On the stability of conventional and nano-structured carbon-based catalysts in the oxidative dehydrogenation of ethylbenzene under industrially relevant conditions

Relevant carbon-based materials, home-made carbon-silica hybrids, commercial activated carbon, and nanostructured multi-walled carbon nanotubes (MWCNT) were tested in the oxidative dehydrogenation of ethylbenzene (EB). Special attention was given to the reaction conditions, using a relatively concentrated EB feed (10 vol.% EB), and limited excess of O2 (O 2:EB = 0.6) in order to work at full oxygen conversion and consequently avoid O2 in the downstream processing and recycle streams. The temperature was varied between 425 and 475 °C, that is about 150-200 °C lower than that of the commercial steam dehydrogenation process. The stability was evaluated from runs of 60 h time on stream. Under the applied reactions conditions, all the carbon-based materials are apparently stable in the first 15 h time on stream. The effect of the gasification/burning was significantly visible only after this period where most of them fully decomposes. The carbon of the hybrids decomposes completely rendering the silica matrix and the activated carbon bed is fully consumed. Nano structured MWCNT is the most stable; the structure resists the demanding reaction conditions showing an EB conversion of ∼30% (but deactivating) with a steady selectivity of ∼80%. The catalyst stability under the ODH reaction conditions is predicted from the combustion apparent activation energies. © 2014 Elsevier Ltd. All rights reserved.

Basin stability approach for quantifying responses of multistable systems with parameters mismatch

Acknowledgement This work is funded by the National Science Center Poland based on the decision number DEC-2015/16/T/ST8/00516. PB is supported by the Foundation for Polish Science (FNP).

Long-Term Reward Patterns Contribute to Personal Goals at Work Among Finnish Managers

The research addresses the impact of long-term reward patterns on contents of personal work goals among young Finnish managers (N = 747). Reward patterns were formed on the basis of perceived and objective career rewards (i.e., career stability and promotions) across four measurements (years 2006 –2012). Goals were measured in 2012 and classified into categories of competence, progression, well-being, job change, job security, organization, and financial goals. The factor mixture analysis identified a three-class solution as the best model of reward patterns: High rewards (77%); Increasing rewards (17%); and Reducing rewards (7%). Participants with Reducing rewards reported more progression, well-being, job change and financial goals than participants with High rewards as well as fewer competence and organizational goals than participants with Increasing rewards. Workplace resources can be in a key role in facilitating goals towards building competence and organizational performance.

Improving the stability of an oxime based electrochemical microsensor for organo-phosphate vapor detection

A micro gas sensor has been developed by our group for the detection of organo-phosphate vapors using an aqueous oxime solution. The analyte diffuses from the high flow rate gas stream through a porous membrane to the low flow rate aqueous phase. It reacts with the oxime PBO (1-Phenyl-1,2,3,-butanetrione 2-oxime) to produce cyanide ions, which are then detected electrochemically from the change in solution potential. Previous work on this oxime based electrochemistry indicated that the optimal buffer pH for the aqueous solution was approximately 10. A basic environment is needed for the oxime anion to form and the detection reaction to take place. At this specific pH, the potential response of the sensor to an analyte (such as acetic anhydride) is maximized. However, sensor response slowly decreases as the aqueous oxime solution ages, by as much as 80% in first 24 hours. The decrease in sensor response is due to cyanide which is produced during the oxime degradation process, as evidenced by the cyanide selective electrode. Solid phase micro-extraction carried out on the oxime solution found several other possible degradation products, including acetic acid, N-hydroxy benzamide, benzoic acid, benzoyl cyanide, 1-Phenyl 1,3-butadione, 2-isonitrosoacetophenone and an imine derived from the oxime. It was concluded that degradation occurred through nucleophilic attack by a hydroxide or oxime anion to produce cyanide, as well as a nitrogen atom rearrangement similar to Beckmann rearrangement. The stability of the oxime in organic solvents is most likely due to the lack of water, and specifically hydroxide ions. The reaction between oxime and organo-phosphate to produce cyanide ions requires hydroxide ions, and therefore pure organic solvents are not compatible with the current micro-sensor electrochemistry. By combining a concentrated organic oxime solution with the basic aqueous buffer just prior to being used in the detection process, oxime degradation can be avoided while preserving the original electrochemical detection scheme. Based on beaker cell experiments with selective cyanide sensitive electrodes, ethanol was chosen as the best organic solvent due to its stabilizing effect on the oxime, minimal interference with the aqueous electrochemistry, and compatibility with the current microsensor material (PMMA). Further studies showed that ethanol had a small effect on micro-sensor performance by reducing the rate of cyanide production and decreasing the overall response time. To avoid incomplete mixing of the aqueous and organic solutions, they were pre-mixed externally at a 10:1 ratio, respectively. To adapt the microsensor design to allow for mixing to take place within the device, a small serpentine channel component was fabricated with the same dimensions and material as the original sensor. This allowed for seamless integration of the microsensor with the serpentine mixing channel. Mixing in the serpentine microchannel takes place via diffusion. Both detector potential response and diffusional mixing improve with increased liquid residence time, and thus decreased liquid flowrate. Micromixer performance was studies at a 10:1 aqueous buffer to organic solution flow rate ratio, for a total rate of 5.5 μL/min. It was found that the sensor response utilizing the integrated micromixer was nearly identical to the response when the solutions were premixed and fed at the same rate.

Multiscale Schemes for the BGK--Vlasov--Poisson System in the Quasi-Neutral and Fluid Limits. Stability Analysis and First Order Schemes

This paper deals with the development and the analysis of asymptotically stable and consistent schemes in the joint quasi-neutral and fluid limits for the collisional Vlasov-Poisson system. In these limits, the classical explicit schemes suffer from time step restrictions due to the small plasma period and Knudsen number. To solve this problem, we propose a new scheme stable for choices of time steps independent from the small scales dynamics and with comparable computational cost with respect to standard explicit schemes. In addition, this scheme reduces automatically to consistent discretizations of the underlying asymptotic systems. In this first work on this subject, we propose a first order in time scheme and we perform a relative linear stability analysis to deal with such problems. The framework we propose permits to extend this approach to high order schemes in the next future. We finally show the capability of the method in dealing with small scales through numerical experiments.

Stability and Local Toxicity Evaluation of a Liposomal Prilocaine Formulation

This study reports a physicochemical stability evaluation of a previously reported liposomal prilocaine (PLC(LUV)) formulation (Cereda el al. J. Pharm. Pharmaceut. Sci. 7:235, 2004) before and after steam sterilization as well as its local toxicity evaluation. Prilocaine (PLC) was encapsulated into extruded unilamellar liposomes (LUVs) composed by egg phosphatidylcholine:cholesterol:alfa-tocopherol (4:3:0.07, mole %). Laser light-scattering analysis (p > 0.05) and thiobarbituric acid reaction (p > 0.05) were used to evaluate the liposomes physical (size) and chemical (oxidation) stability, respectively. The prilocaine chemical stability was followed by (1)H-nuclear magnetic resonance. These tests detected no differences on the physicochemical stability of PLC or PLCLUV, sterilized or not, up to 30 days after preparation (p > 0.05). Finally, the paw edema test and histological analysis of rat oral mucosa were used to assess the possible inflammatory effects of PLC(LUV). PLC(LUV) did not evoke rat paw edema (p > 0.05), and no significant differences were found in histological analysis, when compared to the control groups (p > 0.05). The present work shows that PLC(LUV) is stable for a 30-day period and did not induce significant inflammatory effects both in the paw edema test and in histological analysis, giving supporting evidence for its safely and possible clinical use in dentistry.

Asymptotic stability of a coupled Advection-Diffusion-Reaction system arising in bioreactor processes.

In this work, we perform an asymptotic analysis of a coupled system of two Advection-Diffusion-Reaction equations with Danckwerts boundary conditions, which models the interaction between a microbial population (e.g., bacterias), called biomass, and a diluted organic contaminant (e.g., nitrates), called substrate, in a continuous flow bioreactor. This system exhibits, under suitable conditions, two stable equilibrium states: one steady state in which the biomass becomes extinct and no reaction is produced, called washout, and another steady state, which corresponds to the partial elimination of the substrate. We use the method of linearization to give sufficient conditions for the asymptotic stability of the two stable equilibrium configurations. Finally, we compare our asymptotic analysis with the usual asymptotic analysis associated to the continuous bioreactor when it is modeled with ordinary differential equations.

Chatter avoidance in the milling of thin floors with bull-nose end mills: Model and stability diagrams

The milling of thin parts is a high added value operation where the machinist has to face the chatter problem. The study of the stability of these operations is a complex task due to the changing modal parameters as the part loses mass during the machining and the complex shape of the tools that are used. The present work proposes a methodology for chatter avoidance in the milling of flexible thin floors with a bull-nose end mill. First, a stability model for the milling of compliant systems in the tool axis direction with bull-nose end mills is presented. The contribution is the averaging method used to be able to use a linear model to predict the stability of the operation. Then, the procedure for the calculation of stability diagrams for the milling of thin floors is presented. The method is based on the estimation of the modal parameters of the part and the corresponding stability lobes during the machining. As in thin floor milling the depth of cut is already defined by the floor thickness previous to milling, the use of stability diagrams that relate the tool position along the tool-path with the spindle speed is proposed. Hence, the sequence of spindle speeds that the tool must have during the milling can be selected. Finally, this methodology has been validated by means of experimental tests.

The effect of chaperone compounds on glucocerebrosidase stability and activity in fibroblasts from Gaucher Disease patients with different genotypes

Dissertação de mestrado, Ciências Biomédicas, Departamento de Ciências Biomédicas e Medicina, Universidade do Algarve, 2014

On the Stability of Supersonic Boundary Layers with Injection

The problem of supersonic flow over a 5 degree half-angle cone with injection of gas through a porous section on the body into the boundary layer is studied experimentally. Three injected gases are used: helium, nitrogen, and RC318 (octafluorocyclobutane). Experiments are performed in a Mach 4 Ludwieg tube with nitrogen as the free stream gas. Shaping of the injector section relative to the rest of the body is found to admit a "tuned" injection rate which minimizes the strength of shock waves formed by injection. A high-speed schlieren imaging system with a framing rate of 290 kHz is used to study the instability in the region of flow downstream of injection, referred to as the injection layer. This work provides the first experimental data on the wavelength, convective speed, and frequency of the instability in such a flow. The stability characteristics of the injection layer are found to be very similar to those of a free shear layer. The findings of this work present a new paradigm for future stability analyses of supersonic flow with injection.

Stability and smoothness improvements for an underactuated biped with a tail

In this work we present an important improvement in our model of biped mechanism that allows the elevation in a stable form of the system's feet during the execution of trajectories. This improvement allows for simpler trajectory planning and also facilitates the reduction of losses in the collision between the feet and the ground. On the other hand, we add to the design phase the study of the displacement of the Zero Moment Point, as well as the variation of the normal component of the ground reaction force during the motion of the system. Consideration of the above mentioned magnitudes in the design phase allows us to design the necessary support area of the system. These magnitudes will be used as a smoothness criterion of the ground contact to facilitate the selection of robot parameters and trajectories.

Evaluation of DUALEM, OptRx and Grassmaster II sensors for monitoring the spatial variability and the temporal stability of a Mediterranean pasture

Site-specific management (SSM) is a form of precision agriculture whereby decisions on resource application and agronomic practices are improved to better match soil and crop requirements as they vary in the field. SSM enables the identification of regions (homogeneous management zones) within the area delimited by field boundaries. These subfield regions constitute areas that have similar permanent characteristics. Traditional soil and pasture sampling and the necessary laboratory analysis are time-consuming, labour-intensive and cost prohibitive, not viable from a SSM perspective because it needs a large number of soil and pasture samples in order to achieve a good representation of soil properties, nutrient levels and pasture quality and productivity. The main objective of this work was to evaluate technologies which have potential for monitoring aspects related to spatial and temporal variability of soil nutrients and pasture green and dry matter yield (respectively, GM and DM, in kg/ha) and support to decision making for the farmer. Three types of sensors were evaluated in a 7ha pasture experimental field: an electromagnetic induction sensor (“DUALEM 1S”, which measures the soil apparent electrical conductivity, ECa), an active optical sensor ("OptRx®", which measures the NDVI, “Normalized Difference Vegetation Index”) and a capacitance probe ("GrassMaster II" which estimates plant mass). The results indicate the possibility of using a soil electrical conductivity probe as, probably, the best tool for monitoring not only some of the characteristics of the soil, but also those of the pasture, which could represent an important help in simplifying the process of sampling and support SSM decision making, in precision agriculture projects. On the other hand, the significant and very strong correlations obtained between capacitance and NDVI and between any of these parameters and the pasture productivity shows the potential of these tools for monitoring the evolution of spatial and temporal patterns of the vegetative growth of biodiverse pasture, for identifying different plant species and variability in pasture yield in Alentejo dry-land farming systems. These results are relevant for the selection of an adequate sensing system for a particular application and open new perspectives for other works that would allow the testing, calibration and validation of the sensors in a wider range of pasture production conditions, namely the extraordinary diversity of botanical species that are characteristic of the Mediterranean region at the different periods of the year.