Thermoreversible gelation of hydroxypropylcellulose aqueous solutions

The thermoreversible gelation of hydroxypropylcellulose (HPC)/water solutions is investigated by means of rheological and optical techniques. The linear viscoelasticity of solutions at different concentrations is measured during heating ramps from room temperature. The experimental results suggest that the solution microstructure changes according to two sequential steps, i.e., precipitation and gelation. Temperature, temperature rate of change, and concentration are found to be relevant parameters controlling the phase transition.     

Rheological properties of lightly crosslinked carboxy copolymers in aqueous solutions

The rheological properties of a series of lightly crosslinked carboxy copolymers in aqueous solutions have been evaluated in steady shear and dynamic oscillatory modes. Viscosity profiles and the behavior of storage modulus are related to the chemical composition of the copolymers and their crosslinking density. A maximum in viscosity and in storage modulus which depends on the type of crosslinking agent used is explained by a combination of a chain entanglement mechanism and a closely-packed spheres model. The recovery of viscosity and storage modulus after shearing is very fast and is related to the very fast rearrangement of the microgel structure as a function of time.     

Phase separation effects in the rheology of aqueous solutions of hydroxypropylcellulose

Aqueous solutions of hydroxypropylcellulose (HPC) have been widely used as a model system to study liquid crystalline behavior in polymers. The HPC limiting concentration for mesophase formation in water is about 40% wt, quite independent of molecular weight. Most rheo-optical investigations have been carried out in the concentration range from 50% to 65% wt, on the assumption that only the liquid crystalline phase was present. In this study, by using video-enhanced contrast light microscopy, we show that an isotropic phase in form of tiny droplets is also present at concentrations up to 60% wt, both in quiescent and in sheared samples at room temperature. The isotropic phase can be made to disappear by lowering the temperature. The effects of phase separation on the rheology of the HPC/water system are studied by measuring viscosity as a function of temperature and concentration. A slope of Region I of the viscosity curve close to –0.5 is found only at low temperatures, when the sample is fully anisotropic, whereas an anomalous dependence of the viscosity on temperature is observed when phase separation is significant. This study shows that special care is needed when interpreting experimental results from the HPC/water system in terms of theories for liquid crystalline polymers.     

Electrical double layer and rheological properties of yttria-stabilized zirconia suspensions in solutions of high molecular weight polyacrylic acid polymers

This work deals with the effect of the adsorption of two high molecular weight polyacrylic acid polymers (Carbopol) on the interfacial properties, and the rheology of aqueous zirconia suspensions. Since the Carbopol-covered particles can be thought of as soft colloids, Ohshimas theory was used to gain information on the surface potential and the charge density of the polymer layer (Ohshima H (1995) Electrophoretic mobility of soft particles. Colloids Surf A Physicochem Eng Aspects 103:249–255). The effect of the pH of the solution on the double layer characteristics is related to the different conformations of the adsorbed molecules provoked by the dissociation of the acrylic groups present in polymer molecules. The electrokinetic properties of the suspensions are studied for different pH and Carbopol concentrations in solution in order to investigate the possible stabilization of the suspensions by electrostatic repulsion between the particles. The rheological behavior of the suspensions was investigated in steady-state and dynamic conditions, and the corresponding yield stress and storage modulus were obtained in absence and presence of polymer in solution. The competition between bridging flocculation provoked by polymer adsorption and electrosteric stabilization determines the rheological properties of the suspensions. In the pH range investigated, bridging flocculation predominates at the neutral pH because of the graft of the uncoiled polymer to more than one particle, while at the extreme pH values (pH 3, pH 9) steric or electrosteric stabilization seems to be the predominant mechanism that explains the rheological results. These facts were confirmed by estimating the zirconia particle (or aggregate) diameter in the liquid medium by means of light scattering measurements.     

Rheological and diffusion properties of a dextran-con A polymer in the presence of Insulin and Magnesium

Previous work carried out in our laboratories has focused on the formation and investigation of a dextran and concanavalin A (con A) based gel, which has the ability to alter its conformational structure in the presence and absence of free and terminal glucoses such that a gel–sol phase transition occurs. Here we report the diffusion and rheological investigations in to the effects of the addition of insulin and varyingconcentrations of magnesium chloride hexahydrate (Mg₂Cl₂6H₂O) at 20 and 37 °C. Rheological examination of glucose-sensitive (dextran-con A) gels were conducted using a cone and plate viscometer used in continual rotation and oscillatory modes. The results are interpreted in terms of the structure of the gel network and suggest rheological assessment provides an effective method of assessing the properties of gel systems. The subsequent testing of such formulations in in-vitro diffusion experiments revealed a reduction in the rate of diffusivity in the insulin marker, poly R-478 dye. The performance of this self-regulating drug delivery system has been examined and the addition of insulin and magnesium chloride may alter the way in which the gel operates as a drug delivery device and in the delivery of insulin. This may have implications for other ligands.     

Rheological interpretation of pressure anomalies of aqueous dilute polymer solutions (ADPS) in orifice flow

The response of a considerable number of solutions of several polymers (PEO, HPAM, PAM) with concentrations of less than 100 ppm in orifice flow has been investigated. It is shown that the excess pressure (difference between the ADPS and the solvent total pressure drop) behaves linearly as a function of a superficial strain rate (ratio between a velocity and a length scale). In rheological terms this behaviour is interpreted as the result of a constant elongational viscosity whose values are two to three orders of magnitude larger than the shear viscosity. A formal approach to this phenomenological interpretation is suggested.     

A rheological approach to the stability of humic acid/clay colloidal suspensions

Steady-state, oscillatory, and transient rheological determinations were used to assess the stability of homoionic sodium montmorillonite (NaMt) suspensions at constant ionic strength (10^–2 mol/l NaCl) and different pH values, after adsorption of humic acid (HA) on the particles. The adsorption of the latter was first spectrophotometrically determined, at pH 3 and 9. While at pH 9 adsorption saturation was observed, at pH 3 the adsorption density continued to grow up to the maximum equilibrium HA concentration reached (∼200 mg/l). Considering the similarity between the structure of edge surfaces of NaMt particles and the surfaces of silica and alumina, the adsorption of HA was also investigated on the latter solids. The results suggest that at pH 3 humic acids adsorb preferentially on edge surfaces, mainly through electrostatic attraction with positively charged aluminol groups. This hypothesis is indirectly confirmed by zeta potential, ζ, values: while HA concentration has little effect on ζ for silica, the addition of HA yields the zeta potential of alumina increasingly negative for all pH values. Using shear stress vs shear rate plots, the yield stress of NaMt was determined as a function of particle concentration, C, for pH 3, 5, 7, and 9, with and without addition of 50 mg/l HA. The yield stress, σ_y, was fitted with a power law σ_y∝C ⁿ ; it was found that n values as high as 12 are characteristic of NaMt suspensions at pH 9 in the presence of HA. This indicates a strong stabilizing effect of humic acid. This stabilization was confirmed by oscillometric measurements, as the storage modulus G′ in the viscoelastic linear region also scales with C, displaying large n values at neutral and basic pHs in the presence of HA. The modulus (in the viscoelastic linear region, for a frequency ν=1 Hz) was found to increase with time, but G′ was lower at any time when HA was added, a consequence of the stabilization provided by HA. Similarly, creep-recovery experiments demonstrated that NaMt suspensions containing HA displayed a less elastic behavior, and a permanent deformation. Modeling the results as a Kelvin-Voigt model allowed one to establish a new scaling law of the reciprocal instantaneous deformation with C. As before, high values of n were found for suspensions at pH 9 in the presence of HA.     

Investigation of the band texture occurring in hydroxypropylcellulose solutions using rheo-optical, rheological and small angle light scattering techniques

The band texture occurs in lyotropic and thermotropic main-chain polymers after cessation of flow. This paper begins with a review of work concerned with band texture formation following shear and is followed by the presentation of original results obtained during a recent investigation. The evolution of band texture formation in a Klucel EF, 50% hydroxypropylcellulose (HPC) water solution, has been observed using polarized optical microscopy. The relationship determined between the primary shear rate and the rate of evolution of the band texture is complex and three different behaviours have been observed corresponding to three shear rate regions. Both steady flow and dynamic rheological investigations have been conducted on the HPC solution, the results of which have been related to the optical behaviour of the band texture. Data from steady flow investigations suggest that the viscosity of the solution when the band texture is present, decreases following increasing primary shear rates, is shear thinning and increases linearly with the time following its formation. Dynamic investigations suggest a definite link between the band texture evolution and the evolution of both G′ and G′′. In addition, the perfection of the band texture versus the primary shear rate has been quantified by studying the evolution of tan(δ) following the cessation of the primary shear. Dynamic experiments show that the structure of the band texture remains longer than suggested by the optical aspect of the texture. Small angle light scattering patterns have been correlated with the development of the band texture and confirm the continuing presence of the band texture structure following its optical disappearance. Received: 2 March 1999/Accepted: 26 July 1999     

Molecular dynamics of the glass relaxation process of the soft phase in block copolymers: effect of molecular architecture

To determine the impact of molecular architecture on the molecular dynamics of the glass relaxation processes of soft blocks in different types of block copolymers, model block copolymers with a variation in both molecular architecture and chemical composition were studied. Four block copolymer models, namely, two styrene–butadiene–styrene (S-B-S) block copolymers and two styrene–styrene butadiene–styrene (S-SB-S) were chosen. In each pair of block copolymers, one is linear triblock and the other is star asymmetric. For the sake of comparison, two polybutadiene (PB) homopolymer samples, having similar chain lengths of the PB blocks present in the S-B-S block copolymers, have been investigated. Dynamic mechanical measurements have been carried out for the real and imaginary parts of the complex shear modulus (G′, G”) in the temperature and frequency ranges from −110 to 30 °C and from 10⁻² to 15.9 Hz, respectively. Complete master curves have been constructed for all samples investigated. Moreover, broadband dielectric spectroscopy has been carried out to cover wide temperature and frequency windows, −120 to 0 °C and 10⁻¹ to 10⁷ Hz, respectively. The results showed that the molecular dynamics of the glass relaxation process of the PB or statistical PSB soft phases in the block copolymers is dramatically changed when compared to the PB homopolymer. In addition, the molecular architecture is found to be an important factor in determining the molecular mobility of the soft blocks. The results are discussed in terms of the applied confinement of the counter PS hard phase, block lengths, domain thicknesses and the type of end-to-end junctions between the different polymeric blocks. Paper presented 3rd Annual European Rheology Conference (AERC 2006) April 27–29, 2006, Crete, Greece.     

Effect of polymer bridging on rheological properties of dispersions of charged silica particles in the presence of low-molecular-weight physically adsorbed poly(ethylene oxide)

 The effect of a low-molecular-weight physically adsorbed poly(ethylene oxide) on the rheological behavior of aqueous dispersions of silica particles (as a model system) has been investigated. Particular attention is given to the evolution of the rheological behavior with increasing polymer concentration in the system at different volume fractions of the particles. Experiments were performed in the absence of salt and just the pH of the dispersion was adjusted to 9.5, a condition at which the system is electrostatically stable and electrostatic repulsive forces are long range in nature. It was observed that the shear viscosity and the linear viscoelastic functions of the dispersion at 55 vol% increase initially through the addition of polymer, reach a maximum, and then decrease to a minimum with further addition of polymer to the system. At higher polymer concentrations, there may be an increase in the viscosity of the dispersion owing to an increase in the concentration of free polymer chains in the medium causing depletion flocculation in the system. The increase in the rheological behavior of the dispersion at low polymer coverage is attributed to polymer bridging flocculation caused by a low-molecular-weight poly(ethylene oxide) in the system. Comparison of the data given here with the results of earlier studies on the viscosity behavior of the system in the presence of salt (0.01 M) indicates that the range of the electrostatic repulsion has a significant role in the rheological behavior of the system. Received: 7 February 2001 Accepted: 18 October 2001     

Fabrication of submicron barium sulfate aggregates in the presence of ethylenediaminetetraacetic acid anions

Barium sulfate aggregates with an average size of 0.5 μm were synthesized at pH 7, directed by ethylenediaminetetraacetic acid (EDTA) anions. The particle morphology, chemical composition, and size distribution of the BaSO₄ aggregates were characterized. The as-synthesized BaSO₄ particles were spherical and comprised many interconnected nanoballs, of which the surface properties were affected by the EDTA anions. The adsorption of EDTA anions reversed the charge and weakened the surface polarity of BaSO₄, instigating the formation of aggregates by a self-assembly and transformation process. The resulting BaSO₄ particles at pH 9–10 were ellipsoidal and featured smooth surfaces. Based on the zeta potential of BaSO₄, variations in the morphology induced by changes in pH were closely related to the adsorption of mono- and multi-valent anions onto the electrical double layer of BaSO₄.     

Similarity solutions for MHD thermosolutal Marangoni convection over a flat surface in the presence of heat generation or absorption effects

The problem of steady, laminar, thermosolutal Marangoni convection flow of an electrically-conducting fluid along a vertical permeable surface in the presence of a magnetic field, heat generation or absorption and a first-order chemical reaction effects is studied numerically. The general governing partial differential equations are converted into a set of self-similar equations using unique similarity transformations. Numerical solution of the similarity equations is performed using an implicit, iterative, tri-diagonal finite-difference method. Comparisons with previously published work is performed and the results are found to be in excellent agreement. Approximate analytical results for the temperature and concentration profiles as well as the local Nusselt and sherwood numbers are obtained for the conditions of small and large Prandtl and Schmidt numbers are obtained and favorably compared with the numerical solutions. The effects of Hartmann number, heat generation or absorption coefficient, the suction or injection parameter, the thermo-solutal surface tension ratio and the chemical reaction coefficient on the velocity, temperature and concentration profiles as well as quantitites related to the wall velocity, boundary-layer mass flow rate and the Nusselt and Sherwood numbers are presented in graphical and tabular form and discussed. It is found that a first-order chemical reaction increases all of the wall velocity, Nusselt and Sherwood numbers while it decreases the mass flow rate in the boundary layer. Also, as the thermo-solutal surface tension ratio is increased, all of the wall velocity, boundary-layer mass flow rate and the Nusselt and Sherwood numbers are predicted to increase. However, the exact opposite behavior is predicted as the magnetic field strength is increased.     

Perfecting a method of micro-analysis of water and acetic acid in a cocoa bean in the course of drying: applying to determine transportation coefficients

This article is about the study of the diffusion of water and acetic acid in a grain of cocoa in course of drying. The authors present a method of microanalysis which enables the analysis of each little slice of the grain : a precise measurement of each slice is realised in view of the analysis from the centre to the surface of the grain with the aid of a cutting apparatus, designed and realised to this effect. At each instant of the drying process, the profiles of water and acetic acid contents are then determined. A one dimensional diffusion model enables a shell by shell evaluation of the diffusion of water and acid in the cocoa grain. The results obtained show an augmentation of transport coefficients in course of drying. We however observe a decrease of the diffusion coefficient of water to the low moisture content : what makes us think of the appearance of crusting phenomenon.