Multivariate calibrations on H-1 NMR profiles for prediction of physicochemical parameters of Brazilian commercial gasoline

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Multivariate calibrations in gas chromatographic profiles for prediction of several physicochemical parameters of Brazilian commercial gasoline

Several Brazilian commercial gasoline physicochemical parameters, such as relative density, distillation curve (temperatures related to 10%, 50% and 90% of distilled volume, final boiling point and residue), octane numbers (motor and research octane number and anti-knock index), hydrocarbon compositions (olefins, aromatics and saturates) and anhydrous ethanol and benzene content was predicted from chromatographic profiles obtained by flame ionization detection (GC-FID) and using partial least square regression (PLS). GC-FID is a technique intensively used for fuel quality control due to its convenience, speed, accuracy and simplicity and its profiles are much easier to interpret and understand than results produced by other techniques. Another advantage is that it permits association with multivariate methods of analysis, such as PLS. The chromatogram profiles were recorded and used to deploy PLS models for each property. The standard error of prediction (SEP) has been the main parameter considered to select the "best model". Most of GC-FID-PLS results, when compared to those obtained by the Brazilian Government Petroleum, Natural Gas and Biofuels Agency - ANP Regulation 309 specification methods, were very good. In general, all PLS models developed in these work provide unbiased predictions with lows standard error of prediction and percentage average relative error (below 11.5 and 5.0, respectively). (C) 2007 Elsevier B.V. All rights reserved.

Estimativa de safra para a cultura do milho através do filme infravermelho colorido

O sistema tradicional para estimativas de safra utiliza-se de relatórios técnicos de fontes diversas. A coleta de informações, se inicia antes da época do plantio e as estimativas são vendo ajustadas de acordo com o desenvolvimento das culturas. O trabalho em questão, pretende mostrar as possibilidades do filme infravermelho colorido na estimativa de safra para a cultura do milho. As informações quantitativas foram obtidas através da densitometria de transmissão. Os trabalhos foram conduzidos na Fazenda Experimental São Manuel da Faculdade de Ciências Agronômicas - Campus de Botucatu - UNESP. Os seis tratamentos consistiram em doses diferenciais de adubo, prevendo prováveis quedas em produção. A cultura foi fotografada com filme colorido (Kodak Ektachrome 64 ASA) e infravermelho colorido (Kodak Ektachrome Infrared Film) e a densidade ótica medida em um microdensitômetro de transmissão marca Weston, modelo 877 e abertura de 0,8 mm. Para avaliar a interação entre Produção e Densidade Ótica, utilizou-se das análises de correlação e regressão linear. A análise dos resultados permitiram as seguintes conclusões principais: a) Desde que se faça as necessárias calibrações, o filme infravermelho pode ser utilizado na estimativa de safra para a cultura do milho; b) A utilização do densitômetro de transmissão, para a interpretação quantitativa dos resultados, revelou-se importante sugerindo a aplicação do método em outros tipos de culturas.

New constraints on ages of glasses proposed as reference materials for fission-track dating

New analyses have been performed in order to enhance the data-set on the independent ages of four glasses that have been proposed as reference materials for fission-track dating. The results are as follows. Moldavite - repeated (40)Ar/(39)Ar age determinations on samples from deposits from Bohemia and Moravia yielded an average of 14.34 +/- 0.08 Ma. This datum agrees with other recent determinations and is significantly younger than the (40)Ar/(39)Ar age of 15.21 +/- 0.15 Ma determined in the early 1980s. Macusanite (Peru) -four K-Ar ages ranging from 5.44 +/- 0.06 to 5.72 +/- 0.12 Ma have been published previously. New (40)Ar/(39)Ar ages gave an average of 5.12 +/- 0.04 Ma. Plateau fission-track ages determined using the IRMM-540 certified glass and U and Th thin films for neutron fluence measurements agree better with these new (40)Ar/(39)Ar ages than the previously published ages. Roccastrada glass (Italy) - a new (40)Ar/(39)Ar age, 2.45 +/- 0.04 Ma, is consistent with previous determinations. The Quiron obsidian (Argentina) is a recently discovered glass that has been proposed as an additional reference material for its high spontaneous track density (around 100 000 cm(-2)). Defects that might produce spurious tracks are virtually absent. An independent (40)Ar/(39)Ar age of 8.77 +/- 0.09 Ma was determined and is recommended for this glass. We believe that these materials, which will be distributed upon request to fission-track groups, will be very useful for testing system calibrations and experimental procedures.

Direct determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by simultaneous GFAAS using integrated platforms pretreated with W-Rh permanent modifier together with Pd plus Mg modifier

A method is proposed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by electrothermal atomic absorption spectrometry (ETAAS) using W-Rh permanent modifier together with Pd(NO3)(2) + Mg(NO3)(2) conventional modifier. The integrated platform of a transversely heated graphite atomizer (THGA) was treated with tungsten, followed by rhodium, forming a deposit containing 250 mug W + 200 mug Rh. A 500-muL, volume of fuel ethanol was diluted with 500 muL, of 0.14 mol L-1 HNO3 in an autosampler cup of the spectrometer. Then, 20 muL, of the diluted ethanol was introduced into the pretreated graphite platform followed by the introduction of 5 mug Pd(NO3)(2) + 3 mug Mg(NO3)(2). The injection of this modifier was required to improve arsenic and iron recoveries in fuel ethanol. Calibrations were carried out using multi-element reference solutions prepared in diluted ethanol (1 + 1, v/v) acidified to 0. 14 mol L-1 HNO3. The pyrolysis and atomization temperatures of the heating program were 1200degreesC and 2200degreesC, respectively, which were obtained with multielement reference solutions in acidic diluted ethanol (1 + 1, v/v; 0. 14 mol L-1 HNO3). The characteristic masses for the simultaneous determination in ethanol fuel were 78 pg Al, 33 pg As, 10 pg Cu, 14 pg Fe, 7 pg Mn, and 24 pg Ni. The lifetime of the pretreated tube was about 700 firings. The detection limits (D.L.) were 1.9 mug L-1 Al, 2.9 mug L-1 As, 0.57 mug L-1.Cu, 1.3 mug L-1 Fe, 0.40 mug L-1 Mn, and 1.3 mug L-1 Ni. The relative standard deviations (n = 12) were 4%, 4%, 3%, 1.5%, 1.2%, and 2.2% for Al, As, Cu, Fe, Mn, and Ni, respectively. The recoveries of Al, As, Cu, Fe, Mn, and Ni added to the fuel ethanol samples varied from 81% to 95%, 80% to 98%, 97% to 109%, 85% to 107%, 98% to 106% and 97% to 103%, respectively. Accuracy was checked for the Al, As, Cu, Fe, Mn, and Ni determination in 10 samples purchased at a local gas station in Araraquara-SP City, Brazil. A paired t-test showed that at the 95% confidence level the results were in agreement with those obtained by single-element ETAAS.

The thermal stability of fission tracks in the 612 nist glass standard at room temperature

Two wafers of the NIST (formerly NBS) glass standard SRM 612 recently irradiated have been compared to the pre-irradiated wafers RT3 and RT4 of glass SRM 962-7, stored for 9 years at 5°C, and SRM 962, stored for 20 years at room temperature. Track area densities on internal surfaces of the glass as well as track size measurements suggest that (1) the old SRM 962 and the more recent SRM 962a calibrations are consistent and (2) annealing of the fission tracks in the pre-irradiated wafers is negligible. This last experimental result enables a direct comparison of contemporary and previous fission track age calibrations. © 1995.

Calibration of therapeutic ultrasound equipment

Temporal and spatial acoustic intensity (SATA) of therapeutic ultrasound (US) equipment should be monitored periodically. In order to evaluate the conditions of US equipment in use in the city of Piracicaba-Sao Paulo, Brazil, 31 machines - representing all Brazilian manufacturers - were analysed under continuous and pulsed conditions at a frequency of 1 MHz. Data about temporal and spatial acoustic intensity were collected and the use of equipment was surveyed. Intensities of 0.1, 0.2, 0.5, 0.8, 1.0, 1.5, 2.0, 2.5 and 3.0 Wcm -2, indicated on the equipment panel were analysed using a previously calibrated digital radiation pressure scale, model UPM-DT-1 (Ohmic Instruments Co). The acoustic intensity (I) results were expressed as superior and inferior quartile ranges for transducers with metal surfaces of 9 cm 2 and an effective radiation area (ERA) Of 4 cm 2. The results under continuous conditions were: I 0.1 = -20.0% and -96%. I 0.2 = -3.1% and -83.7%. I 0.5 = -35.0% and -86.5%. I 0.8 = -37.5% and -71.0%. I 2.5 = -49.0% and -69.5%. I 3.0 = -58.1% and -77.6%. For pulsed conditions, intensities were: I 0.1 = -40.0% and -86.2%. I 1.0 = -50.0% and -86.5%. I 1.5 = -62.5% and -82.5%. I 2.0 = -62.5% and -81.6%. I 2.5 = -64.7% and -88.8%. I 3.0 = -87.1% and -94.8%. In reply to the questionnaire drawn up to check the conditions of use of equipment, all users reported the use of hydrosoluble gel as a coupling medium and none had carried out previous calibrations. Most users used intensities in the range of 0.4. to 1.0 Wcm -2 and used machines for 300 to 400 minutes per week. The majority of machines had been bought during the previous seven years and weekly use ranged from less than 100 minutes to 700 minutes (11 hours 40 minutes). Findings confirm previous observations of discrepancy between the intensity indicated on the equipment panel and that emitted by the transducer and highlight the necessity for periodic evaluations of US equipment.

Specific depth cone resistivity measurements to determine soil engineering properties

The University of British Columbia (UBC) began performing piezocone penetration tests (CPTU) with electrical resistivity measurements (RCPTU) in 1989. Since then, RCPTU research at UBC has focused on obtaining geo-environmental parameters such as fluid resistivity and soil engineering properties such as porosity and degree of saturation from measurements of bulk soil electrical resistivity using the empirical relationship proposed by Archie (1942). Within this framework, the paper illustrates and discusses important design and calibration issues for resistivity modules such as the use of isolated circuitry to achieve linear calibrations over large ranges of resistivity. The suitability of RCPTU measurements for determination of geo-environmental and geotechnical parameters are assessed using typical ranges of soil and groundwater properties and methods of isolating individual factors for study are discussed. Illustrative examples of RCPTU research efforts including the environmental characterization of mine tailings, delineation of saline water intrusions in fresh water aquifers and the quality control of geotechnical ground densification are presented throughout the text. It is shown that groundwater temperature and hence ion mobility is not significantly altered by frictional heat generated during piezocone penetration and that ratio-based approaches to monitoring soil porosity can be used to eliminate the requirement for extensive groundwater sampling programs. Lastly, it is shown that RCPTU measurements above the water table can only be made using resistivity modules that are stable over a large range of resistivities and that such measurements are the most difficult to interpret because of grain surface conduction effects and generally unknown fluid resistivities.

Development of a new TDR probe for determining soil water content and dry density

A few traditional methods for determining water content in the field are either inaccurate or time consuming. As an alternative, the time domain reflectometry (TDR) technology has been used in the determination of the soil water content for geotechnical applications. This paper presents the preliminary results on the development of a new TDR probe for determining soil water content and dry density at different depths. This new probe is intended to be pushed into the ground using piezocone equipment. Different from the standard TDR probes with straight rods, the new probe consists of two parallel copper stripes coiled around a PVC-steel core. The probe diameter is the same as the standard 10 cm2 piezocone diameter. Through laboratory calibrations, it is possible to establish expressions relating the soil apparent dielectric constant and the bulk electrical conductivity with the gravimetric water content and the dry density. Copyright ASCE 2007.

Methodology for DSC calibration in high heating rates

Despite the large use of differential scanning calorimetry (DSC) technique in advanced polymer materials characterization, the new methodology called DSC in high heating rates was developed. The heating rate during conventional DSC experiments varying from 10 to 20°C.min-1, sample mass from 10 to 15mg and standard aluminum sample pan weighting, approximately, 27mg. In order to contribute to a better comprehension of DSC behavior in different heating rates, this work correlates as high heating rate influences to the thermal events in DSC experiments. Samples of metallic standard (In, Pb, Sn and Zn) with masses varying from 0.570mg to 20.9mg were analyzed in multiples sample heating rate from 4 to 324°C. min-1. In order to make properly all those experiments, a precise and careful temperature and enthalpy calibrations were performed and deeply discussed. Thus, this work shows a DSC methodology able to generate good and reliable results on experiments under any researcher choice heating rates to characterize the advanced materials used, for example, for aerospace industry. Also it helps the DSC users to find in their available instruments, already installed, a better and more accurate DSC test results, improving in just one shot the analysis sensitivity and resolution. Polypropylene melting and enthalpy thermal events are also studied using both the conventional DSC method and high heating rate method.

Extrapolation of zircon fission-track annealing models

One of the purposes of this study is to give further constraints on the temperature range of the zircon partial annealing zone over a geological time scale using data from borehole zircon samples, which have experienced stable temperatures for ∼1 Ma. In this way, the extrapolation problem is explicitly addressed by fitting the zircon annealing models with geological timescale data. Several empirical model formulations have been proposed to perform these calibrations and have been compared in this work. The basic form proposed for annealing models is the Arrhenius-type model. There are other annealing models, that are based on the same general formulation. These empirical model equations have been preferred due to the great number of phenomena from track formation to chemical etching that are not well understood. However, there are two other models, which try to establish a direct correlation between their parameters and the related phenomena. To compare the response of the different annealing models, thermal indexes, such as closure temperature, total annealing temperature and the partial annealing zone, have been calculated and compared with field evidence. After comparing the different models, it was concluded that the fanning curvilinear models yield the best agreement between predicted index temperatures and field evidence. © 2012 Elsevier Ltd. All rights reserved.

A comparison between neutron-fluence measurements using metal-activation monitors and standard glasses calibrated via thin uranium-fission monitors and via ηq method

The two fundamental approaches to fission-track dating involve either an explicit determination of the thermal neutron fluence (φ-method) or a calibration against age standards (ζ-method). The neutron fluence measurements are carried out with metal-activation monitors or with uranium-fission monitors, co-irradiated with the samples. Uranium-fission monitors consist of either a thin mono-atomic) film, or a thick fission source (standard uranium glass) irradiated against a muscovite external track detector. In this work, different techniques for performing neutron-fluence measurements were compared: based on thin-film calibration, based on thick-source calibration, and based on gamma spectrometry of co-irradiated metal monitors (Au, Co). The results suggest that more experiments are needed to make all calibrations consistent, including new measurements of the length of etched induced tracks in mica. Also the standard glass calibration carried out with thin films should be confirmed with a greater number of calibrating irradiations. © 2013 Elsevier Ltd. All rights reserved.

Estimates of hourly diffuse radiation on tilted surfaces in southeast of brazil

The global radiation incident on a tilted surfaces consists of components direct, diffuse and reflected from the ground. On a hourly database, the direct radiation can be calculated by geometric projections (ratio of the incidence angle to the solar zenith angle). The reflected radiation has a small effect on calculations and may be calculated with an isotropic model. Both components presents dependence of measures in incidence or horizontal surface. The great difficulty is to evaluate the diffuse radiation by variations of circumsolar, brightness horizontal, isotropic and anisotropic subcomponents. This study evaluated twenty models to estimate hourly diffuse radiation incident on tilted surfaces at 12.85° (latitude - 10°), 22.85° (latitude) and 32.85° (latitude + 10°) facing to North, under different cloudiness sky conditions, in Botucatu, São Paulo State, Brazil (22°53' S, 48°26' W and 786 m above the mean sea level). In contrast, models for estimating the diffuse component show major differences, which justify the validation for local calibrations. There is a decrease of the maximum total radiation scattered with increasing atmospheric transmissivity and inclination angle. The best results are obtained by anisotropic models: Ma and Iqbal, Hay, Reindl et al. and Willmott; isotropic: Badescu and Koronakis, and the Circumsolar model. The increase of the inclination angle allows for a reduction in the performance of statistical parametric models for estimating the hourly diffuse radiation.

Levantamento para a implantação de um sistema de gestão da qualidade segundo a norma NBR ISO/IEC 17025:2005 no Laboratório de celulose e papel da UNESP-Itapeva

The aim of this study is to perform a situational analysis of the Laboratory of pulp and paper-UNESP ITAPEVA for conducting proposal the accreditation according to ISO / IEC 17025:2005. The ISO / IEC 17025 establishes the criteria for those laboratories wishing to demonstrate their technical competence, which have an effective quality system and are able to generate technically valid results, establishing a single international standard for certifying the competence of laboratories to carry tests and / or calibrations, including sampling. The case study was conducted on laboratory Pulp and Paper Universidade Estadual Paulista (UNESP), campus Itapeva, where we compared the views of the technician responsible for the laboratory and a regular user. The generated conclusion is that the laboratory is unable to initiate an accreditation process, because it fails the requirements such as quality manual, register of subcontractors, research of customer satisfaction, schedule of internal audits, schedule for completion of critical analysis, profile of the functions required, functions current description, documentation of technical requirements for accommodation and environmental conditions, calibration programs, equipment calibration program, programs calibration standards and reports and / or certificate of test and / or calibration, that are in accordance with ISO / IEC 17025:2005, beyond that there is not the possibility to develop and implement a quality system without the commitment of everyone involved, regardless of the functional hierarchy

Análise comparativa dos resultados obtidos pelos métodos de calibração de campo tridimensional e bidimensional

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)