Investigation of additive effects in enantioselective copper-catalysed C-H insertion and aromatic addition reactions of α-diazocarbonyl compounds

Significant enhancements in enantioselectivities and reaction efficiencies in asymmetric copper-catalysed C-H insertion and aromatic addition reactions of α-diazocarbonyl compounds in the presence of various group I salts are reported. For the first time in carbenoid chemistry, evidence for the critical role of the metal cation is described.

Transferability of Regional Permafrost Disturbance Susceptibility Modelling Using Generalized Linear and Generalized Additive Models

To effectively assess and mitigate risk of permafrost disturbance, disturbance-p rone areas can be predicted through the application of susceptibility models. In this study we developed regional susceptibility models for permafrost disturbances using a field disturbance inventory to test the transferability of the model to a broader region in the Canadian High Arctic. Resulting maps of susceptibility were then used to explore the effect of terrain variables on the occurrence of disturbances within this region. To account for a large range of landscape charac- teristics, the model was calibrated using two locations: Sabine Peninsula, Melville Island, NU, and Fosheim Pen- insula, Ellesmere Island, NU. Spatial patterns of disturbance were predicted with a generalized linear model (GLM) and generalized additive model (GAM), each calibrated using disturbed and randomized undisturbed lo- cations from both locations and GIS-derived terrain predictor variables including slope, potential incoming solar radiation, wetness index, topographic position index, elevation, and distance to water. Each model was validated for the Sabine and Fosheim Peninsulas using independent data sets while the transferability of the model to an independent site was assessed at Cape Bounty, Melville Island, NU. The regional GLM and GAM validated well for both calibration sites (Sabine and Fosheim) with the area under the receiver operating curves (AUROC) N 0.79. Both models were applied directly to Cape Bounty without calibration and validated equally with AUROC's of 0.76; however, each model predicted disturbed and undisturbed samples differently. Addition- ally, the sensitivity of the transferred model was assessed using data sets with different sample sizes. Results in- dicated that models based on larger sample sizes transferred more consistently and captured the variability within the terrain attributes in the respective study areas. Terrain attributes associated with the initiation of dis- turbances were similar regardless of the location. Disturbances commonly occurred on slopes between 4 and 15°, below Holocene marine limit, and in areas with low potential incoming solar radiation

Process Monitoring and Defect Detection of Additive Manufacturing Using Inline Coherent Imaging

With applications ranging from aerospace to biomedicine, additive manufacturing (AM) has been revolutionizing the manufacturing industry. The ability of additive techniques, such as selective laser melting (SLM), to create fully functional, geometrically complex, and unique parts out of high strength materials is of great interest. Unfortunately, despite numerous advantages afforded by this technology, its widespread adoption is hindered by a lack of on-line, real time feedback control and quality assurance techniques. In this thesis, inline coherent imaging (ICI), a broadband, spatially coherent imaging technique, is used to observe the SLM process in 15 - 45 $\mu m$ 316L stainless steel. Imaging of both single and multilayer builds is performed at a rate of 200 $kHz$, with a resolution of tens of microns, and a high dynamic range rendering it impervious to blinding from the process beam. This allows imaging before, during, and after laser processing to observe changes in the morphology and stability of the melt. Galvanometer-based scanning of the imaging beam relative to the process beam during the creation of single tracks is used to gain a unique perspective of the SLM process that has been so far unobservable by other monitoring techniques. Single track processing is also used to investigate the possibility of a preliminary feedback control parameter based on the process beam power, through imaging with both coaxial and 100 $\mu m$ offset alignment with respect to the process beam. The 100 $\mu m$ offset improved imaging by increasing the number of bright A-lines (i.e. with signal greater than the 10 $dB$ noise floor) by 300\%. The overlap between adjacent tracks in a single layer is imaged to detect characteristic fault signatures. Full multilayer builds are carried out and the resultant ICI images are used to detect defects in the finished part and improve upon the initial design of the build system. Damage to the recoater blade is assessed using powder layer scans acquired during a 3D build. The ability of ICI to monitor SLM processes at such high rates with high resolution offers extraordinary potential for future advances in on-line feedback control of additive manufacturing.

Comparazione strutturale di componenti realizzati a terra e nello spazio mediante tecniche additive

Questo lavoro di tesi mira ad indagare, a livello preliminare, quali siano i vantaggi e gli svantaggi a livello strutturale legati alla possibilità di realizzare componenti per mezzi spaziali con tecnologie di Rapid Prototyping direttamente nello spazio: questa possibilità verrà confrontata con il caso in cui gli stessi componenti siano realizzati a terra e poi inviati nello spazio con un lanciatore. Nonostante si siano riscontrati dei limiti derivanti dalla carenza di dati tecnici sulle caratteristiche meccaniche dei materiali, è stata sviluppata una metodologia che ha fornito l’opportunità, seppur con grandi approssimazioni, di valutare il problema. Il punto di partenza dell’attività è stato quello di visionare figure ed immagini di mezzi spaziali e di scegliere alcuni componenti che possano essere oggetto di manutenzione o sostituzione in volo. Sei componenti sono stati poi modellati al CAD, ed è stata condotta un’analisi ad elementi finiti (FEM) mediante il software MSC Patran/Nastran, con lo scopo di simulare la risposta strutturale nelle diverse condizioni di carico prese in considerazione. Seppur a livello qualitativo e del tutto preliminare, sono stati svolti dei confronti in termini di massa e tensioni per valutare in quali casi sembra sia conveniente realizzare un componente a terra con tecnologie tradizionali, e in quali sembra sia vantaggioso utilizzare nuove tecnologie di prototipazione rapida stampando direttamente il componente nello spazio.

Expanding the Design Space: Forging the Transition from 3D Printing to Additive Manufacturing

Thesis (Master's)--University of Washington, 2016-08

Evaluation of Select Food Additive Exposures in Children with Crohn's Disease

Thesis (Master's)--University of Washington, 2016-09

Mixing performance evaluation of additive manufactured milli-scale reactors

The mixing performance of three passive milli-scale reactors with different geometries was investigated at different Reynolds numbers. The effects of design and operating characteristics such as mixing channel shape and volume flow rate were investigated. The main objective of this work was to demonstrate a process design method that uses on Computational Fluid Dynamics (CFD) for modeling and Additive Manufacturing (AM) technology for manufacture. The reactors were designed and simulated using SolidWorks and Fluent 15.0 software, respectively. Manufacturing of the devices was performed with an EOS M-series AM system. Step response experiments with distilled Millipore water and sodium hydroxide solution provided time-dependent concentration profiles. Villermaux-Dushman reaction experiments were also conducted for additional verification of CFD results and for mixing efficiency evaluation of the different geometries. Time-dependent concentration data and reaction evaluation showed that the performance of the AM-manufactured reactors matched the CFD results reasonably well. The proposed design method allows the implementation of new and innovative solutions, especially in the process design phase, for industrial scale reactor technologies. In addition, rapid implementation is another advantage due to the virtual flow design and due to the fast manufacturing which uses the same geometric file formats.

How to deal with uncertainties regarding the occupational exposure to antineoplastic mixtures: additive effect should always be considered?

Risk assessment considerations - The concept that “safe levels of exposure” for humans can be identified for individual chemicals is central to the risk assessment of compounds with known toxicological profiles. Selection of agents for combination chemotherapy regimens involves minimize overlapping of mechanisms of action, antitumor activity and toxicity profile. Although the toxicological profile and mechanism of action of each individual drug is well characterized, the toxicological interactions between drugs are likely, but poorly established at occupational exposure context. The synergistic nature of interactions may help in understanding the adverse health effects observed in healthcare workers, where exposure situations are characterized by complex mixtures of chemical agents, and the levels of individual exposing agents are often not sufficiently high to explain the health complaints. However, if a substance is a genotoxic carcinogen, this would be the “lead effect”; normally, no OEL based on a NOEL would be derived and the level would be set so low that it would be unlikely that other effects would be expected. Aim of the study - Recently research project developed in Portuguese Hospitals characterize the occupational exposure to antineoplastic agents and the health effects related. The project aimed to assess exposure of the different risk groups that handle antineoplastic agents in the hospital setting, namely during preparation and administration of these drugs. Here it is presented and discussed the results in a study developed in two hospitals from Lisbon.

A Study of the State of the Art of Process Planning for Additive Manufacturing

In the manufacturing industry the term Process Planning (PP) is concerned with determining the sequence of individual manufacturing operations needed to produce a given part or product with a certain machine. In this technical report we propose a preliminary analysis of scientific literature on the topic of process planning for Additive Manufacturing (AM) technologies (i.e. 3D printing). We observe that the process planning for additive manufacturing processes consists of a small set of standard operations (repairing, orientation, supports, slicing and toolpath generation). We analyze each of them in order to emphasize the most critical aspects of the current pipeline as well as highlight the future challenges for this emerging manufacturing technology.

AIR SIDE HEAT TRANSFER ENHANCEMENT IN HEAT EXCHANGERS UTILIZING INNOVATIVE DESIGNS AND THE ADDITIVE MANUFACTURING TECHNIQUE

Over the last decade, rapid development of additive manufacturing techniques has allowed the fabrication of innovative and complex designs. One field that can benefit from such technology is heat exchanger fabrication, as heat exchanger design has become more and more complex due to the demand for higher performance particularly on the air side of the heat exchanger. By employing the additive manufacturing, a heat exchanger design was successfully realized, which otherwise would have been very difficult to fabricate using conventional fabrication technologies. In this dissertation, additive manufacturing technique was implemented to fabricate an advanced design which focused on a combination of heat transfer surface and fluid distribution system. Although the application selected in this dissertation is focused on power plant dry cooling applications, the results of this study can directly and indirectly benefit other sectors as well, as the air-side is often the limiting side for in liquid or single phase cooling applications. Two heat exchanger designs were studied. One was an advanced metallic heat exchanger based on manifold-microchannel technology and the other was a polymer heat exchanger based on utilization of prime surface technology. Polymer heat exchangers offer several advantages over metals such as antifouling, anticorrosion, lightweight and often less expensive than comparable metallic heat exchangers. A numerical modeling and optimization were performed to calculate a design that yield an optimum performance. The optimization results show that significant performance enhancement is noted compared to the conventional heat exchangers like wavy fins and plain plate fins. Thereafter, both heat exchangers were scaled down and fabricated using additive manufacturing and experimentally tested. The manifold-micro channel design demonstrated that despite some fabrication inaccuracies, compared to a conventional wavy-fin surface, 15% - 50% increase in heat transfer coefficient was possible for the same pressure drop value. In addition, if the fabrication inaccuracy can be eliminated, an even larger performance enhancement is predicted. Since metal based additive manufacturing is still in the developmental stage, it is anticipated that with further refinement of the manufacturing process in future designs, the fabrication accuracy can be improved. For the polymer heat exchanger, by fabricating a very thin wall heat exchanger (150μm), the wall thermal resistance, which usually becomes the limiting side for polymer heat exchanger, was calculated to account for only up to 3% of the total thermal resistance. A comparison of air-side heat transfer coefficient of the polymer heat exchanger with some of the commercially available plain plate fin surface heat exchangers show that polymer heat exchanger performance is equal or superior to plain plate fin surfaces. This shows the promising potential for polymer heat exchangers to compete with conventional metallic heat exchangers when an additive manufacturing-enabled fabrication is utilized. Major contributions of this study are as follows: (1) For the first time demonstrated the potential of additive manufacturing in metal printing of heat exchangers that benefit from a sophisticated design to yield a performance substantially above the respective conventional systems. Such heat exchangers cannot be fabricated with the conventional fabrication techniques. (2) For the first time demonstrated the potential of additive manufacturing to produce polymer heat exchangers that by design minimize the role of thermal conductivity and deliver a thermal performance equal or better that their respective metallic heat exchangers. In addition of other advantages of polymer over metal like antifouling, anticorrosion, and lightweight. Details of the work are documented in respective chapters of this thesis.

Finding the set of k-additive dominating measures viewed as a flow problem

n this paper we deal with the problem of obtaining the set of k-additive measures dominating a fuzzy measure. This problem extends the problem of deriving the set of probabilities dominating a fuzzy measure, an important problem appearing in Decision Making and Game Theory. The solution proposed in the paper follows the line developed by Chateauneuf and Jaffray for dominating probabilities and continued by Miranda et al. for dominating k-additive belief functions. Here, we address the general case transforming the problem into a similar one such that the involved set functions have non-negative Möbius transform; this simplifies the problem and allows a result similar to the one developed for belief functions. Although the set obtained is very large, we show that the conditions cannot be sharpened. On the other hand, we also show that it is possible to define a more restrictive subset, providing a more natural extension of the result for probabilities, such that it is possible to derive any k-additive dominating measure from it.

Additive Manufacturing: Current Status and Future Prospects

Part 10: Sustainability and Trust

The role of additive manufacturing in patient specific solutions

This dissertation investigates de role of the new additive manufacturing techniques in the treatment of pathologies with a patient-specific approach. Throughout this work the development methodology of these said products is explained in order to understand the different stages required to achieve a tailor made solution. The goal is to demonstrate the importance of the manufacturing technique and its capabilities to tailor-fit devices to patients and the adaptability of the process to tackle the most diverse situations. Three real cases are documented in order to prove the viability of the method and to showcase its advantages. Whenever possible patient-specific solutions are compared to their “off-the-shelf” counterparts in order to establish the pros and cons of each one of them. The dissertation is an insight into a possible future for the medical devices industry, where customization is expected to be the standard approach in the treatment of patients.

Processing and additive manufacturing of bones for the teaching of human anatomy

Traditionally, the teaching of human anatomy in health sciences has been based on the use of cadaveric material and bone parts for practical study. The bone materials get deteriorated and hardly mark the points of insertion of muscles. However, the advent of new technologies for 3D printing and creation of 3D anatomical models applied to teaching, has enabled to overcome these problems making teaching more dynamic, realistic and attractive. This paper presents some examples of the construction of three-dimensional models of bone samples, designed using 3D scanners for posterior printing with addition printers or polymer injection printers.