ABSTRACT
We have examined the spatial distributions of polymer chains in blend films of weakly segregated polystyrene-block-poly(methyl methacrylate) [P(S-b-MMA)] and deuterated polystyrene (dPS). By fine-tuning the composition (ÏPS+dPS = 63.8 vol %) of the total PS/dPS component and annealing temperature (230 and 270 °C), P(S-b-MMA)/dPS blend films mainly form perforated layers with a parallel orientation (hereafter PLs//). The distributions of dPS in PLs// were probed by grazing-incidence small-angle neutron scattering (GISANS) and time-of-flight neutron reflectivity (ToF-NR). GISANS and ToF-NR results offer evidence that dPS chains preferentially locate at the free surface and within the PS layers for blend films that were annealed at 230 °C. Upon annealing at 270 °C, dPS chains distribute within PS layers and perforated PMMA layers. Nevertheless, dPS chains still retain a surface preference for thin films. In contrast, such surface segregation of dPS chains is prohibited for thick films when annealed at 270 °C.
ABSTRACT
We have demonstrated the phase behavior of substrate-supported films of a symmetric weakly segregated polystyrene-block-poly (methyl methacrylate), P(S-b-MMA), block copolymer and its blends with homopolymer polystyrene (PS) at different compositions. Upon increasing the content of added PS in the blends, lamellae (L), perforated layers (PL), double gyroid (DG) and cylinders (C) are obtained in sequence for films. Among these nanodomains, PL and DG only exist in a narrow ÏPS region (ÏPS denotes the volume fraction of PS). At ÏPS = 64%, tuning film thickness and annealing temperature can produce parallel PL or DG with {121}DG lattice planes being parallel to the substrate surface. The effects of annealing temperature and film thickness on the formation of PL and DG are examined. In thin films with n ≈ 3 (n denotes the ratio of initial film thickness to inter-domain spacing), the PL phase solely exists regardless of temperature. However, for thick films with n ≈ 6 and 10, thermal annealing at the most accessible temperature produces films containing both PL and DG of various fractions, but a low temperature tends to favor a greater fraction of PL. The PL phase becomes the only discernible phase if thick films are shortly annealed at 230 °C.
ABSTRACT
We studied the influence of osmotic pressure on nanostructures in thin films of a symmetric weakly-segregated polystyrene-block-poly (methyl methacrylate), P(S-b-MMA), block copolymer and its mixtures with a polystyrene (PS) homopolymer of various compositions. Thin films were deposited on substrates through surface neutralization. The surface neutralization results from the PS mats, which were oxidized and cross-linked by UV-light exposure. Thus, thermal annealing produced perpendicularly oriented lamellae and perforated layers, depending on the content of added PS chains. Nevertheless, a mixed orientation was obtained from cylinders in thin films, where a high content of PS was blended with the P(S-b-MMA). A combination of UV-light exposure and acetic acid rinsing was used to remove the PMMA block. Interestingly, the treatment of PMMA removal inevitably produced osmotic pressure and consequently resulted in surface wrinkling of perpendicular lamellae. As a result, a hierarchical structure with two periodicities was obtained for wrinkled films with perpendicular lamellae. The formation of surface wrinkling is due to the interplay between UV-light exposure and acetic acid rinsing. UV-light exposure resulted in different mechanical properties between the skin and the inner region of a film. Acetic acid rinsing produced osmotic pressure. It was found that surface wrinkling could be suppressed by reducing film thickness, increasing PS content and using high-molecular-weight P(S-b-MMA) BCPs.
