RESUMEN
Small angle x-ray scattering experiments on three model low molar mass diblock copolymer systems containing minority polylactide and majority hydrocarbon blocks demonstrate that conformational asymmetry stabilizes the Frank-Kasper σ phase. Differences in block flexibility compete with space filling at constant density inducing the formation of polyhedral shaped particles that assemble into this low symmetry ordered state with local tetrahedral coordination. These results confirm predictions from self-consistent field theory that establish the origins of symmetry breaking in the ordering of block polymer melts subjected to compositional and conformational asymmetry.
RESUMEN
We report the discovery of a dodecagonal quasicrystalline state (DDQC) in a sphere (micelle) forming poly(isoprene-b-lactide) (IL) diblock copolymer melt, investigated as a function of time following rapid cooling from above the order-disorder transition temperature (TODT = 66 °C) using small-angle X-ray scattering (SAXS) measurements. Between TODT and the order-order transition temperature TOOT = 42 °C, an equilibrium body-centered cubic (BCC) structure forms, whereas below TOOT the Frank-Kasper σ phase is the stable morphology. At T < 40 °C the supercooled disordered state evolves into a metastable DDQC that transforms with time to the σ phase. The times required to form the DDQC and σ phases are strongly temperature dependent, requiring several hours and about 2 d at 35 °C and more than 10 and 200 d at 25 °C, respectively. Remarkably, the DDQC forms only from the supercooled disordered state, whereas the σ phase grows directly when the BCC phase is cooled below TOOT and vice versa upon heating. A transition in the rapidly supercooled disordered material, from an ergodic liquid-like arrangement of particles to a nonergodic soft glassy-like solid, occurs below â¼40 °C, coincident with the temperature associated with the formation of the DDQC. We speculate that this stiffening reflects the development of particle clusters with local tetrahedral or icosahedral symmetry that seed growth of the temporally transient DDQC state. This work highlights extraordinary opportunities to uncover the origins and stability of aperiodic order in condensed matter using model block polymers.
RESUMEN
We have systematically studied the equilibrium structure and dynamics of a polymeric bicontinuous microemulsion (BµE) composed of poly(cyclohexylethylene) (PCHE), poly(ethylene) (PE), and a volumetrically symmetric PCHE-PE diblock copolymer, using dynamic mechanical spectroscopy, small angle X-ray and neutron scattering, and transmission electron microscopy. The BµE was investigated over an 80 °C temperature range, revealing a structural evolution and a rheological response not previously recognized in such systems. As the temperature is reduced below the point associated with the lamellar-disorder transition at compositions adjacent to the microemulsion channel, the interfacial area per chain of the BµE approaches that of the neat (undiluted) lamellar diblock copolymer. With increasing temperature, the diblock-rich interface swells through homopolymer infiltration. Time-temperature-superposed linear dynamic data obtained as a function of frequency show that the viscoelastic response of the BµE is strikingly similar to that of the fluctuating pure diblock copolymer in the disordered state, which we associate with membrane undulations and the breaking and reforming of interfaces. This work provides new insights into the structure and dynamics that characterize thermodynamically stable BµEs in the limits of relatively weak and strong segregation.
RESUMEN
Rheological evidence of composition fluctuations in disordered diblock copolymers near the order-disorder transition (ODT) has been documented in the literature over the past three decades, characterized by a failure of time-temperature superposition (tTS) to reduce linear dynamic mechanical spectroscopy (DMS) data in the terminal viscoelastic regime to a temperature-independent form. However, for some materials, most notably poly(styrene-b-isoprene) (PS-PI), no signature of these rheological features has been found. We present small-angle X-ray scattering (SAXS) results on symmetric poly(cyclohexylethylene-b-ethylene) (PCHE-PE) diblock copolymers that confirm the presence of fluctuations in the disordered state and DMS measurements that also show no sign of the features ascribed to composition fluctuations. Assessment of DMS results published on five different diblock copolymer systems leads us to conclude that the effects of composition fluctuations can be masked by highly asymmetric block dynamics, thereby resolving a long-standing disagreement in the literature and reinforcing the importance of mechanical contrast in understanding the dynamics of ordered and disordered block polymers.
RESUMEN
We have systematically mapped the phase behavior of a series of symmetric CE/C/E ternary copolymer/homopolymer mixtures, where C is poly(cyclohexylethylene) and E is poly(ethylene), identifying the location in composition of the technologically important bicontinuous microemulsion (BµE) channel as a function of diblock molecular weight. The lamellar-to-disorder transition, characterized by dynamic mechanical spectroscopy, small-angle X-ray scattering, and optical transmission measurements, exhibits increasingly second-order behavior as the BµE state is approached with increasing homopolymer content. Real-space transmission electron microscopy images obtained from rapidly frozen specimens evidence the development of large-scale fluctuating smectic correlations in the disordered state as the order-disorder transition is approached. This discovery provides fresh insights into the unexplained role of fluctuations in the formation of the BµE in ternary mixtures formed from binary blends of homopolymers that display an Ising-like critical point and a symmetric diblock copolymer governed by a weak, fluctuation-induced, first-order phase transition.