Molecular Marriage through Partner Preferences in Covalent Cage Formation and Cage-to-Cage Transformation

Unprecedented self-sorting of three-dimensional purely organic cages driven by dynamic covalent bonds is described. Four different cages were first synthesized by condensation of two triamines and two dialdehydes separately. When a mixture of all the components was allowed to react, only two cages were formed, which suggests a high-fidelity self-recognition. The issue of the preference of one triamine for a particular dialdehyde was further probed by transforming a non-preferred combination to either of the two preferred combinations by reacting it with the appropriate triamine or dialdehyde.

Beyond classical dynamic structural plasticity using mesh-free modelling techniques

The problem of modelling the transient response of an elastic-perfectly-plastic cantilever beam, carrying an impulsively loaded tip mass, is,often referred to as the Parkes cantilever problem 25]; The permanent deformation of a cantilever struck transversely at its tip, Proc. R. Soc. A., 288, pp. 462). This paradigm for classical modelling of projectile impact on structures is re-visited and updated using the mesh-free method, smoothed particle hydrodynamics (SPH). The purpose of this study is to investigate further the behaviour of cantilever beams subjected to projectile impact at its tip, by considering especially physically real effects such as plastic shearing close to the projectile, shear deformation, and the variation of the shear strain along the length and across the thickness of the beam. Finally, going beyond macroscopic structural plasticity, a strategy to incorporate physical discontinuity (due to crack formation) in SPH discretization is discussed and explored in the context of tip-severance of the cantilever beam. Consequently, the proposed scheme illustrates the potency for a more refined treatment of penetration mechanics, paramount in the exploration of structural response under ballistic loading. The objective is to contribute to formulating a computational modelling framework within which transient dynamic plasticity and even penetration/failure phenomena for a range of materials, structures and impact conditions can be explored ab initio, this being essential for arriving at suitable tools for the design of armour systems. (C) 2014 Elsevier Ltd. All rights reserved.

Formation Flying with Nonlinear Partial Integrated Guidance and Control

Using the dynamic inversion philosophy, a nonlinear partial integrated guidance and control approach is presented in this paper for formation flying. It is based on the evolving philosophy of integrated guidance and control. However, it also retains the advantages of the conventional guidance then control philosophy by retaining the timescale separation between translational and rotational dynamics explicitly. Simulation studies demonstrate that the proposed technique is effective in bringing the vehicles into formation quickly and maintaining the formation.

Formation of Prestellar Cores via Non-Isothermal Gas Fragmentation

Sheet-like clouds are common in turbulent gas and perhaps form via collisions between turbulent gas flows. Having examined the evolution of an isothermal shocked slab in an earlier contribution, in this work we follow the evolution of a sheet-like cloud confined by (thermal) pressure and gas in it is allowed to cool. The extant purpose of this endeavour is to study the early phases of core-formation. The observed evolution of this cloud supports the conjecture that molecular clouds themselves are three-phase media (comprising viz. a stable cold and warm medium, and a third thermally unstable medium), though it appears, clouds may evolve in this manner irrespective of whether they are gravitationally bound. We report, this sheet fragments initially due to the growth of the thermal instability (TI) and some fragments are elongated, filament-like. Subsequently, relatively large fragments become gravitationally unstable and sub-fragment into smaller cores. The formation of cores appears to be a three stage process: first, growth of the TI leads to rapid fragmentation of the slab; second, relatively small fragments acquire mass via gas-accretion and/or merger and third, sufficiently massive fragments become susceptible to the gravitational instability and sub-fragment to form smaller cores. We investigate typical properties of clumps (and smaller cores) resulting from this fragmentation process. Findings of this work support the suggestion that the weak velocity field usually observed in dense clumps and smaller cores is likely seeded by the growth of dynamic instabilities. Simulations were performed using the smooth particle hydrodynamics algorithm.

Direct measurements of growing amorphous order and non-monotonic dynamic correlations in a colloidal glass-former

The transformation of flowing liquids into rigid glasses is thought to involve increasingly cooperative relaxation dynamics as the temperature approaches that of the glass transition. However, the precise nature of this motion is unclear, and a complete understanding of vitrification thus remains elusive. Of the numerous theoretical perspectives(1-4) devised to explain the process, random first-order theory (RFOT; refs 2,5) is a well-developed thermodynamic approach, which predicts a change in the shape of relaxing regions as the temperature is lowered. However, the existence of an underlying `ideal' glass transition predicted by RFOT remains debatable, largely because the key microscopic predictions concerning the growth of amorphous order and the nature of dynamic correlations lack experimental verification. Here, using holographic optical tweezers, we freeze a wall of particles in a two-dimensional colloidal glass-forming liquid and provide direct evidence for growing amorphous order in the form of a static point-to-set length. We uncover the non-monotonic dependence of dynamic correlations on area fraction and show that this non-monotonicity follows directly from the change in morphology and internal structure of cooperatively rearranging regions(6,7). Our findings support RFOT and thereby constitute a crucial step in distinguishing between competing theories of glass formation.

Spatio-temporal Map Formation Based on a Potential Function

We revisit the problem of temporal self organization using activity diffusion based on the neural gas (NGAS) algorithm. Using a potential function formulation motivated by a spatio-temporal metric, we derive an adaptation rule for dynamic vector quantization of data. Simulations results show that our algorithm learns the input distribution and time correlation much faster compared to the static neural gas method over the same data sequence under similar training conditions.

Dynamic recrystallization induced by plastic deformation at high strain rate in a Monel alloy

An investigation has been made into the plastic deformation behavior of a Monel alloy deformed at high strain rate of 10(5) s(-1) by split Hopkinson bar. The results reveal that there are some equiaxed grains with an average size of 150 nm in diameter in the center of the shear bands, suggesting that this microstructure characteristics be developed by dynamic recrystallization, arising from the deformation and the rapid temperature rise in the band. Analysis shows that the plastic strain rate and the mobile dislocation density play a key role in the new crystallized grain formation and growth. Based on grain boundary energy change and diffusion mechanism, the grain growth kinetics is developed for plastic deformation at a high strain rate.

Shear Localization In Dynamic Deformation: Microstructural Evolution

Investigations made by the authors and collaborators into the microstructural aspects of adiabatic shear localization are critically reviewed. The materials analyzed are low-carbon steels, 304 stainless steel, monocrystalline Fe-Ni-Cr, Ti and its alloys, Al-Li alloys, Zircaloy, copper, and Al/SiCp composites. The principal findings are the following: (a) there is a strain-rate-dependent critical strain for the development of shear bands; (b) deformed bands and white-etching bands correspond to different stages of deformation; (c) different slip activities occur in different stages of band development; (d) grain refinement and amorphization occur in shear bands; (e) loss of stress-carrying capability is more closely associated with microdefects rather than with localization of strain; (f) both crystalline rotation and slip play important roles; and (g) band development and band structures are material dependent. Additionally, avenues for new research directions are suggested.

Evolution of thermoplastic shear localization and related microstructures in Awl/SiCp composites under dynamic compression

The localized shear deformation in the 2024 and 2124 Al matrix composites reinforced with SiC particles was investigated with a split Hopkinson pressure bar (SHPB) at a strain rate of about 2.0x10(3) s(-1). The results showed that the occurrence of localized shear deformation is sensitive to the size of SiC particles. It was found that the critical strain, at which the shear localization occurs, strongly depends on the size and volume fraction of SiC particles. The smaller the particle size, the lower the critical strain required for the shear localization. TEM examinations revealed that Al/SiCp interfaces are the main sources of dislocations. The dislocation density near the interface was found to be high and it decreases with the distance from the particles. The Al matrix in shear bands was highly deformed and severely elongated at low angle boundaries. The Al/SiCp interfaces, particularly the sharp corners of SiC particles, provide the sites for microcrack initiation. Eventual fracture is caused by the growth and coalescence of microcracks along the shear bands. It is proposed that the distortion free equiaxed grains with low dislocation density observed in the center of shear band result from recrystallization during dynamic deformation.

Formation of adiabatic shear band in metal matrix composites

A modified single-pulse loading split Hopkinson torsion bar (SSHTB) is introduced to investigate adiabatic shear banding behavior in SiCp particle reinforced 2024 Al composites in this work. The experimental results showed that formation of adiabatic shear band in the composite with smaller particles is more readily observed than that in the composite with larger particles. To characterize this size-dependent deformation localization behavior of particle reinforced metal matrix composites (MMCp), a strain gradient dependent shear instability analysis was performed. The result demonstrated that high strain gradient provides a deriving force for the formation of adiabatic shear banding in MMCp. (C) 2004 Elsevier Ltd. All rights reserved.

Numerical investigation of dynamic stall of an oscillating aerofoil

The flow structure around an NACA 0012 aerofoil oscillating in pitch around the quarter-chord is numerically investigated by solving the two-dimensional compressible N-S equations using a special matrix-splitting scheme. This scheme is of second-order accuracy in time and space and is computationally more efficient than the conventional flux-splitting scheme. A 'rigid' C-grid with 149 x 51 points is used for the computation of unsteady flow. The freestream Mach number varies from 0.2 to 0.6 and the Reynolds number from 5000 to 20,000. The reduced frequency equals 0.25-0.5. The basic flow structure of dynamic stall is described and the Reynolds number effect on dynamic stall is briefly discussed. The influence of the compressibility on dynamic stall is analysed in detail. Numerical results show that there is a significant influence of the compressibility on the formation and convection of the dynamic stall vortex. There is a certain influence of the Reynolds number on the flow structure. The average convection velocity of the dynamic stall vortex is approximately 0.348 times the freestream velocity.

Chemical equilibrium analysis and CFD simulation of coal combustion and NOx formation

A full two-fluid model of reacting gas-particle flows with an algebraic unified second-order moment (AUSM) turbulence-chemistry model is used to simulate Beijing coal combustion and NOx formation. The sub-models are the k-epsilon-kp two-phase turbulence model, the EBU-Arrhenius volatile and CO combustion model, the six-flux radiation model, coal devolatilization model and char combustion model. The blocking effect on NOx formation is discussed. In addition, the chemical equilibrium analysis is used to predict NOx concentration at different temperature. Results of CID simulation and chemical equilibrium analysis show that, optimizing air dynamic parameters can delay the NOx formation and decrease NOx emission, but it is effective only in a restricted range. In order to decrease NOx emission near to zero, the re-burning or other chemical methods must be used.

Understanding planet formation through high precision photometry and spectroscopy

From studies of protoplanetary disks to extrasolar planets and planetary debris, we aim to understand the full evolution of a planetary system. Observational constraints from ground- and space-based instrumentation allows us to measure the properties of objects near and far and are central to developing this understanding. We present here three observational campaigns that, when combined with theoretical models, reveal characteristics of different stages and remnants of planet formation. The Kuiper Belt provides evidence of chemical and dynamical activity that reveals clues to its primordial environment and subsequent evolution. Large samples of this population can only be assembled at optical wavelengths, with thermal measurements at infrared and sub-mm wavelengths currently available for only the largest and closest bodies. We measure the size and shape of one particular object precisely here, in hopes of better understanding its unique dynamical history and layered composition.

Molecular organic chemistry is one of the most fundamental and widespread facets of the universe, and plays a key role in planet formation. A host of carbon-containing molecules vibrationally emit in the near-infrared when excited by warm gas, T~1000 K. The NIRSPEC instrument at the W.M. Keck Observatory is uniquely configured to study large ranges of this wavelength region at high spectral resolution. Using this facility we present studies of warm CO gas in protoplanetary disks, with a new code for precise excitation modeling. A parameterized suite of models demonstrates the abilities of the code and matches observational constraints such as line strength and shape. We use the models to probe various disk parameters as well, which are easily extensible to others with known disk emission spectra such as water, carbon dioxide, acetylene, and hydrogen cyanide.

Lastly, the existence of molecules in extrasolar planets can also be studied with NIRSPEC and reveals a great deal about the evolution of the protoplanetary gas. The species we observe in protoplanetary disks are also often present in exoplanet atmospheres, and are abundant in Earth's atmosphere as well. Thus, a sophisticated telluric removal code is necessary to analyze these high dynamic range, high-resolution spectra. We present observations of a hot Jupiter, revealing water in its atmosphere and demonstrating a new technique for exoplanet mass determination and atmospheric characterization. We will also be applying this atmospheric removal code to the aforementioned disk observations, to improve our data analysis and probe less abundant species. Guiding models using observations is the only way to develop an accurate understanding of the timescales and processes involved. The futures of the modeling and of the observations are bright, and the end goal of realizing a unified model of planet formation will require both theory and data, from a diverse collection of sources.

Dynamic Stall on Vertical Axis Wind Turbines

In this study the dynamics of flow over the blades of vertical axis wind turbines was investigated using a simplified periodic motion to uncover the fundamental flow physics and provide insight into the design of more efficient turbines. Time-resolved, two-dimensional velocity measurements were made with particle image velocimetry on a wing undergoing pitching and surging motion to mimic the flow on a turbine blade in a non-rotating frame. Dynamic stall prior to maximum angle of attack and a leading edge vortex development were identified in the phase-averaged flow field and captured by a simple model with five modes, including the first two harmonics of the pitch/surge frequency identified using the dynamic mode decomposition. Analysis of these modes identified vortical structures corresponding to both frequencies that led the separation and reattachment processes, while their phase relationship determined the evolution of the flow.

Detailed analysis of the leading edge vortex found multiple regimes of vortex development coupled to the time-varying flow field on the airfoil. The vortex was shown to grow on the airfoil for four convection times, before shedding and causing dynamic stall in agreement with 'optimal' vortex formation theory. Vortex shedding from the trailing edge was identified from instantaneous velocity fields prior to separation. This shedding was found to be in agreement with classical Strouhal frequency scaling and was removed by phase averaging, which indicates that it is not exactly coupled to the phase of the airfoil motion.

The flow field over an airfoil undergoing solely pitch motion was shown to develop similarly to the pitch/surge motion; however, flow separation took place earlier, corresponding to the earlier formation of the leading edge vortex. A similar reduced-order model to the pitch/surge case was developed, with similar vortical structures leading separation and reattachment; however, the relative phase lead of the separation mode, corresponding to earlier separation, necessitated that a third frequency to be incorporated into the reattachment mode to provide a relative lag in reattachment.

Finally, the results are returned to the rotating frame and the effects of each flow phenomena on the turbine are estimated, suggesting kinematic criteria for the design of improved turbines.

Efficient Synthesis of Single-Chain Polymer Nanoparticles via Amide Formation

Single-chain technology (SCT) allows the transformation of individual polymer chains to folded/collapsed unimolecular soft nanoparticles. In this work we contribute to the enlargement of the SCT toolbox by demonstrating the efficient synthesis of single-chain polymer nanoparticles (SCNPs) via intrachain amide formation. In particular, we exploit cross-linking between active methylene groups and isocyanate moieties as powerful "click" chemistry driving force for SCNP construction. By employing poly(methyl methacrylate)- (PMMA-) based copolymers bearing beta-ketoester units distributed randomly along the copolymer chains and bifunctional isocyanate cross-linkers, SCNPs were successfully synthesized at r.t. under appropriate reaction conditions. Characterization of the resulting SCNPs was carried out by means of a combination of techniques including size exclusion chromatography (SEC), infrared (IR) spectroscopy, proton nuclear magnetic resonance (H-1 NMR) spectroscopy, dynamic light scattering (DLS), and elemental analysis (EA).