DIFFUSE-INTERFACE FIELD APPROACH TO MODELING SELF-ASSEMBLY OF HETEROGENEOUS COLLOIDAL SYSTEMS AND RELATED DIPOLE-DIPOLE INTERACTION PHENOMENA

Colloid self-assembly under external control is a new route to fabrication of advanced materials with novel microstructures and appealing functionalities. The kinetic processes of colloidal self-assembly have attracted great interests also because they are similar to many atomic level kinetic processes of materials. In the past decades, rapid technological progresses have been achieved on producing shape-anisotropic, patchy, core-shell structured particles and particles with electric/magnetic charges/dipoles, which greatly enriched the self-assembled structures. Multi-phase carrier liquids offer new route to controlling colloidal self-assembly. Therefore, heterogeneity is the essential characteristics of colloid system, while so far there still lacks a model that is able to efficiently incorporate these possible heterogeneities. This thesis is mainly devoted to development of a model and computational study on the complex colloid system through a diffuse-interface field approach (DIFA), recently developed by Wang et al. This meso-scale model is able to describe arbitrary particle shape and arbitrary charge/dipole distribution on the surface or body of particles. Within the framework of DIFA, a Gibbs-Duhem-type formula is introduced to treat Laplace pressure in multi-liquid-phase colloidal system and it obeys Young-Laplace equation. The model is thus capable to quantitatively study important capillarity related phenomena. Extensive computer simulations are performed to study the fundamental behavior of heterogeneous colloidal system. The role of Laplace pressure is revealed in determining the mechanical equilibrium of shape-anisotropic particles at fluid interfaces. In particular, it is found that the Laplace pressure plays a critical role in maintaining the stability of capillary bridges between close particles, which sheds light on a novel route to in situ firming compact but fragile colloidal microstructures via capillary bridges. Simulation results also show that competition between like-charge repulsion, dipole-dipole interaction and Brownian motion dictates the degree of aggregation of heterogeneously charged particles. Assembly and alignment of particles with magnetic dipoles under external field is studied. Finally, extended studies on the role of dipole-dipole interaction are performed for ferromagnetic and ferroelectric domain phenomena. The results reveal that the internal field generated by dipoles competes with external field to determine the dipole-domain evolution in ferroic materials.

IMPROVEMENTS IN SUSTAINABILITY OF GRAVITY-FED WATER SYSTEMS IN THE COMARCA NGÄBE-BUGLÉ, PANAMA: SPRING CAPTURES AND CIRCUIT RIDER MODEL

Gravity-flow aqueducts are used to bring clean water from mountain springs in the Comarca Ngäbe-Buglé, Panama, to the homes of the indigenous people who reside there. Spring captures enclose a spring to direct the flow of water into the transmission line. Seepage contact springs are most common, with water appearing above either hard basalt bedrock or a dense clay layer. Spring flows vary dramatically during wet and dry seasons, and discharge points of springs can shift, sometimes enough to impact the capture structure and its ability to properly collect all of the available water. Traditionally, spring captures are concrete boxes. The spring boxes observed by the author were dilapidated or out of alignment with the spring itself, only capturing part of the discharge. An improved design approach was developed that mimics the terrain surrounding the spring source to address these issues. Over the course of a year, three different spring sites were evaluated, and spring captures were designed and constructed based on the new approach. Spring flow data from each case study demonstrate increased flow capture in the improved structures. Rural water systems, including spring captures, can be sustainably maintained by the Circuit Rider model, a technical support system in which technical assistance is provided for the operation of the water systems. During 2012-2013, the author worked as a Circuit Rider and facilitated a water system improvement project while exploring methods of community empowerment to increase the capacity for system maintenance. Based on these experiences, recommendations are provided to expand the Circuit Rider model in the Comarca Ngäbe-Buglé under the Panamanian Ministry of Health’s Water and Sanitation Project (PASAP)

Acoustic manipulation and alignment of particles for applications in separation, micro-templating and device fabrication

This dissertation studies the manipulation of particles using acoustic stimulation for applications in microfluidics and templating of devices. The term particle is used here to denote any solid, liquid or gaseous material that has properties, which are distinct from the fluid in which it is suspended. Manipulation means to take over the movements of the particles and to position them in specified locations. ^ Using devices, microfabricated out of silicon, the behavior of particles under the acoustic stimulation was studied with the main purpose of aligning the particles at either low-pressure zones, known as the nodes or high-pressure zones, known as anti-nodes. By aligning particles at the nodes in a flow system, these particles can be focused at the center or walls of a microchannel in order to ultimately separate them. These separations are of high scientific importance, especially in the biomedical domain, since acoustopheresis provides a unique approach to separate based on density and compressibility, unparalleled by other techniques. The study of controlling and aligning the particles in various geometries and configurations was successfully achieved by controlling the acoustic waves. ^ Apart from their use in flow systems, a stationary suspended-particle device was developed to provide controllable light transmittance based on acoustic stimuli. Using a glass compartment and a carbon-particle suspension in an organic solvent, the device responded to acoustic stimulation by aligning the particles. The alignment of light-absorbing carbon particles afforded an increase in visible light transmittance as high as 84.5%, and it was controlled by adjusting the frequency and amplitude of the acoustic wave. The device also demonstrated alignment memory rendering it energy-efficient. A similar device for suspended-particles in a monomer enabled the development of electrically conductive films. These films were based on networks of conductive particles. Elastomers doped with conductive metal particles were rendered surface conductive at particle loadings as low as 1% by weight using acoustic focusing. The resulting films were flexible and had transparencies exceeding 80% in the visible spectrum (400-800 nm) These films had electrical bulk conductivities exceeding 50 S/cm. ^

Applicability of an assessment model for healthcare information systems in a public hospital

Assessment processes are essential to guarantee quality and continuous improvement of software in healthcare, as they measure software attributes in their lifecycle, verify the degree of alignment between the software and its objectives and identify unpredicted events. This article analyses the use of an assessment model based on software metrics for three healthcare information systems from a public hospital that provides secondary and tertiary care in the region of Ribeirão Preto. Compliance with the metrics was investigated using questionnaires in guided interviews of the system analysts responsible for the applications. The outcomes indicate that most of the procedures specified in the model can be adopted to assess the systems that serves the organization, particularly in the attributes of compatibility, reliability, safety, portability and usability.

Improving IT process management through value stream mapping approach: A case study

Value-Stream mapping (VSM) is a helpful tool to identify waste and improvement areas. It has emerged as a preferred way to support and implement the lean approach. While lean principles are well-established and have broad applicability in manufacturing, their extension to information technology is still limited. Based on a case study approach, this paper presents the implementation of VSM in an IT firm as a lean IT improvement initiative. It involves mapping the current activities of the firm and identifying opportunities for improvement. After several interviews with employees who are currently involved in the process, current state map is prepared to describe the existing problem areas. Future state map is prepared to show the proposed improvement action plans. The achievements of VSM implementation are reduction in lead time, cycle time and resources. Our finding indicates that, with the new process change, total lead time can be reduced from 20 days to 3 days – 92% reduction in overall lead time for database provisioning process.

Increasing the value of household appliances by adding a heat pump system

Historically, domestic tasks such as preparing food and washing and drying clothes and dishes were done by hand. In a modern home many of these chores are taken care of by machines such as washing machines, dishwashers and tumble dryers. When the first such machines came on the market customers were happy that they worked at all! Today, the costs of electricity and customers’ environmental awareness are high, so features such as low electricity, water and detergent use strongly influence which household machine the customer will buy. One way to achieve lower electricity usage for the tumble dryer and the dishwasher is to add a heat pump system. The function of a heat pump system is to extract heat from a lower temperature source (heat source) and reject it to a higher temperature sink (heat sink) at a higher temperature level. Heat pump systems have been used for a long time in refrigerators and freezers, and that industry has driven the development of small, high quality, low price heat pump components. The low price of good quality heat pump components, along with an increased willingness to pay extra for lower electricity usage and environmental impact, make it possible to introduce heat pump systems in other household products. However, there is a high risk of failure with new features. A number of household manufacturers no longer exist because they introduced poorly implemented new features, which resulted in low quality and product performance. A manufacturer must predict whether the future value of a feature is high enough for the customer chain to pay for it. The challenge for the manufacturer is to develop and produce a high-performance heat pump feature in a household product with high quality, predict future willingness to pay for it, and launch it at the right moment in order to succeed. Tumble dryers with heat pump systems have been on the market since 2000. Paper I reports on the development of a transient simulation model of a commercial heat pump tumble dryer. The measured and simulated results were compared with good similarity. The influence of the size of the compressor and the condenser was investigated using the validated simulation model. The results from the simulation model show that increasing the cylinder volume of the compressor by 50% decreases the drying time by 14% without using more electricity.  Paper II is a concept study of adding a heat pump system to a dishwasher in order to decrease the total electricity usage. The dishwasher, dishware and water are heated by the condenser, and the evaporator absorbs the heat from a water tank. The majority of the heat transfer to the evaporator occurs when ice is generated in the water tank. An experimental setup and a transient simulation model of a heat pump dishwasher were developed. The simulation results show a 24% reduction in electricity use compared to a conventional dishwasher heated with an electric element. The simulation model was based on an experimental setup that was not optimised. During the study it became apparent that it is possible to decrease electricity usage even more with the next experimental setup.

Talking about quality: exploring how ‘quality’ is conceptualized in European hospitals and healthcare systems

BACKGROUND: Conceptualization of quality of care - in terms of what individuals, groups and organizations include in their meaning of quality, is an unexplored research area. It is important to understand how quality is conceptualised as a means to successfully implement improvement efforts and bridge potential disconnect in language about quality between system levels, professions, and clinical services. The aim is therefore to explore and compare conceptualization of quality among national bodies (macro level), senior hospital managers (meso level), and professional groups within clinical micro systems (micro level) in a cross-national study. METHODS: This cross-national multi-level case study combines analysis of national policy documents and regulations at the macro level with semi-structured interviews (383) and non-participant observation (803 hours) of key meetings and shadowing of staff at the meso and micro levels in ten purposively sampled European hospitals (England, the Netherlands, Portugal, Sweden, and Norway). Fieldwork at the meso and micro levels was undertaken over a 12-month period (2011-2012) and different types of micro systems were included (maternity, oncology, orthopaedics, elderly care, intensive care, and geriatrics). RESULTS: The three quality dimensions clinical effectiveness, patient safety, and patient experience were incorporated in macro level policies in all countries. Senior hospital managers adopted a similar conceptualization, but also included efficiency and costs in their conceptualization of quality. 'Quality' in the forms of measuring indicators and performance management were dominant among senior hospital managers (with clinical and non-clinical background). The differential emphasis on the three quality dimensions was strongly linked to professional roles, personal ideas, and beliefs at the micro level. Clinical effectiveness was dominant among physicians (evidence-based approach), while patient experience was dominant among nurses (patient-centered care, enough time to talk with patients). Conceptualization varied between micro systems depending on the type of services provided. CONCLUSION: The quality conceptualization differed across system levels (macro-meso-micro), among professional groups (nurses, doctors, managers), and between the studied micro systems in our ten sampled European hospitals. This entails a managerial alignment challenge translating macro level quality definitions into different local contexts.

Experimental and modeling studies of forced convection storage and drying systems for sweet potatoes

Sweet potato is an important strategic agricultural crop grown in many countries around the world. The roots and aerial vine components of the crop are used for both human consumption and, to some extent as a cheap source of animal feed. In spite of its economic value and growing contribution to health and nutrition, harvested sweet potato roots and aerial vine components has limited shelf-life and is easily susceptible to post-harvest losses. Although post-harvest losses of both sweet potato roots and aerial vine components is significant, there is no information available that will support the design and development of appropriate storage and preservation systems. In this context, the present study was initiated to improve scientific knowledge about sweet potato post-harvest handling. Additionally, the study also seeks to develop a PV ventilated mud storehouse for storage of sweet potato roots under tropical conditions. In study one, airflow resistance of sweet potato aerial vine components was investigated. The influence of different operating parameters such as airflow rate, moisture content and bulk depth at different levels on airflow resistance was analyzed. All the operating parameters were observed to have significant (P < 0.01) effect on airflow resistance. Prediction models were developed and were found to adequately describe the experimental pressure drop data. In study two, the resistance of airflow through unwashed and clean sweet potato roots was investigated. The effect of sweet potato roots shape factor, surface roughness, orientation to airflow, and presence of soil fraction on airflow resistance was also assessed. The pressure drop through unwashed and clean sweet potato roots was observed to increase with higher airflow, bed depth, root grade composition, and presence of soil fraction. The physical properties of the roots were incorporated into a modified Ergun model and compared with a modified Shedd’s model. The modified Ergun model provided the best fit to the experimental data when compared with the modified Shedd’s model. In study three, the effect of sweet potato root size (medium and large), different air velocity and temperature on the cooling/or heating rate and time of individual sweet potato roots were investigated. Also, a simulation model which is based on the fundamental solution of the transient equations was proposed for estimating the cooling and heating time at the centre of sweet potato roots. The results showed that increasing air velocity during cooling and heating significantly (P < 0.05) affects the cooling and heating times. Furthermore, the cooling and heating times were significantly different (P < 0.05) among medium and large size sweet potato roots. Comparison of the simulation results with experimental data confirmed that the transient simulation model can be used to accurately estimate the cooling and heating times of whole sweet potato roots under forced convection conditions. In study four, the performance of charcoal evaporative cooling pad configurations for integration into sweet potato roots storage systems was investigated. The experiments were carried out at different levels of air velocity, water flow rates, and three pad configurations: single layer pad (SLP), double layers pad (DLP) and triple layers pad (TLP) made out of small and large size charcoal particles. The results showed that higher air velocity has tremendous effect on pressure drop. Increasing the water flow rate above the range tested had no practical benefits in terms of cooling. It was observed that DLP and TLD configurations with larger wet surface area for both types of pads provided high cooling efficiencies. In study five, CFD technique in the ANSYS Fluent software was used to simulate airflow distribution in a low-cost mud storehouse. By theoretically investigating different geometries of air inlet, plenum chamber, and outlet as well as its placement using ANSYS Fluent software, an acceptable geometry with uniform air distribution was selected and constructed. Experimental measurements validated the selected design. In study six, the performance of the developed PV ventilated system was investigated. Field measurements showed satisfactory results of the directly coupled PV ventilated system. Furthermore, the option of integrating a low-cost evaporative cooling system into the mud storage structure was also investigated. The results showed a reduction of ambient temperature inside the mud storehouse while relative humidity was enhanced. The ability of the developed storage system to provide and maintain airflow, temperature and relative humidity which are the key parameters for shelf-life extension of sweet potato roots highlight its ability to reduce post-harvest losses at the farmer level, particularly under tropical climate conditions.

Economic feasibility analysis of the implementation of a high value-added molecule extraction system in an olive oil mill

The production of olive oil generates several by-products that can be seen as an additional business opportunity. Among them are the olive pits, already used for heat and/or electricity generation in some mills. They contain compounds that are commercially very interesting and, if recovered, contribute to the sustainability of the olive mills. The work presented in this paper is a preliminary evaluation of the economic feasibility of implementing a system based on a batch prototype with 1 m3 for the extraction of high value-added bioactive molecules from olive pits that are separated during the production of virgin olive oil. For the analysis, a small representative olive mill in Portugal was considered and the traditional Discounted Cash Flow Method was applied. Based on the assumptions made, the simple payback for implementation a system for the extraction of value-added molecules from the olive pits is around 7 years.

A pointwise constrained version of the Liapunov convexity theorem for vectorial linear first-order control systems

We generalize the Liapunov convexity theorem's version for vectorial control systems driven by linear ODEs of first-order p = 1 , in any dimension d ∈ N , by including a pointwise state-constraint. More precisely, given a x ‾ ( ⋅ ) ∈ W p , 1 ( [ a , b ] , R d ) solving the convexified p-th order differential inclusion L p x ‾ ( t ) ∈ co { u 0 ( t ) , u 1 ( t ) , … , u m ( t ) } a.e., consider the general problem consisting in finding bang-bang solutions (i.e. L p x ˆ ( t ) ∈ { u 0 ( t ) , u 1 ( t ) , … , u m ( t ) } a.e.) under the same boundary-data, x ˆ ( k ) ( a ) = x ‾ ( k ) ( a ) & x ˆ ( k ) ( b ) = x ‾ ( k ) ( b ) ( k = 0 , 1 , … , p − 1 ); but restricted, moreover, by a pointwise state constraint of the type 〈 x ˆ ( t ) , ω 〉 ≤ 〈 x ‾ ( t ) , ω 〉 ∀ t ∈ [ a , b ] (e.g. ω = ( 1 , 0 , … , 0 ) yielding x ˆ 1 ( t ) ≤ x ‾ 1 ( t ) ). Previous results in the scalar d = 1 case were the pioneering Amar & Cellina paper (dealing with L p x ( ⋅ ) = x ′ ( ⋅ ) ), followed by Cerf & Mariconda results, who solved the general case of linear differential operators L p of order p ≥ 2 with C 0 ( [ a , b ] ) -coefficients. This paper is dedicated to: focus on the missing case p = 1 , i.e. using L p x ( ⋅ ) = x ′ ( ⋅ ) + A ( ⋅ ) x ( ⋅ ) ; generalize the dimension of x ( ⋅ ) , from the scalar case d = 1 to the vectorial d ∈ N case; weaken the coefficients, from continuous to integrable, so that A ( ⋅ ) now becomes a d × d -integrable matrix; and allow the directional vector ω to become a moving AC function ω ( ⋅ ) . Previous vectorial results had constant ω, no matrix (i.e. A ( ⋅ ) ≡ 0 ) and considered: constant control-vertices (Amar & Mariconda) and, more recently, integrable control-vertices (ourselves).

Can birds play a role as High Nature Value indicators of montado system?

Montados form a heterogeneous landscape of wooded matrix dominated by cork and/or holm oak with open areas characterized by fuzzy boundaries. Montado supports a high biological diversity associated to low intensity management and a landscape diversity provided by a continuous gradient of land cover. Among other features this permits the classification of montados as a High Nature Value (HNV) system. We assessed the role of birds as HNV indicators for montado, and tested several bird groups—farmland, edge, forest generalists and forest specialists species; and some universal indicators such as species conservation status, Shannon’s diversity index and species richness. Our study areas covered the North–South distribution of cork oak in Portugal, and we surveyed the breeding bird communities across 117 sampling sites. In addition to variables related to management and sanitary status, we considered variables that characterize the landscape heterogeneity inside the montado—trees and shrub density and richness of woody vegetation. Our results suggest that specific bird guilds can be used as HNV indicators of particular typologies of montado, and highlight the need to develop an indicator that could be transversally applied to all types of montado.

System innovation and life cycle thinking in packaging value chain: the circularity of plastics.

Compared to other, plastic materials have registered a strong acceleration in production and consumption during the last years. Despite the existence of waste management systems, plastic_based materials are still a pervasive presence in the environment, with negative consequences on marine ecosystem and human health. The recycling is still challenging due to the growing complexity of product design, the so-called overpackaging, the insufficient and inadequate recycling infrastructure, the weak market of recycled plastics and the high cost of waste treatment and disposal. The Circular economy package, the European Strategy for plastics in a circular economy and the recent European Green Deal include very ambitious programmes to rethink the entire plastic value chain. As regards packaging, all plastic packaging will have to be 100% recyclable (or reusable) and 55% recycled by 2030. Regions are consequently called upon to set up a robust plan able to fit the European objectives. It takes on greater importance in Emilia Romagna where the Packaging valley is located. This thesis supports the definition of a strategy aimed to establish an after-use plastics economy in the region. The PhD work has set the basis and the instruments to establish the so-called Circularity Strategy with the aim to turn about 92.000t of plastic waste into profitable secondary resources. System innovation, life cycle thinking and participative backcasting method have allowed to deeply analyse the current system, orientate the problem and explore sustainable solutions through a broad stakeholder participation. A material flow analysis, accompanied by a barrier analysis, has supported the identification of the gaps between the present situation and the 2030 scenario. Eco-design for and from recycling (and a mass _based recycling rate (based on the effective amount of plastic wastes turned into secondary plastics), valorized by a value_based indicator, are the key-points of the action plan.

Studying the alignment of 5-cyanobiphenyl on a polydimethylsiloxane surface through Molecular Dynamics simulations

For 40 years, at the University of Bologna, a group of researchers coordinated by professor Claudio Zannoni has been studying liquid crystals by employing computational techniques. They have developed effective models of these interesting, and still far from being completely understood, systems. They were able to reproduce with simulations important features of some liquid crystal molecules, such as transition temperature. Then they focused their attention on the interactions that these molecules have with different kinds of surface, and how these interactions affect the alignment of liquid crystals. The group studied the behaviour of liquid crystals in contact with different kinds of surfaces, from silica, either amorphous and crystalline, to organic self assembled monolayers (SAMs) and even some common polymers, such as polymethylmethacrylate (PMMA) and polystyrene (PS). Anyway, a library of typical surfaces is still far from being complete, and a lot of work must be done to investigate the cases which have not been analyzed yet. A hole that must be filled is represented by polydimethylsiloxane (PDMS), a polymer on which the interest of industry has enormously grown up in the last years, thanks to its peculiar features, allowing it to be employed in many fields of applications. It has been observed experimentally that PDMS causes 4-cyano-4’-pentylbiphenyl (well known as 5CB), one of the most common liquid crystal molecules, to align homeotropically (i.e. perpendicular) with respect to a surface made of this polymer. Even though some hypothesis have been presented to rationalize the effect, a clear explanation of this phenomenon has not been given yet. This dissertation shows the work I did during my internship in the group of professor Zannoni. The challenge that I had to tackle was to investigate, via Molecular Dynamics (MD) simulations, the reasons of 5CB homeotropic alignment on a PDMS surface, as the group had previously done for other surfaces.

Synthesis and catalytic activity of new cu-based catalytic systems for the enhanced electrochemical CO2 reduction

This Ph.D. thesis concerns the synthesis of nanostructured Cu-containing materials to be used as electrode modifiers for the CO2 electroreduction in aqueous phase and the evaluation of their catalytic performances. Inspired by the fascinating concept of the artificial photosynthesis-oriented systems, several catalytic layers were electrochemically loaded on carbonaceous gas diffusion membranes, i.e., 3D structures that allow the design of eco-friendly materials for applications in green carbon recycling processes. In particular, early studies on Cu(I-II)-Cu(0) nanostructured materials were carried out to produce films on 4 cm2 sized supports by means of a fast and low-cost electrochemical procedure. Besides, through a screening of potentials, it was possible to find out a selective value for the CH3COOH production at -0.4 V vs RHE with a maximum productivity (1h reaction), ensured by the presence of the Cu+/Cu0 active redox couple (0.31 mmol gcat-1 h-1). On the basis of these results, further optimisations of the electrocatalyst chemical composition were carried out with the aim of (i) facilitating the interaction with CO2, (ii) increasing the dispersion of the catalytic active phase, and (iii) enhancing the CH3COOH productivity. To this aim, novel electrocatalysts based on layered double hydroxides (LDHs) were optimised, having as a final goal the formation of a new Cu2O-Cu0 based electrocatalyst derived from electrochemically achieved CuMgAl LDHs, subjected to calcination and reduction processes. The as-obtained electrocatalysts were tested for the selective production of CH3COOH and unprecedented results were obtained with the pristine CuMgAl LDH (2.0 mmol gcat-1 h-1). Additional characterisations of such an electrocatalyst have highlighted the possibility to achieve a ternary LDH in intimate contact with Cu2O-Cu0 species starting from the electrochemical deposition. The presence of these species, along with an alkaline environment on the electrode surface, were essential to preserve the selectivity towards the desired product, as confirmed by further operando studies.