Oxidation of 4-substituted TEMPO derivatives reveals modifications at the 1-and 4-positions

Potenital pathways for the deactivation of hindered amine light stabilisers (HALS) have been investigated by observing reactions of model compounds-based on 4-substituted derivatives of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-with hydroxyl radicals. In these reactions, dilute aqueous suspensions of photocatalytic nanoparticulate titanium dioxide were irradiated with UV light in the presence of water-soluble TEMPO derivatives. Electron spin resonance (ESR) and electrospray ionisation mass-spectrometry (ESI-MS) data were acquired to provide complementary structural elucidation of the odd-and even-electron products of these reactions and both techniques show evidence for the formation of 4-oxo-TEMPO (TEMPONE). TEMPONE formation from the 4-substituted TEMPO compounds is proposed to be initiated by hydrogen abstraction at the 4-position by hydroxyl radical. High-level ab initio calculations reveal a thermodynamic preference for abstraction of this hydrogen but computed activation barriers indicate that, although viable, it is less favoured than hydrogen abstraction from elsewhere on the TEMPO scaffold. If a radical is formed at the 4-position however, calculations elucidate two reaction pathways leading to TEMPONE following combination with either a second hydroxyl radical or dioxygen. An alternate mechanism for conversion of TEMPOL to TEMPONE via an alkoxyl radical intermediate is also considered and found to be competitive with the other pathways. ESI-MS analysis also shows an increased abundance of analogous 4-substituted piperidines during the course of irradiation, suggesting competitive modification at the 1-position to produce a secondary amine. This modification is confirmed by characteristic fragmentation patterns of the ionised piperidines obtained by tandem mass spectrometry. The conclusions describe how reaction at the 4-position could be responsible for the gradual depletion of HALS in pigmented surface coatings and secondly, that modification at nitrogen to form the corresponding secondary amine species may play a greater role in the stabilisation mechanisms of HALS than previously considered.

p-type doping of ZnO by means of high-density inductively coupled plasmas

A custom-designed inductively coupled plasma assisted radio-frequency magnetron sputtering deposition system has been used to fabricate N-doped p-type ZnO (ZnO:N) thin films on glass substrates from a sintered ZnO target in a reactive Ar + N2 gas mixture. X-ray diffraction and scanning electron microscopy analyses show that the ZnO:N films feature a hexagonal crystal structure with a preferential (002) crystallographic orientation and grow as vertical columnar structures. Hall effect and X-ray photoelectron spectroscopy analyses show that N-doped ZnO thin films are p-type with a hole concentration of 3.32 × 1018 cm- 3 and mobility of 1.31 cm2 V- 1 s- 1. The current-voltage measurement of the two-layer structured ZnO p-n homojunction clearly reveals the rectifying ability of the p-n junction. The achievement of p-type ZnO:N thin films is attributed to the high dissociation ability of the high-density inductively coupled plasma source and effective plasma-surface interactions during the growth process.

Characterisation of thin layer polymer cement mortared concrete masonry bond

Masonry bond is affected by many parameters such as the type of mortar used, the techniques of dispersion of mortar and the surface texture of the concrete blocks. Additionally it is understood from the studies on conventional masonry that the bond characteristics are also influenced by the curing methods as well as the age of the bond at the time of testing. These effects on thin layer mortared masonry employing polymer cement mortars are not well understood. Therefore, the effect of curing methods and age to the bond strength and deformation of masonry containing thin layered polymer cement mortar was investigated as part of an ongoing research program at the Queensland University of Technology. This paper presents an experimental investigation of the flexural and shear bond characteristics of the thin layer mortared concrete masonry. The parameters examined include the effects curing and ageing to the bond development over a period from 14 days to 56 days after fabrication. The results exhibit that dry cured thin layer mortared masonry exhibits higher bond strength and Young’s and shear moduli compared to the wet cured specimens.

Large-Scale Wind Generator Cascaded Tripping

Large scale wind farms are subject to tripping, as a consequence of turbine failure, over-sensitive protection, turbines not equipped with low-voltage ride through (LVRT), and reactive power compensation device defects which can lead to voltage rises. This paper considers pertinent issues which render tripping based on a study of LVRT and wind farm protection, with methods to avoid large scale wind generator tripping proposed. The results of LVRT field tests in Jiuquan, China in December 2012 show that the proposed approaches are effective. The paper also presents work which proposes an early warning system to forecast the risk of wind power tripping.

Viscosity Control for Extrusion Processes Using Recycled Polymers

The aim of this paper is to develop a new extruder control system for recycled materials which has ability to automatically maintain constant a polymer melt viscosity of mixed recycled polymers during extrusion, regardless of variations in the Melt Flow Index (MFI) of recycled mixed grade high density polyethylene (HDPE) feedstock. A closed-loop controller is developed to automatically regulate screw speed and barrel temperature profile to achieve constant viscosity and enable consistent processing of variable grade recycled HDPE materials. The experimental results of real time viscosity measurement and control using a 38mm single screw extruder with different recycled HDPEs with widely different MFIs are reported in this work

Industrial Robotics Applied to Education

This work describes a ludic proposal for programming learning of industrial robots to be developed by groups of engineering students. Two projects are presented: Tic-tac-toe Opponent Robot and Environmentalist Robot. The first project use competitive search techniques of the Artificial Intelligence, computational vision, electronic and pneumatic concepts for ability decision making for a robotic agent on the tic-tae-toe game. The second project consists of a game that contains a questions and answers database about environmental themes. An algorithm selects the group of questions to be answered by the player, analyses the answers and sends the result to a industrial robot through serial port. According with the player performance, the robot makes congratulation movements and giving a gift to the winner player. Otherwise, the robot makes movements, disapproving the player performance.

FROM FACTORY-FLOOR TO UNIVERSITY

The interaction between industry and university is often discussed. Industry participants feel they do not have enough time to spend with academics because of tight deadlines to achieve your goals. The other hand, professors and his students do not have availability and resources for responding quickly to industry activities. Both sides recognize the associated problems and feel the consequences of various forms. One way to reduce the distance between them is to provide industrial labs that resemble the factory floor at the university. Thus not only students may work on a real technological base, but also the industry's problems can be brought to the university laboratory. To ensure that relevant industrial problems will be studied, the industry needs help in the formulation of the problem being researched. The graduate program of Automation and Control Engineering from UNESP Sorocaba is aimed at training human resources with skills in automation and control activities related to the development of automatic control processes, integrating electronic commands, intelligent manufacturing and industrial robotics. In order to achieve its objectives, one of the pillars of the university consists of a wide range of modern equipments and software for industrial automation, which allows the circuit assembly from most primitive until configuration and programming of a complex system of integrated manufacturing. This paper describes industrial automation equipments and laboratory structure offered to students of Control and Automation Engineering graduate program at UNESP Sorocaba as alternative to close technologies and real problems on the job until academic world. The strategic is to do students understand theory and operations in robotic and industrial automation by means to manipulating real production systems locate at university

Influências do Projeto Baja SAE no ensino da engenharia e no desenvolvimento do aluno

This work aims to show the importance of Baja SAE Project in engineering education, as well as the development of the student, being an outstanding tool for the engineering student has an education that meets the objectives of the pedagogical university and also the guidelines Ministry of Education curriculum for engineering courses. The Baja SAE Project provides the engineering students the chance to apply in practice the knowledge acquired in the classroom, to enhance their preparation for the labor market. The student becomes involved with a real case of project development, from concept design, detailed design and construction. The Baja SAE Project redefines the position of the student as an active element in the learning process engineering, leaving behind the simple condition of receiving information. Values procedures that provide students the opportunity to learn in contexts of professional practice, while offering the opportunity to contextualize the execution of a project. From an analysis to develop personal skills, Baja SAE Project has its own characteristics and essential for professional practice, however, not specific to the engineering course. For example, capacity for teamwork, communication skills written and oral, ethical behavior, critical, overview, entrepreneurial spirit, leadership, etc

Metodi per la valutazione strategica dei piani energetici. Applicazione al caso della Provincia di Ravenna.

Lo scopo di questo studio è descrivere nel dettaglio la procedura di Valutazione Ambientale Strategica (VAS) relativa ai Piani Energetici Provinciali (PEP) al fine di delinearne un metodo efficace di valutazione, a partire dallo studio del caso della Provincia di Ravenna. In seguito alla mancanza di Linee Guida sulla VAS, si è ritenuta utile un´analisi comparativa tra metodologie e strumenti, e gli obiettivi specifici e generali che andrebbero rispettati in ogni VAS di un PEP. Lo studio si basa su confronti paralleli tra quattro casi di VAS di Piani Energetici Provinciali al fine di elaborare un modello di valutazione delle VAS, semplice e diretto, basato su contenuti teorici e metodologici provenienti da una selezione di studi e documenti nazionali e internazionali, di cui si è tenuto conto e da cui si sono estrapolate le migliori "Buone Pratiche" per la VAS. L´analisi seguente è stata effettuata attraverso matrici qualitative in cui, per ciascuna connessione tra metodologia e "obiettivo VAS" si è espresso un giudizio che cerca di tenere conto, quando possibile, dei criteri e dei principi generali di sostenibilità dettati dalle maggiori autorità e associazioni internazionali e nazionali di valutazione ambientale. Il confronto tra i quattro casi, ha evidenziato dei punti di debolezza nell´applicazione della Direttiva VAS. Questo studio inoltre, ha tra i suoi obiettivi, quello ambizioso di delineare un metodo efficace di valutazione strategica dei piani energetici provinciali, a partire dallo studio del caso della Provincia di Ravenna. Per questi obiettivi, si è deciso di impostare un programma di lavoro basato sui sistemi informativi geografici, che ha permesso di individuare le aree con potenziale di sviluppo energetico della risorsa solare. Nello specifico è stato possibile calcolare quanta “superficie utile”, presente nelle aree industriali e commerciali della Provincia, potrebbe essere sfruttata installandovi pannelli fotovoltaici. Si è riusciti con questa metodologia a fornire una stima più dettagliata delle reali potenzialità della risorsa solare in Provincia di Ravenna, individuando nel dettaglio territoriale le rispettive quote percentuali che potrebbero essere installate, per raggiungere gli obiettivi di sostenibilità del piano. Il percorso iniziato con questa tesi consente di riflettere sulla necessità di approfondire il tema del rapporto tra valutazione ambientale qualitativa di uno strumento di pianificazione come la VAS, e la stima quantitativa sia della sostenibilità che del danno ambientale legato agli impatti negativi che questo strumento dovrebbe rilevare. Gli sviluppi futuri cui la tesi pone le basi sono l'implementazione di strumenti quantitativi di analisi delle potenzialità energetiche e di valutazione degli scenari. Questi strumenti sono necessari a definire i modelli ambientali per il supporto alle decisioni in campo energetico.

Robotics learning based on collaborative projects

[EN]Nowadays companies demand graduates able to work in multidisciplinary and collaborative projects. Hence, new educational methods are needed in order to support a more advanced society, and progress towards a higher quality of life and sustainability. The University of the Basque Country belongs to the European Higher Education Area, which was created as a result of the Bologna process to ensure the connection and quality of European national educational systems. In this framework, this paper proposes an innovative teaching methodology developed for the "Robotics" subject course that belongs to the syllabus of the B.Sc. degree in Industrial Electronics and Automation Engineering. We present an innovative methodology for Robotics learning based on collaborative projects, aimed at responding to the demands of a multidisciplinary and multilingual society.