The effect of self-generated tension in the backbone of a bottle-brush (BB) macromolecule, adsorbed on an attractive surface, is studied by means of Molecular Dynamics simulations of a coarse-grained bead-spring model in the good solvent regime. The BB-molecule is modeled as a backbone chain of L beads, connected by breakable bonds and with side chains, tethered pairwise to each monomer of the backbone. Our investigation is focused on several key questions that determine the bond scission mechanism and the ensuing degradation kinetics: how are frequency of bond scission and self-induced tension distributed along the BB-backbone at different grafting density σg of the side chains? How does tension f depend on the length of the side chains N , and on the strength of surface adhesion ǫs? We examine the monomer density distribution profiles across the BB-backbone at different ǫs and relate it to adsorption-induced morphological changes of the macromolecule whereby side chains partially desorb while the remaining chains spread better on the surface. Our simulation data are found to be in qualitative agreement with experimental results and recent theoretical predictions. Yet we demonstrate that the interval of parameter values where these predictions hold is limited in N . Thus, at high values of ǫs, too long side chains mutually block each other and freeze effectively the bottle-brush molecule.
International audienceThe paper presents the results of the application of large-eddy simulation (LES) to turbulent channel flow with a varying pressure gradient obtained by an appropriately specified shape of one of the walls. The main objective of the paper is to assess various subgrid scale (SGS) models implemented in two different codes as well as to assess the sensitivity of the predictive accuracy to grid resolution. Additionally, the role of SGS viscosity, controlled by a constant parameter of the SGS model, was investigated. The simulations were performed with inlet conditions corresponding to two Reynolds numbers: and . The consistency and the accuracy of simulations are evaluated using direct numerical simulation (DNS) results. It is demonstrated that all SGS models require a comparable minimum grid refinement in order to capture accurately the recirculation region. Such a test case with a reversal flow, where the turbulence transport is dictated by the dynamics of the large-scale eddies, is well suited to demonstrate the predictive features of the LES technique
The scission kinetics of bottle‐brush molecules in solution and on an adhesive substrate is modeled by means of Molecular Dynamics simulation with Langevin thermostat. Our macromolecules comprise a long flexible polymer backbone with L segments, consisting of breakable bonds, along with two side chains of length N, tethered to segments of the backbone with grafting density σg. In agreement with recent experiments and theoretical predictions, we find that bond cleavage is significantly enhanced on a strongly attractive substrate even though the chemical nature of the bonds remains thereby unchanged. Our simulation results indicate that the mean life time $\langle \tau \rangle $ of covalent bonds decreases by more than an order of magnitude upon adsorption even for brush molecules with comparatively short side chains $N = 1 \div 4$. The distribution of scission probability along the bonds of the backbone is found to change significantly when the length and/or the grafting density of the side chains are varied. The tension, experienced by the covalent bonds is found to grow steadily with increasing σg. The mean life time $\langle \tau \rangle $ declines with growing contour length L as $\langle \tau \rangle {\propto} L^{- 0.17} $, and also with growing side chain length N. The probability distribution of fragment lengths at different times is compatible with experimental observations and reveals a two‐stage (initially fast, then slow) process with different rates. The variation of the mean length L(t) of the fragments with elapsed time characterizes the thermal degradation process as a first order reaction.
We present molecular dynamics study of a generic (coarse-grained) model for single-polymer diffusion confined in a corrugated cylinder. For a narrow tube, i.e., diameter of the cylinder δ < 2.3, the axial diffusion coefficient D(∣∣) scales as D(∣∣) ∝ N(-3∕2), with chain length N, up to N ≈ 100 and then crosses over to Rouse scaling for the larger N values. The N(-3∕2) scaling is due to the large fluctuation of the polymer chain along its fully stretched equilibrium conformation. The stronger scaling, namely N(-3∕2), is not observed for an atomistically smooth tube and/or for a cylinder with larger diameter.
In the present work, the combustion of vitiated hydrogen jets issuing from differently shaped nozzles is modelled using the LES method. We investigate the impact of nozzle cross-sectional geometries (circular, square, triangular, hexagonal and hexagram) and the jet Reynolds numbers (Re= 18,000, 20,000 and 23,600) on the flame lift-off height, its structure, the locations of the temperature maxima and species distributions. The triangular nozzle yields the highest mixing rate and therefore the fastest decay of axial velocity and the fastest growth of the average temperature along the flame axis. It was found that for the largest Re, the zone of intense mixing and the reaction zone occur in distinct regions, while for the lower Re, these regions combine into an indistinguishable zone. Finally, it is shown that the lift-off height of the flames and the mean temperature field are non-linearly correlated with Re and strongly dependent on the nozzle shape.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.