Dynamic surface tension and its diffusional decay of dodecyl ethoxylates with different homologue distribution

Dynamic surface tension and its diffusional decay have been studied with four different polydisperse C12E7 at different temperatures and different concentrations. The CMC and the headgroup area from equilibrium surface tension were shown with polydispersity and temperature. The chain length of oxyethylene on the surface was derived from comparison between the headgroup area of monodisperse dodecyl ethoxylates and that of polydisperse C12E7. The values for (Deff/D) were deduced with a diffusion-controlled adsorption model using parameters obtained from equilibrium surface tension. It was shown at short adsorption time that molecules were really adsorbed onto the surface in a diffusion-controlled manner. At a comparably long adsorption time, the ratios (Deff/D) were calculated by assuming the selective adsorption onto the surface. The modified Arrhenius-type equation was proposed by putting a concentration term in front of the exponential terms. The modified Arrhenius-type equation gave Ea=30 kJ/mole for this system. Ea directly derived without an Arrhenius plot was between 9 to 11 kJ/mole. It was an indication that the activation energy alone was not enough to explain the decay of dynamic surface tensions.     

Adsorption and direct probing of fibrinogen and sodium myristate at the air/water interface

Fibrinogen (FB), a serum protein, is considered a major inhibitor of lung surfactant function at the lining layer of the alveoli. In this study, the adsorption of aqueous bovine FB at the air/water interface was investigated with tensiometry and directly probed for the first time with ellipsometry and infrared reflection adsorption spectroscopy (IRRAS). The tension results show that FB has moderate surface activity. The surface densities of FB were calculated by using two different ellipsometry models to range from 3±0.2 to 17±2 mg/m², for 7.5 to 750 ppm of FB in water at 25°C. Although FB at concentrations from 75 to 750 ppm reached about the same steady surface tension value, the surface densities at 750 ppm FB were substantially larger. The same techniques were used for studying aqueous mixtures of 7.5 to 750 ppm FB with 2 mM of sodium myristate (SM) to investigate a possible interaction of the SM with the protein. The behavior of the FB/SM mixtures was found to be close to that of SM alone. The surface tension of the FB/SM mixtures reached values less than 10 mN/m under surface area oscillation at 20 or 80 rpm. These results and the ellipsometry and the IRRAS results indicate that at a concentration of 2 mM SM, FB, up to 750 ppm, does not inhibit the surfactant surface-tension-lowering function. In certain cases the results demonstrate that FB and SM may act cooperatively in lowering the surface tension.     

Dynamic electrophoretic mobility of a concentrated dispersion of particles with a charge-regulated surface at arbitrary potential

The dynamic electrophoretic mobility of a concentrated dispersion of biocolloids such as cells and microorganisms is modeled theoretically. Here, a biological particle is simulated by a particle, the surface of which contains dissociable functional groups. The results derived provide basic theory for the quantification of the surface properties of a biocolloid through an electroacoustic device, which has the merit of making direct measurement on a concentrated dispersion without dilution. Two key parameters are defined to characterize the phenomenon under consideration: the first, A, is associated with the pH of the dispersion, and the second, B, is associated with the equilibrium constant of the dissociation reaction of the functional group. We show that if A is large and/or B is small, the surface potential is high, and the effect of double-layer polarization becomes significant. In this case the dynamic electrophoretic mobility may have a local maximum and a phase lead as the frequency of the applied electric field varies. Due to the hydrodynamic interaction between neighboring particles, the dynamic electrophoretic mobility decreases with the concentration of dispersion.     

Thermocapillary Alignment of Gas Bubbles Induced by Convective Transport

The effect of a weak convective heat transfer on the thermocapillary interaction of two bubbles with an arbitrary orientation relative to an externally imposed temperature gradient is examined. Asymptotic analysis of the case of large separation distances, Z, suggests that the corrections to the bubbles' velocities are of (Pe/Z²), rather than (Pe²) previously found for an isolated bubble. Equal-sized bubbles are known to move with the same velocities, as if they were isolated, when heat conduction is the only transport mechanism. However, the convective transport results in a relative motion of the bubbles. The tendency of equal bubbles to line up in a plane perpendicular to the applied thermal gradient is shown analytically in the weakly nonlinear limit of small Pe numbers, and an interesting interaction behavior in the case of unequal bubbles is discussed.     

Flow of water through channels filled with deformable polymer gels

A mathematical model is developed for the flow of water through a channel impregnated with a polymer gel that is treated as an elastic and deformable porous medium. The model uses a Brinkman equation along with an experimentally observed velocity-dependent permeability. Numerical and approximate analytical solutions are given. These results show that the gel intrinsic properties, i.e., gel reference permeability and elastic index, control the water flow. First, the permeability of water flow through the gel increases with an increase of gel reference permeability. Second, the velocity of water decreases when the gel velocity exponent increases. Our theoretical results show that the velocity-dependent permeability of water flow through polymer gels is in fact an intrinsic property of the gel rather than a property of the channel or some interaction between the gel and the pore walls.     

Light Scattering Study of Turbid Heat-Set Globular Protein Gels Using Cross-Correlation Dynamic Light Scattering

The structure factor of aqueous solutions of the globular protein β-lactoglobulin was determined as a function of heating time at 76°C. We show how the effect of multiple scattering on the scattered light intensity can be effectively corrected using cross-correlation dynamic light scattering even if the transmission is only 1%. The structure factor of aggregated and gelled proteins can be described by the Ornstein–Zernike equation. The system is characterized by a correlation length that increases with heating time and stabilizes some time after the gel is formed. The correlation length of the protein gels decreases with decreasing concentration. Measurements after progressive dilution of a sample close to the gel point showed that the protein aggregates are initially interpenetrated and disinterpenetrate upon dilution.     

Atomic force microscopy and magnetic force microscopy study of model colloids

Atomic force microscopy (AFM) is used to study the size, shape, and polydispersity of a variety of magnetic and nonmagnetic model colloids, previously imaged by transmission electron microscopy (TEM) only. Both height and phase images are analyzed and special attention is given to 3D morphology and softness of particles, as well as structures and presence of secondary components in the colloid, difficult to investigate with TEM. Several methods of tip characterization followed by deconvolution were applied in order to improve the accuracy of lateral diameter determination. In the case of magnetite particles dispersed in conventional ferrofluids, we explore both experimentally and theoretically the possibility of using magnetic force microscopy (MFM). We propose and discuss several models which allow to estimate the magnetic moment of a single domain superparamagnetic sphere using MFM, which cannot be done with other techniques; alternatively the tip magnetization can be determined.     

Effect of Insoluble Surfactants on Drainage and Rupture of a Film between Drops Interacting under a Constant Force

The deformation, drainage, and rupture of an axisymmetrical film between colliding drops in the presence of insoluble surfactants under the influence of van der Waals forces is studied numerically at small capillary and Reynolds numbers and small surfactant concentrations. Constant-force collisions of Newtonian drops in another Newtonian fluid are considered. The mathematical model is based on the lubrication equations in the gap between drops and the creeping flow approximation of Navier–Stokes equations in the drops, coupled with velocity and stress boundary conditions at the interfaces. A nonuniform surfactant concentration on the interfaces, governed by a convection–diffusion equation, leads to a gradient of the interfacial tension which in turn leads to additional tangential stress on the interfaces (Marangoni effects). The mathematical problem is solved by a finite-difference method on a nonuniform mesh at the interfaces and a boundary-integral method in the drops. The whole range of the dispersed to continuous-phase viscosity ratios is investigated for a range of values of the dimensionless surfactant concentration, Peclét number, and dimensionless Hamaker constant (covering both “nose” and “rim” rupture). In the limit of the large Peclét number and the small dimensionless Hamaker constant (characteristic of drops in the millimeter size range) a fair approximation to the results is provided by a simple expression for the critical surfactant concentration, drainage being virtually uninfluenced by the surfactant for concentrations below the critical surfactant concentration and corresponding to that for immobile interfaces for concentrations above it.     

Hydrodynamic interaction between spheres coated with deformable thin liquid films

In this article, we considered the hydrodynamic interaction between two unequal spheres coated with thin deformable liquids in the asymptotic lubrication regime. This problem is a prototype model for drop coalescence through the so-called "film drainage" mechanism, in which the hydrodynamic contribution comes dominantly from the lubrication region apart from the van der Waals interaction force. First, a general formulation was derived for two unequal coated spheres that experienced a head-to-head collision at a very close proximity. The resulting set of the evolution equations for the deforming film shapes and stress distributions was solved numerically. The film shapes and hydrodynamic interaction forces were determined as functions of the separation distance, film thickness, viscosity ratios, and capillary numbers. The results show that as the two spheres approach each other, the films begin to flatten and eventually to form negative curvature (or a broad dimple) at their forehead areas in which high lubrication pressure is formed. The dimple formation occurs earlier as the capillary number increases. For large capillary numbers, the film liquids are drained out from their forehead areas and the coated liquid films rupture before the two films "touch" each other. Meanwhile, for small capillary numbers, the gap liquid is drained out first and the two liquid films eventually coalesce.     

Preparation of finely dispersed drugs. III. Cyclosporine

Two different precipitation processes are described, which produced dispersions of spherical particles of cyclosporine ranging in diameter from approximately 10 nm to several micrometers. This drug is of interest for its immunosuppressive activity in the antirejection of transplanted organs. The effects of several experimental parameters on the average particles size and uniformity have been investigated. Aging of spherical particles resulted in large crystalline-type aggregates.     

Interactions between Poly(ethylene oxide) and Sodium Alkylcarboxylates As Studied by Conductivity and Gel Permeation Chromatography

The interactions between PEO and sodium alkylcarboxylates (octyl, decyl, and dodecyl) have been investigated by conductivity measurements and gel permeation chromatography (GPC). Also included in the study was sodium dodecyl sulfate. From the conductivity measurements the critical aggregation concentration, ionization degree, and binding ratios were determined; the binding ratio was also determined from GPC. PEO–surfactant interactions were observed for all the studied surfactants, except sodium octanoate. For the polymer–surfactant complexes the ionization degree was in all cases observed to be about 0.2 higher than the ionization degree for the corresponding aqueous micelles. Further, the binding ratio decreased somewhat with decreasing chain length of the alkylcarboxylate. The Gibbs free energy showed that the polymer–surfactant interaction decreases with decreasing chain length of the alkylcarboxylates and is weaker for alkylcarboxylate compared to alkylsulfate of similar chain length.     

Volume Fraction Effects in Electroacoustic Measurements

We measured the dynamic mobility of a polystyrene latex at 1 MHz as a function of volume fraction using the ESA-8000. The volume fraction dependence is compared with a semiempirical equation as well as with some theoretical predictions. It turns out that our polystyrene latex exhibits a volume fraction dependence much weaker than that predicted by any of the theories. This suggests that (polystyrene) latices may not be the ideal model system and that the centrifugation process may influence the surface structure of the particles. We also measured the dynamic mobility spectrum of a silica sol as a function of volume fraction using the Acoustosizer. The experimental spectrum of the silica sol was found to agree reasonably well with the semiempirical and theoretical spectra, especially below φ=0.144. At higher volume fractions we observed positive phase angles that were not predicted by the semiempirical method nor the cell model.     

Molecular Interactions in Mixed Monolayers of Octadecanoic Acid and Three Related Amphiphiles

Binary mixed monolayers of octadecanoic acid and three related amphiphilic compounds (octadecanamide, octadecylamine, octadecylurea) have been investigated at the air/water interface by surface pressure–area (Π–Â) isotherms and their resistances to water evaporation (r). In addition, the excess free energies of mixing (ΔG^E) were calculated using the Goodrich method. Both the ln r vs x and ΔG^E vs x plots exhibit marked deviations from linearity, indicating a high degree of miscibility and nonideal behavior of the components in the mixed films. For all of these binary systems the excess free energies of mixing have been found to be minimum for a certain composition corresponding almost to a maximum in evaporation resistances. Weak interactions were detected in octadecanoic acid/octadecanamide monolayers, whereas significant condensation effects were observed in 1 : 1 mixed films containing octadecanoic acid and octadecylamine. This is attributed to an acid–base equilibrium followed by the formation of a well-ordered arrangement of COO⁻ and NH₃⁺ head groups bound to each other by electrostatic forces. The unusual polymorphism of octadecylurea monolayers could be influenced by adding small amounts of octadecanoic acid. The formation of the low-temperature phase (β-phase) is completely suppressed, if the acid content exceeds 8 mol%. The octadecanoic acid seems to induce the formation of the high-temperature phase (α-phase), which is characterized by a vertical orientation of the hydrocarbon chains.     

Rheology and Permeability of Crosslinked Polyacrylamide Gel

Gels produced by crosslinking polyacrylamide solutions with chromium (III) have been characterized by dynamic rheology studies. To vary the gel strength, different polymer concentrations were used, while keeping the temperature, salinity, and crosslinker concentration constant. Both the loss and storage moduli increased with the polymer concentration for this gel system. The storage modulus at the end of the gelation was used to characterize the gel strength. Steady-state water flow experiments through gel-filled capillary tubes were performed, with the aim of linking the gel strength and flow behavior. The permeability was found to be a function of the water flow rate (velocity) and polymer concentration. Two parameters were used to characterize the flow behavior, intrinsic gel permeability and elasticity index, which are each functions of the polymer concentration. However, only one parameter is needed to fully identify the flow and rheological gel properties, as the elasticity index and storage modulus are linked by a power-law relationship. The loss modulus and intrinsic permeability are correlated with the storage modulus and elasticity index, respectively. A theoretical model for this behavior linking both gel properties based on the dual domain structure was used to demonstrate that the flow and rheological behavior of the gel are indeed related and that the gel strength controls the water permeability. Implications for prediction of flow of water through gels emplaced in a porous medium are discussed.     

Adsorption of 1,4-Benzenedithiol on Gold and Silver Surfaces: Surface-Enhanced Raman Scattering Study

The adsorption behavior of 1,4-benzenedithiol (1,4-BDT) on colloidal gold and silver surfaces has been investigated by means of surface-enhanced Raman scattering (SERS). 1,4-BDT chemisorbed dissociatively on both gold and silver surfaces but as mono- and dithiolate, respectively. Regardless of the bulk concentration of 1,4-BDT, only a monolayer was assembled on the silver surface with a flat orientation by forming two Ag–S bonds. On the gold surface, the monothiolate species,1,4-BDT⁻¹, appeared to assume a rather flat orientation at a very low surface coverage, but as the surface coverage was increased, the adsorbate took a perpendicular orientation. Furthermore, when the bulk concentration of 1,4-BDT was close to that required for a full-monolayer coverage limit, a band assignable to the S–S stretching vibration appeared at 536 cm⁻¹ in the gold sol SERS spectra. A separate ellipsometry measurement performed with vacuum-evaporated gold substrates revealed that up to tetralayers could be assembled on gold in 1 mM n-hexane solution of 1,4-BDT while at best a bilayer formed in either methanol or ethanol solution. The different adsorbate structure of 1,4-BDT on gold and silver was overall quite comparable to that of p-xylene-α,α′-dithiol.     

A structural study of amphiphilic PAMAM (poly(amido amine)) dendrimers in Langmuir and Langmuir-Blodgett films

Two amphiphilic PAMAM dendrimers are synthesized by attaching 12-hydroxydodecanoic acid (HA) chains to a poly(amido amine) (PAMAM) dendrimer core (including generation I and generation II). The limiting molecular area obtained from the surface pressure-area isotherm at the air/water interface suggests the edge-on configuration for both dendrimers in Langmuir films. The edge-on arrangement is also supported by the atomic force microscopic (AFM) studies of the Langmuir-Blodgett films.     

Effect of structural stress on the intercalation rate of kaolinite

Particle size in kaolinite intercalation showed an inverse reactivity trend compared with most chemical reactions: finer particles had lower reactivity and some of the fine particles cannot be intercalated. Although this phenomenon was noted in the early 1960s and several hypotheses have been reported, there is no widely accepted theory about the unusual particle size response in the intercalation. We propose that structural stress is a controlling factor in the intercalation and the stress contributes to the higher reactivity of the coarser particles. In this study, we checked the structural deformation spectroscopically and indirectly proved the structural stress hypothesis. A Georgia kaolinite was separated into nine size fractions and their intercalations by hydrazine monohydrate and potassium acetate were investigated with X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) analyses. The apical Si-O band of kaolinite at 1115 cm(-1) shifted to 1124 cm(-1) when the mineral was intercalated to 1.03 nm by hydrazine monohydrate, and its strong pleochroic properties became much weaker. Similar reduction in pleochroism was observed on the surface OH bands of kaolinite after intercalation. Both the bending vibrations of the inner OH group at 914 cm(-1) and of the surface OH group at 937 cm(-1) shifted to 903 cm(-1) after intercalation by hydrazine. A new band for the inner OH group appeared at 3611 cm(-1) during the deintercalation of the 1.03 nm hydrazine kaolinite complex. Pleochroism change in the apical Si-O band suggested the tetrahedra had increased tilt with respect to the (001) plane. The tilt of the Si-O apical bond could occur only if the octahedra had also undergone structural rearrangement during intercalation. These changes in the octahedral and tetrahedral sheets represent some change in the manner of compensation for the structural misfit of the tetrahedral sheet and octahedral sheet. As the lateral dimensions of a kaolinite particle increases, the cumulative degree of misfit increases. Intercalation breaks the hydrogen bonds between layers and allows for the structure to reduce the accumulated stress in some other manner. The reversed size effect on intercalation probably was not caused by crystallinity differences as reported in the literature, because the Hinckley and Lietard crystallinity indices of the four clay fractions were very close to each other. Impurities, such as dickite- or nacrite-like phases are not significant in the studied sample as suggested by the XRD and IR results, they are not the main reasons for the lower reactivity of the finer particles.     

Advective flow and floc permeability

This work monitored advection flow through a floc by bubble tracking. Close examination of the motion of a swarm of hydrogen bubbles that passed over a free-falling floc allowed the extent of advection flow to be estimated at 53% for the original activated sludge floc, and 12% for the flocculated floc. The interior permeability of the sludge flocs was estimated from this information. The fluid force exerted on the falling floc was also considered.     

Polydispersity and Functional Group Distribution of Dispersant Polymer: Adsorption Properties and Magnetic Paint Dispersion

The quantitative analysis examining the functional group distribution of a dispersant polymer for magnetic paints is conducted by statistical estimation and adsorption experiments. The dispersant polymer contains averagely one or two functional groups on the chain, and has generally large polydispersity. By the calculation based on the random distribution of the functional group and the molecular weight, a typical design of the dispersant polymer is found to contain a significant amount of nonfunctionalized chains and highly functionalized ones. In adsorption experiments, the adsorbed amount of the polymer mass and the functional group are separately measured to determine the functional group distribution. The distribution is also evaluated by a sequential adsorption experiment, in which the chains are fractionated by the adsorption strength. Obtained experimental results agree with the calculated results. A practical method for increasing the effective chains in the paint is to make use of a preferential adsorption of the functionalized chain.