On the absolute calibration of bench-top small-angle X-ray scattering instruments: a comparison of different standard methods

Absolute calibration relates the measured (arbitrary) intensity to the differential scattering cross section of the sample, which contains all of the quantitative information specific to the material. The importance of absolute calibration in small-angle scattering experiments has long been recognized. This work details the absolute calibration procedure of a small-angle X-ray scattering instrument from Bruker AXS. The absolute calibration presented here was achieved by using a number of different types of primary and secondary standards. The samples were: a glassy carbon specimen, which had been independently calibrated from neutron radiation; a range of pure liquids, which can be used as primary standards as their differential scattering cross section is directly related to their isothermal compressibility; and a suspension of monodisperse silica particles for which the differential scattering cross section is obtained from Porod's law. Good agreement was obtained between the different standard samples, provided that care was taken to obtain significant signal averaging and all sources of background scattering were accounted for. The specimen best suited for routine calibration was the glassy carbon sample, due to its relatively intense scattering and stability over time; however, initial calibration from a primary source is necessary. Pure liquids can be used as primary calibration standards, but the measurements take significantly longer and are, therefore, less suited for frequent use.

Kalibrointimenetelmä planaaristen siirtojohtojen mittaamiseen

Tässä diplomityössä tutkittiin TRL-kalibroinnin käyttämistä tasomaisten siirtojohtojen sähköisten parametrien määrittämisessä taajuusalueella 0,3 – 12 GHz. Työssä perehdyttiin TRL-kalibroinnin käyttämiseen piirianalysaattorilla toteutettujen mittauksien mittauskalibrointiin sekä kalibrointiin tarvittavien kalibrointistandardien mitoittamiseen. Kalibrointistandardit suunniteltiin ja toteutettiin sekä mikroliuska- että liuskajohdoille, joiden toiminnallisuutta tarkasteltiin sekä taajuustason että aikatason mittausten avulla. Työssä perehdyttiin myös kalibrointistandardien liityntärajapinnan suunniteluun ja toteuttamiseen. Saatujen tulosten perusteella voitiin osoittaa mikroliuskajohtokitin soveltuvan hyvin mittauskalibroinnin toteuttamiseen tarkoissa mittaussovelluksissa.

Lithography-free micro- and nanostructuring based on conventional plasma etching

In now-a-days semiconductor and MEMS technologies the photolithography is the working horse for fabrication of functional devices. The conventional way (so called Top-Down approach) of microstructuring starts with photolithography, followed by patterning the structures using etching, especially dry etching. The requirements for smaller and hence faster devices lead to decrease of the feature size to the range of several nanometers. However, the production of devices in this scale range needs photolithography equipment, which must overcome the diffraction limit. Therefore, new photolithography techniques have been recently developed, but they are rather expensive and restricted to plane surfaces. Recently a new route has been presented - so-called Bottom-Up approach - where from a single atom or a molecule it is possible to obtain functional devices. This creates new field - Nanotechnology - where one speaks about structures with dimensions 1 - 100 nm, and which has the possibility to replace the conventional photolithography concerning its integral part - the self-assembly. However, this technique requires additional and special equipment and therefore is not yet widely applicable. This work presents a general scheme for the fabrication of silicon and silicon dioxide structures with lateral dimensions of less than 100 nm that avoids high-resolution photolithography processes. For the self-aligned formation of extremely small openings in silicon dioxide layers at in depth sharpened surface structures, the angle dependent etching rate distribution of silicon dioxide against plasma etching with a fluorocarbon gas (CHF3) was exploited. Subsequent anisotropic plasma etching of the silicon substrate material through the perforated silicon dioxide masking layer results in high aspect ratio trenches of approximately the same lateral dimensions. The latter can be reduced and precisely adjusted between 0 and 200 nm by thermal oxidation of the silicon structures owing to the volume expansion of silicon during the oxidation. On the basis of this a technology for the fabrication of SNOM calibration standards is presented. Additionally so-formed trenches were used as a template for CVD deposition of diamond resulting in high aspect ratio diamond knife. A lithography-free method for production of periodic and nonperiodic surface structures using the angular dependence of the etching rate is also presented. It combines the self-assembly of masking particles with the conventional plasma etching techniques known from microelectromechanical system technology. The method is generally applicable to bulk as well as layered materials. In this work, layers of glass spheres of different diameters were assembled on the sample surface forming a mask against plasma etching. Silicon surface structures with periodicity of 500 nm and feature dimensions of 20 nm were produced in this way. Thermal oxidation of the so structured silicon substrate offers the capability to vary the fill factor of the periodic structure owing to the volume expansion during oxidation but also to define silicon dioxide surface structures by selective plasma etching. Similar structures can be simply obtained by structuring silicon dioxide layers on silicon. The method offers a simple route for bridging the Nano- and Microtechnology and moreover, an uncomplicated way for photonic crystal fabrication.

Comparison of two extraction methods for evaluation of volatile constituents patterns in commercial whiskeys: Elucidation of the main odour-active compounds

An analytical procedure based on manual dynamic headspace solid-phase microextraction (HS-SPME) method and the conventional extraction method by liquid–liquid extraction (LLE), were compared for their effectiveness in the extraction and quantification of volatile compounds from commercial whiskey samples. Seven extraction solvents covering a wide range of polarities and two SPME fibres coatings, has been evaluated. The highest amounts extracted, were achieved using dichloromethane (CH2Cl2) by LLE method (LLECH2Cl2)(LLECH2Cl2) and using a CAR/PDMS fibre (SPMECAR/PDMS) in HS-SPME. Each method was used to determine the responses of 25 analytes from whiskeys and calibration standards, in order to provide sensitivity comparisons between the two methods. Calibration curves were established in a synthetic whiskey and linear correlation coefficient (r ) were greater than 0.9929 for LLECH2Cl2LLECH2Cl2 and 0.9935 for SPMECAR/PDMS, for all target compounds. Recoveries greater than 80% were achieved. For most compounds, precision (expressed by relative standard deviation, R.S.D.) are very good, with R.S.D. values lower than 14.78% for HS-SPME method and than 19.42% for LLE method. The detection limits ranged from 0.13 to 19.03 μg L−1 for SPME procedure and from 0.50 to 12.48 μg L−1 for LLE. A tentative study to estimate the contribution of a specific compound to the aroma of a whiskey, on the basis of their odour activity values (OAV) was made. Ethyl octanoate followed by isoamyl acetate and isobutyl alcohol, were found the most potent odour-active compounds.

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 de incerteza de um sistema automatizado para ensaios de aspersores de irrigação

Ensaios de distribuição de água de aspersores são convencionalmente realizados manualmente, requerendo tempo e mão de obra treinada. A automação desses ensaios proporciona redução da demanda por esses recursos e apresenta potencial para minimizar falhas e/ou desvios de procedimento. Atualmente, laboratórios de ensaio e calibração acreditados junto a organismos legais devem apresentar em seus relatórios a incerteza de medição de seus instrumentos e sistemas de medição. Além disso, normas de ensaio e calibração apresentam especificação de incerteza aceitável, como a norma de ensaios de distribuição de água por aspersores, ISO 15886-3 (2012), a qual exige uma incerteza expandida de até 3% em 80% dos coletores. Os objetivos deste trabalho foram desenvolver um sistema automatizado para os ensaios de aspersores em laboratório e realizar a análise de incerteza de medição, para sua quantificação nos resultados de ensaio e para dar suporte ao dimensionamento dos tubos de coleta. O sistema automático foi constituído por um subsistema de gerenciamento, por meio de um aplicativo supervisório, um de pressurização e um de coleta, por meio de módulos eletrônicos microprocessados desenvolvidos. De acordo com instruções do sistema de gerenciamento o sistema de pressurização ajustava a pressão no aspersor por meio do controle da rotação da motobomba, e o sistema de coleta realizava a medição da intensidade de precipitação de água ao longo do raio de alcance do aspersor. A água captada por cada coletor drenava para um tubo de coleta, que estava conectado a uma das válvulas solenoides de um conjunto, onde havia um transmissor de pressão. Cada válvula era acionada individualmente numa sequência para a medição do nível de água em cada tubo de coleta, por meio do transmissor. Por meio das análises realizadas, as menores incertezas foram obtidas para os menores diâmetros de tubo de coleta, sendo que se deve utilizar o menor diâmetro possível. Quanto ao tempo de coleta, houve redução da incerteza de medição ao se aumentar a duração, devendo haver um tempo mínimo para se atingir a incerteza-alvo. Apesar de cada intensidade requer um tempo mínimo para garantir a incerteza, a diferença mínima de nível a ser medida foi a mesma. Portanto, para os ensaios visando atender a incerteza, realizou-se o monitoramento da diferença de nível nos tubos, ou diferença de nível, facilitando a realização do ensaio. Outra condição de ensaio considerou um tempo de coleta para 30 voltas do aspersor, também exigido pela norma ISO 15886-3 (2012). A terceira condição considerou 1 h de coleta, como tradicionalmente realizado. As curvas de distribuição de água obtidas por meio do sistema desenvolvido foram semelhantes às obtidas em ensaios convencionais, para as três situações avaliadas. Para tempos de coleta de 1 h ou 30 voltas do aspersor o sistema automático requereu menos tempo total de ensaio que o ensaio convencional. Entretanto, o sistema desenvolvido demandou mais tempo para atingir a incerteza-alvo, o que é uma limitação, mesmo sendo automatizado. De qualquer forma, o sistema necessitava apenas que um técnico informasse os parâmetros de ensaio e o acionasse, possibilitando que o mesmo alocasse seu tempo em outras atividades.

Tungsten coil atomic emission spectrometry combined with dispersive liquid–liquid microextraction: A synergistic association for chromium determination in water samples

A novel and environment friendly analytical method is reported for total chromium determination and chromium speciation in water samples, whereby tungsten coil atomic emission spectrometry (WCAES) is combined with in situ ionic liquid formation dispersive liquid–liquid microextraction (in situ IL-DLLME). A two stage multivariate optimization approach has been developed employing a Plackett–Burman design for screening and selection of the significant factor involved in the in situ IL-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were complexant concentration: 0.5% (or 0.1%); complexant type: DDTC; IL anion: View the MathML sourcePF6−; [Hmim][Cl] IL amount: 60 mg; ionic strength: 0% NaCl; pH: 5 (or 2); centrifugation time: 10 min; and centrifugation speed: 1000 rpm. Under the optimized experimental conditions the method was evaluated and proper linearity was obtained with a correlation coefficient of 0.991 (5 calibration standards). Limits of detection and quantification for both chromium species were 3 and 10 µg L−1, respectively. This is a 233-fold improvement when compared with chromium determination by WCAES without using preconcentration. The repeatability of the proposed method was evaluated at two different spiking levels (10 and 50 µg L−1) obtaining coefficients of variation of 11.4% and 3.6% (n=3), respectively. A certified reference material (SRM-1643e NIST) was analyzed in order to determine the accuracy of the method for total chromium determination and 112.3% and 2.5 µg L−1 were the recovery (trueness) and standard deviation values, respectively. Tap, bottled mineral and natural mineral water samples were analyzed at 60 µg L−1 spiking level of total Cr content at two Cr(VI)/Cr(III) ratios, and relative recovery values ranged between 88% and 112% showing that the matrix has a negligible effect. To our knowledge, this is the first time that combines in situ IL-DLLME and WCAES.

Evaluation of performance reference compounds in polyethylene-based passive air samplers

Polyethylene-based passive air samplers (PSDs) were loaded with performance reference compounds (PRCs) and deployed in a wind tunnel to examine the effects of wind speed on sampler performance. PRCs could be loaded reproducibly into PSDs, with coefficients of variation only exceeding 20% for the more volatile compounds. When PSDs were exposed to low (0.5-1.5 m s(-1)) and high (3.5-4.5 m s(-1)) wind speeds, PRC loss rate constants generally increased with increasing wind speed and decreased with increasing sampler/air partition coefficients. PSD-based air concentrations calculated using PRC loss rate constants and sampler/air partition coefficients and air concentrations measured using active samplers compared closely. PRCs can be used to account for the effect of differences in wind speeds on sampler performance and measure air concentrations with reasonable accuracy. (c) 2006 Elsevier Ltd. All rights reserved.

Hair as a Biomarker for Manganese Exposure Among Welders

Thesis (Ph.D.)--University of Washington, 2016-08