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Oppositely charged polyelectrolyte-surfactant mixtures are ubiquitous in biology and the basis of numerous consumer healthcare products. Despite their broad use, however, a rational approach to their formulation remains challenging because of the complicated association mechanisms. Through compilation and analysis of literature reports and our own research, we have developed a semiempirical correlation of the binding strength of surfactants to polyelectrolytes in salt-free mixtures as a function of the polyion linear charge density and the surfactant hydrophobicity. We have found that the cooperative binding strength increases as the square of the polyelectrolyte's linear charge density and in proportion to the surfactant's hydrophobicity, such that a quantitative relationship holds across a broad range of polyelectrolytes. Deviations from the correlation reveal the role of system-specific interactions not considered in the analysis. This engineering relationship aids in the rational design of oppositely charged polyelectrolyte-surfactant formulations for consumer products and biomedicines by enabling the prediction of binding strengths in polyelectrolyte-surfactant mixtures based on mesoscale parameters determined from the chemical composition. [ABSTRACT FROM AUTHOR]

Models, theories, and simulations for the low shear viscosity of Brownian, hard-sphere dispersions are examined and evaluated against literature data. Hydrodynamic and thermodynamic contributions are explicitly treated and the volume fraction dependence of the experimental data is validated against the high frequency or high shear viscosity. A good description of the data is realized by a new, semiempirical model based on mode coupling theory, where [lowercase_phi_synonym]m=[lowercase_phi_synonym]g=0.57, supporting dynamical arrest at the ideal glass transition. [ABSTRACT FROM AUTHOR]

Use of glyphosate-based herbicides is increasing worldwide. The authors review the available data related to potential impacts of these herbicides on amphibians and conduct a qualitative meta-analysis. Because little is known about environmental concentrations of glyphosate in amphibian habitats and virtually nothing is known about environmental concentrations of the substances added to the herbicide formulations that mainly contribute to adverse effects, glyphosate levels can only be seen as approximations for contamination with glyphosate-based herbicides. The impact on amphibians depends on the herbicide formulation, with different sensitivity of taxa and life stages. Effects on development of larvae apparently are the most sensitive endpoints to study. As with other contaminants, costressors mainly increase adverse effects. If and how glyphosate-based herbicides and other pesticides contribute to amphibian decline is not answerable yet due to missing data on how natural populations are affected. Amphibian risk assessment can only be conducted case-specifically, with consideration of the particular herbicide formulation. The authors recommend better monitoring of both amphibian populations and contamination of habitats with glyphosate-based herbicides, not just glyphosate, and suggest including amphibians in standardized test batteries to study at least dermal administration. Environ Toxicol Chem 2013;32:1688-1700. © 2013 SETAC [ABSTRACT FROM AUTHOR]

El artículo examina cómo están afrontando la crisis diferentes regímenes de seguridad social en función de sus mecanismos de financiación. Se centra en cinco países de la Unión Europea representativos de los diversos modelos. Muestra que la crisis y las medidas de estímulo o austeridad asociadas han provocado una disminución de los recursos asignados al bienestar social, y que, a corto o medio plazo, los regímenes contributivos son financieramente más sólidos durante las recesiones que los no contributivos. El modelo contributivo continental parece el más estable a largo plazo, al centrarse en el mantenimiento del empleo, principal fuente de ingresos del Estado. [ABSTRACT FROM AUTHOR]

Micellar solutions of hexadecyltrimethylammonium bromide(CTAB)in a protic ionic liquid, ethylammonium nitrate (EAN), are studiedby shear rheology, polarizing optical microscopy (POM), conductivitymeasurements, and small angle neutron scattering (SANS). Three concentrationregimes are examined: A dilute regime (with concentrations [CTAB]< 5 wt %) consisting of noninteracting spherical micelles, a semidiluteregime (5 wt % ≤ [CTAB] ≤ 45 wt %) where micelles interactvia electrostatic repulsions, and a concentrated regime (45 wt % <[CTAB] ≤ 62 wt %) where a reversible, temperature-dependentisotropic (L1) to hexatic (Hex) phase transition is observed.The L1–Hex transition, which has been predictedbut not previously observed, is characterized by (1) a sharp increasein the shear viscosity, (2) the formation of focal conical birefringencetextures (observed by POM), and (3) enhancement of the crystallineorder, evidenced by the appearance of Bragg reflections in the SANSprofiles. Ionic conductivity is not sensitive to the L1–Hex transition, which corroborates the absence of topologicaltransitions. [ABSTRACT FROM AUTHOR]

In this Article, we report the dielectrophoretic assemblyof colloidalparticles and show how the kinetics of assembly and degree of orderingdepend on the particle size, charge, solution ionic strength, andfield strength and frequency. A special dielectrophoresis (DEP) samplecell is constructed and validated to quantitatively measure directedself-assembly via sequential light scattering and optical microscopymeasurements. Our results confirm the recently established scalingfor the order–disorder transition and extend it to higher scaledfrequencies. The limiting scaling of the order–disorder transitionand particle electrophoretic mobility are correctly predicted by thestandard electrokinetic model (SEKM). In particular, the order–disordertransition line is predicted from the particle properties using arecently proposed empirical scaling law and the SEKM over an orderof magnitude in particle size. [ABSTRACT FROM AUTHOR]

Large amplitude oscillatory shear (LAOS) is an increasingly popular nonlinear rheological test method, and the interpretation of the measurements is still an active area of research. Here, we demonstrate a new method whereby the nonlinear parameters of a popular constitutive equation used to model polymeric and other viscoelastic systems, the Giesekus model, may be determined directly from LAOS measurements without complicated, nonlinear model fitting. We define the stress response of the sample as an expansion in deformation strain and oscillation frequency. To leading order in strain, we derive the explicit analytic expressions for the first three harmonics of the stress response during LAOS for the Giesekus constitutive model. This allows for rapid determination of the Giesekus model parameters, including the nonlinear coupling parameter, directly from plots of the response obtained from modern rheological instruments. We demonstrate the validity, utility, and limits of this new method on a well-studied wormlike micelle (WLM) surfactant solution, cetyltrimethylammonium bromide (CTAB), and water. This robust and simple approach is especially advantageous for systems where steady shearing in the nonlinear regime is problematic and can provide rapid determination of parameters in rheological constitutive equations. [ABSTRACT FROM AUTHOR]

Individual members of a population of 'prolonged' breeding amphibian species are asynchronously present at their breeding sites. Therefore, population size estimates can be misleading when based on commonly used closed or open-population capture-mark-recapture approaches. The superpopulation approach, a modified Jolly-Seber model, has been successfully applied in taxa other than amphibians with distinct migratory behaviour and where individuals are asynchronously present at the sampling site. In this paper, we suggest that the superpopulation approach is a useful population size estimator for 'prolonged' breeding amphibian species. Two case studies on European anurans show that superpopulation estimates are much higher than simple population counts. A simulation study showed that superpopulation estimates are unbiased but that accuracy can be low when either survival or detection probabilities (or both) are low. We recommend the superpopulation approach because it matches the natural history and phenology of amphibian species with prolonged breeding seasons. [ABSTRACT FROM AUTHOR]

Frequency- and temperature-dependent complex permittivity or conductivity of a silty clay loam were examined in a broad saturation and porosity range with network analyzer technique (1 MHz–10 GHz, 5 ^\circ\C–40 ^\circ\C, coaxial transmission line and open ended coaxial cells). An advanced mixture model based on the well-known Lichtenecker–Rother model (ALRM) was developed and used to parameterize complex permittivity or conductivity at a measurement frequency of 1 GHz under consideration of a dependence of the so-called structure parameter as well as the apparent pore water conductivity on saturation and porosity. The ALRM is compared with frequently applied mixture models: complex refractive index model, Looyenga–Landau–Lifschitz model, Bruggeman–Hanai–Sen model, and Maxwell–Garnet model as well as empirical calibration functions. Comparison of ALRM applied to the investigated frequency and temperature range with sophisticated broadband relaxation models indicates the potential and the limitation to predict the high-frequency electromagnetic material properties. [ABSTRACT FROM AUTHOR]

The article discusses the role of shear thickening in colloidal dispersions. It states that a change in viscosity will likely to happen when colloidal fluids experience shear stress resulting to the stiffening of the products such as paints, cements and shampoos. It adds that scientists and physics community have studied the highly nonlinear materials to deal the problems occurring in the shear-thickening colloidal dispersions.

High-frequency electromagnetic determination of moisture in porous media, (e.g., soil) is based on the strong relationship between volumetric water content and relative dielectric permittivity. In particular, in fine-grained soils the movement of water is influenced by different surface-bonding forces due to interface processes. The interface effects lead to a number of dielectric relaxation processes (free- and bound-water phase, Maxwell–Wagner effect, counterion relaxation effects). These relaxation processes are the reason for the strong frequency dependence of the electromagnetic material properties below 1 GHz. The matric potential is a measure of the bonding forces on water in the soil. Based on a thermodynamic relationship between soil matric potential and dielectric relaxation behaviour of water in different binding states, a broadband dielectric relaxation model was developed that considers low-frequency dispersion up to 1 MHz as well as losses due to direct-current conductivity. The sensitivity of the model on soil suction was systematically analyzed based on a pedotransfer function (PTF) for soil textures ranging from pure sand up to pure clay. The results are compared with known empirical and semiempirical calibration functions, as well as theoretical mixing models. [ABSTRACT FROM AUTHOR]

Prior work has demonstrated that colloidal suspensions can be ordered with large amplitude oscillatory shear (LAOS), showing that the final type and degree of ordering depends on the frequency and amplitude of the applied oscillation. Here, we present LAOS results for the kinetics of ordering for colloidal particles (d=1 μm) at [lowercase_phi_synonym]=0.54 from a shear disordered state over a range of frequencies and shear amplitudes. A custom rheolight scattering (rheo-LS) device is used to quantify the type and degree of crystalline order observed either as a six spot Bragg pattern or a three streak twinning pattern. The dynamic shear stress and the alignment factor derived from the rheo-LS show the same time-dependent behavior indicative of a primary relaxation that is exponential in time. The rate of ordering to the r-hcp state is found to scale with the amplitude of oscillation and inversely with the frequency over strains from 100% to 300% and frequencies from 0.5 to 5 Hz. These results show that the rate of LAOS ordering does not simply reflect the rate of deformation, but rather a more complex mechanism pointing toward competition between shear ordering and shear-induced defect generation. [ABSTRACT FROM AUTHOR]

Abstract: The complex rheological behaviour of suspensions is very strongly affected by the details of the microstructure and the interparticle forces by which it is controlled. The difficulties involved in characterizing the microstructure, in particular during flow, caused the development of suspension rheology to lag behind that of polymer rheology. Progress in theory, experiments and simulation is rapidly changing the picture, providing opportunities for further significant developments. Possible evolutions in six areas of suspension rheology are discussed here. [Copyright &y& Elsevier]

Abstract: Flow can induce reversible and irreversible structural changes in dispersions. The analysis of flow effects on microstructure and rheology remains one of the challenging problems in colloid science. The rheological manifestation of flow-induced structural changes is a variable viscosity. If the changes are reversible and time dependent, the effect is called thixotropy. The basic elements of this concept are reviewed here, including its definition and the relation with nonlinear viscoelasticity. The omnipresence of thixotropy is illustrated with a wide range of examples from natural and manmade colloidal systems. Its various rheological manifestations are reviewed as well as possible measurement procedures. The microstructural changes due to flow are quite complex and not fully understood. Existing models for thixotropic suspension rheology are categorized and evaluated. [Copyright &y& Elsevier]

Dispersions of multiarm star polymers in an athermal solvent are studied as a model system to explore the effects of soft colloidal interactions on the dynamics of colloidal glasses. Linear viscoelastic measurements in the glassy state are congruent with Mode Coupling Theory predictions for hard sphere glasses at moderate frequencies, indicating similarities in the relaxation processes of hard and soft colloidal glasses near equilibrium. On the other hand, distinct features of the star relaxation (related to arm disengagement) are observed to affect the nonlinear behavior associated with shear melting of the glass, which exhibits transitions previously unreported for hard sphere systems. Whereas a single maximum in G″(γ) is evident under large amplitude oscillatory shear at frequencies near the beta relaxation, secondary transitions between yielding and the onset of macroscopic flow are observed at higher and lower frequencies. The latter are annealed out upon complete fluidization of the star polymer suspension. The overall nonlinear behavior of the soft glassy suspension is interpreted in terms of two primary mechanisms: (i) deformation and yielding of the cage-like glassy microstructure, as in the hard sphere case, and (ii) local stretching and disengagement of interpenetrating arms of the colloidal star polymers. [ABSTRACT FROM AUTHOR]

A micromechanical model for the onset of shear thickening in polymer stabilized colloidal dispersions is derived. The model incorporates both the stabilizing forces of the polymer brush or “coat” and the associated modification of the hydrodynamic interactions. Comparison is made to simulations and experiments on well-characterized dispersions. The model is shown to provide a quantitative prediction for the onset of shear thickening in polymer coated colloidal dispersions as compared to simulations. For comparison with experiments, where independent characterization of some parameters is not available, the onset of shear thickening can be predicted with realistic assumptions for the model parameters. The model quantifies the sensitivity of the shear thickening transition to both the interaction potential and the hydrodynamic permeability of the polymer coat. [ABSTRACT FROM AUTHOR]

The phase behavior of novel hybrid diblock copolymers composed of poly(benzyl ether) dendrons of various generations grafted to deuterated polystyrene tails of varying molecular weights are examined by small angle neutron scattering. Blends of these hybrid copolymers with linear polystyrene of two molecular weights are shown to exhibit dissolution, microphase separation and microphase & mesophase separation depending on the relative molecular weights of the dendrons, tails, and matrix homopolymer. The results suggests that there is a strong entropic penalty against mixing polymers of dendritic architecture with linear chains, and that this driving force can be harnessed to create unique, nanostructured polymer materials. To cite this article: C. R. Chimie 6 (2003). [Copyright &y& Elsevier]

[Display omitted] Colloidal suspensions of anisotropic particles are ubiquitous in particle-based industries. Consequently, there is a need to quantify the effects of particle shape on equilibrium phases and kinetic state transitions, particularly at lower aspect ratios (L / D ≈ 1–10). We present a new, colloidal system comprised of hollow, octadecyl-coated silica rods with 40 nm diameter with controlled aspect ratio and thermoreversible short-range attractions. Rheology and dynamic light scattering measurements on suspensions of these hollow adhesive hard rods with nominal aspect ratio ≈3 suspended in tetradecane exhibit thermoreversible gelation without complicating effects of gravitational settling. Small angle neutron scattering measurements of the microstructure are analyzed to determine the effective strength of attraction in the form of Baxter sticky parameter. Quantitative agreement is found with simulation predictions of the thermoreversible gel transition as a function of volume fraction, further validating a universal state diagram and providing guidance for the effects of aspect ratio on gelation. [ABSTRACT FROM AUTHOR]

The device described measures a two-dimensional projection of the light scattered from a sheared, optically clear colloidal suspension and decomposes the pattern to identify quantitatively the effects of shear on the structure of the dispersion. The evolution of the nonequilibrium structure for a hard-sphere suspension is traced from low to high shear rates at moderate to dense concentrations and is related qualitatively to rheological properties. At high shear rates shear induces order in dense suspensions. Comparison of the measured nonequilibrium structure factor at low shear rates to theoretical predictions based on pairwise additive interactions confirms the importance of many-body hydrodynamics, as suggested by similar discrepancies between measurements of the steady shear viscosity and predictions from the same theory. Scalings that correlate the shear rate dependence of the viscosity appear to work for the microstructure as well. Measurements of a similar suspension with weak long-range repulsions demonstrates the sensitivity of the nonequilibrium microstructure to the form of the interparticle potential. [ABSTRACT FROM AUTHOR]

An expression for the form birefringence of a shearing colloidal suspension is derived from the renormalization of Adriani and Gast [J. Chem. Phys. 91, 6282 (1990)]. Calculations based on recent predictions for the nonequilibrium microstructure of a shearing hard-sphere suspension are compared with previous measurements. The error in the predictions is in agreement with earlier comparisons of this structure against light scattering and rheological measurements. [ABSTRACT FROM AUTHOR]

In the present work, the macroscopic governing equations governing the heat and mass transfer for a general multicomponent system are derived via a systematic nonequilibrium thermodynamics framework. In contrast to previous approaches, the relative (with respect to the mass average velocity) component mass fluxes (relative species momenta) and the heat flux are treated explicitly, in complete analogy with the momentum flux. The framework followed here, in addition to allowing for the description of relaxation phenomena in heat and mass transfer, establishes to the fullest the analogy between all transport processes, momentum, heat, and mass transfer, toward which R. B. Bird contributed so much with his work. The inclusion of heat flux-based momentum as an additional variable allows for the description of relaxation phenomena in heat transfer as well as of mixed (Soret and Dufour) effects, coupling heat and mass transfer. The resulting models are Galilean invariant, thereby resolving a conundrum in the field, and always respect the second law of thermodynamics, for appropriate selection of transport parameters. The general flux-based dynamic equations reduce to the traditional transport equations in the limit when mass species and heat relaxation effects are negligible and are fully consistent with the equations established from the application of kinetic theory in the limit of dilute gases. As an added benefit, for the particular example case of hyperbolic diffusion we illustrate the application of the proposed models as a method to allow the use of powerful numerical solvers normally not available for solving mass transfer models more generally. [ABSTRACT FROM AUTHOR]

The article presents technical comments on a paper by Rabb and Fahrenthold titled, "Evaluation of Shear-Thickening-Fluid Kevlar for Large-Fragment-Containment Applications." The goal of the study was to determine whether Kevlar fabrics treated with shear thickening fluids (STF) could enhance turbine fan-blade confinement barriers. The limitations of the experimental data are discussed in this technical comment, while the conclusions regarding protective applications are questioned.

Future human space exploration and habitation on the lunar and Martian surfaces necessitates in-situ resource utilization (ISRU) for the development of construction materials tailored for infrastructure and environmental protection. Here we explore the use of lunar and Martian regoliths to create construction materials with properties suitable for such structures as landing pads. Alkali activation of a spectrum of lunar and Martian regolith simulants generates geopolymer binders under ambient and vacuum curing conditions as well as exposure to extreme high and low temperatures (600 and −80 °C). Compressive strength is reduced for binders prepared from each simulant after curing under vacuum and exposure to sub-zero temperatures. In lunar simulant binders, the compressive strength is increased after heating to 600 °C, but the opposite effect is observed in the Martian simulant binder. Amorphous aluminosilicate content and percentage of small particles in the simulants are hypothesized to have a positive impact on compressive strength under ambient curing. Iron and magnesium content may be responsible for decreased compressive strength of the Martian binder after heating. This study offers a robust framework for comparing performance of different simulants under the same curing protocols and environmental exposures, as well as offering insight as to the effects of vacuum curing, and exposure to high and low temperature environments on cured binder samples. Developing a landing pad by transporting activator to the lunar surface is shown to be conceptually feasible within current payload constraints. [ABSTRACT FROM AUTHOR]

Presents a commentary on medical education and training in the information age. Relationship of society with professionals; Advantages of mastery of the basics; Suggestion on the education and training of professionals.

The particle size dependence of the reversible shear thickening transition in dense colloidal suspensions is explored. Five suspensions of monodisperse silica are synthesized via the Sto¨ber synthesis. The physicochemical properties of the dispersions are quantified using transmission electron microscopy, dynamic light scattering, small angle light scattering, electrophoresis, and viscometry. Rheology measurements indicate a critical stress marking the onset of reversible shear thickening that depends on the dispersion's particle size, concentration, polydispersity, and interparticle interactions. A simplified two particle force balance between the interparticle repulsive forces and the hydrodynamic compressive forces is used to derive a scaling relationship between this critical shear stress and the suspension properties. The scaling is tested against the fully characterized silica dispersions, which span nearly a decade in particle size. Furthermore, bimodal mixtures of the dispersions are employed to evaluate the accuracy of the scaling to predict the critical shear stress for dispersions with varying degrees of polydispersity. The success of the scaling supports the hydrocluster mechanism for shear thickening and suggests methods for controlling shear thickening by tailoring particle properties. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In Ref. [1], there was an error in the second integral of Eq. (14) due to an erroneous application of Eq. (A3) in Appendix A of that paper. Correction of the above error requires consideration of a more general expression for the gradient of the chemical potential HT ht (obtained from a general equilibrium thermodynamics reference, such as Refs. Note that only when this error is corrected, the (correct) equation for the time evolution for the entropy density, Eq. (29) of Ref. [1], can be derived. [Extracted from the article]

The article focuses on the issues regarding resurrected species which legal implications particularly for conservation with availability of well-preserved DNA, existence of closely related species who may serve as host or surrogate parents. It mentions attempts to restore via cloning such as Pyrenean ibex, Australian gastric-brooding frog. It also mentions Species Survival Commission (SSC) of the International Union for Conservation of Nature (IUCN) published de-extinction guidelines.

Scientific questions surrounding the shear-dependent microstructure of carbon black suspensions are motivated by a desire to predict and control complex rheological and electrical properties encountered under shear. In this work, direct structural measurements over a hierarchy of length scales spanning from nanometers to tens of micrometers are used to determine the microstructural origin of the suspension viscosity measured at high shear rates. These experiments were performed on a series of dense suspensions consisting of high-structured carbon blacks from two commercial sources suspended in two Newtonian fluids, propylene carbonate and light mineral oil. The shear-induced microstructure was measured at a range of applied shear rates using Rheo-VSANS (very small angle neutron scattering) and Rheo-USANS (ultra-small angle neutron scattering) techniques. A shear-thinning viscosity is found to arise due to the self-similar break up of micrometer-sized agglomerates with increasing shear intensity. This self-similarity yields a master curve for the shear-dependent agglomerate size when plotted against the Mason number, which compares the shear force acting to break particle-particle bonds to the cohesive force holding bonds together. It is found that the agglomerate size scales as R g , agg ∼ M n − 1 . Inclusion of the particle stress contribution extends the relevance of the Mason number to concentrated suspensions such as those relevant to the processing of carbon black suspensions for various applications. [ABSTRACT FROM AUTHOR]

Acylated peptides composed of glucagon-like peptide-1 receptor agonists modified with a fatty acid side chain are an important class of therapeutics for type 2 diabetes and obesity but are susceptible to an unusual physical instability in the presence of hydrophobic surfaces, i.e., spontaneous emulsification, also known as ouzo formation in practice. In this work, light scattering, small-angle X-ray scattering, and circular dichroism measurements are used to characterize the physical properties of the semaglutide colloidal phase, including size distribution, shape, secondary structure, internal structure, and internal composition, as a function of solution physico-chemical conditions. The existence and size of the colloids formed are successfully predicted by a classical Rayleigh model, which identifies the parameters controlling their size and formation. Colloid formation is found to be catalyzed by hydrophobic surfaces, and formation rates are modeled as an autocatalytic reaction, enabling the formation of a master curve for various surfaces that elucidates the mechanism. Surfaces differ due to differences in surface wettability, which can be correlated with Hansen solubility parameters. This work provides insights into this unusual colloidal phenomenon and guides the peptide synthesis process and drug product formulation in the pharmaceutical industry. [ABSTRACT FROM AUTHOR]

In-situ resource utilization (ISRU) to construct environmental protection and critical infrastructure is required for long-term human habitation on the Moon and Mars. Analogous to terrestrial construction materials formed from aluminosilicates, i.e., geopolymers, construction materials formed from lunar aluminosilicate regolith are a promising method to create lunar landing pads and habitats. Building on a previous lateral study across multiple regolith simulants, the effects of composition on one specific regolith simulant, Black Point 1 (BP-1), are investigated with the goal of developing relationships between composition and properties. The effects of overall geopolymer composition, activating solution silica and sodium content, and activating solution water content on seven-day compressive strength, strain to fail, and secant modulus are investigated. Decreasing water content has a positive effect on compressive strength and secant modulus of geopolymers formed at ambient-earth conditions, reaching maximum compressive strength at 75 wt% BP-1. Above a compositional limit of Si/H 2 O = 0.6, differences in Si and Al coordination result in variations in compressive strength with the elemental composition of the geopolymer. At high solids in formulation, the observed trend in compressive strength is nonmonotonic with varying silicon and aluminum content, emphasizing the need for a mechanistic understanding of the relationship between composition and structure for optimization of geopolymer material properties. This study provides a robust set of data for a widely available lunar regolith simulant that can guide further development of processing strategies for lunar ISRU. [ABSTRACT FROM AUTHOR]

Recently, Mwasame et al. [“On the macroscopic modeling of dilute emulsions under flow,” J. Fluid Mech. 831, 433 (2017)] developed a macroscopic model for the dynamics and rheology of a dilute emulsion with droplet morphology in the limit of negligible particle inertia using the bracket formulation of non-equilibrium thermodynamics of Beris and Edwards [Thermodynamics of Flowing Systems: With Internal Microstructure (Oxford University Press on Demand, 1994)]. Here, we improve upon that work to also account for particle inertia effects. This advance is facilitated by using the bracket formalism in its inertial form that allows for the natural incorporation of particle inertia effects into macroscopic level constitutive equations, while preserving consistency to the previous inertialess approximation in the limit of zero inertia. The parameters in the resultant Particle Inertia Thermodynamically Consistent Ellipsoidal Emulsion (PITCEE) model are selected by utilizing literature-available mesoscopic theory for the rheology at small capillary and particle Reynolds numbers. At steady state, the lowest level particle inertia effects can be described by including an additional non-affine inertial term into the evolution equation for the conformation tensor, thereby generalizing the Gordon-Schowalter time derivative. This additional term couples the conformation and vorticity tensors and is a function of the Ohnesorge number. The rheological and microstructural predictions arising from the PITCEE model are compared against steady-shear simulation results from the literature. They show a change in the signs of the normal stress differences that is accompanied by a change in the orientation of the major axis of the emulsion droplet toward the velocity gradient direction with increasing Reynolds number, capturing the two main signatures of particle inertia reported in simulations. [ABSTRACT FROM AUTHOR]

• The method to study the microstructure of asphalt binders by SANS was established. • The microstructure of asphalt binders was found and the micelle size was calculated. • The relationship between rheological properties and microstructure of asphalt was analyzed. • The SBS modified mechanism was proved by SANS. The microstructure of asphalt binders is believed to have a significant impact on the performance of binders used in roadway constructions. However, there are only limited studies of their nanoscale to microscale structures. Here, small angle neutron scattering (SANS) is used to study the nanoscale structure of neat asphalt binder, styrene-butadienestyrene (SBS) block copolymers and SBS modified asphalt binder. The SANS pattern for asphalt binder demonstrates that it exhibits a colloidal structure comprised of asphaltenes surrounded by resins dispersed in saturates and aromatics. Fractal-core-shell model fits to these patterns indicate that the asphaltene core size decreases with increasing temperature. Both SANS and rheology confirm that SBS modified asphalt has a thermo-reversible phase transition around 110 °C, where the SBS micelles swell and lose scattering contrast above this temperature. The thermo-reversibility of this phenomenon indicates that the mechanism of SBS modification is mostly a physical modification of the nanoscale structure as proposed in the colloidal model of asphalt. Modeling of the SANS patterns shows that neat SBS and SBS dispersed in asphalt binder have a lamellar structure surrounded by a shell. These results are useful for understanding the relationship between the nanoscale structure of asphalt binder and pavement performance, as well as potentially developing new types of modified asphalt binders. [ABSTRACT FROM AUTHOR]

New in vitro measurements from two human donors for both steady and transient hemorheology are presented that are particularly suited for testing thixotropic and viscoelastic models for human blood and are made available to the community along with the relevant blood physiology. This more complete data set is analyzed within the context of recent thixo-elasto-visco-plastic models, and we improve upon the Horner-Armstrong-Wagner-Beris (HAWB) model to better model transient hemorheology. The improved model features an additional viscoelastic equation for the red blood cell rouleaux within blood, along with simplifications to the structure kinetics equation. The resulting model is fit to additional experimental data on human whole blood for a step shear change and steady shear experiments, and the corresponding parameter values are used to predict oscillatory shear moduli, transient large amplitude oscillatory shear, and unidirectional large amplitude oscillatory shear data. The modified HAWB model shows significant improvement in fitting and predicting the experimental data. Specifically, a significant overshoot is captured in step shear changes from a low shear rate to a moderate shear rate, and a plateau for the storage modulus is observed at low frequencies. Highly nonlinear behavior is observed for the third harmonic in unidirectional large amplitude oscillatory shear in the form of multiple extremum separated widely in frequency, which can be identified with the two dominant mechanisms for generating viscoelasticity in human blood, namely, rouleaux structuring and red blood cell deformation. We also discuss the potential applications and difficulties associated with the constitutive modeling of transient blood rheology and provide insight into microstructural sources of the stress contributions to the bulk flow behavior. [ABSTRACT FROM AUTHOR]

Hemorheology is the study of blood flow and the mechanical stresses and kinematics involved. The Casson constitutive equation is a popular and simple model used to describe the steady shear rheology of blood, with only two parameters that specify an infinite shear viscosity and a yield stress that depend on blood physiology. Previous literature has identified hematocrit and fibrinogen concentration as the two most important physiological factors that affect blood flow, but previous parameterizations of the Casson model may not be reliable due to the use of non-standardized data sets. This study uses machine learning and the largest standardized dataset to improve the parameterization of the Casson model with respect to hematocrit and fibrinogen concentration for healthy individuals. The study also employs machine learning to identify a potential additional factor, the mean corpuscular hemoglobin (MCH), that may affect blood rheology. The proposed approach demonstrates the potential for machine learning to improve the connection between physiology and blood rheology with possible implications in cardiovascular diagnostics. [ABSTRACT FROM AUTHOR]

Carbon black suspensions exhibit complex, shear-dependent macroscopic properties that are a consequence of the state of the suspension microstructure. In this work, the shear-induced microstructure of a model, reversible suspension of conductive carbon black in propylene carbonate is measured using simultaneous steady shear rheology and small angle neutron scattering. These experiments provide microstructural evidence for a bifurcation in the rheological properties. We show that the demarcation line for this bifurcation is the inverse Bingham number, Bi−1, which relates the magnitude of the stress response to an applied shear rate to the yield stress of the presheared suspension. At high shear rates where Bi−1 > 1, the suspension flows homogeneously and exhibits a thixotropic response that arises due to the self-similar breakdown of agglomerates with increasing shear rate. Conversely, at low shear rates where Bi−1 < 1, the applied shear drives the densification and growth of these agglomerates. This densification process leads to a gravitationally driven instability resulting in an inhomogeneous volume fraction distribution along the height of the geometry that is a function of both time under shear and shear rate. Under these shear conditions, the suspension exhibits apparent rheopexy, or antithixotropy, where a significant decline in the viscosity is observed with a step down in shear rate. The unique microstructural measurements presented here reconcile many observations in the literature regarding carbon black suspensions, including an apparent shear-thickening behavior, tunability of both the yield stress and elasticity through shear history, and transient macroscopic properties. [ABSTRACT FROM AUTHOR]

Light scattering measurements determined the ratio of the nonequilibrium to equilibrium static structure factor for suspensions of ‘‘hard spheres’’ undergoing shear flow as a function of volume fraction of the suspended particles, the shear rate, and a limited number of scattering angles. These data are compared with existing theoretical predictions for the static structure factor ratio in the limit of small shear flow rates. We conclude that the existing theories, some which are considered exact at low volume fractions, give increasingly poor estimates of the true structure factor at small scattering angles as the volume fraction increases. [ABSTRACT FROM AUTHOR]

The linear viscoelasticity and steady shear properties of bitumen are established; however, bitumen used in pavement also supports time-varying loading in the nonlinear regime. Consequently, recent research focuses on the nonlinear rheological behavior of bitumen under time-varying flows that is essential for establishing the constitutive model. Here, we propose a protocol to obtain the nonlinear rheological behavior of bitumen under a large amplitude oscillatory shear (LAOS) stress. The LAOS stress rheological response of both a neat bitumen and a modified bitumen is analyzed by Fourier-transform rheology and strain decomposition to an orthogonal set of Chebyshev polynomials. We find that the relative nonlinearity of bitumen increases with increasing stress and decreasing frequency; the relationship between I3/I1 and stress amplitude can obey the sigmoidal function; the intrinsic nonlinearity Q0 decreases with increasing frequency and decreasing temperature. Both the FT analysis results and decomposition results show that the nonlinearity of modified bitumen B is much more significant than neat bitumen A. Bitumen A exhibits stress softening and stress thinning under all the studied test conditions, but bitumen B exhibits stress stiffening under some conditions. [ABSTRACT FROM AUTHOR]

We present new dynamic rheological tests of human blood that motivate an improved model for the thixotropic shear rheology of human blood. Unidirectional large amplitude oscillatory shear (UD-LAOS) is proposed as a dynamic test relevant for understanding in vivo arterial pulsatile blood flow, and data are presented for two healthy donors studied previously using more traditional steady and step-rate experiments. The model analyzes the overall extra stress of the system in two components. A thixotropic component is represented by a structure-kinetics model coupled with a stress expression containing both viscoelastic and thixotropic elements to account for the presence of linear aggregates of red blood cells, known as rouleaux, which form at low shear rates. Another component is viscoelastic, described through an extend White–Metzner approach. It corresponds to the stresses that arise due to the isolated red blood cells, which deform at high shear rates. The combined model is fit to experimental steady shear and UD-LAOS data for two healthy donors and is subsequently used to predict the stress response of the blood sample to UD-LAOS experiments over a broad range of strain amplitudes and frequencies. Comparison to the previous models for transient blood rheology shows a significantly improved fit over a range of physiologically relevant flow conditions. In addition, this analysis demonstrates the usefulness of UD-LAOS tests with regards to understanding the microstructural evolution in blood under transient flow. [ABSTRACT FROM AUTHOR]

A unique feature of inorganic membranes is the ability to operate at high temperature and pressure. Even supercritical solvents can be processed by these membranes, whereas polymer membranes tend to swell and consequently suffer from reduced selectivity and mechanical strength. Carbon membranes open new possibilities, e.g. the processing of high pressure, high temperature fluid streams directly in place or the use in membrane reactors for chemical reactions like H 2 -synthesis by dehydrogenation. This work investigates high pressure adsorption of carbon membrane material for different gases at up to 12 MPa, the selectivity and permeance for CO 2 /N 2 mixtures in a pressure range from 0.1 to 20 MPa and the swelling of carbon material exposed to Oxygen at up to 10 MPa. A model based on Maxwell-Stefan diffusion with parameters gained from measured adsorption and fluxes has been implemented to improve the understanding of the behaviour of high pressure separation with carbon membranes. [ABSTRACT FROM AUTHOR]

The microstructure and rheological properties of colloidal suspensions depend on particle size and shape. This work aims to further control the size, shape, and polydispersity of anisotropic silica colloids, to reduce particle size, and to provide additional mechanistic insights on a prevalent, water-in-oil emulsion synthesis method. Key findings show that the dimensions of anisotropic silica particles can be systematically varied by approximately fivefold, with a limiting minimum particle size (D ≈ 60 nm, L ≈ 300 nm) obtained from emulsions with excess polyvinylpyrrolidone (PVP) and sodium citrate. The synthesis conditions are identified and discussed for which the emulsion composition, temperature, sonication, polymer entanglements, mixing, and other perturbations may induce or mitigate emulsion instabilities, citrate precipitation, a competing mechanism of templated growth, termination of anisotropic growth, irregular silica structures, and fiber formation. An improved mechanistic understanding will expand the roadmap for rational design and synthetic control of anisotropic colloids using sol-gel silica chemistry confined within water-in-oil emulsions. [ABSTRACT FROM AUTHOR]

Multi-injection pharmaceutical products such as insulin must be formulated to prevent aggregation and microbial contamination. Small-molecule preservatives and nonionic surfactants such as poloxamer 188 (P188) are thus often employed in protein drug formulations. However, mixtures of preservatives and surfactants can induce aggregation and even phase separation over time, despite the fact that all components are well dissolvable when used alone in aqueous solution. A systematic study is conducted here to understand the phase behavior and morphological causes of aggregation of P188 in the presence of the preservatives phenol and benzyl alcohol, primarily using small-angle x-ray scattering (SAXS). Based on SAXS results, P188 remains as unimers in solution when below a certain phenol concentration. Upon increasing the phenol concentration, a regime of micelle formation is observed due to the interaction between P188 and phenol. Further increasing the phenol concentration causes mixtures to become turbid and phase-separate over time. The effect of benzyl alcohol on the phase behavior is also investigated. [ABSTRACT FROM AUTHOR]

Environmental pollution and habitat loss are described as underlying causes for population declines in reptiles and especially affect species in agricultural landscapes. Studies dealing with effects of pesticide exposure on reptiles are limited, mainly addressing the orders Testudines and Crocodylia, but largely neglecting the most diverse reptile order Squamata (lizards and snakes). As a consequence, information regarding effects on their organisms, as well as exposure probability and pesticide uptake in the Reptilia has to be considered rather uncharted. We here ask how pesticide applications affect a widely distributed, synanthropic squamate species in Europe. We studied the common wall lizard ( Podarcis muralis ) with regard to enzymatic biomarkers of pesticide exposure (Glutathione-S-Transferase, Glutathione Reductase, Acetylcholinesterase) and body condition. Lizards were sampled from wild populations, along an exposure gradient (three exposed sites with differing land use intensity and one reference site). Our results suggest both dermal and oral uptake of pesticide formulations, with the former being especially relevant during the first two days after a pesticide application. Enzymatic activity slightly differed between exposure gradients, while showing overall similar patterns. Body condition of lizards decreased with increasing pesticide exposure. Furthermore, gender distribution was particularly skewed in favor to males within exposed sample sites. Although reptiles are not target organisms of pesticide applications, many species do come into contact with them, and most probably suffer from dermal and oral uptake. Thus, we believe it is indispensable for reptiles to be integrated in risk assessments in order to improve conservation practice. [ABSTRACT FROM AUTHOR]

A stable dispersion of silica nanoparticles in a common ionic liquid [C4mim][BF4] that exhibits significant shear thickening is formulated by controlling the strength of hydrogen bonding between the nanoparticle surface and the anion of [C4mim][BF4]. Colloidal stability is demonstrated to be due to the formation of solvation layers, the properties of which are determined by scattering measurements. Timetemperature superposition measurements and the onset of yielding behavior in steady shear indicate the increase of particle-particle attraction and loss of stability of colloidal dispersions above 30 °C. Small angle neutron scattering and dynamic light scattering measurements confirm the reduction in solvation layering at elevated temperatures, leading to a transition from stable dispersion to unstable, attractive gel with increasing temperature (i.e., an inverse melting transition). It is demonstrated how controlling specific surface-anion interactions through chemical functionality can be used to formulate nanoparticle dispersions in ionic liquids with specific rheological properties. [ABSTRACT FROM AUTHOR]

The structural anisotropy and shear rheology of colloidal gels under startup of shear flow are calculated by Brownian dynamics simulations modified to include particle surface-mediated attractions, which is a model for thermoreversible colloidal gels. Shear-induced structural changes are analyzed in both real and reciprocal space through computation of the pair distribution function and structure factor. A distinct structural anisotropy is evident as alignment along the compressional and vorticity axes. A spherical harmonics expansion of pair distribution function is calculated to analyze structural anisotropy. In reciprocal space, structural anisotropy is quantified through an alignment factor, which shows overshoot behavior similar to the stresses. Based on the microstructure analysis, the evolution of the structural anisotropy is explained by the anisotropic rupture of the colloidal gel microstructure. This result provides evidence for how shearing creates structural anisotropy. The structural anisotropy during flow startup is quantitatively related to rheological behavior via a stress-small angle neutron scattering (SANS) rule that is modified to consider the influence of the rupture of the colloidal gel structure. A simple structure kinetic equation accounting for bond creation and rupture provides a unifying view of the results. This new, modified stress-SANS rule quantitatively links the shear-induced structural anisotropy to the nonlinear rheology. [ABSTRACT FROM AUTHOR]

Colloidal gels exhibit time-dependent bulk properties. However, the processes and mechanisms by which aging occurs are poorly understood, which complicates the prediction of macroscopic behavior in these systems. Using a model, thermoreversible, adhesive hard sphere system consisting of octadecyl-coated silica nanoparticles dispersed in tetradecane, rheological aging is quantitatively related to structural aging. By simultaneously measuring the bulk properties and gel microstructure using rheometry and small angle neutron scattering, respectively, we show a one-to-one correspondence between the time-dependent storage modulus and the microstructure, and further, that this correspondence is independent of the gel's thermal and shear history. At the working volume fraction, the gel is homogeneous and, unlike phase-separated gels, aging behavior is not due to heterogeneous coarsening. Instead, the results presented here are consistent with homogeneous, local particle rearrangements as the mechanism of rheological aging. By establishing a quantitative and predictive relationship between the underlying microstructure and bulk mechanical properties, the results of this study may be (1) industrially relevant to products that age on commercially relevant timescales, (2) applicable to other dynamically arrested systems, such as metallic glasses, and (3) valuable in the design of new materials. [ABSTRACT FROM AUTHOR]

The chytrid fungus Batrachochytrium salamandrivorans (Bsal) is a dangerous pathogen to salamanders and newts. Apparently native to Asia, it has recently been detected in Western Europe where it is expected to spread and to have dramatic effects on naïve hosts. Since 2010, Bsal has led to some catastrophic population declines of urodeles in the Netherlands and Belgium. More recently, it has been discovered in additional, more distant sites including sites in Germany. With the purpose to contribute to a better understanding of Bsal, we modelled its potential distribution in its invasive European range to gain insights about the factors driving this distribution. We computed Bsal Maxent models for two predictor sets, which represent different temporal resolutions, using three different background extents to account for different invasion stage scenarios. Beside 'classical' bioclimate, we employed weather data, which allowed us to emphasize predictors in accordance with the known pathogen's biology. The most important predictors as well as spatial predictions varied between invasion scenarios and predictor sets. The most reasonable model was based on weather data and the sc.enario of a recent pathogen introduction. It identified temperature predictors, which represent optimal growing conditions and heat limiting conditions, as the most explaining drivers of the current distribution. This model also predicted large areas in the study region as suitable for Bsal. The other models predicted considerably less, but shared some areas which we interpreted as most likely high risk zones. Our results indicate that growth relevant temperatures measured under laboratory conditions might also be relevant on a macroecological scale, if predictors with a high temporal resolution and relevance are used. Additionally, the conditions in our study area support the possibility of a further Bsal spread, especially when considering that our models might tend to underestimate the potential distribution of Bsal. [ABSTRACT FROM AUTHOR]

Dynamic arrest transitions of colloidal suspensions containing nonspherical particles are of interest for the design and processing of various particle technologies. To better understand the effects of particle shape anisotropy and attraction strength on gel and glass formation, we present a colloidal model system of octadecyl-coated silica rods, termed as adhesive hard rods (AHR), which enables control of rod aspect ratio and temperature-dependent interactions. The aspect ratios of silica rods were controlled by varying the initial TEOS concentration following the work of Kuijk et al. (J. Am. Chem. Soc., 2011, 133, 2346-2349) and temperature-dependent attractions were introduced by coating the calcined silica rods with an octadecyl-brush and suspending in tetradecane. The rod length and aspect ratio were found to increase with TEOS concentration as expected, while other properties such as the rod diameter, coating coverage, density, and surface roughness were nearly independent of the aspect ratio. Ultrasmall angle X-ray scattering measurements revealed temperature-dependent attractions between octadecyl-coated silica rods in tetradecane, as characterized by a low-q upturn in the scattered intensity upon thermal quenching. Lastly, the rheology of a concentrated AHR suspension in tetradecane demonstrated thermoreversible gelation behavior, displaying a nearly 5 orders of magnitude change in the dynamic moduli as the temperature was cycled between 15 and 40 °C. The adhesive hard rod model system serves as a tunable platform to explore the combined influence of particle shape anisotropy and attraction strength on the dynamic arrest transitions in colloidal suspensions with thermoreversible, short-range attractions. [ABSTRACT FROM AUTHOR]

We measure the dynamical arrest transition in a model, thermoreversible, adhesive hard sphere dispersion. At low volume fractions ɸ, below the critical point, gelation occurs within the gas-liquid phase boundary. For ɸ slightly below and above the critical concentration, the phase boundary follows the predicted percolation transition. At high ɸ, it melds into the predicted attractive-driven glass transition. Our results demonstrate that for ɸ above ~20% physical gelation is an extension of the attractive-driven glass line and occurs without competition for macroscopic phase separation. [ABSTRACT FROM AUTHOR]