Reflections on the Hydrogen Bond in Crystal Engineering

Comments on aspects of the new definition of the hydrogen bond specific to crystal engineering are given.

Crystal Structure Engineering by Fine-Tuning the Surface Energy: The Case of CdE (E = S/Se) Nanocrystals

We prove that CdS nanocrystals can be thermodynamically stabilized in both wurtzite and zinc-blende crystallographic phases at will, just by the proper choice of the capping ligand. As a striking demonstration of this, the largest CdS nanocrystals (similar to 15 nm diameter) ever formed with the zinc-blende structure have been synthesized at a high reaction temperature of 310 degrees C, in contrast to previous reports suggesting the formation of zinc-blende CdS only in the small size limit (< 4.5 nm) or at a lower reaction temperature (<= 240 degrees C). Theoretical analysis establishes that the binding energy of trioctylphosphine molecules on the (001) surface of zinc-blende CdS is significantly larger than that for any of the wurtzite planes. Consequently, trioctylphosphine as a capping agent stabilizes the zinc-blende phase via influencing the surface energy that plays an important role in the overall energetics of a nanocrystal. Besides achieving giant zinc-blende CdS nanocrystals, this new understanding allows us to prepare CdSe and CdSe/CdS core/shell nanocrystals in the zinc-blende structure.

Critical earthquake input power spectral density function models for engineering structures

The problem of determining optimal power spectral density models for earthquake excitation which satisfy constraints on total average power, zero crossing rate and which produce the highest response variance in a given linear system is considered. The solution to this problem is obtained using linear programming methods. The resulting solutions are shown to display a highly deterministic structure and, therefore, fail to capture the stochastic nature of the input. A modification to the definition of critical excitation is proposed which takes into account the entropy rate as a measure of uncertainty in the earthquake loads. The resulting problem is solved using calculus of variations and also within linear programming framework. Illustrative examples on specifying seismic inputs for a nuclear power plant and a tall earth dam are considered and the resulting solutions are shown to be realistic.

Response, loads and stability of rotors with interconnected blades

An isolated rotor with blades interconnected through viscoelastic elements is analyzed for response, loads and stability in moment trim under forward flight conditions. A conceptual model of a multibladed rotor with rigid flap and lag motions is considered, Although the interconnecting elements are placed in the In-plane direction, considerable coupling between the flap-lag motions of the blades can occur in certain ranges of interblade element stiffness. Interblade coupling can yield significant changes in the response, loads and stability which are dependent on the interblade element and rotor parameters.

Studies in crystal engineering: Effect of fluorine substitution in crystal packing and topological photodimerization of styryl coumarins in the solid state

Styryl coumarins generally yield centrosymmetric (alpha-mode, anti-HT) photodimers when subjected to irradiation in the solid state, However, the substitution of fluorine dramatically alters the packing mode and steers the molecules 4-(4-fluorostyryl)coumarin 1 and 4-(2-fluorostyryl)coumarin 2 to form a stereospecific photodimer, beta-mode, syn-HH across the styrenic double bond (yield 78-85%). The stereochemistry of the photodimer 2a has been established by X-ray crystallography. There is no evidence for the presence of C-H ... F interactions. The true nature of the weak atom-atom interactions called into play when fluorine is substituted is not clear, It is observed that the fluoro substituted compounds have greater crystal density than the corresponding unsubstituted ones.

Some Basic Aspects of Reaction Engineering of Precipitation Processes

Analysis of precipitation reactions is extremely important in the technology of production of fine particles from the liquid phase. The control of composition and particle size in precipitation processes requires careful analysis of the several reactions that comprise the precipitation system. Since precipitation systems involve several, rapid ionic dissociation reactions among other slower ones, the faster reactions may be assumed to be nearly at equilibrium. However, the elimination of species, and the consequent reduction of the system of equations, is an aspect of analysis fraught with the possibility of subtle errors related to the violation of conservation principles. This paper shows how such errors may be avoided systematically by relying on the methods of linear algebra. Applications are demonstrated by analyzing the reactions leading to the precipitation of calcium carbonate in a stirred tank reactor as well as in a single emulsion drop. Sample calculations show that supersaturation dynamics can assume forms that can lead to subsequent dissolution of particles that have once been precipitated.

Growth and development of Thiobacillus ferrooxidans for engineering applications

A bioprocessing approach for the extraction of base, nuclear and precious metals from refractory and lean grade ores has been reviewed in this paper. Characteristic morphological features of Thiobacillus ferrooxidans, the organism which has been extensively used for biooxidation of sulphide ores have been discussed. Mechanisms of chemoautotrophy and mineral oxidation have been illustrated. The current engineering applications of this microorganism have also been brought out. Various methods for accelerating the growth of Thiobacillus ferrooxidans for faster biooxidation and genetic manipulation for development of desired strains have been outlined.

Stochastic Aeroelastic Analysis of Composite Helicopter Rotor

The effect of uncertainty in composite material properties on the aeroelastic response, vibratory loads, and stability of a hingeless helicopter rotor is investigated. The uncertainty impact on rotating natural frequencies of the blade is studied with Monte Carlo simulations and first-order reliability methods. The stochastic aeroelastic analyses in hover and forward flight are carried out with Monte Carlo simulations. The flap, lag, and torsion responses show considerable scatter from their baseline values, and the uncertainty impact varies with the azimuth angle. Furthermore, the blade response shows finite probability of resonance-type conditions caused by modal frequencies approaching multiples of the rotor speed. The 4/rev vibratory forces show large deviations from their baseline values. The lag mode damping shows considerable scatter due to uncertain material properties with an almost 40% probability of instability in hover.

Response, loads, and stability of interconnected rotor-body systems

A rotor-body system with blades interconnected through viscoelastic elements is analyzed for response, loads, and stability in propulsive trim in ground contact and under forward-flight conditions, A conceptual model of a multibladed rotor with rigid flap and lag motions, and the fuselage with rigid pitch and roll motions is considered, Although the interconnecting elements are placed in the in-plane direction, considerable coupling between the flap-lag motions of the blades can occur in certain ranges of interblade element stiffness, Interblade coupling can yield significant changes in the response, loads, and stability that are dependent on the interblade element and rotor-body parameters, Ground resonance stability investigations show that by tuning the interblade element stiffness, the ground resonance instability problem can be reduced or eliminated, The interblade elements with damping and stiffness provide an effective method to overcome the problems of ground and air resonance.

Studies in crystal engineering: Crystal packing, topological photodimerization and structure-reactivity correlations in fluoro-substituted styrylcoumarins

In continuation of our studies on the influence of fluoro substitution on the solid state photobehaviour and packing pattern of styrylcoumarins, the results obtained for 4-(3-fluorostyryl)coumarin 1, 4-styryl-6-fluorocoumarin 2 and 4-styryl-7-fluorocoumarin 3 are presented. The configuration of the dimers was established on the basis of crystal packing of 1 and 2 (alpha-packed). A rationale for the significantly lower dimer yield in the crystal for 2 is proposed. In the observed centrosymmetric arrangement of the reactants the C=O ...pi (phenyl) contacts seem to provide additional attractive interactions. C-H ... O and C-H ... F hydrogen bonding seems to provide stability in these structures.

Studies in crystal engineering: Steering ability of fluorine in styrylcoumarins

In continuation of our studies on crystal engineering using fluorine as a steering group, the photobehaviour of di and tri fluoro 4-styrylcoumarins has been examined. It is found that out of the five derivatives, four crystallize into P-packing mode producing syn-HH photodimer upon irradiation whereas the parent hydrocarbon produces an anti K-T dimer. The packing features of the photolabile crystals of 4-(4-fluorostyryl)-6-fluorocoumarin (1), 4-(2,6-difluorostyryl) 6-fluorocoumarin (2) and the photodimer (3a) of 4-(2,6-fluorostyryl)-7-fluorocoumarin (3) have been determined by single crystal X-ray diffraction studies. The stereochemistry of the photodimer of 4-(2-fluorostyryl)-6-fluorocoumarin (4) is deduced based on preliminary X-ray crystallographic data. However, 4-(2,6-difluorostyryl) coumarin (5) is photoinert. The remarkable steering ability of fluorine is established with the molecular packing in the crystal lattice leading to the formation of syn H-H dimer in the above four examples. (C) 1999 Elsevier Science Ltd. All rights reserved.

Synthesis of nonlinear controller to recover an unstable aircraft from poststall regime

Dynamics of the aircraft configuration considered in this paper show a unique characteristic in that there are no stable attractors in the entire high angle-of-attack flight envelope. As a result, once the aircraft has departed from the normal flight regime, no standard technique can be applied to recover the aircraft. In this paper, using feedback linearization technique, a nonlinear controller is designed at high angles of attack, which is engaged after the aircraft departs from normal flight regime. This controller stabilizes the aircraft into a stable spin. Then a set of synthetic pilot inputs is applied to cause an automatic transition from the spin equilibrium to low angles of attack where the second controller is connected. This controller is a normal gain-scheduled controller designed to have a large domain of attraction at low angles of attack. It traps the aircraft into a low angle-of-attack level flight. This entire concept of recovery has been verified using six-degrees-of-freedom nonlinear simulation. Feedback linearization technique used to design a controller ensures internal stability only if the nonlinear plant has stable zero dynamics. Because zero dynamics depend on the selection of outputs, a new method of choosing outputs is described to obtain a plant that has stable zero dynamics. Certain important aspects pertaining to the implementation of a feedback linearization-based controller are also discussed.

Optimum design of a helicopter rotor for low vibration using aeroelastic analysis and response surface methods

An aeroelastic analysis based on finite elements in space and time is used to model the helicopter rotor in forward flight. The rotor blade is represented as an elastic cantilever beam undergoing flap and lag bending, elastic torsion and axial deformations. The objective of the improved design is to reduce vibratory loads at the rotor hub that are the main source of helicopter vibration. Constraints are imposed on aeroelastic stability, and move limits are imposed on the blade elastic stiffness design variables. Using the aeroelastic analysis, response surface approximations are constructed for the objective function (vibratory hub loads). It is found that second order polynomial response surfaces constructed using the central composite design of the theory of design of experiments adequately represents the aeroelastic model in the vicinity of the baseline design. Optimization results show a reduction in the objective function of about 30 per cent. A key accomplishment of this paper is the decoupling of the analysis problem and the optimization problems using response surface methods, which should encourage the use of optimization methods by the helicopter industry. (C) 2002 Elsevier Science Ltd. All rights reserved.