Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.

Studies on the Production, Properties and Processability of Low Protein Latex

Latex protein allergy is a serious problem faced by users of natural rubber latex products. This is severe in health care workers, who are constantly using latex products like examination gloves, surgical gloves etc. Out of the total proteins only a small fraction is extractable and only these proteins cause allergic reactions in sensitized people. Enzymic deproteinisation of latex and leaching and chlorination of latex products are the common methods used to reduce the severity of the problem.Enzyme deproteinisation is a cubersome process involving high cost and process loss.Physical properties of such films are poor. Leaching is a lengthy process and in leached latex products presence of extractable proteins is observed on further storing. Chlorination causes yellowing of latex products and reduction in tensile properties.In this context a more simple process of removal of extractable proteins from latex itself was investigated. This thesis reports the application of poly propylene glycol (PPG) to displace extractable proteins from natural latex. PPG is added to 60 % centrifuged natural latex to the extent of 0.2 % m/rn, subssequently diluted to 30 % dry rubber content and again concentrated to obtain a low protein latex.Dilution of concentrated latex and subsequent concentration lead to a total reduction in non - rubber solids in the concentrate, especially proteins and reduction in the ionic concentration in the aqueous phase of the latex. It has been reported that proteins in natural rubber / latex affect its behaviour in the vulcanisation process. Ionic concentration in the aqueous phase of latex influence the stability, viscosity and flow behaviour of natural latex. Hence, a detailed technological evaluation was carried out on this low protein latex. In this study, low protein latex was compared with single centrifuged latex ( the raw material to almost every latex product), double centrifuged latex ( because dilution and second concentration of latex is accompanied by protein removal to some extent and reduction in the ionic concentration of the aqueous phase of latex.). Studies were conducted on Sulphur cure in conventional and EV systems under conditions of post ~ cure and prevulcanisation of latex. Studies were conducted on radiation cure in latex stage. Extractable protein content in vulcanised low protein latex films are observed to be very low. lt is observed that this low protein latex is some what slower curing than single centrifuged latex, but faster than double centrifuged latex. Modulus of low protein latex films were slightly low. In general physical properties of vulcanised low protein latex films are only siightly lower than single centrifuged latex. Ageing properties of the low protein latex films were satisfactory. Viscosity and flow behaviour of low protein latex is much better than double centrifuged latex and almost comparable to single centrifuged latex. On observing that the physical properties and flow behaviour of low protein latex was satisfactory, it was used for the preparation of examination gloves and the gloves were evaluated. It is observed that the properties are conforming to the Indian Standard Specifications. It is thus observed that PPG treatment of natural latex is a simple process of preparing low protein latex. Extractable protein content in these films are very low.The physical properties of the films are comparable to ordinary centrifuged latex and better than conventionally deprotenized latex films. This latex can be used for the production of examination gloves.

Studies on Latex Reclaim and its Blends

The primary aim of this work has been to develop a cost effective process that can be operated at room temperature for developing latex reclaim with superior mechanical properties. With this objective in mind the researcher proposes to study the reclaiming action of four different chemicals on latex products waste. Waste latex products are chosen because it has a higher potential to generate good quality rubber hydrocarbon since all latex products are based on either high quality concentrated latex or creamed latex. Moreover, all latex products are only lightly crosslinked and not masticated and hence not mechanically degraded. The author also proposes to fully explore the possible application of latex reclaim in various fields..

Managing Quality Properties of Web Service Compositions

Web services from different partners can be combined to applications that realize a more complex business goal. Such applications built as Web service compositions define how interactions between Web services take place in order to implement the business logic. Web service compositions not only have to provide the desired functionality but also have to comply with certain Quality of Service (QoS) levels. Maximizing the users' satisfaction, also reflected as Quality of Experience (QoE), is a primary goal to be achieved in a Service-Oriented Architecture (SOA). Unfortunately, in a dynamic environment like SOA unforeseen situations might appear like services not being available or not responding in the desired time frame. In such situations, appropriate actions need to be triggered in order to avoid the violation of QoS and QoE constraints. In this thesis, proper solutions are developed to manage Web services and Web service compositions with regard to QoS and QoE requirements. The Business Process Rules Language (BPRules) was developed to manage Web service compositions when undesired QoS or QoE values are detected. BPRules provides a rich set of management actions that may be triggered for controlling the service composition and for improving its quality behavior. Regarding the quality properties, BPRules allows to distinguish between the QoS values as they are promised by the service providers, QoE values that were assigned by end-users, the monitored QoS as measured by our BPR framework, and the predicted QoS and QoE values. BPRules facilitates the specification of certain user groups characterized by different context properties and allows triggering a personalized, context-aware service selection tailored for the specified user groups. In a service market where a multitude of services with the same functionality and different quality values are available, the right services need to be selected for realizing the service composition. We developed new and efficient heuristic algorithms that are applied to choose high quality services for the composition. BPRules offers the possibility to integrate multiple service selection algorithms. The selection algorithms are applicable also for non-linear objective functions and constraints. The BPR framework includes new approaches for context-aware service selection and quality property predictions. We consider the location information of users and services as context dimension for the prediction of response time and throughput. The BPR framework combines all new features and contributions to a comprehensive management solution. Furthermore, it facilitates flexible monitoring of QoS properties without having to modify the description of the service composition. We show how the different modules of the BPR framework work together in order to execute the management rules. We evaluate how our selection algorithms outperform a genetic algorithm from related research. The evaluation reveals how context data can be used for a personalized prediction of response time and throughput.

Mid-term evaluation of African Technology Policy Studies Network Phase VI Strategic Plan: for the period January 1, 2009 to December 31, 2010

The African Technology Policy Studies Network (ATPS) is a multidisciplinary network of researchers, private sector actors, policymakers and civil society. ATPS has the vision to become the leading international centre of excellence and reference in science, technology and innovation (STI) systems research, training and capacity building, communication and sensitization, knowledge brokerage, policy advocacy and outreach in Africa. It has a Regional Secretariat in Nairobi Kenya, and operates through national chapters in 29 countries (including 27 in Africa and two Chapters in the United Kingdom and USA for Africans in the Diaspora) with an expansion plan to cover the entire continent by 2015. The ATPS Phase VI Strategic Plan aims to improve the understanding and functioning of STI processes and systems to strengthen the learning capacity, social responses, and governance of STI for addressing Africa's development challenges, with a specific focus on the Millennium Development Goals (MDGs). A team of external evaluators carried out a midterm review to assess the effectiveness and efficiency of the implementation of the Strategic Plan for the period January 1, 2009 to December 31, 2010. The evaluation methodology involved multiple quantitative and qualitative methods to assess the qualitative and quantitative inputs (human resources, financial resources, time, etc.) into ATPS activities (both thematic and facilitative) and their tangible and intangible outputs, outcomes and impacts. Methods included a questionnaire survey of ATPS members and stakeholders, key informant interviews, and focus group discussions (FGDs) with members in six countries. Effectiveness of Programmes Under all six strategic goals, very good progress has been made towards planned outputs and outcomes. This is evidenced by key performance indicators (KPIs) generated from desk review, ratings from the survey respondents, and the themes that run through the FGDs. Institutional and Programme Cost Effectiveness Institutional Effectiveness: assessment of institutional effectiveness suggests that adequate management frameworks are in place and are being used effectively and transparently. Also technical and financial accounting mechanisms are being followed in accordance with grant agreements and with global good practice. This is evidenced by KPIs generated from desk review. Programme Cost Effectiveness: assessment of cost-effectiveness of execution of programmes shows that organisational structure is efficient, delivering high quality, relevant research at relatively low cost by international standards. The evidence includes KPIs from desk review: administrative costs to programme cost ratio has fallen steadily, to around 10%; average size of research grants is modest, without compromising quality. There is high level of pro bono input by ATPS members. ATPS Programmes Strategic Evaluation ATPS research and STI related activities are indeed unique and well aligned with STI issues and needs facing Africa and globally. The multi-disciplinary and trans-boundary nature of the research activities are creating a unique group of research scientists. The ATPS approach to research and STI issues is paving the way for the so called Third Generation University (3GU). Understanding this unique positioning, an increasing number of international multilateral agencies are seeking partnership with ATPS. ATPS is seeing an increasing level of funding commitments by Donor Partners. Recommendations for ATPS Continued Growth and Effectiveness On-going reform of ATPS administrative structure to continue The on-going reforms that have taken place within the Board, Regional Secretariat, and at the National Chapter coordination levels are welcomed. Such reform should continue until fully functional corporate governance policy and practices are fully established and implemented across the ATPS governance structures. This will further strengthen ATPS to achieve the vision of being the leading STI policy brokerage organization in Africa. Although training in corporate governance has been carried out for all sectors of ATPS leadership structure in recent time, there is some evidence that these systems have not yet been fully implemented effectively within all the governance structures of the organization, especially at the Board and National chapter levels. Future training should emphasize practical application with exercises relevant to ATPS leadership structure from the Board to the National Chapter levels. Training on Transformational Leadership - Leading a Change Though a subject of intense debate amongst economists and social scientists, it is generally agreed that cultural mindsets and attitudes could enhance and/or hinder organizational progress. ATPS’s vision demands transformational leadership skills amongst its leaders from the Board members to the National Chapter Coordinators. To lead such a change, ATPS leaders must understand and avoid personal and cultural mindsets and value systems that hinder change, while embracing those that enhance it. It requires deliberate assessment of cultural, behavioural patterns that could hinder progress and the willingness to be recast into cultural and personal habits that make for progress. Improvement of relationship amongst the Board, Secretariat, and National Chapters A large number of ATPS members and stakeholders feel they do not have effective communications and/or access to Board, National Chapter Coordinators and Regional Secretariat activities. Effort should be made to improve the implementation of ATPS communication strategy to improve on information flows amongst the ATPS management and the members. The results of the survey and the FGDs suggest that progress has been made during the past two years in this direction, but more could be done to ensure effective flow of pertinent information to members following ATPS communications channels. Strategies for Increased Funding for National Chapters There is a big gap between the fundraising skills of the Regional Secretariat and those of the National Coordinators. In some cases, funds successfully raised by the Secretariat and disbursed to national chapters were not followed up with timely progress and financial reports by some national chapters. Adequate training in relevant skills required for effective interactions with STI key policy players should be conducted regularly for National Chapter coordinators and ATPS members. The ongoing training in grant writing should continue and be made continent-wide if funding permits. Funding of National Chapters should be strategic such that capacity in a specific area of research is built which, with time, will not only lead to a strong research capacity in that area, but also strengthen academic programmes. For example, a strong climate change programme is emerging at University of Nigeria Nsukka (UNN), with strong collaborations with Universities from neighbouring States. Strategies to Increase National Government buy-in and support for STI Translating STI research outcomes into policies requires a great deal of emotional intelligence, skills which are often lacking in the first and second generation universities. In the epoch of the science-based or 2GUs, governments were content with universities carrying out scientific research and providing scientific education. Now they desire to see universities as incubators of new science- or technology-based commercial activities, whether by existing firms or start-ups. Hence, governments demand that universities take an active and leading role in the exploitation of their knowledge and they are willing to make funds available to support such activities. Thus, for universities to gain the attention of national leadership they must become centres of excellence and explicit instruments of economic development in the knowledge-based economy. The universities must do this while working collaboratively with government departments, parastatals, and institutions and dedicated research establishments. ATPS should anticipate these shifting changes and devise programmes to assist both government and universities to relate effectively. New administrative structures in member organizations to sustain and manage the emerging STI multidisciplinary teams Second Generation universities (2GUs) tend to focus on pure science and often do not regard the application of their know-how as their task. In contrast, Third Generation Universities (3GUs) objectively stimulate techno-starters – students or academics – to pursue the exploitation or commercialisation of the knowledge they generate. They view this as being equal in importance to the objectives of scientific research and education. Administratively, research in the 2GU era was mainly monodisciplinary and departments were structured along disciplines. The emerging interdisciplinary scientific teams with focus on specific research areas functionally work against the current mono-disciplinary faculty-based, administrative structure of 2GUs. For interdisciplinary teams, the current faculty system is an obstacle. There is a need for new organisational forms for university management that can create responsibilities for the task of know-how exploitation. ATPS must anticipate this and begin to strategize solutions for their member institutions to transition to 3Gus administrative structure, otherwise ATPS growth will plateau, and progress achieved so far may be stunted.

High yield production of a soluble bifidobacterial β-galactosidase (BbgIV) inE. coliDH5α with improved catalytic efficiency for the synthesis of prebiotic galactooligosaccharides

The bifidobacterial β-galactosidase (BbgIV) was produced in E. coli DH5α at 37 and 30 °C in a 5 L bioreactor under varied conditions of dissolved oxygen (dO2) and pH. The yield of soluble BbgIV was significantly (P < 0.05) increased once the dO2 dropped to 0–2% and remained at such low values during the exponential phase. Limited dO2 significantly (P < 0.05) increased the plasmid copy number and decreased the cells growth rate. Consequently, the BbgIV yield increased to its maximum (71–75 mg per g dry cell weight), which represented 20–25% of the total soluble proteins in the cells. In addition, the specific activity and catalytic efficiency of BbgIV were significantly (P < 0.05) enhanced under limited dO2 conditions. This was concomitant with a change in the enzyme secondary structure, suggesting a link between the enzyme structure and function. The knowledge generated from this work is very important for producing BbgIV as a biocatalyst for the development of a cost-effective process for the synthesis of prebiotic galactooligosaccharides from lactose.

Design and techno-economic evaluation of microbial oil production as a renewable resource for biodiesel and oleochemical production

Experimental results from the open literature have been employed for the design and techno-economic evaluation of four process flowsheets for the production of microbial oil or biodiesel. The fermentation of glucose-based media using the yeast strain Rhodosporidium toruloides has been considered. Biodiesel production was based on the exploitation of either direct transesterification (without extraction of lipids from microbial biomass) or indirect transesterifaction of extracted microbial oil. When glucose-based renewable resources are used as carbon source for an annual production capacity of 10,000 t microbial oil and zero cost of glucose (assuming development of integrated biorefineries in existing industries utilising waste or by-product streams) the estimated unitary cost of purified microbial oil is $3.4/kg. Biodiesel production via indirect transesterification of extracted microbial oil proved more cost-competitive process compared to the direct conversion of dried yeast cells. For a price of glucose of $400/t oil production cost and biodiesel production cost are estimated to be $5.5/kg oil and $5.9/kg biodiesel, correspondingly. Industrial implementation of microbial oil production from oleaginous yeast is strongly dependent on the feedstock used and on the fermentation stage where significantly higher productivities and final microbial oil concentrations should be achieved.

Software maintenance project delays prediction using Bayesian Networks

Managing software maintenance is rarely a precise task due to uncertainties concerned with resources and services descriptions. Even when a well-established maintenance process is followed, the risk of delaying tasks remains if the new services are not precisely described or when resources change during process execution. Also, the delay of a task at an early process stage may represent a different delay at the end of the process, depending on complexity or services reliability requirements. This paper presents a knowledge-based representation (Bayesian Networks) for maintenance project delays based on specialists experience and a corresponding tool to help in managing software maintenance projects. (c) 2006 Elsevier Ltd. All rights reserved.

Elementary Petri net inside RFID distributed database (PNRD)

Usually, a Petri net is applied as an RFID model tool. This paper, otherwise, presents another approach to the Petri net concerning RFID systems. This approach, called elementary Petri net inside an RFID distributed database, or PNRD, is the first step to improve RFID and control systems integration, based on a formal data structure to identify and update the product state in real-time process execution, allowing automatic discovery of unexpected events during tag data capture. There are two main features in this approach: to use RFID tags as the object process expected database and last product state identification; and to apply Petri net analysis to automatically update the last product state registry during reader data capture. RFID reader data capture can be viewed, in Petri nets, as a direct analysis of locality for a specific transition that holds in a specific workflow. Following this direction, RFID readers storage Petri net control vector list related to each tag id is expected to be perceived. This paper presents PNRD cornerstones and a PNRD implementation example in software called DEMIS Distributed Environment in Manufacturing Information Systems.

Mapping Attribution Metadata to the Open Provenance Model

A description of a data item's provenance can be provided in dierent forms, and which form is best depends on the intended use of that description. Because of this, dierent communities have made quite distinct underlying assumptions in their models for electronically representing provenance. Approaches deriving from the library and archiving communities emphasise agreed vocabulary by which resources can be described and, in particular, assert their attribution (who created the resource, who modied it, where it was stored etc.) The primary purpose here is to provide intuitive metadata by which users can search for and index resources. In comparison, models for representing the results of scientific workflows have been developed with the assumption that each event or piece of intermediary data in a process' execution can and should be documented, to give a full account of the experiment undertaken. These occurrences are connected together by stating where one derived from, triggered, or otherwise caused another, and so form a causal graph. Mapping between the two approaches would be benecial in integrating systems and exploiting the strengths of each. In this paper, we specify such a mapping between Dublin Core and the Open Provenance Model. We further explain the technical issues to overcome and the rationale behind the approach, to allow the same method to apply in mapping similar schemes.

Uma abordagem dirigida por modelos para gerência de variabilidade e execução de processos de software

This dissertation presents a model-driven and integrated approach to variability management, customization and execution of software processes. Our approach is founded on the principles and techniques of software product lines and model-driven engineering. Model-driven engineering provides support to the specification of software processes and their transformation to workflow specifications. Software product lines techniques allows the automatic variability management of process elements and fragments. Additionally, in our approach, workflow technologies enable the process execution in workflow engines. In order to evaluate the approach feasibility, we have implemented it using existing model-driven engineering technologies. The software processes are specified using Eclipse Process Framework (EPF). The automatic variability management of software processes has been implemented as an extension of an existing product derivation tool. Finally, ATL and Acceleo transformation languages are adopted to transform EPF process to jPDL workflow language specifications in order to enable the deployment and execution of software processes in the JBoss BPM workflow engine. The approach is evaluated through the modeling and modularization of the project management discipline of the Open Unified Process (OpenUP)

Identificação de Enterobacter spp. através de técnicas convencionais e do sistema semi-automatizado Microscan (Autoscan-4)

A hundred and ninety-five (195) strains of Enterobacter spp., isolated from diverse clinical specimens - urine, feces, cateter, blood, wound, tracheal aspirate, vaginal fluid - were submitted to the conventional identification by biochemical tests, and were also submitted to the identification by panels NegCombo 20 of the system automated MicroScan - AutoScan- 4 (Dade Behring Inc., West Sacramento, CA, USA). The samples were from patients of the Clinical Laboratory from the School of Pharmacy and Biochemistry of UNOESTE, Presidente Prudente, SP, and from patients hospitalized at the University Hospital Domingos Leonardo Cerávolo, UNOESTE. Of the total of strains tested, 191 (97.9%) presented agreement between the two approaches utilized and 4 strains (2.1%) presented identification disagreement, that is, the genus identified was different in each approach. By this study, the conclusion is that both the approaches utilized for the identification presented advantages and disadvantages related to the cost, facility of execution, quickness, reliability and some other characteristics. Even so, our results showed that conventional methods represent a reliable tool for Enterobacter identification.

Entre o kháos e o kósmos, a demiourgía da excelência: a seleção de pessoal como regulação, normalização e mediação no contexto das novas políticas de gestão de recursos humanos

Pós-graduação em Psicologia - FCLAS

Comparação de compósitos obtidos via RTM de resina epóxi e fibra de carbono com e sem descontinuidade nos tecidos

Technology is growing interest in the use of composites, due to the requirement of lighter materials and more resistant, factors essential to meet the project specifications and reduce the operational cost. In the production of high performance structural composites, considering the aerospace criteria, the domestic industry has shown interest in the process of resin transfer molding (RTM) for reproducibility and low cost. This process is suitable for producing components of polymeric composites with relatively simple geometries, consistent thicknesses, high quality finish with no size limitations. The objective of this work was machined carbon steel to make a matched-die tooling for RTM and produce two composite plates of epoxy resin and carbon fiber fabric with and without induced discontinuities, which were compared towards their impregnation with ultrasound, their properties via tensile tests and thermal analysis. In ultrasonic inspection, it was found good impregnation of the preform of both composites. In the thermal analysis it was possible to check the degradation temperature of the composites, the glass transition temperature and it was found that the composites showed no effective cure cycles, but presented good performance in the tensile test when compared with aluminum alloy 7050 T7451 . The results showed that the injection strategy was appropriate since the laminate exhibited a good quality for the proposed application

Desenvolvimento de filmes finos de Bi3NbO7 pelo método dos precursores poliméricos em diferentes eletrodos óxidos

Technology always advances and thus the device miniaturization and improved performance, besides multifunctionality, they become extremely necessary. A wave of research on the area tends to grow in number and importance in today's market, it is necessary to search for new materials, new applicability of the existing ones and new processes for increasingly cheaper costs. Dielectric materials are considered a key element in this sector being the main electrical properties its high dielectric constant and low dielectric loss. The Polymeric Precursor Method appears as a good alternative because is a low cost, simple process with controlled stoichiometry. In this method, two steps were performed. In a first step, the precursor solution was decomposed into powders and in a second step the precursor solution was converted in thin films. In this work, was used the polymeric precursor methods to get thin films where they were heat treated and characterized by XRD, SEM and AFM. We have obtained Bi3NbO7 thin films with good homogeneity and uniform distribution of grains were noted. We observed that the best condition to obtain the tetragonal phase is annealing the film at high temperatures for a longer soaking time and with excess of bismuth. Several oxides electrodes were evaluated aiming to obtain textured dielectric thin films