Quantitative analysis of solid-state processes studied with isothermal microcalorimetry

Quantitative analysis of solid-state processes from isothermal microcalorimetric data is straightforward if data for the total process have been recorded and problematic (in the more likely case) when they have not. Data are usually plotted as a function of fraction reacted (α); for calorimetric data, this requires knowledge of the total heat change (Q) upon completion of the process. Determination of Q is difficult in cases where the process is fast (initial data missing) or slow (final data missing). Here we introduce several mathematical methods that allow the direct calculation of Q by selection of data points when only partial data are present, based on analysis with the Pérez-Maqueda model. All methods in addition allow direct determination of the reaction mechanism descriptors m and n and from this the rate constant, k. The validity of the methods is tested with the use of simulated calorimetric data, and we introduce a graphical method for generating solid-state power-time data. The methods are then applied to the crystallization of indomethacin from a glass. All methods correctly recovered the total reaction enthalpy (16.6 J) and suggested that the crystallization followed an Avrami model. The rate constants for crystallization were determined to be 3.98 × 10-6, 4.13 × 10-6, and 3.98 × 10 -6 s-1 with methods 1, 2, and 3, respectively. © 2010 American Chemical Society.

Numerical modeling of holmium-doped fluoride fiber lasers

We combine all the known experimental demonstrations and spectroscopic parameters into a numerical model of the Ho3+ -doped fluoride glass fiber laser system. Core-pumped and cladding-pumped arrangements were simulated for all the population-bottlenecking mitigation schemes that have been tested, and good agreement between the model and the previously reported experimental results was achieved in most but not in all cases. In a similar way to Er3+ -doped fluoride glass fiber lasers, we found that the best match with measurements required scaled-down rate parameters for the energy transfer processes that operate in moderate to highly concentrated systems. The model isolated the dominant processes affecting the performance of each of the bottlenecking mitigation schemes and pump arrangements. It was established that pump excited-state absorption is the main factor affecting the performance of the core-pumped demonstrations of the laser, while energy transfer between rare earth ions is the main factor controlling the performance in cladding-pumped systems.

The effect of slow passage in the pulse-pumped quantum dot laser

In recent years, quantum-dot (QD) semiconductor lasers attract significant interest in many practical applications due to their advantages such as high-power pulse generation because to the high gain efficiency. In this work, the pulse shape of an electrically pumped QD-laser under high current is analyzed. We find that the slow rise time of the pulsed pump may significantly affect the high intensity output pulse. It results in sharp power dropouts and deformation of the pulse profile. We address the effect to dynamical change of the phase-amplitude coupling in the proximity of the excited state (ES) threshold. Under 30ns pulse pumping, the output pulse shape strongly depends on pumping amplitude. At lower currents, which correspond to lasing in the ground state (GS), the pulse shape mimics that of the pump pulse. However, at higher currents the pulse shape becomes progressively unstable. The instability is greatest when in proximity to the secondary threshold which corresponds to the beginning of the ES lasing. After the slow rise stage, the output power sharply drops out. It is followed by a long-time power-off stage and large-scale amplitude fluctuations. We explain these observations by the dynamical change of the alpha-factor in the QD-laser and reveal the role of the slowly rising pumping processes in the pulse shaping and power dropouts at higher currents. The modeling is in very good agreement with the experimental observations. © 2014 SPIE.

Dynamical interplay between ground and excited states in quantum dot laser

Full text: Semiconductor quantum dot lasers are attractive for multipletechnological applications in biophotonics. Simultaneous two-state lasing ofground state (GS) and excited state (ES) electrons and holes in QD lasers ispossible under a certain parameter range. It has already been investigated in steady-stateoperations and in dynamical regimes and is currently a subject of the intesiveresearch. It has been shown that the relaxation frequency in the two-state lasingregime is not a function of the total intensity [1], as could be traditionallyexpected.In this work we study damping relaxation oscillations in QD lasersimultaneously operating at two transitions, and find that under variouspumping conditions, the frequency of oscillations may decrease, increase orstay without change in time as shown in Fig1.The studied QD laser structure wasgrown on a GaAs substrate by molecular-beam epitaxy. The active region includedfive layers of self-assembled InAs QDs separated with a GaAs spacer from a5.3nm thick covering layer of InGaAs and processed into 4mm-wide mesa stripe devices. The 2.5mm long lasers withhigh-and antireflection coatings on the rear and front facets lasesimultaneously at the GS (around 1265nm) and ES (around 1190nm) in the wholerange of pumping. Pulsed electrical pumping obtained from a high power (up to2A current) pulse source was used to achieve high output power operation. We simultaneously detect the total output and merely ES output using aBragg filter transmitting the short-wavelength and reflecting the long-wavelengthradiation. Typical QD does not demonstrate relaxation oscillations frequencybecause of the strong damping [2]. It is confirmed for the low (I<0.68A) andhigh (I>1.2 A) range of the pump currents in our experiments. The situationis different for a short range of the medium currents (0.68A

Dropout dynamics in pulsed quantum dot lasers due to mode jumping

We examine the response of a pulse pumped quantum dot laser both experimentally and numerically. As the maximum of the pump pulse comes closer to the excited-state threshold, the output pulse shape becomes unstable and leads to dropouts. We conjecture that these instabilities result from an increase of the linewidth enhancement factor α as the pump parameter comes close to the excitated state threshold. In order to analyze the dynamical mechanism of the dropout, we consider two cases for which the laser exhibits either a jump to a different single mode or a jump to fast intensity oscillations. The origin of these two instabilities is clarified by a combined analytical and numerical bifurcation diagram of the steady state intensity modes.

Pore confinement effects and stabilization of carbon nitride oligomers in macroporous silica for photocatalytic hydrogen production

An ordered macroporous host (mac-SiO2) has been used to prevent aggregation of layered photocatalysts based on carbon nitride. Using typical carbon nitride synthesis conditions, cyanamide was condensed at 550 °C in the presence and absence of mac-SiO2. Condensation in the absence of mac-SiO2 results in materials with structural characteristics consistent with the carbon nitride, melon, accompanied by ca. 2 wt% carbonization. For mac-SiO2 supported materials, condensation occurs with greater carbonization (ca. 6 wt%). On addition of 3 wt% Pt cocatalyst photocatalytic hydrogen production under visible light is found to be up to 10 times greater for the supported composites. Time-resolved photoluminescence spectroscopy shows that excited state relaxation is more rapid for the mac-SiO2 supported materials suggesting faster electron-hole recombination and that supported carbon nitride does not exhibit improved charge separation. CO2 temperature programmed desorption indicates that enhanced photoactivity of supported carbon nitride is attributable to an increased surface area compared to bulk carbon nitride and an increase in the concentration of weakly basic catalytic sites, consistent with carbon nitride oligomers.

Slow passage through thresholds in quantum dot lasers

A turn on of a quantum dot (QD) semiconductor laser simultaneously operating at the ground state (GS) and excited state (ES) is investigated both experimentally and theoretically. We find experimentally that the slow passage through the two successive laser thresholds may lead to significant delays in the GS and ES turn ons. The difference between the turn-on times is measured as a function of the pump rate of change and reveals no clear power law. This has motivated a detailed analysis of rate equations appropriate for two-state lasing QD lasers. We find that the effective time of the GS turn on follows an -1/2 power law provided that the rate of change is not too small. The effective time of the ES transition follows an -1 power law, but its first order correction in ln is numerically significant. The two turn ons result from different physical mechanisms. The delay of the GS transition strongly depends on the slow growth of the dot population, whereas the ES transition only depends on the time needed to leave a repellent steady state.

Gaussian processes for classification: mean field algorithms:mean-field algorithms

We derive a mean field algorithm for binary classification with Gaussian processes which is based on the TAP approach originally proposed in Statistical Physics of disordered systems. The theory also yields an approximate leave-one-out estimator for the generalization error which is computed with no extra computational cost. We show that from the TAP approach, it is possible to derive both a simpler 'naive' mean field theory and support vector machines (SVM) as limiting cases. For both mean field algorithms and support vectors machines, simulation results for three small benchmark data sets are presented. They show 1. that one may get state of the art performance by using the leave-one-out estimator for model selection and 2. the built-in leave-one-out estimators are extremely precise when compared to the exact leave-one-out estimate. The latter result is a taken as a strong support for the internal consistency of the mean field approach.

A basis function approach to Bayesian inference in diffusion processes

In this paper, we present a framework for Bayesian inference in continuous-time diffusion processes. The new method is directly related to the recently proposed variational Gaussian Process approximation (VGPA) approach to Bayesian smoothing of partially observed diffusions. By adopting a basis function expansion (BF-VGPA), both the time-dependent control parameters of the approximate GP process and its moment equations are projected onto a lower-dimensional subspace. This allows us both to reduce the computational complexity and to eliminate the time discretisation used in the previous algorithm. The new algorithm is tested on an Ornstein-Uhlenbeck process. Our preliminary results show that BF-VGPA algorithm provides a reasonably accurate state estimation using a small number of basis functions.

Imaging the dynamics of the auditory steady-state evoked response

This study used magnetoencephalography (MEG) to examine the dynamic patterns of neural activity underlying the auditory steady-state response. We examined the continuous time-series of responses to a 32-Hz amplitude modulation. Fluctuations in the amplitude of the evoked response were found to be mediated by non-linear interactions with oscillatory processes both at the same source, in the alpha and beta frequency bands, and in the opposite hemisphere. © 2005 Elsevier Ireland Ltd. All rights reserved.

When do firms conform? The effect of regulatory control processes on compliance and opportunism

The authors use social control theory to develop a conceptual model that addresses the effectiveness of regulatory agencies’ (e.g., Food and Drug Administration, Occupational Safety and Health Administration) field-level efforts to obtain conformance with product safety laws. Central to the model are the control processes agencies use when monitoring organizations and enforcing the safety rules. These approaches can be labeled formal control (e.g., rigid enforcement) and informal control (e.g., social instruction). The theoretical framework identifies an important antecedent of control and the relative effectiveness of control’s alternative forms in gaining compliance and reducing opportunism. Furthermore, the model predicts that the regulated firms’ level of agreement with the safety rules moderates the relationships between control and firm responses. A local health department’s administration of state food safety regulations provides the empirical context for testing the hypotheses. The results from a survey of 173 restaurants largely support the proposed model. The study findings inform a discussion of effective methods of administering product safety laws. The authors use social control theory to develop a conceptual model that addresses the effectiveness of regulatory agencies’ (e.g., Food and Drug Administration, Occupational Safety and Health Administration) field-level efforts to obtain conformance with product safety laws. Central to the model are the control processes agencies use when monitoring organizations and enforcing the safety rules. These approaches can be labeled formal control (e.g., rigid enforcement) and informal control (e.g., social instruction). The theoretical framework identifies an important antecedent of control and the relative effectiveness of control’s alternative forms in gaining compliance and reducing opportunism. Furthermore, the model predicts that the regulated firms’ level of agreement with the safety rules moderates the relationships between control and firm responses. A local health department’s administration of state food safety regulations provides the empirical context for testing the hypotheses. The results from a survey of 173 restaurants largely support the proposed model. The study findings inform a discussion of effective methods of administering product safety laws.

A methodology for evaluating and selecting processes for natural gas conditioning

The aim of this work was to develop a generic methodology for evaluating and selecting, at the conceptual design phase of a project, the best process technology for Natural Gas conditioning. A generic approach would be simple and require less time and would give a better understanding of why one process is to be preferred over another. This will lead to a better understanding of the problem. Such a methodology would be useful in evaluating existing, novel and hybrid technologies. However, to date no information is available in the published literature on such a generic approach to gas processing. It is believed that the generic methodology presented here is the first available for choosing the best or cheapest method of separation for natural gas dew-point control. Process cost data are derived from evaluations carried out by the vendors. These evaluations are then modelled using a steady-state simulation package. From the results of the modelling the cost data received are correlated and defined with respect to the design or sizing parameters. This allows comparisons between different process systems to be made in terms of the overall process. The generic methodology is based on the concept of a Comparative Separation Cost. This takes into account the efficiency of each process, the value of its products, and the associated costs. To illustrate the general applicability of the methodology, three different cases suggested by BP Exploration are evaluated. This work has shown that it is possible to identify the most competitive process operations at the conceptual design phase and illustrate why one process has an advantage over another. Furthermore, the same methodology has been used to identify and evaluate hybrid processes. It has been determined here that in some cases they offer substantial advantages over the separate process techniques.

Dynamic simulation of chemical processes

This thesis describes the design and implementation of an interactive dynamic simulator called DASPRII. The starting point of this research has been an existing dynamic simulation package, DASP. DASPII is written in standard FORTRAN 77 and is implemented on universally available IBM-PC or compatible machines. It provides a means for the analysis and design of chemical processes. Industrial interest in dynamic simulation has increased due to the recent increase in concern over plant operability, resiliency and safety. DASPII is an equation oriented simulation package which allows solution of dynamic and steady state equations. The steady state can be used to initialise the dynamic simulation. A robust non linear algebraic equation solver has been implemented for steady state solution. This has increased the general robustness of DASPII, compared to DASP. A graphical front end is used to generate the process flowsheet topology from a user constructed diagram of the process. A conversational interface is used to interrogate the user with the aid of a database, to complete the topological information. An original modelling strategy implemented in DASPII provides a simple mechanism for parameter switching which creates a more flexible simulation environment. The problem description generated is by a further conversational procedure using a data-base. The model format used allows the same model equations to be used for dynamic and steady state solution. All the useful features of DASPI are retained in DASPII. The program has been demonstrated and verified using a number of example problems, Significant improvements using the new NLAE solver have been shown. Topics requiring further research are described. The benefits of variable switching in models has been demonstrated with a literature problem.

Variational inference for diffusion processes

Diffusion processes are a family of continuous-time continuous-state stochastic processes that are in general only partially observed. The joint estimation of the forcing parameters and the system noise (volatility) in these dynamical systems is a crucial, but non-trivial task, especially when the system is nonlinear and multimodal. We propose a variational treatment of diffusion processes, which allows us to compute type II maximum likelihood estimates of the parameters by simple gradient techniques and which is computationally less demanding than most MCMC approaches. We also show how a cheap estimate of the posterior over the parameters can be constructed based on the variational free energy.

Analysing organisational culture : a critical ethnography of public relations and personnel specialists in a state bureaucracy

Following an introductory chapter, I examine (i) typologies which have differentiated the literature on organisational culture and symbolism (Chapter 2), (ii) the contribution of organisation theory to organisation culture (Chapter 3), and (iii) recent literature on organisational culture and symbolism (Chapter 4). Within these chapters, I adopt Habermas' (1972) notion of knowledge-constitutive interests, assessing the contrubutions to understanding organisational culture made by literature guided by technical, practical and emancipatory cognitive interests. In doing so, I suggest that more critical studies on organisational culture and symbolism have been comparatively neglected. Lamenting this neglect, I suggest that Giddens' theory of structuration can be employed to advance the development of a critical, emancipatory conceptualisation of organisational culture. In particular, I argue that this Giddensian analysis, by penetrating the existential, poltical and material processes of cultural reproduction (Chapter 5), is able to disclose some of the more contradictory features of organisation culture. The remainder of the thesis comprises of a critical ethnography of the work cultures of public relations and personnel specialists located in a state bureaucracy. I begin the ethnography with a dicussion of my research methods (Chapter 6) and an overview of the departments studied (Chapter 7): I then examine (i) the work cultures of the specialists (Chapter 8), (ii) the specialists' management of the relationships with the hosts bureaucracy (Chapter 9); and, (iii) opportunities the specialists had for developing an emancipatory praxis (Chapter 10). Finally, in a concluding section, I offer some critical reflections on the contributions of the thesis and suggest areas for future research.