Detailed validation of an automotive catalysis model using spatially resolved measurements within the catalyst substrate

Many kinetic models have appeared in literature in past decades using two main approaches: the traditional global kinetics approach, or the more complex micro-kinetics approach. Whether global or micro-kinetics, kinetic models have been based on experimental data obtained at the end of the monolith. The experimental procedure using end pipe analysis may give an accurate overview of the reaction mechanisms that occur; however, the lack of information from within the catalyst can ultimately lead to inaccuracies in the kinetic model and parameters used.

Using SpaciMS, a spatially resolved experimental technique developed at the Queen's University Belfast, information from within the catalyst can be obtained. This minimally invasive technique provides detailed information of the gas concentration and temperature profile from inside the catalytic monolith. This paper presents a kinetic model and simulations validated against experimental data obtained from three positions inside the catalyst monolith at 2, 14, and 26 mm in, using data from the SpaciMS. Also, simulations of end pipe analysis, using a commercial reactor, for the CO oxidation are presented and analyzed. The simulations presented are for varying concentrations of both CO and O2 (0.5 % and 1 % CO, 0.5 % and 2 % O2) for both the global and micro-kinetic approach.

Probing The effects of Experimental Conditions on the Character of Drug-Polymer Phase Diagrams Constructed Using Flory-Huggins Theory

Purpose: Amorphous drug-polymer solid dispersions have been found to result in improved drug dissolution rates when compared to their crystalline counterparts. However, when the drug exists in the amorphous form it will possess a higher Gibb’s free energy than its associated crystalline state and can recrystallize. Drug-polymer phase diagrams constructed through the application of the Flory Huggins (F-H) theory contain a wealth of information regarding thermodynamic and kinetic stability of the amorphous drug-polymer system. This study was aimed to evaluate the effects of various experimental conditions on the solubility and miscibility detections of drug-polymer binary system. Methods: Felodipine (FD)-Polyvinylpyrrolidone (PVP) K15 (PVPK15) and FD-Polyvinylpyrrolidone/vinyl acetate (PVP/VA64) were the selected systems for this research. Physical mixtures with different drug loadings were mixed and ball milled. These samples were then processed using Differential Scanning Calorimetry (DSC) and measurements of melting point (Tend) and glass transition (Tg) were detected using heating rates of 0.5, 1.0 and 5.0°C/min. Results: The melting point depression data was then used to calculate the F-H interaction parameter (χ) and extrapolated to lower temperatures to complete the liquid–solid transition curves. The theoretical binodal and spinodal curves were also constructed which were used to identify regions within the phase diagram. The effects of polymer selection, DSC heating rate, time above parent polymer Tg and polymer molecular weight were investigated by identifying amorphous drug miscibility limits at pharmaceutically relevant temperatures. Conclusion: The potential implications of these findings when applied to a non-ambient processing method such as Hot Melt Extrusion (HME) are also discussed.

A large scale model experimental study of a tidal turbine in uniform steady flow

An experimental study measuring the performance and wake characteristics of a 1:10th scale horizontal axis turbine in steady uniform flow conditions is presented in this paper.
Large scale towing tests conducted in a lake were devised to model the performance of the tidal turbine and measure the wake produced. As a simplification of the marine environment, towing the turbine in a lake provides approximately steady, uniform inflow conditions. A 16m long x 6m wide catamaran was constructed for the test programme. This doubled as a towing rig and flow measurement platform, providing a fixed frame of reference for measurements in the wake of a horizontal axis tidal turbine. Velocity mapping was conducted using Acoustic Doppler Velocimeters.
The results indicate varying the inflow speed yielded little difference in the efficiency of the turbine or the wake velocity deficit characteristics provided the same tip speed ratio is used. Increasing the inflow velocity from 0.9 m/s to 1.2 m/s influenced the turbulent wake characteristics more markedly. The results also demonstrate that the flow field in the wake of a horizontal axis tidal turbine is strongly affected by the turbine support structure

Simultaneous Measurements of the Channel Response for Multiple Eavesdroppers Operating in the Vicinity of a Body Area Network at 2.45 GHz

Channel randomness can be exploited to generate secret keys. However, to ensure secrecy, it is necessary that the channel response of any eavesdropping party remain sufficiently de-correlated with that of the legitimate users'. In this paper, we investigate whether such de-correlation occurs for a body area network (BAN) operating in an indoor environment at 2.45 GHz. The hypothetical BAN configuration consisted of two legitimate transceivers, one situated on the user's left wrist and the other on the user's waist. The eavesdroppers were positioned in either a co-located or distributed manner in the area surrounding the BAN user. Using the simultaneous channel response measured at the legitimate BAN nodes and the eavesdropper positions for stationary and mobile scenarios, we analyze the localized correlation coefficient. This allows us to determine if it is possible to generate secret keys in the presence of multiple eavesdroppers in an indoor environment. Our experimental results show that although channel reciprocity was observed for both the stationary and the mobile scenarios, a higher de-correlation between the legitimate users' channels was observed for the stationary case. This indicates that mobile scenarios are better suited for secret key generation.

Multiple Markers of Inflammation in Crevicular Fluid During Experimental Gingivitis

Objective: To evaluate temporal changes in GCF levels of substance P, cathepsin G, interleukin 1 beta (IL-1&beta), neutrophil elastase and alpha1-antitrypsin (&alpha1AT) during development of and recovery from experimental gingivitis. Methods: Healthy human volunteers participated in a split-mouth study: experimental gingivitis was induced using a soft vinyl splint to cover test teeth during brushing over 21 days, after which normal brushing was resumed. Modified gingival index (MGI), gingival bleeding index (BI) and modified Quigley and Hein plaque index (PI) were assessed and 30-second GCF samples taken from 4 paired test and contra-lateral control sites in each subject at days 0, 7, 14, 21, 28 and 42. GCF volume was measured and site-specific quantification of one analyte per GCF sample was performed using radioimmunoassay (substance P), enzyme assay (cathepsin G) or ELISA (IL-1&beta, elastase, &alpha1AT). Site-specific data were analysed using analysis of repeated measurements and paired sample tests. Results: 56 subjects completed the study. All measurements at baseline (day 0) and at control sites throughout the study were low. Clinical indices and GCF volumes at the test sites increased from day 0, peaking at day 21 (difference between test and control for PI, BI, MGI and GCF all p<0.0001) and decreased again to control levels by day 28. Levels of four inflammatory markers showed a similar pattern, with significant differences between test and control apparent at 7 days (substance P p=0.0015; cathepsin G p=0.029; IL-1&beta p=0.026; elastase p=0.0129) and peaking at day 21 (substance P p=0.0023; cathepsin G, IL-1&beta and elastase all p<0.0001). Levels of &alpha1AT showed no apparent pattern over the course of the study. Conclusion: GCF levels of substance P, cathepsin G, IL-1&beta and neutrophil elastase have the potential to act as early markers of experimentally-induced gingival inflammation.

Experimental and theoretical photoionization cross sections for Se + from 18 eV to 31 eV

Absolute Se photoionization cross-section measurements and Dirac-Coulomb R -matrix calculations are reported for the photon energy range 18.0 eV – 31.0 eV, which spans the ionization thresholds of the 4 S 0 3/2 ground state and the low-lying 2 D 0 3/2,5/2 and 2 P 0 1/2,3/2 metastable states. The determination of the photoionization and recombination properties of n -capture element ions is motivated by their astrophysical detection and the importance of their elemental abundances in testing theories of nucleosynthesis and stellar structure.

Switched Diversity Techniques for Indoor Off-body Communications Channels: An Experimental Analysis and Modeling

This paper investigates the potential improvement in signal reliability for indoor off-body communications channels operating at 5.8 GHz using switched diversity techniques. In particular we investigate the performance of switch-and-stay combining (SSC), switch-and-examine combining (SEC) and switch-and-examine combining with post-examining selection (SECps) schemes which utilize multiple spatially separated antennas at the base station. During the measurements a test subject, wearing an antenna on his chest, performed a number of walking movements towards and then away from a uniform linear array. It was found that all of the considered diversity schemes provided a worthwhile signal improvement. However, the performance of the diversity systems varied according to the switching threshold that was adopted. To model the fading envelope observed at the output of each of the combiners, we have applied diversity specific equations developed under the assumption of Nakagami-$m$ fading. As a measure of the goodness-of-fit, the Kullback-Leibler divergence between the empirical and theoretical probability density functions (PDFs) was calculated and found to be close to 0. To assist with the interpretation of the goodness-of-fit achieved in this study, the standard deviation, $\sigma$, of a zero-mean, $\sigma^2$ variance Gaussian PDF used to approximate a zero-mean, unit variance Gaussian PDF is also presented. These were generally quite close to 1 indicating that the theoretical models provided an adequate fit to the measured data.

Experimental Study on Channel Reciprocity in Wireless Key Generation

Key generation from wireless channels is a promising alternative to public key cryptography for the establishment of cryptographic keys. It is the first paper to experimentally study the channel reciprocity principle of key generation, through investigating and quantifying channel measurements' cross-correlation relationship affected by noise and non-simultaneous measurements. Channel measurements, both received signal strength and channel state information, are collected from a real experimental platform using the wireless open access research platform (WARP) in a multipath office room. We found that in a slow fading channel (e.g., with a coherence time of about 50~ms), the channel cross-correlation is impacted greatly by noise but little by non-simultaneous measurements with a small sampling time difference (e.g., 0.06 ms). The resolution of the sampling time difference can be satisfied by wireless systems such as IEEE 802.11 to maintain an acceptable cross-correlation coefficient without affecting the bandwidth and communication efficiency.

On the solubility of three disperse anthraquinone dyes in supercritical carbon dioxide: new experimental data and correlation

Solubility measurements of quinizarin. (1,4-dihydroxyanthraquinone), disperse red 9 (1-(methylamino) anthraquinone), and disperse blue 14 (1,4-bis(methylamino)anthraquinone) in supercritical carbon dioxide (SC CO2) were carried out in a flow type apparatus, at a temperature range from (333.2 to 393.2) K and at pressures from (12.0 to 40.0) MPa. Mole fraction solubility of the three dyes decreases in the order quinizarin (2.9 x 10(-6) to 2.9.10(-4)), red 9 (1.4 x 10(-6) to 3.2 x 10(-4)), and blue 14 (7.8 x 10(-8) to 2.2 x 10(-5)). Four semiempirical density based models were used to correlatethe solubility of the dyes in the SC CO2. From the correlation results, the total heat of reaction, heat of vaporization plus the heat of solvation of the solute, were calculated and compared with the results presented in the literature. The solubilities of the three dyes were correlated also applying the Soave-Redlich-Kwong cubic equation of state (SRK CEoS) with classical mixing rules, and the physical properties required for the modeling were estimated and reported.

Upgrade of an experimental volumetric unit for gas adsorption equilibrium studies

In this work, a volumetric unit previously assembled by the research group was upgraded. This unit revamping was necessary due to the malfunction of the solenoid valves employed in the original experimental setup, which were not sealing the gas properly leading to erroneous adsorption equilibrium measurements. Therefore, the solenoid valves were substituted by manual ball valves. After the volumetric unit improvement its operation was validated. For this purpose, the adsorption equilibrium of carbon dioxide (CO2) at 323K and 0 - 20 bar was measured on two different activated carbon samples, in the of extrudates (ANG6) and of a honeycomb monolith (ACHM). The adsorption equilibrium results were compared with data previously measured by the research group, using a high-pressure microbalance from Rubotherm GmbH (Germany) – gravimetric. The results obtained using both apparatuses are coincident thus validating the good operation of the volumetric unit upgraded in this work. Furthermore, the adsorption equilibrium of CO2 at 303K and 0 - 10 bar on Metal-Organic Frameworks (MOFs) Cu-BTC and Fe-BTC was also studied. The CO2 adsorption equilibrium results for both MOFs were compared with the literature results showing good agreement, which confirms the good quality of the experimental results obtained in the new volumetric unit. Cu-BTC sample showed significantly higher CO2 adsorption capacity when compared with the Fe-BTC sample. The revamping of the volumetric unit included a new valve configuration in order to allow testing an alternative method for the measurement of adsorption equilibrium. This new method was employed to measure the adsorption equilibrium of CO2 on ANG6 and ACHM at 303, 323 and 353K within 0-10 bar. The good quality of the obtained experimental data was testified by comparison with data previously obtained by the research group in a gravimetric apparatus.

Transmission measurements using a new far-infrared set-up

A system comprised of a Martin-Puplett type polarizing interferometer and a Helium-3 cryostat was developed to study the transmission of materials in the very-far-infrared region of the spectrum. This region is of significant interest due to the low-energy excitations which many materials exhibit. The experimental transmission spectrum contains information concerning the optical properties of the material. The set-up of this system is described in detail along with the adaptations and improvements which have been made to the system to ensure the best results. Transmission experiments carried out with this new set-up for two different varieties of materials: superconducting thin films of lead and biological proteins, are discussed. Several thin films of lead deposited on fused silica quartz substrates were studied. From the ratio of the transmission in the superconducting state to that in the normal state the superconducting energy gap was determined to be approximately 25 cm-1 which corresponds to 2~/kBTc rv 5 in agreement with literature data. Furthermore, in agreement with theoretical predictions, the maximum in the transmission ratio was observed to increase as the film thickness was increased. These results provide verification of the system's ability to accurately measure the optical properties of thin low-Tc superconducting films. Transmission measurements were carried out on double deionized water, and a variety of different concentrations by weight of the globular protein, Bovine Serum Albumin, in the sol, gel and crystalline forms. The results of the water study agree well with literature values and thus further illustrate the reproducibility of the system. The results of the protein experiments, although preliminary, indicate that as the concentration increases the samples become more transparent. Some weak structure in the frequency dependent absorption coefficient, which is more prominent in crystalline samples, may be due to low frequency vibrations of the protein molecules.

Thermal diffusivity measurements in organic liquids using transient thermal lens calorimetry

Thermal diffusivity measurements are carried out in certain organic liquids using the pulsed dual beam thermal lens technique. The 532 nm pulses from a frequency doubled Q-switched Nd:YAG laser are used as the heating source and an intensity stabilized He-Ne laser serves as the probe beam. Experimental determination of the characteristic time constant of the transient thermal lens signal is verified theoretically. Measured thermal diffusivity values are in excellent agreement with literature values.

Experimental investigation of optical limiting and thermal lensing in toluene solutions of C70

Optical limiting and thermal lensing studies are carried out in C70–toluene solutions. The measurements are performed using 9-ns pulses generated from a frequencydoubled Nd:YAG laser at 532 nm. Optical limiting studies in fullerene molecules lead to the conclusion that reverse saturable absorption is the major mechanism for limiting. Analysis of thermal lensing measurements showed a quadratic dependence of thermal lens signal on incident laser energy, which also supports the view that optical limiting in C70 arises due to sequential two-photon absorption via excited triplet state (reverse saturable absorption).

High‐temperature phase transitions in pure and deuterated ammonium dihydrogen phosphate: Conductivity and dielectric measurements

Results of axiswise measurements of the electrical conductivity (dc and ac) and dielectric constant of NH4H2PO4 confirm the occurrence of the recently suggested high‐temperature phase transition in this crystal (at 133 °C). The corresponding transition in ND4D2PO4 observed here for the first time takes place at 141.5 °C. The mechanism involved in these transitions and those associated with the electrical conduction and dielectric anomalies are explained on the basis of the motional effects of the ammonium ions in these crystals. Conductivity values for deuterated crystals give direct evidence for the predominance of protonic conduction throughout the entire range of temperatures studied (30–260 °C).

Measurements of Electromagnetic Shielding Effect Using Htsc Materials

A simple experimental set-up is described to measure the electromagnetic shielding property of high Tc superconducting samples. Measurements were performed using HTSC materials in the form of laser ablated thin films, powders and sintered pellets. Samples used were Gd-123 in pure and doped form as well as a few Bi-based superconducting ceramics. For comparison, similar measurements were carried out on metals like aluminium, copper and μ metal. Very effective shielding was observed for HTSC materials compared to the conventional materials mentioned above. However it also depended on the sample types and poor shielding was observed for powdered HTSC material in comparison to thin films prepared by laser ablation.