Effect of solvent composition on dispersing ability of reaction sialon suspensions

This work focuses on the optimization of the rheological behavior of suspensions considering different solvent compositions. The effects of methyl ethyl ketone (MEK)/ethanol (E) solvent mixtures on reaction sialon suspensions were investigated by measuring sedimentation behavior, adsorption of dispersant, and flow behavior. It was shown that both the flow behavior and the sedimentation behavior strongly depended on selection of solvent composition. Using 3 wt% KD1 as dispersant, well-dispersed colloidal suspensions could be obtained in MEK-rich solvents. The suspensions with 60 vol% MEK/40 vol% E as solvent could be fitted to the Bingham model with very low yield stress, while suspensions with pure MEK or ethanol-rich mixtures as solvent showed pseudo plastic behavior with relatively high yield stress values. A model was proposed to explain the different flow behaviors of suspensions considering the different configurations of dispersant at particles' surfaces.     

Dispersion of Zirconia in the Presence of Dolapix PC75

The effect of Dolapix PC75 on the electrokinetic and rheological behavior of nano zirconia particles is presented here. The effect of pH, concentration of dispersant, and solids loading on zeta-potential and rheological behavior was studied. Upon interaction with the dispersant, the iso-electric point of zirconia changed and the surface became more negative with increasing concentration of dispersant, suggesting a strong interaction. Maximum charge was obtained in the presence of about 200 ppm of Dolapix. Rheological tests at pH 7 showed that the zirconia suspension is viscous at high solids loading and addition of the dispersant decreased the viscosity substantially especially at high solids loading (>50 wt%). Sedimentation tests confirmed that Dolapix PC75 is a good dispersant for zirconia particles at pH values of 7 and above.     

Rheological behavior of organic suspensions of fluorapatite

A fluorapatite suspension prepared in the azeotrope methyl ethyl ketone-ethyl alcohol (MEK:EtOH) in the presence of the phosphoric ester was investigated. Electrical conductivity, adsorption isotherms, and sedimentation technique showed that the amount of phosphoric ester adsorbed on the fluorapatite surface was equal to, or higher than, 1 wt%. This dispersant concentration led to a good particle packing. The rheological properties of fluorapatite suspensions were studied as a function of phosphoric ester concentration. The data obtained from the viscosity measurements and those previously collected correlated well. In the case of suspensions prepared with 60 wt% in fluorapatite, the dispersion was optimal for a phosphoric ester content of about 1.3 wt%.     

Thermally changing lattice distance of lamella in the hydrated solid of octadecyltrimethylammonium chloride

A temperature scanning small-angle X-ray scattering measurement was carried out for the hydrated solids of octadecyltrimethylammonium chloride (OTAC). A gradual change of the lattice spacing of lamella-like structure from 40 nm at 5 degrees C to 20 nm at 18 degrees C was observed in the melting process of the hydrated solid that was incubated at 4 degrees C for a period of 24 h in the aqueous solution, while little change of the lattice spacing of about 20 nm was observed in the same process of the hydrated solid that was incubated at 4 degrees C for a period about 10 min. This indicates structural changes of the hydrated solid during the incubation at 4 degrees C and in the melting process. Corresponding to the nanostructure changes, broad endothermic peaks were observed at temperatures from 13 to 22 degrees C for the former hydrated solid and at temperatures from 15 to 21 degrees C for the latter hydrated solid in difference scanning calorimetry measurements. The structure change at temperatures below 13 degrees C is considered to be athermal from the fact that no endothermic peak is observed there. Large dielectric dispersions at frequencies at about 10 kHz were observed for the suspensions of hydrated solids but not for the solutions of dissolved solids. It was found that the electric conductance of the hydrated solid suspensions was much lower than that of the solutions of dissolved solids. The observed electric properties indicate that an amount of the free chloride ion is very small and that the chloride ions binding to the ammonium groups are movable in the hydrated solids by responding to an applied electric field. The electric conductance of suspension of the hydrated solid being incubated at 4 degrees C for 10 min was 4 times as large as that of a suspension of the hydrated solid being incubated at the same temperature for 24 h. This indicates that the structural change of the OTAC hydrated solid at 4 degrees C is related to the chloride ion binding to the hydrated solid. The experimental results described above suggest that the lamella in the hydrated solid of OTAC is undulated and that the wavelength of undulation increases with the incubation at a temperature much lower than the melting temperature.     

Mechanisms of micellization and rheology of PEO-PPO-PEO triblock copolymers with various architectures

Micelle formation was followed by micro-DSC and rheology for aqueous solutions of two copolymers of PEO-PPO-PEO, the Pluronic F127 (from BASF) and the EG56 (from PolymerExpert), a branched copolymer built with three chains of F127 type. It is shown that micellization is endothermic and that, for both polymers, the enthalpy of formation/melting is proportional to total concentration. The rheology of the solutions was carefully analyzed, before gelation for F127, and it reveals firstly the progressive changes of solubility of the unimers (decease of relative solution viscosity), followed by micelle formation over a 10 degrees C range. In this range, the micelle concentration dependence on temperature was deduced from enthalpy measurements and the corresponding volume fractions were derived. Viscosity was interpreted within the framework of well-known theories for hard sphere suspensions (Krieger-Dougherty or Quemada) based on an analogy between micelles and nanosized hairy grain suspensions. The gel state is achieved due to formation of the colloidal crystal. For EG56, the rheology is quite different; as the aggregation increases with temperature, a progression is observed from Newtonian to visco-elastic liquid. The characteristic frequency, defined by the relation G(') = G('), for EG56 varies with temperature and the corresponding times increase by two orders of magnitude according to an Arrhenius law. The frequency dependence of G(') and G(') at different temperatures can be superposed with a horizontal shift factor and a small amplitude adjustment. There is no elastic solid formation in this case. The "gelation" of these two copolymers is compared to the physical gelation of cold-set gels (gelatin).     

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.     

WO3/CeO2-ZrO2, a promising catalyst for selective catalytic reduction (SCR) of NOx with NH3 in diesel exhaust

A WO3/CeO2-ZrO2 catalyst system was discovered for selective catalytic reduction of NOx with NH3; the catalyst (10 wt% WO3 loading) showed nearly 100% NOx conversion in a temperature range of 200-500 degrees C, at a space velocity of 90 000 h(-1) in a simulated diesel exhaust containing 550 ppm NOx (NO : NO2 feed ratio at 1.0), 10 vol% H2O and 10 vol% CO2; the catalyst also exhibited high temperature stability.     

Interaction of binders with dispersant stabilised alumina suspensions

The rheological response of selected aqueous alumina suspensions, stabilised with a polyelectrolyte or with an organic polyvalent salt dispersant, and including poly(vinyl) alcohol (PVA) as a binder, are described in this study. The polymer dispersant was composed of an ammonium salt of poly(methacrylate) and the organic polyvalent compound was a sodium salt of an aromatic sulphate. The results show that the addition of PVA, without any included dispersant does not significantly influence the rheology of the system. However, in the presence of a dispersant the rheology is greatly affected. At a given concentration of the dispersant, the viscosity, storage and loss moduli all increase, as the PVA concentration is increased. Also, for a given concentration of the PVA, it is observed that the viscosity, storage and loss moduli values increase as the concentration of the dispersant is increased. It is argued that at low PVA concentrations, an excess concentration of the unadsorbed dispersant causes flocculation of the particles in the suspension by a reduction of the repulsive electrostatic (double layer) effect. In contrast, at higher concentrations of the PVA the flocculation of the suspension is promoted via a depletion mechanism.     

Characterization of concentrated colloidal ceramics suspension: a new approach

The dispersion behavior of a concentrated ceramic suspension (Al(2)O(3)) has been investigated in terms of capillary suction time (CST) with varying solids concentration both in the absence as well as in the presence of dispersant (APC). The CST value is found to be the lowest at the pH(iep) whereas it increases as the pH is changed either to the acid side or alkaline side due to the repulsive forces acting among the neighboring particles keeping them in more dispersed state. It has been further observed that the CST value increases with increasing concentration of solids in the suspension. The dispersability of the suspension has been quantified in terms of dispersion ratio (DR). The higher the dispersion ratio of a particular system above unity, the better is the dispersability and vice versa. Further, quantification of dispersion stability by the CST technique is found to be useful and practical for optimization of different parameters concerning suspension stability. A correlation is found among the CST, zeta potential, colloidal stability, and maximum solids loading. It has been finally concluded that the CST method could be potentially employed as a quantitative and diagnostic technique for characterizing concentrated ceramic suspension.     

Fabrication of Fe3O4/SiO2 core/shell nanoparticles attached to graphene oxide and its use as an adsorbent

Thermoresponsive gelling behavior of concentrated alumina suspensions with poly(acrylic acid) (PAA) and triblock copolymer (PEO(101)-PPO(56)-PEO(101), Pluronic F127) was investigated as a function of PAA concentration (0.4-1.2 mass%) for ceramic solid free forming. The copolymer species assemble into micelles at temperatures above 15°C, yielding aqueous physical gel. In this study, the concentrated alumina aqueous suspensions (φ=35 vol%) were first prepared using the anionic dispersant of PAA, and then the copolymer species (10 mass%) were dissolved at a cooled temperature at 10°C. The addition of the copolymer species had a negligible influence on the adsorption state of PAA onto the alumina surfaces. The PAA concentration needed for the saturation adsorption on the alumina surfaces was ~0.6 mass%. When the PAA concentration was this value or slightly less, the suspension became gel state at 30°C from low viscous state at 10°C. The thermally induced alumina gel had excellent viscoelastic properties, and thereby the three dimensional periodic ceramic structures were successfully fabricated by a direct colloidal printing method that using the gels as "solid" inks at the room temperature. On the other hand, when it exceeded the saturation adsorption limit, the gelling behavior was not observed, indicating that the non-adsorbing PAA species may partly suppress the micellization of the copolymer on the heating.     

Diffusing-Wave Spectroscopy of Concentrated Alumina Suspensions during Gelation

Using diffusing-wave spectroscopy, we followed the aggregation and gelation of concentrated (30 vol%) alumina suspensions. The suspensions were destabilized by either shifting the pH to the isoelectric point or by increasing the ionic strength. Both effects can be achieved continuously and homogeneously by using an enzyme-catalyzed internal chemical reaction. Based on the light-scattering data, we could derive quantitative information about the sol-gel transition and the viscoelastic properties of the gels, as well as a characterization of changes in the microstructure. The elastic moduli determined from light scattering are found to be in good agreement with rheological measurements. Copyright 2001 Academic Press.     

Optimization of LiFePO4 nanoparticle suspensions with polyethyleneimine for aqueous processing

Addition of dispersants to aqueous based lithium-ion battery electrode formulations containing LiFePO(4) is critical to obtaining a stable suspension. The resulting colloidal suspensions enable dramatically improved coating deposition when processing electrodes. This research examines the colloidal chemistry modifications based on polyethyleneimine (PEI) addition and dispersion characterization required to produce high quality electrode formulations and coatings for LiFePO(4) active cathode material. The isoelectric point, a key parameter in characterizing colloidal dispersion stability, of LiFePO(4) and super P C45 were determined to be pH = 4.3 and 3.4, respectively. PEI, a cationic surfactant, was found to be an effective dispersant. It is demonstrated that 1.0 wt % and 0.5 wt % PEI were required to stabilize the LiFePO(4) and super P C45 suspension, respectively. LiFePO(4) cathode suspensions with 1.5 wt % PEI demonstrated the best dispersibility of all components, as evidenced by viscosity and agglomerate size of the suspensions and elemental distribution within dry cathodes. The addition of PEI significantly improved the LiFePO(4) performance.     

Rheology and UV-protecting properties of complex suspensions of titanium dioxides and zinc oxides

Ultra-fine particles of titanium dioxide (TiO(2)) and zinc oxides (ZnO) are very attractive as UV-protecting ingredients in cosmetic products. The UV-scattering behavior of complex suspensions in a silicone oil is studied in relation to rheological properties. To control the dispersion stability of suspensions, three polyoxyethylene (POE)-modified silicones of branch-type, (AB)(n)-type, and ABA-type are used as dispersants. Irrespective of molecular structure, the dispersants can stabilize the TiO(2) and ZnO particles and the flow of both single suspensions is Newtonian with low viscosity. However, the Newtonian flow profiles and high dispersion states are maintained only for complex suspensions prepared with ABA-type dispersant. Since the POE groups which are incorporated between terminal silicones groups attach to the particle surfaces, the steric stabilization is responsible for low viscosity and high dispersions. Because the UV scattering of suspensions is determined by the sizes of flocculated structures, the high transmittance in the visible ranges and low transmittance in the UVA and UVB ranges can be achieved in the presence of ABA-type dispersant.     

Electrical conductivity and stability of concentrated aqueous alumina suspensions

This work describes the effect of solids load and ionic strength on the electrical conductivity (K(S)) of concentrated aqueous suspensions of commercial alpha-alumina (1-35 vol% solids). The results obtained show that the dependency of the electrical conductivity of the suspending liquid (K(L)) on the volume fraction of solids is well described by Maxwell's model. The change in the conductivity of the suspensions relative to that of the suspending liquid (K(S)/K(L)) was found to be inversely proportional to the solids content, as predicted by Maxwell's model. The relative conductivity rate, DeltaK, could be interpreted in terms of the DLVO theory and the particles double layer parameter, kappaa, and used as a stability criterion. As kappaa changes, in response to the changes in ionic strength, so does the conducting to insulating character of the particles and, as such, their contribution to the overall suspension conductivity (expressed by DeltaK). When the particles become insulating, the suspension conductivity decreases when the solids load increases. The turning point in this particle behaviour corresponds to a critical concentration of ions in the solution that destabilises the suspension and is associated with the critical coagulation concentration (ccc). It is the electrical double layer that ultimately determines the conducting or insulating character of the particles, and that character can be made to change, as required for suspension stability, and accessed by the relative conductivity rate.     

On the viscosity of composite suspensions of aluminum and ammonium perchlorate particles dispersed in hydroxyl terminated polybutadiene--New empirical model

The rheological properties of fuel suspensions with various solid loadings up to close their maximum packing fraction and suspending media having different viscosities are investigated using the rotational viscometer at relatively low shear rates in which suspensions behave as Newtonian fluids. Aluminum (Al) and ammonium perchlorate (AP) particles are major solid components of any solid fuel system which should be distributed uniformly inside a polymeric binder based on hydroxyl terminated polybutadiene (HTPB). The experimental data generated in this investigation indicates that the relative viscosity of the suspensions is independent of viscosity of polymer binder, but in addition to solid content, geometrical aspects of the solid particles affect strongly the relative viscosity of suspensions. Maximum packing fraction of filler is found to be suitable quantitative measure of filler characteristics such as size, size distribution, shape and structure. Consequently, it is revealed that the relative viscosity of fuel suspension is a unique function of reduced volume fraction (Phi). Based on analogy of viscosity enhancement of reactive resin with cure conversion and suspension with filler content, an empirical model with two adjustable parameters originated from resin gelation model is suggested. According to this model and experimental results obtained in this investigation, a generalized model is proposed to describe the relative viscosity as a function of solid content in which the adjustable parameters are found to be general constants. The generalized model which is expressed as mu(r) = (1-Phi)(0.3 Phi-2) is found to be quite accurate to predict the experimental data. Furthermore, the applicability and accuracy of the generalized model are evaluated using the viscosity data of some suspension systems reported in the literature.     

Effect of surface interaction of silica nanoparticles modified by silane coupling agents on viscosity of methylethylketone suspension

In order to control the viscosity of a dense silica methylethylketone (MEK) suspension, the surfaces of silica nanoparticles were modified by 3-glycidoxypropyltrimethoxysilane (GPS) or hexyltrimethoxysilane (C6S) in MEK with the addition of a small amount of pH-controlled water. First, the effect of water addition on the amount of chemisorbed coupling agent was investigated. pH-controlled water enhanced the reactivity of the coupling agent in MEK. The amount of chemisorbed coupling agent increased slightly with the addition of pH 3 water and increased remarkably with the addition of pH 12 water. Next, the effect of the organic functional groups of the coupling agent, pH of the additive water, and additive amount of coupling agent on surface interaction were determined by colloid probe AFM. The steric repulsive force between the silica nanoparticles increased due to water addition, particularly when the pH was maintained at 3. The viscosity of the silica MEK suspension reduced effectively when this repulsive force appeared; however, the optimum condition for reducing the suspension viscosity was dependent on the coupling agent species. The viscosity of the dense silica MEK suspension can be controlled by the addition of small amounts of pH-controlled water and the functional groups of the coupling agent.     

Polymer depletion-induced instability of silica suspensions in the presence of flexible and semiflexible polymers

Polymer depletion-induced instability of silica suspensions in dilute toluene solutions of flexible polystyrene (PS) or semiflexible poly(hexyl isocyanate) (PHIC) was investigated by direct observation and oscillatory moduli measurements as functions of silica volume fraction and polymer molecular weight. Addition of the respective polymers to the gelled silica suspensions induces a gel settling. Below the silica volume fraction phi=4 vol%, PS chains compress the volume of the sediment silica phase, whereas PHIC chains expand it and play a role in swelling agents. Thus, PHIC chains lead to the formation of aggregates in the silica suspensions that are larger and less compact than those formed by the PS chains. On the other hand, above phi=4 vol% where the silica suspension occurs gelation, the effect of nonadsorbing polymers on changes in the volume of the silica phase is opposite. Moreover, polymer depletion interaction results in a mechanically stronger gelled phase, leading to the storage modulus G' values larger than those without polymer, but the effects of polymer concentration and polymer molecular weight on the G' values are not clear.     

Stability of dispersions of colloidal alumina particles in aqueous suspensions

The colloidal stability of suspensions of alumina particles has been investigated by measuring particle size distribution, sedimentation, viscosity, and zeta potential. Alumina particles were found to be optimally dispersed at pH around 3 to 7.8 without dispersant and at pH 8.5 and beyond with dispersant. The above results corroborate zeta potential and viscosity measurement data well. The surface charge of alumina powder changed significantly with anionic polyelectrolyte (ammonium polycarboxylate, APC) and the iep shifted toward more acidic range under different dispersant conditions. It was found that the essential role played by pH and dispersant (APC) on the charge generation and shift in the isoelectric point of alumina manifests two features: (i) the stability decreases on approaching the isoelectric point from either side of pH, and (ii) the maximum instability was found at pH 9.1 for alumina only and at pH 6.8 for alumina/APC, which is close to the isoelectric points for both the system, respectively. Using the model based on the electrical double-layer theory of surfactant adsorption through shift in isoelectric points, the authors could estimate the specific free energy of interaction (7.501 kcal/mol) between particles and dispersant. The interaction energy, zeta potential, sedimentation, and viscosity results, were used to explain the colloidal stability of the suspension.     

Cooling effects on a model rennet casein gel system: part I. Rheological characterization

The gelation of a model rennet casein system was studied during cooling at different rates. During cooling, casein network structure development was proposed to evolve over a few steps at different length scales: molecules, particles, flocs, or network. Rennet casein flocs are fractal in nature, and fractal dimension and floc size are two variables affecting the rheology and microstructure of a rennet casein gel. Casein structure formation during cooling from 80 to 5 degrees C at four different rates (0.5, 0.1, 0.05, and 0.025 degrees C/min) was monitored by dynamic rheological tests, and a stronger gel developed at a slower cooling rate. During different cooling schedules, similar fractal dimensions were observed due to a lack of difference in the colloidal interactions. Differences among rheological data were possibly caused by variability in floc size, as observed in the second part of this paper. A larger number of smaller-sized flocs enabled gelation at a higher temperature and created a stronger network at a slower cooling rate. Controlling cooling schemes thus provides an approach for manipulating casein gelation and the microstructure for a system of fixed chemical compositions.     

Effect of Dispersant on the Colloidal Stability of Nano‐sized CuO Suspension

The stabilization of nano‐sized CuO suspensions was examined to look for the primary mechanism of dispersion. The dispersion stability of suspension was characterized by sedimentation tests, Zeta potential, granularity tests, and infrared spectroscopy (IR). Influence factors such as pH and the concentration of the dispersant on the colloidal stability of the suspension were investigated. The results showed that sodium polyacrylate was fit to stabilize the suspension of CuO nanoparticles through electrosteric repulsion. Also, smaller viscosity and better dispersion effects were achieved when sodium polyacrylate mass fraction was 0.4%～0.8% (based on the powder), pH was 10.