A model for the degradation of polyimides due to oxidation

Polyimides, due to their superior mechanical behavior at high temperatures, are used in a variety of applications that include aerospace, automobile and electronic packaging industries, as matrices for composites, as adhesives etc. In this paper, we extend our previous model in [S. Karra, K. R. Rajagopal, Modeling the non-linear viscoelastic response of high temperature polyimides, Mechanics of Materials, In press, doi:10.1016/j.mechmat.2010.09.006], to include oxidative degradation of these high temperature polyimides. Appropriate forms for the Helmholtz potential and the rate of dissipation are chosen to describe the degradation. The results for a specific boundary value problem, using our model compares well with the experimental creep data for PMR-15 resin that is aged in air.Comment: 13 pages, 2 figures, submitted to Mechanics of Time-dependent Material

A thermodynamic framework to develop rate-type models for fluids without instantaneous elasticity

In this paper, we apply the thermodynamic framework recently put into place by Rajagopal and co-workers, to develop rate-type models for viscoelastic fluids which do not possess instantaneous elasticity. To illustrate the capabilities of such models we make a specific choice for the specific Helmholtz potential and the rate of dissipation and consider the creep and stress relaxation response associated with the model. Given specific forms for the Helmholtz potential and the rate of dissipation, the rate of dissipation is maximized with the constraint that the difference between the stress power and the rate of change of Helmholtz potential is equal to the rate of dissipation and any other constraint that may be applicable such as incompressibility. We show that the model that is developed exhibits fluid-like characteristics and is incapable of instantaneous elastic response. It also includes Maxwell-like and Kelvin-Voigt-like viscoelastic materials (when certain material moduli take special values).Comment: 18 pages, 5 figure

Electromagnetic response of a static vortex line in a type-II superconductor : a microscopic study

The electromagnetic response of a pinned Abrikosov fluxoid is examined in the framework of the Bogoliubov-de Gennes formalism. The matrix elements and the selection rules for both the single photon (emission - absorption) and two photon (Raman scattering) processes are obtained. The results reveal striking asymmetries: light absorption by quasiparticle pair creation or single quasiparticle scattering can occur only if the handedness of the incident radiation is opposite to that of the vortex core states. We show how these effects will lead to nonreciprocal circular birefringence, and also predict structure in the frequency dependence of conductivity and in the differential cross section of the Raman scattering.Comment: 14 pages (RevTex

Development of three dimensional constitutive theories based on lower dimensional experimental data

Most three dimensional constitutive relations that have been developed to describe the behavior of bodies are correlated against one dimensional and two dimensional experiments. What is usually lost sight of is the fact that infinity of such three dimensional models may be able to explain these experiments that are lower dimensional. Recently, the notion of maximization of the rate of entropy production has been used to obtain constitutive relations based on the choice of the stored energy and rate of entropy production, etc. In this paper we show different choices for the manner in which the body stores energy and dissipates energy and satisfies the requirement of maximization of the rate of entropy production that leads to many three dimensional models. All of these models, in one dimension, reduce to the model proposed by Burgers to describe the viscoelastic behavior of bodies.Comment: 23 pages, 6 figure

Diabetes causes marked inhibition of mitochondrial metabolism in pancreatic β-cells

Diabetes is a global health problem caused primarily by the inability of pancreatic β-cells to secrete adequate levels of insulin. The molecular mechanisms underlying the progressive failure of β-cells to respond to glucose in type-2 diabetes remain unresolved. Using a combination of transcriptomics and proteomics, we find significant dysregulation of major metabolic pathways in islets of diabetic βV59M mice, a non-obese, eulipidaemic diabetes model. Multiple genes/proteins involved in glycolysis/gluconeogenesis are upregulated, whereas those involved in oxidative phosphorylation are downregulated. In isolated islets, glucose-induced increases in NADH and ATP are impaired and both oxidative and glycolytic glucose metabolism are reduced. INS-1 β-cells cultured chronically at high glucose show similar changes in protein expression and reduced glucose-stimulated oxygen consumption: targeted metabolomics reveals impaired metabolism. These data indicate hyperglycaemia induces metabolic changes in β-cells that markedly reduce mitochondrial metabolism and ATP synthesis. We propose this underlies the progressive failure of β-cells in diabetes.Peer reviewe

Nonequilibrium Quantum Dynamics of Second Order Phase Transitions

We use the so-called Liouville-von Neumann (LvN) approach to study the nonequilibrium quantum dynamics of time-dependent second order phase transitions. The LvN approach is a canonical method that unifies the functional Schr\"{o}dinger equation for the quantum evolution of pure states and the LvN equation for the quantum description of mixed states of either equilibrium or nonequilibrium. As nonequilibrium quantum mechanical systems we study a time-dependent harmonic and an anharmonic oscillator and find the exact Fock space and density operator for the harmonic oscillator and the nonperturbative Gaussian Fock space and density operator for the anharmonic oscillator. The density matrix and the coherent, thermal and coherent-thermal states are found in terms of their classical solutions, for which the effective Hamiltonians and equations of motion are derived. The LvN approach is further extended to quantum fields undergoing time-dependent second order phase transitions. We study an exactly solvable model with a finite smooth quench and find the two-point correlation functions. Due to the spinodal instability of long wavelength modes the two-point correlation functions lead to the $t^{1/4}$-scaling relation during the quench and the Cahn-Allen scaling relation $t^{1/2}$ after the completion of quench. Further, after the finite quench the domain formation shows a time-lag behavior at the cubic power of quench period. Finally we study the time-dependent phase transition of a self-interacting scalar field.Comment: discussion on back-reaction added, typos corrected, references added, final version for PR

Defect Formation and Critical Dynamics in the Early Universe

We study the nonequilibrium dynamics leading to the formation of topological defects in a symmetry-breaking phase transition of a quantum scalar field with \lambda\Phi^4 self-interaction in a spatially flat, radiation-dominated Friedmann-Robertson-Walker Universe. The quantum field is initially in a finite-temperature symmetry-restored state and the phase transition develops as the Universe expands and cools. We present a first-principles, microscopic approach in which the nonperturbative, nonequilibrium dynamics of the quantum field is derived from the two-loop, two-particle-irreducible closed-time-path effective action. We numerically solve the dynamical equations for the two-point function and we identify signatures of topological defects in the infrared portion of the momentum-space power spectrum. We find that the density of topological defects formed after the phase transition scales as a power law with the expansion rate of the Universe. We calculate the equilibrium critical exponents of the correlation length and relaxation time for this model and show that the power law exponent of the defect density, for both overdamped and underdamped evolution, is in good agreement with the "freeze-out" scenario of Zurek. We introduce an analytic dynamical model, valid near the critical point, that exhibits the same power law scaling of the defect density with the quench rate. By incorporating the realistic quench of the expanding Universe, our approach illuminates the dynamical mechanisms important for topological defect formation. The observed power law scaling of the defect density with the quench rate, observered here in a quantum field theory context, provides evidence for the "freeze-out" scenario in three spatial dimensions.Comment: 31 pages, RevTex, 8 figures in EPS forma

Metal organic framework nanosheets in polymer composite materials for gas separation

[EN] Composites incorporating two-dimensional nanostructures within polymeric matrices have potential as functional components for several technologies, including gas separation. Prospectively, employing metal-organic frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of freestanding nanosheets has proved challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometre lateral dimensions and nanometre thickness. Incorporating MOF nanosheets into polymer matrices endows the resultant composites with outstanding CO2 separation performance from CO2/CH4 gas mixtures, together with an unusual and highly desired increase in the separation selectivity with pressure. As revealed by tomographic focused ion beam scanning electron microscopy, the unique separation behaviour stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared with isotropic crystals, which improves the efficiency of molecular discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications.The research leading to these results has received funding (J.G., B.S.) from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 335746, CrystEng-MOF-MMM. T.R. is grateful to TUDelft for funding. G.P. acknowledges the A. von Humboldt Foundation for a research grant. A.C., I.L. and F.X.L.i.X. thank Consolider-Ingenio 2010 (project MULTICAT) and the ‘Severo Ochoa’ programme for support. 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Counting defects in an instantaneous quench

The objective of this paper is to study the formation of defects in a non equilibrium second order phase transition by means of a numerical solution of the full dynamical equations, and to compare the results with theoretical predictions to be found in the literature. We simulate an instantaneous quench to zero temperature in a type II superconductor, measuring the actual density of defects and its theoretically expected value as a function of time. We also characterize quantitatively some aspects of the out of equilibrium phase transition.Comment: 19 pages, 9 figure