Determination of cake thickness and porosity during cross-flow ultrafiltration on a plane ceramic membrane surface using an electrochemical method

The thickness and the porosity of a deposit during ultrafiltration experiments are determined using an electrochemical method. Twenty microelectrodes are mounted flush to a ceramic plane membrane and maps of deposit thickness are determined for three inlet/outlet distributors configurations. Combining an electrochemical method and a step transient method, the determination of the thickness and the porosity of a particles deposit is performed. These local thickness and porosity values are analyzed thanks to wall shear stress local measurements obtained in a previous work [Sep. Sci. Technol. 37 (10) (2002) 2251]. The results emphasize the heterogeneity of the deposit thickness, especially in zones of low wall shear stress. Furthermore, the porosity values of the deposit are ranged between 0.3 and 0.8 as a function of the location at the membrane surface.     

Stress-Structure Relationship of the Reversible Associating Polymer Network under Start-up Shear Flow

We adopt Langevin dynamics to explore the stress-structure relationship of telechelic reversible associating polymer gel during startup shear flow, with shear strengths varying from Wi=12.6 to Wi=12640. At weak shear flow Wi=12.6, the shear stress proportionally increases with shear strain at short times, followed by a strain hardening behavior and then passes through a maximum(σmax, γmax) and finally decreases until it reaches the steady state. During the evolution of stress, the gel network is only slightly broken and essentially maintains its framework, and the strain hardening behavior originates from the excessive stretching of chains. On the other hand, the stress-strain curve at intermediate shear flow Wi=505.6 shows two differences from that at Wi=12.6, namely, the absence of strain hardening and a dramatic increase of stress at large strains,which is caused by the rupture of gel network at small strains and the network recovery at large strains, respectively. Finally, at very strong shear flow Wi=6319.7, the gel network is immediately broken by shear flow and the stress-strain curve exhibits similar behaviors to those of classical polymeric liquids.     

固体粒子对板式膜吸收过程的传质强化

分别采用纯CO2-去离子水和不同浓度的NaOH溶液为实验体系,在板式膜器中研究了第三相固体粒子对膜吸收过程传质效果的影响．分别考察了在不同粒子种类、搅拌转速、传质体系、化学反应强度、膜孔隙率等因素下固体粒子对传质强化的影响．结果表明,随着粒子固含率的增大,传质系数和增强因子均有所提高,当粒子固含率增大到一定范围后,传质系数和增强因子的变化趋于平缓．在固含率一定的条件下,不同种类的固体粒子对膜吸收过程的强化效果随着固体粒子密度的增加而减小．传质系数随着搅拌转速的增大而增大,但高搅拌转速下固体粒子的强化作用减弱．膜吸收过程的传质系数和增强因子随着化学反应强度的增强而增加．随着粒子固含率的增大,不同膜孔隙率对传质效果的差异减小,且孔隙率越小,固体粒子对膜吸收传质过程的强化效果越好．其中,对于纯CO2-去离子水体系,当孔隙率为20％,粒子固含率为1．5gL^（-1）时,固体粒子的加入可使传质系数提高1．45倍,增强因子可达2．45．     

Apparent shear strength of hybrid glass fibre reinforced composite joints

The incorporation of nano or micro ceramic particles into fibre reinforced composites (FRC) to enhance their stiffness and durability has been widely investigated. This mechanism has been attributed to the increase in stiffness of the polymeric matrix phase and shear strength of FRCs due to the presence of particles at the interlaminar regions. In order to elucidate such effect, hybrid single-lap joints consisted of ceramic particles and glass fibre reinforced composites were evaluated to better assess the mechanical interlocking effect provided by silica and cement inclusions. A full factorial design (2³) was performed to identify the effect of the type of particle (silica and cement), particle weight fraction (2.5 and 5 wt%) and glass fibre grammage (200 and 600 g/m²) on the apparent shear strength and adherent strength of single-lap joints under tensile loading. The ceramic particle inclusions led to increased apparent shear strength and adherent strength. The inclusion of 5 wt% ceramic particles into 600 g/m² cross-ply glass fibre composites enhanced both adherent and apparent shear strengths.     

Suction effects on the hydrodynamics in the vicinity of an ultrafiltration plane ceramic membrane

The wall shear stress is determined at the surface of a plane ceramic ultrafiltration membrane in a tangential ultrafiltration module. At first, the shear stress is determined at the surface of a plate of Plexiglas mimicking a membrane and at the plane membrane surface without fouling particles with the aim to investigate the influence of permeation. Then, ultrafiltration of a suspension of spherical rigid particles inducing a deposit at the membrane surface is done. In order to study the influence of the foulant, two concentrations of particles were used for the experiments. The values of the mean wall shear stress and its fluctuations (turbulent intensity rate) were measured by using an electrochemical method. Twenty microelectrodes, on which an electrochemical reaction occurs, are mounted flush to the plate of Plexiglas and to the surface of the membrane to determine the maps of shear stress and turbulent intensity rate for two inlet/outlet distributors’ configurations. This work emphasized the fact that, due to permeation across the membrane, the mean velocity gradient value is enhanced and, on the contrary, its local fluctuations are clearly damped, even in the turbulent flow regime. Thus, the effect of the shape of the inlet/outlet fluid distributors is also minimized compared with the results obtained without permeation at the surface of the Plexiglas plate.     

Rheological Behavior of Titanium Dioxide Suspensions

The rheological properties of titanium dioxide dispersed in water are measured over a wide range of powder concentrations, temperatures, and pH values. The value of intrinsic viscosity of titanium dioxide measured with an Ubbelohde capillary viscometer is 3.55, which is useful for determining the shape and aggregation property of the particles. The yield stress and steady shear viscosity of titanium dioxide with broad and narrow particle size distributions were measured over a wide range of solid volume fractions on a Brabender rheometer. It is observed that the rheological properties of the suspensions are quite different due to the difference in particle size distributions. Quemada, Casson, and Zhou's models were used to fit the experimental data and useful parameters were obtained. Calculated data are also in good agreement with the experimental data. As expected, the shear viscosity and yield stress decrease with increasing temperature. But when the temperature is around 50 degrees C, yield stress increases with increasing temperature while shear viscosity exhibits a complex behavior. The phenomena are very interesting and special. The Peclet number was used to analyze the shear thickening behavior. Models were also used to describe the shear viscosity under different temperatures and the master plots of the reduced variables eta/eta(infinity) vs t(c)gamma; at different temperatures are superimposed, which means the agreement is fair and the models are suitable to describe the rheological properties of titanium dioxide suspensions. pH effects were investigated on a Rheometrics RFS-II rheometer and it was found that pH can change the surface charge of the particles, which also affects the rheological behavior. The pH at which maximum shear viscosity and yield stress occur is in concordance with the isoelectric point. Copyright 2001 Academic Press.     

Thermosensitive core-shell particles as model systems for studying the flow behavior of concentrated colloidal dispersions

We report on a comprehensive investigation of the flow behavior of colloidal thermosensitive core-shell particles at high densities. The particles consist of a solid core of poly(styrene) onto which a network of cross-linked poly(N-isopropylacrylamide) is affixed. Immersed in water the shell of these particles will swell if the temperature is low. Raising the temperature above 32 degrees C leads to a volume transition within this shell which leads to a marked shrinking of the shell. The particles have well-defined core-shell structure and a narrow size distribution. The remaining electrostatic interactions due to a small number of charges affixed to the core particles can be screened by adding 0.05M KCl to the suspensions. Below the lower critical solution temperature at 32 degrees C the particles are purely repulsive. Above this transition, a thermoreversible coagulation takes place. Lowering the temperature again leads to full dissociation of the aggregates formed by this process. The particles crystallize for effective volume fractions between 0.48 and 0.55. The crystallites can be molten by shear in order to reach a fluid sample again. The reduced shear stress measured in this metastable disordered state was found to be a unique function of the shear rate and the effective volume fraction. These reduced flow curves thus obtained can be described quantitatively by the theory of Fuchs and Cates [Phys. Rev. Lett. 89, 248304 (2002)] which is based on the mode-coupling theory of the glass transition.     

On rheophysics of high-concentrated suspensions

Experiments with high-concentrated suspensions of solid particles show that that their viscosity increases by several times or even orders of magnitude, when the shear rate in the suspensions exceeds some critical value, which depends on the concentration and shape of particles and the physicochemical composition of carrier liquids. It is experimentally found that, within a certain range of shear rates, which is also predetermined by the composition of the suspensions, a steady flow becomes unstable, and regular or random oscillations arise in the flow with a period of several seconds. A theory is proposed for these phenomena, which is based on the fact that the increase in the viscosity with the shear rate is explained by the contact friction between particles, while the flow oscillations arise when the differential viscosity of a suspension acquires negative values.     

In‐line monitoring of immiscible polymer blends in a rheometer with a fiber‐optics‐assisted fluorescence detection system

In‐line studies of the initial stages of shear‐induced coalescence in two‐phase polymer blends were carried out with a home‐built device combining a cone and plate rheometer and a fiber‐optic‐assisted fluorescence detection system. A blend of 90 wt % poly(2‐ethylhexyl methacrylate) (PEHMA) and 10 wt % poly(butyl methacrylate) (PBMA) was prepared by the casting of films onto a solid substrate from mixed aqueous latex dispersions of the two polymers. The dispersions were prepared via emulsion polymerization under conditions in which both components were formed as spherical particles with a very narrow size distribution. By using a 14:1 particle ratio of PEHMA to PBMA, we obtained films in which 120‐nm PBMA particles were surrounded by a PEHMA matrix. The blend contained phenanthrene‐labeled PBMA particles and anthracene‐labeled PBMA particles in a ratio of 4:1, whereas the PEHMA matrix polymer was unlabeled. We monitored the anthracene‐to‐phenanthrene fluorescence intensity ratio (I₄₇₀/I₃₆₀) as a measure of direct nonradiative energy transfer from phenanthrene to anthracene, whereas the blend was sheared at different shear rates and temperatures. Under no‐shear conditions, the results of in‐line experiments were in good agreement with the results of off‐line measurements of energy transfer by conventional techniques. In blends under shear, the two sets of experiments, in‐line and off‐line, did not agree with each other. The cause of this disagreement was associated with normal forces in the blend under shear that affected the optical path length and the relative intensities of the fluorescence signals of the phenanthrene and anthracene groups in the blend. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2302–2316, 2001     

Flow-induced patterning of Langmuir monolayers

Insoluble monolayers on water have been patterned at the macroscopic scale (i.e., at the centimeter scale of the flow apparatus) as well as the mesoscopic scale (i.e., down to the micron scale resolvable via optical microscopy). The macroscopic patterning at the air/water interface results from a hydrodynamic instability leading to a steadily precessing flow pattern. The velocity field is measured, and the associated shear stress at the interface is shown to be locally amplified by the flow pattern. The resulting hydrodynamic effects on two different monolayer systems are explored: (1) the pattern in a model monolayer consisting of micron-size, surface-bound particles is visualized to show that the particles are concentrated into isolated regions of converging flow with high shear, and (2) Brewster angle microscopy of a Langmuir monolayer (vitamin K1) shows not only that the monolayer is patterned at the macroscopic scale but also that the localized high-shear flow further patterns the monolayer at the mesoscale.     

煤与生物油的成浆性能研究

利用不同煤种的煤和生物油制备了不同浓度的生物油煤浆,考察了生物油煤浆的成浆浓度、表观黏度、流变特性和稳定性。结果表明,生物油煤浆是具有一定屈服应力的非牛顿流体,其流变特性可用宾汉姆方程来描述;生物油煤浆的屈服应力和表观黏度都随着固体浓度的增加而增大;随着剪切速率的增加,生物油煤浆的表观黏度减小;四种煤中,无烟煤的成浆浓度最高,可达42%,其含碳量高达49%,相当于同种煤制成的74%的水煤浆含量。烟煤次之,褐煤最低;生物油与煤粉之间能够形成絮凝性的大分子网络结构,使得生物油煤浆存在屈服应力并能够保持良好的静态稳定性,4.0~5.0 d天没有软沉淀产生,数月没有硬沉淀产生。     

Pore Modification in Porous Ceramic Membranes With Sol-Gel Process and Determination of Gas Permeability and Selectivity

Summary: The aim of the study was to investigate the variation in total surface area, porosity, pore size, Knudsen and surface diffusion coefficients, gas permeability and selectivity before and after the application of sol-gel process to porous ceramic membrane in order to determine the effect of pore modification. In this study, three different sol-gel process were applied to the ceramic support separately; one was the silica sol-gel process which was applied to increase porosity, others were silica-sol dip coating and silica-sol processing methods which were applied to decrease pore size. As a result of this, total surface area, pore size and porosity of ceramic support and membranes were determined by using BET instrument. In addition to this, Knudsen and surface diffusion coefficients were also calculated. After then, ceramic support and membranes were exposed to gas permeation experiments by using the CO₂ gas with different flow rates. Gas permeability and selectivity of those membranes were measured according to the data obtained. Thus, pore surface area, porosity, pore size and Knudsen diffusion coefficient of membrane treated with silica sol-gel process increased while total surface area was decreasing. Therefore, permeability of ceramic support and membrane treated with silica sol-gel process increased, and selectivity decreased with increasing the gas flow rate. Also, surface area, porosity, pore size, permeability, selectivity, Knudsen and surface diffusion coefficients of membranes treated with silica-sol dip coating and silica-sol processing methods were determined. As a result of this, porosity, pore size, Knudsen and surface diffusion coefficients decreased, total surface area increased in both methods. However, viscous flow and Knudsen flow permeability were detected as a consequence of gas permeability test and Knudsen flow was found to be a dominant transport mechanism in addition to surface diffusive flow owing to the small pore diameter in both methods. It was observed that silica-sol processing method had lower pore diameter and higher surface diffusion coefficient than silica-sol dip coating method.     

Flow mechanisms in the face-centred cubic micellar gel of a diblock copolymer

The mechanisms of flow of a face-centred cubic micellar phase were investigated using small-angle X-ray scattering (SAXS) for samples under either steady or oscillatory shear in two different geometries: Couette cell and planar shear sandwich. The system studied was a gel formed by a poly(oxyethylene)–poly(oxypropylene) diblock copolymer in water. SAXS indicated that under steady shear in a Couette cell, flow occurs via sliding of hexagonal close-packed (hcp) layers with a close-packed [110] direction along the shear direction. Under oscillatory shear in the planar shear sandwich, coexistence between this orientation and one in which the hcp layers are rotated by 30° (and flow is in a [211] direction) was observed; however, when subject to oscillatory shear in the Couette cell, flow only occurred along a [110] direction. This observation of flow in a non-close-packed direction may be due to alignment induced by the walls of the shear sandwich. Received: 24 February 2001 Accepted: 21 March 2001     

Differences in the electrorheological response of a particle suspension under direct current and alternating current electric fields

We have observed an unusual reduction of shear stress with increasing shear rate under direct current electric fields, for an electrorheological fluid composed of sulfonated poly(styrene-co-divinylbenzene) particles dispersed in silicone oil. At all shear rates, the shear stress under the electric field is larger than that in the absence of the field, indicating that there is still some field-induced agglomeration of the particles. In contrast, the behavior under alternating current electric fields is the Bingham-fluid-type response commonly observed with electrorheological fluids. It is suggested that the conventional dipole–dipole interaction approach based on simplified microstructural models would be unable to explain these phenomena. Received: 27 November 2000 Accepted: 22 May 2001     

Particle-stabilized emulsions comprised of solid droplets

We kinetically stabilize oil-in-water emulsions comprising paraffin crystals by adsorbing solid particles (silica) of colloidal size at the oil/water interface. We obtain a set of emulsions that are quiescently stable for a long period of time (months), while the same emulsions are destabilized after only a few hours in the presence of surfactant molecules alone. The emulsions are submitted to a shear stress in order to probe their stability under flow conditions. Partial coalescence and gelation occur when the shear is applied for a sufficiently long period of time. The experiments reveal the existence of a critical droplet mass fraction, phi*, that defines a sharp transition between slow and fast gelation. The process of gelation is rather slow for phi < phi*, occurring at the scale of hours, and becomes almost instantaneous above phi*.     

Rheology of particulate rafts,films, and foams

Liquid foam exhibits remarkable rheological behavior although it is made with simple fluids: it behaves similar to a solid at low shear stress but flows similar to a liquid above a critical shear stress. Such properties, which have been proved to be useful for many applications, are even enhanced by adding solid particles. Depending on their hydrophobicity and size, the particles can have different geometrical configurations at the mesoscopic scale, that is, at the air–liquid interfaces, in the films, or in the interstices between the bubbles. In this review, we present rheological studies performed on granular rafts and films, on spherical armored interfaces, on gas marbles, and on aqueous foams laden with hydrophilic grains.     

Experimental Study of Fibrin/Fibrin-Specific Molecular Interactions Using a Sphere/Plane Adhesion Model

Fibrin, the biopolymer produced in the final step of the coagulation cascade, is involved in the resistance of arterial thrombi to fragmentation under shear flow. However, the nature and strength of specific interactions between fibrin monomers are unknown. Thus, the shear-induced detachment of spherical monodispersed fibrin-coated latex particles in adhesive contact with a plane fibrin-coated glass surface has been experimentally studied, using an especially designed shear stress flow chamber. A complete series of experiments for measuring the shear stress necessary to release individual particles under various conditions (various number of fibrin layers involved in the adhesive contact, absence or presence of plasmin, the main physiological fibrinolytic enzyme) has been performed. The nonspecific DLVO interactions have been shown to be negligible compared to the interactions between fibrin monomers. A simple adhesion model based on the balance of forces and torque on particles, assuming an elastic behavior of the fibrin polymer bonds, to analyze the experimental data in terms of elastic force at rupture of an elementary intermonomeric fibrin bond has been used. The results suggested that this force (of order 400 pN) is an intrinsic quantity, independent of the number of fibrin layers involved in the adhesive contact. Copyright 2001 Academic Press.     

Polyethylene oxides

The aim of this study was to study tablet formation of polyethylene oxides (PEOs) with different molecular masses by means of 3D modeling and comparing the results to those of other more traditional techniques, such as Heckel analysis, analysis by the pressure- time function and energy analysis. The molecular masses ranged between 400,000 and 7,000,000 Da. Material properties, such as water content, particle size and morphology, and glass transition temperature were also studied. To complete this study, elastic recovery dependent on maximum relative density and time were determined. Furthermore, the crushing force of the tablets and their morphology were analyzed. The PEOs consist of smooth edged particles of irregular shape; the particle size is similar to one type of MCC, namely Avicel PH 200. The PEOs are much more ductile during compression than MCC. Elastic recovery after tableting is higher than that for tablets made from MCC and continues for some time after tableting. The crushing force of the resulting tablets is low. In conclusion, with regards to direct compression the PEOs do not appear to be useful as sole tableting excipients.     

微流控芯片流体剪切力和肿瘤坏死因子-α共同作用对大鼠软骨细胞表型的影响

流体剪切力是生物体内普遍存在的一种生物力学形式,是细胞微环境的重要组成部分,对细胞多种生物学行为有重要调节作用。该研究以微流控芯片技术为基础,建立了一种基于流阻原理能同时产生4个不同大小流体剪切力的微流控芯片平台,用以研究低流速的流体剪切力对大鼠原代软骨细胞表型维持的影响。结果表明,流体剪切力可促进软骨细胞的表型维持。还加入了肿瘤坏死因子-α(TNF-α),考察流体剪切力和TNF-α共同作用对软骨细胞表型的影响。结果表明,在剪切力和TNF-α共同作用下,软骨细胞的Ⅱ型胶原和蛋白多糖表达明显下调。该研究为软骨组织工程和骨性关节炎的疾病研究提供有力的研究平台,为骨关节疾病治疗和防治提供了理论依据。     

Parameters of Equilibrium Spectrum of Particles in Coagulating System with Aggregate Disintegration

The formation of equilibrium spectrum of particles in a disperse system with the coagulation–fragmentation of aggregates at a steady-state shear flow was analyzed in terms of two-fraction model. It was suggested that an initial dispersed phase contains only small particles coagulating by the Brownian mechanism; the growth of larger aggregates proceeds by the gradient mechanism and is accompanied by the detachment of fragments. Parameters of equilibrium spectrum characterizing average masses and the number of particles in fine and coarse fractions were determined as functions of a flow shear rate, aggregate fractal dimension, parameters of particle interaction in aggregates, and the properties of the initial dispersed phase.