Synthesis and Some Colloidal Properties of Hydrosols Prepared by the Hydrolysis of Copper(II) Nitrate

The synthesis of hydrosols of copper(II) basic salts by the hydrolysis of copper(II) nitrate in the presence of ammonia was developed. A pH range and an optimal molar ratio [Cu²⁺] : [OH^–] = 1.1 : 1.0, at which hydrosols stable with respect to sedimentation were formed, were determined. The average hydrodynamic radius of dispersed phase particles ranging from 220 to 280 nm was measured by the photon correlation spectroscopy. It was shown that the hydrosols can be stabilized by poly(vinyl alcohol), and its optimal concentration providing their aggregation stability was determined. The thresholds of fast coagulation of the initial and stabilized hydrosols in the presence of potassium chloride and ammonium sulfate were found.     

The dispersion of hydrophilic and hydrophobic flame-hydrolysed silicas in short-chained alkanols

The ultrasonic dispersion of Aerosil 200 and some n-alkyl surface-modified derivatives thereof in alkanols have been examined. The sizes of the aggregates formed during this process were investigated from measurements of sol viscosity and quasi-elastic light scattering (QELS). In the former technique, the aggregate volume ratios (AVR) were calculated at very low volume fractions of silica. The AVR values so obtained indicated that the silica monomers were highly aggregated in all systems, as expected. Differences between the various alkanols were found, however. Decreasing continuum polarity from water to hexan-1-ol produced decreasing AVRs. From hexan-1-ol to octan-1-ol, however, the AVRs increased. The n-alkyl surface-modified silicas gave AVRs substantially different to A 200, related most likely to wetting and solvation of the solid surface during dispersion. QELS measurements were subsequently found to be of limited use for these systems, since the aggregate size distributions in these sols were evidently very broad. The results indicated that these size distribution were non-Gaussian. The use of QELS to investigate systems of such high aggregation appears to be limited.     

Structure and flow behavior of crosslinked ethyl acrylate–methacrylic acid copolymer dispersion particles

 Changes in viscosity, pH and static light scattering behavior on alkali addition of model dispersions of statistical copolymers of ethyl acrylate with 15 and 50 wt% of methacrylic acid prepared by semicontinuous emuslion copolymerization and crosslinked with various amount of N,N′-methylenebisacrylamide were investigated. It was found that about 1% of crosslinking agent was sufficient to prevent unpredictable disintegration of dispersion particles and gauranteed reproducible flow behavior of alkalinized dispersions. The viscosity of alkalinized dispersions of crosslinked particles at low concentration is controlled by the effective hydrodynamic volume of swelled particles which decreases with the crosslinking degree of copolymer. On the other hand, at higher particle concentration close to critical concentration at which the space is filled up by swelled particles the influence of particle interaction prevails and due to lower deformability of crosslinked particles viscosity increases with a crosslinking degree. In comparison with similar dispersions prepared without a crosslinking agent these results indicated much uniform structure of dispersion particles and suppression of influence of random crosslinking due to chain transfer reactions. The study shows that dispersions of crosslinked copolymers of this type could be considered as thickners of latex binders with stable and reproducible thickening properties. Received: 23 February 1998 Accepted: 11 June 1998     

Dispersion of Nanoparticle Clusters by Ball Milling

The full and complete dispersion of nanoparticles is critical to enabling industry to formulate products which exploit the properties of such materials and hence realize the full economic value of such products.

Ball milling is conventionally used for the comminution of particle slurries and, of the various wet milling techniques, is the most effective in producing fine particle sizes. Here we consider the use of a ball mill (also referred to as a stirred media mill) for the dispersion of a slurry of nanoparticle aggregates and compare its performance to a typical rotor‐stator device commonly used by industry. The slurry is an aqueous dispersion of Aerosil 200 V that has a primary particle size of about 12 nm and comes as a dry powder. On dispersion in water it forms large aggregates which are difficult to fully disperse. Aerosil is readily available in quantity and is used in a number of industrially relevant applications and so is an ideal test material for such trials.

A lab scale Fryma Co‐Ball mill (0.5 L volume) is used and the effects of bead fill (40–70%), flow rate (0.1–1 kg/min) and rotor speed (7.5–18 m/s) are investigated. Specific energy is the most effective ways to correlate performance to particle size suggesting that residence time (i.e., flow rate) is the most important process parameter. Lower rotor speeds are also shown to be more energy efficient. The correlations show that the ball mill provides a significant improvement in dispersion (d[3,2]=0.61 µm) over the conventional rotor–stator device.     

Effect of adsorbed polymers on the slow motion of an assemblage of spherical particles relative to a fluid

 The effects of adsorbed polymers on the sedimentation of a homogeneous distribution of colloidal spheres and on the fluid flow through a bed of particles are investigated theoretically. The Reynolds number is assumed to be small, and the surface polymer layers are assumed to be thin with respect to the radius of particles and to the surface-to-surface spacing between neighboring particles. The effects of interaction of the individual particles are taken into explicit account by employing a fundamental cell-model representation which is known to provide good predictions for the motion of a swarm of spheres within a fluid in the absence of adsorbed polymers. To solve the Stokes flow equations within and outside the polymer layer a method of matched asymptotic expansions in a small parameter λ is used, where λ is the ratio of the length scale of the polymer layer to the particle radius. The results for the sedimentation rate and the pressure drop are expressed in terms of an effective hydrodynamic thickness (L) of the polymer layer, which are accurate to O(λ²). When the concentration of particles in a suspension or a bed is increased, L becomes larger, meaning the settling velocity decreases or the pressure drop increases. The O(λ) term for L normalized by its value in the limit λ→0 is found to be independent of the polymer segment distribution, the hydrodynamic inter-actions among the segments, and the volume fraction of the segments. The O(λ²) term for L, however, is a sensitive function of the polymer segment distribution and the volume fraction of the segments. In general, the particle-interaction effects on the motion of polymer-coated particles relative to a fluid can be quite significant. Received: 28 August 1996 Accepted: 23 January 1997     

Stability and Flow-Induced Flocculation of Fumed Silica Suspensions in Mixture of Water-Glycerol

A systematic investigation has been performed to relate the effect of glycerol composition to the rheological properties of aqueous suspensions of hydrophilic fumed silica at pH far from the isoelectric point. Steady state/dynamic rheology and electrophoresis measurements are compared to correlate the stability of the suspension with particle-particle and particle-solvent interactions. Although the extent of electrostatic stability is reduced by addition of glycerol, the rheological properties show a transition from a highly flocculated gel to stable dispersions containing no microstructures. This is attributed to a high degree of hydrogen-bonding between glycerol and the Aerosil surface silanol groups. Small dissociation of NaCl and particles reduce the effect of ion exchange and particle bridging mechanisms when the suspensions destabilise in the presence of glycerol. The high viscosity of glycerol is important with respect to the formation of a thick solvation layer around the particles. These parameters give rise to short-range, non-DLVO repulsive solvation forces, which stabilise the dispersion. At intermediate concentrations of glycerol (30–60 wt%) the apparent viscosity increase abruptly and irreversibly as both the extent and time of shearing are increased. The shear rate for the onset of the shear thickening is found to be retarded by decreasing the particle and salt concentration as well as by increasing the glycerol concentration. It is postulated that at intermediate glycerol concentration, where the height of the energy barrier is small, mechanical forces can activate the particles to overcome the energy barrier to enter the region where attractive forces dominate. Here, domination of the hydrodynamic forces to the colloidal forces under the shear results in formation of irreversible gels which does not relax to its initial condition.     

Hydrodynamic force on a microparticle approaching a wall in a nanoparticle dispersion: observation of a separation-dependent effective viscosity

Colloid probe atomic force microscopy was used to measure the hydrodynamic force exerted on a 30-μm-diameter silica particle being moved toward or away from a silica plate in aqueous dispersions of 22-nm-diameter silica nanoparticles (6 or 8 vol %). Upon comparing the measured force to predictions made using the well-known expression of Cox and Brenner (Cox, R. G.; Brenner, H. Chem. Eng. Sci.1967, 22, 1753-1777) assuming a constant viscosity equal to that of the bulk dispersion, the measured drag force was found to become significantly less than that predicted at smaller particle-plate separation distances (e.g., <500 nm). A recent theoretical paper by Bhattacharya and Blawzdziewicz (Bhattacharya, S.; Blawzdziewicz, J. J. Chem. Phys.2008, 128, 214704) predicted that in a solution of dispersed nanoparticles the effective viscosity characterizing the hydrodynamic force on the particle should vary from that of the solvent at contact to that of the bulk dispersion at large separations. By adjusting the viscosity in the Cox and Brenner expression to make the predicted hydrodynamic force match that measured (i.e., the effective viscosity), a curve showing these exact characteristics was obtained. The effective viscosity profile was not a function of particle speed, and changes in the effective viscosity extended to separation distances of as large as 2 μm (nearly 100 times the hard diameter of the nanoparticles). These results suggest that in the range of typical colloidal forces (on the order of 100 nm), the dynamics of particle motion in such systems are determined by the viscosity of the solvent and not that of the bulk dispersion.     

Taylor dispersion in systems of sedimenting nonspherical Brownian particles : II. Homogeneous ellipsoidal particles

An Aris-type moment scheme is applied to calculate the Taylor-Aris dispersion tensor for the sedimentation of small homogeneous ellipsoidal (and other orthotropic) particles settling under the influence of gravity in a quiescent viscous fluid and undergoing rotational and translational Brownian motions. This generalizes to triaxial particles a prior dispersion result for centrally symmetric bodies of revolution, such as spheroids. An independent Langevin-type dispersivity calculation is shown to yield results identical to those obtained by the moment scheme. The components and of the transversely isotropic dispersion dyadic, parallel and perpendicular, respectively, to the direction of the gravitational field, are shown to be given by the Taylor—Aris-type formulasHere, is the mean settling velocity of the particle, and and

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and (d₁,d₂,d₃) respectively the appropriate diffusivity components along the principal axes of the particle. The dimensionless coefficient γ, which is of order unity, is given by the formulaThis anisometric parameter vanishes identically for spherical particles and other hydrodynamically isotropic particles (e.g., cubes, tetrahedra, octahedra, etc.) whose translational and rotational hydrodynamic resistances are independent of the orientation of the particle relative to the directions of its linear and angular velocity vectors. Upon utilizing the translational and rotational Stokes-Einstein equations, explicit numerical values of and are furnished for ellipsoids of revolution of various aspect ratios and sizes when settling in water. Physical restrictions pertaining to sedimentation-vessel apparatus size and the requirement of reasonable sedimentation times greatly restrict the range of particle sizes whose anisometric properties may be experimentally investigated by this new particle-shape characterization technique.     

Settling of a charged hydrophobic rigid colloid in aqueous media under generalized gravitational field

The hindrance created by the induced electric filed on the sedimentation of a charged colloid in an aqueous media is studied through numerical modeling. The colloid is considered to be hydrophobic, sedimenting under gravity or a centrifugal force (generalized gravity). The deformation of the charge cloud around the colloid induces an electric field, which generates electrical dipole force on the colloid. The sedimentation velocity is governed by the balance of an electric force, hydrodynamic drag, and gravitational force. Governing equations based on the first principle of electrokinetics is solved numerically through a control volume approach. The dependence of the sedimentation velocity on the electrical properties and slip length of the colloid is investigated. The sedimentation velocity of the charged colloid is slower than the corresponding uncharged particle and this deviation magnifies as the charge density as well as particle slip length is increased. An enhanced g-factor creates a size dependency of the charged colloids. The induced sedimentation field is obtained to analyze the electrokinetics. Surface hydrophobicity enhances the sedimentation velocity, which in turn manifests the induced sedimentation field. However, the sedimentation velocity of a charged hydrophobic colloid is lower than the corresponding uncharged hydrophobic particle and this deviation manifests as slip length is increased.     

Particle Size Distribution Measurement and Assessment of Agglomeration of Commercial Nanosized Ceramic Particles

ABSTRACT

Commercially available powders with primary particle sizes of 10–100?nm (transition aluminas, Boehmites, and a commercially available silica dispersion) have been studied using three different instruments, a photocentrifuge (Horiba CAPA 700), photon correlation spectroscopy (PCS, Malvern Zetasizer 4), and an x-ray disc centrifuge (XDC, Brookhaven X-ray Disc Centrifuge BI-XDC). Particle size distributions for five powders were collected with each instrument and in conjunction with nitrogen adsorption measurements an agglomeration factor calculated. An example is given to show the importance of using a light scattering correction when measuring particle size distributions with a photocentrifuge for a gamma alumina powder where the uncorrected data can overestimate the D _V50 by up to a factor of 10 depending on the powder. The importance of the assessment of agglomeration and how different treatments such as milling modifies the agglomeration factor F _AG is illustrated for an “as received” and attrition milled gamma alumina. Results are discussed with respect to the assumptions and limitations of the different instruments. Results are presented after consideration of the hydrodynamic density in the sedimentation methods, and light scattering for the optical based methods. For narrow size distributions in the 15–25?nm range all three instruments show very a good correlation. When the size range approaches the 40–100?nm regime PCS is very sensitivity to small populations of agglomerates. The instrument giving the best resolution in the 10–100?nm range was found to be the XDC. The speed of measurement should also be born in mind and varies enormously from several minutes for the PCS to several hours for the sedimentation techniques. To assess the accuracy of the measured sizes a model spherical silica powder was analyzed on all the instruments as well as by image analysis. The results with the silica powder showed how the accuracy of the sedimentation methods depends strongly on a knowledge of the suspended particles hydrodynamic density. This can be effected greatly by particle or agglomerate porosity and the thickness of the electrical double layer in the aqueous dispersions investigated. The results with the silica suggest accuracy's on the size better than ±20% is difficult without an accurate hydrodynamic density whereas consistency between methods for narrow size distributions can be better than 5% for median volume diameters.     

Synthesis of poly(styrene‐block‐tert‐butyl acrylate) star polymers by atom transfer radical polymerization and micellization of their hydrolyzed polymers

A series of poly(styrene‐block‐tert‐butyl acrylate) heteroatom star block copolymers having various block lengths were prepared by atom transfer radical polymerization (ATRP), using an “as synthesized” cynurate modified trifunctional initiator. The structure of the star polymers was confirmed by the characterization of the individual arms resulting from hydrolysis. Amphiphilic poly(styrene‐block‐acrylic acid) star copolymers were further synthesized by hydrolyzing PtBA blocks using anhydrous trifluoroacetic acid. The characterization data are reported from analyses using gel permeation chromatography, infrared, ¹H and ¹³C NMR spectroscopies. The stable micelle solution was prepared by dialyzing the solution of these polymers in N,N‐dimethylformamide against deionized water. The temperature‐induced associating behavior of these amphiphilic star polymers were studied using dynamic laser light scattering spectroscopy. The hydrodynamic diameter of both micelles and unassociated chains were obtained in the same solution using light scattering cumulant's calculation method. The homogeneity and the size distribution of the micelle population in the solution were determined using centrifuge/sedimentation particle size distribution analyzer. Field emission scanning electron microscope was used to visualize the size of the micelles formed and the micellar aggregates. The influence of the temperature on the viscosity of the micelle solution was studied using an Ubbelohde viscometer. Thermodynamics of micellization of these block copolymers were also investigated. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6367–6378, 2005     

液化膜对胶体悬浮液粘度的影响

Viscosity is one of the most important properties of colloids in mixing, transportation, stabilization, energy consumption, and so on. According to Einstein‘s viscosity equation, the viscosity of a colloidal dispersion increases with the increase of particle concentration. And the equation can be applicable to all micro-particle dispersions, because the effect of solvation films coated on particles can be neglectable in that case. But with the decrease of particle size to nano-scale, the formation of solvation films on nano-particles can greatly affect the viscosity of a dispersion, and Einstein‘s equation may not be applicable to this case. In this work, one kind of micro-size silica particle and two kinds of nano-size silica particles were used to investigate the effect of solvation films on dispersion viscosity, dispersed in water and ethyl alcohol solvents, respectively. The results of theoretical calculation and experimental investigation show that the increase of viscosity is contributed from solvation films by more than 95 percent for nano-particle dispersions, while less than 10 percent for micro-particle dispersions.     

Synthesis and aggregation stability of europium oxohydroxide hydrosols

Europium oxohydroxide hydrosols that are resistant to aggregation have been obtained by the condensation method. The density of dispersed phase particles, phase composition and dispersity of the sols, electrokinetic potential of the particles, and its dependence on medium pH have been determined. The effect of dispersion medium pH on the mechanism and reversibility of particle aggregation has been studied. The nature of the aggregation stability of the synthesized europium oxohydroxide hydrosols has been discussed.     

Viscoelastic properties of sterically stabilized nonaqueous dispersions

The viscoelastic properties of a dispersion of poly(vinyl acetate) particles sterically stabilized by poly(2-ethyl hexyl methacrylate) and dispersed in Isopar G have been measured as a function of particle concentration and frequency at ambient temperature.At low particle concentrations, it was found that the loss modulus was larger than the storage modulus, while at high particle concentrations, i.e.,w>0.40, the storage modulus was found to be larger than the loss modulus. This inversion from a viscous to an elastic response as a function of particle concentration is attributable to the change in the configurational entropy of the steric barrier as a result of increasing the concentration of particles in the dispersion.     

Hydrodynamic studies on model branched polystyrenes

The measurement of the sedimentation velocity coefficient of narrow distribution linear, four-arm and six-arm star and comb polystyrenes in a theta solvent permits the experimental determination of h, i.e., the ratio of the translational friction coefficients of the branched polymer to that of its linear homolog. A comparison of experimental h/g^1/2 values with theoretical predictions can then be made. It was observed that the equivalent hydrodynamic radii derived from sedimentation and intrinsic viscosity measurements are identical within experimental error.     

Structurization of Aerosil OX50 Dispersions

Structural and mechanical properties of aqueous dispersions of Aerosil OX50 were studied by rotary viscometry. The thixotropic properties of concentrated (20-50 wt %) Aerosil dispersions used in the sol-gel synthesis of quartz glass are due to structurization caused by appreciable overlapping of the electrical double layers of the particles. The particle interaction occurring in a limited volume is accompanied by formation of periodic colloidal structures of the second kind. The viscoplastic properties and extrema in the pH dependence of the viscosity are explained in terms of collective interaction of Aerosil particles according to the Deryagin-Landau-Verwey-Overbeek (DLVO) theory.     

The influence of the addition of electrolytes on the degree of dispersion of silver iodide hydrosol

The changes in the degree of dispersion of AgI hydrosols produced by reaction of AgNO₃ and KI with the addition of other electrolytes (1–60 min after addition of AgNO₃ to KI) were investigated by photometric methods. The results obtained suggest that in the process of rapid condensation (caused by a sudden increase in concentration to a value considerably higher than the critical one) colloidal particles do not form by continuous growth of individual nuclei but through disaggregation of loose and amorphous, i. e. thermodynamically unstable clusters of previously formed embryos. This disaggregation process, termed protopeptization by the authors in order to underline its analogy with the peptization process, increases in magnitude with the strengthening adsorption of potential-determining ions (protopeptizing agents) by the particles formed in the precipitation process.     

Characterizing dispersion and fragmentation of fractal, pyrogenic silica nanoagglomerates by small-angle X-ray scattering

Typical characterization of nanoparticle dispersion and compounding processes by dynamic light scattering (DLS) and TEM lack quantitative information on fractal structure, aggregation number, and specific surface area. In this work a synchrotron ultra-small-angle X-ray scattering (USAXS) investigation on diffusion flame and 'Aerosil' silica powders, as well as on their desagglomeration by high-pressure liquid dispersion (200-1400 bar) is presented. Primary particle size, polydispersity, and specific surface area are measured for powders, stirred-in dispersions, and after high-pressure processing with identical results, showing the in-situ applicability of USAXS. These parameters, as well as the hard aggregate mass fractal dimension, with typically Df = 2.15 representing reaction-limited cluster aggregation, are determined by synthesis process conditions. They are unchanged even at the highest hydrodynamic stresses; thus, neither comminution nor agglomerate restructuring nor re-agglomeration occurs. Fragmentation reflects in decreasing radii of gyration, which are compared to mobility equivalent radii from DLS in agreement with theory.     

Preparation of Thermostable Highly Dispersed Titanium Dioxide from Stable Hydrosols

A large set of stable nanodispersed TiO₂ hydrosols differing in particle structure and dispersion medium composition was synthesized. For highly dispersed TiO₂ samples obtained by calcination of dried sols at 500°C phase compositions, sizes of primary crystallites, and specific surface areas were found. The factors affecting thermal stability of TiO₂ nanoparticles were analyzed. The sol containing the most thermostable nanoparticles was used to produce a highly efficient catalyst for cyclohexanone ammoximation.     

The desaggregation of solid particle aggregates by ultrasonication

The influence of some variables (concentration, intensity, and time) of ultrasonication on the mean particle size is determined by ultracentrifugation and capillary viscosimetry. For the fused silica Aerosil 200^® under optimal conditions only an aggregate radius of 23 nm is achieved. That means an irreversible fused aggregate of about 21 primary particles which contains 60% v/v of immobilized water.