Examination of Ni-based superalloy/intermetallic diffusion couples containing multiphase regions

Increasing gas turbine operating temperatures are driving the development of novel coatings for niche applications. One such application is as an anchor phase material for use in the high-pressure turbine stage, for which NiAlTa alloys are a promising candidate. Extended exposure to the high temperatures of this environment can cause interdiffusion of elements between the coating and the underlying blade material. In this study, NiAlTa/CMSX-4 diffusion couples were investigated experimentally and computationally. The couples initially contained two two-phase regions (γ + γ′) and (β + τ1). After heat treatment at 1100 °C, interdiffusion had caused the τ1 Laves phase in the coating to transform to the τ2 Heusler phase, and TCP precipitation was observed in the CMSX-4. A CALPHAD-based model, using Thermo-Calc and DICTRA, developed for this system was able to predict the concentration profiles across the diffusion couple at 1000 °C, with the presence of the predicted phases in the interdiffusion zone verified by x-ray diffraction. However, due to the limited diffusion data for intermetallic phases available in the kinetic database, the model predictions were poor at higher temperatures. In order for the development of intermetallic coatings to be aided by CALPHAD-based simulations, more kinetic data is needed for intermetallic phases than is available at present

Alkali Metal Complexes of Phosphine-Borane-Substituted Benzyl Ligands and Their Application in the Synthesis of B-H\ub7\ub7\ub7Sn Stabilized Dialkylstannylenes

\ua9 2024 The Authors. Published by American Chemical Society.The benzyl-substituted phosphine-boranes PhCH2P(BH3)R2 [R = iPr (1H), Ph (2H), Cy (3H)] are accessible through either the reaction between R2PCl and PhCH2MgBr, followed by treatment with BH3\ub7SMe2 or the reaction between R2P(BH)3Li and PhCH2Br. Treatment of 1H, 2H, or 3H with nBuLi, PhCH2Na, or PhCH2K gave the corresponding alkali metal complexes [{iPr2P(BH3)CHPh}Li(THF)]2 (1Li), [{Ph2P(BH3)CHPh}Li(OEt2)2] (2Li), [{Cy2P(BH3)CHPh}Li(TMEDA)] (3Li), [iPr2P(BH3)CHPh]Na (1Na), [{Ph2P(BH3)CHPh}Na(THF)2]2 (2Na), [Cy2P(BH3)CHPh]Na(THF)0.5 (3Na), [{iPr2P(BH3)CHPh}K]∞ (1K), [{Ph2P(BH3)CHPh}K(THF)]∞ (2K), and [{Cy2P(BH3)CHPh}K.0.5PhMe]∞ (3K). X-ray crystallography revealed that, while 2Li and 3Li crystallize as monomers, 1Li and 2Na crystallize as borane-bridged dimers. The potassium complexes 1K, 2K, and 3K all crystallize with polymeric structures, in which the monomer units are linked to each other through a range of both bridging BH3 groups and multihapto interactions between the potassium cations and the aromatic rings. The reactions between two equivalents of either 1Li or 3Li and Cp2Sn gave the corresponding dialkylstannylenes [{R2P(BH3)CHPh}2Sn] [R = iPr (1Sn), Cy (3Sn)]. These compounds were isolated as mixtures of the rac and meso diastereomers. X-ray crystallography reveals that rac-1Sn and rac-3Sn crystallize as discrete monomers each exhibiting two agostic-type B-H\ub7\ub7\ub7Sn contacts

Temporal Network Analysis of Email Communication Patterns in a Long Standing Hierarchy

An important concept in organisational behaviour is how hierarchy affects the voice of individuals, whereby members of a given organisation exhibit differing power relations based on their hierarchical position. Although there have been prior studies of the relationship between hierarchy and voice, they tend to focus on more qualitative small-scale methods and do not account for structural aspects of the organisation. This paper develops large-scale computational techniques utilising temporal network analysis to measure the effect that organisational hierarchy has on communication patterns within an organisation, focusing on the structure of pairwise interactions between individuals. We focus on one major organisation as a case study - the Internet Engineering Task Force (IETF) - a major technical standards development organisation for the Internet. A particularly useful feature of the IETF is a transparent hierarchy, where participants take on explicit roles (e.g. Area Directors, Working Group Chairs). Its processes are also open, so we have visibility into the communication of people at different hierarchy levels over a long time period. We utilise a temporal network dataset of 989,911 email interactions among 23,741 participants to study how hierarchy impacts communication patterns. We show that the middle levels of the IETF are growing in terms of their dominance in communications. Higher levels consistently experience a higher proportion of incoming communication than lower levels, with higher levels initiating more communications too. We find that communication tends to flow "up" the hierarchy more than "down". Finally, we find that communication with higher-levels is associated with future communication more than for lower-levels, which we interpret as "facilitation". We conclude by discussing the implications this has on patterns within the wider IETF and for other organisations

Raphtory: The temporal graph engine for Rust and Python

Raphtory is a platform for building and analysing temporal networks. The library includes methods for creating networks from a variety of data sources; algorithms to explore their structure and evolution; and an extensible GraphQL server for deployment of applications built on top. Raphtory’s core engine is built in Rust, for efficiency, with Python interfaces, for ease of use. Raphtory is developed by network scientists, with a background in Physics, Applied Mathematics, Engineering and Computer Science, for use across academia and industry

The UK overseas territories: A decade of progress and prosperity?

This article analyses the relationship between the UK and its Overseas Territories since the publication of the 1999 White Paper Partnership for Progress and Prosperity. The article considers the efforts by the UK government to improve links with the territories via a new partnership based on mutual obligations and responsibilities. It focuses on the two most important aspects of the White Paper - governance and economic growth and sustainability. Much has been achieved, but fundamental structural problems in the relationship remain unattended. The article concludes by recommending how the relationship can be improved over the coming years. © 2011 Taylor & Francis

Cell-Type Specific Expression of a Dominant Negative PKA Mutation in Mice

We employed the Cre recombinase/loxP system to create a mouse line in which PKA activity can be inhibited in any cell-type that expresses Cre recombinase. The mouse line carries a mutant Prkar1a allele encoding a glycine to aspartate substitution at position 324 in the carboxy-terminal cAMP-binding domain (site B). This mutation produces a dominant negative RIα regulatory subunit (RIαB) and leads to inhibition of PKA activity. Insertion of a loxP-flanked neomycin cassette in the intron preceding the site B mutation prevents expression of the mutant RIαB allele until Cre-mediated excision of the cassette occurs. Embryonic stem cells expressing RIαB demonstrated a reduction in PKA activity and inhibition of cAMP-responsive gene expression. Mice expressing RIαB in hepatocytes exhibited reduced PKA activity, normal fasting induced gene expression, and enhanced glucose disposal. Activation of the RIαB allele in vivo provides a novel system for the analysis of PKA function in physiology

Trends and variation in the management of oesophagogastric cancer patients: a population-based survey

<p>Abstract</p> <p>Background</p> <p>Previous evidence indicates potential variation in the quality of care of cancer patients. We aimed to examine whether recent changes in the treatment of oesophagogastric cancers have been distributed equally among different patient subgroups.</p> <p>Methods</p> <p>We analysed population-based cancer registry data about the treatment patterning of oesophagogastric cancer (other than oesophageal squamous cell carcinoma) during 1995-2006.</p> <p>Results</p> <p>There were 14,077 patients aged ≥40 years (69% men). There was only limited information on stage, and no information on co-morbidity status. During successive triennia, curative surgery use decreased from 28% to 20% (p < 0.001) whilst chemotherapy use increased from 9% to 30% (p < 0.001). Use of palliative surgery and of radiotherapy increased significantly but modestly (7% to 10%, and 9% to 11%, respectively). In multivariable logistic regression adjusting for age group, gender, diagnosis period and tumour type, curative surgery and chemotherapy were used less frequently in more deprived patients [per increasing deprivation group Odds Ratio (OR) = 0.96, 95% Confidence Interval (CI) 0.93-0.99, and OR = 0.90, 95%CI 0.87-0.93, respectively, p < 0.001 for both)]. Chemotherapy was also used less frequently in women (OR = 0.76, p < 0.001).</p> <p>Conclusions</p> <p>During the study period, curative surgery decreased by a third and chemotherapy use increased by more than three-fold, reflecting improvements in the appropriateness and quality of management, but chemotherapy use, in particular, was unequal, both by socioeconomic status and gender.</p

FRET characterisation for cross-bridge dynamics in single-skinned rigor muscle fibres

In this work we demonstrate for the first time the use of Förster resonance energy transfer (FRET) as an assay to monitor the dynamics of cross-bridge conformational changes directly in single muscle fibres. The advantage of FRET imaging is its ability to measure distances in the nanometre range, relevant for structural changes in actomyosin cross-bridges. To reach this goal we have used several FRET couples to investigate different locations in the actomyosin complex. We exchanged the native essential light chain of myosin with a recombinant essential light chain labelled with various thiol-reactive chromophores. The second fluorophore of the FRET couple was introduced by three approaches: labelling actin, labelling SH1 cysteine and binding an adenosine triphosphate (ATP) analogue. We characterise FRET in rigor cross-bridges: in this condition muscle fibres are well described by a single FRET population model which allows us to evaluate the true FRET efficiency for a single couple and the consequent donor–acceptor distance. The results obtained are in good agreement with the distances expected from crystallographic data. The FRET characterisation presented herein is essential before moving onto dynamic measurements, as the FRET efficiency differences to be detected in an active muscle fibre are on the order of 10–15% of the FRET efficiencies evaluated here. This means that, to obtain reliable results to monitor the dynamics of cross-bridge conformational changes, we had to fully characterise the system in a steady-state condition, demonstrating firstly the possibility to detect FRET and secondly the viability of the present approach to distinguish small FRET variations