932 resultados para phase change
Resumo:
Charge transport and dielectric measurements were carried out on compacted powder and single-crystal samples of bistable RbxMn[Fe(CN)6]y·zH2O in the two valence-tautomeric forms (MnIIFeIII and MnIIIFeII) as a function of temperature (120-350 K) and frequency (10-2-106 Hz). The complex conductivity data reveal universal conductivity behavior and obey the Barton-Nakajima-Namikawa relationship. The charge transport is accompanied by dielectric relaxation that displays the same thermal activation energy as the conductivity. Surprisingly, the activation energy of the conductivity was found very similar in the two valence-tautomeric forms (0.55 eV), and the conductivity change between the two phases is governed mainly by the variation of the preexponential factor in each sample. The phase transition is accompanied by a large thermal hysteresis of the conductivity and the dielectric constant. In the hysteresis region, however, a crossover occurs in the charge transport mechanism at T < 220 K from an Arrhenius-type to a varying activation energy behavior, conferring an unusual “double-loop” shape to the hysteresis.
Resumo:
The following thesis presents results obtained from both numerical simulation and laboratory experimentation (both of which were carried out by the author). When data is propagated along an optical transmission line some timing irregularities can occur such as timing jitter and phase wander. Traditionally these timing problems would have been corrected by converting the optical signal into the electrical domain and then compensating for the timing irregularity before converting the signal back into the optical domain. However, this thesis posses a potential solution to the problem by remaining completely in the optical domain, eliminating the need for electronics. This is desirable as not only does optical processing reduce the latency effect that their electronic counterpart have, it also holds the possibility of an increase in overall speed. A scheme was proposed which utilises the principle of wavelength conversion to dynamically convert timing irregularities (timing jitter and phase wander) into a change in wavelength (this occurs on a bit-by-bit level and so timing jitter and phase wander can be compensated for simultaneously). This was achieved by optically sampling a linearly chirped, locally generated clock source (the sampling function was achieved using a nonlinear optical loop mirror). The data, now with each bit or code word having a unique wavelength, is then propagated through a dispersion compensation module. The dispersion compensation effectively re-aligns the data in time and so thus, the timing irregularities are removed. The principle of operation was tested using computer simulation before being re-tested in a laboratory environment. A second stage was added to the device to create 3R regeneration. The second stage is used to simply convert the timing suppressed data back into a single wavelength. By controlling the relative timing displacement between stage one and stage two, the wavelength that is finally produced can be controlled.
Resumo:
Mass transfer rates were studied using the falling drop method. Cibacron Blue 3 GA dye was the transferring solute from the salt phase to the PEG phase. Measurements were undertaken for several concentrations of the dye and the phase-forming solutes and with a range of different drop sizes, e.g. 2.8, 3.0 and 3.7 mm. The dye was observed to be present in the salt phase as finely dispersed solids but a model confirmed that the mass transfer process could still be described by an equation based upon the Whitman two-film model. The overall mass transfer coefficient increased with increasing concentration of the dye. The apparent mass transfer coefficient ranged from 1 x 10-5 to 2 x 10 -4 m/s. Further experiments suggested that mass transfer was enhanced at high concentration by several mechanisms. The dye was found to change the equilibrium composition of the two phases, leading to transfer of salt between the drop and continuous phases. It also lowered the interfacial tension (i.e. from 1.43 x 10-4 N/m for 0.01% w/w dye concentration to 1.07 x 10-4 N/m for 0.2% w/w dye concentration) between the two phases, which could have caused interfacial instabilities (Marangoni effects). The largest drops were deformable, which resulted in a significant increase in the mass transfer rate. Drop size distribution and Sauter mean drop diameter were studied on-line in a 1 litre agitated vessel using a laser diffraction technique. The effects of phase concentration, dispersed phase hold-up and impeller speed were investigated for the salt-PEG system. An increase in agitation speed in the range 300 rpm to 1000 rpm caused a decrease in mean drop diameter, e.g. from 50 m to 15 m. A characteristic bimodal drop size distribution was established within a very short time. An increase in agitation rate caused a shift of the larger drop size peak to a smaller size.
Resumo:
This thesis explores efforts to conjoin organisational contexts and capabilities in explaining sustainable competitive advantage. Oliver (1997) argued organisations need to balance the need to conform to industry’s requirements to attain legitimization (e.g. DiMaggio & Powell, 1983), and the need for resource optimization (e.g. Barney, 1991). The author hypothesized that such balance can be viewed as movements along the homogeneity-heterogeneity continuum. An organisation in a homogenous industry possesses similar characteristics as its competitors, as opposed to a heterogeneous industry in which organisations within are differentiated and competitively positioned (Oliver, 1997). The movement is influenced by the dynamic environmental conditions that an organisation is experiencing. The author extended Oliver’s (1997) propositions of combining RBV’s focus on capabilities with institutional theory’s focus on organisational context, as well as redefining organisational receptivity towards change (ORC) factors from Butler and Allen’s (2008) findings. The authors contributed to the theoretical development of ORC theory to explain the attainment of sustainable competitive advantage. ORC adopts the assumptions from both institutional and RBV theories, where the receptivity factors include both organisational contexts and capabilities. The thesis employed a mixed method approach in which sequential qualitative quantitative studies were deployed to establish a robust, reliable, and valid ORC scale. The adoption of Hinkin’s (1995) three-phase scale development process was updated, thus items generated from interviews and literature reviews went through numerous exploratory factor analysis (EFA) and confirmatory factor analysis (CFA) to achieve convergent, discriminant, and nomological validities. Samples in the first phase (semi structured interviews) were hotel owners and managers. In the second phase, samples were MBA students, and employees of private and public sectors. In the third phase, samples were hotel managers. The final ORC scale is a parsimonious second higher-order latent construct. The first-order constructs comprises four latent receptivity factors which are ideological vision (4 items), leading change (4 items), implementation capacity (4 items), and change orientation (7 items). Hypotheses testing revealed that high levels of perceived environmental uncertainty leads to high levels of receptivity factor. Furthermore, the study found a strong positive correlation between receptivity factors and competitive advantage, and between receptivity factors and organisation performance. Mediation analyses revealed that receptivity factors partially mediate the relationship between perceived environmental uncertainty, competitive advantage and organisational performance.
Resumo:
Background: Biodiesel is a clean-burning, renewable and biodegradable diesel fuel substitute derived from animal fats and plant oils, which may play an important role in replacing diminishing fossil fuel reserves and combating climate change. Conventional biodiesel production uses soluble base catalysts, such as Na or K alkoxides, to convert oils into fuel, and as a result requires energy intensive aqueous quench cycles to isolate the biodiesel product. Results: Cs-doping nanoparticulate MgO, prepared via a novel, supercritical sol-gel method, yields a solid base catalyst with improved activity for the transesterification of pure triacylglycerides (TAGs) and olive oil. Conclusion: Here, X-ray absorption spectroscopy (XAS) is used to probe the local chemical environment of Cs atoms in order to identify the nature of the catalytically active species as CsMg(CO)(HO). © 2013 Society of Chemical Industry.
Resumo:
Objective: To independently evaluate the impact of the second phase of the Health Foundation's Safer Patients Initiative (SPI2) on a range of patient safety measures. Design: A controlled before and after design. Five substudies: survey of staff attitudes; review of case notes from high risk (respiratory) patients in medical wards; review of case notes from surgical patients; indirect evaluation of hand hygiene by measuring hospital use of handwashing materials; measurement of outcomes (adverse events, mortality among high risk patients admitted to medical wards, patients' satisfaction, mortality in intensive care, rates of hospital acquired infection). Setting: NHS hospitals in England. Participants: Nine hospitals participating in SPI2 and nine matched control hospitals. Intervention The SPI2 intervention was similar to the SPI1, with somewhat modified goals, a slightly longer intervention period, and a smaller budget per hospital. Results: One of the scores (organisational climate) showed a significant (P=0.009) difference in rate of change over time, which favoured the control hospitals, though the difference was only 0.07 points on a five point scale. Results of the explicit case note reviews of high risk medical patients showed that certain practices improved over time in both control and SPI2 hospitals (and none deteriorated), but there were no significant differences between control and SPI2 hospitals. Monitoring of vital signs improved across control and SPI2 sites. This temporal effect was significant for monitoring the respiratory rate at both the six hour (adjusted odds ratio 2.1, 99% confidence interval 1.0 to 4.3; P=0.010) and 12 hour (2.4, 1.1 to 5.0; P=0.002) periods after admission. There was no significant effect of SPI for any of the measures of vital signs. Use of a recommended system for scoring the severity of pneumonia improved from 1.9% (1/52) to 21.4% (12/56) of control and from 2.0% (1/50) to 41.7% (25/60) of SPI2 patients. This temporal change was significant (7.3, 1.4 to 37.7; P=0.002), but the difference in difference was not significant (2.1, 0.4 to 11.1; P=0.236). There were no notable or significant changes in the pattern of prescribing errors, either over time or between control and SPI2 hospitals. Two items of medical history taking (exercise tolerance and occupation) showed significant improvement over time, across both control and SPI2 hospitals, but no additional SPI2 effect. The holistic review showed no significant changes in error rates either over time or between control and SPI2 hospitals. The explicit case note review of perioperative care showed that adherence rates for two of the four perioperative standards targeted by SPI2 were already good at baseline, exceeding 94% for antibiotic prophylaxis and 98% for deep vein thrombosis prophylaxis. Intraoperative monitoring of temperature improved over time in both groups, but this was not significant (1.8, 0.4 to 7.6; P=0.279), and there were no additional effects of SPI2. A dramatic rise in consumption of soap and alcohol hand rub was similar in control and SPI2 hospitals (P=0.760 and P=0.889, respectively), as was the corresponding decrease in rates of Clostridium difficile and meticillin resistant Staphylococcus aureus infection (P=0.652 and P=0.693, respectively). Mortality rates of medical patients included in the case note reviews in control hospitals increased from 17.3% (42/243) to 21.4% (24/112), while in SPI2 hospitals they fell from 10.3% (24/233) to 6.1% (7/114) (P=0.043). Fewer than 8% of deaths were classed as avoidable; changes in proportions could not explain the divergence of overall death rates between control and SPI2 hospitals. There was no significant difference in the rate of change in mortality in intensive care. Patients' satisfaction improved in both control and SPI2 hospitals on all dimensions, but again there were no significant changes between the two groups of hospitals. Conclusions: Many aspects of care are already good or improving across the NHS in England, suggesting considerable improvements in quality across the board. These improvements are probably due to contemporaneous policy activities relating to patient safety, including those with features similar to the SPI, and the emergence of professional consensus on some clinical processes. This phenomenon might have attenuated the incremental effect of the SPI, making it difficult to detect. Alternatively, the full impact of the SPI might be observable only in the longer term. The conclusion of this study could have been different if concurrent controls had not been used.
Resumo:
Abstract PURPOSE: To evaluate ranibizumab 0.5 mg using bimonthly monitoring and individualized re-treatment after monthly follow-up for 6 months in patients with visual impairment due to diabetic macular edema (DME). DESIGN: A phase IIIb, 18-month, prospective, open-label, multicenter, single-arm study in the United Kingdom. PARTICIPANTS: Participants (N = 109) with visual impairment due to DME. METHODS: Participants received 3 initial monthly ranibizumab 0.5 mg injections (day 0 to month 2), followed by individualized best-corrected visual acuity (BCVA) and optical coherence tomography-guided re-treatment with monthly (months 3-5) and subsequent bimonthly follow-up (months 6-18). Laser was allowed after month 6. MAIN OUTCOME MEASURES: Mean change in BCVA from baseline to month 12 (primary end point), mean change in BCVA and central retinal thickness (CRT) from baseline to month 18, gain of ≥10 and ≥15 letters, treatment exposure, and incidence of adverse events over 18 months. RESULTS: Of 109 participants, 100 (91.7%) and 99 (90.8%) completed the 12 and 18 months of the study, respectively. The mean age was 63.7 years, the mean duration of DME was 40 months, and 77.1% of the participants had received prior laser treatment (study eye). At baseline, mean BCVA was 62.9 letters, 20% of patients had a baseline BCVA of >73 letters, and mean baseline CRT was 418.1 μm, with 32% of patients having a baseline CRT <300 μm. The mean change in BCVA from baseline to month 6 was +6.6 letters (95% confidence interval [CI], 4.9-8.3), and after institution of bimonthly treatment the mean change in BCVA at month 12 was +4.8 letters (95% CI, 2.9-6.7; P < 0.001) and +6.5 letters (95% CI, 4.2-8.8) at month 18. The proportion of participants gaining ≥10 and ≥15 letters was 24.8% and 13.8% at month 12 and 34.9% and 19.3% at month 18, respectively. Participants received a mean of 6.8 and 8.5 injections over 12 and 18 months, respectively. No new ocular or nonocular safety findings were observed during the study. CONCLUSIONS: The BCVA gain achieved in the initial 6-month treatment period was maintained with an additional 12 months of bimonthly ranibizumab PRN treatment.
Resumo:
This study describes an optimised modulation strategy based on switching state sequences for the hybrid-clamped multilevel converter. Two key control variables defined as 'phase shift angle' and 'switching state change' for a five-level hybrid-clamped inverter are proposed to improve all switches' operation, and by changing their values, different control methods can be obtained for modulation optimisation purposes. Two example methods can solve the voltage imbalance problem of the dc-link capacitors and furthermore avoid two switches' simultaneous switching transitions and improve the inverter's performance as compared with the traditional phase disposition pulse-width modulation strategy. A 6 kW prototype inverter is developed and a range of simulation and experiments are carried out for validation. It is found that simulation and experimental results are in a good agreement and the proposed modulation strategy is verified in terms of low-order harmonic reduction.
Resumo:
Policy/program implementation, e.g., the process of fulfilling policy/program directives, is fundamentally tied to change. Implementation studies have examined the process, identifying many critical organizational variables although individuals perform the activities.^ Many of the studies are predicated on the rational, goal oriented model of organizations and examine implementation, presenting only the goal-oriented view. Organizational change and its resistance, however, are not fully explained by the rational model of organizations. There are other schools of thought providing different views of organizations from which explanation may emerge. Bolman and Deal (1984, 1991a, 1994) provide a different perspective for examining organizations Bolman and Deal argue organizations should be viewed through four different frames or lenses. Framing and reframing organizational action captures the complexity of action and provides better understanding of organizational processes. Understanding of implementation of policies/programs also will benefit from the use of the four-frame approach.^ The goal of this research is to provide a better understanding of the implementation process by examining individual attitudes toward change, the dependent variable of this research, and studying the relationship between the dependent variable and frame. The research was conducted in two phases. In Phase One, a survey was sent to 306 school administrators and teachers in magnet programs in Dade County, Florida. The survey instrument was composed of 55 questions including six from Bolman and Deal's Leadership Orientation Survey (1988) and 38 questions about organizational change. In Phase Two, more in-depth analysis of four school was conducted, to further explore the relationship between frame and attitude toward change.^ The results revealed that frame was a factor in explaining differences in personal Attitude Toward Change and Comfort Level with Change. Individuals using the symbolic frame had more positive attitudes toward change and were also more comfortable with change. The results of Phase Two of the research partially supported this finding in that the most fully implemented program was the product of an administrator who had chosen the symbolic frame. ^
Resumo:
The successful management of change is a key factor in ensuring growth in the restaurant industry. The author discusses how to evaluate and act on a management change plan beginning with a total understanding and knowledge of the environment within which it operates.
Resumo:
This thesis presents and discusses the results of ambient seismic noise correlation for two different environments: intraplate and Mid-Atlantic Ridge. The coda wave interferometry method has also been tested for the intraplate data. Ambient noise correlation is a method that allows to retrieve the structural response between two receivers from ambient noise records, as if one of the station was a virtual source. It has been largely used in seismology to image the subsurface and to monitor structural changes associated mostly with volcanic eruptions and large earthquakes. In the intraplate study, we were able to detect localized structural changes related to a small earthquake swarm, which main event is mR 3.7, North-East of Brazil. We also showed that the 1-bit normalization and spectral whitening result on the loss of waveform details and that the phase auto-correlation, which is amplitude unbiased, seems to be more sensitive and robust for our analysis of a small earthquake swarm. The analysis of 6 months of data using cross-correlations detect clear medium changes soon after the main event while the auto-correlations detect changes essentially after 1 month. It could be explained by fluid pressure redistribution which can be initiated by hydromechanical changes and opened path ways to shallower depth levels due to later occurring earthquakes. In the Mid-Atlantic Ridge study, we investigate structural changes associated with a mb 4.9 earthquake in the region of the Saint Paul transform fault. The data have been recorded by a single broadband seismic station located at less than 200 km from the Mid-Atlantic ridge. The results of the phase auto-correlation for a 5-month period, show a strong co-seismic medium change followed by a relatively fast post-seismic recovery. This medium change is likely related to the damages caused by the earthquake’s ground shaking. The healing process (filling of the new cracks) that lasted 60 days can be decomposed in two phases, a fast recovery (70% in ~30 days) in the early post-seismic stage and a relatively slow recovery later (30% in ~30 days). In the coda wave interferometry study, we monitor temporal changes of the subsurface caused by the small intraplate earthquake swarm mentioned previously. The method was first validated with synthetics data. We were able to detect a change of 2.5% in the source position and a 15% decrease of the scatterers’ amount. Then, from the real data, we observed a rapid decorrelation of the seismic coda after the mR 3.7 seismic event. This indicates a rapid change of the subsurface in the fault’s region induced by the earthquake.
Resumo:
This thesis presents and discusses the results of ambient seismic noise correlation for two different environments: intraplate and Mid-Atlantic Ridge. The coda wave interferometry method has also been tested for the intraplate data. Ambient noise correlation is a method that allows to retrieve the structural response between two receivers from ambient noise records, as if one of the station was a virtual source. It has been largely used in seismology to image the subsurface and to monitor structural changes associated mostly with volcanic eruptions and large earthquakes. In the intraplate study, we were able to detect localized structural changes related to a small earthquake swarm, which main event is mR 3.7, North-East of Brazil. We also showed that the 1-bit normalization and spectral whitening result on the loss of waveform details and that the phase auto-correlation, which is amplitude unbiased, seems to be more sensitive and robust for our analysis of a small earthquake swarm. The analysis of 6 months of data using cross-correlations detect clear medium changes soon after the main event while the auto-correlations detect changes essentially after 1 month. It could be explained by fluid pressure redistribution which can be initiated by hydromechanical changes and opened path ways to shallower depth levels due to later occurring earthquakes. In the Mid-Atlantic Ridge study, we investigate structural changes associated with a mb 4.9 earthquake in the region of the Saint Paul transform fault. The data have been recorded by a single broadband seismic station located at less than 200 km from the Mid-Atlantic ridge. The results of the phase auto-correlation for a 5-month period, show a strong co-seismic medium change followed by a relatively fast post-seismic recovery. This medium change is likely related to the damages caused by the earthquake’s ground shaking. The healing process (filling of the new cracks) that lasted 60 days can be decomposed in two phases, a fast recovery (70% in ~30 days) in the early post-seismic stage and a relatively slow recovery later (30% in ~30 days). In the coda wave interferometry study, we monitor temporal changes of the subsurface caused by the small intraplate earthquake swarm mentioned previously. The method was first validated with synthetics data. We were able to detect a change of 2.5% in the source position and a 15% decrease of the scatterers’ amount. Then, from the real data, we observed a rapid decorrelation of the seismic coda after the mR 3.7 seismic event. This indicates a rapid change of the subsurface in the fault’s region induced by the earthquake.
Resumo:
This dissertation explores the complex process of organizational change, applying a behavioral lens to understand change in processes, products, and search behaviors. Chapter 1 examines new practice adoption, exploring factors that predict the extent to which routines are adopted “as designed” within the organization. Using medical record data obtained from the hospital’s Electronic Health Record (EHR) system I develop a novel measure of the “gap” between routine “as designed” and routine “as realized.” I link this to a survey administered to the hospital’s professional staff following the adoption of a new EHR system and find that beliefs about the expected impact of the change shape fidelity of the adopted practice to its design. This relationship is more pronounced in care units with experienced professionals and less pronounced when the care unit includes departmental leadership. This research offers new insights into the determinants of routine change in organizations, in particular suggesting the beliefs held by rank-and-file members of an organization are critical in new routine adoption. Chapter 2 explores changes to products, specifically examining culling behaviors in the mobile device industry. Using a panel of quarterly mobile device sales in Germany from 2004-2009, this chapter suggests that the organization’s response to performance feedback is conditional upon the degree to which decisions are centralized. While much of the research on product exit has pointed to economic drivers or prior experience, these central finding of this chapter—that performance below aspirations decreases the rate of phase-out—suggests that firms seek local solutions when doing poorly, which is consistent with behavioral explanations of organizational action. Chapter 3 uses a novel text analysis approach to examine how the allocation of attention within organizational subunits shapes adaptation in the form of search behaviors in Motorola from 1974-1997. It develops a theory that links organizational attention to search, and the results suggest a trade-off between both attentional specialization and coupling on search scope and depth. Specifically, specialized unit attention to a more narrow set of problems increases search scope but reduces search depth; increased attentional coupling also increases search scope at the cost of depth. This novel approach and these findings help clarify extant research on the behavioral outcomes of attention allocation, which have offered mixed results.
Resumo:
Dissolution of non-aqueous phase liquids (NAPLs) or gases into groundwater is a key process, both for contamination problems originating from organic liquid sources, and for dissolution trapping in geological storage of CO2. Dissolution in natural systems typically will involve both high and low NAPL saturations and a wide range of pore water flow velocities within the same source zone for dissolution to groundwater. To correctly predict dissolution in such complex systems and as the NAPL saturations change over time, models must be capable of predicting dissolution under a range of saturations and flow conditions. To provide data to test and validate such models, an experiment was conducted in a two-dimensional sand tank, where the dissolution of a spatially variable, 5x5 cm**2 DNAPL tetrachloroethene source was carefully measured using x-ray attenuation techniques at a resolution of 0.2x0.2 cm**2. By continuously measuring the NAPL saturations, the temporal evolution of DNAPL mass loss by dissolution to groundwater could be measured at each pixel. Next, a general dissolution and solute transport code was written and several published rate-limited (RL) dissolution models and a local equilibrium (LE) approach were tested against the experimental data. It was found that none of the models could adequately predict the observed dissolution pattern, particularly in the zones of higher NAPL saturation. Combining these models with a model for NAPL pool dissolution produced qualitatively better agreement with experimental data, but the total matching error was not significantly improved. A sensitivity study of commonly used fitting parameters further showed that several combinations of these parameters could produce equally good fits to the experimental observations. The results indicate that common empirical model formulations for RL dissolution may be inadequate in complex, variable saturation NAPL source zones, and that further model developments and testing is desirable.
Resumo:
The recently proposed global monsoon hypothesis interprets monsoon systems as part of one global-scale atmospheric overturning circulation, implying a connection between the regional monsoon systems and an in-phase behaviour of all northern hemispheric monsoons on annual timescales (Trenberth et al., 2000). Whether this concept can be applied to past climates and variability on longer timescales is still under debate, because the monsoon systems exhibit different regional characteristics such as different seasonality (i.e. onset, peak, and withdrawal). To investigate the interconnection of different monsoon systems during the pre-industrial Holocene, five transient global climate model simulations have been analysed with respect to the rainfall trend and variability in different sub-domains of the Afro-Asian monsoon region. Our analysis suggests that on millennial timescales with varying orbital forcing, the monsoons do not behave as a tightly connected global system. According to the models, the Indian and North African monsoons are coupled, showing similar rainfall trend and moderate correlation in rainfall variability in all models. The East Asian monsoon changes independently during the Holocene. The dissimilarities in the seasonality of the monsoon sub-systems lead to a stronger response of the North African and Indian monsoon systems to the Holocene insolation forcing than of the East Asian monsoon and affect the seasonal distribution of Holocene rainfall variations. Within the Indian and North African monsoon domain, precipitation solely changes during the summer months, showing a decreasing Holocene precipitation trend. In the East Asian monsoon region, the precipitation signal is determined by an increasing precipitation trend during spring and a decreasing precipitation change during summer, partly balancing each other. A synthesis of reconstructions and the model results do not reveal an impact of the different seasonality on the timing of the Holocene rainfall optimum in the different sub-monsoon systems. They rather indicate locally inhomogeneous rainfall changes and show, that single palaeo-records should not be used to characterise the rainfall change and monsoon evolution for entire monsoon sub-systems.