Thermal expansion of irradiated poly(methyl methacrylate)

The thermal expansion coefficient of irradiated poly(methyl methacrylate) is measured in the temperature range 80–350K using a three-terminal capacitance technique. The samples are irradiated with gamma-rays from a ⁶⁰Co source in air at room temperature. The infra-red spectra are taken to indicate radiation-induced changes. The thermal expansion coefficient of poly(methyl methacrylate) is found to increase with radiation dose, the increase being larger at higher temperatures. This has been explained as due to the relative increase in the van der Waals interaction caused by radiation-induced degradation.     

Chemical composition and corrosion protection of silane films modified with CeO2 nanoparticles

The present work aims at understanding the role of CeO₂ nanoparticles (with and without activation in cerium(III) solutions) used as fillers for hybrid silane coatings applied on galvanized steel substrates.The work reports the improved corrosion protection performance of the modified silane films and discusses the chemistry of the cerium-activated nanoparticles, the mechanisms involved in the formation of the surface coatings and its corrosion inhibition ability.The anti-corrosion performance was investigated using electrochemical impedance spectroscopy (EIS), the scanning vibrating electrode technique (SVET) and d.c. potentiodynamic polarization. The chemical composition of silanised nanoparticles and the chemical changes of the silane solutions due to the presence of additives were studied using X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance spectroscopy (NMR), respectively.The NMR and XPS data revealed that the modified silane solutions and respective coatings have enhanced cross-linking and that silane-cerium bonds are likely to occur.Electrochemical impedance spectroscopy showed that the modified coatings have improved barrier properties and the SVET measurements highlight the corrosion inhibition effect of ceria nanoparticles activated with Ce(III) ions. Potentiodynamic polarization curves demonstrate an enhanced passive domain for zinc, in the presence of nanoparticles, in solutions simulating the cathodic environment.     

Effects of ripening on microstructure and texture of “Ameixa d’Elvas” candied plums

The plums used to produce a traditional candied product, “Ameixa d’Elvas”, were obtained from two orchards, Vila Viçosa (VV) and Cano (CA). These orchards were selected because the fruits were behaving differently: (1) The day of harvesting for candying, established by the total soluble solids and titratable acidity, was one week earlier in VV; (2) VV yielded candied plums with good texture properties whereas CA gave poor processed fruits. In order to understand the origin of these differences, fruits from both orchards were harvested on the day established as the harvesting day for VV (day 1) and for CA (day 8). Comparable texture properties were obtained in firmness, rigidity and deformation work between the VV fresh plums harvested on day 1 and the CA plums harvested on day 8 but these were lower in CA when the flesh was analysed separately, in accordance with the activities of pectin methyl esterase (PME), polygalacturonase (PG) and cellulase (Cel). The increase of the intercellular area of parenchyma cells and the decrease in cell area caused by boiling, which resulted in a pronounced loss of textural properties, were partially recovered after the immersion of the fruits in sucrose syrup. The CA plums harvested on day 8 had a more pronounced degradation with boiling and lower recovery of cell shape, size and textural characteristics than had those of VV harvested on day 1. Upon candying, similar properties were observed for the fruits harvested on the same day: good candied products were observed for VV and CA fruits harvested on day 1 and poor candied products were observed for VV and CA fruits harvested on day 8. This work shows that the characteristics of the flesh of the fresh fruits are key parameters in defining the textural properties of the candied plum. The establishment of the harvesting moment for candying should take into account the changes that occur in the flesh of the plums during ripening.     

Structural study of mullite based ceramics derived from a mica-rich kaolin waste

Mullite-based ceramics have been synthesized by reactive sintering of a mixture containing kaolin and a mica-rich kaolin waste. Samples fired in the temperature range from 1300 to 1500 °C were characterized by X-ray diffraction (XRD). The quantitative phase analysis and unit cell parameters of the mullite were determined by Rietveld refinement analysis of the XRD data. Mullite-based ceramics with 1.2 wt% quartz, 56.3 wt% glass (amorphous phase), 2.64 g/cm³ of apparent density, and 35±1.2 MPa of flexural strength were obtained after firing at 1500 °C. A liquid phase sintering mechanism activated by a total mica content of 13.3 wt% allowed to increase the mullite content to 47.6 wt% (2.3 wt% quartz and 50.1 wt% glass phase) and improve the flexural strength (70±3.9 MPa) after firing at 1400 °C.     

Manufacture and measurement of combinatorial libraries of dielectric ceramics: Part II. Dielectric measurements of Ba1−xSrxTiO3 libraries

Applying combinatorial methods to materials science offers the opportunity to accelerate the discovery of more efficient dielectric ceramics. High-throughput methods have the potential to investigate the effects of a wide range of dopants on the dielectric properties, and to optimise existing systems, encouraging the short innovation cycles that the communications technology industry requires. The London University Search Instrument (LUSI) is a fully automated, high-throughput combinatorial robot that has the potential capability to produce large numbers of sintered bulk ceramic samples with varying composition in 1 day, as combinatorial libraries on alumina substrates. Ba_1−xSr_xTiO₃ (BST) libraries were produced by LUSI as a proof-of-principle, with x = 0–1 in steps of 0.1, and fired to 1350 and 1400 °C for 1 h. Part I of this paper described the manufacture and physical characterisation of BST libraries, showing a regular change in composition with x across the libraries. In this second part, the dielectric properties of BST libraries produced by LUSI are assessed at frequencies between 100 Hz and 1 MHz, and at temperatures between 150 and 500 K. Local piezoelectric properties were also characterised by scanning probe microscope (SPM). All measurements showed evidence of a clear functional gradient varying with x across the library, with measured _r corresponding to expected values for BST.     

Use of SVET and SECM to study the galvanic corrosion of an iron-zinc cell

The work makes use of the scanning vibrating electrode technique (SVET) and the scanning electrochemical microscope (SECM) to investigate microscopic aspects of the electrochemical reactions that occur in an iron-zinc galvanic couple immersed in aqueous sodium chloride solution. Detection of the corrosion processes was made by sensing the phenomena occurring in solution. The SVET provided information on the distribution of ionic currents arising from the metal surface, whereas the SECM measured the concentration of chemical species relevant to the corrosion processes. The two techniques had comparable sensitivity for the corrosion of iron but significant differences were observed concerning the detection of corrosion of zinc.     

Investigating corrosion processes in the micrometric range: A SVET study of the galvanic corrosion of zinc coupled with iron

The galvanic corrosion of an iron/zinc pair immersed in aqueous 0.1 M Na₂SO₄ solution has been investigated by using the scanning vibrating electrode technique (SVET). In this way, investigations in the micrometer range of the progress of the electrochemical reactions involved in galvanic process were performed. The anodic oxidation process is observed to be initiated on the zinc sample in a localized manner, whereas the cathodic reaction involving the electroreduction of dissolved oxygen is homogeneously distributed over the iron sample. This later process is the rate determining step in the overall corrosion process, as demonstrated by the changes in the ionic and galvanic currents measured in the system when the area of the iron specimen is varied relative to that of zinc. The occurrence of coupled chemical reactions in the solution phase involving the products of the corrosion reactions could also be deduced from the integration of the ionic currents measured for each half-reaction during a SVET scan. Thus, the corrosion processes involved in the galvanic coupling of iron and zinc have been further understood by using this microelectrochemical technique appropriately, helping to better interpret large scale measurements.     

NSAID-Based Coordination Compounds for Biomedical Applications: Recent Advances and Developments

After the serendipitous discovery of cisplatin, a platinum-based drug with chemotherapeutic effects, an incredible amount of research in the area of coordination chemistry has been produced. Other transition metal compounds were studied, and several new relevant metallodrugs have been synthetized in the past few years. This review is focused on coordination compounds with first-row transition metals, namely, copper, cobalt, nickel or manganese, or with zinc, which have potential or effective pharmacological properties. It is known that metal complexes, once bound to organic drugs, can enhance the drugs’ biological activities, such as anticancer, antimicrobial or anti-inflammatory ones. NSAIDs are a class of compounds with anti-inflammatory properties used to treat pain or fever. NSAIDs’ properties can be strongly improved when included in complexes using their compositional N and O donor atoms, which facilitate their coordination to metal ions. This review focuses on the research on this topic and on the promising or effective results that complexes of first-row transition metals and NSAIDs can exhibit.     

Stress corrosion cracking at constant load of 304L stainless steel in molten NaCl-CaCl2 at 570°C

The incubation and propagation times of cracks in 304L in molten NaCl-CaCl₂ at 570°C were related to the applied stress value, from creep and creep rate curves. Rest potential versus time curves were recorded simultaneously. The results showed intergranular stress corrosion cracking. When the temperature was kept at 570°C, precipitation of chromium carbide M₂₃C₆ which promoted cracking propagation, was induced. Determination of the crack rate shows that anodic dissolution at the bottom of the cracks is the main process during the stress corrosion crack propagation of 304L stainless steel in the stress range used.