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.     

Perovskites as Precursors for Ni/La2O3 Catalysts in the Dry Reforming of Methane: Synthesis by Constant pH Co‐Precipitation,Reduction Mechanism and Effect of Ru‐Doping

LaNiO₃ perovskite is an interesting precursor for Ni/La₂O₃ catalysts for the dry reforming of methane at high temperatures. Precursors have been synthesized by co‐precipitation without, with 2.5 at %, and with 5 at % Ru doping. The presence of Ru leads to a stabilization of the perovskite structure and hinders the decomposition into NiO and Ruddlesden‐Popper mixed oxides La_n+1Ni_nO_3n+1, which was observed for the Ru‐free sample upon calcination at 1000 °C (n = 3). Upon reduction in hydrogen, a mechanism involving at least two steps was observed and the first major step was identified as the partial reduction of the precursor leading to a LaNiO_2.5‐like intermediate. The second major step is the reduction to Ni metal supported on La₂O₃ independent of the Ru content of the catalyst. In the presence of Ru, indications for Ni‐Ru alloy formation and for a higher dispersion of the metallic phase were found. The catalytic activity in DRM of the catalyst containing 2.5 % Ru was superior to the catalysts with more or without Ru. Furthermore, the propensity of coke formation was reduced by the presence of Ru.     

The nonribosomal peptide synthetase enzyme DdaD tethers N(β)-fumaramoyl-l-2,3-diaminopropionate for Fe(II)/α-ketoglutarate-dependent epoxidation by DdaC during dapdiamide antibiotic biosynthesis

The gene cluster from Pantoea agglomerans responsible for biosynthesis of the dapdiamide antibiotics encodes an adenylation-thiolation didomain protein, DdaD, and an Fe(II)/α-ketoglutarate-dependent dioxygenase homologue, DdaC. Here we show that DdaD, a nonribosomal peptide synthetase module, activates and sequesters N(β)-fumaramoyl-l-2,3-diaminopropionate as a covalently tethered thioester for subsequent oxidative modification of the fumaramoyl group. DdaC catalyzes Fe(II)- and α-ketoglutarate-dependent epoxidation of the covalently bound N(β)-fumaramoyl-l-2,3-diaminopropionyl-S-DdaD species to generate N(β)-epoxysuccinamoyl-DAP (DAP = 2,3-diaminopropionate) in thioester linkage to DdaD. After hydrolytic release, N(β)-epoxysuccinamoyl-DAP can be ligated to l-valine by the ATP-dependent ligase DdaF to form the natural antibiotic N(β)-epoxysuccinamoyl-DAP-Val.     

Simultaneous measurements of heat of hydration and chemical shrinkage on hardening cement pastes

Isothermal calorimetry and chemical shrinkage measurements are two independent techniques used to study the development of hydration in cementitious systems. In this study, calorimetry and chemical shrinkage measurements were combined and simultaneously performed on hydrating cement paste samples. Portland cement pastes with different water to cement ratios and a cement paste containing calcium sulfoaluminate clinker and anhydrite were studied. The combined calorimetry/chemical shrinkage test showed good reproducibility and revealed the different hydration behavior of sealed samples and open samples, i.e., samples exposed to external water during hydration. Large differences between sealed and open samples were observed in a Portland cement paste with low water to cement ratio and in the calcium sulfoaluminate paste; these effects are attributed to self-desiccation of the sealed pastes. Once the setup is fully automatized, it is expected that combined calorimetry/chemical shrinkage measurements can be routinely used for investigating cement hydration.     

Enhanced angular tolerance of resonant waveguide grating reflectors

We introduce an approach to enhance the angular tolerance of resonant waveguide gratings by stacking two resonant structures on top of each other. It is shown that reflectivities close to unity can be retrieved over the entire angular spectrum by a double T-shaped grating configuration. Although a combination of silicon as the high-index and diamond as the low-index material is considered, the principles of our new approach can also be used to realize monolithic silicon structures with similar properties. We illustrate that the functionality of the device can be understood by a decomposition into separated elements. Our approach might have compelling applications as new diffractive-reflective optical components with low-coating thermal noise in the field of high-precision metrology.     

Widely tunable monolithic narrowband grating filter for near-infrared radiation

We propose a monolithic narrowband guided-mode grating filter in fused silica that is widely tunable in the near-IR wavelength region. Based on a recently demonstrated approach for a monolithic reflector comprising an encapsulated grating, we theoretically investigate such a device by means of rigorous modeling aimed at a narrow linewidth. It is demonstrated that upon a spatial variation of the filter's grating period its resonance wavelength can be tuned in a remarkably wide range of near-IR radiation with 800 nm<λ(res)< 1600 nm by translating the laser beam relative to the grating area. The filter performance in terms of linewidth and contrast is essentially preserved over the entire tuning interval.     

Experimental and numerical investigation of paperboard creasing

Laminated paperboard is widely used in packaging products. It usually consists of multiple layers bonded to each other by starch or adhesion. The indentation of fold lines (creasing) plays a crucial role during the whole converting process. It is important to control delamination and other damage effects to arrive at commercial cartons with high quality. Thus, the aim of this study is to describe the material behavior of a laminated paperboard during the creasing process. The paperboard was considered as a laminate of three different layers, and each was modeled separately with an anisotropic elastic-plastic material model while a cohesive zone approach described the opening behavior in between. The initial yielding was given by the Hill's 48 yield criterion, while the isotropic strain hardening was described by a power law hardening function. To calibrate the material parameters, a sequence of tensile and compression tests was conducted for each layer in different directions to account for the material's anisotropy. Finally, the creasing process was investigated using a two-dimensional plane strain finite element model. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experiments and numerical simulations on damage behavior of biaxially loaded specimen

The paper deals with the effect of stress state on damage and failure behavior of isotropic ductile metals. In the continuum damage model the damage behavior of ductile metals is adequately described by a generalized damage condition and an anisotropic damage rule. The damage criterion is based on series of uniaxial experiments with differently notched specimens and corresponding numerical simulations as well as on various numerical calculations on the micro-scale. Different branches of the damage criterion depending on stress triaxiality and Lode parameter are considered. To be able to validate the proposed stress-state-dependent functions new experiments with two-dimensionally loaded specimens have been developed. Corresponding numerical simulations show that these shear-tension and shear-compression tests cover a wide range of stress triaxialities and Lode parameters. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of mixing methods on the dispersion of carbon nanotubes during the solvent-free processing of multiwalled carbon nanotube/epoxy composites

Several solvent-free processing methods to disperse multiwalled carbon nanotubes (MWCNTs) in bisphenol F-based epoxy resin were investigated, including the use of a microfluidizer (MF), planetary shear mixer (PSM), ultrasonication (US) and combinations. The processed mixture was cured with diethyl toluene diamine. Three complimentary techniques were used to characterize the dispersion of the MWCNTs in cured composite samples: optical microscopy, micro Raman spectroscopy, and scanning electron microscopy (SEM). For sample MF + PSM, optical micrographs and Raman images showed reduced agglomeration and a homogeneous distribution of MWCNTs in the epoxy matrix. SEM analysis of fractured specimen after tensile testing revealed breakage of nanotubes along the fracture surface of the composite. A comparison of the MWCNT dispersion in the epoxy samples processed using different methods showed that a combination of MF and PSM processing yields a more homogeneous sample than the PSM or US + PSM processed samples. Mechanical testing of the composites showed about 15% improvement in the tensile strength of samples processed by the MF + PSM method over other methods. Thermogravimetric analysis (TGA) results showed a small decrease in the onset degradation temperature for poorly dispersed samples produced by PSM compared with the well-mixed samples (MF + PSM). These results strongly suggest that the MF + PSM processing method yield better-dispersed and stronger MWCNT/epoxy composites. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Excited-State Properties of Thymidine and Their Relevance to Its Heterogeneous Emission in Double-Stranded DNA

Published results on synthetic polynucleotides point to T as the major emitting fluorophore in DNA. We have reported also that the bases of the nonalternating polynucleotide poly(dA).poly(dT), in which T was selectively excited, undergo large-amplitude motions on the picosecond-nanosecond time scales (S. Georghiou et al., Biophys. J. 70, 1909-1922, 1996). In that study, the fluorescence decay profile of the T bases of this polynucleotide was found to contain a number of components; these may be considered to be the result of the motions of the bases that give rise to a distribution of stacked geometries of varying rigidity as well as dispersion and polar interactions. Here, we report the results of a study that we have undertaken in order to test this hypothesis. To this effect, we have studied the photophysical properties of thymidine (1) in aqueous buffer and in a number of organic solvents and (2) in aqueous sucrose solutions of viscosity extending to 149 cP. The results suggest that the fluorescence quantum yield decreases with an increase in the polarizability of the solvent, whereas it increases with an increase in the solvent polarity (on the basis of the empirical parameter of solvent polarity ETN) or viscosity. These findings suggest the following for the photophysical properties of the T bases in DNA: (1) Base stacking results in two antagonistic effects, namely it causes a reduction in fluorescence as a result of dispersion interactions and an enhancement as a result of a reduction in the motions of the bases and (2) exposure of the bases to the aqueous environment results in fluorescence enhancement.