Homogenization and analysis of an expanded long-term monthly rainfall network for the Island of Ireland (1850–2010)

Long-term precipitation series are critical for understanding emerging changes to the hydrological cycle. To this end we construct a homogenized Island of Ireland Precipitation (IIP) network comprising 25 stations and a composite series covering the period 1850–2010, providing the second-longest regional precipitation archive in the British-Irish Isles. We expand the existing catalogue of long-term precipitation records for the island by recovering archived data for an additional eight stations. Following bridging and updating of stations HOMogenisation softwarE in R (HOMER) homogenization software is used to detect breaks using pairwise and joint detection. A total of 25 breakpoints are detected across 14 stations, and the majority (20) are corroborated by metadata. Assessment of variability and change in homogenized and extended precipitation records reveal positive (winter) and negative (summer) trends. Trends in records covering the typical period of digitization (1941 onwards) are not always representative of longer records. Furthermore, trends in post-homogenization series change magnitude and even direction at some stations. While cautionary flags are raised for some series, confidence in the derived network is high given attention paid to metadata, coherence of behaviour across the network and consistency of findings with other long-term climatic series such as England and Wales precipitation. As far as we are aware, this work represents the first application of HOMER to a long-term precipitation network and bodes well for use in other regions. It is expected that the homogenized IIP network will find wider utility in benchmarking and supporting climate services across the Island of Ireland, a sentinel location in the North Atlantic.

Expanded porphyrins and their evaluation as anion chemosensors

Expanded porphyrins are synthetic analogues of porphyrins, differing from the last ones and other naturally occurring tetrapyrrolic macrocycles by containing a larger central core, with a minimum of 17 atoms, while retaining the extended conjugation features that are a tremendous feature of these biological pigments. The core expansion results in various systems with novel spectral and electronic features, often uniques. Most of these systems can also coordinate cations and/or anions, and in some cases they can bind more than one of these species. In many cases, these molecules display structural features, such as non-planar structures, that have no antecedents in the chemistry of porphyrins or related macrocyclic compounds. This work will discuss several synthetic approaches for the synthesis of expanded porphyrins, namely the construction of new building blocks by Michael addition, as well as potential synthetic routes towards expanded porphyrins. The synthesis of smaller oligopyrrolic compounds namely, bipyrroles and dipyrromethanes, not only were developed for the synthesis of expanded porphyrins as they were also used in Knoevenagel condensations furnishing chromogenic compounds able to recognize different anions in solution. Also, an approach to the synthesis of novel expanded porphyrins namely sapphyrins has been done by aza-Michael additions. Several synthetic routes towards the synthesis of pyridyl and pyridinium N-Fused pentaphyrins and hexaphyrins have been explored in order to achieve compounds with potential applications in catalysis and PDI, respectively. Studies on the synthesis of compounds with potential anion binding properties, led to the structural characterization and NMR anion binding studies of [28]hexaphyrins functionalized with several diamines in the para position of their pentafluorophenyl groups. These compounds allow NH hydrogen bond interactions with various anions. All synthesized compounds were fully characterized by modern spectroscopic techniques.

Utilization of waste expanded polystyrene: Blends with silica-filled natural rubber

Expanded polystyrene (EPS) constitutes a considerable part of thermoplastic waste in the environment in terms of volume. In this study, this waste material has been utilized for blending with silica-reinforced natural rubber (NR). The NR/EPS (35/5) blends were prepared by melt mixing in a Brabender Plasticorder. Since NR and EPS are incompatible and immiscible a method has been devised to improve compatibility. For this, EPS and NR were initially grafted with maleic anhydride (MA) using dicumyl peroxide (DCP) to give a graft copolymer. Grafting was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy. This grafted blend was subsequently blended with more of NR during mill compounding. Morphological studies using Scanning Electron Microscopy (SEM) showed better dispersion of EPS in the compatibilized blend compared to the noncompatibilized blend. By this technique, the tensile strength, elongation at break, modulus, tear strength, compression set and hardness of the blend were found to be either at par with or better than that of virgin silica filled NR compound. It is also noted that the thermal properties of the blends are equivalent with that of virgin NR. The study establishes the potential of this method for utilising waste EPS

Predicting random effects with an expanded finite population mixed model

Prediction of random effects is an important problem with expanding applications. In the simplest context, the problem corresponds to prediction of the latent value (the mean) of a realized cluster selected via two-stage sampling. Recently, Stanek and Singer [Predicting random effects from finite population clustered samples with response error. J. Amer. Statist. Assoc. 99, 119-130] developed best linear unbiased predictors (BLUP) under a finite population mixed model that outperform BLUPs from mixed models and superpopulation models. Their setup, however, does not allow for unequally sized clusters. To overcome this drawback, we consider an expanded finite population mixed model based on a larger set of random variables that span a higher dimensional space than those typically applied to such problems. We show that BLUPs for linear combinations of the realized cluster means derived under such a model have considerably smaller mean squared error (MSE) than those obtained from mixed models, superpopulation models, and finite population mixed models. We motivate our general approach by an example developed for two-stage cluster sampling and show that it faithfully captures the stochastic aspects of sampling in the problem. We also consider simulation studies to illustrate the increased accuracy of the BLUP obtained under the expanded finite population mixed model. (C) 2007 Elsevier B.V. All rights reserved.

Effect of microstructure on the stability of retained austenite in transformation-induced-plasticity steels

Two Fe-0.2C-1.55Mn-1.5Si (in wt pet) steels, with and without the addition of 0.039Nb (in wt pet), were studied using laboratory rolling-mill simulations of controlled thermomechanical processing. The microstructures of all samples were characterized by optical metallography, X-ray diffraction (XRD), and transmission electron microscopy (TEM). The microstructural behavior of phases under applied strain was studied using a heat-tinting technique. Despite the similarity in the microstructures of the two steels (equal amounts of polygonal ferrite, carbide-free bainite, and retained austenite), the mechanical properties were different. The mechanical properties of these transformation-induced-plasticity (TRIP) steels depended not only on the individual behavior of all these phases, but also on the interaction between the phases during deformation. The polygonal ferrite and bainite of the C-Mn-Si steel contributed to the elongation more than these phases in the C-Mn-Si-Nb-steel. The stability of retained austenite depends on its location within the microstructure, the morphology of the bainite, and its interaction with other phases during straining. Granular bainite was the bainite morphology that provided the optimum stability of the retained austenite.

An analysis of the transition between strain dependent and independent softening in austenite

The post-deformation softening behaviour of austenite has been studied for various compositions and deformation conditions. The strain at which the transition from strain dependent to strain independent post-deformation softening behaviour occurs (ε*) has been found to coincide closely with the strain to the peak stress (εp) under certain conditions but not under others. It has been proposed that the relationship between ε* and εp may be described geometrically using the initial grain size and the dynamically recrystallised grain size.

Nucleation sites for ultrafine ferrite produced by deformation of austenite during single-pass strip rolling

An austenitic Ni-30 wt pct Fe alloy, with a stacking-fault energy and deformation characteristics similar to those of austenitic low-carbon steel at elevated temperatures, has been used to examine the defect substructure within austenite deformed by single-pass strip rolling and to identify those features most likely to provide sites for intragranular nucleation of ultrafine ferrite in steels. Samples of this alloy and a 0.095 wt pct C-1.58Mn-0.22Si-0.27Mo steel have been hot rolled and cooled under similar conditions, and the resulting microstructures were compared using transmission electron microscopy (TEM), electron diffraction, and X-ray diffraction. Following a single rolling pass of ∼40 pct reduction of a 2mm strip at 800 °C, three microstructural zones were identified throughout its thickness. The surface zone (of 0.1 to 0.4 mm in depth) within the steel comprised a uniform microstructure of ultrafine ferrite, while the equivalent zone of a Ni-30Fe alloy contained a network of dislocation cells, with an average diameter of 0.5 to 1.0 µm. The scale and distribution and, thus, nucleation density of the ferrite grains formed in the steel were consistent with the formation of individual ferrite nuclei on cell boundaries within the austenite. In the transition zone, 0.3 to 0.5 mm below the surface of the steel strip, discrete polygonal ferrite grains were observed to form in parallel, and closely spaced “rafts” traversing individual grains of austenite. Based on observations of the equivalent zone of the rolled Ni-30Fe alloy, the ferrite distribution could be correlated with planar defects in the form of intragranular microshear bands formed within the deformed austenite during rolling. Within the central zone of the steel strip, a bainitic microstructure, typical of that observed after conventional hot rolling of this steel, was observed following air cooling. In this region of the rolled Ni-30Fe alloy, a network of microbands was observed, typical of material deformed under plane-strain conditions.

Australian consumers expectations for expanded nursing roles in general practice - choice not gatekeeping

While research has focussed on the current and potential role of the practice nurse (PN) in Australia, the acceptability of this role by consumers has not been investigated. In 2002, two independent studies were carried out into consumer perceptions of PNs. A discussion between the two groups of researchers at the inaugural National Practice Nurse Conference in 2003, identified significant similarities in the findings of these studies. This article reports the combined findings as they relate to consumers' desire for access to the health practitioner of their choice, and their concern that PNs may assume a gatekeeping role. These perceptions may have significant impact on the acceptance of PNs across Australia.

Numerical investigation of austenite grain size distribution in square-diamond pass hot bar rolling

In this study, the austenite grain size (AGS) for hot bar rolling of AISI4135 steel was predicted based on two different AGS evolution models available in the literature. In order to predict the AGS more accurately, both models were integrated with a three-dimensional non-isothermal finite element program by implementing a modified additivity rule. The predicted results based on two models for the square-diamond (S-D) and round-oval (R-O) pass bar rolling processes were compared with the experimental data available in the literature. Then, numerical predictions depending on various process parameters such as interpass time, temperature, and roll speed were made to compare both models and investigate the effect of these parameters on the AGS distributions. Such numerical results were found to be beneficial to understand the effect of the microstructure evolution model on the rolling processes better and control the processes more accurately.