Effect of Colloidal Interactions and Hydrodynamic Stress on Particle Deposition in a Single Micropore.

Clogging is ubiquitous. It happens in a wide range of material processing and causes severe performance degradation or process breakdown. In this study, we investigate clogging dynamics in a single micropore by controlling the surface property of the particle and processing condition. Microfluidic observation is conducted to investigate particle deposition in a contraction microchannel where polystyrene suspension is injected as a feed solution. The particle deposition area is quantified using the images taken using a CCD camera in both upstream and downstream of the microchannel. Pressure drop across the microchannel is also measured. When the particle interaction is repulsive, the deposition occurs mostly in downstream, while an opposite tendency is identified when the particle interaction is attractive. More complex deposition characteristics are found as the flow rate is changed. Particle flux density and the ratio of lift force to colloidal force are introduced to explain the clogging dynamics. This study provides a useful insight to alleviate clogging issues by controlling the colloidal interaction and hydrodynamic stress.

Stratification Mechanism in the Bidisperse Colloidal Film Drying Process: Evolution and Decomposition of Normal Stress Correlated with Microstructure.

The evolution of the normal stress and microstructure in the drying process of bidisperse colloidal films is studied using the Brownian dynamics simulation. Here, we show that the formation process of small-on-top stratification can be explained by normal stress development. At high PeL's, a stratified layer with small particles is formed near the interface. The accumulated particles near the interface induce the localization of normal stress so that the normal stress at the interface increases from the beginning of drying. We analyze this stress development from two points of view, on the global length scale and particle length scale. On the global length scale, the localization of normal stress is quantified by the scaled normal stress difference between the interface and substrate. For all PeL's tested in this study, the scaled normal stress difference increases until the accumulation region reaches the substrate. After the maximum, the stress difference remains at the maximum at lower PeL's, while it decreases at higher PeL's. The microstructural analysis shows that this stress development is explained through the evolution of the particle contact number distribution at the interface and substrate. On the particle length scale, we derive the scaled local force applied to each type of particle by decomposing the local normal stress. At high PeL's, the scaled local force for the large particle is large compared to that for the small particle near the interface, indicating that the large particles are strongly pushed away from the interface. Associating the volume fraction profile with the local force field, we suggest that the strong scaled force for the large particle is attributed to the significant increase in the average number of small particles in contact with large ones. This study has significance in probing the drying mechanism of bidisperse colloidal films and the stratification mechanism.

The first normal stress difference of non-Brownian hard-sphere suspensions in the oscillatory shear flow near the liquid and crystal coexistence region.

We carry out a numerical study to investigate the dynamics of non-Brownian hard-sphere suspensions near the liquid and crystal coexistence region in small to large amplitude oscillatory shear flow. The first normal stress difference (N1) and related rheological functions are carefully analyzed, focusing on the strain stiffening phenomenon, which occurs in the large strain amplitude region. Under oscillatory shear, we observe several unique behaviors of N1. A negative nonzero mean value of N1 (N1,0) is observed for the applied strain amplitudes. The change of the sign, from negative to positive, at the maximum value of N1 (N1,max) is observed at a specific point, which is not consistent with the critical strain amplitude (γ0,c) at which the modulus begins to deviate from linear viscoelasticity. The behavior of N1 in the oscillatory shear flow is different from that of N1 in steady shear flow, that is, the characteristics of N1 in strain stiffening and shear thickening are quite distinguished from each other. We also perform structural analysis to confirm the relationship between the rheological properties and microstructure of the suspension. A strong correlation is observed between the global bond order parameter (Ψ6) and the distortions in both nonlinear shear and normal stresses. The most noticeable characteristic is captured through the maximum of the global bond order parameter (Ψ6,max). The strain amplitude at the slope change of Ψ6,max corresponds to the point where a unique behavior of N1 is observed, i.e. the change of the sign in N1,max, but a strong correlation is not captured at γ0,c. This demonstrates that the normal stress responds to particle ordering more sensitively than other rheological functions based on shear stress like dynamic moduli. As far as we are concerned, the behavior of N1 has rarely been fully explored and related with the strain stiffening of non-Brownian suspensions so far. Therefore, this study has significance as the first report to strictly analyze strain stiffening along with the first normal stress difference N1.

Agglomerate Breakup of Destabilized Polystyrene Particles under a Cross-Channel Planar Extensional Flow.

Deformation and breakup of a single agglomerate exposed to pure planar extensional flow in a cross-channel were experimentally investigated. Aggregation was generated by applying shear with destabilized polystyrene particles, and the fractal dimension, df, of the agglomerate was 2.25. The aggregation focused on the center of the channel by sheath flow was rotated while approaching stagnant point. Then, the aspect ratio increased as it deformed close to the stagnant point. The probability of the breakup and the fragment distribution were dependent upon the viscosity and flow rate and were superimposed on a master curve as a function of applied stress. With the increase in stress, the projected area of the fragment that was split by the flow decreased with a power-law relationship, and the exponent was in agreement with the model prediction.

Orthogonal superposition rheometry of colloidal gels: time-shear rate superposition.

We explore the relaxation behavior of model colloidal gels under steady shear flow by means of orthogonal superposition rheometry. Fumed silica and carbon black dispersions in Newtonian matrices are used as a model system. As shear rate increases, the frequency dependent orthogonal moduli of the gels shift along the frequency axis without changing their shape, which finally can be superimposed to yield a single master curve. This indicates that the shear rate tunes a master clock for overall relaxation modes in the sheared colloidal gels to produce a "time-shear rate superposition (TSS)", as temperature does in polymeric liquids to produce a time-temperature superposition (TTS). The horizontal shift factor required at each shear rate to obtain the master curve is found to be directly proportional to the suspension viscosity for all the cases. From this result, we suggest that the suspension viscosity determines the overall relaxation time of the particles in the flowing colloidal gel.

Depletion stabilization in nanoparticle-polymer suspensions: multi-length-scale analysis of microstructure.

We study the mechanism of depletion stabilization and the resultant microstructure of aqueous suspensions of nanosized silica and poly(vinyl alcohol) (PVA). Rheology, small-angle light scattering (SALS), and small-angle X-ray scattering (SAXS) techniques enable us to analyze the microstructure at broad length scale from single particle size to the size of a cluster of aggregated particles. As PVA concentration increases, the microstructure evolves from bridging flocculation, steric stabilization, depletion flocculation to depletion stabilization. To our surprise, when depletion stabilization occurs, the suspension shows the stabilization at the cluster length scale, while maintaining fractal aggregates at the particle length scale. This sharply contrasts previously reported studies on the depletion stabilization of microsized particle and polymer suspensions, which exhibits the stabilization at the particle length scale. On the basis of the evaluation of depletion interaction, we propose that the depletion energy barrier exists between clusters rather than particles due to the comparable size of silica particle and the radius gyration of PVA.

Nanoparticle-Induced Gelation of Bimodal Slurries with Highly Size-Asymmetric Particles: Effect of Surface Chemistry and Concentration.

A systematic study has been performed to investigate the effect of surface potential of nanoparticles on the rheological behavior of bimodal suspensions, using a model system consisting of polystyrene latex (primary size ∼530 nm) and alumina-coated silica (primary size ∼12 nm) particles. The surface potential of small particles was tuned by varying the solution pH, causing them to be repulsive to each other, attractive to each other, and oppositely charged to the large particles, while the large particles remained electrostatically stabilized. We found that the rheological properties could be dramatically changed from viscous to gel-like depending on the surface potential and concentration of small particles. A colloidal gel was induced by small particles when the small particles had the opposite charge to the large particles and a volume fraction of 10(-4) < ϕsmall < 10(-3), and when the small particles were attractive to each other above a critical threshold, ϕsmall > 10(-4). Cryo-SEM distinguished the gel structures to be either short bridging gels produced by oppositely charged small particles or long bridging gels or dense gels produced by attractive small particles. On the basis of this rheological behavior and microstructure, we prepared a phase diagram of highly size-asymmetric bimodal colloids with respect to the surface chemistry and concentration of small particles.

Structural change and dynamics of colloidal gels under oscillatory shear flow.

The dynamics and rheological behavior of colloidal gels under oscillatory shear flow have been studied by using the Brownian dynamics simulations. The dynamics is studied under the oscillatory shear of small, medium, and large amplitudes. In the small amplitude oscillatory shear (SAOS) regime, the colloidal gel retains a rigid-chain network structure. The colloidal gel oscillates with small structural fluctuations and the elastic stress shows a linear viscoelastic response. In the medium amplitude oscillatory shear (MAOS) regime, the rigid network structure is ruptured, and a negative correlation between the absolute value of strain and the average bond number is observed. The elastic stress shows a transient behavior in between the SAOS and LAOS responses. In the large amplitude oscillatory shear (LAOS) regime, the colloidal gel shows a soft chain structure. Contrary to the negative correlation in the MAOS regime, the colloidal gel shows an oscillating dynamics with a positive correlation between the absolute value of strain and the average bond number. The soft chain structure exhibits no elasticity at small strain, while it shows strong elasticity at large strain. The oscillating dynamics and the rheological behavior are discussed in terms of the microstructural change from the rigid to soft chain structure.

Rheology and microstructure of non-Brownian suspensions in the liquid and crystal coexistence region: strain stiffening in large amplitude oscillatory shear.

Concentrated hard-sphere suspensions in the liquid and crystal coexistence region show a unique nonlinear behavior under a large amplitude oscillatory shear flow, the so-called strain stiffening, in which the viscosity or modulus suddenly starts to increase near a critical strain amplitude. Even though this phenomenon has been widely reported in experiments, its key mechanism has never been investigated in a systematic way. To have a good understanding of this behavior, a numerical simulation was performed using the lattice Boltzmann method (LBM). Strain stiffening was clearly observed at large strain amplitudes, and the critical strain amplitude showed an angular frequency dependency. The distortion of the shear stress appeared near the critical strain amplitude, and the nonlinear behavior was quantified by the Fourier transformation (FT) and the stress decomposition methods. Above the critical strain amplitude, an increase in the global bond order parameter Ψ(6) was observed at the flow reversal. The maximum of Ψ(6) and the maximum shear stress occurred at the same strain. These results show how strongly the ordered structure of the particles is related to the stress distortion. The ordered particles maintained a bond number of "two" with alignment with the compressive axis, and they were distributed over a narrow range of angular distribution (110°-130°). In addition, the ordered structure was formed near the lowest shear rate region (the flow reversal). The characteristics of the ordered structure were remarkably different from those of the hydroclusters which are regarded as the origin of shear thickening. It is clear that strain stiffening and shear thickening originate from different mechanisms. Our results clearly demonstrate how the ordering of the particles induces strain stiffening in the liquid and crystal coexistence region.

High-throughput DNA separation in nanofilter arrays.

We numerically investigated the dynamics of short double-stranded DNA molecules moving through a deep-shallow alternating nanofilter, by utilizing Brownian dynamics simulation. We propose a novel mechanism for high-throughput DNA separation with a high electric field, which was originally predicted by Laachi et al. [Phys. Rev. Lett. 2007, 98, 098106]. In this work, we show that DNA molecules deterministically move along different electrophoretic streamlines according to their length, owing to geometric constraint at the exit of the shallow region. Consequently, it is more probable that long DNA molecules pass over a deep well region without significant lateral migration toward the bottom of the deep well, which is in contrast to the long dwelling time for short DNA molecules. We investigated the dynamics of DNA passage through a nanofilter facilitating electrophoretic field kinematics. The statistical distribution of the DNA molecules according to their size clearly corroborates our assumption. On the other hand, it was also found that the tapering angle between the shallow and deep regions significantly affects the DNA separation performance. The current results show that the nonuniform field effect combined with geometric constraint plays a key role in nanofilter-based DNA separation. We expect that our results will be helpful in designing and operating nanofluidics-based DNA separation devices and in understanding the polymer dynamics in confined geometries.

Flow instability due to coupling of shear-gradients with concentration: non-uniform flow of (hard-sphere) glasses.

Flow-induced instabilities that lead to non-uniform stationary flow profiles have been observed in many different soft-matter systems. Two types of instabilities that lead to banded stationary states have been identified, which are commonly referred to as gradient- and vorticity-banding. The molecular origin of these instabilities is reasonably well understood. A third type of instability that has been proposed phenomenologically [Europhys. Lett., 1986, 2, 129 and Phys. Rev. E, 1995, 52, 4009] is largely unexplored. Essential to this "Shear-gradient Concentration Coupling" (SCC-) instability is a mass flux that is induced by spatial gradients of the shear rate. A possible reason that this instability has essentially been ignored is that the molecular origin of the postulated mass flux is not clear, and no explicit expressions for the shear-rate and concentration dependence of the corresponding transport coefficient exist. It is therefore not yet known what types of flow velocity- and concentration-profiles this instability gives rise to. In this paper, an expression for the transport coefficient corresponding to the shear-gradient induced mass flux is derived in terms of the shear-rate dependent pair-correlation function, and Brownian dynamics simulations for hard-spheres are presented that specify the shear-rate and concentration dependence of the pair-correlation function. This allows to explicitly formulate the coupled advection-diffusion equation and an equation of motion for the suspension flow velocity. The inclusion of a non-local contribution to the stress turns out to be essential to describe the SCC-banding transition. The coupled equations of motion are solved numerically, and flow- and concentration-profiles are discussed. It is shown that the SCC-instability occurs within the glass state at sufficiently small shear rates, leading to a banded flow-profile where one of the bands is non-flowing.

Role of shear-induced dynamical heterogeneity in the nonlinear rheology of colloidal gels.

We report the effect of flow-induced dynamical heterogeneity on the nonlinear elastic modulus of weakly aggregated colloidal gels that have undergone yielding by an imposed step strain deformation. The gels are comprised of sterically stabilized poly(methyl methacrylate) colloids interacting through short-ranged depletion attractions. When a step strain of magnitude varying from γ = 0.1 to 80.0 is applied to the quiescent gels, we observe the development of a bimodal distribution in the single-particle van Hove self-correlation function. This distribution is consistent with the existence of a fast and slow subpopulation of colloids within sheared gels. We evaluate the effect of incorporating the properties of the slow, rigid subpopulation of the colloids into a recent mode coupling theory for the nonlinear elasticity of colloidal gels.

A comparative study of blood viscometers of 3 different types.

 The greater the viscosity of the blood, the more difficult its flow becomes, leading to an increased incidence of diseases caused by blood circulation disorders. These diseases are commonly associated with the cardiovascular and cerebrovascular systems. High blood viscosity is a primary cause of circulatory system diseases. Studies have shown that accurately measuring blood viscosity and applying this data in clinical trials can help prevent circulatory system diseases. Viscosity data can vary depending on the measurement methods used, even when these methods are based on hydrodynamic principles. Despite using approved blood viscometers, the results often differ depending on the type of viscometer used, potentially causing confusion within the medical field. Informing the medical community about these differences and the level of error associated with each measurement method can help reduce this confusion. To our knowledge, the degree of difference in viscosity measurement results due to different measurement methods and the reasons for these differences have not yet been thoroughly explored. In this study, we selected three blood viscosity measurement methods registered with the Ministry of Food and Drug Safety of Korea to analyze the same canine blood. The viscosity measurements were carried out using each device and compared. The parallel plate and scanning capillary methods yielded similar viscosity values, while the cone plate method showed lower viscosity values. The viscosity of blood, as measured by the three viscometers, differed, indicating that more experimental data must be accumulated to evaluate the cause of these differences. In this paper, we identified several causes of inconsistency and suggested measures to avoid this confusion. However, confirming that the test results show systematic differences is expected to assist clinicians who diagnose and prescribe treatments based on blood viscosity results. The findings of this comparative study are anticipated to serve as a starting point for establishing guidelines or standards for blood viscosity measurement methods.

Prediction of coating thickness in the convective assembly process.

Convective assembly is a coating method to fabricate thin films with ordered particle structures that can be used extensively for biochemical sensors, data storage devices, optical devices, and other applications. The fluid flow into or through the close-packed region causes the convective assembly, and it is important to understand the formation mechanism of the close-packed region. In this paper, the length of the close-packed region was predicted, and the dimensionless coating thickness as well as the dimensionless length of the close-packed region was found to be the functions of only three dimensionless variables: two capillary numbers and the initial volume fraction. From the modeling results, coating process regime maps that predict the dimensionless coating thickness in terms of the dimensionless variables were created. In addition, the length of the close-packed region was measured under various coating conditions to validate the model prediction. The experiments firmly supported the model predictions.

Latex migration in battery slurries during drying.

We used real-time fluorescence microscopy to investigate the migration of latex particles in drying battery slurries. The time evolution of the fluorescence signals revealed that the migration of the latex particles was suppressed above the entanglement concentration of carboxymethyl cellulose (CMC), while it was significantly enhanced when CMC fully covered the surfaces of the graphite particles. In particular, a two-step migration was observed when the graphite particles flocculated by depletion attraction at high CMC/graphite mass ratios. The transient states of the nonadsorbing CMC and graphite particles in a medium were discussed, and the uses of this novel measurement technique to monitor the complex drying processes of films were demonstrated.

Drying of a charge-stabilized colloidal suspension in situ monitored by vertical small-angle X-ray scattering.

We report a first application of vertical small-angle X-ray scattering to investigate the drying process of a colloidal suspension by overcoming gravity related restrictions. From the observation of the drying behavior of charge-stabilized colloidal silica in situ, we find the solidification of the colloidal particles exhibits an initial ordering, followed by a sudden aggregation when they overcome an electrostatic energy barrier. The aggregation can be driven not only by capillary pressure but also by thermal motion of the particles. The dominating contribution is determined by the magnitude of the energy barrier at the transition, which significantly decreases during drying due to an increased ionic strength.

Optimization of experimental parameters to determine the jetting regimes in electrohydrodynamic printing.

The harmony of ink and printing method is of importance in producing on-demand droplets and jets of ink. Many factors including the material properties, the processing conditions, and the nozzle geometry affect the printing quality. In electrohydrodynamic (EHD) printing where droplets or jets are generated by the electrostatic force, the physical as well as the electrical properties of the fluid should be taken into account to achieve the desired performance. In this study, a systematic approach was suggested for finding the processing windows of the EHD printing. Six dimensionless parameters were organized and applied to the printing system of ethanol/terpineol mixtures. On the basis of the correlation of the dimensionless voltage and the charge relaxation length, the jet diameter of cone-jet mode was characterized, and the semicone angle was compared with the theoretical Taylor angle. In addition, the ratio of electric normal force and electric tangential force on the charged surface of the Taylor cone was recommended as a parameter that determines the degree of cone-jet stability. The cone-jet became more stable as this ratio got smaller. This approach was a systematic and effective way of obtaining the Taylor cone of the cone-jet mode and evaluating the jetting stability. The control of the inks with optimized experimental parameters by this method will improve the jetting performance in EHD inkjet printing.

Floatable photocatalytic hydrogel nanocomposites for large-scale solar hydrogen production.

Storing solar energy in chemical bonds aided by heterogeneous photocatalysis is desirable for sustainable energy conversion. Despite recent progress in designing highly active photocatalysts, inefficient solar energy and mass transfer, the instability of catalysts and reverse reactions impede their practical large-scale applications. Here we tackle these challenges by designing a floatable photocatalytic platform constructed from porous elastomer-hydrogel nanocomposites. The nanocomposites at the air-water interface feature efficient light delivery, facile supply of water and instantaneous gas separation. Consequently, a high hydrogen evolution rate of 163 mmol h-1 m-2 can be achieved using Pt/TiO2 cryoaerogel, even without forced convection. When fabricated in an area of 1 m2 and incorporated with economically feasible single-atom Cu/TiO2 photocatalysts, the nanocomposites produce 79.2 ml of hydrogen per day under natural sunlight. Furthermore, long-term stable hydrogen production in seawater and highly turbid water and photoreforming of polyethylene terephthalate demonstrate the potential of the nanocomposites as a commercially viable photocatalytic system.

High blood viscosity in acute ischemic stroke.

Background: The changes in blood viscosity can influence the shear stress at the vessel wall, but there is limited evidence regarding the impact on thrombogenesis and acute stroke. We aimed to investigate the effect of blood viscosity on stroke and the clinical utility of blood viscosity measurements obtained immediately upon hospital arrival. Methods: Patients with suspected stroke visiting the hospital within 24 h of the last known well time were enrolled. Point-of-care testing was used to obtain blood viscosity measurements before intravenous fluid infusion. Blood viscosity was measured as the reactive torque generated at three oscillatory frequencies (1, 5, and 10 rad/sec). Blood viscosity results were compared among patients with ischemic stroke, hemorrhagic stroke, and stroke mimics diagnosed as other than stroke. Results: Among 112 enrolled patients, blood viscosity measurements were accomplished within 2.4 ± 1.3 min of vessel puncture. At an oscillatory frequency of 10 rad/sec, blood viscosity differed significantly between the ischemic stroke (24.2 ± 4.9 centipoise, cP) and stroke mimic groups (17.8 ± 6.5 cP, p < 0.001). This finding was consistent at different oscillatory frequencies (134.2 ± 46.3 vs. 102.4 ± 47.2 at 1 rad/sec and 39.2 ± 11.5 vs. 30.4 ± 12.4 at 5 rad/sec, Ps < 0.001), suggesting a relationship between decreases in viscosity and shear rate. The area under the receiver operating curve for differentiating cases of stroke from stroke mimic was 0.79 (95% confidence interval, 0.69-0.88). Conclusion: Patients with ischemic stroke exhibit increases in whole blood viscosity, suggesting that blood viscosity measurements can aid in differentiating ischemic stroke from other diseases.

Highly Efficient Nitrogen-Fixing Microbial Hydrogel Device for Sustainable Solar Hydrogen Production.

Conversion of sunlight and organic carbon substrates to sustainable energy sources through microbial metabolism has great potential for the renewable energy industry. Despite recent progress in microbial photosynthesis, the development of microbial platforms that warrant efficient and scalable fuel production remains in its infancy. Efficient transfer and retrieval of gaseous reactants and products to and from microbes are particular hurdles. Here, inspired by water lily leaves floating on water, a microbial device designed to operate at the air-water interface and facilitate concomitant supply of gaseous reactants, smooth capture of gaseous products, and efficient sunlight delivery is presented. The floatable device carrying Rhodopseudomonas parapalustris, of which nitrogen fixation activity is first determined through this study, exhibits a hydrogen production rate of 104 mmol h-1  m-2 , which is 53 times higher than that of a conventional device placed at a depth of 2 cm in the medium. Furthermore, a scaled-up device with an area of 144 cm2 generates hydrogen at a high rate of 1.52 L h-1  m-2 . Efficient nitrogen fixation and hydrogen generation, low fabrication cost, and mechanical durability corroborate the potential of the floatable microbial device toward practical and sustainable solar energy conversion.