Multidimensional characterization,Landau levels and Density of States in epitaxial graphene grown on SiC substrates

Using high-temperature annealing conditions with a graphite cap covering the C-face of, both, on axis and 8° off-axis 4H-SiC samples, large and homogeneous single epitaxial graphene layers have been grown. Raman spectroscopy shows evidence of the almost free-standing character of these monolayer graphene sheets, which was confirmed by magneto-transport measurements. On the best samples, we find a moderate p-type doping, a high-carrier mobility and resolve the half-integer quantum Hall effect typical of high-quality graphene samples. A rough estimation of the density of states is given from temperature measurements.     

The development of a silica nanoparticle-based label-free DNA biosensor

A silica nanoparticle-based DNA biosensor capable of detecting Bacillus anthracis bacteria through the use of unlabelled ss-oligonucleotides has been developed. The biosensor makes use of the optical changes that accompany a nanoparticle-immobilized cationic conjugated polymer (polythiophene) interacting with single-stranded vs. hybridized oligonucleotides, where a fluorescence signal appears only when hybridized DNA is present (i.e. only when the ss-oligonucleotide interacting with the polymer has hybridized with its complement). In order to enhance the sensitivity of the biosensor, two different nanoparticle architectures were developed and used to elucidate how the presence of neighboring fluorophores on the nanoparticle surface affects F?rster-resonant energy transfer (FRET) between the polythiophene/oligonucleotide complex (FRET donor) and the fluorophores (FRET acceptors). We demonstrate that the silica nanoparticle-based FRET platform lowers the limit of detection at least 10-fold in comparison to the polythiophene itself, and allows the detection of ～2 × 10(-12) moles of ss-oligonucleotide in a 100 μL sample with a standard fluorimeter (i.e. has a limit of detection of ～2 nM ssDNA). Such nanoparticle-based biosensor platforms are beneficial because of the robustness and stability inherent to their covalent assembly and they provide a valuable new tool that may allow for the sensitive, label-free detection (the target DNA that produces the fluorescence signal is unlabelled) without the use of polymerase chain reaction.     

Mesoscopic Monte Carlo simulations of interfacial films in ZnO-Bi2O3 ceramics

This paper reports mesoscopic Monte Carlo simulations (in which a ‘mesoscopic particle’ corresponds to a group of atoms or molecules) of interfacial films in ZnO-Bi₂O₃ binary ceramics. We observe the formation of Bi₂O₃-rich interfacial phases at the surface of ZnO grains (surface amorphous films) or at the grain-boundary between ZnO grains (intergranular films). In qualitative agreement with the experimental results reported on premelting of ceramics, the thickness of these films increases as the temperature increases up to the eutectic temperature. Moreover, the Bi₂O₃ concentration in the surficial or intergranular films is found to be larger than in the bulk. These surficial films exhibit both some layering and lateral ordering.     

Iron oxide magnetic nanoparticles used as probing agents to study the nanostructure of mixed self-assembled monolayers

Self-assembled monolayers (SAMs) of organic molecules are of exceptional technological importance since they represent a convenient, flexible, and simple system for tuning the chemical and physical properties of surfaces. The fine control of surface properties is directly dependent on the structure of mixed SAMs which is difficult to characterize at the nanoscale with usual techniques such as scanning probe microscopies. In this study, we report on a general method to investigate at the nanoscale the structure of molecular patterns which consist in SAMs of two components. Iron oxide nanoparticles (NPs) have been used as probing agents to study indirectly the structure of mixed SAMs. Mixed SAMs were prepared by the replacement of mercaptododecane (MDD) adsorbed by mercaptoundecanoic acid (MUA) molecules on gold substrates. Therefore, the SAM surface displays both chelating carboxylic terminal groups and non-chelating methylene terminal groups. As NPs have been previously demonstrated to specifically interact with carboxylic acid groups, the increasing density in NPs was correlated with the evolution of the COOH/CH(3) terminal groups ratio. Therefore the structure of mixed SAMs was studied indirectly as well as the kinetic of the replacement reaction and its mechanism. With this aim, we took advantage of the SPR properties of the gold substrate and of the high refractive index of iron oxide nanoparticles to follow their assembling on mixed SAMs as a time resolved study. The high sensitivity and tuning of the SPR signal over a wide range of wavelengths are correlated with the NP density. Furthermore, SEM combined with image analysis has allowed studying the replacement rate of MDD by MUA in SAMs. We took also advantages of the magnetic properties of NPs to evaluate qualitatively the replacement of thiol molecules.     

Effect of the plant waste onto the properties of use and the microstructure of phyllosilicates based ceramics

The present study aimed at using plant waste (Musa Paradisiaca) for manufacturing clay-based ceramics in order to promote lower sintering temperature while preserving the properties of use. Two kaolinic-illitic clays (NZ1 and KO) from Central African Republic were used mixed with 1 to 10 mass% of the plant waste (MP). The clays and the waste exhibited accessory phases: quartz and iron oxides, and K₂O respectively. MP was collected, dried and sieved (<100 μm) previously to its mixture with clays. According to the sintering behavior of KO and NZ1 derived from thermodilatometry, the densification was obtained after firing at 1200°C. Results showed that open porosity decreased from 35% to 17% with increasing temperature in the range 900 to 1200°C for KO and NZ1. This porosity remained in the range 30%-40% while increasing the MP content (firing at 1000°C for 1h.). The optimized MP content was 3 and 5 mass% for KO and NZ1 clay materials respectively. The compressive strength and thermal conductivities were improved compared to clay samples without MP fired at 1200°C. Moreover a significant decrease in the sintering temperature was achieved, leading to energy saving in line with sustainability issues.     

Guaiacol HDO on La-modified Pt/Al2O3: Influence of rare-earth loading

The stability of the catalyst used in hydrodeoxygenation (HDO) of biomass-derived oils needs improvement. La has been applied in delaying Al₂O₃ phase-change under reaction conditions. Lanthanum (0.5–8 wt.%)-γ-alumina was studied as Pt (1 wt.%) carrier aimed at guaiacol (GUA) HDO. Materials characterization included N₂ physisorption, X-ray diffraction (XRD), thermal analysis, FTIR, UV–vis, and TPR. Solids pore size (~8–10 nm) was suitable for GUA (kinetic diameter~0.668 nm) hydrotreating. Mixed carriers were amorphous (XRD), suggesting well-dispersed La domains; meanwhile, carbonates/bicarbonates were formed (from CO₂) due to the basic surface properties of modified supports (FTIR). That could impart catalyst stability by inhibiting coking through the passivation of Lewis acidity on Al₂O₃. Pt reducibility increased with La loading in various formulations. However, that was not reflected in enhanced GUA HDO (T = 488 K and P = 3.2 MPa, batch reactor), presumably due to the strong metal–support interaction (SMSI), where LaO_x covered the metallic Pt particle surface. GUA HDO on various catalysts was approximated by pseudo-first-order kinetics (integral regime, k), where deviations were observed as La loading increased, presumably by an SMSI state that could affect the rate-determining step of the reaction mechanism. Basic sites provided by rare-earth could contribute to altering HDO reaction pathways as well. At 1 wt.% rare-earth, GUA HDO was maximized (k~25% higher than that on Pt/Al₂O₃), with that material also exhibiting similar deoxygenation (85%–90% at total GUA conversion) to the latter Pt over pristine alumina. Conversely, both parameters significantly diminished over the catalyst of the highest La content. Materials at low rare-earth concentrations deserve further studies focused on catalyst stability under HDO conditions.     

Parameter estimation and prediction uncertainties for multi-response kinetic models with uncertain inputs

Error-in-variables model (EVM) methods are used for parameter estimation when independent variables are uncertain. During EVM parameter estimation, output measurement variances are required as weighting factors in the objective function. These variances can be estimated based on data from replicate experiments. However, conducting replicates is complicated when independent variables are uncertain. Instead, pseudo-replicate runs may be performed where the target values of inputs for repeated runs are the same, but the true input values may be different. Here, we propose a method to estimate output-measurement variances for use in multivariate EVM estimation problems, based on pseudo-replicate data. We also propose a bootstrap technique for quantifying uncertainties in resulting parameter estimates and model predictions. The methods are illustrated using a case study involving n-hexane hydroisomerization in a well-mixed reactor. Case-study results reveal that assumptions about input uncertainties can have important influences on parameter estimates, model predictions and their confidence intervals.     

Simulation of polymer flow through a coat-hanger die: A comparison of two numerical approaches

Coat-hanger dies are commonly used for the extrusion of plastic sheets and films. To describe the flow of a molten polymer through a coat-hanger die, a two-dimensional approach is necessary. Moreover, the thermal effects, which play an important role in the flow distribution, have to be taken into account. In this paper, two numerical models for the simulation of coat-hanger dies are described and compared. These models differ mainly in the simplifying assumptions used and in the treatment of the thermal problem. The simulations obtained with the two models were compared with each other and with experimental data. The discrepancies between the two models can be explained by the different theoretical treatments.     

Environmental assessment of flue gas cleaning processes of municipal solid waste incinerators by means of the life cycle assessment approach

Life cycle assessment (LCA) is an environmental assessment tool generally applied to products but also to processes. Features of the LCA of processes are presented in this paper. This approach was used to compare two flue gas cleaning processes: the typical wet-type process and the new transported droplets column process. The LCA result shows that the global environmental burden is similar between the two processes, which confirms the viability of the transported droplets column. The distribution of the environmental burden, however, is different between the two processes. The weak points of the transported droplets column are the pollution transfer from air to water and a larger volume to stabilize. Its strong point: it is more efficient in capturing dust particles and toxic pollutants. This process could be improved from an environmental standpoint by adding an electrostatic filter upstream of the transported droplets column to capture the particles. The laboratory results of the transported droplets column need, however, to be confirmed at a larger scale.