Radio frequency plasma-induced hydrogen bonding on kaolinite

The radio frequency (RF) plasma-modified surfaces of kaolinite were investigated by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) and deuteration techniques to determine the nature of RF plasma-induced surface functional groups, the altered sites in the lattice, and interaction mechanism between RF plasma and the surface of the kaolinite. It has been concluded that the RF plasma-induced infrared (IR) vibration absorption bands at 2805, 3010, and 3100 cm(-1) are attributable to the stretching vibration of hydrogen-bonded hydroxyl groups, and the band at 1407 cm(-1) is attributable to the bending vibration of (HO-)Al-O or (HO-)Si-O groupings with hydrogen-bonded hydroxyl groups. Structural alteration occurred on both the surface and subsurface region of the kaolinite during RF plasma treatment. Further structural alteration or adjustment was also observed on well-modified and well-deuterated kaolinite. There are two types of OD bands visible in the DRIFT spectra of this kaolinite, one type which decreased rapidly as a function of time in moist air, and the other which remained unchanged during the measurement. Furthermore, the appearance of broad IR bands at 3500-3100 cm(-1) as a result of deuteration is evidence of structural disturbance by RF plasma treatment lattice deuteration. An RF plasma-induced hydrogen bonding model on the surface of the kaolinite is proposed.

On the evaluation of some differential formulations for the pom-pom constitutive model

In recent years, progress has been made in modelling long chain branched polymers by the introduction of the so-called pompom model. Initially developed by McLeish and Larson (1998), the model has undergone several improvements or alterations, leading to the development of new formulations. Some of these formulations however suffer from certain mathematical defects. The purpose of the present paper is to review some of the formulations of the pom-pom constitutive model, and to investigate their possible mathematical defects. Next, an alternative formulation is proposed, which does not appear to exhibit mathematical defects, and we explore its modelling performance by comparing the predictions with experiments in non-trivial rheometric flows of an LDPE melt. The selected rheometric flows are the double step strain, as well as the large amplitude oscillatory shear experiments. For LAOS experiments, the comparison involves the use of Fourier-transform analysis.

Síntese, aplicação e avaliação da toxicidade aguda de complexo orgânico à base de európio proposto como marcador fotoluminescente para a Identificação de resíduos de tiro

Um complexo de alta fotoluminescência é proposto como marcador óptico para a identificação de resíduos de tiro (GSR). O marcador é o complexo [Eu(PIC)3(NMK)3], de fórmula molecular Eu(C6H2N3O7)3.(C7H13NO)3, que apresenta o íon Eu3+ e os ligantes ácido pícrico (PIC) e n-metil-Ɛ-caprolactama (NMK). Foi realizada a caracterização quimicamente através de espectroscopia de emissão, espectroscopia de infravermelho com transformada de Fourier (FTIR), termogravimetria e análise térmica diferencial (TG/DTA), e espectrometria de massas com ionização por eletrospray e ressonância ciclotrônica de íons por transformada de Fourier (ESI-FT-ICR MS), e, em seguida, foram adicionadas diferentes massas do complexo a munições convencionais (de 2 a 50 mg por cartucho). Após os tiros, o GSR marcado foi visualmente e quimicamente detectado por irradiação UV (ʎ = 395 nm) e ESI-FT-ICR MS, respectivamente. Os resultados mostraram uma fotoluminescência eficiente e duradoura, sendo facilmente visível sobre a superfície do alvo, no ambiente, no cartucho deflagrado, na arma de fogo, e sobre as mãos e braços do atirador quando utilizada massa a partir de 25 mg do marcador em cartuchos .38 e 50 mg em cartuchos .40. Sua toxicidade aguda também foi avaliada empregando-se o Protocolo 423 da Organização para a Cooperação e Desenvolvimento Econômico (OECD) e apresentou DL50 de 1000 mg.kg-1, sendo classificado como de categoria 4 na escala do Sistema Globalmente Harmonizado de Classificação e Rotulagem de Produtos Químicos (GHS), considerado, portanto, de média toxicidade. O composto mostrou ser menos tóxico do que os componentes inorgânicos de munições convencionais (em especial o Pb), justificando o seu emprego como marcador de GSR.

Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Análise de vibrações em caixas redutoras

A vibração em equipamento industrial pode ser tanto um sinal de que o equipamento está a funcionar normalmente como pode revelar que o mesmo apresenta problemas. É assim importante que o técnico de manutenção consiga distinguir entre níveis normais e aceitáveis de vibração e os que requerem atenção imediata para monitorar. Nesta dissertação é estudado o problema de análise de vibrações em caixas redutoras - uma em bom estado e outra com desgaste no par de engrenagens. A escolha desta dissertação prende-se com a importância e uso generalizado de caixas de engrenagens - neste caso de caixas redutoras - nas grandes indústrias. Como tal, hoje em dia, as caixas redutoras estão geralmente providas de sistema de monitorização “online” que alertam o técnico responsável de quando algo foge dos parâmetros definidos pelo utilizador - aumento súbito de temperatura, de amplitude de vibração, entre outros. Esta dissertação pretende assim responder a algumas questões pertinentes: • Como responde uma caixa redutora quando se variam os parâmetros de velocidade e carga e como as variações dos mesmos se traduzem nos espectros de frequência? • Qual dos parâmetros - velocidade e carga - tem uma maior influência nas amplitudes de vibração registadas para as várias frequências típicas de uma caixa redutora? • O que é registado ao nível do espectro de frequências, no estudo de uma caixa redutora com o defeito de desgaste? • A teoria consultada para as caixas redutoras é comparável com os dados obtidos na prática? • Porquê a importância de utilizar a análise de vibrações quando se monitorizam caixas redutoras? Para ajudar a responder estas questões foi utilizada uma aplicação designada de Enlive, um programa de controlo de condição de máquinas para sistemas “online” - ou seja, para sistemas em contínua monitorização. A análise dos sinais provenientes das caixas redutoras foi realizada com recurso à transformada rápida de Fourier - Fast Fourier Trabsform. No fim da realização desta dissertação foi possível responder a todos os pontos referidos anteriormente. Foi possível confirmar a maior importância do factor carga no aumento da amplitude de engrenamento, harmónicas e bandas laterais. Este aumento é mais pronunciado no caso da caixa redutora com desgaste. A análise de vibrações assume-se assim, mais uma vez, como uma ferramenta importante no diagnóstico de avarias, permitindo poupar tempo e recursos - tanto financeiros como humanos - e salvaguardar a contínua eficácia e produtividade de uma empresa, pois permite diminuir o tempo que uma máquina não se encontra em funcionamento.

Femtosecond laser ablation of dentin

The surface morphology, structure and composition of human dentin treated with a femtosecond infrared laser (pulse duration 500 fs, wavelength 1030 nm, fluences ranging from 1 to 3 J cm(-2)) was studied by scanning electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The average dentin ablation threshold under these conditions was 0.6 +/- 0.2 J cm(-2) and the ablation rate achieved in the range 1 to 2 mu m/pulse for an average fluence of 3 J cm(-2). The ablation surfaces present an irregular and rugged appearance, with no significant traces of melting, deformation, cracking or carbonization. The smear layer was entirely removed by the laser treatment. For fluences only slightly higher than the ablation threshold the morphology of the laser-treated surfaces was very similar to the dentin fracture surfaces and the dentinal tubules remained open. For higher fluences, the surface was more porous and the dentin structure was partially concealed by ablation debris and a few resolidified droplets. Independently on the laser processing parameters and laser processing method used no sub-superficial cracking was observed. The dentin constitution and chemical composition was not significantly modified by the laser treatment in the processing parameter range used. In particular, the organic matter is not preferentially removed from the surface and no traces of high temperature phosphates, such as the beta-tricalcium phosphate, were observed. The achieved results are compatible with an electrostatic ablation mechanism. In conclusion, the high beam quality and short pulse duration of the ultrafast laser used should allow the accurate preparation of cavities, with negligible damage of the underlying material.

Entropy analysis of DNA code dynamics in human chromosomes

Deoxyribonucleic acid, or DNA, is the most fundamental aspect of life but present day scientific knowledge has merely scratched the surface of the problem posed by its decoding. While experimental methods provide insightful clues, the adoption of analysis tools supported by the formalism of mathematics will lead to a systematic and solid build-up of knowledge. This paper studies human DNA from the perspective of system dynamics. By associating entropy and the Fourier transform, several global properties of the code are revealed. The fractional order characteristics emerge as a natural consequence of the information content. These properties constitute a small piece of scientific knowledge that will support further efforts towards the final aim of establishing a comprehensive theory of the phenomena involved in life.

Fractional dynamics in DNA

This paper addresses the DNA code analysis in the perspective of dynamics and fractional calculus. Several mathematical tools are selected to establish a quantitative method without distorting the alphabet represented by the sequence of DNA bases. The association of Gray code, Fourier transform and fractional calculus leads to a categorical representation of species and chromosomes.

On the DNA of eleven mammals

This paper studies the DNA code of eleven mammals from the perspective of fractional dynamics. The application of Fourier transform and power law trendlines leads to a categorical representation of species and chromosomes. The DNA information reveals long range memory characteristics.

Structural, physical, and chemical modifications induced by microwave heating on native agar-like galactans

Native agars from Gracilaria vermiculophylla produced in sustainable aquaculture systems (IMTA) were extracted under conventional (TWE) and microwave (MAE) heating. The optimal extracts from both processes were compared in terms of their properties. The agars’ structure was further investigated through Fourier transform infrared and NMR spectroscopy. Both samples showed a regular structure with an identical backbone, β-D-galactose (G) and 3,6-anhydro-α-L-galactose (LA) units; a considerable degree of methylation was found at C6 of the G units and, to a lesser extent, at C2 of the LA residues. The methylation degree in the G units was lower for MAEopt agar; the sulfate content was also reduced. MAE led to higher agar recoveries with drastic extraction time and solvent volume reductions. Two times lower values of [η] and Mv obtained for the MAEopt sample indicate substantial depolymerization of the polysaccharide backbone; this was reflected in its gelling properties; yet it was clearly appropriate for commercial application in soft-texture food products.

Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells

Purpose: The sorption of sulfamethoxazole, a frequently detected pharmaceutical compound in the environment, onto walnut shells was evaluated. Methods: The sorption proprieties of the raw sorbent were chemically modified and two additional samples were obtained, respectively HCl and NaOH treated. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric (TG/DTG) techniques were applied to investigate the effect of the chemical treatments on the shell surface morphology and chemistry. Sorption experiments to investigate the pH effect on the process were carried out between pH 2 and 8. Results: The chemical treatment did not substantially alter the structure of the sorbent (physical and textural characteristics) but modified the surface chemistry of the sorbent (acid–base properties, point of zero charge—pHpzc). The solution pH influences both the sorbent’s surface charge and sulfamethoxazole speciation. The best removal efficiencies were obtained for lower pH values where the neutral and cationic sulfamethoxazole forms are present in the solution. Langmuir and Freundlich isotherms were applied to the experimental adsorption data for sulfamethoxazole sorption at pH 2, 4, and 7 onto raw walnut shell. No statistical difference was found between the two models except for the pH 2 experimental data to which the Freundlich model fitted better. Conclusion: Sorption of sulfamethoxazole was found to be highly pH dependent in the entire pH range studied and for both raw and treated sorbent.

Novos receptores moleculares baseados em calix[4]arenos: aplicação à química sensorial

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química

Diagnóstico de máquinas elétricas pela análise de vibração

O diagnóstico de máquinas elétricas pela análise de vibração é utilizado num plano de manutenção, onde é dado a conhecer a “real condição do equipamento”, e surgiu da necessidade de detetar vibrações indesejáveis nas máquinas elétricas, de uma forma simples e com custos acessíveis. Numa fase inicial é obtido um sinal correspondente á vibração da máquina, recorrendo a um acelerômetro, que dependendo da aceleração da máquina, constrói uma forma de onda correspondente. A forma de onda fica guardada em formato de áudio *.wav. Posteriormente, em software Matlab o ficheiro *.wav irá ser carregado, e comparado com o ficheiro *.wav original da máquina. Ao comparar os ficheiros o software analisa o espectro original da máquina através da transformada de Fourier, com o espectro atual. Se este espectro sair do intervalo de segurança, o software deteta nesse espectro a origem da vibração, pois cada vibração tem uma frequência associada. Percorridos os passos descritos, o software disponibiliza ao utilizador as respetivas formas de onda e todo o restante diagnóstico de forma a uma possível intervenção antecipada da avaria.

Real-time scheduling with resource sharing on uniform multiprocessors

Consider the problem of scheduling a set of implicit-deadline sporadic tasks to meet all deadlines on a uniform multiprocessor platform where each task may access at most one of |R| shared resources and at most once by each job of that task. The resources have to be accessed in a mutually exclusive manner. We propose an algorithm, GIS-vpr, which offers the guarantee that if a task set is schedulable to meet deadlines by an optimal task assignment scheme that allows a task to migrate only when it accesses or releases a resource, then our algorithm also meets the deadlines with the same restriction on the task migration, if given processors 4 + 6|R| times as fast. The proposed algorithm, by design, limits the number of migrations per job to at most two. To the best of our knowledge, this is the first result for resource sharing on uniform multiprocessors with proven performance guarantee.

Analysis of stock market indices with multidimensional scaling and wavelets

Stock market indices SMIs are important measures of financial and economical performance. Considerable research efforts during the last years demonstrated that these signals have a chaotic nature and require sophisticated mathematical tools for analyzing their characteristics. Classical methods, such as the Fourier transform, reveal considerable limitations in discriminating different periods of time. This paper studies the dynamics of SMI by combining the wavelet transform and the multidimensional scaling MDS . Six continuous wavelets are tested for analyzing the information content of the stock signals. In a first phase, the real Shannon wavelet is adopted for performing the evaluation of the SMI dynamics, while their comparison is visualized by means of the MDS. In a second phase, the other wavelets are also tested, and the corresponding MDS plots are analyzed.