Growth and Raman scattering characterization of Cu2ZnSnS4 thin films

In the present work we report the results of the growth, morphological and structural characterization of Cu2ZnSnS4 (CZTS) thin films prepared by sulfurization of DC magnetron sputtered Cu/Zn/Sn precursor layers. The adjustment of the thicknesses and the properties of the precursors were used to control the final composition of the films. Its properties were studied by SEM/EDS, XRD and Raman scattering. The influence of the sulfurization temperature on the morphology, composition and structure of the films has been studied. With the presented method we have been able to prepare CZTS thin films with the kesterite structure.

Study of polycrystalline Cu2ZnSnS4 films by Raman scattering

Cu2ZnSnS4 (CZTS) is a p-type semiconductor that has been seen as a possible low-cost replacement for Cu(In,Ga)Se2 in thin film solar cells. So far compound has presented difficulties in its growth, mainly, because of the formation of secondary phases like ZnS, CuxSnSx+1, SnxSy, Cu2−xS and MoS2. X-ray diffraction analysis (XRD), which is mostly used for phase identification cannot resolve some of these phases from the kesterite/stannite CZTS and thus the use of a complementary technique is needed. Raman scattering analysis can help distinguishing these phases not only laterally but also in depth. Knowing the absorption coefficient and using different excitation wavelengths in Raman scattering analysis, one is capable of profiling the different phases present in multi-phase CZTS thin films. This work describes in a concise form the methods used to grow chalcogenide compounds, such as, CZTS, CuxSnSx+1, SnxSy and cubic ZnS based on the sulphurization of stacked metallic precursors. The results of the films’ characterization by XRD, electron backscatter diffraction and scanning electron microscopy/energy dispersive spectroscopy techniques are presented for the CZTS phase. The limitation of XRD to identify some of the possible phases that can remain after the sulphurization process are investigated. The results of the Raman analysis of the phases formed in this growth method and the advantage of using this technique in identifying them are presented. Using different excitation wavelengths it is also analysed the CZTS film in depth showing that this technique can be used as non destructive methods to detect secondary phases.

Mapas por microscopia de Raman caso de estudo: cerâmicas arqueológicas portuguesas da idade do ferro provenientes do Castro de Azougada

Dissertação de Mestrado em Conservação e Restauro área de Especialização de Cerâmica e Vidro

Controlo de reacções de polimerização em miniemulsão através de técnicas de espectroscopia NIR e Raman

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Untersuchungen zur Nutzvolumenkapazität von stark sauren Kationenaustauschern

Ionenaustausch zieht sich durch viele Wissenschafts- und Wirtschaftsanwendungen. Diese Technologie wird allgemein zur Entfernung von gelösten Ionen aus einer wässrigen Phase genutzt. Erst in den 1950er Jahren entwickelt, ist sie heute voll ausgereift. Ihre Anwendung findet diese Technologie vor allem in der Wasseraufbereitung, Lebensmittel-, Chemie- und Pharmaindustrie. Die Demineralisierung von Wasser und die Wasserenthärtung sind vor allem in der Pharmaindustrie durch ihre hohen Wasserqualitätsansprüche von Bedeutung. Sogar für wertvolle Materialien, wie Uran und Plutonium, aus dem Abfall der nuklearen Industrie können Ionenaustauscher eingesetzt werden. Die elektrostatische Sorption in das Ionenaustauschermaterial ist entscheidend. Die entfernten Ionen aus dem Austauscher, werden durch die gleiche Ionenanzahl dergleichen Ladung in der Lösung ersetzt. Der Ionenaustausch wird durch verschiedene Parameter beeinflusst. Ein wichtiger Parameter ist die Kapazität und somit die Nutzzeit des Austauscherharzes im Betrieb. Somit spiegelt die Kapazität die Wirtschaftlichkeitdes Harzes wieder. Die Kapazität wird in Gesamtkapazität und nutzbare Kapazität unterschieden. Die Gesamtkapazität stellt die Gesamtzahl der austauschbaren Ionen dar. Die nutzbare Kapazität ist stets niedriger. Diese misst die Anzahl der Aktivgruppen,wo Ionenaustausch in der Sättigungsphase wirklich stattgefunden hat. Diese Arbeit soll einen Überblick über das große Thema der Ionenaustauscher geben. Dabei wird erläutert, was Ionenaustauscher sind und wie sie funktionieren. Im experimentellen Teil wird die nutzbare Kapazität eines stark sauren Kationenaustauschers bestimmt.

The Discrimination of Colored Acrylic, Cotton, and Wool Textile Fibers Using Micro-Raman Spectroscopy. Part 1 : In Situ Detection and Characterization of Dyes

Raman spectroscopy has been applied to characterize fiber dyes and determine the discriminating ability of the method. Black, blue, and red acrylic, cotton, and wool samples were analyzed. Four excitation sources were used to obtain complementary responses in the case of fluorescent samples. Fibers that did not provide informative spectra using a given laser were usually detected using another wavelength. For any colored acrylic, the 633-nm laser did not provide Raman information. The 514-nm laser provided the highest discrimination for blue and black cotton, but half of the blue cottons produced noninformative spectra. The 830-nm laser exhibited the highest discrimination for red cotton. Both visible lasers provided the highest discrimination for black and blue wool, and NIR lasers produced remarkable separation for red and black wool. This study shows that the discriminating ability of Raman spectroscopy depends on the fiber type, color, and the laser wavelength.

The application of chemometrics on Infrared and Raman spectra as a tool for the forensic analysis of paints

The aim of this work is to evaluate the capabilities and limitations of chemometric methods and other mathematical treatments applied on spectroscopic data and more specifically on paint samples. The uniqueness of the spectroscopic data comes from the fact that they are multivariate - a few thousands variables - and highly correlated. Statistical methods are used to study and discriminate samples. A collection of 34 red paint samples was measured by Infrared and Raman spectroscopy. Data pretreatment and variable selection demonstrated that the use of Standard Normal Variate (SNV), together with removal of the noisy variables by a selection of the wavelengths from 650 to 1830 cm−1 and 2730-3600 cm−1, provided the optimal results for infrared analysis. Principal component analysis (PCA) and hierarchical clusters analysis (HCA) were then used as exploratory techniques to provide evidence of structure in the data, cluster, or detect outliers. With the FTIR spectra, the Principal Components (PCs) correspond to binder types and the presence/absence of calcium carbonate. 83% of the total variance is explained by the four first PCs. As for the Raman spectra, we observe six different clusters corresponding to the different pigment compositions when plotting the first two PCs, which account for 37% and 20% respectively of the total variance. In conclusion, the use of chemometrics for the forensic analysis of paints provides a valuable tool for objective decision-making, a reduction of the possible classification errors, and a better efficiency, having robust results with time saving data treatments.

Evaluation de spectromètres portables Raman, Infrarouge et Proche Infrarouge pour la détection de contrefaçons de médicaments

La contrefaçon de médicaments est un délit qui n'a cessé d'augmenter ces dernières années. Diff érents spectromètres portables ont été proposés sur le marché afi n de permettre une détection rapide des contrefaçons sur le terrain. Les spectroscopies Raman, Infrarouge et Proche Infrarouge présentent des caractéristiques intéressantes pour l'analyse de médicaments douteux, propriétés qui sont exposées dans cet article. Une comparaison des diff érents instruments portables permet de présenter l'intérêt d'utiliser ces spectromètres pour la détection de contrefaçons.

Applications of a transportable Raman spectrometer for the in situ detection of controlled substances at border controls

A transportable Raman spectrometer was tested for the detection of illicit drugs seized during border controls. In a first step, the analysis methodology was optimized using reference substances such as diacetylmorphine (heroin), cocaine and amphetamine (as powder or liquid forms). Adequate focalisation distance and times of analysis, influence of daylight and artificial light sources, repeatability and limits of detection were studied. In a second step the applications and limitations of the technique to detect the illicit substances in different mixtures and containers was evaluated. Transportable Raman spectroscopy was found to be adequate for a rapid screen of liquids and powders for the detection and identification of controlled substances. Additionally, it had the advantage over other portable techniques, such as ion mobility spectrometry, of being non-destructive and capable of rapid analysis of large quantities of substances through containers such as plastic bags and glass bottles.

Identification of pharmaceutical tablets by Raman spectroscopy and chemometrics

Raman spectroscopy has become an attractive tool for the analysis of pharmaceutical solid dosage forms. In the present study it is used to ensure the identity of tablets. The two main applications of this method are release of final products in quality control and detection of counterfeits. Twenty-five product families of tablets have been included in the spectral library and a non-linear classification method, the Support Vector Machines (SVMs), has been employed. Two calibrations have been developed in cascade: the first one identifies the product family while the second one specifies the formulation. A product family comprises different formulations that have the same active pharmaceutical ingredient (API) but in a different amount. Once the tablets have been classified by the SVM model, API peaks detection and correlation are applied in order to have a specific method for the identification and allow in the future to discriminate counterfeits from genuine products. This calibration strategy enables the identification of 25 product families without error and in the absence of prior information about the sample. Raman spectroscopy coupled with chemometrics is therefore a fast and accurate tool for the identification of pharmaceutical tablets.

Detection, Determination of Chemical Composition and Chemical Profiling of Counterfeit Medicines by Raman Spectroscopy.

Raman spectroscopy has become a widespread technique for the analysis ofpharmaceutical solid forms. The application proposed here is the investigationof counterfeit medicines. This serious global issue requires quick and accurateidentification methods to fight against this phenomenon. Thanks to its chemicalselectivity, rapidity of analysis and potential of generating repeatable spectralprofiles, Raman spectroscopy presents distinct advantages for the analysis ofcounterfeits. Combined with chemometric tools, the technique enablesthe detection, the determination of chemical composition and the profiling ofmedicine counterfeits.

Volatilização de N-NH3 na cultura de milho:: II. avaliação de fontes sólidas e fluidas em sistema de plantio direto e convencional

Foram desenvolvidos dois experimentos em campo, em sistema de plantio direto (SPD) sobre cobertura de aveia-preta, em latossolo vermelho-escuro, distrófico, argiloso, e em sistema de plantio convencional (SPC), após cultivo de soja, em latossolo vermelho-amarelo distrófico arenoso, no Centro de Pesquisa Novartis-Seeds e na Fazenda Stª. Teresinha, Uberlândia (MG) respectivamente. O estudo objetivou avaliar as perdas por volatilização de N-NH3 da cobertura nitrogenada na cultura de milho com cerca de 100 kg ha-1 de N, de cinco fontes nitrogenadas em ambos os sistemas de plantio. As fontes nitrogenadas - sulfato de amônio, nitrato de amônio, uréia e duas soluções nitrogenadas constituídas de uréia + nitrato de amônio (uran) e uréia + nitrato de amônio + sulfato de amônio (sulfuran) - foram aplicadas na superfície e incorporadas no meio da entrelinha. Após a aplicação da cobertura, instalaram-se, ao acaso, três coletores do tipo semi-aberto estático, por tratamento, sendo efetuadas seis amostragens de N-NH3 volatilizado, em intervalos de quatro a cinco dias. No SPD, as perdas acumuladas de N-NH3 provenientes das fontes uréia, uran e sulfuran aplicadas na superfície foram, respectivamente, de 78,0; 37,2 e 26,9% do N aplicado. No SPC, as perdas mais significativas foram de uréia (30,7%) e uran (9,7%). O nitrato de amônio e o sulfato de amônio apresentaram perdas inferiores a 15,0% do N aplicado à superfície. A correlação das perdas por volatilizacão de N-NH3 e a produtividade dos dois experimentos mostraram um ajuste linear negativo, de tal forma que no SPD houve uma queda de produção de 13,3 kg de grãos e no SPC, de 11,8 kg de grãos para cada quilograma de N volatilizado.

L'application de la spectroscopie Raman en criminalistique pour l'analyse du colorant des fibres textiles en acrylique, coton et laine

RESUME La méthode de la spectroscopie Raman est une technique d'analyse chimique basée sur l'exploitation du phénomène de diffusion de la lumière (light scattering). Ce phénomène fut observé pour la première fois en 1928 par Raman et Krishnan. Ces observations permirent à Raman d'obtenir le Prix Nobel en physique en 1930. L'application de la spectroscopie Raman a été entreprise pour l'analyse du colorant de fibres textiles en acrylique, en coton et en laine de couleurs bleue, rouge et noire. Nous avons ainsi pu confirmer que la technique est adaptée pour l'analyse in situ de traces de taille microscopique. De plus, elle peut être qualifiée de rapide, non destructive et ne nécessite aucune préparation particulière des échantillons. Cependant, le phénomène de la fluorescence s'est révélé être l'inconvénient le plus important. Lors de l'analyse des fibres, différentes conditions analytiques ont été testées et il est apparu qu'elles dépendaient surtout du laser choisi. Son potentiel pour la détection et l'identification des colorants imprégnés dans les fibres a été confirmé dans cette étude. Une banque de données spectrale comprenant soixante colorants de référence a été réalisée dans le but d'identifier le colorant principal imprégné dans les fibres collectées. De plus, l'analyse de différents blocs de couleur, caractérisés par des échantillons d'origine inconnue demandés à diverses personnes, a permis de diviser ces derniers en plusieurs groupes et d'évaluer la rareté des configurations des spectres Raman obtenus. La capacité de la technique Raman à différencier ces échantillons a été évaluée et comparée à celle des méthodes conventionnelles pour l'analyse des fibres textiles, à savoir la micro spectrophotométrie UV-Vis (MSP) et la chromatographie sur couche mince (CCM). La technique Raman s'est révélée être moins discriminatoire que la MSP pour tous les blocs de couleurs considérés. C'est pourquoi dans le cadre d'une séquence analytique nous recommandons l'utilisation du Raman après celle de la méthode d'analyse de la couleur, à partir d'un nombre de sources lasers le plus élevé possible. Finalement, la possibilité de disposer d'instruments équipés avec plusieurs longueurs d'onde d'excitation, outre leur pouvoir de réduire la fluorescence, permet l'exploitation d'un plus grand nombre d'échantillons. ABSTRACT Raman spectroscopy allows for the measurement of the inelastic scattering of light due to the vibrational modes of a molecule when irradiated by an intense monochromatic source such as a laser. Such a phenomenon was observed for the first time by Raman and Krishnan in 1928. For this observation, Raman was awarded with the Nobel Prize in Physics in 1930. The application of Raman spectroscopy has been undertaken for the dye analysis of textile fibers. Blue, black and red acrylics, cottons and wools were examined. The Raman technique presents advantages such as non-destructive nature, fast analysis time, and the possibility of performing microscopic in situ analyses. However, the problem of fluorescence was often encountered. Several aspects were investigated according to the best analytical conditions for every type/color fiber combination. The potential of the technique for the detection and identification of dyes was confirmed. A spectral database of 60 reference dyes was built to detect the main dyes used for the coloration of fiber samples. Particular attention was placed on the discriminating power of the technique. Based on the results from the Raman analysis for the different blocs of color submitted to analyses, it was possible to obtain different classes of fibers according to the general shape of spectra. The ability of Raman spectroscopy to differentiate samples was compared to the one of the conventional techniques used for the analysis of textile fibers, like UV-Vis Microspectrophotometry (UV-Vis MSP) and thin layer chromatography (TLC). The Raman technique resulted to be less discriminative than MSP for every bloc of color considered in this study. Thus, it is recommended to use Raman spectroscopy after MSP and light microscopy to be considered for an analytical sequence. It was shown that using several laser wavelengths allowed for the reduction of fluorescence and for the exploitation of a higher number of samples.

Balanço da adubação nitrogenada sólida e fluida de cobertura na cultura de milho, em sistema plantio direto no Triângulo Mineiro (MG)

Foi desenvolvido um experimento com as fontes uréia e uran aplicadas superficialmente ou incorporadas (5-7 cm) na cobertura nitrogenada de milho, no sistema plantio direto, com o objetivo de efetuar, na colheita, um balanço do N-uréia (15N) e quantificar as perdas por volatilização de N-NH3 nesses tratamentos, assim como nos adicionais, testemunha e misturas de uréia + KCl (sólida) e uran + KCl (fluida), na formulação 6-0-9 (N-P2O5-K2O), aplicadas somente em superfície. Os tratamentos originaram-se de um fatorial 1 + (2 x 2) + 2, sendo a testemunha + o fatorial 2 x 2 (duas fontes; uréia e uran x duas formas de localização) + dois tratamentos adicionais, misturas uréia + KCl (sólida) e uran + KCl (fluida), dispostos em blocos casualizados com quatro repetições. O ensaio foi realizado em Latossolo Vermelho-Escuro muito argiloso fase cerrado relevo plano, no Centro de Pesquisa Novartis - Seeds do município de Uberlândia (MG). Cerca de 100 kg ha-1 de N foram aplicados no estádio fenológico de seis a oito folhas. Após 26 dias da adubação, as perdas acumuladas de N-NH3 nos tratamentos em superfície foram de 54, 41, 17 e 14% do N aplicado, para uréia, uréia + KCl, uran e uran + KCl, respectivamente. Quando a uréia e o uran foram incorporados ao solo, as perdas acumuladas de N-NH3 foram de 5,0 e 3,5% do N aplicado, respectivamente. Na colheita, o N da uréia absorvido pela planta (raízes + colmos + folhas + grãos) foi de 19,9 kg ha-1 (20,8% do N aplicado) e de 29,5 kg ha-1 (29,5% do N aplicado), quando aplicado na superfície e incorporado, respectivamente. O N-uréia do uran absorvido pela planta foi de 11,4 kg ha-1 (26,1% do N aplicado) e de 11,7 kg ha-1 (26,8% do N aplicado), quando aplicado na superfície ou incorporado, respectivamente. O N da uréia imobilizado na camada de 0-45 cm de profundidade foi, em média, de 9,9 kg ha-1 (10,0% do N aplicado), da aplicação superficial ou incorporada, e do N-uréia do uran foi de 3,3 kg ha-1 (7,6% do N aplicado). O N-mineral no solo derivado do N da uréia e do N-uréia do uran aplicados na superfície, no perfil de 0-150 cm, foi, respectivamente, de 2,4 e 3,2%, e de 5,9 e 2,5%, com as fontes incorporadas. No balanço global de N, em média, 13,7 e 50,3% do N da uréia não foram recuperados no sistema solo-planta, respectivamente, para a aplicação superficial ou incorporada; para o N-uréia do uran, obtiveram-se, respectivamente, 47,7 e 57,6%.

Volatilização de N-NH3 de fontes nitrogenadas em cana-de-açúcar colhida sem despalha a fogo

Com a colheita da cana sem queima, espessa camada de palha é depositada sobre o solo. A presença da palha modifica o agroecossistema, exigindo reformulação na tecnologia de manejo da cultura. Na adubação nitrogenada da cana-de-açúcar, a uréia é a fonte de N mais utilizada e, quando aplicada sobre a palha, apresenta elevadas taxas de perda de N-NH3 por volatilização. O objetivo deste estudo foi avaliar a eficiência agronômica de fontes nitrogenadas em sistema de colheita de cana sem queima prévia por meio de medidas das perdas de nitrogênio por volatilização da amônia, da determinação da qualidade e produtividade da cultura. Este estudo foi desenvolvido a partir de um experimento de campo, realizado na região canavieira de Piracicaba (SP), com a terceira soca do cultivar SP 80-1842, cultivado em Argissolo Vermelho-Amarelo distrófico arenoso, colhido sem queima e mecanicamente. A dose de nitrogênio foi de 100 kg ha-1. Os tratamentos estudados foram: T0- testemunha, T1- uréia, T2- uran, T3- uréia + sulfato de amônio e T4- resíduo líquido enriquecido com N. Perdas por volatilização de amônia foram avaliadas por meio de coletores semi-abertos estáticos. Os tratamentos T1 e T3 apresentaram maiores perdas por volatilização de NH3 (36 e 35 %, respectivamente)e os tratamentos T2 e T4 apresentaram menores perdas (15 e 9 %, respectivamente). As soqueiras responderam em produtividade à adubação nitrogenada e às perdas ocorridas por volatilização de N-NH3.