A reactive molecular dynamics model of thermal decomposition in polymers: I. Poly(methyl methacrylate)

The theory and implementation of reactive molecular dynamics (RMD) are presented. The capabilities of RMD and its potential use as a tool for investigating the mechanisms of thermal transformations in materials are demonstrated by presenting results from simulations of the thermal degradation of poly(methyl methacrylate) (PMMA). While it is known that depolymerization must be the major decomposition channel for PMMA, there are unanswered questions about the nature of the initiation reaction and the relative reactivities of the tertiary and primary radicals formed in the degradation process. The results of our RMD simulations, performed directly in the condensed phase, are consistent with available experimental information. They also provide new insights into the mechanism of the thermally induced conversion of this polymer into its constituent monomers.     

Growth of ZnSe∶Mn Nanocrystals from Vapour Phase

ZnSe∶Mn nanocrystals were grown by chemical vapour transport method using the matrix of SiO2 aerogels. The cubic structure of the nanocrystals was confirmed by powder X-ray diffraction (XRD) and electron diffraction (ED) studies. The size of the crystals was observed using transmission electron microscope (TEM). The oxidation state of Mn in ZnSe nanocrystal was found using electron spin resonance (ESR) spectrum. The room temperature luminescence measurements show the peaks corresponding to both bandgap of the material and Mn in ZnSe.     

Application of the blind source separation method to feature extraction of machine sound signals

As the result of vibration emission in air, a machine sound signal carries important information about the working condition of machinery. But in practice, the sound signal is typically received with a very low signal-to-noise ratio. To obtain features of the original sound signal, uncorrelated sound signals must be removed and the wavelet coefficients related to fault condition must be retrieved. In this paper, the blind source separation technique is used to recover the wavelet coefficients of a monitored source from complex observed signals. Since in the proposed blind source separation (BSS) algorithms it is generally assumed that the number of sources is known, the Gerschgorin disk estimator method is introduced to determine the number of sound sources before applying the BSS method. This method can estimate the number of sound sources under non-Gaussian and non-white noise conditions. Then, the partial singular value analysis method is used to select these significant observations for BSS analysis. This method ensures that signals are separated with the smallest distortion. Afterwards, the time-frequency separation algorithm, converted to a suitable BSS algorithm for the separation of a non-stationary signal, is introduced. The transfer channel between observations and sources and the wavelet coefficients of the source signals can be blindly identified via this algorithm. The reconstructed wavelet coefficients can be used for diagnosis. Finally, the separation results obtained from the observed signals recorded in a semi-anechoic chamber demonstrate the effectiveness of the presented methods .     

Magnetic Resonance Visualisation of Flow and Pore Structure in Packed Beds with Low Aspect Ratio

Different NMR techniques were combined to obtain the structure and velocity information for a systematic investigation of fixed beds with low aspect ratio (tube diameter to particle diamter, d_t/d_p) in the range 1.4 to 32. The structure of the void space was determined for a variety of packed beds of glass beads or regular and irregular porous pellets by magnetic resonance imaging (MRI). Based on the images the radial distribution of the voids within the bed was obtained. Ordering effects were found even for non‐spherical and polydisperse particles, and a maximum of the fluid density near the tube wall was confirmed for all pellet geometries and sizes. By combining MRI with velocity encoding, velocity profiles and distributions of flow velocity components of a single fluid phase through packed beds have been acquired. The radial velocity distribution follows an oscillatory pattern which largely reflects the ordering of the particles, which can be accessed from the density distribution of the interparticle fluid. Maximum velocities of up to four times the average value were found to occur near the tube wall. This wall effect was observed for all but the smallest particles, where the aspect ratio was d_t/d_p = 32. Moreover, a visualisation of flow pattern in the presence of packed particles was achieved by using a tagging technique, and the stationary flow field could be identified for an experimental time of several hours.     

An Electron Spin Resonance Study of Evolution of Organic Free Radicals in Irradiated Pepper During Heat Treatment

ABSTRACT: The thermal evolution behavior of the organic free radicals induced in irradiated black pepper was studied by electron spin resonance spectroscopy. To analyze the time-dependent evolution process, we used the theory of transient phenomena, that is, an ordinal differential equation, as well as the nonlinear least squares numerical method. We found that the radical evolution that occurred in the irradiated pepper obeys a single exponential function and yields a unique time constant. The evolution of the organic free radical undergoes a simple reaction process of a single radical species.     

Numerical simulation of substrate effects on spinodal decomposition in polymer binary mixture: Effects of the surface potential

The surface-directed spinodal decomposition (SDSD) of polymer binary mixture with different values of surface potential is numerically simulated in three-dimension (3D) by cell dynamic systems (CDS). Furthermore, the growth laws of the wetting layer are theoretically analyzed by the current equation and the dynamical scaling. The results show that the thickness of the wetting layer increases with the increasing surface potential. The crossover, which is later for larger values of surface potential, appears in the evolution curve of the wetting layer. Before the crossover, the growth law is the surface potential dependant growth law. Subsequently, the growth law is the typical Lifshitz-Slyozov (LS) growth law. The results indicate that the surface potential can result in the mutual transformation between completely wetting and partially wetting for the substrate interface. It can be found that the higher surface potential leads to the faster and stronger transmission of the effect of the substrate on the spinodal decomposition in the bulk.     

On transitive orientations with restricted covering graphs

We consider the problem of finding a transitive orientation of a comparability graph, such that the edge set of its covering graph contains a given subset of edges. We propose a solution which employs the classical technique of modular tree decomposition. The method leads to a polynomial time algorithm to construct such an orientation or report that it does not exist.     

Restricted overlapping balancing domain decomposition methods and restricted coarse problems for the Helmholtz problem

Overlapping balancing domain decomposition methods and their combination with restricted additive Schwarz methods are proposed for the Helmholtz equation. These new methods also extend previous work on non-overlapping balancing domain decomposition methods toward simplifying their coarse problems and local solvers. They also extend restricted Schwarz methods, originally designed to overlapping domain decomposition and Dirichlet local solvers, to the case of non-overlapping domain decomposition and/or Neumann and Sommerfeld local solvers. Finally, we introduce coarse spaces based on partitions of unity and planes waves, and show how oblique projection coarse problems can be designed from restricted additive Schwarz methods. Numerical tests are presented.     

Investigations of ultrathin polypyrrole films: Formation and effects of doping/dedoping processes on its optical properties by electrochemical surface plasmon resonance (ESPR)

In the present work an investigation of the effects of the electropolymerization mode on the optical properties associated to the doping/dedoping processes of nanometric films of polypyrrole (PPy) is reported, monitoring in situ and in real time using simultaneously surface plasmon resonance and electrochemical techniques (ESPR). The electropolymerization of pyrrole was performed by potentiostatic, potentiodynamic and galvanostatic methods and the use of the ESPR technique showed that the electropolymerization mode is essential to the stability of polymer and the reversibility of its optical properties during the doping and dedoping processes. Thus, the optical properties of oxidized and reduced film were obtained by nonlinear least square fitting using Fresnel equations for a four-layer system. Then, the values of the real and imaginary parts of the complex dielectric constant for PPy fims were correlated with the polymer doping level. Finally, quartz crystal microbalance measurements were also applied to obtain correlation between doping/dedoping processes and the changes in the real and imaginary parts of the dielectric constant of the polypyrrole film, showing that the doping and dedoping processes in the polypyrrole film can act directly on its optical properties while the ESPR technique can give the same information indirectly.     

ΝΗ<Subscript>3</Subscript> decomposition in a proton conducting solid electrolyte cell

The reaction of NH₃ decomposition was studied on Ag in a proton conducting double chamber cell-reactor. The proton conductor was a strontia-ceria-ytterbia (SCY) perovskite of the form SrCe_0.95Yb_0.05O_3−α. The reaction was studied at 350–700 °C and atmospheric total pressure. The proton transference number (PTN) was calculated by simultaneous measurement of the imposed current and the proton flux and it was found to vary between 0.5 and 0.7. The effects of imposed current, temperature and inlet gas composition on the reaction rate and the PTN, were examined. Although the faradaic efficiency (Λ) remained near unity in all experiments, reaction rate enhancements (ρ) as high as 57 were achieved. An up to 90% decrease in the activation energy of the reaction was observed when protons were electrochemically “pumped” away from the catalyst.