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Ouzo is a well-known drink in Mediterranean countries, with ingredients water, alcohol and trans-anethole oil. The oil is insoluble in water, but completely soluble in alcohol, so when water is added to the spirit, the available alcohol is depleted and the mixture exhibits spontaneous emulsification. This process is commonly known as the louche or ouzo effect. Although the phase boundaries of this archetypal ternary mixture are well known, the properties of coexisting phases have not previously been studied. Here, we present a detailed experimental investigation into the phase behaviour, including tie-lines connecting coexisting phases, determination of the critical point (also called the plait point in ternary systems) and measurements of the surface tension and density for varying alcohol concentrations. Additionally, we present a theory for the thermodynamics and phase diagram of the system. With suitable selection of the interaction parameters, the theory captures nearly all features of the experimental work. This simple model can be used to determine both bulk and non-uniform (e.g. interfacial) properties, paving the way for a wide range of future applications of the model to ternary mixtures in general. We show how our accurate equilibrium phase diagram can be used to provide improved understanding of non-equilibrium phenomena.
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The effects of particle interactions on the size segregation and assembly of colloidal mixtures during drying were investigated. A cationic surfactant was added to a binary latex/silica colloidal dispersion that has been shown to self-stratify upon drying at room temperature. Atomic force microscopy was used to show that the change in particle interactions due to the presence of surfactants reduced the degree of stratification and, in some cases, suppressed the effect altogether. Colloidal dispersions containing higher surfactant concentrations can undergo a complete morphology change, resulting instead in the formation of armored particles consisting of latex particles coated with smaller silica nanoparticles. To further prove that armored particles are produced and that stratification is suppressed, cross-sectional images were produced with energy-dispersive X-ray spectroscopy and confocal fluorescence microscopy. The growth of armored particles was also measured using dynamic light scattering. To complement this research, Brownian dynamics simulations were used to model the drying. By tuning the particle interactions to make them more attractive, the simulations showed the presence of armored particles, and the size segregation process was hindered. The prevention of segregation also results in enhanced transparency of the colloidal films. Overall, this research proves that there is a link between particle interactions and size segregation in drying colloidal blends and provides a valuable tool to control the assembly of different film architectures using an extremely simple method.
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We investigate bulk thermodynamic and microscopic structural properties of amorphous solids in the framework of the phase-field crystal (PFC) model. These are metastable states with a non-uniform density distribution, having no long-range order. From extensive numerical simulations, we determine the distribution of free energy density values in varying size amorphous systems and also the point-to-set correlation length, which is the radius of the largest volume of amorphous one can take while still having the particle arrangements within the volume determined by the particle ordering at the surface of the chosen volume. We find that in the thermodynamic limit, the free energy density of the amorphous tends toward a value that has a slight dependence on the initial state from which it was formed-i.e., it has a formation history dependence. The amorphous phase is observed to form on both sides of the liquid linear-stability limit, showing that the liquid to amorphous transition is first order, with an associated finite free energy barrier when the liquid is metastable. In our simulations, this is demonstrated when the noise in the initial density distribution is used to induce nucleation events from the metastable liquid. Depending on the strength of the initial noise, we observe a variety of nucleation pathways, in agreement with previous results for the PFC model, which show that amorphous precursor mediated multi-step crystal nucleation can occur in colloidal systems.
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We develop a dynamical density functional theory based model for the drying of colloidal films on planar surfaces. We consider mixtures of two different sizes of hard-sphere colloids. Depending on the solvent evaporation rate and the initial concentrations of the two species, we observe varying degrees of stratification in the final dried films. Our model predicts the various structures described in the literature previously from experiments and computer simulations, in particular the small-on-top stratified films. Our model also includes the influence of adsorption of particles to the interfaces.
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Understanding the wetting properties of premelting films requires knowledge of the film's equation of state, which is not usually available. Here we calculate the disjoining pressure curve of premelting films and perform a detailed thermodynamic characterization of premelting behavior on ice. Analysis of the density profiles reveals the signature of weak layering phenomena, from one to two and from two to three water molecular layers. However, disjoining pressure curves, which closely follow expectations from a renormalized mean field liquid state theory, show that there are no layering phase transitions in the thermodynamic sense along the sublimation line. Instead, we find that transitions at mean field level are rounded due to capillary wave fluctuations. We see signatures that true first order layering transitions could arise at low temperatures, for pressures between the metastable line of water-vapor coexistence and the sublimation line. The extrapolation of the disjoining pressure curve above water-vapor saturation displays a true first order phase transition from a thin to a thick film consistent with experimental observations.
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Hard-core/soft shell (HCSS) particles have been shown to self-assemble into a remarkably rich variety of structures under compression due to the simple interplay between the hard-core and soft-shoulder length scales in their interactions. Most studies in this area model the soft shell interaction as a square shoulder potential. Although appealing from a theoretical point of view, the potential is physically unrealistic because there is no repulsive force in the soft shell regime, unlike in experimental HCSS systems. To make the model more realistic, here we consider HCSS particles with a range of soft shell potential profiles beyond the standard square shoulder form and study the model using both minimum energy calculations and Monte Carlo simulations. We find that by tuning density and the soft shell profile, HCSS particles in the thin shell regime (i.e., shell to core ratio ) can form a large range of structures, including hexagons, chains, squares, rhomboids and two distinct zig-zag structures. Furthermore, by tuning the density and r1/r0, we find that HCSS particles with experimentally realistic linear ramp soft shoulder repulsions can form honeycombs and quasicrystals with 10-fold and 12-fold symmetry. Our study therefore suggests the exciting possibility of fabricating these exotic 2D structures experimentally through colloidal self-assembly.
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Bacterial cellulose (BC) has interesting properties including high crystallinity, tensile strength, degree of polymerisation, water holding capacity (98%) and an overall attractive 3D nanofibrillar structure. The mechanical and electrochemical properties can be tailored upon incomplete BC dehydration. Under different water contents (100, 80 and 50%), the rheology and electrochemistry of BC were evaluated, showing a progressive stiffening and increasing resistance with lower capacitance after partial dehydration. BC water loss was mathematically modelled for predicting its water content and for understanding the structural changes of post-dried BC. The dehydration of the samples was determined via water evaporation at 37 °C for different diameters and thicknesses. The gradual water evaporation observed was well-described by the model proposed (R2 up to 0.99). The mathematical model for BC water loss may allow the optimisation of these properties for an intended application and may be extendable for other conditions and purposes.
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In classical density functional theory (DFT), the part of the Helmholtz free energy functional arising from attractive inter-particle interactions is often treated in a mean-field or van der Waals approximation. On the face of it, this is a somewhat crude treatment as the resulting functional generates the simple random phase approximation (RPA) for the bulk fluid pair direct correlation function. We explain why using standard mean-field DFT to describe inhomogeneous fluid structure and thermodynamics is more accurate than one might expect based on this observation. By considering the pair correlation function g(x) and structure factor S(k) of a one-dimensional model fluid, for which exact results are available, we show that the mean-field DFT, employed within the test-particle procedure, yields results much superior to those from the RPA closure of the bulk Ornstein-Zernike equation. We argue that one should not judge the quality of a DFT based solely on the approximation it generates for the bulk pair direct correlation function.
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Using classical density functional theory(DFT), we calculate the density profile ρ(ð«) and local compressibility χ(ð«) of a simple liquidsolvent in which a pair of blocks with (microscopic) rectangular cross section are immersed. We consider blocks that are solvophobic, solvophilic and also ones that have both solvophobic and solvophilic patches. Large values of χ(ð«) correspond to regions in space where the liquid density is fluctuating most strongly. We seek to elucidate how enhanced density fluctuations correlate with the solvent mediated force between the blocks, as the distance between the blocks and the chemical potential of the liquid reservoir vary. For sufficiently solvophobic blocks, at small block separations and small deviations from bulk gas-liquid coexistence, we observe a strongly attractive (near constant) force, stemming from capillary evaporation to form a low density gas-like intrusion between the blocks. The accompanying χ(ð«) exhibits a structure which reflects the incipient gas-liquid interfaces that develop. We argue that our model system provides a means to understanding the basic physics of solvent mediated interactions between nanostructures, and between objects such as proteins in water that possess hydrophobic and hydrophilic patches.
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For a film of liquid on a solid surface, the binding potential g(h) gives the free energy as a function of the film thickness h and also the closely related (structural) disjoining pressure Π=-∂g/∂h. The wetting behaviour of the liquid is encoded in the binding potential and the equilibrium film thickness corresponds to the value at the minimum of g(h). Here, the method we developed in the work of Hughes et al. [J. Chem. Phys. 142, 074702 (2015)], and applied with a simple discrete lattice-gas model, is used with continuum density functional theory (DFT) to calculate the binding potential for a Lennard-Jones fluid and other simple liquids. The DFT used is based on fundamental measure theory and so incorporates the influence of the layered packing of molecules at the surface and the corresponding oscillatory density profile. The binding potential is frequently input in mesoscale models from which liquid drop shapes and even dynamics can be calculated. Here we show that the equilibrium droplet profiles calculated using the mesoscale theory are in good agreement with the profiles calculated directly from the microscopic DFT. For liquids composed of particles where the range of the attraction is much less than the diameter of the particles, we find that at low temperatures g(h) decays in an oscillatory fashion with increasing h, leading to highly structured terraced liquid droplets.
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The wetting behavior of a liquid on solid substrates is governed by the nature of the effective interaction between the liquid-gas and the solid-liquid interfaces, which is described by the binding or wetting potential g(h) which is an excess free energy per unit area that depends on the liquid film height h. Given a microscopic theory for the liquid, to determine g(h), one must calculate the free energy for liquid films of any given value of h, i.e., one needs to create and analyze out-of-equilibrium states, since at equilibrium there is a unique value of h, specified by the temperature and chemical potential of the surrounding gas. Here we introduce a Nudged Elastic Band (NEB) approach to calculate g(h) and illustrate the method by applying it in conjunction with a microscopic lattice density functional theory for the liquid. We also show that the NEB results are identical to those obtained with an established method based on using a fictitious additional potential to stabilize the non-equilibrium states. The advantages of the NEB approach are discussed.
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The contribution to the free energy for a film of liquid of thickness h on a solid surface due to the interactions between the solid-liquid and liquid-gas interfaces is given by the binding potential, g(h). The precise form of g(h) determines whether or not the liquid wets the surface. Note that differentiating g(h) gives the Derjaguin or disjoining pressure. We develop a microscopic density functional theory (DFT) based method for calculating g(h), allowing us to relate the form of g(h) to the nature of the molecular interactions in the system. We present results based on using a simple lattice gas model, to demonstrate the procedure. In order to describe the static and dynamic behaviour of non-uniform liquid films and drops on surfaces, a mesoscopic free energy based on g(h) is often used. We calculate such equilibrium film height profiles and also directly calculate using DFT the corresponding density profiles for liquid drops on surfaces. Comparing quantities such as the contact angle and also the shape of the drops, we find good agreement between the two methods. We also study in detail the effect on g(h) of truncating the range of the dispersion forces, both those between the fluid molecules and those between the fluid and wall. We find that truncating can have a significant effect on g(h) and the associated wetting behaviour of the fluid.
Assuntos
Modelos Teóricos , Propriedades de Superfície , Molhabilidade , Adsorção , Gases/químicaRESUMO
Fluids with competing short range attraction and long range repulsive interactions between the particles can exhibit a variety of microphase separated structures. We develop a lattice-gas (generalised Ising) model and analyse the phase diagram using Monte Carlo computer simulations and also with density functional theory (DFT). The DFT predictions for the structures formed are in good agreement with the results from the simulations, which occur in the portion of the phase diagram where the theory predicts the uniform fluid to be linearly unstable. However, the mean-field DFT does not correctly describe the transitions between the different morphologies, which the simulations show to be analogous to micelle formation. We determine how the heat capacity varies as the model parameters are changed. There are peaks in the heat capacity at state points where the morphology changes occur. We also map the lattice model onto a continuum DFT that facilitates a simplification of the stability analysis of the uniform fluid.
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We present a theory for the interfacial wetting phase behavior of binary liquid mixtures on rigid solid substrates, applicable to both miscible and immiscible mixtures. In particular, we calculate the binding potential as a function of the adsorptions, i.e., the excess amounts of each of the two liquids at the substrate. The binding potential fully describes the corresponding interfacial thermodynamics. Our approach is based on classical density functional theory. Binary liquid mixtures can exhibit complex bulk phase behavior, including both liquid-liquid and vapor-liquid phase separation, depending on the nature of the interactions among all the particles of the two different liquids, the temperature, and the chemical potentials. Here we show that the interplay between the bulk phase behavior of the mixture and the properties of the interactions with the substrate gives rise to a wide variety of interfacial phase behaviors, including mixing and demixing situations. We find situations where the final state is a coexistence of up to three different phases. We determine how the liquid density profiles close to the substrate change as the interaction parameters are varied and how these determine the form of the binding potential, which in certain cases can be a multivalued function of the adsorptions. We also present profiles for sessile droplets of both miscible and immiscible binary liquids.
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We present dynamical density functional theory results for the time evolution of the density distribution of a sedimenting model two-dimensional binary mixture of colloids. The interplay between the bulk phase behaviour of the mixture, its interfacial properties at the confining walls, and the gravitational field gives rise to a rich variety of equilibrium and non-equilibrium morphologies. In the fluid state, the system exhibits both liquid-liquid and gas-liquid phase separation. As the system sediments, the phase separation significantly affects the dynamics and we explore situations where the final state is a coexistence of up to three different phases. Solving the dynamical equations in two-dimensions, we find that in certain situations the final density profiles of the two species have a symmetry that is different from that of the external potentials, which is perhaps surprising, given the statistical mechanics origin of the theory. The paper concludes with a discussion on this.
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Dermatofibrosarcoma protuberans (DFSP) is a rare, slow-growing malignancy that often presents with an ambiguous clinical presentation due to its nonspecific findings. We present the case of a 41-year-old male who presented with a slow-growing mass on his abdomen that became protuberant and firm, prompting his desire to pursue excision. Upon return of histologic examination, the specimen was noted to be DFSP. DFSP is a rare cutaneous neoplasm that originates from the dermis and invades the underlying tissue creating a classic protuberant appearance. In some cases, chemotherapy and radiation may be indicated based on margins and locations. The sarcoma is notoriously complicated with early recurrence, making the disease process difficult to control. Surgeons should be familiar with this malignancy due to the indication of additional nonsurgical treatments and the necessity for long-term follow-up for surveillance of recurrence.
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Matter self-assembling into layers generates unique properties, including structures of stacked surfaces, directed transport, and compact area maximization that can be highly functionalized in biology and technology. Smectics represent the paradigm of such lamellar materials - they are a state between fluids and solids, characterized by both orientational and partial positional ordering in one layering direction, making them notoriously difficult to model, particularly in confining geometries. We propose a complex tensor order parameter to describe the local degree of lamellar ordering, layer displacement and orientation of the layers for simple, lamellar smectics. The theory accounts for both dislocations and disclinations, by regularizing singularities within defect cores and so remaining continuous everywhere. The ability to describe disclinations and dislocation allows this theory to simulate arrested configurations and inclusion-induced local ordering. This tensorial theory for simple smectics considerably simplifies numerics, facilitating studies on the mesoscopic structure of topologically complex systems.
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Syringocystadenoma papilliferum (SCAP) is a rare, hamartomatous tumor of the apocrine glands, which typically manifests in the head and neck region. We present a case of 60-year-old male with a several-year history of the lesion located on the abdominal wall and a second case of a 58-year-old male with a history of a slow-growing lesion located on the tragus. Despite varying presentations and locations, both patients were identified to have SCAP on pathological evaluation. Appropriate treatments of SCAP range from CO2 laser treatment to surgical excision; we recommend surgical excision due to the risk of malignant transformation.
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Aperiodic (quasicrystalline) tilings, such as Penrose's tiling, can be built up from, e.g., kites and darts, squares and equilateral triangles, rhombi- or shield-shaped tiles, and can have a variety of different symmetries. However, almost all quasicrystals occurring in soft matter are of the dodecagonal type. Here we investigate a class of aperiodic tilings with hexagonal symmetry that are based on rectangles and two types of equilateral triangles. We show how to design soft-matter systems of particles interacting via pair potentials containing two length scales that form aperiodic stable states with two different examples of rectangle-triangle tilings. One of these is the bronze-mean tiling, while the other is a generalization. Our work points to how more general (beyond dodecagonal) quasicrystals can be designed in soft matter.
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Adenoid cystic carcinoma (ACC), characterized by proliferating glands and stromal and basement membrane elements, is a tumor most commonly occurring in the salivary glands; very rarely does this tumor present as a primary tumor in the breast. We present the case of a 53-year-old female who presented with a breast mass noted to be concerning on imaging and confirmed to be ACC on biopsy. The mass was amenable to surgical excision with referrals to medical and radiation oncology. Due to the rarity of the disease, there is no consensus regarding the optimal treatment strategy for the pathology, including the use of chemotherapy and radiation. Long-term follow-up is, however, recommended in order to monitor for recurrence.