Hydrogenation of dinitriles on Raney-type Ni catalysts: kinetic and mechanistic aspects

The mechanism of the hydrogenation of aliphatic C₄–C₆ dinitriles (succinonitrile, glutaronitrile, and adiponitrile) over Raney-type Ni catalysts was investigated in a fed-batch autoclave at 350 K and 5.0 MPa. The results are interpreted based on the strength of adsorption, the interaction with the solvent and intramolecular interactions. The kinetics of the hydrogenation of aliphatic dinitriles is highly dependent on the hydrocarbon chain length. Short dinitriles like succinonitrile adsorb stronger on the catalyst surface than longer dinitriles like adiponitrile. The yield of the intermediate aminonitriles decreases with increasing hydrocarbon chain length, due to the enhanced competitiveness of dinitrile and aminonitrile for the same active sites. It is proposed that the reactivity of dinitriles and aminonitriles is caused by difference in solvent interaction. It is remarkable that the stronger the adsorption, the higher the reactivity. The reactivity decreases in the order: succinonitrile > glutaronitrile > adiponitrile. In contrast, the reaction rate of the aminonitriles is fairly independent of the hydrocarbon chain length. The formation of undesired secondary amines in the form of cyclic compounds is under kinetic control and increases with decreasing chain length. It is found that adiponitrile can be very selectively hydrogenated to primary diamines. Promoting Raney-type Ni catalysts with traces of Mo, Cr or Fe enhances the performance in the hydrogenation of dinitriles. This gives the best opportunity for process improvement towards the desired primary amines.     

Influence of Microstructure and Surface Activation of Dual‐Phase Membrane Ce0.8Gd0.2O2−δ–FeCo2O4 on Oxygen Permeation

Dual‐phase oxygen transport membranes are fast‐growing research interest for application in oxyfuel combustion process. One such potential candidate is CGO‐FCO (60 wt% Ce_0.8Gd_0.2O_2?δ–40 wt% FeCo₂O₄) identified to provide good oxygen permeation flux with substantial stability in harsh atmosphere. Dense CGO‐FCO membranes of 1 mm thickness were fabricated by sintering dry pellets pressed from powders synthesized by one‐pot method (modified Pechini process) at 1200°C for 10 h. Microstructure analysis indicates presence of a third orthorhombic perovskite phase in the sintered composite. It was also identified that the spinel phase tends to form an oxygen deficient phase at the grain boundary of spinel and CGO phases. Surface exchange limitation of the membranes was overcome by La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF) porous layer coating over the composite. The oxygen permeation flux of the CGO‐FCO screen printed with a porous layer of 10 μm thick LSCF is 0.11 mL/cm² per minute at 850°C with argon as sweep and air as feed gas at the rates of 50 and 250 mL/min.     

The ability of limited exposure sampling to detect effects of interventions that reduce the occurrence of pronounced trunk inclination

Ergonomics interventions often focus on reducing exposure in those parts of the job having the highest exposure levels, while leaving other parts unattended. A successful intervention will thus change the form of the job exposure distribution. This disqualifies standard methods for assessing the ability of various exposure measurement strategies to correctly detect an intervention's effect on the overall job exposure of an individual worker, in particular for the safety or ergonomics practitioner who with limited resources can only collect a few measurements. This study used a non-parametric simulation procedure to evaluate the relationship between the number of measurements collected during a self-paced manufacturing job undergoing ergonomics interventions of varying effectiveness, and the probability of correctly determining whether and to which extent the interventions reduced the overall occurrence of pronounced trunk inclination, defined as an inclination of at least 20°. Sixteen video-recordings taken at random times on multiple days for each of three workers were used to estimate the time distribution of each worker's exposure to pronounced trunk inclination. Nine hypothetical ergonomics intervention scenarios were simulated, in which the occurrence of pronounced trunk inclination in the upper 1/8, 1/4, and 1/2 of the job exposure distribution was reduced by 10%, 30% and 50%. Ten exposure measurement strategies were explored, collecting from one to ten pre- and post-intervention exposure samples from an individual worker. For each worker, intervention scenario and sampling strategy, data were bootstrapped from the measured (pre-intervention) and simulated (post-intervention) exposure distributions to generate empirical distributions of the estimated intervention effect. Results showed that for the one to three intervention scenarios that had the greatest effect on the overall occurrence of trunk inclination in the job, one to four pre- and post-intervention measurements, depending on worker, were sufficient to reach an 80% probability of detecting that the intervention did, indeed, have an effect. However, even for the intervention scenario that had the greatest effect on job exposure, seven or more samples were needed for two of the three workers to obtain a probability larger than 50% of estimating the magnitude of the intervention effect to within ±50% of its true size. For almost all interventions affecting 1/8 or 1/4 of the job, limited exposure sampling led to low probabilities of detecting any intervention effect, let alone its correct size.     

Third–Generation Pleated Pneumatic Artificial Muscles for Robotic Applications: Development and Comparison with McKibben Muscle

This paper introduces the third generation of Pleated Pneumatic Artificial Muscles (PPAM), which has been developed to simplify the production over the first and second prototype. This type of artificial muscle was developed to overcome dry friction and material deformation, which is present in the widely used McKibben muscle. The essence of the PPAM is its pleated membrane structure which enables the muscle to work at low pressures and at large contractions. In order to validate the new PPAM generation, it has been compared with the mathematical model and the previous generation. The new production process and the use of new materials introduce improvements such as 55% reduction in the actuator’s weight, a higher reliability, a 75% reduction in the production time and PPAMs can now be produced in all sizes from 4 to 50?cm. This opens the possibility to commercialize this type of muscles so others can implement it. Furthermore, a comparison with experiments between PPAM and Festo McKibben muscles is discussed. Small PPAMs present similar force ranges and larger contractions than commercially available McKibben-like muscles. The use of series arrangements of PPAMs allows for large strokes and relatively small diameters at the same time and, since PPAM 3.0 is much more lightweight than the commong McKibben models made by Festo, it presents better force-to-mass and energy to mass ratios than Festo models.     

Psychological significance of pupillary movements.

Pupillary dilation, the light reflex, and spontaneous fluctuations in pupil size have been used as dependent variables in psychological investigations. A review of these studies provides evidence for the effectiveness of the pupil as an index of autonomic activity in psychophysiological research. Methodological problems in the pupillary literature are discussed, and directions for further research are suggested. (105 ref.) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Job enlargement and mechanical exposure variability in cyclic assembly work

Cyclic assembly work is known to imply a high risk for musculoskeletal disorders. To have operators rotate between work tasks is believed to be one way of decreasing this risk, since it is expected to increase variation in mechanical and psychological exposures (physical and mental loads). This assumption was investigated by assessing mechanical exposure variability in three assembly tasks in an electronics assembly plant, each on a separate workstation, as well as in a 'job enlargement' scenario combining all three stations. Five experienced operators worked for 1 h on each station. Data on upper trapezius and forearm extensor muscle activity were obtained by means of electromyography (EMG), and working postures of the head and upper arms were assessed by inclinometry. The cycle-to-cycle variance of parameters representing the three exposure dimensions: level, frequency and duration was estimated using ANOVA algorithms for each workstation separately as well as for a balanced combination of all three. For a particular station, the variability of trapezius EMG activity levels relative to the mean was higher than for extensor EMG: between-cycles coefficients of variation (CV) about 0.15 and 0.10, respectively. A similar relationship between CV applied to the parameter describing frequency of EMG activity. Except for head inclination levels, the between-cycles CV was larger for posture parameters than for EMG. The between-cycles variance increased up to six fold in the job enlargement scenario, as compared to working at only one station. The difference in mean exposure between workstations was larger for trapezius EMG parameters than for forearm extensor EMG and postures, and hence the effect of job enlargement on exposure variability was more pronounced for the trapezius. For some stations, job enlargement even implied less cycle-to-cycle variability in forearm extensor EMG parameters than working at that station only. Whether the changes in exposure variability associated with job enlargement were sufficient to imply a decreased risk for musculoskeletal disorders is not known.     

The affective consequences of social comparison: Either direction has its ups and downs.

Research on social comparison processes has assumed that a comparison in a given direction (upward or downward) will lead to a particular affective reaction. In contrast, the present 2 studies proposed and found that a comparison can produce either positive or negative feelings about oneself, independent of its direction. Several factors moderated the tendency to derive positive or negative affect from upward and downward comparisons. In Study 1, cancer patients low in self-esteem and with low perceived control over their symptoms and illness were more likely to see downward comparisons as having negative implications for themselves. Those low in self-esteem were also more likely to perceive upward comparisons as negative. In Study 2, individuals with high marital dissatisfaction and those who felt uncertain about their marital relationship were more likely to experience negative affect from upward and downward comparisons. The implications of these findings for social comparison theory and for the coping and adaptation literature are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A RAPID METHOD FOR DETERMINING BIOTIN ACTIVITY IN RAW MATERIALS FOR FERMENTATION

The biotin activity of a raw material towards yeast may consist of the sum of the activities of biotin, desthiobiotin, oxybiotin, biocytin and possibly other factors. Some of these substances only stimulate certain strains of yeast; on the other hand, the strains of lactobacilli generally used for estimation of biotin activity utilize only D-biotin. It is thus desirable to have a method available in which a manufacturer's own strain of yeast is used as test organism for biotin activity. A simple method for biotin determination based on the cup plate assay is described. Biotin-free agar is inoculated with yeast and a series of standard solutions of D-biotin and a series of dilutions of the raw material under investigation are placed in holes cut in the agar. After incubation, the zones of growth are measured and from their diameters the biotin activity can be calculated.