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.

Glycerol dialkyl glycerol tetraethers (GDGT) abundance of sediment core GeoB15103-1

Marine microorganisms adapt to their habitat by structural modification of their membrane lipids. This concept is the basis of numerous molecular proxies used for paleoenvironmental reconstruction. Archaeal tetraether lipids from ubiquitous marine planktonic archaea are particularly abundant, well preserved in the sedimentary record and utilized in several molecular proxies. We here introduce the direct, extraction-free analysis of these compounds in intact sediment core sections using laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). LDI FTICR-MS can detect the target lipids in single sub-mm sized spots on sediment sections, equivalent to a sample mass in the nanogram range, and could thus pave the way for biomarker-based reconstruction of past environments and ecosystems at subannual to decadal resolution. We demonstrate that ratios of selected archaeal tetraethers acquired by LDI FTICR-MS are highly correlated with values obtained by conventional LC/MS protocols. The ratio of the major archaeal lipids, caldarchaeol and crenarchaeol, analyzed in a 6.2-cm intact section of Mediterranean sapropel S1 at 250-µm resolution (~4-year temporal resolution), provides an unprecedented view of the fine-scale patchiness of sedimentary biomarker distributions and the processes involved in proxy signal formation. Temporal variations of this lipid ratio indicate a strong influence of the 200-yr de Vries solar cycle on reconstructed sea surface temperatures with possible amplitudes of several degrees, and suggest signal amplification by a complex interplay of ecological and hydrological factors. Laser-based biomarker analysis of geological samples has the potential to revolutionize molecular stratigraphic studies of paleoenvironments.

Light self-focusing in the atmosphere:thin window model

Ultra-high power (exceeding the self-focusing threshold by more than three orders of magnitude) light beams from ground-based laser systems may find applications in space-debris cleaning. The propagation of such powerful laser beams through the atmosphere reveals many novel interesting features compared to traditional light self-focusing. It is demonstrated here that for the relevant laser parameters, when the thickness of the atmosphere is much shorter than the focusing length (that is, of the orbit scale), the beam transit through the atmosphere in lowest order produces phase distortion only. This means that by using adaptive optics it may be possible to eliminate the impact of self-focusing in the atmosphere on the laser beam. The area of applicability of the proposed "thin window" model is broader than the specific physical problem considered here. For instance, it might find applications in femtosecond laser material processing.

Formation of sub-7 nm feature size PS-b-P4VP block copolymer structures by solvent vapour process

The nanometer range structure produced by thin films of diblock copolymers makes them a great of interest as templates for the microelectronics industry. We investigated the effect of annealing solvents and/or mixture of the solvents in case of symmetric Poly (styrene-block-4vinylpyridine) (PS-b-P4VP) diblock copolymer to get the desired line patterns. In this paper, we used different molecular weights PS-b-P4VP to demonstrate the scalability of such high χ BCP system which requires precise fine-tuning of interfacial energies achieved by surface treatment and that improves the wetting property, ordering, and minimizes defect densities. Bare Silicon Substrates were also modified with polystyrene brush and ethylene glycol self-assembled monolayer in a simple quick reproducible way. Also, a novel and simple in situ hard mask technique was used to generate sub-7nm Iron oxide nanowires with a high aspect ratio on Silicon substrate, which can be used to develop silicon nanowires post pattern transfer.

Site controlled red-yellow-green light emitting InGaN quantum discs on nano-tipped GaN rods

We report a method of growing site controlled InGaN multiple quantum discs (QDs) at uniform wafer scale on coalescence free ultra-high density (>80%) nanorod templates by metal organic chemical vapour deposition (MOCVD). The dislocation and coalescence free nature of the GaN space filling nanorod arrays eliminates the well-known emission problems seen in InGaN based visible light sources that these types of crystallographic defects cause. Correlative scanning transmission electron microscopy (STEM), energy-dispersive X-ray (EDX) mapping and cathodoluminescence (CL) hyperspectral imaging illustrates the controlled site selection of the red, yellow and green (RYG) emission at these nano tips. This article reveals that the nanorod tips' broad emission in the RYG visible range is in fact achieved by manipulating the InGaN QD's confinement dimensions, rather than significantly increasing the In%. This article details the easily controlled method of manipulating the QDs dimensions producing high crystal quality InGaN without complicated growth conditions needed for strain relaxation and alloy compositional changes seen for bulk planar GaN templates.

Stable oxygen isotope ratios of diatoms and relative species abundances in ODP Site 145-882

Recent research has increasingly advocated a role for the North Pacific Ocean in modulating global climatic changes over both the last glacial cycle and further back into the geological record. Here a diatom d18O record is presented from Ocean Drilling Program Site 882 over the Pliocene/Quaternary boundary from 2.73 Ma to 2.52 Ma (MIS G6-MIS 99). Large changes in d18Odiatom of c. 4 per mil from 2.73 Ma onwards are documented to occur on a timeframe broadly coinciding with glacial-interglacial cycles. These changes are primarily attributed to large scale inputs of meltwater from glacials surrounding the North Pacific Basin and the Bering Sea. Despite these inputs and associated change in surface water salinity, on the basis of existing opal and UK37 temperature data and new modelled water column densities, no evidence exists to suggests a removal of the halocline stratification or a resumption of the high productivity system similar to that which prevailed prior to 2.73 Ma. The permanence of the halocline suggests that the region played a key role in driving global climatic changes over the early glacial-interglacial cycles that followed the onset of major Northern Hemisphere Glaciation by inhibiting deep water upwelling and ventilation of CO2 to the atmosphere.

Age determination of sediment core GIK16523-1

High-resolution studies of a planktonic foraminifer core record from the South China Sea (SCS) (31KL: 18°45.4'N, 115°52.4'E, water depth 3360 m) reveal changes driven by ice-volume forcings in the climate of the East Asian monsoon in the western Pacific marginal sea during the late Quaternary. The analyses of planktonic foraminifer faunal abundance data from the core indicate significant variations in the relative abundances of the dominant taxa over the past 100,000 years since the isotope stage 5. The transfer function estimates of faunal sea surface temperatures (SST) correlate well with a long-term (104-105 years) trend of global glaciation. About 65,000 years ago, there was an observable change in the mode of SST variability as many low-latitude records have shown. These findings suggest that the SCS surface circulation and the East Asian winter monsoon systems are mainly driven by variations in global glaciation levels. The association of surface ocean cooling in the SCS with global climatic events suggests that fluctuations in the strength of the East Asian winter monsoon may be linked to shifts in the latitudinal position of the westerly winds and the Siberian high-pressure system.

Oxygen isotope ratios on calcite from the Piànico lake record

Stable oxygen isotope analyses at annual, 2-, 5-, 10- and 20-varve sample resolutions were carried out on two selected varve intervals from the interglacial sediment record of the Piànico palaeolake. These sediments are particularly suitable for ultra-high-resolution isotope analyses on lacustrine endogenic calcite because of the exceptionally well-preserved varve structure. A bias through detrital contamination can be excluded because microscopically controlled sampling enabled selecting detritus-free samples. The studied sediment intervals comprise 352 and 88 continuous varve series formed during periods of rapid climate change at the onset and end of a marked millennial-scale cool interval during the Piànico Interglacial. The most intriguing result is a pronounced short-term oscillation in the bi-annually resolved isotope record superimposed on the general decreasing and increasing d18O trends at the climatic transitions that is recorded at lower sample resolution. Spectral analyses of the bi-annual time series reveal periodicities indicating solar and NAO controls on the d18O record. Multiple d18O measurements from endogenic calcite of individual varves showed variations of up to 0.6 per mil, thus larger than the observed inter-annual variability and most likely explained by seasonal effects.

Geochemical investigations of sediment profiles in the Norwegian-Greenland Sea

High-, i.e. 15-140-yr-resolution climate records from sediment cores 23071, 23074, and PS2644 from the Nordic Seas were used to recon:;truct changes in the surface and deep water circulation during marine isotope stages 1-5.1, i.e. the last 82 000 yr. From this the causal links between the paleoceanographic signals and the Dansgaard-Oeschger events 1-21 revealed in 0180-ice-core records from Greenland were determined. The stratigraphy of the cores is based on the planktic 0180 curves, the minima of which were directly correlated with the GISP2-0180 record, numerous AMS 14C ages, and some ash layers. The planktic d18O and dl3C curves of all three cores reveal numerous meltwater events, the most pronounced of which were assigned to the Heinrich events 1-6. The meltwater events, among other things also accompanied by cold sea surface temperatures and high IRD concentration, correlate with the stadial phases of the Dansgaard-Oeschger cycles and in the western Iceland Sea also to colder periods or abrupt drops in 0180 within a few longer interstadials. Besides being more numerous, the meltwater events also show isotope values lighter in the Iceland Sea than in the central Norwegian Sea, especially if compared to core 23071. This implies a continuous inflow of relative warm Atlantic water into the Norwegian Sea and a cyclonic circulation regime.

Raman Analysis of Dilute Aqueous Samples by Localized Evaporation of Submicroliter Droplets on the Tips of Superhydrophobic Copper Wires

Raman analysis of dilute aqueous solutions is normally prevented by their low signal levels. A very general method to increase the concentration to detectable levels is to evaporate droplets of the sample to dryness, creating solid deposits which are then Raman probed. Here, superhydrophobic (SHP) wires with hydrophilic tips have been used as supports for drying droplets, which have the advantage that the residue is automatically deposited at the tip. The SHP wires were readily prepared in minutes using electroless galvanic deposition of Ag onto copper wires followed by modification with a polyfluorothiol (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanethiol, HDFT). Cutting the coated wires with a scalpel revealed hydrophilic tips which could support droplets whose maximum size was determined by the wire diameter. Typically, 230 μm wires were used to support 0.6 μL droplets. Evaporation of dilute melamine droplets gave solid deposits which could be observed by scanning electron microscopy (SEM) and Raman spectroscopy. The limit of detection for melamine using a two stage evaporation procedure was 1 × 10^-6 mol dm^-3. The physical appearance of dried droplets of sucrose and glucose showed that the samples retained significant amounts of water, even under high vacuum. Nonetheless, the Raman detection limits of sucrose and glucose were 5 × 10^-4 and 2.5 × 10^-3 mol dm^-3, respectively, which is similar to the sensitivity reported for surface-enhanced Raman spectroscopy (SERS) detection of glucose. It was also possible to quantify the two sugars in mixtures at concentrations which were similar to those found in human blood through multivariate analysis.

Endonuclease Controlled Aggregation of Gold Nanoparticles for the Ultrasensitive Detection of Pathogenic Bacterial DNA

The development of an ultrasensitive biosensor for the low-cost and on-site detection of pathogenic DNA could transform detection capabilities within food safety, environmental monitoring and clinical diagnosis. Herein, we present an innovative approach exploiting endonuclease-controlled aggregation of plasmonic gold nanoparticles (AuNPs) for label-free and ultrasensitive detection of bacterial DNA. The method utilizes RNA-functionalized AuNPs which form DNA-RNA heteroduplex structures through specific hybridization with target DNA. Once formed, the DNA-RNA heteroduplex is susceptible to RNAse H enzymatic cleavage of the RNA probe, allowing the target DNA to liberate and hybridize with another RNA probe. This continuously happens until all of the RNA probes are cleaved, leaving the nanoparticles unprotected and thus aggregated upon exposure to a high electrolytic medium. The assay is ultrasensitive, allowing the detection of target DNA at femtomolar level by simple spectroscopic analysis (40.7 fM and 2.45 fM as measured by UV-vis and dynamic light scattering (DLS), respectively). The target DNA spiked food matrix (chicken meat) is also successfully detected at a concentration of 1.2 pM (by UV-vis) or 18.0 fM (by DLS). In addition to the ultra-high sensitivity, the total analysis time of the assay is less than 3 hours, thus demonstrating its practicality for food analysis.

Messkonzept und Methodik zur Konfiguration und zum Nachweis

Radio Frequenzidentifikation (RFID) auf Basis pas-siver Transponder im Ultra-High-Frequenzbereich (UHF) findet in der Logistik immer häufiger Anwen-dung. Zur Ausschöpfung der Potenziale dieser AutoID-Technologie wird vorausgesetzt, dass die Identifikation der Waren und Güter zuverlässig erfolgt. Dies gestaltet sich aufgrund von Umgebungseinflüssen auf das elek-tromagnetische Lesefeld, das die passiven Transponder zur Identifikation mit Energie versorgt, oftmals sehr schwierig. Die Kenntnis der elektromagnetischen Feld-stärkeverteilung im Raum kann somit als Grundlage für die Bewertung der zuverlässigen Erfassung durch RFID-Installationen herangezogen werden. Das im Bei-trag vorgestellte Messkonzept mit Methodik zeigt eine Möglichkeit zur schnellen Erfassung der Lese-feldausprägung auf, um anhand der Ergebnisse die Kon-figuration dieser Systeme zu erleichtern.

Fabrication and Characterization of Efficient Optical Filter Arrays Implemented by 3D Nanoimprint

In dieser Arbeit werden optische Filterarrays für hochqualitative spektroskopische Anwendungen im sichtbaren (VIS) Wellenlängenbereich untersucht. Die optischen Filter, bestehend aus Fabry-Pérot (FP)-Filtern für hochauflösende miniaturisierte optische Nanospektrometer, basieren auf zwei hochreflektierenden dielektrischen Spiegeln und einer zwischenliegenden Resonanzkavität aus Polymer. Jeder Filter erlaubt einem schmalbandigem spektralen Band (in dieser Arbeit Filterlinie genannt) ,abhängig von der Höhe der Resonanzkavität, zu passieren. Die Effizienz eines solchen optischen Filters hängt von der präzisen Herstellung der hochselektiven multispektralen Filterfelder von FP-Filtern mittels kostengünstigen und hochdurchsatz Methoden ab. Die Herstellung der multiplen Spektralfilter über den gesamten sichtbaren Bereich wird durch einen einzelnen Prägeschritt durch die 3D Nanoimprint-Technologie mit sehr hoher vertikaler Auflösung auf einem Substrat erreicht. Der Schlüssel für diese Prozessintegration ist die Herstellung von 3D Nanoimprint-Stempeln mit den gewünschten Feldern von Filterkavitäten. Die spektrale Sensitivität von diesen effizienten optischen Filtern hängt von der Genauigkeit der vertikalen variierenden Kavitäten ab, die durch eine großflächige ‚weiche„ Nanoimprint-Technologie, UV oberflächenkonforme Imprint Lithographie (UV-SCIL), ab. Die Hauptprobleme von UV-basierten SCIL-Prozessen, wie eine nichtuniforme Restschichtdicke und Schrumpfung des Polymers ergeben Grenzen in der potenziellen Anwendung dieser Technologie. Es ist sehr wichtig, dass die Restschichtdicke gering und uniform ist, damit die kritischen Dimensionen des funktionellen 3D Musters während des Plasmaätzens zur Entfernung der Restschichtdicke kontrolliert werden kann. Im Fall des Nanospektrometers variieren die Kavitäten zwischen den benachbarten FP-Filtern vertikal sodass sich das Volumen von jedem einzelnen Filter verändert , was zu einer Höhenänderung der Restschichtdicke unter jedem Filter führt. Das volumetrische Schrumpfen, das durch den Polymerisationsprozess hervorgerufen wird, beeinträchtigt die Größe und Dimension der gestempelten Polymerkavitäten. Das Verhalten des großflächigen UV-SCIL Prozesses wird durch die Verwendung von einem Design mit ausgeglichenen Volumen verbessert und die Prozessbedingungen werden optimiert. Das Stempeldesign mit ausgeglichen Volumen verteilt 64 vertikal variierenden Filterkavitäten in Einheiten von 4 Kavitäten, die ein gemeinsames Durchschnittsvolumen haben. Durch die Benutzung der ausgeglichenen Volumen werden einheitliche Restschichtdicken (110 nm) über alle Filterhöhen erhalten. Die quantitative Analyse der Polymerschrumpfung wird in iii lateraler und vertikaler Richtung der FP-Filter untersucht. Das Schrumpfen in vertikaler Richtung hat den größten Einfluss auf die spektrale Antwort der Filter und wird durch die Änderung der Belichtungszeit von 12% auf 4% reduziert. FP Filter die mittels des Volumengemittelten Stempels und des optimierten Imprintprozesses hergestellt wurden, zeigen eine hohe Qualität der spektralen Antwort mit linearer Abhängigkeit zwischen den Kavitätshöhen und der spektralen Position der zugehörigen Filterlinien.