Utilização da cinza da casca de arroz em cimentação de poços de petróleo

Pozzolanic materials such as rice husk ash are widely used to substitute part of cement, because they react with calcium hydroxide (CH) producing calcium silicate hydrate (C-S-H), which aggregate better physical, chemical and mechanical properties to the cement slurry. The usage of rice husk biomass ash from agribusiness in addition to or partially replacing cement is a noble purpose and a good way of sustainable development which currently is an obsession around the world. The ashes utilized in this study were characterized by: scanning electron microscopy technique (SEM), Fourier transform infrared spectroscopy (FTIR), Energy-dispersive X-ray spectroscopy (EDX) and BET method. The pozzolanic activity of RHA and WRHA in cement slurries was evaluated by: thermal-gravimetric technique and derivative thermogravimetry (TGA/DTG), X-ray diffraction (XRD) and Compressive Strength. The slurries formulated with additions of 10% and 20% of RHA and WRHA were cured for 28 days at 58 °C. The results of thermal analysis demonstrated that a 20% WRHA addition caused a reduction of approximately 73% of Portlandite (calcium hydroxide – CH) phase related to standard slurry (STD). The XRD scans also demonstrated the reduction of the Portlandite peaks’ intensity for each slurry compared with STD slurry. The RHA and WRHA react chemically with Portlandite producing calcium silicate hydrate (C-S-H), confirming their effect as a pozzolanic agent. The WRHA presented the best results as a pozzolanic material.

Estudo e aplicação da transformada de Fourier na regularização de dados sísmicos na exploração de petróleo

In the oil prospection research seismic data are usually irregular and sparsely sampled along the spatial coordinates due to obstacles in placement of geophones. Fourier methods provide a way to make the regularization of seismic data which are efficient if the input data is sampled on a regular grid. However, when these methods are applied to a set of irregularly sampled data, the orthogonality among the Fourier components is broken and the energy of a Fourier component may "leak" to other components, a phenomenon called "spectral leakage". The objective of this research is to study the spectral representation of irregularly sampled data method. In particular, it will be presented the basic structure of representation of the NDFT (nonuniform discrete Fourier transform), study their properties and demonstrate its potential in the processing of the seismic signal. In this way we study the FFT (fast Fourier transform) and the NFFT (nonuniform fast Fourier transform) which rapidly calculate the DFT (discrete Fourier transform) and NDFT. We compare the recovery of the signal using the FFT, DFT and NFFT. We approach the interpolation of seismic trace using the ALFT (antileakage Fourier transform) to overcome the problem of spectral leakage caused by uneven sampling. Applications to synthetic and real data showed that ALFT method works well on complex geology seismic data and suffers little with irregular spatial sampling of the data and edge effects, in addition it is robust and stable with noisy data. However, it is not as efficient as the FFT and its reconstruction is not as good in the case of irregular filling with large holes in the acquisition.

Estudo e aplicação da transformada de Fourier na regularização de dados sísmicos na exploração de petróleo

In the oil prospection research seismic data are usually irregular and sparsely sampled along the spatial coordinates due to obstacles in placement of geophones. Fourier methods provide a way to make the regularization of seismic data which are efficient if the input data is sampled on a regular grid. However, when these methods are applied to a set of irregularly sampled data, the orthogonality among the Fourier components is broken and the energy of a Fourier component may "leak" to other components, a phenomenon called "spectral leakage". The objective of this research is to study the spectral representation of irregularly sampled data method. In particular, it will be presented the basic structure of representation of the NDFT (nonuniform discrete Fourier transform), study their properties and demonstrate its potential in the processing of the seismic signal. In this way we study the FFT (fast Fourier transform) and the NFFT (nonuniform fast Fourier transform) which rapidly calculate the DFT (discrete Fourier transform) and NDFT. We compare the recovery of the signal using the FFT, DFT and NFFT. We approach the interpolation of seismic trace using the ALFT (antileakage Fourier transform) to overcome the problem of spectral leakage caused by uneven sampling. Applications to synthetic and real data showed that ALFT method works well on complex geology seismic data and suffers little with irregular spatial sampling of the data and edge effects, in addition it is robust and stable with noisy data. However, it is not as efficient as the FFT and its reconstruction is not as good in the case of irregular filling with large holes in the acquisition.

Structure, energetics and reactions of metal cation complexes of dipeptides in the gas phase

Structure, energetics and reactions of ions in the gas phase can be revealed by mass spectrometry techniques coupled to ions activation methods. Ions can gain enough energy for dissociation by absorbing IR light photons introduced by an IR laser to the mass spectrometer. Also collisions with a neutral molecule can increase the internal energy of ions and provide the dissociation threshold energy. Infrared multiple photon dissociation (IRMPD) or sustained off-resonance irradiation collision-induced dissociation (SORI-CID) methods are combined with Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometers where ions can be held at low pressures for a long time. The outcome of ion activation techniques especially when it is compared to the computational methods results is of great importance since it provides useful information about the structure, thermochemistry and reactivity of ions of interest. In this work structure, energetics and reactivity of metal cation complexes with dipeptides are investigated. Effect of metal cation size and charge as well as microsolvation on the structure of these complexes has been studied. Structures of bare and hydrated Na and Ca complexes with isomeric dipeptides AlaGly and GlyAla are characterized by means of IRMPD spectroscopy and computational methods. At the second step unimolecular dissociation reactions of singly charged and doubly charged multimetallic complexes of alkaline earth metal cations with GlyGly are examined by CID method. Also structural features of these complexes are revealed by comparing their IRMPD spectra with calculated IR spectra of possible structures. At last the unimolecular dissociation reactions of Mn complexes are studied. IRMPD spectroscopy along with computational methods is also employed for structural elucidation of Mn complexes. In addition the ion-molecule reactions of Mn complexes with CO and water are explored in the low pressures obtained in the ICR cell.

Effect of reaction mechanism on precursor exposure time in atomic layer deposition of silicon oxide and silicon nitride

Atomic layer deposition (ALD) of highly conformal, silicon-based dielectric thin films has become necessary because of the continuing decrease in feature size in microelectronic devices. The ALD of oxides and nitrides is usually thought to be mechanistically similar, but plasma-enhanced ALD of silicon nitride is found to be problematic, while that of silicon oxide is straightforward. To find why, the ALD of silicon nitride and silicon oxide dielectric films was studied by applying ab initio methods to theoretical models for proposed surface reaction mechanisms. The thermodynamic energies for the elimination of functional groups from different silicon precursors reacting with simple model molecules were calculated using density functional theory (DFT), explaining the lower reactivity of precursors toward the deposition of silicon nitride relative to silicon oxide seen in experiments, but not explaining the trends between precursors. Using more realistic cluster models of amine and hydroxyl covered surfaces, the structures and energies were calculated of reaction pathways for chemisorption of different silicon precursors via functional group elimination, with more success. DFT calculations identified the initial physisorption step as crucial toward deposition and this step was thus used to predict the ALD reactivity of a range of amino-silane precursors, yielding good agreement with experiment. The retention of hydrogen within silicon nitride films but not in silicon oxide observed in FTIR spectra was accounted for by the theoretical calculations and helped verify the application of the model.

FTIR-inferred biogeochemical properties for the past 3.6 Myr in the sediment record of core ICDP5011-1 in Lake Elgygytgyn, NE Russia

A number of studies have shown that Fourier transform infrared spectroscopy (FTIR) can be applied to quantitatively assess lacustrine sediment constituents. In this study, we developed calibration models based on FTIR for the quantitative determination of biogenic silica (BSi; n = 420; gradient: 0.9-56.5%), total organic carbon (TOC; n = 309; gradient: 0-2.9%), and total inorganic carbon (TIC; n= 152; gradient: 0-0.4%) in a 318 m-long sediment record with a basal age of 3.6 million years from Lake El'gygytgyn, Far East Russian Arctic. The developed partial least squares (PLS) regression models yield high cross-validated (CV) R2CV = 0.86-0.91 and low root mean square error of cross-validation (RMSECV) (3.1-7.0% of the gradient for the different properties). By applying these models to 6771 samples from the entire sediment record, we obtained detailed insight into bioproductivity variations in Lake El'gygytgyn throughout the middle to late Pliocene and Quaternary. High accumulation rates of BSi indicate a productivity maximum during the middle Pliocene (3.6-3.3 Ma), followed by gradually decreasing rates during the late Pliocene and Quaternary. The average BSi accumulation during the middle Pliocene was ~3 times higher than maximum accumulation rates during the past 1.5 million years. The indicated progressive deterioration of environmental and climatic conditions in the Siberian Arctic starting at ca. 3.3 Ma is consistent with the first occurrence of glacial periods and the finally complete establishment of glacial-interglacial cycles during the Quaternary.

A 2.8 Ma sedimentological, geochemical and palynological record of sediment core ICDP5011-1 in Lake Elgygytgyn, NE Russia

The reliability of Arctic climate predictions is currently hampered by insufficient knowledge of natural climate variability in the past. A sediment core from Lake El'gygytgyn (NE Russia) provides a continuous high-resolution record from the Arctic spaning the past 2.8 Ma. The core reveals numerous "super interglacials" during the Quaternary, with maximum summer temperatures and annual precipitation during marine benthic isotope stages (MIS) 11c and 31 ~4-5 °C and ~300 mm higher than those of MIS 1 and 5e. Climate simulations show these extreme warm conditions are difficult to explain with greenhouse gas and astronomical forcing alone, implying the importance of amplifying feedbacks and far field influences. The timing of Arctic warming relative to West Antarctic Ice Sheet retreats implies strong interhemispheric climate connectivity.

A 3.6 Ma sedimentological, geochemical and palynological record of sediment core ICDP5011-1 in Lake Elgygytgyn, NE Russia

Understanding the evolution of Arctic polar climate from the protracted warmth of the middle Pliocene into the earliest glacial cycles in the Northern Hemisphere has been hindered by the lack of continuous, highly resolved Arctic time series. Evidence from Lake El'gygytgyn, NE Arctic Russia, shows that 3.6-3.4 million years ago, summer temperatures were ~8°C warmer than today when pCO2 was ~400 ppm. Multiproxy evidence suggests extreme warmth and polar amplification during the middle Pliocene, sudden stepped cooling events during the Pliocene-Pleistocene transition, and warmer than present Arctic summers until ~2.2 Ma, after the onset of Northern Hemispheric glaciation. Our data are consistent with sea-level records and other proxies indicating that Arctic cooling was insufficient to support large-scale ice sheets until the early Pleistocene.

A Mineralogical Study of a Dravitic Tourmaline from the Grenville Province

Tourmaline from a gem-quality deposit in the Grenville province has been studied with X-ray diffraction, visible-near infrared spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, electron microprobe and optical measurements. The tourmaline is found within tremolite-rich calc-silicate pods hosted in marble of the Central Metasedimentary Belt. The crystals are greenish-greyish-brown and have yielded facetable material up to 2.09 carats in size. Using the classification of Henry et al. 2011 the tourmaline is classified as a dravite, with a representative formula shown to be (Na0.73Ca0.2380.032)(Mg2+2.913Fe2+0.057Ti4+0.030) (Al3+5.787Fe3+0.017Mg2+0.14)(Si6.013O18)(BO3)3(OH)3((OH,O)0.907F0.093). Rietveld analysis of powder diffraction data gives a = 15.9436(8) Å, c = 7.2126(7) Å and a unit cell volume of 1587.8 Å3. A polished thin section was cut perpendicular to the c-axis of one tourmaline crystal, which showed zoning from a dark brown core into a lighter rim into a thin darker rim and back into lighter zonation. Through the geochemical data, three key stages of crystal growth can be seen within this thin section. The first is the core stage which occurs from the dark core to the first colourless zone; the second is from this colourless zone increasing in brown colour to the outer limit before a sudden absence of colour is noted; the third is a sharp change from the end of the second and is entirely colourless. These events are the result of metamorphism and hydrothermal fluids resulting from nearby felsic intrusive plutons. Scanning electron microscope, and electron microprobe traverses across this cross-section revealed that the green colour is the result of iron present throughout the system while the brown colour is correlated with titanium content. Crystal inclusions in the tourmaline of chlorapatite, and zircon were identified by petrographic analysis and confirmed using scanning electron microscope data and occur within the third stage of formation.

Synthesis, Modification, and Application of Siloxane Materials for Environmental Sensing

As human populations and resource consumption increase, it is increasingly important to monitor the quality of our environment. While laboratory instruments offer useful information, portable, easy to use sensors would allow environmental analysis to occur on-site, at lower cost, and with minimal operator training. We explore the synthesis, modification, and applications of modified polysiloxane in environmental sensing. Multiple methods of producing modified siloxanes were investigated. Oligomers were formed by using functionalized monomers, producing siloxane materials containing silicon hydride, methyl, and phenyl side chains. Silicon hydride-functionalized oligomers were further modified by hydrosilylation to incorporate methyl ester and naphthyl side chains. Modifications to the siloxane materials were also carried out using post-curing treatments. Methyl ester-functionalized siloxane was incorporated into the surface of a cured poly(dimethylsiloxane) film by siloxane equilibration. The materials containing methyl esters were hydrolyzed to reveal carboxylic acids, which could later be used for covalent protein immobilization. Finally, the siloxane surfaces were modified to incorporate antibodies by covalent, affinity, and adsorption-based attachment. These modifications were characterized by a variety of methods, including contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, dye labels, and 1H nuclear magnetic resonance spectroscopy. The modified siloxane materials were employed in a variety of sensing schemes. Volatile organic compounds were detected using methyl, phenyl, and naphthyl-functionalized materials on a Fabry-Perot interferometer and a refractometer. The Fabry-Perot interferometer was found to detect the analytes upon siloxane extraction by deformation of the Bragg reflectors. The refractometer was used to determine that naphthyl-functionalized siloxanes had elevated refractive indices, rendering these materials more sensitive to some analytes. Antibody-modified siloxanes were used to detect biological analytes through a solid phase microextraction-mediated enzyme linked immunosorbent assay (SPME ELISA). The SPME ELISA was found to have higher analyte sensitivity compared to a conventional ELISA system. The detection scheme was used to detect Escherichia coli at 8500 CFU/mL. These results demonstrate the variety of methods that can be used to modify siloxanes and the wide range of applications of modified siloxanes has been demonstrated through chemical and biological sensing schemes.

BLOCK COPOLYMERS CONTAINING A LOW-SURFACE-ENERGY BLOCK AND THEIR APPLICATIONS

This thesis reports the synthesis and/or applications of three types of block copolymers that each bear a low-surface-energy block. First, poly(dimethylsiloxane)-block-poly(2-cinnamoyloxyethyl acrylate) (PDMS-b-PCEA) was synthesized and characterized. Cotton coating using a micellar solution of this block copolymer yielded superhydrophobic cotton fabrics. X-ray photoelectron spectroscopy (XPS) and surface property analyses indicated that the PDMS block topped the polymer coating. Photocuring the cotton swatches crosslinked the underlying PCEA layer and yielded permanent coatings. More interestingly, hydrophilically patterned superhydrophobic cotton fabrics were produced using photolithography that allowed the crosslinking of the coating around irradiated fibers but the removal, by solvent extraction, of the coating on fibers that were not irradiated. Since water-based ink only permeated the uncoated regions, such patterned fabric was further used to print ink patterns onto substrates such as fabrics, cardboard, paper, wood, and aluminum foil. Then, another PDMS-based diblock copolymer poly(dimethylsiloxane)-block-poly(glycidyl methacrylate) (PDMS-b-PGMA) was prepared. Different from PCEA that photocrosslinked around cotton fibers, PGMA reacted with hydroxyl groups on cotton fiber surfaces to get covalently attached. Further, different PGMA chains crosslinked with each other. PDMS-b-PGMA-coated cotton fabrics have been used for oil-water separations. In addition, polymeric nanoparticles were grafted onto cotton fiber surface before PDMS-b-PGMA was used to cover the surfaces of the grafted spheres and the residual surfaces of the cotton fibers. These two types of fabrics, coated by the block copolymer alone or by the polymer nanospheres and then the copolymer, were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and water repellency analyses. A comprehensive comparative study was made of their performances in oil-water separation. Finally, a fluorinated ABC triblock copolymer poly(acrylic acid)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(2-perfluorooctylethyl methacrylate) (PAA-b-PCEMA-b-PFOEMA) was used to iii encapsulate air nanobubbles. The produced air nanobubbles were thermodynamically stable in water and were some 100 times more stable than commercially available perfluorocarbon-filled microbubbles under ultrasound. These nanobubbles, due to their small sizes and thus ability to permeate the capillary networks of organs and to reach tumors, may expand the applications of microbubbles in diagnostic ultrasonography and find new applications in ultrasound-regulated drug delivery.

RELATIONSHIP BETWEEN PHYSICAL AND CHEMICAL PROPERTIES OF STRAIGHT AND RECOVERED ASPHALT BINDERS FROM ONTARIO

Thermal and fatigue cracking are the major pavement distresses that contribute to a drastic reduction of the pavement’s service life and performance in Ontario. Chemical oxidation and hardening of asphalt binders deteriorates its physical properties since physical properties of asphalts depend on its chemical composition. This thesis is aimed to establish a relationship between physical and chemical properties of asphalt binders. A secondary objective is to show the strong correlation between CTOD and temperature. All recovered and straight Ministry of Transportation of Ontario (MTO) samples were investigated using conventional Superpave® test method dynamic shear rheometer (DSR) as well as improved MTO test methods such as extended bending beam rheometer (eBBR) and double-edge-notched tension (DENT) test. DENT test was conducted for all Ontario contract samples at three different temperatures based on their performance grade after three hours of thermal conditioning and compared the results in terms of essential work of fracture, plastic work of fracture and CTOD at different temperatures. Good correlation exists between CTOD and temperature according to the DENT data. X-ray fluorescence (XRF) analysis was conducted to detect the presence of heavy metals such as zinc and molybdenum believed to have originated from waste engine oil. Fourier transform infra-red spectroscopy (FTIR) was performed to determine the abundance of functional groups such as carbonyl, sulfoxides, polyisobutylene, etc. XRF and FTIR analysis confirmed that most of the samples contain waste engine oil and/or oxidized residues, which is believed to be a root cause of premature pavement failures.

Dynamically mechanical and nano-impact (fatigue) analysis of touch screen thin films deposited on polyethylene terephthalate substrate

Nano-scale touch screen thin film have not been thoroughly investigated in terms of dynamic impact analysis under various strain rates. This research is focused on two different thin films, Zinc Oxide (ZnO) film and Indium Tin Oxide (ITO) film, deposited on Polyethylene Terephthalate (PET) substrate for the standard touch screen panels. Dynamic Mechanical Analysis (DMA) was performed on the ZnO film coated PET substrates. Nano-impact (fatigue) testing was performed on ITO film coated PET substrates. Other analysis includes hardness and the elastic modulus measurements, atomic force microscopy (AFM), Fourier Transform Infrared Spectroscopy (FTIR) and the Scanning Electron Microscopy (SEM) of the film surface.
Ten delta of DMA is described as the ratio of loss modulus (viscous properties) and storage modulus (elastic properties) of the material and its peak against time identifies the glass transition temperature (Tg). Thus, in essence the Tg recognizes changes from glassy to rubber state of the material and for our sample ZnO film, Tg was found as 388.3 K. The DMA results also showed that the Ten delta curve for Tg increases monotonically in the viscoelastic state (before Tg) and decreases sharply in the rubber state (after Tg) until recrystallization of ZnO takes place. This led to an interpretation that enhanced ductility can be achieved by negating the strength of the material.
For the nano-impact testing using the ITO coated PET, the damage started with the crack initiation and propagation. The interpretation of the nano-impact results depended on the characteristics of the loading history. Under the nano-impact loading, the surface structure of ITO film suffered from several forms of failure damages that range from deformation to catastrophic failures. It is concluded that in such type of application, the films should have low residual stress to prevent deformation, good adhesive strength, durable and good resistance to wear.

The VLT-FLAMES tarantula survey:XII. Rotational velocities of the single O-type stars

Context. The 30 Doradus (30 Dor) region of the Large Magellanic Cloud, also known as the Tarantula nebula, is the nearest starburst region. It contains the richest population of massive stars in the Local Group, and it is thus the best possible laboratory to investigate open questions on the formation and evolution of massive stars. Aims. Using ground-based multi-object optical spectroscopy obtained in the framework of the VLT-FLAMES Tarantula Survey (VFTS), we aim to establish the (projected) rotational velocity distribution for a sample of 216 presumably single O-type stars in 30 Dor. The sample is large enough to obtain statistically significant information and to search for variations among subpopulations - in terms of spectral type, luminosity class, and spatial location - in the field of view. Methods. We measured projected rotational velocities, 3e sin i, by means of a Fourier transform method and a profile fitting method applied to a set of isolated spectral lines. We also used an iterative deconvolution procedure to infer the probability density, P(3e), of the equatorial rotational velocity, 3e. Results. The distribution of 3e sin i shows a two-component structure: a peak around 80 km s1 and a high-velocity tail extending up to 600 km s^-1 This structure is also present in the inferred distribution P(3e) with around 80% of the sample having 0 <3e ≤ 300 km s^-1 and the other 20% distributed in the high-velocity region. The presence of the low-velocity peak is consistent with what has been found in other studies for late O- and early B-type stars. Conclusions. Most of the stars in our sample rotate with a rate less than 20% of their break-up velocity. For the bulk of the sample, mass loss in a stellar wind and/or envelope expansion is not efficient enough to significantly spin down these stars within the first few Myr of evolution. If massive-star formation results in stars rotating at birth with a large portion of their break-up velocities, an alternative braking mechanism, possibly magnetic fields, is thus required to explain the present-day rotational properties of the O-type stars in 30 Dor. The presence of a sizeable population of fast rotators is compatible with recent population synthesis computations that investigate the influence of binary evolution on the rotation rate of massive stars. Even though we have excluded stars that show significant radial velocity variations, our sample may have remained contaminated by post-interaction binary products. That the highvelocity tail may be populated primarily (and perhaps exclusively) by post-binary interaction products has important implications for the evolutionary origin of systems that produce gamma-ray bursts. © 2013 Author(s).

Banana and abaca fiber-reinforced plastic composites obtained by rotational molding process

Natural fibers can be used in rotational molding process to obtain parts with improved mechanical properties. Different approaches have been followed in order to produce formulations containing banana or abaca fiber at 5% weight, in two- and three-layer constructions. Chemically treated abaca fiber has also been studied, causing some problems in processability. Fibers used have been characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), optical microscopy, and single-fiber mechanical tests. Rotomolded parts have been tested for tensile, flexural, and impact properties, demonstrating that important increases in elastic modulus are achieved with these fibers, although impact properties are reduced. © 2013 Copyright Taylor and Francis Group, LLC.