Thermal Degradation Processes in Poly(xylylene sulfides) Investigated by Comparative Direct Pyrolysis MS and Flash Pyrolysis GC/MS Experiments

The thermal degradation processes of two sulfur polymers, poly(xylylene sulfide) (PXM) and poly(xylylene disulfide) (PXD), were investigated in parallel by direct pyrolysis mass spectrometry (DPMS) and flash pyrolysis GC/MS (Py-GC/MS). Thermogravimetric data showed that these polymers decompose with two separate steps in the temperature ranges of 250-280 and 600-650 degrees C, leaving a high amount of residue (about 50% at 800 degrees C). The pyrolysis products detected by DPMS in the first degradation step of PXM and PXD were terminated by three types of end groups, -CH3, -CH2SH, and -CH=S, originating from thermal cleavage reactions involving a series of homolytic chain scissions followed by hydrogen transfer reactions, generating several oligomers containing some intact xylylene sulfide repeating units. The presence of pyrolysis compounds containing some stilbene-like units in the first degradation step has also been observed. Their formation has been accounted for with a parallel cleavage involving the elimination of H2S from the PXM main chains. These unsaturated units can undergo cross-linking at higher temperatures, producing the high amount of char residue observed. The thermal degradation compounds detected by DPMS in the second decomposition step at about 600-650 degrees C were constituted of condensed aromatic molecules containing dihydrofenanthrene and fenanthrene units. These compounds might be generated from the polymer chains containing stilbene units, by isomerization and dehydrogenation reactions. The pyrolysis products obtained in the Py-GC/MS of PXM and PXD at 610 degrees C are almost identical. The relative abundance in the pyrolysate and the spectral properties of the main pyrolysis products were found to be in generally good agreement with those obtained by DPMS. Polycyclic aromatic hydrocarbons (PAHs) were also detected by Py-GC/MS but in minor amounts with respect to DPMS. This apparent discrepancy was due to the simultaneous detection of PAHs together with all pyrolysis products in the Py-GC/MS, whereas in DPMS they were detected in the second thermal degradation step without the greatest part of pyrolysis compounds generated in the first degradation step. The results obtained by DPMS and PSI-GC/MS experiments showed complementary data for the degradation of PXM and PXD and, therefore, allowed the unequivocal formulation of the thermal degradation mechanism for these sulfur-containing polymers.

A direct adaptive neural command controller design for an unstable helicopter

This paper presents an off-line (finite time interval) and on-line learning direct adaptive neural controller for an unstable helicopter. The neural controller is designed to track pitch rate command signal generated using the reference model. A helicopter having a soft inplane four-bladed hingeless main rotor and a four-bladed tail rotor with conventional mechanical controls is used for the simulation studies. For the simulation study, a linearized helicopter model at different straight and level flight conditions is considered. A neural network with a linear filter architecture trained using backpropagation through time is used to approximate the control law. The controller network parameters are adapted using updated rules Lyapunov synthesis. The off-line trained (for finite time interval) network provides the necessary stability and tracking performance. The on-line learning is used to adapt the network under varying flight conditions. The on-line learning ability is demonstrated through parameter uncertainties. The performance of the proposed direct adaptive neural controller (DANC) is compared with feedback error learning neural controller (FENC).

Satellite-derived direct radiative effect of aerosols dependent on cloud cover

Aerosols from biomass burning can alter the radiative balance of the Earth by reflecting and absorbing solar radiation(1). Whether aerosols exert a net cooling or a net warming effect will depend on the aerosol type and the albedo of the underlying surface(2). Here, we use a satellite-based approach to quantify the direct, top-of-atmosphere radiative effect of aerosol layers advected over the partly cloudy boundary layer of the southeastern Atlantic Ocean during July-October of 2006 and 2007. We show that the warming effect of aerosols increases with underlying cloud coverage. This relationship is nearly linear, making it possible to define a critical cloud fraction at which the aerosols switch from exerting a net cooling to a net warming effect. For this region and time period, the critical cloud fraction is about 0.4, and is strongly sensitive to the amount of solar radiation the aerosols absorb and the albedo of the underlying clouds. We estimate that the regional-mean warming effect of aerosols is three times higher when large-scale spatial covariation between cloud cover and aerosols is taken into account. These results demonstrate the importance of cloud prediction for the accurate quantification of aerosol direct effects.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

A Jacobian-Based Algorithm for Planning Attitude Maneuvers Using Forward and Reverse Rotations

Algorithms for planning quasistatic attitude maneuvers based on the Jacobian of the forward kinematic mapping of fully-reversed (FR) sequences of rotations are proposed in this paper. An FR sequence of rotations is a series of finite rotations that consists of initial rotations about the axes of a body-fixed coordinate frame and subsequent rotations that undo these initial rotations. Unlike the Jacobian of conventional systems such as a robot manipulator, the Jacobian of the system manipulated through FR rotations is a null matrix at the identity, which leads to a total breakdown of the traditional Jacobian formulation. Therefore, the Jacobian algorithm is reformulated and implemented so as to synthesize an FR sequence for a desired rotational displacement. The Jacobian-based algorithm presented in this paper identifies particular six-rotation FR sequences that synthesize desired orientations. We developed the single-step and the multiple-step Jacobian methods to accomplish a given task using six-rotation FR sequences. The single-step Jacobian method identifies a specific FR sequence for a given desired orientation and the multiple-step Jacobian algorithm synthesizes physically feasible FR rotations on an optimal path. A comparison with existing algorithms verifies the fast convergence ability of the Jacobian-based algorithm. Unlike closed-form solutions to the inverse kinematics problem, the Jacobian-based algorithm determines the most efficient FR sequence that yields a desired rotational displacement through a simple and inexpensive numerical calculation. The procedure presented here is useful for those motion planning problems wherein the Jacobian is singular or null.

The Implication Problem for Functional and Multivalued Dependencies

Computation of the dependency basis is the fundamental step in solving the implication problem for MVDs in relational database theory. We examine this problem from an algebraic perspective. We introduce the notion of the inference basis of a set M of MVDs and show that it contains the maximum information about the logical consequences of M. We propose the notion of an MVD-lattice and develop an algebraic characterization of the inference basis using simple notions from lattice theory. We also establish several properties of MVD-lattices related to the implication problem. Founded on our characterization, we synthesize efficient algorithms for (a) computing the inference basis of a given set M of MVDs; (b) computing the dependency basis of a given attribute set w.r.t. M; and (c) solving the implication problem for MVDs. Finally, we show that our results naturally extend to incorporate FDs also in a way that enables the solution of the implication problem for both FDs and MVDs put together.

Direct precipitation of lead zirconate titanate by the hydrothermal method

Direct precipitation of fine powders of lead zirconate titanate (PZT) in the complete range of solid solution, is investigated under hydrothermal conditions, starting from lead oxide and titania/zirconia mixed gels. The perovskite phase is formed in the temperature range of 165 – 340°C. Sequence of the hydrothermal reactions is studied by identifying the intermediate phases. The initial formation of PbO: TiO2 solid solution is followed by the reaction of the same with the remaining mixed gels giving rise to X-ray amorphous PZT phase. Further, through crystallite growth, the X-ray crystalline PZT is formed. This method can be extended for the preparation of PLZT powder as well. The resulting powders are sinterable to high density ceramics.

Fasteners in Composite Plates - Effects of Interfacial Friction

The effects of tangential friction at pin—hole interfaces are appropriately modelled for the analysis of fasteners in large composite (orthotropic) plate loaded along its edges. The pin—hole contact could be of interference, clearance or neat fit. When the plate load is monotonically increased, interference fits give rise to receding contact, whereas clearance fits result in advancing contact. In either case, the changing contact situations lead to non-linear moving boundary value problems. The neat fit comes out as a special case in which the contact and separation regions are invariant with the applied load level and so the problem remains linear. The description of boundary conditions in the presence of tangential friction, will depend on whether the problem is one of advancing or receding contact, advancing contact presenting a special problem. A model is developed for the limiting case of a rigid pin and an ideally rough interface (infinitely large friction coefficient). The non-linearity resulting from the continuously varying proportions of contact and separation at the interface, is handled by an “Inverse Formulation” which was successfully applied earlier by the authors for smooth (zero friction) interfacial conditions. The additional difficulty introduced by advancing contact is handled by adopting a “Marching Solution”. The modelling and the procedure are illustrated in respect of symmetric plate load cases. Numerical results are presented bringing out the effects of interfacial friction and plate orthotropy on load-contact relations and plate stresses.

Quantum first-passage problem

Formulation of quantum first passage problem is attempted in terms of a restricted Feynman path integral that simulates an absorbing barrier as in the corresponding classical case. The positivity of the resulting probability density, however, remains to be demonstrated.

Analysis of a finite composite plate with smooth rigid pin

A continuum method of analysis is presented in this paper for the problem of a smooth rigid pin in a finite composite plate subjected to uniaxial loading. The pin could be of interference, push or clearance fit. The plate is idealized to an orthotropic sheet. As the load on the plate is progressively increased, the contact along the pin-hole interface is partial above certain load levels in all three types of fit. In misfit pins (interference or clearance), such situations result in mixed boundary value problems with moving boundaries and in all of them the arc of contact and the stress and displacement fields vary nonlinearly with the applied load. In infinite domains similar problems were analysed earlier by ‘inverse formulation’ and, now, the same approach is selected for finite plates. Finite outer domains introduce analytical complexities in the satisfaction of boundary conditions. These problems are circumvented by adopting a method in which the successive integrals of boundary error functions are equated to zero. Numerical results are presented which bring out the effects of the rectangular geometry and the orthotropic property of the plate. The present solutions are the first step towards the development of special finite elements for fastener joints.

A simple circuit to aid direct measurement of capture cross sections of deep level impurities

An inexpensive and simple circuit to aid the direct measurement of majority carrier capture cross sections of impurity levels in the band gap of a semiconductor by the variable width filling pulse technique is presented. With proper synchronisation, during the period of application of the pulse, the device is disconnected from the capacitance meter to avoid distortion of the pulse and is reconnected again to the meter to record the emission transient. Modes of operation include manual triggering for long emission transients, repetitive triggering for isothermal and DLTS measurements and the DLTS mode which is to be used with signal analysers that already provide a synchronising pulse for disconnection.

On the direct parallel solution of systems of linear equations: New algorithms and systolic structures

The paper presents two new algorithms for the direct parallel solution of systems of linear equations. The algorithms employ a novel recursive doubling technique to obtain solutions to an nth-order system in n steps with no more than 2n(n −1) processors. Comparing their performance with the Gaussian elimination algorithm (GE), we show that they are almost 100% faster than the latter. This speedup is achieved by dispensing with all the computation involved in the back-substitution phase of GE. It is also shown that the new algorithms exhibit error characteristics which are superior to GE. An n(n + 1) systolic array structure is proposed for the implementation of the new algorithms. We show that complete solutions can be obtained, through these single-phase solution methods, in 5n−log2n−4 computational steps, without the need for intermediate I/O operations.

Elastic analysis of pin joints in plates under some combined pin and plate loads

Joints are primary sources of weakness in structures. Pin joints are very common and are used where periodic disassembly of components is needed. A circular pin in a circular hole in an infinitely large plate is an abstraction of such a pin joint. A two-dimensional plane-stress analysis of such a configuration is carried out, here, subjected to pin-bearing and/or biaxial-plate loading. The pin is assumed to be rigid compared to the plate material. For pin load the reactive stresses at the edges of the infinite plate tend to zero though their integral over the external boundary equals to the pin load. The pin-hole interface is unbonded and so beyond some load levels the plate separates from the pin and the extent of separation is a non-linear function of load level. The problem is solved by inverse technique where the extent of contact is specified and the causative loads are evaluated directly. In the situations where combined load is acting the separation-contact zone specification generally needs two parameters (angles) to be specified. The present report deals with analysing such a situation in metallic (or isotropic) plates. Numerical results are provided for parametric representation and the methodology is demonstrated.

Determination of chemical shift anisotropy without a reference and of direct and indirect spin-spin couplings between heteronuclei

A method employing two liquid crystals of opposite diamagnetic anisotropies to determine chemical shift anisotropy without using any reference compound is described. It also provides individual values of the direct and the indirect spin-spin coupling constants between heteronuclei. The parameters for acetonitrile are reported.

Pin-Loaded Holes in Large Orthotropic Plates

Pin-loaded holes commonly occur in engineering structures. However, accurate analysis of such holes presents formidable difficulties because of the load-dependent contact of the pin with the plate. Significant progress has recently been achieved in the analysis of holes in isotropic plates. This paper develops a simple and accurate method for the partial contact analysis of pin-loaded holes in composites. The method is based on an inverse formulation that seeks to determine loads in a given contact-separation configuration. A unified approach for all types of fit was used. Continuum solutions were obtained for infinitely large plates of various typical orthotropic properties with holes loaded by smooth rigid pins. These solutions were then compared with those for isotropic plates. The effects of orthotropy and the type of fit were studied through load-contact relationships, distribution of stresses and displacements, and their variation with load. The results are of direct relevance to the analysis and design of pin joints in composite plates.