Chemisorbed and physisorbed Structures for 1,10-Phenanthroline and Dipyrido[3,2-a:2',3'-c]phenazine on Au(111)

Scanning tunneling microscopy (STM) images of 1,10-phenanthroline (PHEN) and dipyrido[3,2-a:2‘,3‘-c]phenazine (DPPZ) on Au(111) are recorded using both in situ and ex situ techniques. The images of PHEN depict regimes of physisorption and chemisorption, whereas DPPZ is only physisorbed. All physisorbed structures are not pitted and fluctuate dynamically, involving aligned (4 × 4) surface domains with short-range (ca. 20 molecules) order for PHEN but unaligned chains with medium-range (ca. 100 molecules) order for DPPZ. In contrast, the chemisorbed PHEN monolayers remain stable for days, are associated with surface pitting, and form a (4 × √13)R46° lattice with long-range order. The density of pitted atoms on large gold terraces is shown to match the density of chemisorbed molecules, suggesting that gold adatoms link PHEN to the surface. For PHEN, chemisorbed and physisorbed adsorbate structures are optimized using plane-wave density-functional theory (DFT) calculations for the surface structure. Realistic binding energies are then obtained adding dispersive corrections determined using complete-active-space self-consistent field calculations using second-order perturbation theory (CASPT2) applied to cluster-interaction models. A fine balance between the large adsorbate−adsorbate dispersive forces, adsorbate−surface dispersive forces, gold ligation energy, and surface mining energy is shown to dictate the observed phenomena, leading to high surface mobility and substrate/surface lattice incommensurability. Increasing the magnitude of the dispersive forces through use of DPPZ, rather than PHEN, to disturb this balance produced physisorbed monolayers without pits and/or surface registration but with much longer-range order. Analogies are drawn with similar but poorly understood processes involved in the binding of thiols to Au(111).

Structuring in liquid alkanes between solid surfaces : force measurements and mean-field theory

Measurements have been made of the solvation forces between mica surfaces in the even-numbered n-alkanes from hexane to hexadecane. In all cases the force law is qualitatively very similar, characterized by a decaying oscillatory function of distance, as occurs for simple isotropic liquids. The spacing between successive minima in the force does not increase with carbon number, and is comparable to the width of a linear alkane molecule rather than its length or any average diameter. This suggests that the alkanes have some tendency towards a parallel orientation near the mica surfaces. The measurements give no indication of any strong repulsive component expected from mean-field theories of higher alkanes or polymers. The results of one such theory are presented, and the reasons for its failure to match the experimental data are discussed.

Transport properties in ionic liquids and ionic liquid mixtures : the challenges of NMR pulsed field gradient diffusion measurements

Pulsed field gradient NMR is a powerful method for the measurement of diffusion coefficients in liquids and solids and has begun to attract much attention in the ionic liquids field. However, aspects of the methodology as traditionally applied to solutions may not be uniformly applicable in these more viscous and chemically complex systems. In this paper we present data which shows that the Pulsed Gradient Spin Echo (PGSE) method in particular suffers from intrinsic internal gradients and can produce apparent diffusion coefficients which vary by as much as 20% for different ¹H nuclei within a given moleculean obvious anomaly. In contrast, we show that the Pulsed Gradient Stimulated Echo method does not suffer from this problem to the same extent and produces self-consistent data to a high degree of accuracy (better than 1%). This level of significance has allowed the detection, in this work, of subtle mixing effects in [C₃mpyr][NTf₂] and [C₄mpyr][NTf₂] mixtures.

Using Mead's Theory of Emergence as a framework for sociological inquiry into pre-service teacher education

In this paper we take up Chang's (2004) challenge to apply Mead's theory of emergence in sociological inquiry. Largely overlooked by scholars, this theory is shown to prove explanatory in one field where limited solutions have been found to date. Specifically, the theory sheds light on how the theory-practice gap is created and sustained in pre-service teacher education. The argument is that under current institutional arrangements the trainee/beginning teacher encounters different and oft-times conflicting environmental, social and cultural conditions in the two 'fields of interaction' (Mead, 1934: 249) of their training program, namely, the on-campus pre-service program and the school. The argument draws on interview and focus group data collected via a study of first-year graduate teachers of an Australian pre-service teacher education program. We conclude that the Meadian mechanisms of role taking and self-regulated behaviour within the two environmental fields of interaction inhibit the trainee/beginning teacher from exercising the power of agency to implement theory learned at university in practice in the classroom. In this sense Mead's theory of emergence predicts the obduracy of the gap between theory and practice in teacher education.

Bringing Bourdieu to policy sociology : codification, misrecognition and exchange value in the UK context

The task of social scientists is to find ways of investigating and understanding the social, political and economic world, in order to offer insights into everyday and public life in the past, present and future. Bourdieu’s tool kit offers a particular way of theorizing the rules, narratives and self-held truths of social phenomena and of educational policy as a specific object of analysis. In this article I develop a series of propositions about the ways in which field theory might be applied to explain the abrupt public policy shift effected by the Thatcher government and the adjustments made to it by the Blair government. I suggest that a Bourdieuian approach shows policy working as a means of codification, as a doxa of misrecognition and as currency exchange within and across fields. I conclude with some thoughts about the difficulties of explicating interactions between fields.

The mediatization of the knowledge based economy : an Australian field based account

This paper presents an empirical account of mediatization from a Bourdieuian perspective, based on the development of a number of new concepts, such as cross-field effects and the rescaling of such effects as linked to processes of globalization. Built on an Australian empirical case relating to educational policy and the knowledge based economy, this paper argues that mediatization can be understood in relation to the cross-field effects of different fields of journalism on subsequent fields, which have their genesis in forms of practice that cross different social fields. Specifically, the case analysis details interactions between the field of print journalism and the field of policy over the course of an Australian science capability review, chaired by the then chief scientist, Dr Robin Batterham, which led to Australia adopting a national version of the knowledge economy. The empirical case also leads us to consider the impact of both global and national fields of journalism on fields of educational policy in relation to mediatization.

Sharpening the focus of force field analysis

The purpose is to explore the inherent complexity of Kurt Lewin's force field theory through applied analysis of organizational case examples and related methods. The methodology applies a range of tools from the consultancy research domain, including force field analysis of complex organizational scenarios, and applies bricolage and corroboration to emerging discoveries from semi-structured interviews, author experience, critical reflection and literature survey. Findings are that linear representation of internal and external forces in organizational applications of field theory does not fully explain the paradox of inverse vectors in the forces of change. The force field is not an impermeable thing; instead, it morphs. Examples of the inverse principle and its effects are detailed and extended in this analysis. The implications of the research are that force field analysis and related change processes promoted in organizational change literature run the risk of missing key complexities. The inclusion of the inverse principle can provide enhanced, holistic understanding of the prevailing forces for change. The augmentation of the early work of Kurt Lewin, and extension of previous analyses of his legacy in the Journal of Change Management and elsewhere, provide, in this article, change analysis insights that align well with current organizational environments.

Modeling the effect of asymmetric rolling on mechanical properties of Al-Mg alloys

The mechanical behavior under uniaxial tension of Al-Mg alloy 5182 pre-deformed in conventional rolling (CR), asymmetric rolling-continuous (ASRC), and asymmetric rolling-reversed (ASRR) was investigated and modeled with a rate dependent crystal plasticity finite element method and VPSC (Visco-Plastic Self Consistent) model. M-K theory combined with Yld2000 model by Barlat et al. (Int. J. Plasticity 2003, 19, 1297) was used to predict the strain-based and stress-based formability for AA 5182 material. It was concluded that the new ASRR process has very compatible formability with improved strength compared to CR process. These merits can be directly applied for clam-shell resistant design in rigid-packaging industry.

The determination of the local conditions for void initiation in front of a crack tip for materials with second-phase particles

A procedure is proposed to determine, for second-phase particles near a crack tip, the maximum particle stresses at the moment of void initiation by either particle fracture or particle/matrix interface separation. A digital image analysis system is applied to perform a quantitative analysis of corresponding fracture surface regions from stereo image pairs taken in the scanning electron microscope. The fracture surface analysis is used to measure, for individual particles, the crack tip opening displacement at the moment of void initiation and the particle location with respect to the crack tip. From these data, the stress tensor at the moment of void initiation is calculated from the Hutchinson–Rice–Rosengren (HRR) field theory. The corresponding average local stresses within the particle are evaluated by a non-linear Mori–Tanaka-type approach. These stresses are compared to estimates according to the models by Argon et al. [A.S. Argon, J. Im, R. Safoglu, Metall. Trans. 6 (1975) 825] and Beremin [F.M. Beremin, Metall. Trans. 12 (1981) 723]. The procedure is demonstrated on an Al6061–10% Al2O3 metal matrix composite.

An active stereo vision-based learning approach for robotic tracking, fixating and grasping control

In this paper, an active stereo vision-based learning approach is proposed for a robot to track, fixate and grasp an object in unknown environments. First, the functional mapping relationships between the joint angles of the active stereo vision system and the spatial representations of the object are derived and expressed in a three-dimensional workspace frame. Next, the self-adaptive resonance theory-based neural networks and the feedforward neural networks are used to learn the mapping relationships in a self-organized way. Then, the approach is verified by simulation using the models of an active stereo vision system which is installed in the end-effector of a robot. Finally, the simulation results confirm the effectiveness of the present approach.

Investigation of deformation mechanisms involved in the plasticity of AZ31 Mg alloy: in situ neutron diffraction and EPSC modelling

In situ neutron diffraction and Elasto-Plastic Self-Consistent (EPSC) polycrystal modelling have been employed to investigate which deformation mechanisms are involved in the plasticity of extruded AZ31 Mg alloy during the tensile loading along the extrusion direction. On the basis of this study we were able to determine the relative activity of the slip and twinning deformation modes. By tuning the parameters of the EPSC model (i.e. the critical resolved shear strengths and hardening parameters), excellent agreement with the experimental data has been achieved. It is shown that the strain in the crystallographic ⟨c ⟩direction is accommodated mainly by ⟨c + a ⟩ dislocation slip on second-order pyramidal planes. The results further indicate that either slip of ⟨a ⟩dislocations occurs on {10.1} pyramidal planes or cross-slip from basal and prismatic planes takes place.

Identification and rationalization of secondary twin variants in a magnesium alloy

The present work combines electron backscatter diffraction, transmission electron microscopy and Schmid analysis to investigate secondary twinning in the magnesium alloy Mg-3AI-1Zn. Inspection of the misorientations between the parent matrix and {1011} - {1012} doubly twinned volumes reveals that there are four possible variants. One of these variants characterized by 38°< 1210 > misorientation with the matrix is favoured much more than the others. This variant involves activation of the secondary twinning systems that are quite inconsistent with the Schmid-type behaviour. For the secondary twin to grow significantly it must take on a shape enforced by the primary twin, however, this is not optimal for strain compatibility. It is argued that the 38° < 1210 > variant occurs most frequently because it provides the closest match between the primary and secondaty twinning planes, thus minimizing the compatibility strain. This conjecture is confirmed by the simulations of twin activity m ellipsoidal grains performed using the visco-plastic self-consistent crystal plasticity model.

Determinants of female fertility in Taiwan, 1966–2001 : empirical evidence from cointegration and variance decomposition analysis

This study investigates the determinants of the fertility rate in Taiwan over the period 1966–2001. Consistent with theory, the key explanatory variables in Taiwan's fertility model are real income, infant mortality rate, female education and female labor force participation rate. The test for cointegration is based on the recently developed bounds testing procedure while the long-run and short-run elasticities are based on the autoregressive distributed lag model. Among our key results, female education and female labor force participation rate are found to be the key determinants of fertility in Taiwan in the long run. The variance decom-position analysis indicates that in the long run approximately 45percent of the variation in fertility is explained by the combined impact of female labor force participation, mortality and income, implying that socioeconomic development played an important role in the fertility transition in Taiwan. This result is consistent with the traditional structural hypothesis.

An econometric analysis of the determinants of fertility for China, 1952-2000

This study investigates the determinants of the fertility rate in China over the 1952-2000 period. Consistent with theory, the key explanatory variables in our fertility model are real per capita income, infant mortality rate, female illiteracy and female labour force participation rates. The long-run results and the test for cointegration are based on the Johansen (1988) and Johansen & Juselius (1990) approach. Our long-run results conform to theory in that all variables appear with their expected signs, and the dummy variable used to capture the effects of the family planning policy indicates that in the years of the policy, fertility rates have been falling by around 10-12%. Our results suggest that socio-economic development - consistent with the traditional structural hypothesis - played a key role in China's fertility transition.