suggesting a spinodal demixing mechanism. Solvent effects are particularly relevant for 50% and 20% PCHMA samples showing morphologies composed of PCHMA rich domains, in a matrix of solvent-dependent compositions. Samples cast from chloroform are more homogeneous and the matrix is always highly fluorescent. In contrast, the domains of samples cast from THF are heterogeneous in size and shape and the matrix is non-fluorescent, being thus formed by nearly pure PVAc. Small voids are formed in the polymer-air interface. They are submicrometric for THF cast films and disappear with annealing at 122°C. For chloroform cast samples they are much less frequent and appear well ordered, forming a mostly hexatic two dimensional network.
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