Theoretical study on behaviour of superplastic forming/diffusion bonding of bulk metallic glasses

Based on the behaviour of the superplastic deformation of metallic glasses and Pilling’s model, a diffusion bonding model suitable for metallic glasses is proposed in the present study. In the current model, the diffusion bonding processes consists of two stages: one is the plastic deformation stage and the other is the void shrinkage stage, in which, the atom diffusion and superplastic deformation are responsible for the void shrinkage. Applying this model to the diffusion bonding of a Zr based metallic glass, the predicted bonding time is in good agreement with the experimental result. A map for determining the bonding temperature and time to achieve high quality bonding in a Zr based metallic glass is suggested.

Iridium(III) N-heterocyclic carbene complexes: an experimental and theoretical study of structural, spectroscopic, electrochemical and electrogenerated chemiluminescence properties

Four cationic heteroleptic iridium(III) complexes have been prepared from methyl- or benzyl-substituted chelating imidazolylidene or benzimidazolylidene ligands using a Ag(I) transmetallation protocol. The synthesised iridium(III) complexes were characterised by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for three complexes were determined by single crystal X-ray diffraction. A combined theoretical and experimental investigation into the spectroscopic and electrochemical properties of the series was performed in order to gain understanding into the factors influencing photoluminescence and electrochemiluminescence efficiency for these complexes, with the results compared with those of similar NHC complexes of iridium and ruthenium. The N^C coordination mode in these complexes is thought to stabilise thermally accessible non-emissive states relative to the case with analogous complexes with C^C coordinated NHC ligands, resulting in low quantum yields. As a result of this and the instability of the oxidised and reduced forms of the complexes, the electrogenerated chemiluminescence intensities for the compounds are also low, despite favourable energetics. These studies provide valuable insights into the factors that must be considered when designing new NHC-based luminescent complexes.

Theoretical study of quantum capacitance and associated delay in armchair-edge graphene nanoribbons

This work presents a comprehensive investigation of the quantum capacitance and the associated effects on the carrier transit delay in armchair-edge graphene nanoribbons (A-GNRs) based on semi-analytical method. We emphasize on the realistic analysis of bandgap with taking edge effects into account by means of modified tight binding (TB) model. The results show that the edge effects have significant influence in defining the bandgap which is a necessary input in the accurate analyses of capacitance. The quantum capacitance is discussed in both nondegenerate (low gate voltage) and degenerate (high gate voltage) regimes. We observe that the classical capacitance limits the total gate (external) capacitance in the degenerate regime, whereas, quantum capacitance limits the external gate capacitance in the nondegenerate regime. The influence of gate capacitances on the gate delay is studied extensively to demonstrate the optimization of switching time. Moreover, the high-field behavior of a GNR is studied in the degenerate and nondegenerate regimes. We find that a smaller intrinsic capacitance appears in the channel due to high velocity carrier, which limits the quantum capacitance and thus limit the gate delay. Such detail analysis of GNRs considering a realistic model would be useful for the optimized design of GNR-based nanoelectronic devices.

Theoretical study on the (1-012) deformation twinning and cracking in coarse-grained magnesium alloys

This paper theoretically and systematically investigates: (1) the effect of local transformed strains within deformation twinning on twin intersection; (2) the fracture mode based on type I co-zone tensile twin intersection in coarse-grained magnesium alloys, as well as the impacts of twin intersection and grain diameter on interfacial crack nucleation along twin boundaries; and (3) the influence of the local stresses arising from the encountered twin bands on crack growth. A novel dislocation-based strain nucleus model and a Green's function method, which are applicable to any material with local transformations in which elastic properties are reasonably approximated as isotropic, are specifically employed to model the concentrated transformed strain and calculate the local stress field resulting from deformation twinning and the stress intensity factors at crack tips in the magnesium alloys, respectively. In addition, an electron backscatter diffraction (EBSD) measurement is provided for crack nucleation originating from Type I co-zone tensile twin intersection. The theoretical modeling indicates: (i) the local strains within barrier twins strongly dictate the growth of incident twins and enhance the twin propagation stress; (ii) larger grains favor brittle fracture. More specifically, the dislocation reactions and pile-ups at the junctions between tensile twins can result in interfacial crack nucleation and growth along the twin boundaries, which is a brittle fracture mode based on lower twinning stress and stress concentration in the coarse-grained magnesium alloys; and (iii) the direction of crack propagation is easily changed by high-density twin bands and twin intersections owing to the local strains.

Synthesis, structure and spectral properties of dithiocarbamato bridged dirhenium(III,II) complexes: a combined experimental and theoretical study

Sodium salts of dimethyldithiocarbamate, diethyldithiocarbamate and pyrrolidinedithiocarbamate react with the multiply bonded paramagnetic dirhenium(III,II) complex Re₂(μ-O₂CCH₃)Cl₄(μ-dppm)₂, 1 (dppm = Ph₂PCH₂PPh₂) in refluxing ethanol to afford the paramagnetic substitution products of the type Re₂(η²-S,S)₂(μ-S,S)(μ-Cl)₂(μ-dppm), where S,S represents the dithiocarbamato ligands [S,S = S₂CNMe₂, 4(L_Me); S₂CNEt₂, 4(L_Et) and S₂CN(CH₂)₄, 4(L_Pyr)]. These are the first examples of dirhenium complexes that contain bridging dithiocarbamato ligand along with the dppm ligand. These complexes have very similar spectral (UV-Vis, IR, EPR) and electrochemical properties which are also reported. The identity of 4(L_Et) has been established by single-crystal X-ray structure determination (Re-Re distance 2.6385 (9) Å) and is shown to have edge-shared bioctahedral structure. The electronic structure and the absorption spectra of the complexes are scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analyses.

Study of the creep behaviour of stitched woven composites

An experimental and theoretical study of the tensile creep behaviour of woven fibre composites stitched with cotton, and carbon threads, along or perpendicular to the loading direction with different densities is presented. The results of creep tests, conducted at ambient temperature and various elevated temperatures with low to high stress levels are reported.

Integrated health impact assessment into the triple bottom line concept

This theoretical study explores the links between the Triple Bottom Line (TBL) concept and the principles of HIA and considers the potential role of HIA to provide a mechanism for integrating health concerns within a broader agenda of government and business. TBL is a framework linked to the broader sustainability agenda that underpins and reviews environmental, economic and social performance of organizations. In its simplest form, TBL acts as a tool for reporting to stakeholders/shareholders organizational performance and the nature of the impacts on the community. The links to HIA are clear as both seek to determine the impact (potential and actual) on the health and well-being of the population.

The study found that TBL can operate at four levels within organizations ranging from reporting through to full integration with the organization's goals and practices. Health is narrowly defined and there are tensions about how to undertake the social accountability functions. The study shows the potential role for HIA within the broader policy and accountability agenda. As health is one of the main outcomes of an organization's activities it needs to be taken into account at all levels of activity.

Effect of transformation volume contraction on the toughness of superelastic shape memory alloys

Shape memory alloys (SMAs) exhibit two very important properties: shape memory phenomenon and superelastic deformation due to intrinsic thermoelastic martensitic transformation. To fully exploit the potential of SMAs in developing functional structures or smart structures in mechanical and biomechanical engineering, it is important to understand and quantify the failure mechanisms of SMAs. This paper presents a theoretical study of the effect of phase-transformation-induced volume contraction on the fracture properties of superelastic SMAs. A simple model is employed to account for the forward and reverse phase transformation with pure volume change, which is then applied to numerically study the transformation field near the tip of a tensile crack. The results reveal that during steady-state crack propagation, the transformation zone extends ahead of the crack tip due to forward transformation while partial reverse transformation occurs in the wake. Furthermore, as a result of the volume contraction associated with the austenite-to-martensite transformation, the induced stress-intensity factor is positive. This is in stark contrast with the negative stress-intensity factor achieved in zirconia ceramics, which undergoes volume expansion during phase transformation. The reverse transformation has been found to have a negligible effect on the induced stress-intensity factor. An important implication of the present results is that the phase transformation with volume contraction in SMAs tends to reduce their fracture resistance and increase the brittleness.

Journeying on the frinj of outdoor education

In this chapter we offer a conceptualisation of the construction of the pedagogical relationship between people and place. This conceptualisation considers pedagogical experiences that might prompt students to think differently about relations between people and places of learnng often utilised within outdoor education. We see ourselves as journeying on the fiinj of outdoor education in so far as we are arguing for a reconceptualisation of what constitutes good 'pedagogical' practice within this field of inquiry. This observation is based on what we believe is a troubling perception that distinguishes between outdoor activities as a site for the refinement of practical knowledge, and the classroom as a space for the 'theoretical study of environmental history, ecology and the social studies of human-nature relationships' (Victorian Curriculum and Assessment Authority, 2005, p.1). Our objective is to argue for the value of a pedagogical approach that situates study of these rheoretical issues while journeying in the outdoors.

Colloidal interaction between a rigid solid and a fluid drop

We present results of a theoretical study of the effect of surface deformation on a macroscopic system composed of a solid surface interacting with a fluid drop through electrostatic double-layer forces. The analysis involves numerically solving a Laplace equation suitably modified to describe the shape of a liquid drop subjected to a repulsive double-layer force. The latter is evaluated in nonlinear mean-field theory. Some analytical results are also given. The results indicate that although deformation need not be significant on the macroscopic scale, its effect on the interaction is significant and modifies the picture usually presented in DLVO theory. The decay length of the exponential repulsion deviates marginally from the Debye length, dependent on the interfacial tension of the drop. More significantly, at separations where the double-layer force becomes comparable to the internal pressure of the drop, the net force between the two bodies, the local radius of curvature of the drop, and the amount of deformation grow abruptly. The results of this work are relevant to emulsion stability, micelle, vesicle, and cell interactions, and recent experiments on bubble-particle interaction.

Modeling and analysis on the propagation dynamics of modern email malware

Due to the critical security threats imposed by email-based malware in recent years, modeling the propagation dynamics of email malware becomes a fundamental technique for predicting its potential damages and developing effective countermeasures. Compared to earlier versions of email malware, modern email malware exhibits two new features, reinfection and self-start. Reinfection refers to the malware behavior that modern email malware sends out malware copies whenever any healthy or infected recipients open the malicious attachment. Self-start refers to the behavior that malware starts to spread whenever compromised computers restart or certain files are visited. In the literature, several models are proposed for email malware propagation, but they did not take into account the above two features and cannot accurately model the propagation dynamics of modern email malware. To address this problem, we derive a novel difference equation based analytical model by introducing a new concept of virtual infected user. The proposed model can precisely present the repetitious spreading process caused by reinfection and self-start and effectively overcome the associated computational challenges. We perform comprehensive empirical and theoretical study to validate the proposed analytical model. The results show our model greatly outperforms previous models in terms of estimation accuracy. © 2013 IEEE.

Acetylacetonato chelated ruthenium organometallics incorporating imine-phenol function: spectroscopic, structural, electrochemical and cytotoxicity studies

The heterogeneous phase reaction of Ru(η²-RL)(PPh₃)₂(CO)Cl, 1 with lithium acetylacetonate (Liacac) afforded the complexes of the type Ru(η¹-RL)(PPh₃)₂(CO)(acac), 2 in excellent yield where η²-RL is C₆H₂O-2-CHNHC₆H₄R(p)-3-Me-5 and η¹-RL is C₆H₂OH-2-CHNC₆H₄R(p)-3-Me-5 and R is H, Me, Cl. The chelation of acac is attended with the cleavage of Ru-O and Ru-Cl bonds and iminium-phenolato → imine-phenol prototropic shift. A sterically controlled change in rotational conformation is involved in the 1 → 2 conversion. The conversion is irreversible and the type 2 species are thermodynamically more stable than the carboxylate, nitrite and nitrate complexes of 1. The crystal structures of Ru(η¹-MeL)(PPh₃)₂(CO)(acac), 2(Me) and Ru(η¹-ClL)(PPh₃)₂(CO)(acac), 2(Cl) are reported. Spectral (UV-Vis, IR, ¹H NMR) and electrochemical data of the complexes are also reported. The electronic structure and the absorption spectra of the complexes are scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analyses. The complexes were also screened in vitro for their antiproliferative properties against the MCF-7 breast cancer cell lines by using the MTT assay. Flow cytometric analysis showed that the complexes arrested the cell cycle in the sub G0 phase.