Preparation and characterization of Nickel-and cobalt-doped magnetites

Trabalho apresentado no I Simpósio Mineiro de Ciências dos Materiais, Ouro Preto, Novembro de 2001.

Estudo da corrosão dos aços AISI 1010 e AISI 316L em soluções com elevado teor de cloreto e em ácido naftênico

A mudança no mercado global do petróleo nos últimos anos, com o declínio das reservas de óleo leve, têm forçado a busca por novos campos petrolíferos em ambientes mais remotos, como nos campos localizados na camada pré-sal, e a exploração de óleos pesados que possuem elevado teor de ácidos naftênicos. Isso acarreta em grandes desafios para a previsão do desempenho de materiais frente às novas condições ambientais em que estão inseridos. No presente trabalho, o comportamento da corrosão do aço carbono AISI 1010 e do aço inoxidável AISI 316L foi estudado em soluções aquosas com elevado teor de cloreto e em solução de ácido naftênico ciclopentanóico a fim de ter melhor entendimento da ação dessas espécies no processo de corrosão e simular a corrosão pela água de produção na indústria petrolífera. Foram aplicadas as técnicas de potencial de circuito aberto, polarização potenciodinâmica, voltametria cíclica, espectroscopia de impedância eletroquímica, espectroscopia Raman, microscopia eletrônica de varredura e microscopia de força atômica, usadas, em cada caso, de acordo com a conveniência. O aumento da [Cl-] na faixa de 1,2–2,8 mol.L-1 não altera os processos catódicos e anódicos perto do Ecorr para os aços AISI 1010 e AISI 316L. Em condições de sobrepotenciais afastados do Ecorr, o aumento de [Cl-] aumenta os processos oxidativos de corrosão, o que é expresso pelas maiores densidades de corrente e carga anódica e aumento da perda de massa sofrida pelos eletrodos de ambos os aços. Portanto, os danos da corrosão são mais intensos quando se aumenta a [Cl-]. O aço AISI 1010 é ativo nas soluções de NaCl e a corrosão se propaga livremente de forma uniforme. Para o aço AISI 316L, uma ampla faixa de passividade pode ser vista nas soluções de NaCl; no Epit ocorre a ruptura do filme passivo e o crescimento de pites estáveis. Após 24 h de imersão em soluções de sulfato de sódio (branco) e de ácido naftênico ciclopentanóico ocorre crescimento de filme de óxido e as fases α-Fe2O3, Fe3O4 e δ-FeO(OH) foram identificadas nos espécimes de aço AISI 1010 e Fe3O4 foi identificado nos defeitos do filme prévio presente na superfície do aço AISI 316L. Os filmes formados em solução de ácido ciclopentanóico possuem menor resistência à polarização, maior rugosidade e maior taxa de corrosão quando comparado aos filmes crescidos na solução branco, para ambos os aços. A presença do ácido naftênico muda a forma como a reação de corrosão se procede e contribui para o aumento da corrosão. A corrosão naftênica foi mais pronunciada no aço carbono porque a presença dos elementos de liga no aço inox reduzem o número de sítios ativos ricos em Fe e tornam menos oportuna a ligação do Fe com o naftenato.

Estudo da corrosão e inibição dos aços carbono AISI 1010, inoxidável AISI 316 e duplex UNS S31803 em meio de solução de íons cloreto

O comportamento da corrosão e inibição à corrosão dos aços carbono AISI 1010, inox AISI 316 e duplex UNS S31803 foi estudado em meio de solução de íons cloreto à 3,0% (m/v), na ausência e presença do benzimidazol e imidazol como inibidores. A caracterização química e morfológica dos aços foi realizada por meio das técnicas de espectrometria de emissão ótica, difração de raios X (DRX), microscopia ótica, microscopia eletrônica de varredura (MEV) e energia dispersiva de raios X (EDX). As análises eletroquímicas foram realizadas através das técnicas de polarização potenciodinâmica e espectroscopia de impedância eletroquímica. As análises de DRX e de metalografia mostraram as fases presentes em cada aço, sendo o aço AISI 1010 composto pela fase ferrita, o aço AISI 316 pelas fases de FeNi e Cr e o aço UNS S31803 pelas fases austenita e ferrita. Além disso, a metalografia e as análises de MEV e EDX permitiram identificar regiões e certos elementos presentes nos aços que propiciam à ocorrência da corrosão, tais como inclusões. Os inibidores foram testados em diferentes concentrações (25 ppm, 50 ppm, 100 ppm, 500 ppm e 1000 ppm) para os três aços, através das curvas de polarização e impedância eletroquímica, e verificou-se que para todas as concentrações houve aumento da resistência à corrosão dos aços. Pelas curvas de polarização verificou-se que o benzimidazol proporcionou aos aços AISI 1010, AISI 316 e UNS S31803, eficiências de inibição de cerca de 51%, 71% e 75%, respectivamente. Enquanto que o imidazol apresentou eficiência de cerca de 73%, 95% e 86%, respectivamente. Os resultados de impedância eletroquímica mostraram que as eficiências de inibição do benzimidazol foram de aproximadamente 52%, 73% e 71%, respectivamente, para os aços AISI 1010, AISI 316 e UNS S31803. E por sua vez, o imidazol apresentou eficiências de aproximadamente 96% para os aços AISI 1010 e AISI 316 e 85% para o aço UNS S31803. O teste de perda de massa mostrou que para o aço AISI 1010 tanto o benzimidazol quanto e o imidazol inibiram a corrosão, sendo que reduziram a corrosão em cerca de 17% e 24%, respectivamente. Nas análises das curvas de polarização em estudos com a água do mar observou-se que os inibidores foram menos eficientes do que em meio de solução de cloreto. O benzimidazol obteve eficiências de cerca de 14%, 50% e 33%, respectivamente, para os aços AISI 1010, AISI 316 e UNS S31803. Enquanto que o imidazol apresentou eficiências de aproximadamente 21%, 59% e 34%, respectivamente. Em todas as análises eletroquímicas e análise de perda de massa, o imidazol se mostrou o melhor inibidor para os aços estudados.

Cristalização de Biomateriais Vitrocerâmicos e Mineralização em Meio Fisiológico Simulado

We propose new theoretical models, which generalize the classical Avrami-Nakamura models. These models are suitable to describe the kinetics of nucleation and growth in transient regime, and/or with overlapping of nucleation and growth. Simulations and predictions were performed for lithium disilicate based on data reported in the literature. One re-examined the limitations of the models currently used to interpret DTA or DSC results, and to extract the relevant kinetic parameters. Glasses and glass-ceramics with molar formulation 0.45SiO2? (0.45-x)MgO?xK2O?0.1(3CaO.P2O5) (0?x?0.090) were prepared, crystallized and studied as potential materials for biomedical applications. Substitution of K+ for Mg2+ were used to prevent devritification on cooling, to adjust the kinetics of crystallization and to modify the in vitro behaviour of resulting biomaterials. The crystallization of the glass frits was studied by DTA, XRD and SEM. Exothermic peaks were detected corresponding to bulk crystallization of whitlockite-type phosphate, Ca9MgK(PO4)7, at approximately 900ºC, and surface crystallization of a predominant forsterite phase (Mg2SiO4) at higher temperatures. XRD also revealed the presence of diopside (CaMgSi2O6 in some samples. The predominant microstructure of the phosphate phase is of the plate-type, seemingly crystallizing by a 2-dimensional growth mechanism. Impedance spectroscopy revealed significant changes in electrical behaviour, associated to crystallization of the phosphate phase. This showed that electrical measurements can be used to study the kinetics of crystallization for cases when DTA or DSC experiments reveal limitations, and to extract estimates of relevant parameters from the dependence of crystallization peak temperature, and its width at half height. In vitro studies of glasses and glass-ceramics in acelular SBF media showed bioactivity and the development of apatite layers The morphology, composition and adhesion of the apatite layer could be changed by substitution of Mg2+ by K+. Apatite layers were deposited on the surface of glass-ceramics of the nominal compositions with x=0 and 0.09, in contact with SBF at 37ºC. The adhesion of the apatite layer was quantified by the scratch test technique, having been related with SBF?s immersion time, with composition and structure of the glass phase, and with the morphology of the crystalline phase of the glass-ceramics. The structure of three glasses (x=0, 0.045 and 0.090) were investigated by MAS-NMR ( 29Si and 31P), showing that the fraction of Q3 structural units increases with the contents of Mg, and that the structure of these glasses includes orthophosphate groups (PO43-) preferentially connected to Ca2+ ions. Mg2+ ions show preference towards the silicate network. Substitution of Mg2+ by K+ allowed one to change the bioactivity. FTIR data revealed octacalcium phosphate precipitation (Ca8H2(PO4)6.5H2O) in the glass without K, while the morphology of the layer acquires the shape of partially superimposed hemispheres, spread over the surface. The glasses with K present a layer of acicular hidroxyapatite, whose crystallinity and needles thickness tend to increase along with K content.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.

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.

Structural and Microanalytical Studies of CrO2 Thin Films on c-Sapphire by High Resolution Electron Microscopy Methods

Chromium dioxide (CrO2) has been extensively used in the magnetic recording industry. However, it is its ferromagnetic half-metallic nature that has more recently attracted much attention, primarily for the development of spintronic devices. CrO2 is the only stoichiometric binary oxide theoretically predicted to be fully spin polarized at the Fermi level. It presents a Curie temperature of ∼ 396 K, i.e. well above room temperature, and a magnetic moment of 2 mB per formula unit. However an antiferromagnetic native insulating layer of Cr2O3 is always present on the CrO2 surface which enhances the CrO2 magnetoresistance and might be used as a barrier in magnetic tunnel junctions.

Fabrication of Three-Dimensional Dendritic Ni-Co Films By Electrodeposition on Stainless Steel Substrates

Co-deposition of nickel and cobalt was carried out on austenitic stainless steel (AISI 304) substrates by imposing a square waveform current in the cathodic region. The innovative procedure applied in this work allows creating a stable, fully developed, and open porous three-dimensional (3D) dendritic structure, which can be used as electrode for redox supercapacitors. This study investigates in detail the influence of the applied current density on the morphology, mass, and chemical composition of the deposited Ni-Co films and the resulting 3D porous network dendritic structure. The morphology and the physicochemical composition were studied by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (W). The electrochemical behavior of the materials was evaluated by cyclic voltammetry (CV). The results highlight the mechanism involved in the coelectrodeposition process and how the lower limit current density tailors the film composition and morphology, as well as its electrochemical activity.

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.

Dosimetric effect by shallow air cavities in high energy electron beams

This study evaluates the dosimetric impact caused by an air cavity located at 2 mm depth from the top surface in a PMMA phantom irradiated by electron beams produced by a Siemens Primus linear accelerator. A systematic evaluation of the effect related to the cavity area and thickness as well as to the electron beam energy was performed by using Monte Carlo simulations (EGSnrc code), Pencil Beam algorithm and Gafchromic EBT2 films. A home-PMMA phantom with the same geometry as the simulated one was specifically constructed for the measurements. Our results indicate that the presence of the cavity causes an increase (up to 70%) of the dose maximum value as well as a shift forward of the position of the depthedose curve, compared to the homogeneous one. Pronounced dose discontinuities in the regions close to the lateral cavity edges are observed. The shape and magnitude of these discontinuities change with the dimension of the cavity. It is also found that the cavity effect is more pronounced (6%) for the 12 MeV electron beam and the presence of cavities with large thickness and small area introduces more significant variations (up to 70%) on the depthedose curves. Overall, the Gafchromic EBT2 film measurements were found in agreement within 3% with Monte Carlo calculations and predict well the fine details of the dosimetric change near the cavity interface. The Pencil Beam calculations underestimate the dose up to 40% compared to Monte Carlo simulations; in particular for the largest cavity thickness (2.8 cm).

Nutritional status and overhydration: can bioimpedance spectroscopy be useful in haemodialysis patients?

Background: Protein-energy wasting (PEW), associated with inflammation and overhydration, is common in haemodialysis (HD) patients and is associated with high morbidity and mortality. Objective: Assess the relationship between nutritional status, markers of inflammation and body composition through bioimpedance spectroscopy (BIS) in HD patients. Methods: This observational, cross-sectional, single centre study, carried out in an HD centre in Forte da Casa (Portugal), involved 75 patients on an HD programme. In all participating patients, the following laboratory tests were conducted: haemoglobin, albumin, C-reactive protein (CRP) and 25-hydroxyvitamin D3 [25(OH)D3]. The body mass index of all patients was calculated and a modified version of subjective global assessment (SGA) was produced for patients on dialysis. Intracellular water (ICW) and extracellular water (ECW) were measured by BIS (Body Composition Monitor®, Fresenius Medical Care®) after the HD session. In statistical analysis, Spearman’s correlation was used for the univariate analysis and linear regression for the multivariate analysis (SPSS 14.0). A P value of <.05 was considered statistically significant. Results: PEW, inversely assessed through the ICW/body weight (BW) ratio, was positively related to age (P<.001), presence of diabetes (P=.004), BMI (P=.01) and CRP (P=.008) and negatively related to albumin (p=.006) and 25(OH)D3 (P=.007). Overhydration, assessed directly through the ECW/BW ratio, was positively related with CRP (P=.009) and SGA (P=.03), and negatively with 25(OH)D3 (P=.006) and BMI (P=.01). In multivariate analysis, PEW was associated with older age (P<.001), the presence of diabetes (P=.003), lower 25(OH)D3 (P=.008), higher CRP (P=.001) and lower albumin levels (P=.004). Over-hydration was associated with higher CRP (P=.001) and lower levels of 25(OH)D3 (P=.003). Conclusions: Taking these results into account, the ICW/BW and ECW/BW ratios, assessed with BIS, have proven to be good markers of the nutritional and inflammatory status of HD patients. BIS may be a useful tool for regularly assessing the nutritional and hydration status in these patients and may allow nutritional advice to be improved and adjusted.

Sequencing of a 17.6 kb segment on the right arm of yeast chromosome VII reveals 12 ORFs, including CCT, ADE3 and TR-I genes, homologues of the yeast PMT and EF1G genes, of the human and bacterial electron-transferring flavoproteins (beta-chain) and of the Escherichia coli phosphoserine phosphohydrolase, and five new ORFs.

A 17.6 kb DNA fragment from the right arm of chromosome VII of Saccharomyces cerevisiae has been sequenced and analysed. The sequence contains twelve open reading frames (ORFs) longer than 100 amino acids. Three genes had already been cloned and sequenced: CCT, ADE3 and TR-I. Two ORFs are similar to other yeast genes: G7722 with the YAL023 (PMT2) and PMT1 genes, encoding two integral membrane proteins, and G7727 with the first half of the genes encoding elongation factors 1gamma, TEF3 and TEF4. Two other ORFs, G7742 and G7744, are most probably yeast orthologues of the human and Paracoccus denitrificans electron-transferring flavoproteins (beta chain) and of the Escherichia coli phosphoserine phosphohydrolase. The five remaining identified ORFs do not show detectable homology with other protein sequences deposited in data banks. The sequence has been deposited in the EMBL data library under Accession Number Z49133.

Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

In this work, we investigated structural, morphological, electrical, and optical properties from a set of Cu2ZnSnS4 thin films grown by sulfurization of metallic precursors deposited on soda lime glass substrates coated with or without molybdenum. X-ray diffraction and Raman spectroscopy measurements revealed the formation of single-phase Cu2ZnSnS4 thin films. A good crystallinity and grain compactness of the film was found by scanning electron microscopy. The grown films are poor in copper and rich in zinc, which is a composition close to that of the Cu2ZnSnS4 solar cells with best reported efficiency. Electrical conductivity and Hall effect measurements showed a high doping level and a strong compensation. The temperature dependence of the free hole concentration showed that the films are nondegenerate. Photoluminescence spectroscopy showed an asymmetric broadband emission. The experimental behavior with increasing excitation power or temperature cannot be explained by donor-acceptor pair transitions. A model of radiative recombination of an electron with a hole bound to an acceptor level, broadened by potential fluctuations of the valence-band edge, was proposed. An ionization energy for the acceptor level in the range 29–40 meV was estimated, and a value of 172 ±2 meV was obtained for the potential fluctuation in the valence-band edge.

Admittance spectroscopy of Cu2ZnSnS4 based thin film solar cells

In this report, we propose an AC response equivalent circuit model to describe the admittance measurements of Cu2ZnSnS4 thin film solar cell grown by sulphurization of stacked metallic precursors. This circuit describes the contact resistances, the back contact, and the heterojunction with two trap levels. The study of the back contact resistance allowed the estimation of a back contact barrier of 246 meV. The analysis of the trap series with varying temperature revealed defect activation energies of 45 meV and 113 meV. The solar cell’s electrical parameters were obtained from the J-V curve: conversion efficiency, 1.21%; fill factor, 50%; open circuit voltage, 360 mV; and short circuit current density, 6.8 mA/cm2.

A study of ternary Cu2SnS3 and Cu3SnS4 thin films prepared by sulfurizing stacked metal precursors

Thin films of Cu2SnS3 and Cu3SnS4 were grown by sulfurization of dc magnetron sputtered Sn–Cu metallic precursors in a S2 atmosphere. Different maximum sulfurization temperatures were tested which allowed the study of the Cu2SnS3 phase changes. For a temperature of 350 ◦C the films were composed of tetragonal (I -42m) Cu2SnS3. The films sulfurized at a maximum temperature of 400 ◦C presented a cubic (F-43m) Cu2SnS3 phase. On increasing the temperature up to 520 ◦C, the Sn content of the layer decreased and orthorhombic (Pmn21) Cu3SnS4 was formed. The phase identification and structural analysis were performed using x-ray diffraction (XRD) and electron backscattered diffraction (EBSD) analysis. Raman scattering analysis was also performed and a comparison with XRD and EBSD data allowed the assignment of peaks at 336 and 351 cm−1 for tetragonal Cu2SnS3, 303 and 355 cm−1 for cubic Cu2SnS3, and 318, 348 and 295 cm−1 for the Cu3SnS4 phase. Compositional analysis was done using energy dispersive spectroscopy and induced coupled plasma analysis. Scanning electron microscopy was used to study the morphology of the layers. Transmittance and reflectance measurements permitted the estimation of absorbance and band gap. These ternary compounds present a high absorbance value close to 104 cm−1. The estimated band gap energy was 1.35 eV for tetragonal (I -42m) Cu2SnS3, 0.96 eV for cubic (F-43m) Cu2SnS3 and 1.60 eV for orthorhombic (Pmn21) Cu3SnS4. A hot point probe was used for the determination of semiconductor conductivity type. The results show that all the samples are p-type semiconductors. A four-point probe was used to obtain the resistivity of these samples. The resistivities for tetragonal Cu2SnS3, cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4 are 4.59 × 10−2 cm, 1.26 × 10−2 cm, 7.40 × 10−4 cm, respectively.