Influence of free volume fraction,inter/intramolecular energy ratio,and chain segment density on the Gibbs-DiMarzio theory of the glass transition

Based upon computer analysis, the Gibbs-DiMarzio (G-DM) theory is evaluated for the case of (a) constant V₀ and (b) constant r where V₀ is the fractional free volume at T_g and r is the ratio of the hole (E₀) to the flex (ε) energy. For each respective case, results are presented in a reduced variables format that indicate the extent to which r and V₀ vary at the transition temperature as a function of the reciprocal degree of polymerization (P^?1). To further account for chemical differences that exist among polymers, an index (n) is introduced that ultimately incorporates the effective number average of chain atom segments (x?) per P?. Using these reduced variables plots, the effects of V₀, r, and n are compared with the T_g data for four well-documented polymers. Although the theory adequately describes the PMMA, PS, and PVC data, for PαMS the fit is doubtful. The analysis demonstrates that, in order to maintain V₀ within the range of 0.015–0.045, r must remain within approximately 1.0–1.1. Moreover, under conditions of either constant V₀ or r, other more flexible polymers require that $\text{n?10}$.     

Effects of fluctuating river flow on groundwater/surface water mixing in the hyporheic zone of a regulated,large cobble bed river

Physicochemical relationships in the boundary zone between groundwater and surface water (i.e. the hyporheic zone) are controlled by surface water hydrology and the hydrogeologic properties of the riverbed. We studied how sediment permeability and river discharge altered the vertical hydraulic gradient (VHG) and water quality of the hyporheic zone within the Hanford Reach of the Columbia River. The Columbia River at Hanford is a large, cobble‐bed river where water level fluctuates up to 2 m daily because of hydropower generation. Concomitant with river stage recordings, continuous readings were made of water temperature, specific conductance, dissolved oxygen and water level of the hyporheic zone. The water level data were used to calculate VHG between the river and hyporheic zone. Sediment permeability was estimated using slug tests conducted in piezometers installed into the river bed. The response of water quality measurements and VHG to surface water fluctuations varied widely among study sites, ranging from no apparent response to covariance with river discharge. At some sites, a hysteretic relationship between river discharge and VHG was indicated by a time lag in the response of VHG to changes in river stage. The magnitude, rate of change and hysteresis of the VHG response varied the most at the least permeable location (hydraulic conductivity (K) = 2.9 × 10^?4 cms^?1) and the least at the most permeable location (K = 8.0 × 10^?3 cms^?1). Our study provides empirical evidence that sediment properties and river discharge both control the water quality of the hyporheic zone. Regulated rivers, like the Columbia River at Hanford, that undergo large, frequent discharge fluctuations represent an ideal environment in which to study hydrogeologic processes over relatively short time periods (i.e. days to weeks) that would require much longer periods (i.e. months to years) to evaluate in unregulated systems. Copyright © 2006 John Wiley & Sons Ltd.     

Is a sense of inequity an ancestral primate trait? Testing social inequity in cotton top tamarins (Saguinus oedipus).

To address a controversy in the literature concerning whether monkeys show an aversion to inequity, individuals of a New World monkey species, cotton top tamarins (Saguinus oedipus) were tested in an offering task and in a bartering task. At issue was whether the monkeys rejected rewards because of a violation of expectancy of the preferred reward, or whether they rejected rewards because of a sensitivity to socially mediated inequity. The data from both tasks indicated that the subjects were more likely to reject when preferred rewards were presented, either because of another animal eating the reward (the social condition) or because of rewards being presented but inaccessible. The bartering task led to the only behavioral indication of aversion due specifically to social inequity, which was demonstrated when tamarins' sensitivity to the difference in rewards increased with exposure to other tamarins working to receive the preferred rewards. The results suggest that social inequity aversion will be assessed by tamarins, and possibly by other primates, only under conditions of limited resources and a requirement of work, which may make the situation a bit more competitive and thus drives attention toward both social and reward evaluation. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Optimal levels of emotional arousal in experiential therapy of depression.

Objective: To determine the relationship between length of time spent expressing highly aroused emotion and therapeutic outcome. Method: Thirty-eight clients (14 male, 24 female) between the ages of 22 and 60 years (M = 39.5, SD = 9.71), treated for depression with experiential therapy, were rated on working alliance and expressed emotional arousal (with the Client Expressed Emotional Arousal Scale) in their three highest arousal sessions. Among the clients, 34 were of European ethnicity, 2 were of Asian ethnicity, 1 was of Latino ethnicity, and 1 was of Caribbean–Canadian ethnicity. Clients were administered the short form of the Working Alliance Inventory following their 4th therapy session and also completed, pre- and posttherapy, the Beck Depression Inventory (BDI), the Global Severity Index (GSI) of the Symptom Checklist–90–Revised (SCL-90-R), the Inventory of Interpersonal Problems, and the Rosenberg Self-Esteem Scale. Results: Hierarchical regressions showed that a nonlinear pattern of expressed emotional arousal predicted outcome significantly above the alliance. This combination predicted 30% of outcome variance on the BDI and 24% on the GSI (p     

Hydrogen evolution reaction measurements of dealloyed porous NiCu

Porous metals are of interest for their high surface area and potential for enhanced catalytic behavior. Electrodeposited NiCu thin films with a range of compositions were electrochemically dealloyed to selectively remove the Cu component. The film structure, composition, and reactivity of these samples were characterized both before and after the dealloying step using scanning electron microscopy, energy-dispersive spectroscopy, and electrochemical measurements. The catalytic behavior of the dealloyed porous Ni samples towards the hydrogen evolution reaction was measured and compared to that of the as-deposited samples. The dealloyed samples were generally more reactive than their as-deposited counterparts at low overpotentials, making the dealloying procedure a promising area of exploration for improved hydrogen evolution catalysts.     

Self-blocking of dislocations in intermetallic compound Ni<Subscript>3</Subscript>Ge: Cubic slip

Self-blocking of dislocations belonging to the cube plane has been detected in the intermetallic compound Ni₃Ge. The nature of cubic slip has been clarified. The experiments included deformation at a temperature above T _max (the temperature of the yield-stress peak) and subsequent heating without stress. In addition, changes in the dislocation structure upon slow cooling from the temperature of the preliminary deformation have been investigated; in doing so, self-blocking of dislocations has been revealed for the first time. Based on the totality of experimental data, a conclusion has been made on the two-valley potential relief for a dislocation motion in the cube plane. It is the difference in the depths between the Peierls valley (a diffuse core in the cube plane) and the deepest valley (a superpartial dislocation split in the octahedron plane) that provides for the driving force of self-blocking in the absence of an external stress. Different aspects of cubic slip have been considered: the disappearance of cubic slip at T < T _max and, correspondingly, the nonobservation of an anomalous behavior of the yield stress, as well as the disappearance of octahedral slip at T > T _max.     

Dissolved gases as partitioning tracers for determination of hydrogeological parameters

In this study, dissolved Kr and SF6 gases were used to determine various hydrogeological parameters of laboratory columns under water-saturated and partially saturated conditions as a function of the flow velocity. The dissolved gases behaved conservatively in saturated columns but were significantly retarded in unsaturated conditions as a direct function of the Henry's law constant (KH) and the ratio of column pore spaces filled with air and water (Vg/Vw). Lower aqueous diffusion coefficients for SF6 compared to that for Kr also resulted in significant rate-limited mass transport across gas-water interface. This effect was exacerbated at higher flow velocities as was indicated by the asymmetric shape of breakthrough curves, more so in the case of SF6. A nonequilibrium advective-dispersive transport model accurately described tracer breakthrough and was used to estimate parameters such as final Vg/Vw under partially saturated conditions and partitioning rates. Internally consistent model results were obtained for both dissolved gases despite the wide range in physical properties (e.g., KH and aqueous diffusion coefficients), suggesting that dissolved Kr and SF6 may be used in conjunction to delineate and validate aquifer characteristics simultaneously from a single pulse injection of the tracer.