Due to its exceptional mechanical and electrical properties, graphene (one layer sheet of carbon atoms) has attracted a lot of attention since its discovery in 2004. The purpose of this research is to compare the Raman spectra of graphene with plasma treated graphene sheets which have been treated by changing the different parameters affecting the plasma treatment like gas flow, power and pressure and treatment time. The graphene we used for our high pressure studies are 4-5 layer CVD deposited graphene samples prepared by our collaborators in Dr. W. B. Choi’s group. First we report a Raman spectroscopy study of graphene on copper substrate at high pressures. Diamond anvil cell (DAC) was used to generate pressure. In situ Raman spectra were collected at pressures up to 10 GPa. The results indicate that the G band of graphene shifts with pressure significantly (about 5 cm-1/GPa) whereas the 2D band changes very little. The plasma treated samples were loaded into DAC. Raman spectrum was captured. Parts of the spectrum which were not related to the grapheme peak position were eliminated. The background was reduced. Peaks were found and fitted using FITYK software and the shift of each peak compared to its last position was observed when the pressure was increased. Next we studied plasma treated graphene samples treated with different partial pressure treatments under high pressure and compared them to each other using zirconia anvil cell with the same method.

Les enjeux économiques autour du vin sont importants et induisent de nombreuses fraudes. De nombreuses méthodes d'analyse chimique existent mais elles sont souvent destructives et invasives. La spectroscopie Raman est à priori prometteuse et n'a jamais été exploitée à des fins d'analyse, de traçabilité et d'authentification des vins. Le but de cette thèse est d'en évaluer le potentiel à travers l'étude d'un panel de vins et de solutions modèles. Nous avons en particulier, par une approche combinant expérience et simulations DFT, cherché à identifier les familles moléculaires à l'origine de la diffusion Raman et de l'émission de fluorescence induites par laser. / The economic stakes around the wine are important and lead to many frauds. Many methods of chemical analysis exist, but they are often destructive and invasive. Although Raman spectroscopy is a promising technique, it has never been used for analysis, traceability and anthentication of wines. The aim of this thesis is to evaluate its potential through the study of panel of wines and model solutions. It has been tried to identify, by an approach combining experiment and DFT simulations, the molecular families which lead to the Raman scattering and also to the emission of laser-induced fluorescence.

Polarized Raman Spectroscopy (PRS) is one of the experimental methods which can be employed to deduce orientational order parameters, e.g. 〈P_200 〉, 〈P_400 〉, in liquid crystals from the experimental depolarization ratio graph via fitting. However, it has long been known that the order parameters deduced from the different vibrational modes are found to be different within the same sample. As a result, only certain vibrational modes can be reliably selected for analysis, limiting the application of PRS. The possible explanations are discussed in this thesis. The first explanation is given by considering a dipole tilt β_0 which is defined as the tilt angle of the dipole vibrational direction and the molecular long axis. A second explanation comes from assuming different vibrational symmetries, i.e. cylindrical or elliptic cylindrical. Molecular biaxial order parameters are introduced in both explanations. A systematic check via calculation shows that a common set of order parameters (including molecular biaxial order parameters) can be obtained with different depolarization ratio graphs when the explanations are considered. Both depolarization ratio graphs can also agree well with that obtained from phenyl and cyano stretching modes experimentally. A supplementary discussion shows that by using the first explanation, 〈P_400 〉 which, in previous fitting, shown an excessive value by using cyano stretching mode is reduced (15% reduced at β_0=15°, 〈P_402 〉=0.0536). PRS is also employed to analyse the order parameters in a bent-core system using a molecular model with the bend angle Ω and tilt angle B_0. The effects of each of the uniaxial and phase biaxial order parameters are considered. With a total Raman tensor generated by the sum of Raman tensor from each arm, reasonable uniaxial order parameters fitting values can be obtained from PRS without considering biaxial order parameters. These results agree well with those deduced from the refractive index measurements, which shows a new approach to the investigation of bent-core systems. However, it is also shown that introducing phase biaxial order parameters can’t provide robust fitting, leading inaccurate fitting values in the end. Several different liquid crystals (5CB, E7, HAT-6 and SSY) have been examined on seeking graphene/graphene oxide dispersions in liquid crystal systems. Unfortunately, no stable dispersion was obtained by applying simple experimental techniques. However, a highlight comes from the test of a lyotropic liquid crystal formed by a discotic molecule in NMP suggesting a possible dispersion medium for graphene. Meanwhile, by using Raman spectroscopy, the interaction between liquid crystal molecules and graphene can be obtained from the peak shift of vibrational modes. The experimental results suggest a stronger interaction in E7 compared to 5CB. No shift in ZLI-1695 indicates the different effects from the rigid core. Further, the discotic liquid crystal (HAT-6) shows a strong interaction with graphene. These facts lead to a conclusion that the interaction still exists in the graphene/liquid crystal dispersion providing a guide on controlling and optimizing the dispersion quality for the future research.

Raman spectroscopy has been used to monitor the deformation of natural cellulose whisker polymer nanocomposites. Cotton and tunicate whiskers were used as reinforcements in polymer matrices. Raman spectra from the nanocomposites highlight an intense band located at the 1095 cm-1 position. This band is reported to shift towards a lower wavenumber under the application of tensile deformation. On the other hand, the compressive deformation of the composite gives rise to an increase in the position of this Raman band. The shifts correspond to the direct deformation of the molecular backbone of cellulose, which is dominated by a C-O stretching mode. The Raman band located at 1095 cm-1 is shown to shift non-linearly before it reaches a plateau due to the breakdown of the whisker-matrix interface. The initial shift rate is associated with the stiffness of the cellulose whiskers. The stiffnesses of single whiskers of cotton and tunicate are found to be 58 and 155 GPa respectively, assuming two dimensional (2D) in-plane distribution of whiskers. Cyclic deformation tests of the composites provide an insight into understanding the behaviour of the whisker-polymer matrix interface under tension and compression. It is found that residual compressive stress occurs during each cycle of the deformation. The level of disruption at the whisker-matrix interface is determined by estimating the energy dissipation, which is proportional to the hysteresis area. Local orientation is also observed in the nanocomposites produced by solution casting and subsequent melt pressing. Dark regions of the composites viewed under a polarised optical microscopy are found to represent areas in which the cellulose whiskers form a randomly oriented whisker network. A shift rate for the Raman band initially located at 1095 cm-1 obtained in the dark regions of 12.2 vol% tunicate whisker poly(vinyl acetate) nanocomposites is found to be -0.5±0.07 cm-1%-1, which is lower than -1.2±0.04 cm-1%-1 from the bright regions. Exposure to water and temperature during the deformation of the nanocomposites results in significant changes in stress transfer between the whiskers and the matrix. It is shown that the interface can be 'switched-off' for the poly(vinyl acetate)/whisker system in the presence of water and also at temperature above the glass transition.

In this work, structure/property relationships in polypropylene (PP) nanocomposites have been investigated for different nanofillers. Nanofillers of modified clay based on montmorillonite (MMT) and multi-wall carbon nanotubes (MWNTs) have been selected and incorporated to the PP matrix as either single nanofillers or hybrid nanofillers. Melt mixing via a twin screw extruder and further moulding by injection moulding have been used to prepare PP nanocomposites. Moreover, the dilution of MWNT masterbatch has been used to prepare PP/MWNT and PP/clay/MWNT nanocomposites. Three types of the PP nanocomposites have been obtained: PP/clay, PP/MWNT and PP/clay/MWNT nanocomposites. In all three types of the PP nanocomposites, α- and -PP crystals were observed in the wide angle X-ray diffraction (WAXD) patterns. Furthermore, the addition of nanofillers to the PP did not appear to affect the PP orientation. Slight PP orientation in the PP nanocomposites was shown in the two-dimensional X-ray diffraction (2D-XRD) patterns. Mixed clay layers were combined in the PP/clay and PP/clay/MWNT nanocomposites and investigated by WAXD as well as transmission electron microscopy (TEM). In addition, the aggregated and individual MWNTs were present in both the PP/MWNT and PP/clay/MWNT nanocomposites TEM images. A rough fracture surface with cracks was revealed from the scanning electron microscopy (SEM) images of the three types of PP nanocomposites. Polarized optical microscopy (POM) micrographs were taken at different temperatures during cooling in a hot stage and revealed the limitation of PP spherulite growth upon adding the nanofillers to the PP. The incorporation of nanofillers was found not to affect the glass transition temperature (Tg) of PP which investigated by dynamic mechanical analysis (DMA). However, the increase of both the peak melting temperature (Tm) and the peak crystallization temperature (Tc) of PP with adding the nanofillers was shown by differential scanning calorimetry (DSC) thermograms. In addition, the nanofillers also have been shown to act as nucleating agents. The thermal stability of PP in a nitrogen atmosphere was enhanced by the nanofillers when examined by thermogravimatric analysis (TGA). DMA and tensile testing were performed and showed that the nanofillers act as reinforcement for the PP. The distribution, orientation and deformation of MWNTs in the PP/MWNT and PP/clay/MWNT nanocomposites have been followed by Raman spectroscopy. Significant shifts of the Raman G'-band from the MWNTs was obtained during deformation of the MWNT nanocomposites and the hybrid clay/MWNT nanocomposites as the stress transfer from the PP matrix to the MWNTs has occurred. A correlation between calculated modulus from deformation and measured modulus from DMA and tensile testing has been found for PP/MWNT and PP/clay/MWNT nanocomposites. Finally, the PP nanocomposites have been considered for use in packaging applications.

Orientadores: Ronei Jesus Poppi, Cesar Alexandre de Mello / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T13:51:34Z (GMT). No. of bitstreams: 1 Ribeiro_DiorginisBuenoMontrazi_D.pdf: 1788617 bytes, checksum: f8b9685d4131466922bc03a5fa000661 (MD5) Previous issue date: 2009 / Resumo: Nesta tese metodologias analíticas foram desenvolvidas empregando espectroscopia Raman de baixa resolução amplificada por superfície (SERS) e calibração multivariada baseada no método dos mínimos quadrados parciais (PLS) para determinação dos pesticidas endosulfan e metamidofos (e misturas deles) em água, e do hormônio tireoestimulante (TSH) em plasma. Para a construção dos modelos de calibração dos pesticidas, um total de 70 e 30 amostras compuseram os conjuntos de calibração e validação, respectivamente, sendo a divisão realizada pelo algoritmo de Kennard-Stone. Já na construção dos modelos de calibração para a determinação quantitativa dos pesticidas nas misturas, um total de 38 e 11 amostras foram utilizadas na calibração e validação respectivamente. Para construção dos modelos de calibração para quantificação de TSH, um total de 39 mostras foram utilizadas na calibração e 14 amostras de plasma foram utilizadas na validação. As amostras também foram divididas pelo algoritmo de Kennard-Stone. Os modelos foram desenvolvidos utilizando diferentes tipos de pré-processamentos de sinais e comparados através dos erros de previsão (RMSEP). Foram utilizados como pré-processamento, o filtro de transformada de Fourier, a correção de espalhamento multiplicativa, a transformação padrão normal de variação, a ortogonalização de espectros pelo metodo de Gram-Schmidt, a centralização e autoescalamento dos dados. Os melhores modelos foram validados através da determinação de figuras de merito. Foram avaliados a exatidão, sensibilidade, sensibilidade analítica, seletividade, ajuste, razão sinal/ruído, limites de detecção e quantificação. A metodologia proposta mostrou-se rápida, de baixo custo e apresentou erros abaixo de 10mg/L para os pesticidas e abaixo de 0,8 mUI/mL para TSH, podendo facilmente ser adaptada para o monitoramento de pesticidas em águas e também em análises laboratoriais de rotina para determinação de TSH. / Abstract: In this thesis analytical methodologies were developed employing low resolution surface enhanced Raman spectroscopy (SERS) and multivariate calibration based on partial least squares method (PLS) for determination of the pesticides endosulfan and methamidophos (and mixtures of them) in water and the thyroid stimulating hormone (TSH) in plasma. For the pesticides calibration model development, a total of 70 and 30 samples composed the calibration and validation sets, respectively, using the Kennard-Stone algorithm for samples separation. In the model development for the mixture of pesticides, a total of 38 and 11 samples were used in the calibration and validation sets, respectively. For the model development in the TSH determination, 39 samples were used in the calibration set and 14 in the validation set. Also the Kennard-Stone algorithm was used to split the samples into the two data sets. The models were developed using different preprocessing methods and compared by using the prediction errors (RMSEP). The following pre-processing were tested: Fourier transform filter, multiplicative scatter correction, standard normal variate, spectra orthogonalization by Gram-Schmidt method, mean center and autoscaling. The best models were validated by figures of merit determination. It was assessed the accuracy, sensibility, analytical sensibility, selectivity, fit, signal/noise ratio, detection and quantification limits. The proposed methodology is fast, has low cost and presented prediction errors below to 10 mg/L for the pesticides and below to 0.8mìUI/mL for TSH. It may easily be adapted for the pesticides monitoring in waters and also for routine laboratory analysis in TSH determination. / Doutorado / Quimica Analitica / Doutor em Ciências

Orientador: Italo Odone Mazali / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T22:22:44Z (GMT). No. of bitstreams: 1 Silva_IsaiasdeCastro_M.pdf: 4959698 bytes, checksum: 34689bf94c26337d3043ec67881ba30e (MD5) Previous issue date: 2015 / Resumo: Dado que o óxido de cério(IV) é um composto não-estequiométrico e que apresenta uma banda Raman sensível a mudanças na rede cristalina, utilizou-se a estratégia de oxidação e redução in situ empregando gases como agentes redutores e oxidantes para investigar as mudanças ocorridas no perfil da banda Raman do óxido de cério(IV), sintetizado em várias morfologias nanométricas com exposição específica de faces, em condições de controle da concentração de vacâncias de oxigênio não-estequiométricas. Foi observado um deslocamento para menores números de onda da freqüência do máximo da banda Raman quando a amostra se encontrava sob atmosfera redutora, e esse comportamento se mostrou reversível, de modo que a freqüência do máximo da banda deslocou-se para maiores números de onda quando em atmosfera oxidante. Esse deslocamento foi mais pronunciado na morfologia de nanobastões cominuídos, na qual predominam faces de índice {110}, que são favoráveis à formação de vacâncias de oxigênio não-estequiométricas. Ao correlacionar os resultados da espectroscopia Raman com outras técnicas sensíveis ao grau de não-estequiometria do composto, se observou aumento no parâmetro de rede na difratometria de raios X e perda de massa na determinação da capacidade de estoque de oxigênio, medida por termogravimetria, sob atmosfera redutora. As observações mostram que as responsáveis pelo deslocamento da frequência da banda Raman do óxido de cério(IV) são as vacâncias de oxigênio não-estequiométricas. Como certos espectros Raman apresentaram bandas assimétricas, a razão para tal poderia ser a ressonância de Fano, o que foi investigado variando-se a energia da radiação incidente. A razão para a assimetria não foi atribuída à ressonância de Fano, mas sim há outra banda relacionada a modos vibracionais de superfície. Por fim se comparou as atividades catalíticas dos cristais de diferentes morfologias de óxido de cério(IV) frente à oxidação de monóxido de carbono, sendo que a morfologia de nanobastões cominuídos apresentou melhor desempenho. Como o mecanismo de oxidação depende das vacâncias de oxigênio não-estequiométricas, a formação dessas é facilitada na morfologia de nanobastões cominuídos, e por isso o deslocamento da banda Raman é mais pronunciado nessa morfologia / Abstract: One remarking property of cerium(IV) oxide (CeO2) is its oxygen storage capacity (OSC). This property is related to the presence of oxygen vacancies, as CeO2 is a non-stoichiometric oxide. Once CeO2 presents only one Raman active mode, which is sensitive to changes in CeO2 lattice like the oxygen vacancies, it has been investigated the influence of oxygen vacancies over CeO2 Raman band. The crystals were synthesized in different nanometric morphologies, with exposure of specific facets. The samples were characterized by X-ray powder diffraction, transmission electron microscopy, OSC measurements by thermogravimetric equipment and Raman spectroscopy. Besides the microscopy, all other characterizations were performed with in situ control of temperature and atmosphere. The morphology with dominant {110} facets, favorable for oxygen vacancies generation, presents lattice parameter expansion, loss of mass and Raman band maximum red-shift after reduction with hydrogen-containing atmosphere, and sequent lattice parameter contraction, gain of mass and Raman band maximum blue-shift after oxidation with oxygen-containing atmosphere. These observations present reversible behavior as the atmospheres are alternated, consequence of generation or extinction of oxygen vacancies. Thereby, the correct morphology choice for a CeO2 crystal favors oxygen vacancies generation, and once generated they result in CeO2 Raman band maximum red-shift / Mestrado / Quimica Inorganica / Mestre em Química

Photopolymerization of epoxy-acrylate hybrid resins takes advantages of inherent properties present in the free-radical and cationic reactions to reduce oxygen inhibition problems that plague free-radical reactions. Similarly, the combined reaction mechanisms reduce moisture sensitivity of the cationic reactions. Despite the advantages of epoxy-acrylate hybrid resins, problems persist that need to be addressed. For example, low conversion and polymerization rate of the epoxides are a problem, because the fast acrylate conversion prevents the epoxide from reaching high conversion. Controlling phase separation is challenging, since two moieties with different properties are reacting. The physical properties of the polymer will be impacted by the availability of different moieties. High shrinkage stress results from the acrylate moiety, causing buckling and cracking in film and coating applications. The overall goal of this study is to use the fundamental knowledge of epoxy-acrylate hybrid resins to formulate industrially viable polymers. In order to achieve this goal, the study focuses on the following objectives: (I) determine the apparent activation energy of the hybrid monomer METHB, (II) increase epoxide conversion and polymerization rate of hybrid formulations, and (III) control physical properties in epoxy-acrylate hybrid resins. In order to increase the epoxide conversion and rate of polymerization, the sensitivity of epoxides to alcohol is used to facilitate the activated monomer (AM) mechanism and induce a covalent bond between the epoxide and acrylate polymers through the hydroxyl group. It is hypothesized that if the AM mechanism is facilitated, epoxide conversion will increase. As a result, the resins can be tailored to control phase separation and physical properties, and shrinkage stress can be reduced. In pursuit of these objectives, the hybrid monomer METHB was polymerized at temperatures ranging from 30°C to 70°C to obtain apparent activation energy of 23.49 kJ/mol for acrylate and 57 kJ/mol for epoxide moeities. Then, hybrid systems pairing hydroxyl-containing acrylates with epoxides were formulated to promote the faster AM mechanism. Monomer composition was changed in the presence of hydroxyl-containing acrylate, and initiators were carefully selected in order to control phase separation. The conversion of acrylate and epoxide was monitored in real time by Raman spectroscopy. The physical and mechanical properties were monitored using dynamic mechanical analysis. Epoxide conversion and rate of polymerization in epoxide-acrylate hybrid monomer systems were shown to increase through the introduction of a hydroxyl group on the meth/acrylate monomer, taking advantage of the faster AM mechanism. In addition, this covalent bond linking the epoxide network to the meth/acrylate polymer chains resulted in little or no phase separation and a reduction of the Tg for the hybrid polymer compared to the neat epoxide. Fundamental knowledge gained from this research will enable the use of epoxy-acrylate hybrid resins in variety of applications. For instance, shrinkage may be reduced in dental fillings, noise and vibration problems in aircraft and other machinery may be controlled, and photopolymerization cost could be reduced in thin film applications.

Electrodeposition is a novel method for fabrication of diamond-like carbon (DLC) films on metal substrates. In this work, DLC was electrochemically deposited on different substrates based on an anodic oxidation cyclization of acetylene in liquid ammonia. Successfully anodic deposition was carried out for DLC onto nickel substrate at temperatures below -40°C. Comparative studies were performed on a series of different carbon sources (acetylene, sodium acetylide, and a mixture of acetylene and sodium acetylide). The films were characterized using a variety of methods including Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), XPS valence band spectra, and/or scanning electron microscopy (SEM). Raman spectroscopy is used as a bench mark technique to verify the presence of deposited DLC films, to access the films homogeneities, and to provide the ratio of the different carbon phases, mainly disordered graphite (D) and graphite (G) phases in the films. A combination of the Raman with FTIR and valence band spectra analysis allowed the distinction between hydrogenated DLC and unhydrogenated DLC films. Three different kinds of DLC [(1) hydrogenated DLC (a-C:H); (2) tetrahedral hydrogenated DLC (ta-C:H); and (3) graphitic-like DLC] were deposited depending upon the deposition conditions and substrates. Temperature and current density are the most important parameters to govern the quality of the deposited films, where adding of acetylide into the electrolyte led to films with a higher degree of graphitic phases. The proposed mechanism for acetylene anodic oxidation does not involve direct electron transfer but electrochemical cyclization of acetylene radical cations and hydrogen abstraction at the termination steps. Sodium acetylide, however, dissociates to an acetylenic ion, C2H-, in liquid ammonia. The electrochemistry heterogeneity also leads to island and two-dimensional (2D) nucleation growth of DLC films. Different bond formations of metal to carbon and different chemisorptions of acetylene on metal play important roles in governing the film properties. Using mixed C2HNa and C2H2 as electrolyte, polycrystalline diamond and hexagonal diamond are formed on Mo and stainless steel, respectively. This is the first time to report that polycrystalline diamond can be grown electrochemically at temperature below -40ºC. The preliminary studies on substrate pretreatment with diamond powder and SiC 600 are studied. The effect of the substrate on the film quality for the electrodeposited DLC films described herein is similar to that for diamond deposition via chemical vapor deposition (CVD).

Surface-enhanced Raman spectroscopy (SERS) is an emerging and sensitive technique in food analysis providing advantages of rapid detection, simple sample preparation and on-site detection capability over GC and LC methods. Most SERS applications focus on detecting trace amount of analyte in liquid as an alternative approach to HPLC. Herein, we invented an innovative SERS-active needle which is composed with an injection needle and a gold-nanoparticles coated fiber inside the injection needle. The gold nanoparticles-coated fiber was fabricated by reducing gold (III) on a chemically etched stainless wire. The SERS needle can be used to insert into the headspace and liquid sample for simultaneous multiphase sample detection, or a soft tissue like a tomato fruit to detect the analyte inside of the tissue with minimum invasion. Using this needle, we can detect as low as 5 ppb of fonofos in the headspace of water and apple juice samples, compared with the dip method, which cannot detect lower than 10 ppb in water and 50 ppb in apple juice. The SERS needle was also applied in real time pesticide translocation study to monitor internalized thiabendazole in tomato fruit after root uptake. The SERS needle detected thiabendazole inside tomato fruits 30 days after the pesticide exposure in a hydroponic planting environment. Moreover, realizing the advantage of detecting volatile components in the headspace of food sample, we applied the SERS needle in a ground beef spoilage study to detect the spoilage biomarkers in the headspace of the raw beef. As a result, the SERS needle detected volatile spoilage compounds produced by bacteria Lactobacillus. Overall, this invention opens a new field of SERS strategy for broad analytical applications.