Annotated record of the detailed examination of Mn nodules recovered from the VA04 expedition (R/V Valdivia) in the Pacific Ocean

Twenty-four manganese nodules from the surface of the sea floor and fifteen buried nodules were studied. With three exceptions, the nodules were collected from the area covered by Valdivia Cruise VA 04 some 1200 nautical miles southeast of Hawaii. Age determinations were made using the ionium method. In order to get a true reproduction of the activity distribution in the nodules, they were cut in half and placed for one month on nuclear emulsion plates to determine the alpha-activity of the ionium and its daughter products. Special methods of counting the alpha-tracks resolution to depth intervals of 0.125 mm. For the first time it was possible to resolve zones of rapid growth (impulse growth) with growth rates, s > 50 mm/106 yr and interruptions in growth. With few exceptions the average rate of growth of all nodules was surprisingly uniform at 4-9 mm/10 yr. No growth could be recognized radioactively in the buried nodules. One exceptional nodule has had recent impulse growth and, in the material formed, the ionium is not yet in equilibrium with its daughter products. Individual layers in one nodule from the Indian Ocean could be dated and an average time interval of t = 2600±400 yr was necessary to form one layer. The alternation between iron and manganese-rich parts of the nodules was made visible by colour differences resulting from special treatment of cut surfaces with HCl vapour. The zones of slow growth of one nodule are relatively enriched in iron. Earlier attempts to find paleomagnetic reversals in manganese nodules have been continued. Despite considerable improvement in areal resolution, reversals were not detected in the nodules studied. Comparisons of the surface structure, microstructure in section and the radiometric dating show that there are erosion surfaces and growth surfaces on the outer surfaces of the manganese nodules. The formation of cracks in the nodules was studied in particular. The model of age-dependent nodule shrinkage and cracking surprisingly indicates that the nodules break after exceeding a certain age and/or size. Consequently, the breaking apart of manganese nodules is a continuous process not of catastrophic or discontinuous origin. The microstructure of the nodules exhibits differences in the mechanism of accretion and accretion rate of material, shortly referred to as accretion form. Thus non-directional growth inside the nodules as well as a directional growth may be observed. Those nodules with large accretion forms have grown faster than smaller ones. Consequently, parallel layers indicate slow growth. The upper surfaces of the nodules, protruding into the bottom water appear to be more prone to growth disturbances than the lower surfaces, immersed in the sediment. Features of some nodules show, that as they develop, they neither turned nor rolled. Yet unknown is the mechanism that keeps the nodules at the surface during continuous sedimentation. All in all, the nodules remain the objects of their own distinctive problems. The hope of using them as a kind of history book still seems to be very remote.

Simulação da destilação molecular de filme descendente para o petróleo

The heavy part of the oil can be used for numerous purposes, e.g. to obtain lubricating oils. In this context, many researchers have been studying alternatives such separation of crude oil components, among which may be mentioned molecular distillation. Molecular distillation is a forced evaporation technique different from other conventional processes in the literature. This process can be classified as a special distillation case under high vacuum with pressures that reach extremely low ranges of the order of 0.1 Pascal. The evaporation and condensation surfaces must have a distance from each other of the magnitude order of mean free path of the evaporated molecules, that is, molecules evaporated easily reach the condenser, because they find a route without obstacles, what is desirable. Thus, the main contribution of this work is the simulation of the falling-film molecular distillation for crude oil mixtures. The crude oil was characterized using UniSim® Design and R430 Aspen HYSYS® V8.5. The results of this characterization were performed in spreadsheets of Microsoft® Excel®, calculations of the physicochemical properties of the waste of an oil sample, i.e., thermodynamic and transport. Based on this estimated properties and boundary conditions suggested by the literature, equations of temperature and concentration profiles were resolved through the implicit finite difference method using the programming language Visual Basic® (VBA) for Excel®. The result of the temperature profile showed consistent with the reproduced by literature, having in their initial values a slight distortion as a result of the nature of the studied oil is lighter than the literature, since the results of the concentration profiles were effective allowing realize that the concentration of the more volatile decreases and of the less volatile increases due to the length of the evaporator. According to the transport phenomena present in the process, the velocity profile tends to increase to a peak and then decreases, and the film thickness decreases, both as a function of the evaporator length. It is concluded that the simulation code in Visual Basic® language (VBA) is a final product of the work that allows application to molecular distillation of petroleum and other similar mixtures.

Síntese de ferritas de cobalto e níquel dopadas com zinco e caracterização de suas propriedades eletromagnéticas

This work shows that the synthesis by combustion is a prominent alternative to obtain ceramic powders of higher oxides, nanostructured and of high purity, as the ferrites of formulas Co(1-x)Zn(x)Fe2O4 e Ni(1-x)Zn(x)Fe2O4 with x ranging from 0.2 mols, in a range from 0.2 ≤ x ≥ 1.0 mol, that presents magnetic properties in coexistence of ferroelectric and ferrimagnetic states, which can be used in antennas of micro tapes and selective surfaces of low frequency in a range of miniaturized microwaves, without performance loss. The obtainment occurred through the combustion process, followed by appropriate physical processes and ordered to the utilization of the substrate sinterization process, it gave us a ceramic material, of high purity degree in a nanometric scale. The Vibrating Sample Magnetometer (VSM) analysis showed that those ferritic materials presents parameters, as materials hysteresis, that have own behavior of magnetic materials of good quality, in which the magnetization states can be suddenly changed with a relatively small variation of the field intensity, having large applications on the electronics field. The X-ray Diffraction (XRD) analysis of the ceramic powders synthesized at 900 °C, characterize its structural and geometrical properties, the crystallite size and the interplanar spacing. Other analysis were developed, as Scanning Electron Microscopy (SEM), X-ray Fluorescence (XRF), electric permittivity and the tangent loss, in high frequencies, through the equipment ZVB - 14 Vector Network Analyzer 10 MHz-14 GHz, of ROHDE & SCHWART.

Investigating the Structure of FtsZ to Understand its Functional Role in Bacterial Cell Division

FtsZ, a bacterial tubulin homologue, is a cytoskeleton protein that plays key roles in cytokinesis of almost all prokaryotes. FtsZ assembles into protofilaments (pfs), one subunit thick, and these pfs assemble further to form a “Z ring” at the center of prokaryotic cells. The Z ring generates a constriction force on the inner membrane, and also serves as a scaffold to recruit cell-wall remodeling proteins for complete cell division in vivo. FtsZ can be subdivided into 3 main functional regions: globular domain, C terminal (Ct) linker, and Ct peptide. The globular domain binds GTP to assembles the pfs. The extreme Ct peptide binds membrane proteins to allow cytoplasmic FtsZ to function at the inner membrane. The Ct linker connects the globular domain and Ct peptide. In the present studies, we used genetic and structural approaches to investigate the function of Escherichia coli (E. coli) FtsZ. We sought to examine three questions: (1) Are lateral bonds between pfs essential for the Z ring? (2) Can we improve direct visualization of FtsZ in vivo by engineering an FtsZ-FP fusion that can function as the sole source of FtsZ for cell division? (3) Is the divergent Ct linker of FtsZ an intrinsically disordered peptide (IDP)?

One model of the Z ring proposes that pfs associate via lateral bonds to form ribbons; however, lateral bonds are still only hypothetical. To explore potential lateral bonding sites, we probed the surface of E. coli FtsZ by inserting either small peptides or whole FPs. Of the four lateral surfaces on FtsZ pfs, we obtained inserts on the front and back surfaces that were functional for cell division. We concluded that these faces are not sites of essential interactions. Inserts at two sites, G124 and R174 located on the left and right surfaces, completely blocked function, and were identified as possible sites for essential lateral interactions. Another goal was to find a location within FtsZ that supported fusion of FP reporter proteins, while allowing the FtsZ-FP to function as the sole source of FtsZ. We discovered one internal site, G55-Q56, where several different FPs could be inserted without impairing function. These FtsZ-FPs may provide advances for imaging Z-ring structure by super-resolution techniques.

The Ct linker is the most divergent region of FtsZ in both sequence and length. In E. coli FtsZ the Ct linker is 50 amino acids (aa), but for other FtsZ it can be as short as 37 aa or as long as 250 aa. The Ct linker has been hypothesized to be an IDP. In the present study, circular dichroism confirmed that isolated Ct linkers of E. coli (50 aa) and C. crescentus (175 aa) are IDPs. Limited trypsin proteolysis followed by mass spectrometry (LC-MS/MS) confirmed Ct linkers of E. coli (50 aa) and B. subtilis (47 aa) as IDPs even when still attached to the globular domain. In addition, we made chimeras, swapping the E. coli Ct linker for other peptides and proteins. Most chimeras allowed for normal cell division in E. coli, suggesting that IDPs with a length of 43 to 95 aa are tolerated, sequence has little importance, and electrostatic charge is unimportant. Several chimeras were purified to confirm the effect they had on pf assembly. We concluded that the Ct linker functions as a flexible tether allowing for force to be transferred from the FtsZ pf to the membrane to constrict the septum for division.

Active Surface Deformation Technology for Management of Marine Biofouling

Biofouling, the accumulation of biomolecules, cells, organisms and their deposits on submerged and implanted surfaces, is a ubiquitous problem across various human endeavors including maritime operations, medicine, food industries and biotechnology. Since several decades, there have been substantial research efforts towards developing various types of antifouling and fouling release approaches to control bioaccumulation on man-made surfaces. In this work we hypothesized, investigated and developed dynamic change of the surface area and topology of elastomers as a general approach for biofouling management. Further, we combined dynamic surface deformation of elastomers with other existing antifouling and fouling-release approaches to develop multifunctional, pro-active biofouling control strategies.

This research work was focused on developing fundamental, new and environment-friendly approaches for biofouling management with emphasis on marine model systems and applications, but which also provided fundamental insights into the control of infectious biofilms on biomedical devices. We used different methods (mechanical stretching, electrical-actuation and pneumatic-actuation) to generate dynamic deformation of elastomer surfaces. Our initial studies showed that dynamic surface deformation methods are effective in detaching laboratory grown bacterial biofilms and barnacles. Further systematic studies revealed that a threshold critical surface strain is required to debond a biofilm from the surface, and this critical strain is dependent on the biofilm mechanical properties including adhesion energy, thickness and modulus. To test the dynamic surface deformation approach in natural environment, we conducted field studies (at Beaufort, NC) in natural seawater using pneumatic-actuation of silicone elastomer. The field studies also confirmed that a critical substrate strain is needed to detach natural biofilm accumulated in seawater. Additionally, the results from the field studies suggested that substrate modulus also affect the critical strain needed to debond biofilms. To sum up, both the laboratory and the field studies proved that dynamic surface deformation approach can effectively detach various biofilms and barnacles, and therefore offers a non-toxic and environmental friendly approach for biofouling management.

Deformable elastomer systems used in our studies are easy to fabricate and can be used as complementary approach for existing commercial strategies for biofouling control. To this end, we aimed towards developed proactive multifunctional surfaces and proposed two different approaches: (i) modification of elastomers with antifouling polymers to produce multifunctional, and (ii) incorporation of silicone-oil additives into the elastomer to enhance fouling-release performance.

In approach (i), we modified poly(vinylmethylsiloxane) elastomer surfaces with zwitterionic polymers using thiol-ene click chemistry and controlled free radical polymerization. These surfaces exhibited both fouling resistance and triggered fouling-release functionalities. The zwitterionic polymers exhibited fouling resistance over short-term (∼hours) exposure to bacteria and barnacle cyprids. The biofilms that eventually accumulated over prolonged-exposure (∼days) were easily detached by applying mechanical strain to the elastomer substrate. In approach (ii), we incorporated silicone-oil additives in deformable elastomer and studied synergistic effect of silicone-oils and surface strain on barnacle detachment. We hypothesized that incorporation of silicone-oil additive reduces the amount of surface strain needed to detach barnacles. Our experimental results supported the above hypothesis and suggested that surface-action of silicone-oils plays a major role in decreasing the strain needed to detach barnacles. Further, we also examined the effect of change in substrate modulus and showed that stiffer substrates require lower amount of strain to detach barnacles.

In summary, this study shows that (1) dynamic surface deformation can be used as an effective, environmental friendly approach for biofouling control (2) stretchable elastomer surfaces modified with anti-fouling polymers provides a pro-active, dual-mode approach for biofouling control, and (3) incorporation of silicone-oils additives into stretchable elastomers improves the fouling-release performance of dynamic surface deformation technology. Dynamic surface deformation by itself and as a supplementary approach can be utilized biofouling management in biomedical, industrial and marine applications.

Heat Transfer in an Airfoil Shaped Strut

The heat transfer from a hot primary flow stream passing over the outside of an airfoil shaped strut to a cool secondary flow stream passing through the inside of that strut was studied experimentally and numerically. The results showed that the heat transfer on the inside of the strut could be reliably modeled as a developing flow and described using a power law model. The heat transfer on the outside of the strut was complicated by flow separation and stall on the suction side of the strut at high angles of attack. This separation was quite sensitive to the condition of the turbulence in the flow passing over the strut, with the size of the separated wake changing significantly as the mean magnitude and levels of anisotropy were varied. The point of first stall moved by as much as 15% of the chord, while average heat transfer levels changed by 2-5% as the inlet condition was varied. This dependence on inlet conditions meant that comparisons between experiment and steady RANS based CFD were quite poor. Differences between the CFD and experiment were attributed to anisotropic and unsteady effects. The coupling between the two flows was shown to be quite low - that is to say, heat transfer coefficients on both the inner and outer surfaces of the strut were relatively unaffected by the temperature of the strut, and it was possible to predict the temperature on the strut surface quite reliably using heat transfer data from decoupled tests, especially for CFD simulations.

Changes detected at Corralejo dune field from 1994 to 2014

[EN]Understanding coastal dune field evolution is a challenge because of their complex dynamic nature. This work has been carried out by means of photointerpretation of 5 orthophotos covering the period 1994-2014. A geographical information system has been developed, including information of the three geomorphological landforms (sand sheets, dune areas, and deflation surfaces) present in the area, as well two additional information layers (vegetation and artificial structures) that interact with the previous ones. The GIS also includes information of the dune crests movement over the same period, which has been correlated with gust wind data.

A influência de decisões arquitetônicas na eficiência energética do Campus vol. 1/UFRN

Building design is an effective way to achieve HVAC energy consumption reduction. However, this potentiality is often neglected by architects due to the lack of references to support design decisions. This works intends to propose architectural design guidelines for energy efficiency and thermal performance of Campus/UFRN buildings. These guidelines are based on computer simulations results using the software DesignBuilder. The definition of simulation models has begun with envelope variables, partially done after a field study of thirteen buildings at UFRN/Campus. This field study indicated some basic envelope patterns that were applied in simulation models. Occupation variables were identified with temperature and energy consumption monitoring procedures and a verification of illumination and equipment power, both developed at the Campus/UFRN administration building. Three simulation models were proposed according to different design phases and decisions. The first model represents early design decisions, simulating the combination of different types of geometry with three levels of envelope thermal performance. The second model, still as a part of early design phase, analyses thermal changes between circulation halls lateral and central and office rooms, as well as the heat fluxes and monthly temperatures in each circulation hall. The third model analyses the influence of middle-design and detail design decisions on energy consumption and thermal performance. In this model, different solutions of roofs, shading devices, walls and external colors were simulated. The results of all simulation models suggest a high influence of thermal loads due to the incidence of solar radiation on windows and surfaces, which highlights the importance of window shading devices, office room orientation and absorptance of roof and walls surfaces

Bacterioplâncton de quatro lagos rasos subtropicais com distintas características tróficas

O papel exercido pelas bactérias é reconhecido como fundamental no metabolismo de qualquer sistema aquático, não só pela mineralização da matéria orgânica, como também pela transferência de matéria e energia para níveis tróficos superiores (“microbial loop”). Para a realização deste estudo foram escolhidos quatro lagos com diferentes estados tróficos no Campus Carreiros da Universidade Federal do Rio Grande – FURG - RS. O Lago Biguás e o da Base possuem características de ambientes eutrófico - hipereutrófico, enquanto que, o Lago Polegar é caracterizado como um ambiente oligo-mesotrófico e o Lago Negro é considerado um ambiente distrófico. Em um estudo anterior em nove lagos rasos nesta mesma região, incluindo os quatro analisados no presente trabalho, Souza (2007) sugeriu que as bactérias livres atuariam como mineralizadoras e o seu crescimento seria limitado pela disponibilidade de fosfato (controle “bottom-up”), enquanto que as bactérias aderidas participariam da decomposição dos agregados orgânicos. Também foi sugerido que as bactérias aderidas seriam controladas principalmente pela predação por flagelados e ciliados (controle “top-down”), provavelmente devido ao seu maior biovolume. Porém, estas informações foram obtidas a partir de relações estatísticas de dados coletados em uma única amostragem. Assim, neste estudo a comunidade bacteriana (abundância e biomassa) e outros parâmetros físicos, químicos e biológicos dos quatro lagos rasos sub-tropicais foram estudados em amostragens quinzenais no decorrer de um ano entre junho de 2008 e maio de 2009. Nossos resultados indicam que a disponibilidade de carbono orgânico dissolvido produzido pelo fitoplâncton parece ser um dos principais fatores controladores da dinâmica de bactérias nestes lagos. Entretanto, a predação no Lago Negro parece ter sido de maior magnitude no controle das bactérias neste ambiente, uma vez que não houve um incremento na abundância bacteriana deste lago proporcional ao incremento da clorofila a. A presença de um maior número de nano - e microflagelados neste lago dá suporte a esta hipótese. Para testar esta hipótese, foi realizado um experimento utilizando-se a Técnica da Diluição em conjunto com a técnica a de FISH (Hibridização in situ Fluorescente) para identificar as taxas de produção e consumo não só dos diferentes morfotipos, mas também dos diferentes grupos filogenéticos (Archaea, Eubacteria, Alfa- Beta- e Gama-Proteobacteria e Cytophaga-Flavobacter) de uma amostra de água do Lago Negro. Os resultados deste experimento indicaram que as bactérias estão, de fato, sendo consumidas por vi protozoários na mesma proporção que estão sendo produzidas. Além disso, no Lago Negro a predação parece estar vinculada ao tamanho/biovolume celular, sendo os morfotipos de tamanho reduzido mais resistentes a predação e, por isso, mais abundantes.

Desenvolvimento e caracterização de filmes a base de isolado protéico de resíduos de corvina (micropogonias furnieri) e óleo de palma

Nas últimas duas décadas, o descarte e o acúmulo de embalagens não biodegradáveis têm agravado os problemas ambientais. Uma das soluções encontradas, particularmente na área de embalagens de alimentos, é o desenvolvimento de filmes a partir de polímeros que possam substituir os materiais sintéticos. Fontes alternativas de proteína, como os resíduos de pescados, tornam-se importante, pois estes representam de 60 a 70% da matéria-prima e são descartados pelas indústrias de filetagem contribuindo com os danos ao meio ambiente. As propriedades funcionais dos filmes biodegradáveis são resultantes das características das macromoléculas utilizadas, das interações entre os constituintes envolvidos na formulação (macromolécula, solvente, plastificante e outros aditivos), dos parâmetros de fabricação (temperatura, tipo de solvente, pH, entre outras), do processo de dispersão da solução filmogênica (pulverização, espalhamento, etc.) e das condições de secagem. Um problema limitante no uso de filmes biodegradáveis a base de proteínas de pescado é a sua susceptibilidade à umidade, devido à hidrofilicidade dos aminoácidos das moléculas de proteína. O objetivo geral do trabalho foi desenvolver e caracterizar filmes a base de isolado proteico de resídeos de corvina (IPC) e óleo de palma (OP). O desenvolvimento dos filmes foi estudado em duas etapas. Neste estudo utilizou-se resíduos de corvina (Micropogonias furnieri) para a obtenção do isolado protéico, glicerol como plastificante e óleo de palma para conferir hidrofobicidade ao filme. Na primeira etapa, o objetivo foi investigar o efeito das concentrações de IPC, de glicerol e do pH sobre as propriedades dos filmes de proteína de resíduos de corvina (Micropogonias furnieri). Os filmes foram avaliados quanto aos parâmetros de cor, opacidade, propriedades mecânicas, espessura, solubilidade em água, permeabilidade de vapor de água (PVA) e propriedades morfológicas. Como resultado foi observado que a opacidade e a luminosidade dos filmes não foram afetados pelas variáveis do processo. Os filmes de IPC ficaram amarelados e opacos. Apresentaramse mais claros quando elaborados com baixas concentrações de IPC e altas concentrações de glicerol nas soluções filmogênicas. A menor solubilidade em água ocorreu nos filmes com pH baixo e menores concentrações de glicerol. Com relação as propriedades mecânicas, os filmes apresentaram alta elongação e sua resistência à tração aumentou quando utilizadas maiores concentrações de IPC, menores concentrações de glicerol e pHs mais baixos.Os filmes apresentaram superficies ásperas e irregulares. Na segunda etapa foram elaborados filmes biodegradáveis de IPC contendo diferentes concentrações de óleo de palma (OP) (10 e 20 g de OP /100g de IPC) e suas propriedades de barreira, mecânicas, físico-químicas, térmicas e morfológicas foram estudadas. A adição de OP aumentou as espessuras dos filmes com 2 e 4% de IPC, no entanto a solubilidade não foi afetada pela adição do OP. Os filmes com 3 e 4% de IPC ficaram menos permeáveis a água quando incorporado 20% de OP nos mesmos. A opacidade dos filmes aumentou com a adição do OP. A incorporação do OP nos filmes resultou em uma diminuição da resistência à tração e no aumento da elongação dos filmes. Nos filmes com 2% de IPC o aumento na elongação foi significativo apenas quando adicionado 20% de OP. O aparecimento de apenas uma temperatura de fusão nos filmes sugeriu uma homogeneidade dos mesmos. A decomposição térmica dos filmes iniciou em torno de 120 -173ºC. Os filmes apresentaram uma superfície descontínua.

Development of Myasthenia Gravis in Systemic Lupus Erythematosus

Objectives: To perform a literature review and estimate MG incidence in an SLE cohort. Materials and methods: We searched MEDLINE and PubMed for case reports of SLE and MG. We also calculated MG incidence within our clinical SLE cohort (females only). Results: Eleven articles met our criteria, providing 13 SLE patients who developed MG. The majority were female (84.6%), with the average ages of 25.6 and 33.5 years at diagnoses of SLE and MG, respectively. In 380 SLE female patients followed for 2,850 person-years, one MG case occurred. Conclusion: MG in SLE is a rare event.

Balancing the demands of two tasks: an investigation of cognitive-motor dual-tasking in relapsing remitting multiple sclerosis

Background: People with relapsing remitting MS (PwRRMS) suffer disproportionate decrements in gait under dual-task conditions, when walking and a cognitive task are combined. There has been much less investigation of the impact of cognitive demands on balance. This study investigated whether: (1) PwRRMS show disproportionate decrements in postural stability under dual-task conditions compared to healthy controls; (2) dual-task decrements are associated with everyday dual-tasking difficulties. In addition, the impact of mood, fatigue and disease severity on dual-tasking were also examined. Methods: 34 PwRRMS and 34 matched controls completed cognitive (digit span) and balance (movement of centre of pressure on a Biosway, on stable and unstable surfaces) tasks under single and dual-task conditions. Everyday dual-tasking was measured using the DTQ. Mood was measured by the HADS. Fatigue was measured via the MFIS. Results: No differences in age, gender, years of education, estimated pre-morbid IQ or baseline digit span between the groups. Compared to healthy controls, PwRRMS showed a significantly greater decrement in postural stability under dual-task conditions on an unstable surface (p=0.007), but not a stable surface (p=0.679). PwRRMS reported higher levels of everyday dual-tasking difficulties (p<0.001). Balance decrement scores were not correlated with everyday dual-tasking difficulties, or with fatigue. Stable surface balance decrement scores were significantly associated with levels of anxiety (rho=0.527, p=0.001) and depression (rho=0.451, p=0.007). Conclusion: RRMS causes difficulties with dual-tasking, impacting balance, particularly under challenging conditions, which may contribute to an increased risk of gait difficulties and falls. The striking relationship between anxiety/depression and dual-task decrement suggests that worry may be contributing to dual-task difficulties.

Antimicrobial effect of polymeric biomaterials for bone infection treatment

Dissertação de mestrado em Bioquímica, apresentada à Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa, 2016.

Towards the systematic simplification of mechanistic models

Mechanistic models used for prediction should be parsimonious, as models which are over-parameterised may have poor predictive performance. Determining whether a model is parsimonious requires comparisons with alternative model formulations with differing levels of complexity. However, creating alternative formulations for large mechanistic models is often problematic, and usually time-consuming. Consequently, few are ever investigated. In this paper, we present an approach which rapidly generates reduced model formulations by replacing a model’s variables with constants. These reduced alternatives can be compared to the original model, using data based model selection criteria, to assist in the identification of potentially unnecessary model complexity, and thereby inform reformulation of the model. To illustrate the approach, we present its application to a published radiocaesium plant-uptake model, which predicts uptake on the basis of soil characteristics (e.g. pH, organic matter content, clay content). A total of 1024 reduced model formulations were generated, and ranked according to five model selection criteria: Residual Sum of Squares (RSS), AICc, BIC, MDL and ICOMP. The lowest scores for RSS and AICc occurred for the same reduced model in which pH dependent model components were replaced. The lowest scores for BIC, MDL and ICOMP occurred for a further reduced model in which model components related to the distinction between adsorption on clay and organic surfaces were replaced. Both these reduced models had a lower RSS for the parameterisation dataset than the original model. As a test of their predictive performance, the original model and the two reduced models outlined above were used to predict an independent dataset. The reduced models have lower prediction sums of squares than the original model, suggesting that the latter may be overfitted. The approach presented has the potential to inform model development by rapidly creating a class of alternative model formulations, which can be compared.

High Precision Plasma Etch for Pattern Transfer: Towards Fluorocarbon Based Atomic Layer Etching

A basic requirement of a plasma etching process is fidelity of the patterned organic materials. In photolithography, a He plasma pretreatment (PPT) based on high ultraviolet and vacuum ultraviolet (UV/VUV) exposure was shown to be successful for roughness reduction of 193nm photoresist (PR). Typical multilayer masks consist of many other organic masking materials in addition to 193nm PR. These materials vary significantly in UV/VUV sensitivity and show, therefore, a different response to the He PPT. A delamination of the nanometer-thin, ion-induced dense amorphous carbon (DAC) layer was observed. Extensive He PPT exposure produces volatile species through UV/VUV induced scissioning. These species are trapped underneath the DAC layer in a subsequent plasma etch (PE), causing a loss of adhesion. Next to stabilizing organic materials, the major goals of this work included to establish and evaluate a cyclic fluorocarbon (FC) based approach for atomic layer etching (ALE) of SiO2 and Si; to characterize the mechanisms involved; and to evaluate the impact of processing parameters. Periodic, short precursor injections allow precise deposition of thin FC films. These films limit the amount of available chemical etchant during subsequent low energy, plasma-based Ar+ ion bombardment, resulting in strongly time-dependent etch rates. In situ ellipsometry showcased the self-limited etching. X-ray photoelectron spectroscopy (XPS) confirms FC film deposition and mixing with the substrate. The cyclic ALE approach is also able to precisely etch Si substrates. A reduced time-dependent etching is seen for Si, likely based on a lower physical sputtering energy threshold. A fluorinated, oxidized surface layer is present during ALE of Si and greatly influences the etch behavior. A reaction of the precursor with the fluorinated substrate upon precursor injection was observed and characterized. The cyclic ALE approach is transferred to a manufacturing scale reactor at IBM Research. Ensuring the transferability to industrial device patterning is crucial for the application of ALE. In addition to device patterning, the cyclic ALE process is employed for oxide removal from Si and SiGe surfaces with the goal of minimal substrate damage and surface residues. The ALE process developed for SiO2 and Si etching did not remove native oxide at the level required. Optimizing the process enabled strong O removal from the surface. Subsequent 90% H2/Ar plasma allow for removal of C and F residues.