Improvement of the Derjaguin-Broekhoff-de Boer theory for capillary condensation/evaporation of nitrogen in mesoporous systems and its implications for pore size analysis of MCM-41 silicas and related materials

In this work, we propose an improvement of the classical Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in mesoporous systems. The primary idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the surface tension changes in mesopores. In addition, the statistical film thickness (so-called t-curve) evaluated accurately on the basis of the adsorption isotherms measured for the MCM-41 materials is used instead of the originally proposed t-curve (to take into account the excess of the chemical potential due to the surface forces). It is shown that the aforementioned modifications of the original DBdB theory have significant implications for the pore size analysis of mesoporous solids. To verify our improvement of the DBdB pore size analysis method (IDBdB), a series of the calcined MCM-41 samples, which are well-defined materials with hexagonally ordered cylindrical mesopores, were used for the evaluation of the pore size distributions. The correlation of the IDBdB method with the empirically calibrated Kruk-Jaroniec-Sayari (KJS) relationship is very good in the range of small mesopores. So, a major advantage of the IDBdB method is its applicability for small mesopores as well as for the mesopore range beyond that established by the KJS calibration, i.e., for mesopore radii greater than similar to4.5 nm. The comparison of the IDBdB results with experimental data reported by Kruk and Jaroniec for capillary condensation/evaporation as well as with the results from nonlocal density functional theory developed by Neimark et al. clearly justifies our approach. Note that the proposed improvement of the classical DBdB method preserves its original simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the mean pore size by the powder X-ray diffraction method.

Pore size distribution analysis of activated carbons: Application of density functional theory using nongraphitized carbon black as a reference system

The application of nonlocal density functional theory (NLDFT) to determine pore size distribution (PSD) of activated carbons using a nongraphitized carbon black, instead of graphitized thermal carbon black, as a reference system is explored. We show that in this case nitrogen and argon adsorption isotherms in activated carbons are precisely correlated by the theory, and such an excellent correlation would never be possible if the pore wall surface was assumed to be identical to that of graphitized carbon black. It suggests that pore wall surfaces of activated carbon are closer to that of amorphous solids because of defects of crystalline lattice, finite pore length, and the presence of active centers.. etc. Application of the NLDFT adapted to amorphous solids resulted in quantitative description of N-2 and Ar adsorption isotherms on nongraphitized carbon black BP280 at their respective boiling points. In the present paper we determined solid-fluid potentials from experimental adsorption isotherms on nongraphitized carbon black and subsequently used those potentials to model adsorption in slit pores and generate a corresponding set of local isotherms, which we used to determine the PSD functions of different activated carbons. (c) 2005 Elsevier Ltd. All rights reserved.

Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

Work-life balance benefits:employee attitudes and behaviors through the lens of social exchange theory

The question of what to provide employees in order that they reciprocate with desirable behaviors in the work place has resulted in a great amount of work in the area of social exchange. Although offering fair compensation, including salary or wages and employee benefits, has been extensively studied, the effects of offering specific types of benefits, such as work-life balance benefits, and the intangible rewards that such an offering inadvertently offers, has only been minimally explored. Utilizing past literature, this current research examined the offering of work-life balance benefits, the value employees place on those benefits, the communication of the benefits by the organization to employees, and their effect on employee attitudes and behaviors. The goal was to identify the effect on desirable outcomes when work-life balance benefits are offered to determine the usefulness to the organization of offering such benefits. To test these effects, a study of an organization known to offer a strong work-life balance benefits package was undertaken. This was accomplished through the distribution of questionnaires to identify the possible relationships involving 408 employee respondents and their 79 supervisors. This was followed with interviews of 12 individuals to ascertain the true reasons for links observed through analysis. Analysis of the data was accomplished through correlation analysis, multilevel analysis and regression analysis generated by SPSS. The results of the quantitative analysis showed support for a relationship between the offering of work-life balance benefits and perceived organizational support, perceived distributive justice, job satisfaction and OCBO. The analysis also showed a lack of support for a relationship between the offering of work-life balance benefits and organizational commitment, OCBI and IRB. The interviews offered possible reasons for the lack of support regarding the relationship between the offering of work-life balance benefits and organizational commitment as well as organizational citizenship behaviors (OCBI and IRB). The implications of these findings on future research, theory and practice in the offering of work-life balance benefits are discussed.

The correlation of indentation size effect experiments with pyramidal and spherical indenters

Experiments were conducted in annealed iridium using pyramidal and spherical indenters over a wide range of load. For a Berkovich pyramidal indenter, the hardness increased with decreasing depth of penetration. However, for spherical indenters, hardness increased with decreasing sphere radius. Based on the number of geometrically necessary dislocations generated during indentation, a theory that takes into account the work hardening differences between pyramidal and spherical indenters is developed to correlate the indentation size effects measured with the two indenters. The experimental results verify the theoretical correlation.

The Operators Aγ = γA + -γA for a Class of Nondissipative Operators A with a Limit of the Corresponding Correlation Function

2000 Mathematics Subject Classification: Primary 47A48, Secondary 60G12

Extending the Theory of Planned Behavior in the exercise domain: A study of community college students in an urban multicultural setting

The purpose of this study was to assess the intention to exercise among ethnically and racially diverse community college students using the Theory of Planned Behavior (TPB). In addition to identifying the variables associated with motivation or intention of college students to engage in physical activity, this study tested the model of the Theory of Planned Behavior, asking: Does the TPB model explain intention to exercise among a racially/ethnically diverse group of college students? ^ The relevant variables were the TPB constructs (behavioral beliefs, normative beliefs, and control beliefs), which combined to form a measure of intention to exercise. Structural Equation Modeling was used to test the predictive power of the TPB constructs for predicting intention to exercise. Following procedures described by Ajzen (2002), the researcher developed a questionnaire encompassing the external variables of student demographics (age, gender, work status, student status, socio-economic status, access to exercise facilities, and past behavior), major constructs of the TPB, and two questions from the Godin Leisure Time Questionnaire (GLTQ; Godin & Shephard, 1985). Participants were students (N = 255) who enrolled in an on-campus wellness course at an urban community college. ^ The demographic profile of the sample revealed a racially/ethnically diverse study population. The original model that was used to reflect the TPB as developed by Ajzen was not supported by the data analyzed using SEM; however, a revised model that the researcher thought was theoretically a more accurate reflection of the causal relations between the TPB constructs was supported. The GLTQ questions were problematic for some students; those data could not be used in the modeling efforts. The GLTQ measure, however, revealed a significant correlation with intention to exercise (r = .27, p = .001). Post-hoc comparisons revealed significant differences in normative beliefs and attitude toward exercising behavior between Black students and Hispanic students. Compared to Black students, Hispanic students were more likely to (a) perceive “friends” as approving of them being physically active and (b) rate being physically active for 30 minutes per day as “beneficial”. No statistically significant difference was found among groups on overall intention to exercise. ^

An investigation of the strategies used by organizations participating in the welfare-to-work network program and correlation of the strategies with the retention data to determine best practices for job retention among former welfare recipients

This ex post facto study (N = 209) examined the relationships between employer job strategies and job retention among organizations participating in Florida welfare-to-work network programs and associated the strategies with job retention data to determine best practices. ^ An internet-based self-report survey battery was administered to a heterogeneous sampling of organizations participating in the Florida welfare-to-work network program. Hypotheses were tested through correlational and hierarchical regression analytic procedures. The partial correlation results linked each of the job retention strategies to job retention. Wages, benefits, training and supervision, communication, job growth, work/life balance, fairness and respect were all significantly related to job retention. Hierarchical regression results indicated that the training and supervision variable was the best predictor of job retention in the regression equation. ^ The size of the organization was also a significant predictor of job retention. Large organizations reported higher job retention rates than small organizations. There was no statistical difference between the types of organizations (profit-making and non-profit) and job retention. The standardized betas ranged from to .26 to .41 in the regression equation. Twenty percent of the variance in job retention was explained by the combination of demographic and job retention strategy predictors, supporting the theoretical, empirical, and practical relevance of understanding the association between employer job strategies and job retention outcomes. Implications for adult education and human resource development theory, research, and practice are highlighted as possible strategic leverage points for creating conditions that facilitate the development of job strategies as a means for improving former welfare workers’ job retention.^

Self-determination theory and student motivation in social studies in an urban Broward County public high school

This study investigated how students perceived their motivation in high school social studies classes in school and to determine if a correlation exists between students’ grade level, race, gender, and their motivation. The sample included 337 high school students in Broward County, Florida. To assess students’ perceptions on their motivation the academic self-regulation questionnaire was utilized. Results indicate that social studies students show high levels of external regulation, with a mean score at 22.31 on a scale of 36 points. The results show a mean score of 24 on a scale of 28 points for identified regulation among social studies students. Findings revealed that student motivation could be gauged. No statistical significance was found between high school students’ grade level, race, gender, and their motivation in social studies classes. The findings of this study have shown that students at Boyd H. Anderson High School want to learn social studies.

The relationship of immigrant status to perceptions of reading and reading literacy among young Black students: A test of the Cultural -Ecological Theory of School Performance

This study tests Ogbu and Simons' Cultural-Ecological Theory of School Performance using data from the Progress in International Reading Literacy Study of 2001 (PIRLS), a large-scale international survey and reading assessment involving fourth grade students from 35 countries, including the United States. This theory argues that Black immigrant students outperform their non-immigrant counterparts, academically, and that achievement differences are attributed to stronger educational commitment in Black immigrant families. Four hypotheses are formulated to test this theory: Black immigrant students have (a) more receptive attitudes toward reading; (b) a more positive reading self-concept; and (c) a higher level of reading literacy. Furthermore, (d) the relationship of immigrant status to reading perceptions and literacy persists after including selected predictors. These hypotheses are tested separately for girls and boys, while also examining immigrant students' generational status (i.e., foreign-born or second-generation). ^ PIRLS data from a subset of Black students (N=525) in the larger U.S. sample of 3,763 are analyzed to test the hypotheses, using analysis of variance, correlation and multiple regression techniques. Findings reveal that hypotheses a and b are not confirmed (contradicting the Cultural-Ecological Theory) and c and d are partially supported (lending partial support to the theory). Specifically, immigrant and non-immigrant students did not differ in attitudes toward reading or reading self-concept; second-generation immigrant boys outperformed both non-immigrant and foreign-born immigrant boys in reading literacy, but no differences were found among girls; and, while being second-generation immigrant had a relatively stronger relationship to reading literacy for boys, among girls, selected socio-cultural predictors, number of books in the home and length of U.S. residence, had relatively stronger relationship to reading self-concept than did immigrant status. This study, therefore, indicates that future research employing the Cultural-Ecological Theory should: (a) take gender and generational status into account (b) identify additional socio-cultural predictors of Black children's academic perceptions and performance; and (c) continue to build on this body of evidence-based knowledge to better inform educational policy and school personnel in addressing needs of all children. ^

An epistemic event -based correlation scheme for pervasive network management

Computer networks produce tremendous amounts of event-based data that can be collected and managed to support an increasing number of new classes of pervasive applications. Examples of such applications are network monitoring and crisis management. Although the problem of distributed event-based management has been addressed in the non-pervasive settings such as the Internet, the domain of pervasive networks has its own characteristics that make these results non-applicable. Many of these applications are based on time-series data that possess the form of time-ordered series of events. Such applications also embody the need to handle large volumes of unexpected events, often modified on-the-fly, containing conflicting information, and dealing with rapidly changing contexts while producing results with low-latency. Correlating events across contextual dimensions holds the key to expanding the capabilities and improving the performance of these applications. This dissertation addresses this critical challenge. It establishes an effective scheme for complex-event semantic correlation. The scheme examines epistemic uncertainty in computer networks by fusing event synchronization concepts with belief theory. Because of the distributed nature of the event detection, time-delays are considered. Events are no longer instantaneous, but duration is associated with them. Existing algorithms for synchronizing time are split into two classes, one of which is asserted to provide a faster means for converging time and hence better suited for pervasive network management. Besides the temporal dimension, the scheme considers imprecision and uncertainty when an event is detected. A belief value is therefore associated with the semantics and the detection of composite events. This belief value is generated by a consensus among participating entities in a computer network. The scheme taps into in-network processing capabilities of pervasive computer networks and can withstand missing or conflicting information gathered from multiple participating entities. Thus, this dissertation advances knowledge in the field of network management by facilitating the full utilization of characteristics offered by pervasive, distributed and wireless technologies in contemporary and future computer networks.

Theory and Practice in Sustainability Science: Influence of Urban Form on the Urban Heat Island and Implications for Urban Systems

As the world population continues to grow past seven billion people and global challenges continue to persist including resource availability, biodiversity loss, climate change and human well-being, a new science is required that can address the integrated nature of these challenges and the multiple scales on which they are manifest. Sustainability science has emerged to fill this role. In the fifteen years since it was first called for in the pages of Science, it has rapidly matured, however its place in the history of science and the way it is practiced today must be continually evaluated. In Part I, two chapters address this theoretical and practical grounding. Part II transitions to the applied practice of sustainability science in addressing the urban heat island (UHI) challenge wherein the climate of urban areas are warmer than their surrounding rural environs. The UHI has become increasingly important within the study of earth sciences given the increased focus on climate change and as the balance of humans now live in urban areas.

In Chapter 2 a novel contribution to the historical context of sustainability is argued. Sustainability as a concept characterizing the relationship between humans and nature emerged in the mid to late 20th century as a response to findings used to also characterize the Anthropocene. Emerging from the human-nature relationships that came before it, evidence is provided that suggests Sustainability was enabled by technology and a reorientation of world-view and is unique in its global boundary, systematic approach and ambition for both well being and the continued availability of resources and Earth system function. Sustainability is further an ambition that has wide appeal, making it one of the first normative concepts of the Anthropocene.

Despite its widespread emergence and adoption, sustainability science continues to suffer from definitional ambiguity within the academe. In Chapter 3, a review of efforts to provide direction and structure to the science reveals a continuum of approaches anchored at either end by differing visions of how the science interfaces with practice (solutions). At one end, basic science of societally defined problems informs decisions about possible solutions and their application. At the other end, applied research directly affects the options available to decision makers. While clear from the literature, survey data further suggests that the dichotomy does not appear to be as apparent in the minds of practitioners.

In Chapter 4, the UHI is first addressed at the synoptic, mesoscale. Urban climate is the most immediate manifestation of the warming global climate for the majority of people on earth. Nearly half of those people live in small to medium sized cities, an understudied scale in urban climate research. Widespread characterization would be useful to decision makers in planning and design. Using a multi-method approach, the mesoscale UHI in the study region is characterized and the secular trend over the last sixty years evaluated. Under isolated ideal conditions the findings indicate a UHI of 5.3 ± 0.97 °C to be present in the study area, the magnitude of which is growing over time.

Although urban heat islands (UHI) are well studied, there remain no panaceas for local scale mitigation and adaptation methods, therefore continued attention to characterization of the phenomenon in urban centers of different scales around the globe is required. In Chapter 5, a local scale analysis of the canopy layer and surface UHI in a medium sized city in North Carolina, USA is conducted using multiple methods including stationary urban sensors, mobile transects and remote sensing. Focusing on the ideal conditions for UHI development during an anticyclonic summer heat event, the study observes a range of UHI intensity depending on the method of observation: 8.7 °C from the stationary urban sensors; 6.9 °C from mobile transects; and, 2.2 °C from remote sensing. Additional attention is paid to the diurnal dynamics of the UHI and its correlation with vegetation indices, dewpoint and albedo. Evapotranspiration is shown to drive dynamics in the study region.

Finally, recognizing that a bridge must be established between the physical science community studying the Urban Heat Island (UHI) effect, and the planning community and decision makers implementing urban form and development policies, Chapter 6 evaluates multiple urban form characterization methods. Methods evaluated include local climate zones (LCZ), national land cover database (NCLD) classes and urban cluster analysis (UCA) to determine their utility in describing the distribution of the UHI based on three standard observation types 1) fixed urban temperature sensors, 2) mobile transects and, 3) remote sensing. Bivariate, regression and ANOVA tests are used to conduct the analyses. Findings indicate that the NLCD classes are best correlated to the UHI intensity and distribution in the study area. Further, while the UCA method is not useful directly, the variables included in the method are predictive based on regression analysis so the potential for better model design exists. Land cover variables including albedo, impervious surface fraction and pervious surface fraction are found to dominate the distribution of the UHI in the study area regardless of observation method.

Chapter 7 provides a summary of findings, and offers a brief analysis of their implications for both the scientific discourse generally, and the study area specifically. In general, the work undertaken does not achieve the full ambition of sustainability science, additional work is required to translate findings to practice and more fully evaluate adoption. The implications for planning and development in the local region are addressed in the context of a major light-rail infrastructure project including several systems level considerations like human health and development. Finally, several avenues for future work are outlined. Within the theoretical development of sustainability science, these pathways include more robust evaluations of the theoretical and actual practice. Within the UHI context, these include development of an integrated urban form characterization model, application of study methodology in other geographic areas and at different scales, and use of novel experimental methods including distributed sensor networks and citizen science.

An Epistemic Event-based Correlation Scheme for Pervasive Network Management

Computer networks produce tremendous amounts of event-based data that can be collected and managed to support an increasing number of new classes of pervasive applications. Examples of such applications are network monitoring and crisis management. Although the problem of distributed event-based management has been addressed in the non-pervasive settings such as the Internet, the domain of pervasive networks has its own characteristics that make these results non-applicable. Many of these applications are based on time-series data that possess the form of time-ordered series of events. Such applications also embody the need to handle large volumes of unexpected events, often modified on-the-fly, containing conflicting information, and dealing with rapidly changing contexts while producing results with low-latency. Correlating events across contextual dimensions holds the key to expanding the capabilities and improving the performance of these applications. This dissertation addresses this critical challenge. It establishes an effective scheme for complex-event semantic correlation. The scheme examines epistemic uncertainty in computer networks by fusing event synchronization concepts with belief theory. Because of the distributed nature of the event detection, time-delays are considered. Events are no longer instantaneous, but duration is associated with them. Existing algorithms for synchronizing time are split into two classes, one of which is asserted to provide a faster means for converging time and hence better suited for pervasive network management. Besides the temporal dimension, the scheme considers imprecision and uncertainty when an event is detected. A belief value is therefore associated with the semantics and the detection of composite events. This belief value is generated by a consensus among participating entities in a computer network. The scheme taps into in-network processing capabilities of pervasive computer networks and can withstand missing or conflicting information gathered from multiple participating entities. Thus, this dissertation advances knowledge in the field of network management by facilitating the full utilization of characteristics offered by pervasive, distributed and wireless technologies in contemporary and future computer networks.

Extending the Theory of Planned Behavior in the Exercise Domain: A Study of Community College Students in an Urban Multicultural Setting

The purpose of this study was to assess the intention to exercise among ethnically and racially diverse community college students using the Theory of Planned Behavior (TPB). In addition to identifying the variables associated with motivation or intention of college students to engage in physical activity, this study tested the model of the Theory of Planned Behavior, asking: Does the TPB model explain intention to exercise among a racially/ethnically diverse group of college students? The relevant variables were the TPB constructs (behavioral beliefs, normative beliefs, and control beliefs), which combined to form a measure of intention to exercise. Structural Equation Modeling was used to test the predictive power of the TPB constructs for predicting intention to exercise. Following procedures described by Ajzen (2002), the researcher developed a questionnaire encompassing the external variables of student demographics (age, gender, work status, student status, socio-economic status, access to exercise facilities, and past behavior), major constructs of the TPB, and two questions from the Godin Leisure Time Questionnaire (GLTQ; Godin & Shephard, 1985). Participants were students (N = 255) who enrolled in an on-campus wellness course at an urban community college. The demographic profile of the sample revealed a racially/ethnically diverse study population. The original model that was used to reflect the TPB as developed by Ajzen was not supported by the data analyzed using SEM; however, a revised model that the researcher thought was theoretically a more accurate reflection of the causal relations between the TPB constructs was supported. The GLTQ questions were problematic for some students; those data could not be used in the modeling efforts. The GLTQ measure, however, revealed a significant correlation with intention to exercise (r = .27, p = .001). Post-hoc comparisons revealed significant differences in normative beliefs and attitude toward exercising behavior between Black students and Hispanic students. Compared to Black students, Hispanic students were more likely to (a) perceive “friends” as approving of them being physically active and (b) rate being physically active for 30 minutes per day as “beneficial”. No statistically significant difference was found among groups on overall intention to exercise.

Equitable representation in councils: theory and an application to the United Nations Security Council

We analyze democratic equity in council voting games (CVGs). In a CVG, a voting body containing all members delegates decision-making to a (time-varying) subset of its members, as describes, e.g., the relationship between the United Nations General Assembly and the United Nations Security Council (UNSC). We develop a theoretical framework for analyzing democratic equitability in CVGs at both the country and region levels, and for different assumptions regarding preference correlation. We apply the framework to evaluate the equitability of the UNSC, and the claims of those who seek to reform it. We find that the individual permanent members are overrepresented by between 21.3 times (United Kingdom) and 3.8 times (China) from a country-level perspective, while from a region perspective Eastern Europe is the most heavily overrepresented region with more than twice its equitable representation, and Africa the most heavily underrepresented. Our equity measures do not preclude some UNSC members from exercising veto rights, however.