Conductivity and Electrokinetic Potential of Microcrystalline Cellulose Particles in Aqueous HCl and NaOH Solutions

The conductivity of microcrystalline cellulose (MCC) dispersions in aqueous 10^–5–10^–2 M HCl and NaOH solutions was measured as a function of the particle volume fraction by the conductometry. The dependence of the relative conductivity of MCC particles on pH of equilibrium solutions was determined using the Wagner equation. The electrophoretic mobility of MCC particles in the aforementioned solutions was measured by the microelectrophoresis, and corresponding dependences of the particle potentials on pH of aqueous HCl and NaOH solutions (pH 2–11) were calculated using the Smoluchowski and Henry equations of the electrophoresis theory. It was shown that, in the case of MCC, the Henry equation, which allows for the significant conductivity of the dispersed particles, as compared with the dispersion medium, makes it possible to calculate more accurate potential values and, consequently, to derive the (pH) dependence, which is satisfactorily consistent with the effect of the surface charge and solution ionic strength on the potential in a wide pH range.     

Physical Chemistry or Biological Interfaces A. Baszkin & W. Norde,editors. Marcel Dekker,Inc. New York, 1999, hardbound,pp. ix + 836; $225

The size distribution and morphology of microcrystalline cellulose (MCC) particles and the effect of pH on the rheological properties of their dilute aqueous dispersion were studied. The 0.3 wt% aqueous dispersion of fine particles (89 nm) also showed solid‐like dynamic viscoelastic behavior at low pHs (below pH 3), in contrast to liquid‐like behavior at high pHs. These findings suggest that at lower pHs the electrostatic repulsion force between MCC particles decreases to induce the aggregation of particles into a three‐dimensional network structure. The minimum empty space in the network structure is expected to be 450 nm or more.     

Synthesis and electrochemical performances of amorphous carbon-coated Sn–Sb particles as anode material for lithium-ion batteries

The amorphous carbon coating on the Sn–Sb particles was prepared from aqueous glucose solutions using a hydrothermal method. Because the outer layer carbon of composite materials is loose cotton-like and porous-like, it can accommodate the expansion and contraction of active materials to maintain the stability of the structure, and hinder effectively the aggregation of nano-sized alloy particles. The as-prepared composite materials show much improved electrochemical performances as anode materials for lithium-ion batteries compared with Sn–Sb alloy and carbon alone. This amorphous carbon-coated Sn–Sb particle is extremely promising anode materials for lithium secondary batteries and has a high potentiality in the future use.     

1H-NMR Relaxation of Water Molecules in the Aqueous Microcrystalline Cellulose Suspension Systems and Their Viscosity

An intensive study for aqueous microcrystalline cellulose (MCC) suspensions was carried out in view of the relationship between a viscosity and a 1H spin-spin relaxation time (T2) of water. An investigation was carried out for four suspension systems with the different particle size distributions. The proton mole ratio () of bound water against MCC particles and T2 of bound water (T2,b) were evaluated from the T2 values obtained by Carr-Purcell- Meiboom-Gill (C.P.M.G) method and those by solid echo method, respectively. As a result of these analyses, the T2,b value for the aqueous MCC suspension was evaluated as 5 × 10–3 s and it was found that the system having a larger tended to show a higher viscosity. By relating the above results to the observation of the suspensions by an optical microscope, it was concluded that a network formed by MCC particles plays an important role in generating a high viscosity of MCC suspension, and that an averaged mobility of water molecules is sensitively affected by the network structure.     

Aggregation Stability of SiO2, FeOOH, ZrO2, CeO2, and Natural Diamond Sols and Their Binary Mixtures: 2. The Photometric Study of Heterocoagulation of SiO2–FeOOH, SiO2–ZrO2, SiO2–CeO2, and CeO2–Natural Diamond Binary Systems in KCl Solutions

The aggregation stability of 1 : 1 and 3 : 1 (by volume) binary mixtures of two hydrophobic (SiO₂–FeOOH), one hydrophobic and one hydrophilic (SiO₂–ZrO₂, SiO₂–CeO₂), and two hydrophilic (CeO₂–natural diamond) sols was studied by photometry over a wide range of KCl concentrations at pH 6 and 3. The stability of the mixed binary sols was determined by the stability of the sol with a predominant particle number concentration. In the SiO₂–FeOOH system, the phenomenon of heteroadagulation stabilization was caused by the electrostatic factor of the stability of adsorbed SiO₂ particles and, in the SiO₂–ZrO₂ system, by the structural factor of the stability of adsorbed hydrophilic ZrO₂ particles. The stability of binary mixtures containing one or two hydrophobic components is qualitatively explained in terms of the Derjaguin theory of heterocoagulation of hydrophobic colloids. The stability of the binary system of two hydrophilic components (CeO₂–natural diamond) is determined by the structural component of the interaction energy of particles.     

Capillary force required to detach micron-sized particles from solid surfaces—Validation with bubbles circulating in water and 2 μm-diameter latex spheres

The adhesion forces holding micron-sized particles to solid surfaces can be studied through the detachment forces developed by the transit of an air–liquid interface in a capillary. Two key variables affect the direction and magnitude of the capillary detachment force: (i) the thickness of the liquid film between the bubble and the capillary walls, and (ii) the effective angle of the triple phase contact between the particles and the interface. Variations in film thickness were calculated using a two-phase flow model. Film thickness was used to determine the time-variation of the capillary force during transit of the bubble. The curve for particle detachment was predicted from the calculated force. This curve proved to be non-linear and gave in situ information on the effective contact angle developing at the particle–bubble interface during detachment. This approach allowed an accurate determination of the detachment force. This theoretical approach was validated using latex particles 2 μm in diameter.     

Orthokinetic Aggregation in Two Dimensions of Monodisperse and Bidisperse Colloidal Systems

Orthokinetic aggregation of colloids trapped at the air–liquid interface was studied by direct imaging in a couette cell. This method allowed us to follow the temporal evolution of both the cluster-mass distribution and the cluster structure at a shear rate where Brownian aggregation is suppressed. The interactions between the monodisperse latex particles floating at the air–liquid interface were controlled either by varying the electrolyte concentration or by creating a bidisperse system through the addition of small particles. The results show that the clusters in all of the systems are characterized by a high fractal dimension, indicating that the clusters are rearranged and densified by the shear. Kinetic analysis suggests that aggregation of monodisperse systems mainly proceeds through homogeneous aggregation, i.e., large clusters sticking to other large clusters. The bidisperse system, finally, with a size ratio around 10, favored a more heterogeneous aggregation among small and large clusters throughout the aggregation process; a slightly lower fractal dimension was observed compared to the strongly aggregated monodisperse system.     

An Enthalpic Analysis on the Aggregation of Colloidal Particles Studied by Microcalorimetry

There are different theories concerning the stability of colloidal suspensions. Most of them arise from the well-known DLVO theory which relates colloidal stability to intermolecular forces between particles. Experimental corroboration of these theories has been obtained mainly by using different optical techniques that analyze changes in the optical properties of the solution while particles aggregate. However, no attention has been paid to studying the aggregation process thermodynamically. This is why we have focussed on studying the heat released during the agglutination of polystyrene particles. The enthalpy change in this aggregation process was detected by using a highly sensitive and modern technique called isothermal titration calorimetry. In addition, some results about repeptization, that is, reversibility in the aggregation process, are also shown. Copyright 2001 Academic Press.     

Synthesis and Some Properties of Cerium Dioxide Hydrosols

Cerium dioxide hydrosols are synthesized by peptizing with nitric acid a precipitate obtained by hydrolyzing cerium(III) nitrate. The synthesized sols are stable with respect to aggregation in both acidic (pH 1.5–3.0) and alkaline media (pH 9.0–11.0). The mean hydrodynamic radius of particles is about 25 nm. The isoelectric point corresponds to pH 6.2. The phase composition of sol particles is determined by X-ray diffraction at pH of the dispersion medium ranging from 1.5 to 3.0. The sol coagulation thresholds are determined in the presence of sodium nitrate and sulfate, as well as of mixed magnesium salt at various pH values of the dispersion medium. Assumptions are made concerning the nature of the aggregative stability of sols.     

Effect of a weak magnetic field on hematite sol in stationary and flowing systems

The effect of a weak magnetic field on the aggregation state and electrophoretic mobility of hematite sol was studied in flowing (dynamic) systems as a function of time and electrolyte concentration (0–60 mmol/dm³ KCl) and compared with the effect of the field in stationary (static) systems and flow in the absence of the field. During the entire treatment period, the pH remained almost constant (4.06–4.24). Conductance varied with KCl concentration, but except for minor fluctuations appeared to be unaffected by any form of treatment. While aggregation of hematite was observed during dynamic magnetic treatment (change in turbidity, scattered light intensity, and photon correlation spectroscopy), little effect on aggregation state was observed for the static systems or for the flowing systems in the absence of the field. Mobility also increased during the first 30 min of static and dynamic magnetic treatment. After longer treatment periods (90–120 min), the mobility decreased, but in almost all cases remained larger than in the case of untreated systems. Changes in both mobility and particle aggregation state also showed a significant dependence on electrolyte concentration. These effects are discussed in terms of a magnetohydrodynamic interaction between the magnetic field and the charged colloidal particles, which results only when the particles are made to pass rapidly through the field.     

Aggregation phenomena in the suspension polymerization of VCM

In the suspension polymerization of VCM, insoluble polymer particles are formed inside the monomer droplets. The growth and aggregation of these particles are responsible for important polymer properties, such as porosity. It is well established that the most characteristic polymer particles, the primary particles, are of a narrow distribution with a size (diameter) ranging from 0.10–0.20 m. This work studied the formation of primary particles based on the aggregation phenomena that take place inside a monomer droplet. This was done by formulating a population balance equation, which was based on the following considerations: a) polymerization occurs in both the monomer and the polymer phases; b) there is continuous formation of the basic particles in the monomer phase; c) the growth of the polymer particles occurs as a result of both polymerization in the polymer phase and aggregation of the particles; d) the colloidal properties of the particles that are responsible for the aggregation phenomena were considered to be the net result of attraction and repulsion energies.It was shown that for particles carrying a constant charge it was not possible to predict the formation of primary particles of size 0.10–0.20 m. The particle size distribution had a mode diameter equal to the diameter of the basic particles. Consequently, the particle charge was allowed to vary in a way proportional to the particle radius raised to a power coefficient. For values of the coefficient greater than zero, i. e., when the particle charge increased during polymerization, the aggregation of the basic particles was efficient enough to result in the formation of large primary particles.     

Electrosurface Properties of Microcrystalline Cellulose of Different Origin in 1 : 1 Electrolyte Solutions

Electrosurface characteristics (the exchange capacity and the electrokinetic potential) of the samples of cotton and wood microcrystalline celluloses (MCC) were studied as functions of the pH and the concentration of background electrolyte (10^–3–1M NaCl). It was found that the MCC samples are negatively charged over the studied pH range (3.5–10.0). The results of measuring exchange capacities were used for calculating constants of surface reactions. The values of dissociation constants of the surface groups allow us to state that the charge of the MCC surface within the studied pH range is mainly determined by the dissociation of carboxyl groups. The surface and electrokinetically mobile charges, concentrations of fixed and mobile ions, as well as Donnan's potentials were calculated for the studied samples.     

Sizes and Conformation of the Molecules of DNA–Surfactant Complexes in Dilute Solutions and on the Atomic Smooth Substrates

The conformations of the molecules of DNA–surfactant complexes in dilute solutions and on the atomic smooth surfaces of mica and highly oriented pyrolytic graphite were comparatively studied by the methods of isothermal diffusion, electric birefringence, and atomic force microscopy. The DNA–surfactant complexes were deposited onto the substrates from a chloroform solution. The number of particles of the DNA–surfactant complex on the substrate was changed by varying the concentration of the initial solution within three orders of magnitude. The particles of a shape close to ellipsoidal, 25–70 nm in diameter and 2–4 nm high, were observed at the lowest concentration of DNA–surfactant solution on the mica substrate. The shape and size of these particles correspond to those of a single DNA–surfactant complex, calculated from its translational diffusion coefficient and the time of orientational relaxation in dilute solutions. An increase in the number of molecules deposited onto the substrate leads to an increase in the characteristic sizes of DNA–surfactant complex particles observed by the atomic force microscopy. This may be associated with the aggregation of DNA–surfactant complexes.     

Colloidal properties of aqueous dispersions of ultradispersed Al<Subscript>2</Subscript>O<Subscript>3</Subscript> prepared by explosion synthesis

The electrosurface properties of aluminum oxide particles prepared by shock—wave loading of aluminum powder in an oxygen-containing atmosphere and the aggregation stability of its aqueous dispersions are studied by the macroelectrophoresis method, potentiometric titration, and photometry. The enhanced stability of the dispersions in acid media and in the vicinity of the isoelectric point compared to that in alkaline media is explained by the effect of the structural component of the disjoining pressure, which appears due to the predominant hydration of the cationic forms of aluminum that are present on the surface of dispersed phase particles.Translated from Kolloidnyi Zhurnal, Vol. 67, No. 1, 2005, pp. 128–131. Original Russian Text Copyright © 2005 by Chiganova, Nafikova.     

Formation of rodlike micelles of dimethyloleylamine oxide in aqueous solutions: effects of addition of HCl and NaCl on the micelle size and the intermicellar interaction

Angular dependence of light scattering has been measured for aqueous solutions of dimethyloleylamine oxide in the presence of HCl and NaCl. In micellar solutions more concentrated than 0.1×10^–2 g cm^–3, rodlike micelles are dominantly formed, and their properties are strongly reflected in the characteristics of the solutions. The aggregation number, radius of gyration and even flexibility of the rodlike micelles increase with the addition of HCl as well as NaCl. The increase of HCl concentration up to 10^–3 N makes the aggregation number of rodlike micelles as large as 58,000, when 0.01 M NaCl is present. The large micelle size would be stabilized by the dehydration of the amine oxide group and the hydrogen bonding between nonprotonated and protonated molecules in a micelle.In aqueous solutions without HCl and NaCl or in their presence at very low concentrations, the light scattering is subject to the effects of both external and internal interferences. The effect of external interference can be separated from the effect of internal interference by applying the Zernike-Prins equation to the observed angular dependence of light scattering. Then the second virial coefficient and the pair interaction potential of rodlike micelles can be derived by means of certain approximate methods. The addition of HCl to 10^–3 N makes both repulsive and attractive forces stronger and the resulting potential well deeper, but the addition of NaCl depresses such an effect of HCl considerably.     

Structure Relaxation of n-alkanes Observed by the Simultaneous DSC-FTIR Method

Phase transitions of hexatriacontane (C36) and octacosane (C28), both as the solution grown single crystal (SGC) and polycrystalline aggregates (MCC) prepared by cooling at 1 K min^–1 from the isotropic liquid state, were measured by the simultaneous DSC-FTIR method. MCC of C36 showed the freezing of the high temperature stable phase, which had a slight lower order of the lattice vibration mode comparing with the room temperature stable phase. MCC of C28 demonstrated thermo-reversible phase transition, however, had a binomial distribution of crystal stability of the monoclinic phase.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effects of Microcrystalline Cellulose on Suspension Stability of Cocoa Beverage

The rheological properties and particle size distributions of cocoa beverage as well as aggregate structures of solid particles were studied to elucidate the effects of microcrystalline cellulose (MCC) on suspension stability of solid particles in cocoa beverage. Fluidity curve, dynamic viscoelasticity, particle size distribution, and SEM observation were made for beverage samples containing 0.1–0.5 wt% MCC and 11 model samples with various combinations of six ingredients. This revealed that cocoa and MCC particles are highly cohered into an aggregate and the aggregated particles further interact weakly with the milk component, leading to stabilization of the whole system of cocoa beverage.     

Selective recovery of micrometer particles from mixtures using a combination of selective aggregation and dissolved-air flotation

Particle–particle separation in biotechnology has gained interest over the years due to the large number of processes that yield particle mixtures. Direct isolation of the product-containing particles is a logical and efficient downstream processing route in these processes. Dissolved-air flotation is applicable for these separations when the particles that require separation have different interactions with the air bubbles and/or differ in aggregation behaviour.

In this work, model particles consisting of micrometer-sized protein-coated polystyrene particles were used to investigate the requirements for the application of dissolved-air flotation for particle–particle separation in biotechnology. These model particles have heterogeneous surfaces with surface groups (brushes) that extend out into the solution. Therefore, steric (or brush) repulsion and so-called hydrophobic interactions between the particles need to be taken into account. The flotation behaviour of the protein-coated particles was related to the size of the aggregates and the foaming behaviour of the proteins. Prediction of their aggregation behaviour was performed on the basis of calculations of the Van der Waals, electrostatic, hydrophobic and brush interactions. The brush interaction force proves to be essential for the prediction of the aggregation behaviour of the particles.     

A Novel Method for Stabilizing Zein Gel Particles to Salt Ion-Induced Aggregation

The destabilization of zein gel particles by salt ions seriously limits their practical application. In this study, zein gel particles exhibiting excellent stability to salt ions were developed by grafting gum arabic with tannic acid. Gum arabic (GA) was first coated onto the surface of zein gel particles, followed by addition of tannic acid to further reinforce non-covalent cross-linking between GA and the zein gel particle surface. The stability of the gel particle dispersions was characterized by Turbiscan analysis, gel particle diameter changes and visual inspection of phase separation. The tannic acid-treated zein–GA gel particles were highly protected from precipitation or aggregation in the presence of NaCl (0–3 mol/L) at different pH values (4.0, 7.0 or 8.5). The gel particles prepared in this study will therefore have broader applicability in different pH and salt ions ion environments.