Orientations of the lamellar phase of block copolymer melts under oscillatory shear flow

We develop a theory to describe the reorientation phenomena in the lamellar phase of block copolymer melt under reciprocating shear flow. We show that similar to the steady-shear, the oscillating flow anisotropically suppresses fluctuations and gives rise to the parallel-perpendicular orientation transition. The experimentally observed high-frequency reverse transition is explained in terms of interaction between the melt and the shear-cell walls.Comment: RevTex, 3 pages, 1 figure, submitted to PR

Dynamics of Polymers: a Mean-Field Theory

We derive a general mean-field theory of inhomogeneous polymer dynamics; a theory whose form has been speculated and widely applied, but not heretofore derived. Our approach involves a functional integral representation of a Martin-Siggia-Rose type description of the exact many-chain dynamics. A saddle point approximation to the generating functional, involving conditions where the MSR action is stationary with respect to a collective density field $\rho$ and a conjugate MSR response field $\phi$, produces the desired dynamical mean-field theory. Besides clarifying the proper structure of mean-field theory out of equilibrium, our results have implications for numerical studies of polymer dynamics involving hybrid particle-field simulation techniques such as the single-chain in mean-field method (SCMF)

Hydrodynamic Self-Consistent Field Theory for Inhomogeneous Polymer Melts

We introduce a mesoscale technique for simulating the structure and rheology of block copolymer melts and blends in hydrodynamic flows. The technique couples dynamic self consistent field theory (DSCFT) with continuum hydrodynamics and flow penalization to simulate polymeric fluid flows in channels of arbitrary geometry. We demonstrate the method by studying phase separation of an ABC triblock copolymer melt in a sub-micron channel with neutral wall wetting conditions. We find that surface wetting effects and shear effects compete, producing wall-perpendicular lamellae in the absence of flow, and wall-parallel lamellae in cases where the shear rate exceeds some critical Weissenberg number.Comment: Revised as per peer revie

Reliability considerations in the design, assembly, and testing of the mariner iv power system

Reliability considerations in design, assembly, and testing of Mariner IV power syste

Spin facilitated Ising model with long range interaction

We study the dynamics of a spin facilitated Ising model with long range kinetic constraints. To formulate those restrictions within an analytical approach we introduce the size of a kinetic active environment of a given spin. Based on a Master equation in second quantized form, the spin-autocorrelation function is calculated. It exhibits a pronounced slow dynamics, manifested by a logarithmic decay law of the spin-autocorrelation function. In case of an infinite kinetic interaction the mean field solution yields an asymptotic exact expression for the autocorrelation function which is in excellent agreement with Monte Carlo Simulations for finite interaction lengths. With increasing size of the active zone the cooperative processes, characterizing the facilitated model with short range kinetic interaction, become irrelevant. We demonstrate that the long range kinetic interaction dominates the actual spin configurations of the whole system and the mean field solution is the exact one.Comment: 18 pages, 5 figure

Microphase separation in polyelectrolytic diblock copolymer melt : weak segregation limit

We present a generalized theory of microphase separation for charged-neutral diblock copolymer melt. Stability limit of the disordered phase for salt-free melt has been calculated using Random Phase Approximation (RPA) and self-consistent field theory (SCFT). Explicit analytical free energy expressions for different classical ordered microstructures (lamellar, cylinder and sphere) are presented. We demonstrate that chemical mismatch required for the onset of microphase separation ($\chi^{\star} N$) in charged-neutral diblock melt is higher and the period of ordered microstructures is lower than those for the corresponding neutral-neutral diblock system. Theoretical predictions on the period of ordered structures in terms of Coulomb electrostatic interaction strength, chain length, block length, and the chemical mismatch between blocks are presented. SCFT has been used to go beyond the stability limit, where electrostatic potential and charge distribution are calculated self-consistently. Stability limits calculated using RPA are in perfect agreement with the corresponding SCFT calculations. Limiting laws for stability limit and the period of ordered structures are presented and comparisons are made with an earlier theory. Also, transition boundaries between different morphologies have been investigated

An external potential dynamic study on the formation of interface in polydisperse polymer blends

The formation of interface from an initial sharp interface in polydisperse A/B blends is studied using the external potential dynamic method. The present model is a nonlocal coupling model as we take into account the correlation between segments in a single chain. The correlation is approximately expressed by Debye function and the diffusion dynamics are based on the Rouse chain model. The chain length distribution is described by the continuous Schulz distribution. Our numerical calculation indicates that the broadening of interface with respect to time obeys a power law at early times, and the power law indexes are the same for both monodisperse and polydisperse blend. The power law index is larger than that in the local coupling model. However there is not a unified scaling form of the broadening of the interface width if only the interfacial width at equilibrium is taken into account as the characteristic length of the system, because the correlation makes an extra characteristic length in the system, and the polydispersity is related to this length.Comment: 15 pages, 5 figure

Reactions at polymer interfaces: A Monte Carlo Simulation

Reactions at a strongly segregated interface of a symmetric binary polymer blend are investigated via Monte Carlo simulations. End functionalized homopolymers of different species interact at the interface instantaneously and irreversibly to form diblock copolymers. The simulations, in the framework of the bond fluctuation model, determine the time dependence of the copolymer production in the initial and intermediate time regime for small reactant concentration $\rho_0 R_g^3=0.163 ... 0.0406$. The results are compared to recent theories and simulation data of a simple reaction diffusion model. For the reactant concentration accessible in the simulation, no linear growth of the copolymer density is found in the initial regime, and a $\sqrt{t}$-law is observed in the intermediate stage.Comment: to appear in Macromolecule

Effects of polydispersity on the phase coexistence diagrams in multiblock copolymers with Laser block length distribution

Phase behavior of AB-multiblock copolymer melts which consists of chains with Laser distribution of A and B blocks have been investigated in the framework of the mean-field theory, where the polydispersity of copolymer is a function of two parameters K and M. The influence of the Laser distribution on higher order correlation functions (up to sixth order) are computed for various values of K and M, and their contributions on the phase diagrams and phase coexistence are presented. It is shown that, with increasing polydispersity (decreasing K and increasing M) the transition lines of all phases shift upwards, consequently polydispersity destabilize the system.Comment: 15 pages, Late

Determination of complex dielectric functions of ion implanted and implanted‐annealed amorphous silicon by spectroscopic ellipsometry

Measuring with a spectroscopic ellipsometer (SE) in the 1.8–4.5 eV photon energy region we determined the complex dielectric function (ϵ = ϵ1 + iϵ2) of different kinds of amorphous silicon prepared by self‐implantation and thermal relaxation (500 °C, 3 h). These measurements show that the complex dielectric function (and thus the complex refractive index) of implanted a‐Si (i‐a‐Si) differs from that of relaxed (annealed) a‐Si (r‐a‐Si). Moreover, its ϵ differs from the ϵ of evaporated a‐Si (e‐a‐Si) found in the handbooks as ϵ for a‐Si. If we use this ϵ to evaluate SE measurements of ion implanted silicon then the fit is very poor. We deduced the optical band gap of these materials using the Davis–Mott plot based on the relation: (ϵ2E2)1/3 ∼ (E− Eg). The results are: 0.85 eV (i‐a‐Si), 1.12 eV (e‐a‐Si), 1.30 eV (r‐a‐Si). We attribute the optical change to annihilation of point defects