The relationship between solution properties, film-forming methods, and the solid surface structures of random copolymers composed of butyl methacrylate and dodecafluorheptyl methylacrylate (DFHMA) was investigated by contact angle measurements, X-ray photoelectron spectroscopy, sum frequency generation vibrational spectroscopy, and surface tension measurements. The results, based on thermodynamic considerations, demonstrated that the random copolymer chain conformation at the solution/air interface greatly affected the surface structure of the resulting film, thereby determining the surface segregation of fluorinated moieties on films obtained by various film-forming techniques. When the fluorinated monomer content of the copolymer solution was low, entropic forces dominated the interfacial structure, with the perfluoroalkyl groups unable to migrate to the solution/air interface and thus becoming buried in a random-coil chain conformation. When employing this copolymer solution for film preparation by spin-coating, the copolymer chains in solution were likely extended due to centrifugal forces, thereby weakening the entropy effect of the polymer chains. Consequently, this resulted in the segregation of the fluorinated moieties on the film surface. For the films prepared by casting, the perfluoroalkyl groups were, similar to those in solution, incapable of segregating at the film surface and were thus buried in the random-coil chains. When the copolymers contained a high content of DFHMA, the migration of perfluoroalkyl groups at the solution/air interface was controlled by enthalpic forces, and the perfluoroalkyl groups segregated at the surface of the film regardless of the film-forming technique. The aim of the present work was to obtain an enhanced understanding of the formation mechanism of the chemical structure on the surface of the polymer film, while demonstrating that film-forming methods may be used in practice to promote the segregation of fluorinated moieties on film surfaces.
Colonization dynamics of periphytic ciliate communities were studied in coastal waters of the Yellow Sea, northern China from May to June 2010, using an artificial substratum. Samples were collected at two depths of 1 and 3 m. The temporal patterns of ciliate colonization had similar dynamics and were fitted to the MacArthur–Wilson and logistic models in colonization and growth curves at both depths, respectively. The ciliate communities reached equilibrium in species composition within at least 10-days exposure time. However, they differed in both structural and functional parameters between the two layers, despite similar species composition. The species diversity, evenness, the colonization rate (G) and maximum abundance (Amax) were distinctly higher, but the time for reaching 90% equilibrium species number (T90%) was shorter at the depth of 1 m than those at a deeper layer. Results suggest that it is an optimal strategy to collect the ciliate communities within shorter exposure time at 1 m for ecological research and a monitoring programme in marine ecosystems.
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