Design, construction, and applications of a high-resolution terahertz time-domain spectrometer

This thesis reports on the design, construction, and initial applications of a high-resolution terahertz time-domain ASOPS spectrometer. The instrument employs asynchronous optical sampling (ASOPS) between two Ti:sapphire ultrafast lasers operating at a repetition rate of approximately 80 MHz, and we thus demonstrate a THz frequency resolution approaching the limit of that repetition rate. This is an order of magnitude improvement in resolution over typical THz time-domain spectrometers. The improved resolution is important for our primary effort of collecting THz spectra for far-infrared astronomy. We report on various spectroscopic applications including the THz rotational spectrum of water, where we achieve a mean frequency error, relative to established line centers, of 27.0 MHz. We also demonstrate application of the THz system to the long-duration observation of a coherent magnon mode in a anti-ferromagnetic yttrium iron oxide (YFeO3) crystal. Furthermore, we apply the all-optical virtual delay line of ASOPS to a transient thermoreflectance experiment for quickly measuring the thermal conductivity of semiconductors.

L1 track finding for a time multiplexed trigger

At the HL-LHC, proton bunches will cross each other every 25. ns, producing an average of 140 pp-collisions per bunch crossing. To operate in such an environment, the CMS experiment will need a L1 hardware trigger able to identify interesting events within a latency of 12.5. μs. The future L1 trigger will make use also of data coming from the silicon tracker to control the trigger rate. The architecture that will be used in future to process tracker data is still under discussion. One interesting proposal makes use of the Time Multiplexed Trigger concept, already implemented in the CMS calorimeter trigger for the Phase I trigger upgrade. The proposed track finding algorithm is based on the Hough Transform method. The algorithm has been tested using simulated pp-collision data. Results show a very good tracking efficiency. The algorithm will be demonstrated in hardware in the coming months using the MP7, which is a μTCA board with a powerful FPGA capable of handling data rates approaching 1. Tb/s.

Design and Applications of a Decade-Spanning Terahertz Frequency Comb Spectrometer: Doppler-limited Rotational Spectroscopy of Methanol and Methanol-OD

This thesis details the design and applications of a terahertz (THz) frequency comb spectrometer. The spectrometer employs two offset locked Ti:Sapphire femtosecond oscillators with repetition rates of approximately 80 MHz, offset locked at 100 Hz to continuously sample a time delay of 12.5 ns at a maximum time delay resolution of 15.6 fs. These oscillators emit continuous pulse trains, allowing the generation of a THz pulse train by the master, or pump, oscillator and the sampling of this THz pulse train by the slave, or probe, oscillator via the electro-optic effect. Collecting a train of 16 consecutive THz pulses and taking the Fourier transform of this pulse train produces a decade-spanning frequency comb, from 0.25 to 2.5 THz, with a comb tooth width of 5 MHz and a comb tooth spacing of ~80 MHz. This frequency comb is suitable for Doppler-limited rotational spectroscopy of small molecules. Here, the data from 68 individual scans at slightly different pump oscillator repetition rates were combined, producing an interleaved THz frequency comb spectrum, with a maximum interval between comb teeth of 1.4 MHz, enabling THz frequency comb spectroscopy.

The accuracy of the THz frequency comb spectrometer was tested, achieving a root mean square error of 92 kHz measuring selected absorption center frequencies of water vapor at 10 mTorr, and a root mean square error of 150 kHz in measurements of a K-stack of acetonitrile. This accuracy is sufficient for fitting of measured transitions to a model Hamiltonian to generate a predicted spectrum for molecules of interest in the fields of astronomy and physical chemistry. As such, the rotational spectra of methanol and methanol-OD were acquired by the spectrometer. Absorptions from 1.3 THz to 2.0 THz were compared to JPL catalog data for methanol and the spectrometer achieved an RMS error of 402 kHz, improving to 303 kHz when excluding low signal-to-noise absorptions. This level of accuracy compares favorably with the ~100 kHz accuracy achieved by JPL frequency multiplier submillimeter spectrometers. Additionally, the relative intensity performance of the THz frequency comb spectrometer is linear across the entire decade-spanning bandwidth, making it the preferred instrument for recovering lineshapes and taking absolute intensity measurements in the THz region. The data acquired by the Terahertz Frequency Comb Spectrometer for methanol-OD is of comparable accuracy to the methanol data and may be used to refine the fit parameters for the predicted spectrum of methanol-OD.

Improved Dynamic Headspace Sampling and Detection using Capillary Microextraction of Volatiles Coupled to Gas Chromatography Mass Spectrometry

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

Exoplanet atmospheres Characterization Observatory payload short-wave infrared channel: EChO SWiR

EChO (Exoplanet atmospheres Characterization Observatory), a proposal for exoplanets exploration space mission, is considered the next step for planetary atmospheres characterization. It would be a dedicated observatory to uncover a large selected sample of planets spanning a wide range of masses (from gas giants to super-Earths) and orbital temperatures (from hot to habitable). All targets move around stars of spectral types F, G, K, and M. EChO would provide an unprecedented view of the atmospheres of planets in the solar neighbourhood. The consortium formed by various institutions of different countries proposed as ESA M3 an integrated spectrometer payload for EChO covering the wavelength interval 0.4 to 16 µm. This instrument is subdivided into 4 channels: a visible channel, which includes a fine guidance system (FGS) and a VIS spectrometer, a near infrared channel (SWiR), a middle infrared channel (MWiR), and a long wave infrared module (LWiR). In addition, it contains a common set of optics spectrally dividing the wavelength coverage and injecting the combined light of parent stars and their exoplanets into the different channels. The proposed payload meets all of the key performance requirements detailed in the ESA call for proposals as well as all scientific goals. EChO payload is based on different spectrometers covering the spectral range mentioned above. Among them, SWiR spectrometer would work from 2.45 microns to 5.45 microns. In this paper, the optical and mechanical designs of the SWiR channel instrument are reported on.

Calibração radiométrica de instrumentação óptica espectrofotométrica

Os espectrómetros instalados a bordo de satélites e à superfície da Terra têm desempenhado um papel fundamental na compreensão da química e dinâmica da atmosfera e na monitorização da poluição ambiental. O SPATRAM (SPectrometer for Atmosferic TRAcers Measurements) é um espectrómetro ultravioleta – Visível que compreende a região espectral entre 250-950nm e se encontra instalado no Instituto de Ciências da Terra (ICT) desde Abril de 2004. Enquanto isso, em 2012, um novo modelo do instrumento SPATRAM foi desenvolvido no ICT e foi chamado SPATRAM2. O objectivo do trabalho proposto é a calibração radiométrica do espectrómetro SPATRAM2, utilizando uma lâmpada de halogéneo e uma esfera de integração. A calibração radiométrica do sistema SPATRAM2 permitirá obter a radiação solar directa, com alta resolução espectral, o que actualmente não se encontra disponível. Este tipo de medição poderá ter um papel importante na investigação e desenvolvimento na área da energia solar e aplicações; Radiometric Calibration of Spectrophotometric Optical Instrumentation Abstract: Spectrometers installed aboard satellites and located on Earth’s surface have played a fundamental role to understand atmosphere’s chemistry and dynamic and to monitor environmental pollution. The SPATRAM (SPectrometer for Atmosferic TRAcers Measurements) instrument is an ultraviolet spectrometer – visible that covers spectral region between 250-950nm and it is installed in Instituto de Ciências da Terra (Institute of Earth Sciencies), ICT, since April 2004. Meanwhile, in 2012, a new model of SPATRAM instrument was developed in ICT and was called SPATRAM2. The goal of this project is the radiometric calibration of the SPATRAM2 spectrometer using a halogen lamp and an integrating sphere. Radiometric calibration of SPATRAM2 system will provide direct solar radiation, with high spectral resolution, that is not available nowadays. This type of measurement may play an important role in solar energy’s progress and investigation.

Uso da espectroscopia de reflectância do infravermelho próximo (NIRS) para previsão da composição bromatológica de vagens de algaroba e palma forrageira.

Espécies forrageiras adaptadas às condições semiáridas são uma alternativa para reduzir os impactos negativos na cadeia produtiva de ruminantes da região Nordeste brasileira devido à sazonalidade na oferta de forragem, além de reduzir custo com o fornecimento de alimentos concentrados. Dentre as espécies, a vagem de algaroba (Prosopis juliflora SW D.C.) e palma forrageira (Opuntia e Nopalea) ganham destaque por tolerarem o déficit hídrico e produzirem em períodos onde a oferta de forragem está reduzida, além de apresentam bom valor nutricional e serem bem aceitas pelos animais. Porém, devido à variação na sua composição, seu uso na alimentação animal exige o conhecimento profundo da sua composição para a elaboração de dietas balanceadas. No entanto, devido ao custo e tempo para análise, os produtores não fazem uso da prática de análise da composição químico-bromatológica dos alimentos. Por isto, a espectroscopia de reflectância no infravermelho próximo (NIRS) representa uma importante alternativa aos métodos tradicionais. Objetivou-se com este estudo desenvolver e validar modelos de predição da composição bromatológica de vagem de algaroba e palma forrageira baseados em espectroscopia NIRS, escaneadas em dois modelos de equipamentos e com diferentes processamentos da amostra. Foram coletadas amostras de vagem de algaroba nos estados do Ceará, Bahia, Paraíba e Pernambuco, e amostras de palma forrageira nos estados do Ceará, Paraíba e Pernambuco, frescas (in natura) ou pré-secas e moídas. Para obtenção dos espectros utilizaram-se dois equipamentos NIR, Perten DA 7250 e FOSS 5000. Inicialmente os alimentos foram escaneados in natura em aparelho do modelo Perten, e, com o auxílio do software The Unscrambler 10.2 foi selecionado um grupo de amostras para o banco de calibração. As amostras selecionadas foram secas e moídas, e escaneadas novamente em equipamentos Perten e FOSS. Os valores dos parâmetros de referência foram obtidos por meio de metodologias tradicionalmente aplicadas em laboratório de nutrição animal para matéria seca (MS), matéria mineral (MM), matéria orgânica (MO), proteína bruta (PB), estrato etéreo (EE), fibra solúvel em detergente neutro (FDN), fibra solúvel em detergente ácido (FDA), hemicelulose (HEM) e digestibilidade in vitro da matéria seca (DIVMS). O desempenho dos modelos foi avaliado de acordo com os erros médios de calibração (RMSEC) e validação (RMSECV), coeficiente de determinação (R2 ) e da relação de desempenho de desvio dos modelos (RPD). A análise exploratória dos dados, por meio de tratamentos espectrais e análise de componentes principais (PCA), demonstraram que os bancos de dados eram similares entre si, dando segurança de desenvolver os modelos com todas as amostras selecionadas em um único modelo para cada alimento, algaroba e palma. Na avaliação dos resultados de referência, observou-se que a variação dos resultados para cada parâmetro corroboraram com os descritos na literatura. No desempenho dos modelos, aqueles desenvolvidos com pré-processamento da amostra (pré-secagem e moagem) se mostraram mais robustos do que aqueles construídos com amostras in natura. O aparelho NIRS Perten apresentou desempenho semelhante ao equipamento FOSS, apesar desse último cobrir uma faixa espectral maior e com intervalos de leituras menores. A técnica NIR, associada ao método de calibração multivariada de regressão por meio de quadrados mínimos (PLS), mostrou-se confiável para prever a composição químico-bromatológica de vagem de algaroba e da palma forrageira. Abstract: Forage species adapted to semi-arid conditions are an alternative to reduce the negative impacts in the feed supply for ruminants in the Brazilian Northeast region, due to seasonality in forage availability, as well as in the reducing of cost by providing concentrated feedstuffs. Among the species, mesquite pods (Prosopis juliflora SW DC) and spineless cactus (Opuntia and Nopalea) are highlighted for tolerating the drought and producion in periods where the forage is scarce, and have high nutritional value and also are well accepted by the animals. However, its use in animal diets requires a knowledge about its composition to prepare balanced diets. However, farmers usually do not use feed composition analysis, because their high cost and time-consuming. Thus, the Near Infrared Reflectance Spectroscopy in the (NIRS) is an important alternative to traditional methods. The objective of this study to develop and validate predictive models of the chemical composition of mesquite pods and spineless cactus-based NIRS spectroscopy, scanned in two different spectrometers and sample processing. Mesquite pods samples were collected in the states of Ceará, Bahia, Paraiba and Pernambuco, and samples of forage cactus in the states of Ceará, Paraíba and Pernambuco. In order to obtain the spectra, it was used two NIR equipment: Perten DA 7250 and FOSS 5000. sSpectra of samples were initially obtained fresh (as received) using Perten instrument, and with The Unscrambler software 10.2, a group of subsamples was selected to model development, keeping out redundant ones. The selected samples were dried and ground, and scanned again in both Perten and FOSS instruments. The values of the reference analysis were obtained by methods traditionally applied in animal nutrition laboratory to dry matter (DM), mineral matter (MM), organic matter (OM), crude protein (CP), ether extract (EE), soluble neutral detergent fiber (NDF), soluble acid detergent fiber (ADF), hemicellulose ( HEM) and in vitro digestibility of dry matter (DIVDM). The performance of the models was evaluated according to the Root Mean Square Error of Calibration (RMSEC) and cross-validation (RMSECV), coefficient of determination (R2 ) and the deviation of Ratio of performance Deviation of the models (RPD). Exploratory data analysis through spectral treatments and principal component analysis (PCA), showed that the databases were similar to each other, and may be treated asa single model for each feed - mesquite pods and cactus. Evaluating the reference results, it was observed that the variation were similar to those reported in the literature. Comparing the preprocessing of samples, the performance ofthose developed with preprocessing (dried and ground) of the sample were more robust than those built with fresh samples. The NIRS Perten device performance similar to FOSS equipment, although the latter cover a larger spectral range and with lower readings intervals. NIR technology associate do multivariate techniques is reliable to predict the bromatological composition of mesquite pods and cactus.

RICORDACI: Research on the Conservation, Restoration and Diagnosis of Cinematographic Films

This thesis is the result of the RICORDACI project, a three-year European-funded initiative involving the collaboration between the University of Bologna and the restoration laboratory of the Cineteca di Bologna, L'immagine Ritrovata, which aimed to develop innovative solutions and technologies for the preservation of cinematographic film heritage. In particular, this thesis presents new analytical methodologies to exploit two types of portable miniaturized Near Infrared spectrometers working in Diffuse Reflectance over the Short Wave Infrared (SWIR) range, to study the near infrared (NIR) spectral behavior of film base materials for an accurate, non-invasive and fast characterization of the polymer type; and for films with cellulose acetate supports, they can be employed as a diagnostic tool for monitoring the Degree of substitution (DS) affected by the loss of acetyl groups. The proposed methods offer non-invasive, fast, inexpensive and simple alternatives for the characterization and diagnosis of film bases to help the strategic planning and decision-making regarding storage, digitalization and intervention of film collections. Secondly, the thesis includes the evaluation of new green cleaning systems and solvents for the effective, fast and innocuous removal of undesired substances from degraded cinematographic films bases; these tests compared the efficiency of traditional systems and solvents against the new proposals. Firstly, the use of Deep Eutectic Solvent formulations for removing softened gelatin residues from cellulose nitrate bases; and secondly, the employment of green volatile solvents with different application methods, including the use of new electrospun nylon mats, for avoiding the dangerous use of friction for the removal of Triphenyl Phosphate blooms from the surface of cellulose acetate bases. The results obtained will help improving the efficiency of the interventions needed before the digitalization of historical cinematographic films and will pave the way for further investigation on the use of green solvents for cleaning polymeric heritage objects.