Surface functionalization on the thermal conductivity of graphene–polymer nanocomposites

Exploring thermal transport in graphene-polymer nanocomposite is significant to its applications with better thermal properties. Interfacial thermal conductance between graphene and polymer matrix plays a critical role in the improvement of thermal conductivity of graphene-polymer nanocomposite. Unfortunately, it is still challenging to understand the interfacial thermal transport between graphene nanofiller and polymer matrix at small material length scale. To this end, using non-equilibrium molecular dynamics simulations, we investigate the interfacial thermal conductance of graphene-polyethylene (PE) nanocomposite. The influence of functionalization with hydrocarbon chains on the interfacial thermal conductance of graphene-polymer nanocomposites was studied, taking into account of the effects of model size and thermal conductivity of graphene. An analytical model is also used to calculate the thermal conductivity of nanocomposite. The results are considered to contribute to development of new graphene-polymer nanocomposites with tailored thermal properties.

Entropic bounds for multi-scale and multi-physics coupling in earth sciences

The ability to understand and predict how thermal, hydrological,mechanical and chemical (THMC) processes interact is fundamental to many research initiatives and industrial applications. We present (1) a new Thermal– Hydrological–Mechanical–Chemical (THMC) coupling formulation, based on non-equilibrium thermodynamics; (2) show how THMC feedback is incorporated in the thermodynamic approach; (3) suggest a unifying thermodynamic framework for multi-scaling; and (4) formulate a new rationale for assessing upper and lower bounds of dissipation for THMC processes. The technique is based on deducing time and length scales suitable for separating processes using a macroscopic finite time thermodynamic approach. We show that if the time and length scales are suitably chosen, the calculation of entropic bounds can be used to describe three different types of material and process uncertainties: geometric uncertainties,stemming from the microstructure; process uncertainty, stemming from the correct derivation of the constitutive behavior; and uncertainties in time evolution, stemming from the path dependence of the time integration of the irreversible entropy production. Although the approach is specifically formulated here for THMC coupling we suggest that it has a much broader applicability. In a general sense it consists of finding the entropic bounds of the dissipation defined by the product of thermodynamic force times thermodynamic flux which in material sciences corresponds to generalized stress and generalized strain rates, respectively.

Two-scale computational modelling of unsaturated flow in soils exhibiting small scale heterogeneities

Unsaturated water flow in soil is commonly modelled using Richards’ equation, which requires the hydraulic properties of the soil (e.g., porosity, hydraulic conductivity, etc.) to be characterised. Naturally occurring soils, however, are heterogeneous in nature, that is, they are composed of a number of interwoven homogeneous soils each with their own set of hydraulic properties. When the length scale of these soil heterogeneities is small, numerical solution of Richards’ equation is computationally impractical due to the immense effort and refinement required to mesh the actual heterogeneous geometry. A classic way forward is to use a macroscopic model, where the heterogeneous medium is replaced with a fictitious homogeneous medium, which attempts to give the average flow behaviour at the macroscopic scale (i.e., at a scale much larger than the scale of the heterogeneities). Using the homogenisation theory, a macroscopic equation can be derived that takes the form of Richards’ equation with effective parameters. A disadvantage of the macroscopic approach, however, is that it fails in cases when the assumption of local equilibrium does not hold. This limitation has seen the introduction of two-scale models that include at each point in the macroscopic domain an additional flow equation at the scale of the heterogeneities (microscopic scale). This report outlines a well-known two-scale model and contributes to the literature a number of important advances in its numerical implementation. These include the use of an unstructured control volume finite element method and image-based meshing techniques, that allow for irregular micro-scale geometries to be treated, and the use of an exponential time integration scheme that permits both scales to be resolved simultaneously in a completely coupled manner. Numerical comparisons against a classical macroscopic model confirm that only the two-scale model correctly captures the important features of the flow for a range of parameter values.

High pressure in situ diffraction studies of metal–hydrogen systems

“Hybrid” hydrogen storage, where hydrogen is stored in both the solid material and as a high pressure gas in the void volume of the tank can improve overall system efficiency by up to 50% compared to either compressed hydrogen or solid materials alone. Thermodynamically, high equilibrium hydrogen pressures in metal–hydrogen systems correspond to low enthalpies of hydrogen absorption–desorption. This decreases the calorimetric effects of the hydride formation–decomposition processes which can assist in achieving high rates of heat exchange during hydrogen loading—removing the bottleneck in achieving low charging times and improving overall hydrogen storage efficiency of large hydrogen stores. Two systems with hydrogenation enthalpies close to −20 kJ/mol H2 were studied to investigate the hydrogenation mechanism and kinetics: CeNi5–D2 and ZrFe2−xAlx (x = 0.02; 0.04; 0.20)–D2. The structure of the intermetallics and their hydrides were studied by in situ neutron powder diffraction at pressures up to 1000 bar and complementary X-ray diffraction. The deuteration of the hexagonal CeNi5 intermetallic resulted in CeNi5D6.3 with a volume expansion of 30.1%. Deuterium absorption filled three different types of interstices, Ce2Ni2 and Ni4 tetrahedra, and Ce2Ni3 half-octahedra and was accompanied by a valence change for Ce. Significant hysteresis was observed between deuterium absorption and desorption which profoundly decreased on a second absorption cycle. For the Al-modified Laves-type C15 ZrFe2−xAlx intermetallics, deuteration showed very fast kinetics of H/D exchange and resulted in a volume increase of the FCC unit cells of 23.5% for ZrFe1.98Al0.02D2.9(1). Deuterium content, hysteresis of H/D uptake and release, unit cell expansion and stability of the hydrides systematically change with the amount of Al content. In the deuteride D atoms exclusively occupy the Zr2(Fe,Al)2 tetrahedra. Observed interatomic distances are Zr–D = 1.98–2.11; (Fe, Al)–D = 1.70–1.75A˚ . Hydrogenation slightly increases the magnetic moment of the Fe atoms in ZrFe1.98Al0.02 and ZrFe1.96Al0.04 from 1.9 �B at room temperature for the alloy to 2.2 �B for its deuteride.

Energy-based motion control of marine vehicles using interconnection and damping assignment passivity-based control : a survey

This paper reviews some recent results in motion control of marine vehicles using a technique called Interconnection and Damping Assignment Passivity-based Control (IDA-PBC). This approach to motion control exploits the fact that vehicle dynamics can be described in terms of energy storage, distribution, and dissipation, and that the stable equilibrium points of mechanical systems are those at which the potential energy attains a minima. The control forces are used to transform the closed-loop dynamics into a port-controlled Hamiltonian system with dissipation. This is achieved by shaping the energy-storing characteristics of the system, modifying its interconnection structure (how the energy is distributed), and injecting damping. The end result is that the closed-loop system presents a stable equilibrium (hopefully global) at the desired operating point. By forcing the closed-loop dynamics into a Hamiltonian form, the resulting total energy function of the system serves as a Lyapunov function that can be used to demonstrate stability. We consider the tracking and regulation of fully actuated unmanned underwater vehicles, its extension to under-actuated slender vehicles, and also manifold regulation of under-actuated surface vessels. The paper is concluded with an outlook on future research.

Non-linear refined finite element elastic analysis of steel frames with generalized transverse member loads

In the finite element modelling of steel frames, external loads usually act along the members rather than at the nodes only. Conventionally, when a member is subjected to these transverse loads, they are converted to nodal forces which act at the ends of the elements into which the member is discretised by either lumping or consistent nodal load approaches. For a contemporary geometrically non-linear analysis in which the axial force in the member is large, accurate solutions are achieved by discretising the member into many elements, which can produce unfavourable consequences on the efficacy of the method for analysing large steel frames. Herein, a numerical technique to include the transverse loading in the non-linear stiffness formulation for a single element is proposed, and which is able to predict the structural responses of steel frames involving the effects of first-order member loads as well as the second-order coupling effect between the transverse load and the axial force in the member. This allows for a minimal discretisation of a frame for second-order analysis. For those conventional analyses which do include transverse member loading, prescribed stiffness matrices must be used for the plethora of specific loading patterns encountered. This paper shows, however, that the principle of superposition can be applied to the equilibrium condition, so that the form of the stiffness matrix remains unchanged with only the magnitude of the loading being needed to be changed in the stiffness formulation. This novelty allows for a very useful generalised stiffness formulation for a single higher-order element with arbitrary transverse loading patterns to be formulated. The results are verified using analytical stability function studies, as well as with numerical results reported by independent researchers on several simple structural frames.

Total energy shaping of a class of underactuated Port-Hamiltonian Systems using a new set of closed-loop potential shape variables

This paper proposes a method for designing set-point regulation controllers for a class of underactuated mechanical systems in Port-Hamiltonian System (PHS) form. A new set of potential shape variables in closed loop is proposed, which can replace the set of open loop shape variables-the configuration variables that appear in the kinetic energy. With this choice, the closed-loop potential energy contains free functions of the new variables. By expressing the regulation objective in terms of these new potential shape variables, the desired equilibrium can be assigned and there is freedom to reshape the potential energy to achieve performance whilst maintaining the PHS form in closed loop. This complements contemporary results in the literature, which preserve the open-loop shape variables. As a case study, we consider a robotic manipulator mounted on a flexible base and compensate for the motion of the base while positioning the end effector with respect to the ground reference. We compare the proposed control strategy with special cases that correspond to other energy shaping strategies previously proposed in the literature.

Photoelectron spectroscopy of HCCN- and HCNC- reveals the quasilinear triplet carbenes, HCCN and HCNC

Negative ion photoelectron spectroscopy has been used to study the HCCN- and HCNC- ions. The electron affinities (EA) of cyanocarbene have been measured to be EA(HCCN (X) over tilde (3)Sigma(-)=2.003+/-0.014 eV and EA(DCCN (X) over tilde (3)Sigma(-))=2.009+/-0.020 eV. Photodetachment of HCCN- to HCCN (X) over tilde (3)Sigma(-) shows a 0.4 eV long vibrational progression in nu(5), the H-CCN bending mode; the HCCN- photoelectron spectra reveal excitations up to 10 quanta in nu(5). The term energies for the excited singlet state are found to be T-0(HCCN (a) over tilde (1)A('))=0.515+/-0.016 eV and T-0(DCCN (a) over tilde (1)A('))=0.518+/-0.027 eV. For the isocyanocarbene, the two lowest states switch and HCNC has a singlet ground state and an excited triplet state. The electron affinities are EA(HCNC (X) over tilde (1)A('))=1.883+/-0.013 eV and EA((X) over tilde (1)A(') DCNC)=1.877+/-0.010 eV. The term energy for the excited triplet state is T-0(HCNC (a) over tilde (3)A("))=0.050+/-0.028 eV and T-0(DCNC (a) over tilde (3)A("))=0.063+/-0.030 eV. Proton transfer kinetics in a flowing afterglow apparatus were used to re-measure the enthalpy of deprotonation of CH3NC to be Delta(acid)H(298)(CH3NC)=383.6+/-0.6 kcal mol(-1). The acidity/EA thermodynamic cycle was used to deduce D-0(H-CHCN)=104+/-2 kcal mol(-1) [Delta(f)H(0)(HCCN)=110+/-4 kcal mol(-1)] and D-0(H-CHNC)=106+/-4 kcal mol(-1) [Delta(f)H(0)(HCNC)=133+/-5 kcal mol(-1)]. (C) 2002 American Institute of Physics.

Implication of calcium hydroxide in the seawater neutralisation of bauxite refinery liquors

Tricalcium aluminate, hydrocalumite and residual lime have been identified as reversion contributing compounds after the seawater neutralisation of bauxite refinery residues. The formation of these compounds during the neutralisation process is dependent on the concentration of residual lime, pH and aluminate concentrations in the residue slurry. Therefore, the effect of calcium hydroxide (CaOH2) in bauxite refinery liquors was analysed and the degree of reversion monitored. This investigation found that the dissolution of tricalcium aluminate, hydrocalumite and CaOH2 caused reversion and continued to increase the pH of the neutralised residue until a state of equilibrium was reached at a solution pH of 10.5. The dissolution mechanism for each compound has been described and used to demonstrate the implications that this has on reversion in seawater neutralised Bayer liquor. This investigation describes the limiting factors for the dissolution and formation of these trigger compounds as well as confirming the formation of Bayer hydrotalcite (mixture of Mg6Al2(OH)16(CO32-,SO42-)•xH2O and Mg8Al2(OH)12(CO32-,SO42-)•xH2O) as the primary mechanism for reducing reversion during the neutralisation process. This knowledge then allowed for a simple but effective method (addition of magnesium chloride or increased seawater to Bayer liquor ratio) to be devised to reduce reversion occurring after the neutralisation of Bayer liquors. Both methods utilise the formation of Bayer hydrotalcite to permanently (stable in neutralised residue) remove hydroxyl (OH-) and aluminate (Al(OH)4-) ions from solution.

Dynamic modelling of long-term care decisions

This paper describes and analyzes research on the dynamics of long-term care and the policy relevance of identifying the sources of persistence in caregiving arrangements (including the effect of dynamics on parameter estimates, implications for family welfare, parent welfare, child welfare, and cost of government programs). We discuss sources and causes of observed persistence in caregiving arrangements including inertia/state dependence (confounded by unobserved heterogeneity) and costs of changing caregivers. We comment on causes of dynamics including learning/human capital accumulation; burnout; and game-playing. We suggest how to deal with endogenous geography; dynamics in discrete and continuous choices; and equilibrium issues (multiple equilibria, dynamic equilibria). We also present an overview of commonly used longitudinal data sets and evaluate their relative advantages/disadvantages. We also discuss other data issues related to noisy measures of wealth and family structure. Finally, we suggest some methods to handle econometric problems such as endogeneous geography. © 2014 Springer Science+Business Media New York.

Fertility choice, land, and the Malthusian hypothesis

In a standard overlapping generations growth model, with a fixed amount of land and endogenous fertility, the competitive economy converges to a steady state with a zero population growth rate and positive consumption per capita. The Malthusian hypothesis is interpreted as a positive statement about the relationship between population growth and consumption per-capita, when production exhibits diminishing returns to labor and there is a fixed amount of land essential for production. Even when individuals care only about the number of their children and not about their children's welfare, the equilibrium is such that they eventually would choose to have only one child for each adult. Hence, if Malthus's "positive check' on population is the result of the response of optimizing agents to competitively determined prices, Malthus's pessimistic conjecture is not necessarily true, even though his other assumptions hold. -from Authors

Formal home health care, informal care, and family decision making

We use the 1993 wave of the Assets and Health Dynamics Among the Oldest Old (AHEAD) data set to estimate a game-theoretic model of families' decisions concerning the provision of informal and formal care for elderly individuals. The outcome is the Nash equilibrium where each family member jointly determines her consumption, transfers for formal care, and allocation of time to informal care, market work, and leisure. We use the estimates to decompose the effects of adult children's opportunity costs, quality of care, and caregiving burden on their propensities to provide informal care. We also simulate the effects of a broad range of policies of current interest. © (2009) by the Economics Department of the University of Pennsylvania and the Osaka University Institute of Social and Economic Research Association.

Amplitude equations and asymptotic expansions for multi-scale problems

In this paper we introduce a new technique to obtain the slow-motion dynamics in nonequilibrium and singularly perturbed problems characterized by multiple scales. Our method is based on a straightforward asymptotic reduction of the order of the governing differential equation and leads to amplitude equations that describe the slowly-varying envelope variation of a uniformly valid asymptotic expansion. This may constitute a simpler and in certain cases a more general approach toward the derivation of asymptotic expansions, compared to other mainstream methods such as the method of Multiple Scales or Matched Asymptotic expansions because of its relation with the Renormalization Group. We illustrate our method with a number of singularly perturbed problems for ordinary and partial differential equations and recover certain results from the literature as special cases. © 2010 - IOS Press and the authors. All rights reserved.

Generalized azimuthal shear deformations in compressible isotropic elastic materials

In this article we study the azimuthal shear deformations in a compressible Isotropic elastic material. This class of deformations involves an azimuthal displacement as a function of the radial and axial coordinates. The equilibrium equations are formulated in terms of the Cauchy-Green strain tensors, which form an overdetermined system of partial differential equations for which solutions do not exist in general. By means of a Legendre transformation, necessary and sufficient conditions for the material to support this deformation are obtained explicitly, in the sense that every solution to the azimuthal equilibrium equation will satisfy the remaining two equations. Additionally, we show how these conditions are sufficient to support all currently known deformations that locally reduce to simple shear. These conditions are then expressed both in terms of the invariants of the Cauchy-Green strain and stretch tensors. Several classes of strain energy functions for which this deformation can be supported are studied. For certain boundary conditions, exact solutions to the equilibrium equations are obtained. © 2005 Society for Industrial and Applied Mathematics.

On helical shear of a compressible elastic circular cylindrical tube

In this paper we examine the combined azimuthal and axial shear of a compressible isotropic elastic circular cylindrical tube of finite extent, otherwise referred to as helical shear (which is an isochoric deformation). The equilibrium equations are formulated in terms of the principal stretches, and explicit necessary and sufficient conditions on the strain-energy function for the material to support this deformation are obtained and compared with those obtained previously for this problem. Several classes of strain-energy functions are derived and in some general cases complete solutions of the equilibrium equations are obtained. Existing results are recovered as special cases and some new results for the strain-energy functions derived are determined and discussed.