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Using large scale molecular dynamics simulations, we study the thermal conductivity of bare and surface passivated silicon nanowires (SiNWs). For the cross-sectional widths $w \le 2$ nm, SiNWs become unstable because of the surface amorphosization and also due to the evaporation of a certain fraction of Si atoms. The observed surface (in-)stability is related to a large excess energy $\Delta$ of the surface Si atoms with respect to the bulk Si, resulting from the surface atoms being less coordinated and having dangling bonds.We first propose a practically relevant method that uses $\Delta$ as a guiding tool to passivate these dangling bonds with hydrogen or oxygen, stabilizing the SiNWs. These passivated SiNWs are used to calculate the thermal conductivity coefficient $\kappa$.While the expected trend of $\kappa \propto w$ is observed for all SiNWs, surface passivation provides an added flexibility of tuning $\kappa$ with the surface coverage concentration $c$ of passivated atoms.Indeed, with respect to the bulk $\kappa$, passivation of SiNW reduces $\kappa$ by 75-80\% for $c \to 50\%$ and recovers again by 50\% for the fully passivated samples. Analyzing the phonon band structures via spectral energy density, we discuss separate contributions from the surface and the core to $\kappa$. Our results also reveal that surface passivation increases SiNW stiffness, contributing to the tunability in $\kappa$.

Aneurysms are localized bulges of arteries, and they can rupture with fatal consequences. Complex mechanobiological factors preclude in vivo testing to assess the rupture risk of an aneurysm, and size based criteria are often used in clinical practice to guide surgical interventions. It is often found that tortuous and buckled aneurysms can exceed in size recommended for surgical intervention, and yet do not rupture. This study addresses why buckled aneurysms exhibit this intriguing behaviour by combining in vitro inflation experiments on hyperelastic tubes with finite element calculations. Using a biologically relevant material model for an arterial wall, we show that buckled aneurysms can grow in size without rupturing under favourable arterial pre-tensions. Stretch reversal phenomenon exhibited by arteries governs whether buckling or bulging occurs first. Exponential stiffening favours the axial propagation of an aneurysm instead of radial growth in size. The choice of failure criteria based on Ogden's strain energy function, Gent's first stretch invariant, and Cauchy stress are discussed. Failure maps incorporating post bifurcation (bulging and buckling) response are constructed to delineate the regimes of growth, buckling and rupture of an aneurysm.

Acoustic phonons play a special role in lattice heat transport, and confining these low-energy modes in low-dimensional materials may enable nontrivial transport phenomena. By applying lowest-order anharmonic perturbation theory to an atomistic model of a carbon nanotube, we investigate numerically and analytically the spectrum of three-phonon scattering channels in which at least one phonon is of low energy. Our calculations show that acoustic longitudinal (LA), flexural (FA), and twisting (TW) modes in nanotubes exhibit a distinct dissipative behavior in the long-wavelength limit, $|k| \rightarrow 0$, which manifests itself in scattering rates that scale as $\Gamma_{\rm{LA}}\sim |k|^{-1/2}$, $\Gamma_{\rm{FA}}\sim k^0$, and $\Gamma_{\rm{TW}}\sim |k|^{1/2}$. These scaling relations are a consequence of the harmonic lattice approximation and critically depend on the condition that tubes are free of mechanical strain. In this regard, we show that small amounts of tensile lattice strain $\epsilon$ reduce the strength of anharmonic scattering, resulting in strain-modulated rates that, in the long-wavelength limit, obey $\Gamma \sim \epsilon^{r} |k|^{s}$ with $r\leq 0$ and $s\geq 1$, irrespectively of acoustic mode polarization. Under the single-mode relaxation time approximation of the linearized Peierls-Boltzmann equation (PBE), the long-tube limit of lattice thermal conductivity in stress-free and stretched tube configurations can be unambiguously characterized. Going beyond relaxation time approximations, analytical results obtained in the present study may help to benchmark numerical routines which aim at deriving the thermal conductivity of nanotubes from an exact solution of the PBE.

Mechanical instability in a pre-tensioned finite hyperelastic tube subjected to a slowly increasing internal pressure produces a spatially localized bulge at a critical pressure. The subsequent fate of the bulge, under continued inflation, is critically governed by the end-conditions, and the initial tension in the tube. In a tube with one end fixed and a dead weight attached to the other freely moving end, the bulge propagates axially at low initial tension, growing in length and the tube relaxes by extension. Rupture occurs when the tension is high. In contrast, the bulge formed in a tube, initially stretched and held fixed at both its ends can buckle or rupture, depending on the amount of initial tension. Experiments on inflated latex rubber tubes are presented for different initial tensions and boundary conditions. Failure maps in the stretch parameter space and in stretch-tension space are constructed, by extending the theories for bulge formation and buckling analyses to the experimentally relevant boundary conditions. The fate of the bulge according to the failure maps deduced from the theory is verified; the underlying assumptions are critically assessed. It is concluded that buckling provides an alternate route to relieve the stress built up during inflation. Hence buckling, when it occurs, is a protective fail safe mechanism against the rupture of a bulge in an inflated elastic tube.

The application of a polymer brush in sensing, actuation, self-folding, among others acutely depends on the tuneable bending of a brush-grafted substrate caused by the stress in the brush. However, the stress in a stimuli-responsive brush has not been investigated. In this work, we study the stress in the stimuli-responsive planar polymer brushes of neutral water-soluble polymers with low to very high graft densities using strong stretching theory (SST). First, SST with the Langevin force-extension relation for a polymer chain is extended to the study of stimuli-responsive brushes. Stress profile and other properties of a Poly(N-isopropylacrylamide) (PNIPAm) brush are then obtained using the extended SST and an empirical Flory-Huggins parameter. The model predicts that the stress in a PNIPAm brush is inhomogeneous and compressive at all temperatures and graft densities. The resultant stress is predicted to increase in magnitude with increasing graft density. Moreover, it decreases in magnitude with an increase in temperature before plateauing in low graft density brushes. In contrast, its magnitude increases weakly with increasing temperature in high density brushes. This contrasting behavior is traced to the minimum in interaction free energy density \emph{vs} polymer volume fraction curve for PNIPAm solution at a large volume fraction, and stiffening of chains due to finite extensibility. Furthermore, our results indicate that the ability to tune the resultant stress by changing temperature diminishes with increasing graft density.

Heat propagation in quasi-one dimensional materials (Q1DMs) often appears paradoxical. While an isolated Q1DM, such as a nanowire, carbon nanotube, or polymer, can exhibit a high thermal conductivity \k{appa}, forests of the same materials show a reduction in \k{appa}. Here, the complex structures of these assemblies have hindered the emergence of a clear molecular picture of this intriguing phenomenon. We combine multiscale (coarse-grained) simulation with the concepts known from polymer physics and thermal transport to unveil a generic (microscopic) picture of \k{appa} reduction in molecular forests. We show that a delicate balance between the bond orientations, the persistence length of the Q1DM and the flexural vibrations govern the knock-down of \k{appa}.

In this article, we address lattice heat transport in single-walled carbon nanotubes (CNTs) by a quantum mechanical calculation of three-phonon scattering rates in the framework of the Boltzmann transport equation (BTE) and classical molecular dynamics (MD) simulation. Under a consistent choice of an empirical, realistic atomic interaction potential, we compare the tube length dependence of the lattice thermal conductivity (TC) at room temperature determined from an iterative solution of the BTE and from a nonequilibrium MD (NEMD) approach. Qualitatively similar trends are found in the limit of short tubes, where an extensive regime of ballistic heat transport prevailing in CNTs of lengths $L\lesssim 1\,\rm{\mu m}$ is independently confirmed. In the limit of long tubes, the BTE approach suggests a saturation of TC with tube length, whereas direct NEMD simulations of tubes extending up to $L=10\,\rm{\mu m}$ are demonstrated to be insufficient to settle the question of whether a fully diffusive heat transport regime and an intrinsic value of TC exist for CNTs. Noting that acoustic phonon lifetimes lie at the heart of a saturation of TC with tube length as per the BTE framework, we complement the quantum mechanical prediction of acoustic phonon lifetimes with an analysis of phonon modes in the framework of equilibrium MD (EMD). A normal mode analysis (NMA) with an emphasis on long wavelength acoustic modes corroborates the BTE prediction that heat transport in CNTs in the long tube limit is governed by the low attenuation rates of longitudinal and twisting phonons.

We study the stress distribution in a polymer brush material over a range of graft densities using molecular dynamics (MD) simulations and theory. Flexible polymer chains are treated as beads connected by nonlinear springs governed by a modified finitely extensible nonlinear elastic (FENE) potential in MD simulations. Simulations confirmed the quartic variation of the normal stress parallel to the substrate, within the bulk of the brush, as predicted in our previous work, for low graft densities. However, in the high graft density regime, the Gaussian chain elasticity assumption is violated by finite extensibility effects (force-extension divergence) and the restriction to binary interaction among monomers is insufficient. This motivated us to extend a semi-analytical strong stretching mean field theory (SST) for polymer brushes, based on Langevin chains and a modified Carnahan-Starling equation of state to model monomer interactions. Our extended theory elucidates the stress and monomer density profiles obtained from MD simulations, as well as reproduces Gaussian chain results for small graft densities. A good agreement is observed between predictions of MD and Langevin chain SST for monomer density profile, end density profile and stress profile in high graft density regime, without fitting parameters (virial coefficients). Quantitative comparisons of MD results with various available theories suggest that excluded volume correlations may be important.

Brush-like structures emerge from stretching of long polymer chains, densely grafted on to the surface of an impermeable substrate. They arise due to the competition between conformational entropic elasticity of polymer chains and excluded volume interactions from the intra and interchain monomer repulsions. Recently, stimuli responsive polymer brush based soft materials have been developed to produce controllable and reversible large deformations of the host substrate. To understand these systems, and improve their functional properties, we study elastic stress distribution and surface stress-curvature relations of a neutral polymer brush grafted on to an elastic beam, made of a soft material. In the strongly stretched brush regime, we combine mean field theory from polymer physics with a continuum mechanics model and show that the residual stress variation is a quartic function of distance from the grafting surface, with maximum stress occurring at the grafted surface. Idealizing the brush as a continuum elastic surface layer with residual stress, we derive a closed form expression for surface stress and the surface elasticity of the layer as a function of brush parameters, such as graft density and molecular weight. The generalized continuum beam model accounts for the Young-Laplace and Ogden-Steigman curvature elasticity correction terms, and yields a surface stress-curvature relation, which contains existing relations in the literature as special cases. Further, we report experiments on a thermoresponsive random copolymer brush, Poly(N- isopropylacrylamide)-co-Poly(N,N-Dimethylacrylamide) (PNIPAm-co-PDMA) brush, grafted on one side of a plasticized pPVC thin film. Estimated surface stress from measured curvature is on the order of $-10~N/m$, and it decreases gradually, and reversibly, with increasing ambient temperature from $15~^\circ{}C$ to $55~^\circ{}C$.

We study the interaction among dispersion, nonlinearity, and disorder effects in the context of wave transmission through a discrete periodic structure, subjected to continuous harmonic excitation in its stop band. We consider a damped nonlinear periodic structure of finite length with disorder. Disorder is introduced throughout the structure by small changes in the stiffness parameters drawn from a uniform statistical distribution. Dispersion effects forbid wave transmission within the stop band of the linear periodic structure. However, nonlinearity leads to supratransmission phenomenon, by which enhanced wave transmission occurs within the stop band of the periodic structure when forced at an amplitude exceeding a certain threshold. The frequency components of the transmitted waves lie within the pass band of the linear structure, where disorder is known to cause Anderson localization. There is therefore a competition between dispersion, nonlinearity, and disorder in the context of supratransmission. We show that supratransmission persists in the presence of disorder. The influence of disorder decreases in general as the forcing frequency moves away from the pass band edge, reminiscent of dispersion effects subsuming disorder effects in linear periodic structures. We compute the dependence of the supratransmission force threshold on nonlinearity and strength of coupling between units. We observe that nonlinear forces are confined to the driven unit for weakly coupled systems. This observation, together with the truncation of higher-order nonlinear terms, permits us to develop closed-form expressions for the supratransmission force threshold. In sum, in the frequency range studied here, disorder does not influence the supratransmission force threshold in the ensemble-average sense, but it does reduce the average transmitted wave energy., Comment: 29 pages, 25 figures