In situ imaging and height reconstruction of phase separation processes in polymer blends during spin coating

Spin coating polymer blend thin films provides a method to produce multiphase functional layers of high uniformity covering large surface areas. Applications for such layers include photovoltaics and light-emitting diodes where performance relies upon the nanoscale phase separation morphology of the spun film. Furthermore, at micrometer scales, phase separation provides a route to produce self-organized structures for templating applications. Understanding the factors that determine the final phase-separated morphology in these systems is consequently an important goal. However, it has to date proved problematic to fully test theoretical models for phase separation during spin coating, due to the high spin speeds, which has limited the spatial resolution of experimental data obtained during the coating process. Without this fundamental understanding, production of optimized micro- and nanoscale structures is hampered. Here, we have employed synchronized stroboscopic illumination together with the high light gathering sensitivity of an electron-multiplying charge-coupled device camera to optically observe structure evolution in such blends during spin coating. Furthermore the use of monochromatic illumination has allowed interference reconstruction of three-dimensional topographies of the spin-coated film as it dries and phase separates with nanometer precision. We have used this new method to directly observe the phase separation process during spinning for a polymer blend (PS-PI) for the first time, providing new insights into the spin-coating process and opening up a route to understand and control phase separation structures. © 2011 American Chemical Society.

Integrating strategic groups and the resource based perspective:understanding the competitive process

Although the strategic group and resource based perspectives are frequently presented as mutually exclusive, we argue otherwise. The resource based view informs strategic group analysis through a firm's product or service portfolio by offering a richer perspective on strategy and an additional lens for competitive group interpretation. Products act as the locus and bedrock for corporate decisions and form the backbone upon which market strategies are constructed. A "corporate genome" analogy is presented to illustrate how this process occurs within the U.K. pharmaceutical industry. © 2005 Elsevier Ltd. All rights reserved.

The pH-induced swelling and collapse of a polybase brush synthesized by atom transfer radical polymerization

We have used neutron reflectometry to characterize the swelling behaviour of brushes of poly[2-(diethyl amino)ethyl methacrylate], a polybase, as a function of pH. The brushes, synthesized by the "grafting from" method of atom transfer radical polymerization, were observed to approximately double their thickness in low pH solutions, although the pK is shifted to a lower pH than in dilute solution. The composition-depth profile obtained from the reflectometry experiments for the swollen brushes reveals a region depleted in polymer between the substrate and the extended part of the brush.

Controlled growth of poly(2-(diethylamino)ethyl methacrylate) brushes via atom transfer radical polymerisation on planar silicon surfaces

Progress in making pH-responsive polyelectrolyte brushes with a range of different grafting densities is reported. Polymer brushes of poly(2-(diethylamino)ethyl methacrylate) were synthesised via atom transfer radical polymerisation on silicon wafers using a 'grafted from' approach. The [11-(2-bromo-2-methyl) propionyloxy]undecyl trichlorosilane initiator was covalently attached to the silicon via silylation, from which the brushes were grown using a catalytic system of copper(I) chloride and pentamethyldiethylenetriamine in tetrahydrofuran at 80°C. X-ray reflectivity was used to assess the initiator surfaces and an upper limit on the grafting density of the polymer was determined. The quality of the brushes produced was analysed using ellipsometry and atomic force microscopy, which is also discussed.

Mechanical actuation by responsive polyelectrolyte brushes and triblock gels

Progress in the development of actuating molecular devices based on responsive polymers is reviewed. The synthesis and characterization of "grafted from brushes and triblock copolymers is reported. The responsive nature of polyelectrolyte brushes, grown by surface initiated atomic transfer radical polymerization (ATRP), has been characterized by scanning force microscopy, neutron reflectometry, and single molecule force measurements. The molecular response is measured directly for the brushes in terms of both the brush height and composition and the force generated by a single molecule. Triblock copolymers, based on hydrophobic end blocks and polyacid midblock, have been used to produce polymer gels where the deformation of the molecules can be followed directly by small angle Xray scattering (SAXS), and a correlation between molecular shape change and macroscopic deformation has been established. A Landolt pHoscillator, based on bromate/sulfite/ferrocyanide, with a room temperature period of 20 min and a range of 3.1

Responsive brushes and gels as components of soft nanotechnology

Progress in the development of generic molecular devices based on responsive polymers is discussed. Characterisation of specially synthesised polyelectrolyte gels, "grafted from" brushes and triblock copolymers is reported. A Landolt pH-oscillator, based on bromate/ sulfite/ferrocyanide, with a room temperature period of 20 min and a range of 3.1

Directed phase separation of PFO:PS blends during spin-coating using feedback controlled in situ stroboscopic fluorescence microscopy

Uniform thin-films of polymer blends can be produced through spin-coating, which is used on an industrial scale for the production of light emitting diodes, and more recently organic photovoltaic devices. Here, we present the results of the direct observation, and control, over the phase separation of polystyrene and poly(9,9′-dioctylfluorene) during spin-coating using high speed stroboscopic fluorescence microscopy. This new approach, imaging the fluorescence, from a blend of fluorescent + non-fluorescent polymers allows for intensity to be directly mapped to composition, providing a direct determination of composition fluctuations during the spin-coating process. We have studied the compositional development and corresponding structural development for a range of compositions, which produce a range of different phase separated morphologies. We initially observe domains formed by spinodal decomposition, coarsening via Ostwald Ripening until an interfacial instability causes break-up of the bicontinuous morphology. Ostwald ripening continues, and depending upon composition a bicontinuous morphology is re-established. By observing compositional and morphological development in real-time, we are able to direct and control morphological structure development through control of the spin coating parameters via in situ feedback. © 2013 The Royal Society of Chemistry.

Howard Johnson's: Rise and Fall of an American Icon

The Howard Johnson’s restaurant chain was one of the first franchise success stories in the United States. Climbing in size to be over 1,000 restaurants, the chain today boasts fewer than 30 units. How could such a successful company spiral downward to virtually nothing? This article examines the history of the chain and offers reasons for its success and demise.

Paradigm shift in determining Neoproterozoic atmospheric oxygen

ACKNOWLEDGMENTS We thank the Geological Survey of Australia for permission to sample the Empress 1A and Lancer 1 cores, the Natural Sciences and Engineering Research Council of Canada for financial support (grant #7961–15) of U. Brand, and the National Natural Science Foundation of China for support of F. Meng and P. Ni (grants 41473039 and 4151101015). We thank M. Lozon (Brock University) for drafting and constructing the figures. We thank the editor, Brendan Murphy, as well as three reviewers (Steve Kesler, Erik Sperling, and an anonymous reviewer), for improving the manuscript into its final form ©The Authors Gold Open Access: This paper is published under the terms of the CC-BY license.

Enhanced microbial activity in carbon-rich pillow lavas, Ordovician, Great Britain and Ireland

Date of acceptance: 09/07/2015

Geochemical evidence for a Cretaceous oil sand (Bima oil sand) in the Chad Basin, Nigeria

Timothy Bata is thankful to the Petroleum Technology Development Fund of Nigeria (PTDF) (PTDF/E/OSS/PHD/BTP/359/11) for sponsoring his PhD research at the University of Aberdeen, and the management of Abubakar Tafawa Balewa University, Bauchi, Nigeria, for permitting him to proceed on study leave. We are grateful to Colin Taylor for his help during laboratory work and S. Bowden for advice on the interpretation of the gas chromatographic data.

Enhanced microbial activity in carbon-rich pillow lavas, Ordovician, Great Britain and Ireland

Date of acceptance: 09/07/2015

Geochemical evidence for a Cretaceous oil sand (Bima oil sand) in the Chad Basin, Nigeria

Timothy Bata is thankful to the Petroleum Technology Development Fund of Nigeria (PTDF) (PTDF/E/OSS/PHD/BTP/359/11) for sponsoring his PhD research at the University of Aberdeen, and the management of Abubakar Tafawa Balewa University, Bauchi, Nigeria, for permitting him to proceed on study leave. We are grateful to Colin Taylor for his help during laboratory work and S. Bowden for advice on the interpretation of the gas chromatographic data.

A micrometeorite record in Ordovician Durness Group limestones, Isle of Skye

Peer reviewed

Anomalous supply of bioessential molybdenum in mid-Proterozoic surface environments

Date of Acceptance: 29/12/2015 We are grateful to A. Sandison and W. Thayalon for skilled technical support, and Mike Porter and an anonymous reviewer, who helped to clarify the manuscript.