How coherent structures dominate the residence time in a bubble wake: an experimental example

Mixing timescales and residence times in reactive multiphase flows can be essential for product selectivity. For instance when a gas species is consumed e.g. by a competitive consecutive reaction with moderate reaction kinetics where reaction timescales are comparable to relevant mixing timescales. To point out the importance of the details of the fluid flow, we analyze experimental velocity data from a Taylor bubble wake by means of Lagrangian methods. By adjusting the channel diameter in which the Taylor bubble rises, and thus the rise velocity, we obtain three different wake regimes. Remarkably the normalized residence times of passive particles advected in the wake velocity field show a peak for intermediate rise velocities. This fact seems unintuitive at first glance because one expects a faster removal of passive tracers for a faster overall flow rate. However, the details of the flow topology analyzed using Finite Time Lyapunov Exponent (FTLE) fields and Lagrangian Coherent Structures (LCS) reveal the existence of a very coherent vortical pattern in the bubble wake which explains the long residence times. The increased residence times within the vortical structure and the close bubble interface acting as a constant gas species source could enhance side product generation of a hypothetical competitive consecutive reaction, where the first reaction with the gas species forms the desired product and the second the side product.Comment: 13 pages, 7 figures, 1 tabl

New Guanidine-Pyridine Copper Complexes and Their Application in ATRP

The guanidine hybrid ligands, (tetramethylguanidine)methylenepyridine (TMGpy) and (dimethylethyleneguanidine)methylenepyridine (DMEGpy), were proven to be able to stabilize copper complexes active in the solvent-free polymerization of styrene at 110 degrees C using 1-phenylethylbromide as the initiator. The polymerization proceeded after first-order kinetics, and polystyrenes with polydispersities around 1.2 could be obtained. Using the ligand, DMEGpy, three new copper guanidine-pyridine complexes could be synthesized and structurally characterized. Their structural characteristics are discussed

New Guanidine-Pyridine Copper Complexes and Their Application in ATRP

The guanidine hybrid ligands, (tetramethylguanidine)methylenepyridine (TMGpy) and (dimethylethyleneguanidine)methylenepyridine (DMEGpy), were proven to be able to stabilize copper complexes active in the solvent-free polymerization of styrene at 110 degrees C using 1-phenylethylbromide as the initiator. The polymerization proceeded after first-order kinetics, and polystyrenes with polydispersities around 1.2 could be obtained. Using the ligand, DMEGpy, three new copper guanidine-pyridine complexes could be synthesized and structurally characterized. Their structural characteristics are discussed

Towards New Robust Zn(II) Complexes for the Ring-Opening Polymerization of Lactide Under Industrially Relevant Conditions

The synthesis of bio-based and biodegradable plastics is a hot topic in research due to growing environmental problems caused by omnipresent plastics. As a result, polylactide, which has been known for years, has seen a tremendous increase in industrial production. Nevertheless, the manufacturing process using the toxic catalyst Sn(Oct)2 is very critical. As an alternative, five zinc acetate complexes have been synthesized with Schiff base-like ligands that exhibit high activity in the ring-opening polymerization of non-purified lactide. The systems bear different side arms in the ligand scaffold. The influence of these substituents has been analyzed. For a detailed description of the catalytic activities, the rate constants kapp and kp were determined using in-situ Raman spectroscopy at a temperature of 150 °C. The polymers produced have molar masses of up to 71 000 g mol−1 and are therefore suitable for a variety of applications. Toxicity measurements carried out for these complexes proved the nontoxicity of the systems. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Optically Induced Avoided Crossing in Graphene

Degenerate states in condensed matter are frequently the cause of unwanted fluctuations, which prevent the formation of ordered phases and reduce their functionalities. Removing these degeneracies has been a common theme in materials design, pursued for example by strain engineering at interfaces. Here, we explore a non-equilibrium approach to lift degeneracies in solids. We show that coherent driving of the crystal lattice in bi- and multilayer graphene, boosts the coupling between two doubly-degenerate modes of E1u and E2g symmetry, which are virtually uncoupled at equilibrium. New vibronic states result from anharmonic driving of the E1u mode to large amplitdues, boosting its coupling to the E2g mode. The vibrational structure of the driven state is probed with time-resolved Raman scattering, which reveals laser-field dependent mode splitting and enhanced lifetimes. We expect this phenomenon to be generally observable in many materials systems, affecting the non-equilibrium emergent phases in matter.Comment: 13 pages, 4 figure

Using a bio-inspired copper complex to investigate reactive mass transfer around an oxygen bubble rising freely in a thin-gap cell

The present study describes an original colorimetric method to visualize and quantify the local oxygen mass transfer around a rising bubble in reactive media. This method is based on the use of a colorless bio-inspired copper complex, Cu(btmgp)I, specially tailored for the study, which, dissolved in acetonitrile, oxidizes into an orange copper-complex [Cu2O2(btmgp)2]I2. The latter complex, unstable at ambient temperature, decays quite fast into two Cu(II) complexes, leaving a permanent pale-green color as final products. The flow investigated consists in a pure oxygen single bubble rising freely in a confined thin-gap cell (400 × 200 × 1 mm). A wide range of motion regimes for the bubbles are observed as the Archimedes number ranges from and the Reynolds number from . A high-resolution 16-bit sCMOS camera, combined with specific filters, is used to capture images from a region-of-interest of the cell, illuminated by a white LED backlight panel. An ad hoc calibration protocol is developed to correlate the grey-levels from the colored signal to the equivalent oxygen concentrations. This procedure then allows to measure indirectly the amount of oxygen transferred to the liquid phase. The series of images are also treated to identify the bubble motion and properties. Thanks to this method, equivalent oxygen concentration fields, gap-averaged and time-averaged, can be reached with high precision in the far-field wake of the bubbles, enabling thus to deeply characterize the mass transfer mechanisms under reactive conditions in such confined configuration, and to establish a dimensionless representation in terms of Sherwood number versus Peclet number. At last, thanks to the knowledge of the kinetic rate of the reaction and of the diffusion coefficients, the Hatta number and the enhancement factor are estimated, and thus the intrinsic Sherwood numbers; these results demonstrate that the enhancement of the mass transfer by the reactions involved with the copper-complexes is not negligible (almost 12–15%)

Simple Zn(ii) complexes for the production and degradation of polyesters

Nine new complexes based on thioether appended iminophenolate (ONS) ligands have been prepared and fully characterized in solution by NMR spectroscopy. Solid-state structures were also obtained for seven complexes. In solution, all complexes were monomeric. The complexes were highly active for the polymerization of purified rac-lactide ([M] : [Zn] : [BnOH] = 10 000 : 1 : 30 at 180 °C) reaching TOF values up to 250 000 h−1. The kinetics of the polymerization have been probed by in situ Raman spectroscopy. The rate of reaction was dramatically reduced using technical grade rac-lactide with increased initiator loading. To move towards a circular economy, it is vital that catalysts are developed to facilitate chemical recycling of commodity and emerging polymeric materials. In this vein, the complexes have been assessed for their ability to break down poly(lactic acid) and poly(ethylene terephthalate). The results from both the polymerization and degradation reactions are discussed in terms of ligand functionality