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Register a new userOrder-disorder transition and alignment dynamics of a block copolymer under high magnetic fields by in situ x-ray scattering
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We present results of temperature resolved scattering studies of a liquid crystalline block copolymer undergoing an order-disorder transition (ODT) in the presence of magnetic fields and time-resolved measurements during isothermal field annealing at sub-ODT temperatures. In each case, field interactions produced strongly textured mesophases with the cylindrical microdomains aligned parallel to the field. We find there is no measurable field-induced shift in the ODT temperature ($T_{ODT}$) which suggests that selective melting does not play a role in mesophase alignment during isothermal experiments. Our data indicate instead that sub-ODT alignment occurs by slow, large scale grain rotation whereas alignment during cooling from the disordered melt is rapid and driven by the nucleation of weakly ordered but preferentially aligned material. We identify an optimum sub-cooling that maximizes alignment during isothermal field annealing. This is corroborated by a simple model incorporating the competing effects of an exponentially decreasing mobility and divergent, increasing magnetic anisotropy on cooling below $T_{ODT}$. The absence of measurable field-effects on $T_{ODT}$ is consistent with rough estimates derived from the relative magnitudes of the free energy due to field interaction and the enthalpy of the isotropic-LC transition.
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Using dissipative particle dynamics (DPD) simulation method, we study the phase separation dynamics in block copolymer (BCP) melt in $d=3$, subjected to external stimuli such as light. An initial homogeneous BCP melt is rapidly quenched to a temperature $T < T_c$, where $T_c$ is the critical temperature. We then let the system go through alternate light on and off cycles. An on-cycle breaks the stimuli-sensitive bonds connecting both the blocks A and B in BCP melt, and during the off-cycle, broken bonds reconnect. By simulating the effect of light, we isolate scenarios where phase separation begins with the light off (set 1); the cooperative interactions within the system allow it to undergo microphase separation. When the phase separation starts with the light on (set 2), the system undergoes macrophase separation due to the bond breaking. Here, we report the role of alternate cycles on domain morphology by varying bond-breaking probability for both the sets 1 and 2, respectively. We observe that the scaling functions depend upon the conditions mentioned above that change the time scale of the evolving morphologies in various cycles. However, in all the cases, the average domain size respects the power-law growth: $R(t)sim t^{phi}$ at late times, here $phi$ is the dynamic growth exponent. After a short-lived diffusive growth ($phi sim 1/3$) at early times, $phi$ illustrates a crossover from the viscous hydrodynamic ($phi sim 1$) to the inertial hydrodynamic ($phi sim 2/3$) regimes at late times.
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