Contamination in Sodium Dodecyl Sulfate Solutions: Insights from the Measurements of Surface Tension and Surface Rheology.

The presence of contamination in sodium dodecyl sulfate (SDS) solutions in the form of dodecanol (LOH) is known to drastically affect the resulting interfacial properties such as surface tension (SFT) and rheology. Dodecanol molecules, which are the product of SDS hydrolysis and are inherently present in SDS solutions, have higher surface activity compared to SDS because they are less soluble in water. A characteristic dip in the SFT isotherm is an indicator of the dodecanol contamination in the sample. The presence of an electrolyte in the solution impacts the surface activity of SDS and its critical micelle concentration, and could yield SFT isotherms that closely match those obtained for pure SDS samples. The interpretation of the isotherms in such cases could thus lead to misinterpretation of the surface purity. In this work, we have examined the SFT isotherms for SDS solutions in both the absence and presence of electrolyte. We have fitted the isotherms to three different thermodynamic adsorption models to estimate the amount of dodecanol present in the sample. We have applied the estimated values for the LOH content in a two-component rheological model to predict the viscoelasticity of such surfactant-laden surfaces. We have compared these results with the experimentally measured interfacial rheological properties. Our findings demonstrate that the presence of impurities can be captured under dynamic expansion and contractions, even for solutions containing background electrolyte.

Recycling Polymeric Solid Wastes for Energy-Efficient Water Purification, Organic Distillation, and Oil Spill Cleanup.

Conventional approaches (e.g., pyrolysis) for managing waste polymer foams typically require highly technical skills and consume large amounts of energy resources. This paper presents an ultrafacile, cost-effective, and highly efficient alternative method for recycling waste packaging and cleaning foam (e.g., polymelamine-formaldehyde foam). The designed solar absorber, a polypyrrole-coated melamine foam (PMF), features a highly porous structure, excellent mechanical strength, low thermal conductivity, and rapid water transport capacity. These exceptional properties render the PMF suitable for multiple applications, including energy-efficient solar-powered water purification, ethanol distillation, and oil absorption. In water purification, the PMF yields a solar-thermal conversion efficiency as high as 87.7%, stability that is maintained for more than 35 operation cycles, and antifouling capabilities (when purifying different water types). In solar distillation, the PMF achieves a concentration increase up to 75 vol% when distilling a 10 vol% ethanol solution. In oil absorption, the PMF offers an oil-absorption capacity of ≈70 g g-1 with only a 7% loss in capacity after 100 absorbing-squeezing cycles. Thus, systems combining solar energy with various waste foams are highly promising as durable, renewable, and portable systems for water purification, organic distillation, and oil absorption, especially in remote regions or emergency situations.

Production of erythrocyte microparticles in a sub-hemolytic environment.

Microparticles are produced by various cells due to a number of different stimuli in the circulatory system. Shear stress has been shown to injure red blood cells resulting in hemolysis or non-reversible sub-hemolytic damage. We hypothesized that, in the sub-hemolytic shear range, there exist sufficient mechanical stimuli for red blood cells to respond with production of microparticles. Red blood cells isolated from blood of healthy volunteers were exposed to high shear stress in a microfluidic channel to mimic mechanical trauma similar to that occurring in ventricular assist devices. Utilizing flow cytometry techniques, both an increase of shear rate and exposure time showed higher concentrations of red blood cell microparticles. Controlled shear rate exposure shows that red blood cell microparticle concentration may be indicative of sub-hemolytic damage to red blood cells. In addition, properties of these red blood cell microparticles produced by shear suggest that mechanical trauma may underlie some complications for cardiovascular patients.

Oil-water interfaces with surfactants: A systematic approach to determine coarse-grained model parameters.

In order to investigate the interfacial region between oil and water with the presence of surfactants using coarse-grained computations, both the interaction between different components of the system and the number of surfactant molecules present at the interface play an important role. However, in many prior studies, the amount of surfactants used was chosen rather arbitrarily. In this work, a systematic approach to develop coarse-grained models for anionic surfactants (such as sodium dodecyl sulfate) and nonionic surfactants (such as octaethylene glycol monododecyl ether) in oil-water interfaces is presented. The key is to place the theoretically calculated number of surfactant molecules on the interface at the critical micelle concentration. Based on this approach, the molecular description of surfactants and the effects of various interaction parameters on the interfacial tension are investigated. The results indicate that the interfacial tension is affected mostly by the head-water and tail-oil interaction. Even though the procedure presented herein is used with dissipative particle dynamics models, it can be applied for other coarse-grained methods to obtain the appropriate set of parameters (or force fields) to describe the surfactant behavior on the oil-water interface.

Flow-Field Simulations and Hemolysis Estimates for the Food and Drug Administration Critical Path Initiative Centrifugal Blood Pump.

The design of blood pumps for use in ventricular assist devices, which provide life-saving circulatory support in patients with heart failure, require remarkable precision and attention to detail to replicate the functionality of the native heart. The United States Food and Drug Administration (FDA) initiated a Critical Path Initiative to standardize and facilitate the use of computational fluid dynamics in the study and development of these devices. As a part of the study, a simplified centrifugal blood pump model generated by computer-aided design was released to universities and laboratories nationwide. The effects of changes in fluid rheology due to temperature, hematocrit, and turbulent flow on key metrics of the FDA pump were examined in depth using results from a finite volume-based commercial computational fluid dynamics code. Differences in blood damage indices obtained using Eulerian and Lagrangian formulations were considered. These results are presented and discussed awaiting future validation using experimental results, which will be released by the FDA at a future date.

An Approach for Assessing Turbulent Flow Damage to Blood in Medical Devices.

In this work, contributing factors for red blood cell (RBC) damage in turbulence are investigated by simulating jet flow experiments. Results show that dissipative eddies comparable or smaller in size to the red blood cells cause hemolysis and that hemolysis corresponds to the number and, more importantly, the surface area of eddies that are associated with Kolmogorov length scale (KLS) smaller than about 10 µm. The size distribution of Kolmogorov scale eddies is used to define a turbulent flow extensive property with eddies serving as a means to assess the turbulence effectiveness in damaging cells, and a new hemolysis model is proposed. This empirical model is in agreement with hemolysis results for well-defined systems that exhibit different exposure times and flow conditions, in Couette flow viscometer, capillary tube, and jet flow experiments.

The effects of shear and particle shape on the physical adsorption of polyvinyl pyrrolidone on carbon nanoparticles.

The effects of shear and particle shape on the physical adsorption of a polymer (polyvinyl pyrrolidone, PVP) on carbon nanoparticles (CNPs) were studied with dissipative particle dynamics (DPD) methods. It was found that the conformation of the polymer during adsorption and desorption from the nanoparticle can be classified into three possible types, i.e. adsorbed, shear-affected and separated, depending on the magnitude of the shear rate in the flow. Spherical and graphene sheet-shaped particles with adsorbed PVP were manipulated in a Couette flow to determine the threshold shear rates leading to changes in the polymer adsorption state. It was found that the polymer was stably adsorbed under higher shear conditions for graphene sheets. In addition, the end-to-end distance and the radius of gyration of the polymer adsorbate was clearly related to the adsorption state, as the polymer underwent a transition from adsorbed to the separated state when the shear rate increased. The critical shear rate at which the polymer desorbed from the surface could be useful in applications where nanoparticles can be used as a molecular delivery system. The physical adsorption and desorption of the same polymer molecules on a flat surface were also investigated. The desorption of the polymer from the flat surface occurred when the shearing force was stronger than the attraction between the PVP and the surface.

Adsorption of anionic and non-ionic surfactants on carbon nanotubes in water with dissipative particle dynamics simulation.

The morphology of surfactants physically adsorbed on the surface of carbon nanotubes (CNTs) has a significant impact on the dispersion of CNTs in the solution. The adsorption of the surfactants alfoterra 123-8s (AF) and tergitol 15-s-40 (TG) on CNTs was investigated with dissipative particle dynamics (DPD) simulations, as well as the behavior of the binary surfactant system with CNTs. Properties of surfactants (i.e., critical micelle concentration, aggregation number, shape and size of micelle, and diffusivity) in water were determined to validate the simulation model. Results indicated that the assembly of surfactants (AF and TG) on CNTs depends on the interaction of the surfactant tail and the CNT surface, where surfactants formed mainly hemimicellar structures. For surfactants in solution, most micelles had spherical shape. The particles formed by the CNT and the adsorbed surfactant became hydrophilic, due to the outward orientation of the head groups of the surfactants that formed monolayer adsorption. In the binary surfactant system, the presence of TG on the CNT surface provided a considerable hydrophilic steric effect, due to the EO groups of TG molecules. It was also seen that the adsorption of AF was more favorable than TG on the CNT surface. Diffusion coefficients for the surfactants in the bulk and surface diffusion on the CNT were calculated. These results are applicable, in a qualitative sense, to the more general case of adsorption of surfactants on the hydrophobic surface of cylindrically shaped nanoscale objects.

Effect of Sodium Dodecyl Sulfate Adsorption on the Behavior of Water inside Single Walled Carbon Nanotubes with Dissipative Particle Dynamics Simulation.

Dissipative particle dynamics (DPD) simulations were utilized to investigate the ability of sodium dodecyl sulfate (SDS) to adsorb inside a single-walled, arm-chair carbon nanotube (SWCNT), as well as the effect of surfactant on the properties of water inside the SWCNT. The diameter of the SWCNT varied from 1 to 5 nm. The radial and axial density profiles of water inside the SWCNTs were computed and compared with published molecular dynamics results. The average residence time and diffusivity were also calculated to show the size effect on mobility of water inside the SWCNT. It was found that nanotubes with diameter smaller than 3 nm do not allow SDS molecules to enter the SWCNT space. For larger SWCNT diameter, SDS adsorbed inside and outside the nanotube. When SDS was adsorbed in the hollow part of the SWCNT, the behavior of water inside the nanotube was found to be significantly changed. Both radial and axial density profiles of water inside the SWCNT fluctuated strongly and were different from those in bulk phase. In addition, SDS molecules increased the retention of water beads inside SWCNT (d ≥ 3nm) while water diffusivity was decreased.

Hemolysis Related to Turbulent Eddy Size Distributions Using Comparisons of Experiments to Computations.

Turbulent blood flow in medical devices contributes to blood trauma, yet the exact mechanism(s) have not been fully elucidated. Local turbulent stresses, viscous stresses, and the rate of dissipation of the turbulent kinetic energy have been proffered as hypotheses to describe and predict blood damage. In this work, simulations of experiments in a Couette flow viscometer and a capillary tube were used to examine extensive properties of the turbulent flow field and to investigate contributing factors for red blood cell hemoglobin release in turbulence by eddy analysis. It was found that hemolysis occurred when dissipative eddies were comparable in size to the red blood cells. The Kolmogorov length scale was used to quantify the size of smaller turbulent eddies, indicating correspondence of hemolysis with number and surface area of eddies smaller than about 10 µm when a k-ε turbulence model is adopted.

Mesoscopic modeling of cancer photothermal therapy using single-walled carbon nanotubes and near infrared radiation: insights through an off-lattice Monte Carlo approach.

Single-walled carbon nanotubes (SWNTs) are promising heating agents in cancer photothermal therapy when under near infrared radiation, yet few efforts have been focused on the quantitative understanding of the photothermal energy conversion in biological systems. In this article, a mesoscopic study that takes into account SWNT morphologies (diameter and aspect ratio) and dispersions (orientation and concentration), as well as thermal boundary resistance, is performed by means of an off-lattice Monte Carlo simulation. Results indicate that SWNTs with orientation perpendicular to the laser, smaller diameter and better dispersion have higher heating efficiency in cancer photothermal therapy. Thermal boundary resistances greatly inhibit thermal energy transfer away from SWNTs, thereby affecting their heating efficiency. Through appropriate interfacial modification around SWNTs, compared to the surrounding healthy tissue, a higher temperature of the cancer cell can be achieved, resulting in more effective cancer photothermal therapy. These findings promise to bridge the gap between macroscopic and microscopic computational studies of cancer photothermal therapy.

Liquid water can slip on a hydrophilic surface.

Understanding and predicting the behavior of water, especially in contact with various surfaces, is a scientific challenge. Molecular-level understanding of hydrophobic effects and their macroscopic consequences, in particular, is critical to many applications. Macroscopically, a surface is classified as hydrophilic or hydrophobic depending on the contact angle formed by a water droplet. Because hydrophobic surfaces tend to cause water slip whereas hydrophilic ones do not, the former surfaces can yield self-cleaning garments and ice-repellent materials whereas the latter cannot. The results presented herein suggest that this dichotomy might be purely coincidental. Our simulation results demonstrate that hydrophilic surfaces can show features typically associated with hydrophobicity, namely liquid water slip. Further analysis provides details on the molecular mechanism responsible for this surprising result.

Prediction of the aggregation rate of nanoparticles in porous media in the diffusion-controlled regime.

The fate and aggregation of nanoparticles (NPs) in the subsurface are important due to potentially harmful impacts on the environment and human health. This study aims to investigate the effects of flow velocity, particle size, and particle concentration on the aggregation rate of NPs in a diffusion-limited regime and build an equation to predict the aggregation rate when NPs move in the pore space between randomly packed spheres (including mono-disperse, bi-disperse, and tri-disperse spheres). The flow of 0.2 M potassium chloride (KCl) through the random sphere packings was simulated by the lattice Boltzmann method (LBM). The movement and aggregation of cerium oxide (CeO2) particles were then examined by using a Lagrangian particle tracking method based on a force balance approach. This method relied on Newton's second law of motion and took the interaction forces among particles into account. The aggregation rate of NPs was found to depend linearly on time, and the slope of the line was a power function of the particle concentration, the Reynolds (Re) and Schmidt (Sc) numbers. The exponent for the Sc number was triple that of the Re number, which was evidence that the random movement of NPs has a much stronger effect on the rate of diffusion-controlled aggregation than the convection.

Effects of Nanoparticle Wettability on the Meniscus Stability of Oil-Water Systems: A Coarse-Grained Modeling Approach.

A coarse-grained modeling approach is employed to probe the effect of nanoparticles and their wettability on the stability of the interface between two immiscible fluids. In this study, pure oil (dodecane) and water are placed side by side in a nanochannel, forming a meniscus. Homogeneous hydrophilic nanoparticles, Janus particles, and homogeneous hydrophobic nanoparticles are placed at the oil-water interface, and their dynamics are studied as they rearrange at the oil-water interface. The results show that when the water is set in motion, two instabilities occur: the formation of fingers and the detachment of water from the channel wall. It is observed that the formation of fingers is affected by the wettability of the nanoparticles. The second instability may lead to the formation of a drop that propagates through the channel. However, it is found that the wetting properties of the nanoparticles do not affect the critical flow rate for the detachment of the water from the wall. Therefore, detachment occurs at the same three-phase contact angle regardless of the nanoparticle wetting properties. These findings can be important for industrial applications such as enhanced oil recovery, separation technologies, and microfluidic and nanofluidic technologies.

Aggregation of nanoparticles and morphology of aggregates in porous media with computations.

HYPOTHESIS: The main hypothesis is that the aggregation process for nanoparticles (NPs) propagating in porous media is affected by the structure of the flow field as well as by the properties of the primary NPs. If this were true, then the aggregation could be predicted and controlled. However, to obtain reliable results from computations, one needs to account for the interactions between the NPs as well as the details of the fluid velocity, thus making advances over prior efforts that either ignored the aggregation of NPs, or used probabilistic methods to model aggregation. EXPERIMENTS: Computational experiments were conducted using the lattice Boltzmann method in conjunction with Lagrangian particle tracking (LPT). The LPT accounted for the physicochemical interaction forces among NPs. Computationally obtained aggregation kinetics and fractal dimensions of Cerium oxide (CeO2) particles, suspended in potassium chloride (KCl) solutions with different concentration, were verified against experimental results. The model was then employed to investigate the effects of ionic strength, fluid velocity, and particle size on the aggregation kinetics and the aggregate morphology, as NPs propagated in the pore space between randomly packed spheres. FINDINGS: The aim of this study was to develop a computational model to simulate the aggregation of NPs and obtain the morphology of aggregates in confined geometries, based on the physics of NP interactions and the flow field. The most important factor that impacted both the aggregation process and the aggregate structure was found to be the concentration of the electrolyte. The pore velocity influenced the aggregation kinetics and the NP fractal dimension, especially in diffusion-limited aggregation. The primary particle size affected the diffusion-limited aggregation kinetics and the fractal dimension of reaction-limited aggregates noticeably.

Effect of Janus particles and non-ionic surfactants on the collapse of the oil-water interface under compression.

HYPOTHESIS: Janus particles (JPs) and surfactants express different behaviors at the oil-water interface under compression. When both are present at the interface, their synergies result in a different collapse mechanism than when present individually depending on the concentration of the JPs and surfactants. EXPERIMENTS: Coarse-grained modeling methods were used to probe the synergies between Janus nanoparticles and nonionic surfactants on the stability of an oil-water interface under compression. When both JPs and surfactants were present, the interface was covered at 0-55% area by JPs and contained surfactants at 0-40% of the interfacial surfactant concentration corresponding to the critical micelle concentration (CMC). FINDINGS: Compression of the interface with only surfactants resulted in the expulsion of surfactant molecules to the water phase once the interfacial concentration of surfactant molecules reached the CMC value. Compression of a Janus particle-laden interface past the closed-packing point led to a buckled interface, so that the total interfacial area remained constant upon further compression. When both surfactants and JPs were present on the interface, JPs still caused buckling, which helped retain the surfactant molecules on the interface. The interface exhibited a higher level of deformation in presence of surfactants. When the surfactant concentration was high, under compression, the surfactants partitioned into the water phase, but the buckling of the interface persisted.

Janus Nanoparticle and Surfactant Effects on Oil Drop Migration in Water under Shear.

The effects of surface-active nanoparticles and surfactants on the behavior of oil-water interfaces have implications for a variety of industrial processes related to multiphase flows including separation processes, enhanced oil recovery, and environmental remediation. In this work, the migration of an oil droplet in shear flow is investigated with the presence of surface-active molecules and nanoparticles at the oil-water interface. Pure oil (heptadecane) in water and oil with the presence of Janus nanoparticles (JPs) and/or octaethylene glycol monododecyl ether, a nonionic surfactant, were examined using coarse-grained computations. The shear flow field was created utilizing a Couette flow, where the top wall of a channel moved with a specified velocity and the bottom wall was kept stationary. The dissipative particle dynamics (DPD) method was applied. The oil drop was placed on the stationary wall, and its displacement was recorded over time. When surfactants were added at the oil-water interface, the slip of the water over the oil drop was reduced, leading to a larger displacement of the drop. Moreover, surfactant molecules tended to concentrate toward the rear side of the oil drop rather than the front as the drop moved in the flow field. The presence of only JPs on the oil-water interface resulted in slower droplet migration. In the presence of both JPs and surfactants, the effect of JPs on the oil-surfactant-water system was investigated by changing the number of JPs on the drop surface while keeping the concentration of the surfactant constant. Under the same shear rate, the droplet's migration speed increased in the presence of both surfactants and JPs compared to the case of bare oil. The JPs appeared to follow a repeated pattern of motion while residing close to the solid substrate-oil drop contact line. These findings elucidate the contribution of both surfactants and JPs on oil drop displacement for enhanced oil recovery or remediation of an oil-contaminated subsurface.

Distribution and history of extensional stresses on vWF surrogate molecules in turbulent flow.

The configuration of proteins is critical for their biochemical behavior. Mechanical stresses that act on them can affect their behavior leading to the development of decease. The von Willebrand factor (vWF) protein circulating with the blood loses its efficacy when it undergoes non-physiological hemodynamic stresses. While often overlooked, extensional stresses can affect the structure of vWF at much lower stress levels than shear stresses. The statistical distribution of extensional stress as it applies on models of the vWF molecule within turbulent flow was examined here. The stress on the molecules of the protein was calculated with computations that utilized a Lagrangian approach for the determination of the molecule trajectories in the flow filed. The history of the stresses on the proteins was also calculated. Two different flow fields were considered as models of typical flows in cardiovascular mechanical devises, one was a Poiseuille flow and the other was a Poiseuille-Couette flow field. The data showed that the distribution of stresses is important for the design of blood flow devices because the average stress can be below the critical value for protein damage, but tails of the distribution can be outside the critical stress regime.

Coarse Grained Modeling of Multiphase Flows with Surfactants.

Coarse-grained modeling methods allow simulations at larger scales than molecular dynamics, making it feasible to simulate multifluid systems. It is, however, critical to use model parameters that represent the fluid properties with fidelity under both equilibrium and dynamic conditions. In this work, dissipative particle dynamics (DPD) methods were used to simulate the flow of oil and water in a narrow slit under Poiseuille and Couette flow conditions. Large surfactant molecules were also included in the computations. A systematic methodology is presented to determine the DPD parameters necessary for ensuring that the boundary conditions were obeyed, that the oil and water viscosities were represented correctly, and that the velocity profile for the multifluid system agreed with the theoretical expectations. Surfactant molecules were introduced at the oil-water interface (sodium dodecylsulfate and octaethylene glycol monododecyl ether) to determine the effects of surface-active molecules on the two-phase flow. A critical shear rate was found for Poiseuille flow, beyond which the surfactants desorbed to form the interface forming micelles and destabilize the interface, and the surfactant-covered interface remained stable under Couette flow even at high shear rates.

Computations of the shear stresses distribution experienced by passive particles as they circulate in turbulent flow: A case study for vWF protein molecules.

The stress distribution along the trajectories of passive particles released in turbulent flow were computed with the use of Lagrangian methods and direct numerical simulations. The flow fields selected were transitional Poiseuille-Couette flow situations found in ventricular assist devices and turbulent flows at conditions found in blood pumps. The passive particle properties were selected to represent molecules of the von Willebrand factor (vWF) protein. Damage to the vWF molecule can cause disease, most often related to hemostasis. The hydrodynamic shear stresses along the trajectories of the particles were calculated and the changes in the distribution of stresses were determined for proteins released in different locations in the flow field and as a function of exposure time. The stress distributions indicated that even when the average applied stress was within a safe operating regime, the proteins spent part of their trajectories in flow areas of damaging stress. Further examination showed that the history of the distribution of stresses applied on the vWF molecules, rather than the average, should be used to evaluate hydrodynamically-induced damage.