Metal deposition using Ionic liquids

There is an interest to create zinc/tin alloys to replace cadmium as a corrosion protective coating material. Existing aqueous electroplating systems for these alloys are commercially available but have several limitations. Dangerous and highly toxic complexing agents are uses e.g. cyanides. To overcome these problems, ionic liquids could provide a solution to obtain an alloy containing 20 to 30% of zinc. Ionic liquids (IL’s) often have wider electrochemical windows which allow the deposition of e.g. refractive metals that can not be deposited from aqueous solutions. In IL’s it is often not necessary to add complexing agents. The Zn/Sn alloy deposition from IL’s is therefore a promising application for the plating industry. Nevertheless, there are some issues with this alternative for aqueous systems. The degradation of the organic components, the control of the concentration of two metals and the risk of a two phase deposition instead of an alloy had to be overcome first. It is the main purpose of this thesis to obtain a Zn/Sn alloy with 20% zinc using IL’s as an electrolyte. First a separate study was performed on both the zinc and the tin deposition. Afterwards, an attempt to deposit a Zn/Sn alloy was made. An introduction to a study about the electrodeposition of refractive metals concludes this work. It initiated the research for oxygen-free IL’s to deposit molybdenum or tungsten. Several parameters (temperature, metal source and concentration, organic complexing agents,…) were optimized for both the zinc, tin and zinc/tin deposition. Experiments were performed both in a parallel plate cell and a Hull cell, so as to investigate the effect of current density as well. Ethaline200 was selected as electrolyte. As substrate, brass and iron were selected, while as anode a plate of the metal to deposit was chosen, tin for the alloy. The best efficiencies were always obtained on brass; however the iron substrate resulted in the best depositions. A concentration of 0.27M ZnCl2, 0.07M SnCl2 with 0.015M of K3-HEDTA as complexant resulted in a deposition containing the desired alloy with the amount of 20% zinc and 80% tin with good appearance. Refractory metals as molybdenum and tungsten cannot be electrodeposited from aqueous solutions without forming a co-deposition with Ni, Co or Fe. Here, IL’s could again provide a solution. A first requirement is the dissolution of a metal source. MoO3 could be suitable, however there are doubts about using oxides. Oxygen-free IL’s were sought for. A first attempt was the combination of ZnCl2 with chlormequat (CCC), which gave liquids below 150°C in molar ratios of 2 : 1 and 3 : 1. Unfortuna tely, MoO3 didn’t dissolve in these IL’s. Another route to design oxygen-free IL’s was the synthesis of quaternary ammonium salts. None of the methods used, proved viable as reaction time was long and resulted in very low yields. Therefore, no sufficient quantities were obtained to perform the possible electrochemical behavior of refractive metals.

Aplicação de metodologias lean na manutenção da simoldes aços

O trabalho presente nesta dissertação incidiu sobre a aplicação das metodologias Lean no âmbito da manutenção de uma empresa metalomecânica de produção de Moldes – Simoldes Aços. No atual enquadramento, com os mercados nacionais e internacionais debaixo de feroz competição, as empresas são obrigadas a estudar métodos e técnicas que permitam eliminar desperdícios, reduzir custos e tempos de produção, ao mesmo tempo que são exigidos maiores níveis de qualidade dos produtos fabricados com vista ao aumento da competitividade. Sendo a Manutenção uma área funcional com um impacto elevado no desempenho da produção, é percebido que o desempenho desta, tem influência direta no comportamento do fluxo produtivo e nos respetivos níveis de eficácia e eficiência. No decorrer do trabalho desta dissertação de mestrado foi realizada uma análise abrangente do estado atual do sector de atividade de manutenção na empresa SIMOLDES SA, o que permitiu identificar as áreas e os pontos a intervir e desenhar as soluções de melhoria na atividade de manutenção. Na fase concludente do trabalho foram implementadas algumas dessas propostas de melhoria, ao passo que outras ficaram agendadas para futura implementação. Na base do trabalho desenvolvido esteve a metodologia Lean, que apresenta um papel relevante na implementação de uma abordagem integrada da função manutenção na manutenção dos objetivos da produção. O presente projeto baseou a sua estratégia de implementação na aplicação da ferramenta do 5S’ em paralelo com o TPM (Total Productive Maintenance). Ambas as ferramentas visam a redução de desperdícios e o aumento da fiabilidade dos processos, pelo aumento da disponibilidade dos equipamentos, da melhoria do desempenho dos processos e da plena integração de todos os colaboradores no processo de fabrico. Com a implementação das melhorias propostas, foram observados melhorias significativas no fluxo das atividades da manutenção, assim como uma maior visibilidade das mesmas em todo o processo produtivo.

Development of electrochemical methods for determination of tramadol - analytical application to pharmaceutical dosage forms

A square-wave voltammetric (SWV) method and a flow injection analysis system with amperometric detection were developed for the determination of tramadol hydrochloride. The SWV method enables the determination of tramadol over the concentration range of 15-75 µM with a detection limit of 2.2 µM. Tramadol could be determined in concentrations between 9 and 50 µM at a sampling rate of 90 h-1, with a detection limit of 1.7 µM using the flow injection system. The electrochemical methods developed were successfully applied to the determination of tramadol in pharmaceutical dosage forms, without any pre-treatment of the samples. Recovery trials were performed to assess the accuracy of the results; the values were between 97 and 102% for both methods.

Determination of pesticides in fruit and fruit juices by chromatographic methods. An overview

In order to combat a variety of pests, pesticides are widely used in fruits. Several extraction procedures (liquid extraction, single drop microextraction, microwave-assisted extraction, pressurized liquid extraction, supercritical fluid extraction, solid-phase extraction, solid-phase microextraction, matrix solid-phase dispersion, and stir bar sorptive extraction) have been reported to determine pesticide residues in fruits and fruit juices. The significant change in recent years is the introduction of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods in these matrices analysis. A combination of techniques reported the use of new extraction methods and chromatography to provide better quantitative recoveries at low levels. The use of mass spectrometric detectors in combination with liquid and gas chromatography has played a vital role to solve many problems related to food safety. The main attention in this review is on the achievements that have been possible because of the progress in extraction methods and the latest advances and novelties in mass spectrometry, and how these progresses have influenced the best control of food, allowing for an increase in the food safety and quality standards.

Electrochemical methods in pesticides control

The state of the art of voltammetric and amperometric methods used in the study and determination of pesticides in crops, food, phytopharmaceutical products, and environmental samples is reviewed. The main structural groups of pesticides, i.e., triazines, organophosphates, organochlorides, nitrocompounds, carbamates, thiocarbamates, sulfonylureas, and bipyridinium compounds are considered with some degradation products. The advantages, drawbacks, and trends in the development of voltammetric and amperometric methods for study and determination of pesticides in these samples are discussed.

Evaluation of distinct input methods of an intelligent wheelchair in simulated and real environments: a performance and usability study

This paper focuses on evaluating the usability of an Intelligent Wheelchair (IW) in both real and simulated environments. The wheelchair is controlled at a high-level by a flexible multimodal interface, using voice commands, facial expressions, head movements and joystick as its main inputs. A Quasi-experimental design was applied including a deterministic sample with a questionnaire that enabled to apply the System Usability Scale. The subjects were divided in two independent samples: 46 individuals performing the experiment with an Intelligent Wheelchair in a simulated environment (28 using different commands in a sequential way and 18 with the liberty to choose the command); 12 individuals performing the experiment with a real IW. The main conclusion achieved by this study is that the usability of the Intelligent Wheelchair in a real environment is higher than in the simulated environment. However there were not statistical evidences to affirm that there are differences between the real and simulated wheelchairs in terms of safety and control. Also, most of users considered the multimodal way of driving the wheelchair very practical and satisfactory. Thus, it may be concluded that the multimodal interfaces enables very easy and safe control of the IW both in simulated and real environments.

Local fractional variational iteration and decomposition methods for wave equation on cantor sets within local fractional operators

We perform a comparison between the fractional iteration and decomposition methods applied to the wave equation on Cantor set. The operators are taken in the local sense. The results illustrate the significant features of the two methods which are both very effective and straightforward for solving the differential equations with local fractional derivative.

Real-time scheduling of parallel tasks in the Linux Kernel

This paper proposes a global multiprocessor scheduling algorithm for the Linux kernel that combines the global EDF scheduler with a priority-aware work-stealing load balancing scheme, enabling parallel real-time tasks to be executed on more than one processor at a given time instant. We state that some priority inversion may actually be acceptable, provided it helps reduce contention, communication, synchronisation and coordination between parallel threads, while still guaranteeing the expected system’s predictability. Experimental results demonstrate the low scheduling overhead of the proposed approach comparatively to an existing real-time deadline-oriented scheduling class for the Linux kernel.

Supporting real-time parallel task models with work-stealing

Dynamic parallel scheduling using work-stealing has gained popularity in academia and industry for its good performance, ease of implementation and theoretical bounds on space and time. Cores treat their own double-ended queues (deques) as a stack, pushing and popping threads from the bottom, but treat the deque of another randomly selected busy core as a queue, stealing threads only from the top, whenever they are idle. However, this standard approach cannot be directly applied to real-time systems, where the importance of parallelising tasks is increasing due to the limitations of multiprocessor scheduling theory regarding parallelism. Using one deque per core is obviously a source of priority inversion since high priority tasks may eventually be enqueued after lower priority tasks, possibly leading to deadline misses as in this case the lower priority tasks are the candidates when a stealing operation occurs. Our proposal is to replace the single non-priority deque of work-stealing with ordered per-processor priority deques of ready threads. The scheduling algorithm starts with a single deque per-core, but unlike traditional work-stealing, the total number of deques in the system may now exceed the number of processors. Instead of stealing randomly, cores steal from the highest priority deque.

Parallel real-time support for distributed adaptive embedded applications

Real-time embedded applications require to process large amounts of data within small time windows. Parallelize and distribute workloads adaptively is suitable solution for computational demanding applications. The purpose of the Parallel Real-Time Framework for distributed adaptive embedded systems is to guarantee local and distributed processing of real-time applications. This work identifies some promising research directions for parallel/distributed real-time embedded applications.

A framework for the development of parallel and distributed real-time embedded systems

Embedded real-time applications increasingly present high computation requirements, which need to be completed within specific deadlines, but that present highly variable patterns, depending on the set of data available in a determined instant. The current trend to provide parallel processing in the embedded domain allows providing higher processing power; however, it does not address the variability in the processing pattern. Dimensioning each device for its worst-case scenario implies lower average utilization, and increased available, but unusable, processing in the overall system. A solution for this problem is to extend the parallel execution of the applications, allowing networked nodes to distribute the workload, on peak situations, to neighbour nodes. In this context, this report proposes a framework to develop parallel and distributed real-time embedded applications, transparently using OpenMP and Message Passing Interface (MPI), within a programming model based on OpenMP. The technical report also devises an integrated timing model, which enables the structured reasoning on the timing behaviour of these hybrid architectures.

Dynamic global scheduling of parallel real-time tasks

High-level parallel languages offer a simple way for application programmers to specify parallelism in a form that easily scales with problem size, leaving the scheduling of the tasks onto processors to be performed at runtime. Therefore, if the underlying system cannot efficiently execute those applications on the available cores, the benefits will be lost. In this paper, we consider how to schedule highly heterogenous parallel applications that require real-time performance guarantees on multicore processors. The paper proposes a novel scheduling approach that combines the global Earliest Deadline First (EDF) scheduler with a priority-aware work-stealing load balancing scheme, which enables parallel realtime tasks to be executed on more than one processor at a given time instant. Experimental results demonstrate the better scalability and lower scheduling overhead of the proposed approach comparatively to an existing real-time deadline-oriented scheduling class for the Linux kernel.

Server-based scheduling of parallel real-time tasks

Multicore platforms have transformed parallelism into a main concern. Parallel programming models are being put forward to provide a better approach for application programmers to expose the opportunities for parallelism by pointing out potentially parallel regions within tasks, leaving the actual and dynamic scheduling of these regions onto processors to be performed at runtime, exploiting the maximum amount of parallelism. It is in this context that this paper proposes a scheduling approach that combines the constant-bandwidth server abstraction with a priority-aware work-stealing load balancing scheme which, while ensuring isolation among tasks, enables parallel tasks to be executed on more than one processor at a given time instant.

Software transactional memory as a building block for parallel embedded realtime systems

The recent trends of chip architectures with higher number of heterogeneous cores, and non-uniform memory/non-coherent caches, brings renewed attention to the use of Software Transactional Memory (STM) as a fundamental building block for developing parallel applications. Nevertheless, although STM promises to ease concurrent and parallel software development, it relies on the possibility of aborting conflicting transactions to maintain data consistency, which impacts on the responsiveness and timing guarantees required by embedded real-time systems. In these systems, contention delays must be (efficiently) limited so that the response times of tasks executing transactions are upper-bounded and task sets can be feasibly scheduled. In this paper we assess the use of STM in the development of embedded real-time software, defending that the amount of contention can be reduced if read-only transactions access recent consistent data snapshots, progressing in a wait-free manner. We show how the required number of versions of a shared object can be calculated for a set of tasks. We also outline an algorithm to manage conflicts between update transactions that prevents starvation.

A parallel programming model for ada

Over the last three decades, computer architects have been able to achieve an increase in performance for single processors by, e.g., increasing clock speed, introducing cache memories and using instruction level parallelism. However, because of power consumption and heat dissipation constraints, this trend is going to cease. In recent times, hardware engineers have instead moved to new chip architectures with multiple processor cores on a single chip. With multi-core processors, applications can complete more total work than with one core alone. To take advantage of multi-core processors, parallel programming models are proposed as promising solutions for more effectively using multi-core processors. This paper discusses some of the existent models and frameworks for parallel programming, leading to outline a draft parallel programming model for Ada.