Structure and Rheology of Cationic Molecular Hydrogels of Quinuclidine Grafted Bile Salts. Influence of the Ionic Strength and Counter-Ion type

Quinuclidine grafted cationic bile salts are forming salted hydrogels. An extensive investigation of the effect of the electrolyte and counterions on the gelation has been envisaged. The special interest of the quinuclidine grafted bile salt is due to its broader experimental range of gelation to study the effect of electrolyte. Rheological features of the hydrogels are typical of enthalpic networks exhibiting a scaling law of the elastic shear modulus with the concentration (scaling exponent 2.2) modeling cellular solids in which the bending modulus is the dominant parameter. The addition of monovalent salt (NaCl) favors the formation of gels in a first range (0.00117 g cm-3 (0.02 M) < TNaCl < 0.04675 g cm-3 (0.8 M)). At larger salt concentrations, the gels become more heterogeneous with nodal zones in the micron scale. Small-angle neutron scattering experiments have been used to characterize the rigid fibers ( ≈ 68 Å) and the nodal zones. Stress sweep and creeprecovery measurements are used to relate the lack of linear viscoelastic domain to a mechanism of disentanglement of the fibers from their associations into fagots. The electrostatic interactions can be screened by addition of salt to induce a progressive evolution toward flocculation. SEM, UV absorbance, and SAXS study of the Bragg peak at large Q-values complete the investigation.

Stability Of Large Damped Flexible Spacecraft With Stored Angular Momentum

Vibrational stability of large flexible structurally damped spacecraft carrying internal angular momentum and undergoing large rigid body rotations is analysed modeling the systems as elastic continua. Initially, analytical solutions to the motion of rigid gyrostats under torque-free conditions are developed. The solutions to the gyrostats modeled as axisymmetric and triaxial spacecraft carrying three and two constant speed momentum wheels, respectively, with spin axes aligned with body principal axes are shown to be complicated. These represent extensions of solutions for simpler cases existing in the literature. Using these solutions and modal analysis, the vibrational equations are reduced to linear ordinary differential equations. Equations with periodically varying coefficients are analysed applying Floquet theory. Study of a few typical beam- and plate-like spacecraft configurations indicate that the introduction of a single reaction wheel into an axisymmetric satellite does not alter the stability criterion. However, introduction of constant speed rotors deteriorates vibrational stability. Effects of structural damping and vehicle inertia ratio are also studied.

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.

Partial Loss Of Support And Frame-Soil Interaction

An interaction analysis has been conducted to study the effects of a local loss of support beneath the beam footing of a two-bay plane frame. The results of the study indicate that the magnitude of increase in the bending moment and axial force in the structure due to the presence of a void are dependent, not only on the extent of support loss, but also on the relative stiffnesses between foundation beam and soil, and between superstructure and soil. The increase in bending moment even for a void span of 1/12 of the foundation beam length can become so significant as to exceed the safety provisions. The study shows that the effect of a void on the superstructure moments can be greatly minimized by a combination of rigid foundation and flexible superstructure.

Flow through a plateau border of cellular foam

Experimentally measured average velocities through plateau borders of stationary cellular foam, when compared with those calculated with the assumption of rigid Plateau Border walls, show that the assumption of rigid walls severely underestimates the velocities. An analysis of the situation wherein plateau border walls have velocities, as decided by the surface viscosity of the system, is presented here. The plateau border is idealized as a pipe of equilateral triangular cross-section with vertices of the triangle having zero velocity. The pertinent form of Navier-Stoke's equations with inhomogeneous boundary conditions and its solution through a procedure of successive approximations is presented in dimensionless form. The solution reduces to the known solution of slow steady flow through a triangular pipe, when surface viscosity is infinite. Results indicate that the assumption of rigid plateau border walls is valid only when value of the inverse of dimensionless surface viscosity is less than 0.044. Beyond that the assumption severely underestimates the flow and the effect of nonrigidity of the wall must be considered.

Helmholtz Instability In Stratified Shear Flows With Magnetic-Fields

The stability characteristics of a Helmholtz velocity profile in a stratified Boussinesq fluid in the presence of a rigid boundary is studied, A jump in the magnetic field is introduced at a level different from the velocity discontinuity. New unstable modes in addition to the Kelvin-Helmhottz mode are found. The wavelengths of these unstable modes are close to the wavelengths of internal Alfv6n gravity waves in the atmospher.

Microcontinuum approach to the pulsatile flow in tubes with and without longitudinal vibration

A fully developed pulsatile flow in a circular rigid tube is analysed by a microcontinuum approach. Solutions for radial variation of axial velocity and cell rotational velocity across the tube are obtained using the momentum integral method. Simplified forms of the solutions are presented for the relevant physiological data. Marked deviations in the results are observed when compared to a Newtonian fluid model. It is interesting to see that there is sufficient reduction in the mass flow rate, phase lag and friction due to the micropolar character of the fluid.

A laser flash photolysis study of pivalothiophenone triplets: steric and electronic effects in thione photoreaction kinetics

Upon laser pulse excitation (Aex = 532 nm) into the lowest-lying '(n,a*) band system, pivalothiophenones in benzene solutions give rise to short-lived triplets (Ama: = 325-335 nm, em: = (1 1-15) X lo3 M-' cm-I) with quantitative intersystem crossing efficiencies. The triplet yields decrease slightly (by 10-30%) upon changing A, to 308 nm (Le., upon excitation into S2). Kinetic data are presented for intrinsic triplet lifetimes, self-quenching, and quenching by oxygen, di-tert-butylnitroxy radical, and various reagents capable of interacting with the triplets via energy, electron, or hydrogen-atom transfer and by biradical formation (possibly leading to cycloaddition). The mechanisms of the quenching processes are discussed. Relative to rigid aromatic thiones, namely, xanthione and thiocoumarin, the interaction of pivalothiophenone triplets with most of the quenchers are kinetically inefficient. This is interpreted primarily as a manifestation of the steric crowding at positions a to the thiocarbonyl group.

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.

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.

Conformation of antibiotic X-537A (lasalocid-A) and its calcium complex in acetonitrile solvent using circular dichroism spectroscopy

The calcium binding characteristics of antibiotic X-537A (lasalocid-A) in a lipophilic solvent, acetonitrile (CH3CN), have been studied using circular dichroism (CD) spectroscopy. The analysis of the data indicated that in this medium polar solvent, X-537A forms predominantly the charged complexes of stoichiometries 2:1 and 1:1, the relative amounts of the two being dependent on [Ca2+]. The conformation of the complexes, arrived at on the basis of the data, seem to indicate a rigid part encompassing Ca2+, liganded to 3 oxygens of the molecule, viz., the carbonyl, the substituted tetrahydrofuran ring and the substituted pyran ring oxygens (apart from possibly, the liganding provided by nitrogen atoms of the solvent molecules), and a flexible part consisting of the salicylic acid group of the molecule.

Development of special fastener elements

A special finite element (FASNEL) is developed for the analysis of a neat or misfit fastener in a two-dimensional metallic/composite (orthotropic) plate subjected to biaxial loading. The misfit fasteners could be of interference or clearance type. These fasteners, which are common in engineering structures, cause stress concentrations and are potential sources of failure. Such cases of stress concentration present considerable numerical problems for analysis with conventional finite elements. In FASNEL the shape functions for displacements are derived from series stress function solutions satisfying the governing difffferential equation of the plate and some of the boundary conditions on the hole boundary. The region of the plate outside FASNEL is filled with CST or quadrilateral elements. When a plate with a fastener is gradually loaded the fastener-plate interface exhibits a state of partial contact/separation above a certain load level. In misfit fastener, the extent of contact/separation changes with applied load, leading to a nonlinear moving boundary problem and this is handled by FASNEL using an inverse formulation. The analysis is developed at present for a filled hole in a finite elastic plate providing two axes of symmetry. Numerical studies are conducted on a smooth rigid fastener in a finite elastic plate subjected to uniaxial loading to demonstrate the capability of FASNEL.

Transmission loss analysis of rectangular expansion chamber with arbitrary location of inlet/outlet by means of Green's functions

Transmission loss of a rectangular expansion chamber, the inlet and outlet of which are situated at arbitrary locations of the chamber, i.e., the side wall or the face of the chamber, are analyzed here based on the Green's function of a rectangular cavity with homogeneous boundary conditions. The rectangular chamber Green's function is expressed in terms of a finite number of rigid rectangular cavity mode shapes. The inlet and outlet ports are modeled as uniform velocity pistons. If the size of the piston is small compared to wavelength, then the plane wave excitation is a valid assumption. The velocity potential inside the chamber is expressed by superimposing the velocity potentials of two different configurations. The first configuration is a piston source at the inlet port and a rigid termination at the outlet, and the second one is a piston at the outlet with a rigid termination at the inlet. Pressure inside the chamber is derived from velocity potentials using linear momentum equation. The average pressure acting on the pistons at the inlet and outlet locations is estimated by integrating the acoustic pressure over the piston area in the two constituent configurations. The transfer matrix is derived from the average pressure values and thence the transmission loss is calculated. The results are verified against those in the literature where use has been made of modal expansions and also numerical models (FEM fluid). The transfer matrix formulation for yielding wall rectangular chambers has been derived incorporating the structural–acoustic coupling. Parametric studies are conducted for different inlet and outlet configurations, and the various phenomena occurring in the TL curves that cannot be explained by the classical plane wave theory, are discussed.

Proton magnetic resonance study of molecular dynamics in (NH4)2CdI4

Proton magnetic resonance and spin-lattice relaxation studies have been carried out on (NH4)2CdI4 as a function of temperature (77–400 K) and Larmor frequency (10, 20 and 30 MHz). The T1 data indicate isotropic tumbling of ammonium ions at equivalent sites till 160 K. There is an indication of a phase transition at 265 K, the activation energy for molecular reorientation increases from 2.8 kcal/mole to 4.6 kcal/mole. The relaxation results and the linewidth data support the presence of two inequivalent sites at low temperatures, one having an environment corresponding to near-rigid-lattice limit and the other undergoing fast reorientations. The behaviour of the free induction decay with temperature below 120 K suggests a coherent motion for the faster species.

Analysis of an internally mountable accelerometer balance system for use with non-isotropic models in shock tunnels

Knowledge of drag force is an important design parameter in aerodynamics. Measurement of aerodynamic forces at hypersonic speed is a challenge and usually ground test facilities like shock tunnels are used to carry out such tests. Accelerometer based force balances are commonly employed for measuring aerodynamic drag around bodies in hypersonic shock tunnels. In this study, we present an analysis of the effect of model material on the performance of an accelerometer balance used for measurement of drag in impulse facilities. From the experimental studies performed on models constructed out of Bakelite HYLEM and Aluminum, it is clear that the rigid body assumption does not hold good during the short testing duration available in shock tunnels. This is notwithstanding the fact that the rubber bush used for supporting the model allows unconstrained motion of the model during the short testing time available in the shock tunnel. The vibrations induced in the model on impact loading in the shock tunnel are damped out in metallic model, resulting in a smooth acceleration signal, while the signal become noisy and non-linear when we use non-isotropic materials like Bakelite HYLEM. This also implies that careful analysis and proper data reduction methodologies are necessary for measuring aerodynamic drag for non-metallic models in shock tunnels. The results from the drag measurements carried out using a 60 degrees half angle blunt cone is given in the present analysis.