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- Demixing instability in coil-rod blends undergoing polycondensation reactionsPublication . Teixeira, PauloThe authors extend their earlier work on the stability of a reacting binary polymer blend with respect to demixing [D. J. Read, Macromolecules 31, 899 (1998); P. I. C. Teixeira , Macromolecules 33, 387 (2000)] to the case where one of the polymers is rod-like and may order nematically. As before, the authors combine the random phase approximation for the free energy with a Markov chain model for the chemistry to obtain the spinodal as a function of the relevant degrees of reaction. These are then calculated by assuming a simple second-order chemical kinetics. Results are presented, for linear systems, which illustrate the effects of varying the proportion of coils and rods, their relative sizes, and the strength of the nematic interaction between the rods. (c) 2007 American Institute of Physics.
- Shear-induced lamellar phase of an ionic liquid crystal at room temperaturePublication . Godinho, M. H.; Cruz, C.; Teixeira, Paulo; Ferreira, A. J.; Costa, Carla; Kulkarni, P. S.; Afonso, C. A. M.The phase behaviour of a number of N-alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50 degrees C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at "Plateau borders" with three or more sides. Where walls meet three at a time, they do so at approximately 120 degrees angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self-organised monodomains, as observed in these systems, is expected to play an important role in potential applications.
- Simulation and theory of hybrid aligned liquid crystal filmsPublication . Teixeira, Paulo; Barmes, F.; Anquetil-Deck, C.; Cleaver, D. J.We present a study of the effects of nanoconfinement on a system of hard Gaussian overlap particles interacting with planar substrates through the hard-needle-wall potential, extending earlier work by two of us [D. J. Cleaver and P. I. C. Teixeira, Chem. Phys. Lett. 338, 1 (2001)]. Here, we consider the case of hybrid films, where one of the substrates induces strongly homeotropic anchoring, while the other favors either weakly homeotropic or planar anchoring. These systems are investigated using both Monte Carlo simulation and density-functional theory, the latter implemented at the level of Onsager's second-virial approximation with Parsons-Lee rescaling. The orientational structure is found to change either continuously or discontinuously depending on substrate separation, in agreement with earlier predictions by others. The theory is seen to perform well in spite of its simplicity, predicting the positional and orientational structure seen in simulations even for small particle elongations.
- Tuneable micro- and nano-periodic structures in urethane/urea networksPublication . Godinho, M. H.; Figueirinhas, J. L.; Brogueira, Pedro; Teixeira, PauloMicro- and nano-patterned materials are of great importance for the design of new nanoscale electronic, optical and mechanical devices, ranging from sensors to displays. A prospective system that can support a designed functionality is elastomeric polyurethane thin films with nano- or micromodulated surface structures ("wrinkles"). These wrinkles can be induced on different lengthscales by mechanically stretching the films, without the need for any sophisticated lithographic techniques. In the present article we focus on the experimental control of the wrinkling process. A simple model for wrinkle formation is also discussed, and some preliminary results reported. Hierarchical assembly of these tunable structures paves the way for the development of a new class of materials with a wide range of applications, from electronics to biomedicine.
- Foam as a geometerPublication . Teixeira, Paulo; Buescu, J.Foams are found everywhere: in nature, in technology, in our home. They are examples of cellular materials: assemblies or clusters of cells (from Latin cella: a small compartment or enclosed region) packed together so that they fill space without gaps. Foams come in different kinds. Ordinary liquid foam is an experimental system that solves some difficult geometry problems.
- Contact angle of a hemispherical bubble: An analytical approachPublication . Teixeira, M. A. C.; Teixeira, PauloWe have calculated the equilibrium shape of the axially symmetric Plateau border along which a spherical bubble contacts a flat wall, by analytically integrating Laplace's equation in the presence of gravity, in the limit of small Plateau border sizes. This method has the advantage that it provides closed-form expressions for the positions and orientations of the Plateau border surfaces. Results are in very good overall agreement with those obtained from a numerical solution procedure, and are consistent with experimental data. In particular we find that the effect of gravity on Plateau border shape is relatively small for typical bubble sizes, leading to a widening of the Plateau border for sessile bubbles and to a narrowing for pendant bubbles. The contact angle of the bubble is found to depend even more weakly on gravity. (C) 2009 Elsevier Inc. All rights reserved.
- How to mimic the shapes of plant tendrils on the nano and microscale: spirals and helices of electrospun liquid crystalline cellulose derivativesPublication . Godinho, M. H.; Canejo, João; Pinto, L. F. V.; Borges, J. P.; Teixeira, PauloWe show that suspended nano and microfibres electrospun from liquid crystalline cellulosic solutions will curl into spirals if they are supported at just one end, or, if they are supported at both ends, will twist into a helix of one handedness over half of its length and of the opposite handedness over the other half, the two halves being connected by a short straight section. This latter phenomenon, known as perversion, is a consequence of the intrinsic curvature of the fibres and of a topological conservation law. Furthermore, agreement between theory and experiment can only be achieved if account is taken of the intrinsic torsion of the fibres. Precisely the same behaviour is known to be exhibited by the tendrils of climbing plants such as Passiflora edulis, albeit on a lengthscale of millimetres, i.e., three to four orders of magnitude larger than in our fibres. This suggests that the same basic, coarse-grained physical model is applicable across a range of lengthscales.
- How foam-like is the shear-induced lamellar phase of an ionic liquid crystal?Publication . Cruz, C.; Godinho, M. H.; Ferreira, A. J.; Kulkarni, P. S.; Afonso, C. A. M.; Teixeira, PauloIn a recent article [ M. H. Godinho et al., Liq. Cryst. 35, 103 ( 2008)] we reported that sheared films of two n-alkylimidazolium salts exhibit liquid crystalline behaviour below their bulk equilibrium freezing temperature. The resulting morphologies are strongly reminiscent of two-dimensional liquid foams: the materials partition into dark domains ( cells) separated by brighter ( birefringent) walls, which are approximately arcs of circle and meet at vertices ("Plateau borders") with three or more sides. Here we investigate whether they satisfy known quantitative results for foams [see, e. g. D. Weaire and S. Hutzler, The Physics of Foams ( Oxford University Press, Oxford, 1999)]. We find that: (i) where three walls meet, they do so at approximately 120 degrees angles, for all times studied; (ii) Lewis's law of linear relation between cell area and number of sides is approximately satisfied at late times; (iii) the morphological patterns coarsen in time, both T1 and T2 processes are observed and, at late times, evolution is consistent with von Neumann's law; and (iv) relatively large numbers of 5-sided cells survive up to fairly late times. Results ( i) and ( iii) suggest that surface tension may play a key role in determining the physics of this system, as it does in low-viscosity liquid foams.
- How patchy can one get and still condense? The role of dissimilar patches in the interactions of colloidal particlesPublication . Tavares, Jose; Teixeira, Paulo; Gama, MargaridaWe investigate the influence of strong directional, or bonding, interactions on the phase diagram of complex fluids, and in particular on the liquid-vapour critical point. To this end we revisit a simple model and theory for associating fluids which consist of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the interactions between each pair of spots have strengths [image omitted], [image omitted] and [image omitted]. The theory is applied over the whole range of bonding strengths and results are interpreted in terms of the equilibrium cluster structures of the coexisting phases. In systems where unlike sites do not interact (i.e. where [image omitted]), the critical point exists all the way to [image omitted]. By contrast, when [image omitted], there is no critical point below a certain finite value of [image omitted]. These somewhat surprising results are rationalised in terms of the different network structures of the two systems: two long AA chains are linked by one BB bond (X-junction) in the former case, and by one AB bond (Y-junction) in the latter. The vapour-liquid transition may then be viewed as the condensation of these junctions and we find that X-junctions condense for any attractive [image omitted] (i.e. for any fraction of BB bonds), whereas condensation of the Y-junctions requires that [image omitted] be above a finite threshold (i.e. there must be a finite fraction of AB bonds).
- Helical Twisting of Electrospun Liquid Crystalline Cellulose Micro- and NanofibersPublication . Canejo, João; Borges, João P.; Godinho, M. Helena; Brogueira, Pedro; Teixeira, Paulo; Terentje, Eugene M.Helically twisted fibers can be produced by electrospinning liquid-crystalline cellulose solutions. Fiber topographies are studied by atomic force microscopy, scanning electron microscopy (see figure) and polarized optical microscopy. The fibers have a nearly universal pitch-to-diameter ratio and comprise both right- and left-handed helices.