ABSTRACT
The microphase-separation of Langmuir-Blodgett (LB) monolayers of a rhodamine B (RhB) end-labeled double hydrophilic block copolymer (DHBC), RhB-Poly(N,N-dimethylacrylamide)-b-poly(N,N-diethylacryl-amide) (RhB-PDMA(207)b-PDEA177) and the 1:1 segmental mixture of PDEA and RhB-PDMA homopolymers was followed by AFM. The DHBC LB films revealed a loose distribution of nano-aggregates with variable geometries below the lower critical solution temperature (LCST) of PDEA (32 degrees C) and low surface pressure (3 mN m(-1)). By increasing either the temperature above the LCST of PDEA or the surface pressure beyond the immersion regime of PDMA in the subphase (7 mN m(-1)) a dense nanopatterning was obtained. The absence of a corresponding regular nanopatterning in LB films of mixed homopolymers with the same composition highlights the role of the covalent bonding between PDEA and PDMA on the self-segregation of the two blocks at the air-water interface.
Subject(s)
Membranes, Artificial , Microscopy, Atomic Force/methods , Nanostructures/chemistry , Nanostructures/ultrastructure , Polymethacrylic Acids/chemistry , Materials Testing , Particle Size , Surface Properties , TemperatureABSTRACT
The interfacial behavior of poly(isoprene-b-methyl methacrylate) diblock copolymers (PI-b-PMMA), with similar PMMA blocks but differing in the percentage of PI segments, SP19 (5% PI) and SP38 (52% PI), was studied at the air-water interface. The surface pressure-area (pi-A) isotherms, compression-expansion cycles, and relaxation curves were compared with those of the PMMA homopolymer. The short hydrophobic PI block of SP19 does not contribute to the mean molecular area at low surface pressures and yet has a negative contribution (condensing effect) when the surface pressure increases. On the contrary, the long PI block of SP38 contributes considerably to the surface area from low to high surface pressures. The A-t relaxation curves compare well with those of PMMA at low surface pressures (pi = 2 mN.m-1), but not at intermediate and high pressures (pi = 10, 30 mN.m-1), where a clear dependence on the length of the PI block was observed. The quantitative analysis of the relaxation curves at high pressures shows both a fast and slow component, attributed mostly to the local and middle-to-long-range reorganization of PMMA chains, respectively. PI-b-PMMA diblocks and PMMA were further blended with PS. The PS and PMMA are immiscible at the air-water interface. The addition of PS does not change the pi-A isotherm of PMMA, but the copolymers blended with PS form films that are more condensed at low pressures. The Langmuir-Blodgett (LB) films transferred onto mica substrates were analyzed by atomic force microscopy (AFM). The LB films of single diblocks are uniform, while those of PI-b-PMMA and PMMA blended with PS show aggregates with variable patterns.
