High-temperature cation ordering in olivine: an in situ Mössbauer study of synthetic (Mg0.55Fe0.45)2 SiO4

High-temperature in situ Mössbauer spectroscopy measurements (300–950°C) were done on synthetic olivine of composition (Mg_0.55Fe_0.45)₂ SiO₄ (=Fa45) in order to study the distribution of Fe^2?+? over the M1 and M2 octahedral sites. The spectra are fit with two doublets, which are assigned to Fe^2?+? at the M1 (smaller splitting) and M2 sites. The Fe^2?+? site-occupancies at M1 and M2, obtained from the Mössbauer relative areas, suggest that Fe^2?+? has a slight preference for the M1 site at temperatures below ~500°C, with a tendency of disordering around this temperature. At higher temperatures, Fe^2?+? again prefers to occupy the M1 site, where it shows a considerable order at this site up to 750°C. At still higher temperatures, the spectra indicated partial reduction of the Fa-component into metallic iron and the resolution of the doublets was severely deteriorated.     

Polarization correlations in the two�Cphoton decay of hydrogen�Clike ions

Polarization properties of the photons emitted in the two?Cphoton decay of hydrogen?Clike ions are studied within the framework of the density matrix and second-order perturbation theory. In particular, we derive the polarization correlation function that gives the probability of the (two?Cphoton) coincidence measurement performed by polarization?Csensitive detectors. Detailed calculations of this function are performed for the 2s _1/2 ??1s _1/2 transition in neutral hydrogen as well as Xe^53?+? and U^91?+? ions. The obtained results allow us to understand the influence of relativistic and non?Cdipole effects on the polarization correlations in the bound?Cbound two?Cphoton transitions in heavy ions.     

Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Theoretical study on the reaction of CH3CHCl + NO2

The detailed reaction mechanism of 1-chloroethyl radical with NO₂ is investigated theoretically. The results show that the title reaction is more favourable on the singlet potential energy surface than on the triplet one. For the singlet PES of CH₃CHCl?+?NO₂, it is shown that the CH₃CHCl radical can react with NO₂ to barrierlessly generate adduct a (H₃CHClCNO₂), b₁ (H₃CHClCONO-trans), and b₂ (H₃CHClCONO-cis), respectively. A total of six energetically reaction pathways and ten products are found. However, the most competitive path way is P₁ (CH₃CHO?+?ClNO), which can further dissociate to give P₆ (CH₃CHO?+?Cl?+?NO) and P₂ (CH₃CClO?+?HNO). The present results can lead to a deep understanding of the mechanism of the title reaction and may be helpful for understanding the halogenated ethyl chemistry.     

First-principles study of LiMPO4 compounds (M=Mn,Fe, Co,Ni) as electrode material for lithium batteries

The intercalation voltages of cathode materials for rechargeable lithium-ion batteries are calculated for lithium-orthophosphate oxides LiMPO₄ (M=Mn, Fe, Co and Ni) using density-functional theory within the local-density (LDA) and LDA?+?U approximations. We show that the LDA?+?U approximation is able to reproduce the experimental volumes as well as the experimentally observed magnetic structures of the lithiated and non-lithiated compounds for which LDA qualitatively fail. Moreover, we find that, using the LDA?+?U approach, the experimental evolution of the lithium intercalation voltage along the series can be reproduced accurately.     

Experimental and kinetic modeling study of α-methylnaphthalene laminar flame speeds

α-Methylnaphthalene (AMN) is the primary reference bicyclic aromatic compound of diesel, and it is commonly used as a component of diesel, kerosene and jet-fuel surrogates formulated to describe real fuel combustion kinetics. However, few experimental data on neat AMN combustion are available in the literature. This work provides the first measurements of laminar flame speed profiles of AMN/air mixtures at 1 bar varying the initial temperature from 425 to 484 K, and equivalence ratio (φ) between 0.8 and 1.35 paving the way for the kinetic study of AMN combustion chemistry at high temperatures (>1800 K). The experimental data obtained in a spherical reactor are compared with kinetic model simulations. Specifically, the AMN kinetics is implemented from its analogous monocyclic aromatic compound, i.e., toluene, through the analogy and rate rule approach. This method allows to develop kinetic mechanisms of large species from the kinetics of smaller ones characterized by analogous chemical features, namely the aromaticity and the methyl functionality in the case of toluene and AMN. In doing so, it is possible to overcome the need of high-level electronic structure calculations for the evaluation of rate constants, as their computational cost increases exponentially with the number of heavy atoms of the selected species. To assess the validity of this approach, ab initio calculations are performed to derive the rate constants of the H-atom abstraction reactions by H, OH and CH₃ radicals from both toluene and AMN. The kinetic model obtained satisfactorily agrees with the measured laminar flame speed profiles. Sensitivity and flux analyses are performed to investigate similarities and differences between the main reaction channels of toluene and AMN combustion, with the former leading to ∼6 cm/s faster flame speed at almost identical conditions (P=1 bar, T∼425 K), as evidenced by both kinetic model simulations and experimental findings.     

Determination of Copper(II) Ion Concentration by Lifetime Measurements of Green Fluorescent Protein

The understanding of cellular processes and functions and the elucidation of their physiological mechanisms is an important aim in the life sciences. One important aspect is the uptake and the release of essential substances as well as their interactions with the cellular environment. As green fluorescent protein (GFP) can be genetically encoded in cells it can be used as an internal sensor giving a deeper insight into biochemical pathways. Here we report that the presence of copper(II) ions leads to a decrease of the fluorescence lifetime (τ _fl) of GFP and provide evidence for Förster resonance energy transfer (FRET) as the responsible quenching mechanism. We identify the His₆-tag as the responsible binding site for Cu^2?+? with a dissociation constant K _d ?=?9 ±2 μM and a Förster radius R ₀?=?2.1 ±0.1 nm. The extent of the lifetime quenching depends on [Cu^2?+?] which is comprehended by a mathematical titration model. We envision that Cu^2?+? can be quantified noninvasively and in real-time by measuring τ _fl of GFP.     

Composites of polyester + glass fiber residues vs. composites with mineral fillers

Polymer composites, such as those composed of a polyester, glass fibers (GFs), and mineral fillers (e.g. CaCO₃), pose a threat to the environment because of the growing amount of residues and due to difficulties in their recycling. Therefore, we have studied effects of incorporation of (polyester?+?GFs) waste material as a filler into virgin composites. Two types of polyester?+?glass fiber composites were developed using hot compression molding, one of them with recycled (polyester?+?glass fiber) material obtained via knife or ball milling; the other, a control group, contained CaCO₃, a traditional filler in this field. Dynamic friction and wear rate were determined using a pin-on-disk tribometer and a stylus profilometer, respectively. As expected, the presence of the residues significantly decreases dynamic friction and wear rate when compared to CaCO₃, since the main constituent of the residues is a polymeric material. Thus, polyester?+?glass fiber composite residues are a candidate for a partial substitution of CaCO₃. This should lower the environmental contamination caused by discarding the residues as well as provide composites with lower wear rates.     

Niobian iron oxides as heterogeneous Fenton catalysts for environmental remediation

Heterogeneous Fenton or Fenton-like reagents consist of a mixture of an iron-containing solid matrix and a liquid medium with H₂O₂. The Fenton system is based on the reaction between Fe^2?+? and H₂O₂ to produce highly reactive intermediate hydroxyl radicals (^???OH), which are able to oxidize organic contaminants, whereas the Fenton-like reaction is based on the reaction between Fe^3?+? and H₂O₂. These heterogeneous systems offer several advantages over their homogeneous counterparts, such as no sludge formation, operation at near-neutral pH and the possibility of recycling the iron promoter. Some doping transition cations in the iron oxide structure are believed to enhance the catalytic efficiency for the oxidation of organic substrates in water. In this work, goethites synthesized in presence of niobium served as precursors for the preparation of magnetites (niobian magnetites) via chemical reduction with hydrogen at 400°C. These materials were used as Fenton-like catalysts. Both groups of (Nb, Fe)-oxide samples were characterized by ⁵⁷Fe Mössbauer spectroscopy at 298 K. The results show that increasing niobium contents raise the catalytic potential for decomposition of methylene blue, which was, in this work, used as a model molecule for organic substrates in water.     

A kinetic modeling study on the oxidation of primary reference fuel-toluene mixtures including cross reactions between aromatics and aliphatics

A detailed chemical kinetic model for the mixtures of primary reference fuel (PRF: n-heptane and iso-octane) and toluene has been proposed. This model is divided into three parts; a PRF mechanism [T. Ogura, Y. Sakai, A. Miyoshi, M. Koshi, P. Dagaut, Energy Fuels 21 (2007) 3233-3239], toluene sub-mechanism and cross reactions between PRF and toluene. Toluene sub-mechanism includes the low temperature kinetics relevant to engine conditions. A chemical kinetic mechanism proposed by Pitz et al. [W.J. Pitz, R. Seiser, J.W. Bozzelli, et al., in: Chemical Kinetic Characterization of the Combustion of Toluene, Proceedings of the Second Joint Meeting of the U.S. Sections of the Combustion Institute, 2001] was used as a starting model and modified by updating rate coefficients. Theoretical estimations of rate coefficients were performed for toluene and benzyl radical reactions important at low temperatures. Cross reactions between alkane, alkene, and aromatics were also included in order to account for the acceleration by the addition of toluene into iso-octane recently found in the shock tube study of the ignition delay [Y. Sakai, H. Ozawa, T. Ogura, A. Miyoshi, M. Koshi, W.J. Pitz, Effects of Toluene Addition to Primary Reference Fuel at High Temperature, SAE 2007-01-4104, 2007]. Validations of the model were performed with existing shock tube and flow tube data. The model well predicts the ignition characteristics of PRF/toluene mixtures under the wide range of temperatures (500-1700 K) and pressures (2-50 atm). It is found that reactions of benzyl radical with oxygen molecule determine the reactivity of toluene at low temperature. Although the effect of toluene addition to iso-octane is not fully resolved, the reactions of alkene with benzyl radical have the possibility to account for the kinetic interactions between PRF and toluene.     

A DFT-based microkinetic theory for Fe2O3 reduction by CO in chemical looping

Redox kinetics of oxygen carrier in chemical looping is an important component for material preparation, reactor design and process demonstration. How to bridge the gap between the microscale density functional theory (DFT) and the macroscale redox kinetics and develop a first-principle-based theoretical model is still a challenge in the field of chemical looping. This study addresses this challenge and proposes a DFT-based microkinetic rate equation theory to calculate the heterogeneous kinetics of Fe₂O₃ reduction by CO in chemical looping. Firstly, the DFT calculation is adopted to search the reaction pathways and to obtain the energy barriers of elementary reactions. Secondly, the DFT results are introduced into the transition state theory (TST) to calculate the reaction rate constants and build the rate equations of elementary surface reactions. Finally, by considering the bulk diffusion, a rate equation is developed to bridge the gap between the elementary surface reactions and the grain conversion. In the theory, the reaction mechanism obtained from DFT and kinetic rate constants obtained from TST are directly implemented into the rate equation to predict the reduction kinetics of oxygen carriers without fitting experimental data. The accuracy of the developed theory is validated by experimental data of two Fe₂O₃ oxygen carriers obtained from the thermogravimetric analyzer (TGA). The microkinetic rate equation theory is based on the first principles calculation and can predict directly the redox kinetics of oxygen carriers without depending on the experimental kinetic data, therefore, it provides a powerful theoretical tool to screen the oxygen carrier materials and optimize the microstructure of oxygen carriers.     

Strangeness production in AA collisions at SIS18

Aluminium oxides doped with 1% ⁵⁷Fe were prepared by sol-gel method, and annealed for 3 hours at various temperatures between 550°C and 1100°C. Amorphous phases were obtained below 1000°C, and crystalline α–Al₂O₃ was formed at 1100°C. Although Al₂O₃ itself shows diamagnetism, the light doping of Fe ions into aluminium oxide induced a very weak ferromagnetism, but the ferromagnetism disappeared by longer annealing. M?ssbauer spectra were composed of paramagnetic Fe^2?+? and Fe^3?+? species for samples heated below 750°C, and of paramagnetic Fe^3?+? above 850°C, in addition to a magnetic sextet and relaxation peaks of Fe^3?+?. The magnetic and quadrupole interactions of the sextet and the relaxation peaks and the density functional calculations suggest that the lightly doped Fe^3?+? ions are substituted at Al sites in the Al₂O₃ lattice.     

Static dissolution rate of tungsten film versus chemical adjustments of a reused slurry for chemical mechanical polishing

Tungsten is widely used as deposited layer for the multi-level interconnection structures of wafers. The chemical composition of abrasive slurry plays an important role in chemical mechanical polishing (CMP) process. Removal of tungsten is driven by complex oxidation mechanisms between slurry components. The slurry for tungsten CMP generally contains oxidizer, iron catalyst, complexing agents and stabilizers in a pH adjusted solution of abrasive particles. Interaction between iron complex and H₂O₂ in the slurry is the main factor governing the chemical mode of material removal, oxidation potencies and kinetics.In this study, we investigate the effects of chemical additives in silica (SiO₂)-based slurry on the removal rate of the tungsten film. Experiments were carried out in static batch as a preliminary study to understand and optimize chemical mechanisms in CMP-Tungsten process. Experiment designs were conducted to understand the influence of the chemical additives on the main performances of W-CMP. Used slurry, concentrated and retreated with chemical adjustments, is compared to the original slurry as a reference.     

A comparative study on the effect of hydrodynamic interactions in the non-sequential deposition of concentrated colloidal dispersions: stochastic rotation dynamics and Brownian dynamics simulations

Irreversible adsorption of particles onto a flat surface as a consequence of sedimentation colloidal suspension has been studied by two simulation techniques: Brownian dynamics (BD) and stochastic rotation dynamics (SRD). The purpose of using both methods is to investigate the effect of hydrodynamic interactions on adsorption kinetics and structure of the first monolayer of sediment obtained from the sedimentation of a concentrated and monodisperse colloidal suspension. Three systems were studied, characterised by the Péclet numbers: 0.1, 1.0 and 10. To physically understand the kinetic behaviour, simulation results were analysed using a kinetic model based on chemical reactions. High values of jamming limit (θ_∞ > 0.61) were obtained for both simulation techniques, with the SRD showing the highest figures (0.631) due to the hydrodynamics effect that takes into account the fluid backflow produced on particle sedimentation. A two-step adsorption mechanism was proposed based on the observed kinetic behaviour.     

Shock-tube study on high-temperature CO formation during dry methane reforming

The use of natural-gas-fueled combustion engines at unusual operating conditions to provide electrical and/or chemical energy on demand emphasizes the need for fundamental research on decomposition and formation of base chemicals at these conditions. In this work, the CO formation behind reflected shock waves from the pyrolysis of CO₂/CH₄ mixtures was investigated for the first time in the context of engine-based dry methane reforming, to understand the interaction of CO₂ and CH₄ at high temperatures and to test the validity of literature reaction mechanisms. Different CO₂/CH₄ mixtures at atmospheric pressure and temperatures between 1900 K and 2700 K were investigated. Time-resolved CO measurements were performed by laser absorption using a quantum cascade laser.With increasing CO₂ addition later reaction onset was observed, showing a reduction in the overall reactivity. Rate of production and sensitivity analyses highlight competing reactions in the pyrolysis and oxidation pathways and that the number of available H radicals is limited, which is attributed to the reduced reactivity. However, the analysis shows that CO₂ is also a source for OH radicals (via CO₂ + H ⇌ CO + OH), which enhance methane decomposition. The comparison with literature reaction mechanisms showed that none of the tested mechanisms can perfectly predict the time-resolved CO formation, highlighting the need for the validation of detailed kinetics models under nontypical conditions.     

Computational study on mechanisms and pathways of the atmospheric NH2 + IO reaction

ABSTRACT

The potential-energy surfaces of the amino radical (NH₂) with IO reaction have been studied at the CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) level. Two kinds of pathways are revealed, namely H-abstraction and addition/elimination. Rice–Ramsperger–Kassel–Marcus theory and transition state theory are employed to calculate the overall and individual rate constants over a wide range of temperatures and pressures. It is predicted that, at atmospheric pressure with N2 as bath gas, the formation of P1 (HI?+?HNO) is the dominant pathways at 200–700?K, while the direct H-abstraction leading to P3 (³NH?+?HOI) takes over the reaction at a temperature above 700?K. At the high-pressure limit, IM1 [IONH₂] formed by collisional stabilisation is dominant at 200–700?K; the direct H-abstraction resulting in P3 (³NH?+?HOI) plays an important role at higher temperatures. However, the total rate constants are independence on the pressure; however, the individual rate constants are sensitive to pressure. The atmospheric lifetime of NH₂ in IO is around one week. TD-DFT computations imply that IM1 [IONH₂], IM1A [IONH₂′], IM2 [IN(H₂)O], IM3 [OINH₂], IM4 [HOINH], tra-IM5 [tra-HON(H)I] and cis-IM5 [cis-HON(H)I] will photolyze under the sunlight.     

57Fe hyperfine interactions in M1 and M2 sites of olivine from Omolon meteorite: study using Mössbauer spectroscopy

Study of olivine (Fe, Mg)₂SiO₄ from Omolon meteorite was performed using Mössbauer spectroscopy with a high velocity resolution at 295 and 90 K. Components related to ⁵⁷Fe in crystallographically non-equivalent M1 and M2 sites in olivine were determined and its Mössbauer hyperfine parameters were evaluated at both temperatures. A Fe^2?+?–Mg^2?+? distribution coefficient and a temperature of cation equilibrium distribution for olivine from Omolon were evaluated on the basis of Mössbauer parameters.     

Finding confined water in the hexagonal phase of Bi0.05Eu0.05Y0.90PO4·xH2O and its impact for identifying the location of luminescence quencher

¹H MAS NMR spectra of Bi_0.05Eu_0.05Y_0.90PO₄·xH₂O show chemical shift from ?0.56 ppm at 300 K to ?3.8 ppm at 215 K and another one at 5–6 ppm, which are related to the confined or interstitial water in the hexagonal structure and water molecules on the surface of the particles, respectively. Negative value of the chemical shift indicates that H of H₂O is closer to metal ions (Y^3?+? or Eu^3?+?), which is a source of luminescence quencher. H coupling and decoupling ³¹P MAS NMR spectra at 300 and 250 K show the same chemical shift (?0.4 ppm) indicating that there is no direct bond between P and H. It is concluded that the confined water is not frozen even at 215 K because of the less number of H-bonding.     

Shock tube study of natural gas oxidation at propulsion relevant conditions

Global climate change and rising crude oil prices have motivated search of clean, sustainable and economic fuel. Methane, having the highest hydrogen to carbon ratio is ideally the best option towards carbon neutral emissions and reduce greenhouse gas emissions. However, there the economic benefits are minimal when using pure methane because of purification costs. Natural gas primarily consists of methane but with appreciable amounts of C₂C₄ alkanes which significantly impact oxidation performance, especially when compared to pure methane at high pressures and temperatures, studies of natural gas have been scarce and there is new interest in studying natural gas for its application to propulsion devices. This single pulse shock tube study investigates the effect of natural gas composition on species yields as a function of temperature at various stoichiometric conditions (φ ≈ 0.5, 1.0, 2.0) and high pressure (240 atm) over a nominal reaction time of 2.5 ms. The experimentally measured speciation results for one real natural gas sample from Boise, ID (USA) and a reference natural gas sample are compared to species yield predictions using well established chemical kinetic mechanisms, to check the feasibility of using these mechanisms in the design of propulsion devices. The chemical kinetic simulations are carried out using the constant pressure approach as well as the changing pressure approach which considers the exact measured pressure change in the shock tube. The experiments provide a large speciation data set for optimizing chemical kinetic mechanisms for natural gas applications and to understand the effect of composition on natural gas chemical kinetics. The predictions vary significantly between models tested and effect of composition variation was evident. Aramco Mech 3.0 could predict the experiments almost perfectly, especially at fuel rich conditions.