Spatially resolved measurements of soot and gaseous precursors in ethylene counterflow diffusion flames up to 32 atm

We investigate the effect of pressure on both flame structure and soot formation in nitrogen diluted counterflow diffusion flames of ethylene in the 8–32atm pressure range. Capillary-probe gas sampling is performed to resolve spatially the profiles of gaseous species up to three-ring aromatics by GC/MS analysis and multi-color pyrometry is used to quantify the soot volume fraction and dispersion exponent. Self-similarity of flames is preserved by keeping constant mixture fraction and strain rate, so that profiles of concentrations and temperature, normalized with respect to their peak values, are unaffected by changes in pressure, once the axial coordinate is nondimensionalized with respect to the pressure-dependent diffusion length scale. When conditions are chosen so that the overall soot loading is approximately constant and compatible with the diagnostics, it is found that both the soot volume fraction and the profiles of key aromatics in the high-temperature nucleation region are virtually invariant. For it to happen, a twofold increase in pressure must be compensated by a ～100 K decrease in peak flame temperature and, therefore, in the temperature across the soot forming region. The implication is that from the perspective of the chemical kinetics of soot formation these two actions counterbalance each other. As pressure increases (and temperature decreases) the peak production rate of the high-temperature soot mechanism decreases and, further downstream, towards the particle stagnation plane, a low-temperature soot mechanism sets in, yielding an increase in soot H/C content. This mechanism is enhanced as the pressure is raised, causing a higher overall soot volume production rate in the 16atm flame and, especially, in the 32atm one. The role of C4/C2 species in the formation of C₆H₆ increases with increasing pressure and dominates over the recombination of propargyl radical at sufficiently high pressures. A comprehensive database is established for soot models at high pressures of relevance to applications.     

Study of MILD combustion using LES and advanced analysis tools

A cylindrical confined combustor operating under MILD condition is investigated using LES. The combustion and its interaction with turbulence are modeled using two reactor based models, PaSR and EDC. Results show that the Partially Stirred Reactor (PaSR) model yields improved estimation for mean temperature and species mole fractions compared to Eddy Dissipation Concept (EDC). LES data are analysed using advanced post-processing methods such as the chemical Tangential Stretching Rate (TSR), balance analysis and local Principle Component (PCA) analysis. TSR can identify chemical explosive (ignition-like) and contractive (burnt) regions. With the balance analysis of the convective, diffusive and reactive terms in temperature equation, regions with substantial heat release coming from ignition or flame are identified. The local PCA analysis classifies the whole domain into clusters (regions with specific features) and provides the leading species in each cluster. The three analyses correlate well with one another and it is observed that the most chemically active region locates upstream (in the near-field). Also, both autoignition and flame-like structures play equally important roles in MILD combustion.     

New insights into the seleniranium ion promoted cyclization of prenyl and propenylbenzene aryl ethers

The chromane core is widely represented in nature being part of a wide array of secondary metabolites of plant, fungal, and bacterial origin. In this paper an improved method for the chemical synthesis of differently substituted chromanes is described. Substituted 2H-1-benzopyrans have been synthesized in good to excellent yields (52–81%) by treatment of 3,3-dimethylallyl and propenylbenzene ethers of differently substituted phenols with phenylselenyl chloride.     

Vibration reduction in a flexible-link mechanism through synthesis of an optimal controller

In this paper, reduction of vibration of a flexible planar mechanism is achieved through synthesis of an optimal controller. A finite element model, based on the equivalent rigid-link system theory, is used to accurately describe the dynamic behavior of the system. The model, which accounts for geometric and inertial nonlinearities of the mechanism, has been fully validated through experimental tests. In order to be able to employ the classical optimal control theory, a suitable linear model has been derived from the original one by means of a suitable linearization procedure. Vibration reduction can then be obtained by first defining an adequate performance index, which accounts for vibration amplitude, then by solving Riccati’s equation in order to find the controller that minimizes the performance index, i.e. the optimal controller. The results of several tests that have been carried out are also reported, to show the effectiveness of the synthesized control system.     

Fast preparation of hydroxyapatite/superhydrophilic vertically aligned multiwalled carbon nanotube composites for bioactive application

A method for the electrodeposition of hydroxyapatite films on superhydrophilic vertically aligned multiwalled carbon nanotubes is presented. The formation of a thin homogeneous film with high crystallinity was observed without any thermal treatment and with bioactivity properties that accelerate the in vitro biomineralization process and osteoblast adhesion.     

Photoluminescence in Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>-doped silica-titania inverse opal structures

Er³⁺ photoluminescence (PL) and Yb³⁺ → Er³⁺ energy transfer (ET) phenomena in the near infrared (NIR) have been studied in three-dimensional (3-D) inverse opal (IO) structures synthesized by a colloidal/sol–gel route, starting with the deposition of polystyrene microsphere (235 nm and 460 nm diameter) direct opal templates by convective self-assembly, followed by infiltration of the interstices with Er³⁺/Yb³⁺-doped silica, titania and silica-titania sols and heat-removal of the polymeric template material. The crystalline quality of the IOs has been optimized through suitable substrate treatments, plus the control of temperature and humidity during deposition of the templates. The structural and optical properties of the 3-D opal and IO structures have been studied by field emission scanning electron microscopy and visible-NIR reflection spectroscopy, in order to assess the relationship between microstructure and the photonic properties obtained. Photonic bandgaps have been evidenced by the corresponding stop bands in the reflection spectra. The shape and the intensity of the Er^{3+ 4}I_13/2 → ⁴I_15/2 transition at ~1.5 μm were modified in most IOs relatively to similar matrix deposits without a photonic crystal structure, particularly in the case of pure silica and titania IOs, where the PL peak narrowed and intensified. It was not possible at this stage to detect Yb³⁺ → Er³⁺ ET phenomena in the IOs structures.     

UV‐Dissipation Mechanisms in the Eumelanin Building Block DHICA

The UV‐dissipative mechanisms of the eumelanin building block 5,6‐dihydroxyindole‐2‐carboxylic acid (DHICA) and the 4,7‐dideutero derivative (DHICA‐d₂) in buffered H₂O or D₂O have been characterized by using ultrafast time‐resolved fluorescence spectroscopy. Excitation of the carboxylate anion form, the dominating state at neutral pH, leads to dual fluorescence. The band peaking at λ=378 nm is caused by emission from the excited initial geometry. The second band around λ=450 nm is owed to a complex formed between the mono‐anion and specific buffer components. In the absence of complex formation, the mono‐anion solely decays non‐radiatively or by emission with a lifetime of about 2.1 ns. Excitation of the neutral carboxylic acid state, which dominates at acidic pH, leads to a weak emission around λ=427 nm with a short lifetime of 240 ps. This emission originates from the zwitterionic state, formed upon excitation of the neutral state by sub‐ps excited‐state intramolecular proton transfer (ESIPT) between the carboxylic acid group and the indole nitrogen. Future studies will unravel whether this also occurs in larger building blocks and ESIPT is a built‐in photoprotective mechanism in epidermal eumelanin.