Synchrotron SAXS/WAXD and rheological studies of clay suspensions in silicone fluid

Suspensions of two commercial smectite clays, montmorillonite KSF and montmorillonite K10, in a low-viscosity silicone oil (Dow Corning 245 Fluid) were studied by simultaneous synchrotron small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) techniques and rheological measurements. In the 0.5% (w/v) KSF clay suspension and two K10 clay suspensions (0.5% and 1.0%), WAXD profiles below 2theta=10.0 degrees did not display any characteristic reflection peaks associated with the chosen montmorillonite clays, while corresponding SAXS profiles exhibited distinct scattering maxima, indicating that both clays were delaminated by the silicone oil. In spite of the large increase in viscosity, the clay suspensions exhibited no gel characteristics. Dynamic rheological experiments indicated that the clay/silicone oil suspensions exhibited the behavior of viscoelasticity, which could be influenced by the type and the concentration of the clay. For the K10 clay suspensions, the frequency-dependent loss modulus (G") was greater in magnitude than the storage modulus (G') in the concentration range from 0.5 to 12.0%. The increase in the clay concentration shifted the crossover point between G' and G" into the accessible frequency range, indicating that the system became more elastic. In contrast, the KSF clay suspension exhibited lower G' and G" values, indicating a weaker viscoelastic response. The larger viscoelasticity response in the K10 clay suspension may be due to the acid treatment generating a higher concentration of silanol groups on the clay surface.     

Rheology and UV protection properties of suspensions of fine titanium dioxides in a silicone oil

Ultrafine particles of titanium dioxide (TiO2) are very attractive as a UV protection ingredient in cosmetic products. The UV-scattering behavior of TiO2 suspensions in a silicone oil are studied in relation to rheological properties. To control the dispersion stability of suspensions, two types of polyether-modified silicones are used as dispersants. When the suspensions are prepared with branch-type dispersants in which the polyether groups are incorporated as side chains along the backbone, the flow is shear-thinning even at low shear rates. The appearance of plateaus in the frequency-dependence curves of storage modulus implies the solidlike responses. On the other hand, the suspensions prepared with linear conformation dispersants, in which the silicone group and polyether group are alternately repeated in one long chain, are Newtonian at low shear rates. The suspensions are regarded as liquids, because the storage modulus decreases rapidly in the low-frequency region. The suspension rheology is strongly associated with flocculated structures that are primarily controlled by the interparticle attractions. The differences in rheological behavior can be explained by the differences in the adsorbed conformation of dispersant silicones. From optical measurements, it is confirmed that UV scattering increases with decreasing flocculation degree. Therefore, good agreement is established between rheological properties and UV protection ability.     

Effect of cationic polymethacrylates on the rheology and flocculation of microfibrillated cellulose

Using two cationic methacrylate polymers: poly([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide) (PDMQ) and poly[(stearyl methacrylate)-stat-([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide)] (PSMA13Q), we modified microfibrillated cellulose (MFC) water suspensions. The aim was to affect the flocculation and rheological behavior of the MFC suspension. PDMQ is a strongly cationic polymer while PSMA13Q, also a cationic polymer, contains hydrophobic segments. We studied the MFC/polymer suspension rheological properties with a rotational rheometer in oscillatory and flow measurements. To observe structural changes in suspensions at different shear rates, we measured flow curves with transparent outer geometry and photographed the sample with a digital camera. The oscillatory measurements showed that a small amount of the cationic PDMQ in the MFC suspension strengthened the gel, whereas a small amount of amphiphilic PSMA13Q weakened it. Increased amounts of either polymer increased the gel strength. PSMA13Q also changed the rheological character of the MFC suspension turning it more fluid-like. When we photographed the flow curve measurement, we saw a clear change in the floc structure. This floc structure rupture coincided with a transient region in the flow curve.     

Interparticle interactions in concentrated suspensions and their bulk (rheological) properties

The interparticle interactions in concentrated suspensions are described. Four main types of interactions can be distinguished: (i) "Hard-sphere" interactions whereby repulsive and attractive forces are screened. (ii) "Soft" or electrostatic interactions determined by double layer repulsion. (iii) Steric repulsion produced by interaction between adsorbed or grafted surfactant and polymer layers. (iv)and van der Waals attraction mainly due to London dispersion forces. Combination of these interaction energies results in three main energy-distance curves: (i) A DLVO type energy-distance curves produced by combination of double layer repulsion and van der Waals attraction. For a stable suspension the energy-distance curve shows a "barrier" (energy maximum) whose height must exceed 25kT (where k is the Boltzmann constant and T is the absolute temperature). (ii) An energy-distance curve characterized by a shallow attractive minimum at twice the adsorbed layer thickness 2δ and when the interparticle-distance h becomes smaller than 2δ the energy shows a sharp increase with further decrease of h and this is the origin of steric stabilization. (iii) an energy-distance curve characterized by a shallow attractive minimum, an energy maximum of the DLVO type and a sharp increase in energy with further decrease of h due to steric repulsion. This is referred to as electrosteric repulsion. The flocculation of electrostatically and sterically stabilized suspensions is briefly described. A section is devoted to charge neutralization by polyelectrolytes and bridging flocculation by polymers. A distinction could be made between "dilute", "concentrated" and "solid suspensions" in terms of the balance between the Brownian motion and interparticle interaction. The states of suspension on standing are described in terms of interaction forces and the effect of gravity. The bulk properties (rheology) of concentrated suspensions are described starting with the case of very dilute suspensions (the Einstein limit with volume fraction Φ≤0.01), moderately concentrated suspensions (0.2>Φ≥0.1) taking into account the hydrodynamic interaction and concentrated suspensions (Φ>0.2) where semi-empirical theories are available. The rheological behavior of the above four main types of interactions is described starting with "hard-sphere" systems where the relative viscosity-volume fraction relationship could be described. The rheology of electrostatically stabilized suspensions was described with particular reference to the effect of electrolyte that controls the double layer extension. The rheology of sterically stabilized systems is described using model polystyrene suspensions with grafter poly(ethylene oxide) layers. Finally the rheology of flocculated suspensions was described and a distinction could be made between weakly and strongly flocculated systems.     

Rheology of binary colloidal structures assembled via specific biological cross-linking

The selectivity and range of energies offered by specific biological interactions serve as valuable tools for engineering the assembly of colloidal particles into novel materials. In this investigation, high affinity biological interactions between biotin-coated "A" particles (RA = 0.475 microm) and streptavidin-coated "B" particles (RB = 2.75 microm) drive the self-assembly of a series of binary colloidal structures, from colloidal micelles (a large B particle coated by smaller A particles) to elongated chain microstructures (alternating A and B particles), as the relative number of small (A) to large (B) particles (2 < or = NA/NB < or = 200) is decreased at a low total volume fraction (10(-4) < or = phiT < or = 10(-3)). At a significantly higher total volume fraction (phiT > or = 10(-1)) and a low number ratio (NA/NB = 2), the rheological behavior of volume-filling particle networks connected by streptavidin-biotin bonds is characterized. The apparent viscosity (eta) as a function of the shear rate gamma, measured for networks at phiT = 0.1 and 0.2, exhibits shear-rate-dependent flow behavior, and both the apparent viscosity and the extent of shear thinning increase upon an increase of a factor of 2 in the total volume fraction. Micrographs taken before and after shearing show a structural breakdown of the flocculated binary particle network into smaller flocs, and ultimately a fluidlike suspension, with increasing shear rate. Rheological measurements provide further proof that suspension microstructure is governed by specific biomolecular interactions, as control experiments in which the streptavidin molecules on particles were blocked displayed Newtonian flow behavior. This investigation represents the first attempt at measuring the rheology of colloidal suspensions where assembly is driven by biomolecular cross-linking.     

Correlation of viscoelastic properties of stable and flocculated suspensions with their interparticle interactions

This review starts with a general introduction on the properties of concentrated suspensions. The distinction between “dilute”, “solid” and “concentrated” suspensions is given in terms of the balance between Brownian, hydrodynamic and interparticle interactions. A section is given on interparticle interactions and their combinations. The four different types of interactions, namely hard-sphere, electrostatic, steric and van der Waals are described. The flocculation of both electrostatically and sterically stabilized suspensions is also discussed. The next section covers the principles of rheological measurements. Transient (static), dynamic (oscillatory), shear wave propagation and steady state measurements are described. The last part of the review deals with the viscoelastic properties of concentrated suspensions. Four different systems were described and examples were given: (a) Suspensions with hard-sphere interactions; (b) Stable systems with soft (electrostatic) interaction; (c) Sterically stabilised systems; (d) Flocculated and coagulated systems. Both weakly and strongly flocculated systems were discussed.In the above review, particular emphasis was given to the relationship between the viscoelastic properties of concentrated suspensions and their interparticle interactions. As far as was possible, the results obtained from rheological measurements were quantitatively analysed in terms of such interparticle forces. The review demonstrated that such correlation is generally followed and this illustrated the powerful use of rheology for studying interparticle interactions.     

Flocculation of cellular suspensions by polyelectrolytes

The regularities, kinetics and mechanisms of flocculation of Escherichia coli and B. thuringiensis var. israelensis (Bti) cellular suspensions by water-soluble polymers-and first of all cationic polyelectrolytes of different charge density and stiffness of the macromolecule chain have been investigated. The effect of the focculant dose and nature, its charge density, the hydrophobic-hydrophilic balance in macromolecule, the suspension concentration, the mode of adding the reagent, the pH and the medium composition on the degree of aggregation of cells both in perikinetic regime and in a flowing system is considered. It has been shown that the main laws of microorganism's suspension flocculation are the same as the laws of flocculation of inorganic dispersions but at the same time the first process is much more complicated because the cell-flocculant interactions are strongly affected by products of cell metabolism, components of the culture liquor, pH value, electrolyte content as well as by the changing structure of the cell surface. On the basis of complex measurements of polymer adsorption and its effect on the electrokinetic potential and degree of aggregation of cells, a conclusion is made that the aggregation of E. coli cells by flexible polyelectrolytes like polydiethylaminoethylmetacrylate and its copolymers with acrylic acid, acrylamide and vinylpyrrolidone is due to charge neutralization, while the flocculation in the presence of rigid-chain chitosan and its derivatives is caused mainly by "bridging" between cells via adsorbed macromolecules. Extraction of cells from suspension can be enhanced by combination of electroflotation and flocculation by cationic polyelectrolytes. It has been shown that dilute suspensions of Bti bacteria can be effectively flocculated and concentrated using different cationic and anionic polyelectrolytes that is necessary for its formulation and use as anti-mosquito agent.     

Dynamics of shearing in flocculating fine sediment suspensions

The variability of rheological properties in cohesive sediment suspensions are studied and related to the flocculation process. It was found that the steady state shear stress increases exponentially with increasing sediment concentration and increases logarithmically by increasing the salinity of the suspension. The salinity dependence of the shear stress was correlated with changes in the floc-size. These results reflect the dominant influence of fluid-sediment interactions on the flocculation behavior of the suspension. An analytic model predicting shear stress as a function of the physical and electrochemical properties of the fine sediment suspension is developed.     

Dispersions of nanocrystalline cellulose in aqueous polymer solutions: structure formation of colloidal rods

The steady-state shear and linear viscoelastic deformations of semidilute suspensions of rod-shaped nanocrystalline cellulose (NCC) particles in 1.0% hydroxyethyl cellulose and carboxymethyl cellulose solutions were investigated. Addition of NCC at the onset of semidilute suspension concentration significantly altered the rheological and linear viscoelastic properties of semidilute polymer solutions. The low-shear viscosity values of polymers solutions were increased 20-490 times (depending on polymer molecular weight and functional groups) by the presence of NCC. NCC suspensions in polymer solutions exhibited yield stresses up to 7.12 Pa. Viscoelasticity measurements also showed that NCC suspended polymer solutions had higher linear elastic moduli than the loss moduli. All of those results revealed the gel formation of NCC particles and presence of internal structures. The formation of a weak gel structure was due to the nonadsorbing macromolecules which caused the depletion-induced interaction among NCC particles. A simple interaction energy model was used to show successfully the flocculation of NCC particles in the presence of nonadsorbing polymers. The model is based on the incorporation of the depletion interaction term between two parallel plates into the DLVO theory for cubic prismatic rod shaped NCC particles.     

Effect of electrolyte in silicone oil-in-water emulsions stabilised by fumed silica particles

Partially hydrophobised fumed silica particles are used to make silicone oil-in-water emulsions at natural pH of the aqueous phase. The stability and rheological properties of the emulsions and suspensions are studied at NaCl concentrations in the range 0-100 mM. It is found that all emulsions are very stable to coalescence irrespective of the NaCl concentration. However, a strong effect of electrolyte on the creaming and rheological properties is observed and linked to the particle interactions in aqueous suspensions. The creaming rate and extent are large at low electrolyte concentrations but both abruptly decrease at salt concentrations exceeding the critical flocculation concentration of the suspension (approximately 1 mM NaCl). The drastic improvement of the stability to creaming is attributed to the formation of a visco-elastic three-dimensional network of interconnected particles and emulsion droplets.     

Flocculation, deflocculation, and ions migration in latex suspensions

We have studied the dynamics of the flocculation of poly(styrene-butadiene-acrylic acid) latex suspensions. These suspensions were flocculated by the addition of Ca2+ ions at high concentrations of latex particles. Using diffusing wave spectroscopy and dynamic single light scattering after dilution, we have observed--depending on the pH and on the Ca2+ concentration--several scenarios for flocculation including successive flocculation and deflocculation. This complex behavior reveals that the Ca2+ migration within the shell of the latex is slow in acidic solvent but fast in basic solvent.     

Experimental investigation of nanoparticle dispersion by beads milling with centrifugal bead separation

A new type of beads mill for dispersing nanoparticles into liquids has been developed. The bead mill utilizes centrifugation to separate beads from nanoparticle suspensions and allows for the use of small sized beads (i.e. 15-30 microm in diameter). The performance of the beads mill in dispersing a suspension of titanium dioxide nanoparticle with 15 nm primary particles was evaluated experimentally. Dynamic light scattering was used to measure titania particle size distributions over time during the milling process, and bead sizes in the 15-100 microm range were used. It was found that larger beads (50-100 microm) were not capable of fully dispersing nanoparticles, and particles reagglomerated after long milling times. Smaller beads (15-30 microm) were capable of dispersing nanoparticles, and a sharp peak around 15 nm in the titania size distribution was visible when smaller beads were used. Because nanoparticle collisions with smaller beads have lower impact energy, it was found by X-ray diffraction and transmission electron microscopy that changes in nanoparticle crystallinity and morphology are minimized when smaller beads are used. Furthermore, inductively-coupled plasma spectroscopy was used to determine the level of bead contamination in the nanoparticle suspension during milling, and it was found that smaller beads are less likely to fragment and contaminate nanoparticle suspensions. The new type of beads mill is capable of effectively dispersing nanoparticle suspensions and will be extremely useful in future nanoparticle research.     

Specific screening method for dextran and hydroxyethyl starch in human urine by size exclusion chromatography–in-source collision-induced dissociation–time-of-flight mass spectrometry

The use of plasma volume expanders (PVE), such as dextran (DEX) and hydroxyethyl starch (HES), is prohibited in sports. DEX is a naturally occurring glucose polymer, whereas HES is synthetically produced from amylopectin starch by substitution with hydroxyethyl groups. In doping control, the commonly applied enzymatic and colorimetric screening methods are lacking adequate specificity for DEX and HES. Also, gas chromatographic–mass spectrometic (GC-MS) screening methods have specificity issues with DEX. In addition, due to the nature of the target compounds, time-consuming derivatisation steps are required in GC-MS. Based on the high molecular weight of carbohydrate polymers excreted in urine after administration of DEX and HES, a screening method was developed involving size exclusion chromatography (SEC) combined with time-of-flight mass spectrometry (TOFMS). By using solely a SEC guard column as an analytical column allowed sufficient chromatographic resolution in a minimal amount of time and with reasonable repeatability (average RSD of 10%). Detector response was linear throughout the measurement range with R ² > 0.99 for both analytes. Limits of detection were 100 and 250 μg mL⁻¹ for DEX and HES, respectively. Ion suppression was found to be 52% at maximum. In-source collision-induced dissociation (ISCID) was used to produce characteristic fragments at a mass accuracy better than 2 mDa. The specificity of the SEC–ISCID–TOFMS method was demonstrated with 120 PVE negative doping control samples analyzed in parallel with a routine GC-MS screening method. In addition, seven urine samples from diabetic athletes, causing interpretation problems in routine GC-MS, showed here a definitely negative profile.     

Rheological Characterization of Alumina Ceramic Suspensions in Presence of a Dispersant and a Binder

The rheological responses of aqueous alumina suspensions, stabilized with an organic polyvalent salt dispersant called “Aluminon,” and including a poly(vinyl) alcohol (PVA) binder, are described in this study. It is observed that the addition of PVA, without any dispersant does not significantly influence the rheology. However, in the presence of the dispersant the rheology is affected significantly. At a given concentration of the dispersant, the viscosity, the storage and loss modulii all increase with the PVA concentration. Also, for a given concentration of the PVA, the viscosity, the storage and loss modulii values increases as the concentration of the dispersant is increased. At relatively low PVA concentrations, an excess concentration of the dispersant, causes flocculation of the particles in the suspension by a reduction of the electrostatic (double layer) effect. On the contrary, at higher concentrations of the PVA the flocculation of the suspension occurs via a depletion mechanism.     

The effect of particle shape on the structure and rheological properties of carbon-based particle suspensions

The structure and rheological properties of carbon-based particle suspensions, i.e., carbon black(CB), multi-wall carbon nanotube(MWNT), graphene and hollow carbon sphere(HCS) suspended in polydimethylsiloxane(PDMS), are investigated. In order to study the effect of particle shape on the structure and rheological properties of suspensions, the content of surface oxygen-containing functional groups of carbon-based particles is controlled to be similar. Original spherical-like CB(fractal filler), rod-like MWNT and sheet-like graphene form large agglomerates in PDMS, while spherical HCS particles disperse relatively well in PDMS. The dispersion state of carbon-based particles affects the critical concentration of forming a rheological percolation network. Under weak shear, negative normal stress differences(ΔN) are observed in CB, MWNT and graphene suspensions, while ΔN is nearly zero for HCS suspensions. It is concluded that the vorticity alignment of CB, MWNT and graphene agglomerates under shear results in the negative ΔN. However, no obvious structural change is observed in HCS suspension under weak shear, and accordingly, the ΔN is almost zero.     

Effects of Surface Properties on Rheological and Interfacial Properties of Pickering Emulsions Prepared by Fumed Silica Suspensions Pre-Adsorbed Poly(N-Isopropylacrylamide)

The hydrophobic fumed silica suspensions physically pre-adsorbed poly(N-isopropylacrylamide) (PNIPAM) in water could prepare oil dispersed in water (O/W) Pickering emulsion by mixing of silicone oil. The resulting Pickering emulsions were characterized by the measurements of volume factions of emulsified silicone oil, adsorbed amounts of the silica suspensions, oil droplet size, and some rheological responses, such as stress-strain sweep curve and dynamic viscoelastic moduli as a function of the added amount of PNIPAM. Moreover, their characteristics were compared with those of the O/W Pickering emulsions prepared by the hydrophilic fumed silica suspensions pre-adsorbed PNIPAM. For the emulsions prepared by the hydrophobic silica suspensions, an increase in the added amount of PNIPAM led to (1) a decrease in the volume fraction of the emulsified oil in the emulsified phase, (2) both the size of oil droplets and the adsorbed amount of the corresponding silica suspensions being almost constant, except for the higher added amounts, and (3) both the storage modulus (G′) and the yield shear strain being constant. The term of 1 is the same for the emulsions prepared by the hydrophilic silica suspensions, whereas both the adsorbed amount of the corresponding silica suspension and the G′ value increase and both the droplet size and the yield shear strain decrease with an increase in the added amount of PNIPAM. The differences between the rheological properties of the emulsions prepared by the hydrophilic silica suspensions and those by the hydrophobic ones are attributed to the hydrophobic interactions of the flocculated silica particles in the Pickering emulsions.     

表面活性剂对氧化锰悬浮体系流变学振荡行为的影响

对介孔氧化锰的溶胶-凝胶法合成和用表面活性剂（脂肪醇聚氧乙烯醚, AEO_9)的模板合成过程中所得的悬浮体系的流变性质进行了对比研究。结果表明： 上述体系均具有触变性,且无论是否预剪切,其表观粘度均随时间作周期性振荡; 同时上述体系的储能模量G'和损耗模量G"亦具有周期性的振荡行为。但表面活性剂 AEO_9的引入使体系的触变性大为减弱,屈服值明显降低,凝胶结构强度减弱。同 时还发现引入AEO_9的模板合成过程中,不仅体系的表观粘度及G'大幅度下降,且 G'与G"的振荡周期显著增大,振幅亦明显减小。这说明体系中两亲分子与无机物存 在较强的相互作用,作者还对这些现象进行了讨论。     

Flocculation and reflocculation of clay suspension by different polymer systems under turbulent conditions

The focused beam reflectance measurement (FBRM), also known as scanning laser microscopy (SLM), was used as a real-time monitor to study the flocculation and reflocculation of clay suspensions under different shear conditions in the presence of single polymer, dual polymer, microparticle and poly(ethylene oxide)/phenolformaldehyde (PEO/PFR) flocculation systems. For initial flocculation, the high molecular weight PEO and cationic polyacrylamide (CPAM) produced larger flocs than others. However, reflocculation of clay suspensions formed by these non- or low-charged polymers was insignificant after the initial flocs were broken under high shear force. In contrast, high charge density polymers, such as poly(diallyldimethylammonium chloride) (PDADMAC), do not form large initial flocs, but they showed significant reflocculation ability under a continuous shear condition. It is concluded that high flocculation can be obtained by effective polymer bridging, but high reflocculation can only be induced by high electrostatic attractive forces between suspended particles.     

Scaling Behavior of the Rheological Properties of Montmorillonite Suspensions: Correlation between Interparticle Interaction and Degree of Flocculation

In this work we investigate some aspects of the rheological behavior of sodium montmorillonite (NaMt) suspensions in the pH range 3 to 9, of NaCl concentrations between 10(-3) and 10(-1) M, and of solid concentrations between 5 and 11% w/v. Three kinds of experiments were performed: steady-state viscometry, oscillatory test, and creep recovery. The physical quantities of interest were the yield stress sigma(y) of the suspensions, the elastic rigidity modulus G', and the instantaneous elastic compliance. Furthermore, G' was obtained from oscillatory tests in three different experiments: determination of the viscoelastic linear region, oscillograms, and the gelation process. All quantities were found to scale with the concentration of solids, C, according to a power law of the form Y=k(y)C(n). The exponents n were found to change from approximately 3 to approximately 6 when the pH was increased from 3 to 9 (at constant ionic strength 10(-2) M), although values as high as 10 were estimated when the NaCl concentration was reduced to 1 mM. Such values of n correlate well with the characteristics of the edge-to-face (E-F), edge-to-edge (E-E), and face-to-face (F-F) interparticle interactions. The minimum values of n correspond to maximum E-F attractions, whereas the largest n are associated with strong F-F repulsions. Copyright 2001 Academic Press.     

Synthesis and Characterization of the Mixed Mg/Al Hydrotalcite‐Like Compounds

A series of mixed MgAl‐HTlc, Mg_1?xAl_x‐NO₃‐HTlc (where X=M(III)/(M(III)+ M(II))=1/3 in the starting solution) were prepared following the coprecipitation method at a constant pH under different synthesis temperatures. Their structural, textual and rheological properties were examined respectively. It is found from the results that the increase of the synthesis temperature will increase the interlayer spacing of the layered compounds, but under the room temperature, the sample shows the best crystallinity. Nitrogen adsorption isotherms were used to determine the surface areas and pore structure of these compounds, and the effect of the synthesis temperature on the surface characteristics is discussed. It is thought that the microporosity was related to the treatment temperature, and most of the samples contain large amount of micropores about 1.5 nm. The results of the hydrated diameters showed that all the samples are polydispersity, but flocculation occurred in the samples, which were prepared under higher temperatures. The flow curve of the suspension showed that the samples, which were prepared under relatively low temperatures, behaved as Newton‐like behavior with a slight shear–thickening, whereas the flow curves of the other samples, which were prepared under higher temperatures, are shear‐thinning, typical behavior of the flocculated system. The result of the rheology is accordant with the results of the hydrated diameters, the coagulation suspension showed the non‐Newton flow behavior, whereas the other suspensions showed the Newton‐like flow.