Linear Viscoelastic Properties of Suspensions of Rigid Hairy Particles in a Polymeric Matrix

The aim of this work is to use a recently developed statistical model of dispersions with non‐hydrodynamic interactions (Dagréou et al., 2002) to describe the linear viscoelastic properties of suspensions of rigid hairy particles in a polymeric matrix. We first present numerical simulations of our model applied to this system; we demonstrate that taking physical interactions into account allows one to predict the complex relaxation behaviour of filled polymers. We then compare the statistical model to experimental results on suspensions of grafted silica particles in a polystyrene matrix and show that they are in reasonable agreement up to volume fractions close to percolation.     

Steady state flow of cement suspensions: A micromechanical state of the art

Fresh cementitious pastes can be viewed as suspensions of particles of many different sizes (from several tens of nm to 100 μm) in a continuous fluid phase. This broad poly-dispersity implies that various interactions such as surface forces (or colloidal interactions), Brownian forces, hydrodynamic forces or various contact forces between particles interplay. Depending on the volume fraction of the particles in the mixture, the use of admixtures or the magnitude of either the applied stress or strain rate, one or several of these interactions dominate. Our objective here is not to quantitatively predict rheology of cement pastes but rather to understand and classify the situations where, depending on composition and processing, one or other of the physical phenomena will control the macroscopic behavior. The result of this analysis is a conceptual diagram of predominant interactions in flowing cementitious suspensions under simple shear, as a function of shear rate and solid fraction.     

Reaction induced phase-separation controlled by molecular topology

Binary phase-separation driven by a difference in branch content of the two components has been widely reported in polyolefins. This concept is applied to polysiloxanes in an attempt to control morphology in chemically driven phase separation. It is shown that self-assembled, non-reversible spinodal morphologies (SD) as well as low-polydispersity nucleation and growth morphologies can be controlled through the rate of network formation in these systems. Time-resolved light scattering and optical microscopy were used to determine the character and kinetics of phase separation. The mechanism of phase separation in two similar systems was dictated by the rates of the crosslinking reactions. Both morphologies were ‘locked-in’ by network formation and late-stage phase-ripening was prevented by low surface energy associated with topologically driven phase-separation.     

A comparative study on the synthesis mechanism and microstructural development of hierarchical porous mullite monoliths obtained by the sol–gel process with three different silicon sources

Hierarchical porous mullite monoliths have been prepared via a sol–gel process accompanied by phase separation. Propylene oxide (PO) acted as an acid scavenger to mediate the gelation, poly(ethylene oxide) (PEO) as the phase-separation inducer and network former, aluminum chloride hexahydrate (AlCl₃·6H₂O) as the aluminum source. The route was improved by using hypotoxic tetraethylorthosilicate (TEOS) and nontoxic aqueous colloidal silica (Aq) instead of tetramethoxysilane (TMOS). The synthesis mechanism and microstructural development were comparatively investigated by scanning electron microscopy (SEM), thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and nitrogen adsorption–desorption. It was found that the mixing degree of precursors and concurrent process of gelation and phase separation are key elements to get well-defined hierarchical porous mullite monoliths. In addition, the monoliths with high relative crystallinity are more likely to be obtained under low transformation temperature in organic silicon sources system.     

Rheometry of aging of colloidal melamine–urea–formaldehyde polycondensates

Aged and whitened melamine–urea–formaldehyde (MUF) resins in a colloidal state were tested with parallel‐plate rheometry to determine the extent of their viscoelastic behavior. Only in advanced colloidal states, and so only when aggregated colloidal clusters occurred, did the resins present clear indications of viscoelastic responses, as illustrated by the crossover of elastic modulus and viscous modulus curves at lower strain percentages. These colloidal clusters were labile microstructures, which, broken by applied shear, justified the known thixotropic behavior of these resins sufficiently advanced by aging or other means. MUF resins already in the colloidal state, but for which colloidal clustering had not yet occurred, behaved exclusively as viscous liquids. Two different cases of physical gelation were observed, reversible physical gelation and irreversible physical gelation, underlying which a true gel situation possibly occurred. Physical gelation due to colloidal superstructures occurred in both, but the difference in the resin average molecular masses revealed if the physical gelation was reversible or irreversible and, therefore, if the liquid/cluster separation was defined as the terminal phase of physical gelation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 655–659, 2005     

Suspensions and Sediments. Part I. Particle-Particle Interactions in Dilute Solid-Liquid Suspensions

Abstract

This article gives a general review of sedimentation behavior relating to dilute suspensions of solids in liquids. There is a strong assumption that partial-fluid association is the factor responsible for variations of sedimentation behavior from one suspension system to another. Studies are therefore cited to acquire an understanding of the hydrodynamic interactions between the solids and liquids within suspensions. Behavior of colloidal suspensions is also included, and the effects of such factors as liquid dielectric constant, charge density, and electrical potential on the interaction of particles are discussed.     

Removal of colloidal particles utilizing gelation reaction of sodium alginate

A novel technique utilizing the gelation reaction of natural polymers has been proposed for the separation of solid from liquid in difficult-to-filter colloidal suspensions. This technique is especially effective in the treatment of colloidal muddy water of high solid concentration, which is often produced as a byproduct of certain construction processes. Colloidal suspensions are mixed with a sodium alginate solution, and this mixture is added to a calcium chloride solution, resulting in the entrapping of colloidal particles by the calcium alginate gel. Gel suspensions are then drained gravitationally, followed by mechanical expression of gel particles. Fundamental aspects of this process are investigated by using sodium bentonite as an experimental material. The alginate-bentonite mixture is added dropwise to the calcium solution. Decreasing the droplet size of the mixture expedites gelation since the diffusion of calcium ions into droplets determines the rate of gelation reactions. Reducing the alginate content expedites expression of the gel since alginate content is inversely proportional to the rate of expression.     

Experimental characterization and population balance modelling of the dense silica suspensions aggregation process

Concentrated suspensions of nanoparticles subjected to transport or shear forces are commonly encountered in many processes where particles are likely to undergo processes of aggregation and fragmentation under physico-chemical interactions and hydrodynamic forces. This study is focused on the analysis of the behavior of colloidal silica in dense suspensions subjected to hydrodynamic forces in conditions of destabilization.A colloidal silica suspension of particles with an initial size of about 80 nm was used. The silica suspension concentration was varied between 3% and 20% of weight. The phenomenon of aggregation was observed in the absence of any other process such as precipitation and the destabilization of the colloidal suspensions was obtained by adding sodium chloride salt.The experiments were performed in a batch agitated vessel. The evolution of the particle size distributions versus time during the process of aggregation was particularly followed on-line by acoustic spectroscopy in dense conditions. Samples were also analyzed after an appropriate dilution by laser diffraction. The results show the different stages of the silica aggregation process whose kinetic rates depend either on physico-chemical parameters or on hydrodynamic conditions. Then, the study is completed by a numerical study based on the population balance approach. By the fixed pivot technique of Kumar and Ramkrishna [1996. On the solution of population balance equations by discretization—I. A fixed pivot technique. Chemical Engineering Science 51 (8), 1311-1332], the hypothesis on the mechanisms of the aggregation and breakage processes were justified. Finally, it allows a better understanding of the mechanisms of the aggregation process under flowing conditions.     

A New Theoretical Approach To Electroosmotic Dewatering (Eod) Based On Non-Equilibrium Thermodynamics☆

ABSTRACT

A novel theoretical approach to electroosmotic dewatering (EOD), with or without a pressure gradient, of clays, sludges and other colloidal suspensions is proposed. The treatment is based on nan-equilibrium thermodynamics as developed in the work of Overbeek, De Groot and others. The interpretation of electrokinetic phenomena in terms of the cancepts of irreversible thermodynamics when combined with Onsager's relations, it has been shown by Overbeek, provides a complete framework for understanding all electrokinetic phenomena.

We have applied this approach here to the electroosmotic dewatering. both in the presence and absence of applied hydrostatic pressure.

The approach provides much clarification on the nature and significance of currents and fluxes observed during EOD: these are composed of three components, during combined pressure electroosmotic dewatering: (i) electrochemicavelectrical current; (ii) hydrodynamic flux: (iii) electroosmotic current.

We have also shown the manner in which the proposed new approach to EOD based on irreversible thermodynamics can be connected to the conventional approach based on the Helmholzu-Smoluchowski equation.     

Unveiling the evolution of early phase separation induced by P2O5 for controlling crystallization in lithium disilicate glass system

The nucleation and crystallization of glass-ceramics are typically influenced by early phase separation, which can impact glass properties. However, it has been challenging to characterize the nanoscale phase separation and understand the nucleation mechanism of lithium disilicate (L₂S) glass-ceramics, which has resulted in some controversy. Here, we raised the direct evidence of nanoscale clustering in the glassy phase prior to formal nucleation and crystallization by element distribution. Firstly, the amorphous Li₃PO₄ phase formed on the boundary between the phase separation area and residual glass matrix, and then nucleation tended to start on this phase boundary. Furthermore, the effect of phase-separation on nucleation and final crystallize products was illustrated. By sufficient phase-separation, the formation of desired Li₂Si₂O₅ and LiAlSi₄O₁₀ microcrystals was effectively motivated, which is prerequisite for high mechanical properties and transparency. We hope this work provides guidance to rationally understand the early phase separation in glass for subsequent controlling crystallization.     

Dynamic interplay between phase separation and crystallization in a poly(?-caprolactone)/poly(ethylene glycol) oligomer blend

We have investigated the crystallization effect on the phase separation of a poly(?-caprolactone) and poly(ethylene glycol) oligomer (PCL/PEGo) blending system using simultaneous small-angle light scattering and differential scanning calorimetry (SALS/DSC) as well as simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and DSC (SAXS/WAXS/DSC). When the PCL/PEGo system, of a weight ratio of 7/3, is quenched from a melt state (160 °C) to temperatures below the spinodal point and the melting temperature of PCL (63 °C), the structural evolution observed exhibits characteristics of (I) early stage of spinodal decomposition (SD), (II) transient pinning, (III) crystallization-induced depinning, and (IV) diffusion-limited crystallization. The time-dependent scattering data of SALS, SAXS and WAXS, covering a wide range of length scale, clearly show that the crystallization of PCL intervenes significantly in the ongoing viscoelastic phase separation of the system, only after the early stage of SD. The effect of preordering before crystallization revives the structural evolution pinned by the viscoelastic phase separation. The growth of SAXS intensity during the preordering period conforms to the Cahn-Hilliard theory. In the later stage of the phase separation, the PCL-rich matrix, of spherulite crystalline domains developed due to the faster crystallization kinetics, traps the isolated PEGo-rich domains of a slower viscoelastic separation.     

Mechanics and Microstructures of Concentrated Particle Gels

It is often assumed that the viscoelastic properties of dense colloids are determined by the colloid volume fraction, the interaction potential, as well as the particle size distribution and shape. The dependence of the viscoelastic behavior of particle suspensions and gels on these parameters has been widely studied, and is well understood in many cases. In contrast, our knowledge on the influence of microstructure on mechanical and rheological properties, in particular for high solid loading suspensions as used in ceramic processing, is much less developed. This aspect has been the focus of recent experiments, which show that small changes in microstructure can have dramatic effects on the mechanics and dynamics of concentrated colloidal gels. In this article, we attempt to give an overview of the influence of microstructure on the mechanical and rheological properties of colloidal systems. Particular attention is given to colloidal particle gels at high volume fractions.     

Rheological behavior of thermoset/thermoplastic blends during isothermal curing: Experiments and modeling

The evolution of the viscoelastic properties of a molten thermoplastic/thermoset system during the course of the isothermal polymerization of the thermoset precursors has been investigated and modeled. Such systems are initially homogenous and phase separate upon polymerization of the monomers. In the present study, atactic polystyrene (85 and 60 wt%) is blended to a stoichiometric mixture diglycidyl ether of bisphenol A with 4,4′-methylenebis(2,6-diethylaniline). During the polymerization, polystyrene becomes the thermoplastic-rich matrix and an epoxy-rich dispersed phase appears. Both phases experience changes in their composition and viscoelastic properties. A rheokinetic model is proposed to take into account four contributions to the viscoelastic behavior: progressive deplastification of the polystyrene matrix involving a modification of the glass transition and thus of free volume, dilution of the network of entanglements of the matrix by the non yet converted low molar weight molecules, emulsion behavior after the separation of the epoxy-rich phase and finally interparticular interactions being assimilated to a mechanical percolation. Provided that the glass transition temperature of the matrix and the dynamic moduli of the neat components are known, the changes in the viscoelastic behavior of the system with time can be predicted with no ad hoc parameter and model calculations are in good agreement with the experimental data.     

Gel casting of aqueous suspensions of BaTiO3 nanopowders

Commercial nano-BaTiO₃ powders have been formed into green bodies using colloidal forming routes. A study of the rheological behaviour of the suspensions as a function of dispersant concentration and homogenisation time was made in order to prepare stable concentrated suspensions of the nanopowders. Bulk components were then manufactured using aqueous slip and gel casting involving polysaccharides that gel on cooling, i.e. agar. The performance of theses consolidation techniques for obtaining dense green bodies from the BaTiO₃ nanopowders was studied. It was possible to prepare relatively big gel cast samples with a similar density and microstructure and in a shorter time compared to those obtained by slip casting.     

Electro-Acoustic Dewatering (EAD) a Novel Approach for Food Processing,and Recovery

Abstract

Separation of liquids from fine particle suspensions plays an important role in many industrial processes. In the past few years a number of technologies have been developed for the separation of slurries with coarse particle suspensions and intermediate particle sizes. However, separation of fine particles from their suspensions can be difficult and prohibitively costly.

Battelle has developed a solid/liquid separation technology that utilizes differences in electro-kinetic and acoustic properties to enhance the efficiency of conventional solid/liquid separation techniques such as vacuum filters or presses. This method can dewater colloidal stable suspensions better than conventional techniques. Typical applications of this technology to food processing will be presented. Mechanisms involved during separation will also be discussed.     

Interparticle and particle-matrix interactions in polyethylene reinforcement and viscoelasticity

Composites of surface treated and untreated non-colloidal CaCO₃ particles and high-density polyethylene (HDPE) with different filler loading (0-30 vol%) were prepared. Their viscoelastic properties were studied by dynamic strain sweep and small amplitude oscillatory shear and correlated to the particle-particle and particle-matrix interactions. The results gave insight into the mechanism of polymer reinforcement by solid inclusions and the factors that lead to the often observed solid-like response in the terminal zone. With increasing filler volume fraction, the particles tend to agglomerate and build clusters (local structures) that can be disintegrated by shearing. Up to 30 vol% no evidence for a space-filling particle network could be found. The presence of clusters increases the viscosity, the moduli and the viscoelastic non-linearity of the composites. Coating the filler surface by a stearic acid monolayer reduces its tendency to agglomerate as well as the adhesion between the particles and the polymer, leading to lower viscosity and interfacial slippage with increasing strain amplitude. Solid inclusions increase the storage modulus more than the loss modulus, hence decrease the material damping. The hydrodynamic reinforcement is frequency independent and dominates at high frequency. Polymer adsorption on the particles surface results in a transient filler-polymer network, which together with the topological restraints exerted by the inclusions on the polymer chain reptation leads to slow relaxation. These slow relaxation processes are sensitive to the oscillation frequency and strongly contribute to the polymer reinforcement at low frequencies. Agglomerates differ in shape and packing from the nearly spherical primary particles, and exert strong restraints on the polymer chain relaxation, hence offer an additional contribution to the composite's moduli. The sum of these effects results in higher moduli and a shift of the crossover (liquid-like to solid-like) frequency to lower values with increasing filler volume fraction. They also lead to the often-observed tendency towards a solid-like response in the terminal zone before a space-filling filler network is formed. Hydrodynamic and micromechanical models can only predict the hydrodynamic reinforcement, provided that the polymer strongly adheres to the inclusions.     

Conformational properties and Rouse dynamics of different dendrimer molecules

A coarse-grained model previously proposed to perform Monte Carlo simulations for several dendrimer molecules with different topologies and chemical compositions in solution is employed now to obtain structural properties, such as the bead density profile, the asphericity and the molecular scattering factor, or form factor. It is also used to study the Rouse dynamics, including Rouse spring forces consistent with the equilibrium averages of distances between connected frictional beads and hydrodynamic interactions (Rouse-Zimm scheme). With this approach, the Rouse relaxation times and the frequency-dependent viscoelastic modulus are calculated. Since hydrodynamic interactions are included in their preaveraged form, the effect of the preaveraging approximation is explicitly discussed. The influence of the different structural and topological dependence on the dendrimer static and dynamic properties is analysed and discussed.     

萃取分离体系分子间弱相互作用的研究进展

萃取反应和传质大多发生在溶液相界面,而萃取体系的新相生成和相分离行为取决于溶液相内分子微观聚集结构的变化。研究萃取分离过程溶液相内及相界面发生的各种分子间弱相互作用及其随萃取反应条件的变化、加和与协同效应,是国际上萃取分离化学化工的前沿热点,对于深入认识萃取分离过程微观机理、调控分离选择性具有重要意义。本文从萃取分离体系的界面分子间相互作用出发,总结评述了国内外近年来利用各种实验手段表征液液萃取分离体系分子间弱相互作用的一些代表性工作和最新研究进展。     

Aqueous suspension processing of multicomponent submicronic Y-TZP/Al2O3/SiC particles for suspension plasma spraying

In order to obtain thermal barrier coatings by Suspension Plasma Spraying (SPS) process with potential new self-healing ability multicomponent submicronic Y-TZP/Al₂O₃/SiC suspensions were prepared. For this purpose, concentrated aqueous suspensions of individual components, as well as the multicomponent mixture were studied and characterised, in terms of colloidal stability and rheological behaviour to determine the best conditions for processing and preparation of the coatings. In the study, different dispersant contents and sonication times were tested. Subsequently, low concentrated suspensions were prepared to obtain preliminary thermal barrier coatings with the optimised feedstock. Thus, ceramic coatings were deposited by SPS and then characterised in order to assess the microstructure and phase distribution, in particular, the degree of preservation of the sealing agent, SiC, in the final coating as a previous indicator of its self-healing ability.     

Colloidal gel from amphiphilic heteroarm polyelectrolyte stars in aqueous media

We report on the gelation capability of polystyrene/poly(2-vinyl pyridine) amphiphilic heteroarm polyelectrolyte stars in acidic salt-free aqueous media. The star polymers associate through hydrophobic interactions, by retraction of the stretched arms under no interdigitation conditions, in the dilute regime forming colloidal soft nanoparticles comprising about 6 stars, At concentrations significantly higher than the hydrodynamic overlap concentration (c > 40c^∗), the crowding of the colloidal nanoparticles drives a jamming transition, leading to a colloidal gel. The intermediate overlap regime (c^∗ < c < 40c^∗) is characterized by a significant compaction of the polyelectrolyte entities prior interdigitation and jamming.