Influence of the electrical interface properties on the rheological behavior of sonicated soy lecithin dispersions

A significant effect, on the rheological behavior, due to the electrical properties of vesicles formed from concentrated soy lecithin dispersions have been studied in this work. The rheopectic behavior of concentrated soy lecithin dispersions (120, 150, 180, 210 and 240 g L-1) prepared by swelling-light sonication-freezing-unfreezing procedure is studied and it is specially emphasized on the transition under steady shear from lamellar phase of planar sheets to closed structures as multilamellar vesicles. Samples have been exposed to a different number of sonication cycles (from 0 to 100) and the changes in the hysteresis loop area, the apparent viscosity and the electrophoretic mobility have been studied. When the number of sonication cycles increases, the size and number of bilayers of these multilamellar vesicles decrease and therefore the total number of the vesicles and the volume fraction occupied by them show an increase.     

Rheological and swelling behavior of semi‐interpenetrating networks of polyacrylamide and scleroglucan

Preparation and characterization of novel semi‐interpenetrating polymer network (semi‐IPN) hydrogels based on partially hydrolyzed polyacrylamide (HPAM) and scleroglucan solution crosslinked with chromium triacetate are described. Effects of scleroglucan concentration on the gelation process and swelling behavior of synthesized hydrogels in different media were investigated using dynamic rheometery and swelling tests, respectively. Oscillatory shear rheology showed that the limiting storage modulus of the semi‐IPN gels increased with increase in scleroglucan concentration. It was also found that the viscous energy dissipating properties of the semi‐IPN gels decreased with increase in the crosslinker concentration of the gelation system. In addition, the loss factor slightly decreased by increasing the scleroglucan content, indicating that the viscous properties of this gelling system decreased more than its elastic properties. The swelling tests showed that the equilibrium swelling ratio (ESR) of the semi‐IPN networks decreased with increase in scleroglucan content, due to the decrease of ionic groups of polyelectrolyte hydrogel. However, the semi‐IPN gels showed lower salt sensitivity in synthetic oil reservoir water as compared with HPAM gels. Therefore, these semi‐IPN hydrogels may be considered potentially good candidates for enhanced oil recovery (EOR) applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface properties and swelling behaviour of hyperbranched polyester films in aqueous media

Thin films of hydroxyl (POH) and carboxyl (PCOOH) terminated aromatic hyperbranched polyesters (HBPs) were prepared by spin coating on silicon wafers and subsequently annealed above their glass transition temperature (T_g). The surface properties and the swelling behaviour of these films in aqueous buffer solutions were studied as a function of annealing time using contact angle measurements and ellipsometry. Non-annealed films were hydrophilic with surface free energies of 51 mJ/m² for POH and 49 mJ/m² for PCOOH, respectively. The swelling behaviour of the polymer films in buffer solution with pH 7.4 was described in terms of changes of the thickness and effective refractive index of the swollen layer. Under identical conditions a lower water uptake was found for hydroxyl terminated HBPs (POH) which were annealed more then 2 h. The lower water uptake correlates with the surface properties of the films. The annealed films were less hydrophilic. Their surface free energy was 38 mJ/m² independent of the annealing. Films of carboxyl terminated HBPs (PCOOH) showed similar surface properties after annealing. However, these films were unstable under the same conditions in aqueous solutions. Stable PCOOH films were obtained by additional covalent binding to the substrate using an epoxy silane as a coupling agent.     

Evaluation of corrosion behaviour of selected metallic samples by electrochemical noise measurements

Electrochemical noise (EN) denotes spontaneous fluctuations in potential and current originating from the corrosion processes. In this work, EN was measured for three model metallic materials of known corrosion properties: Al, Fe and Fe30Al. Corrosion behaviour was assessed in neutral, acidic or alkaline solutions containing 4 wt% NaCl. Correlation between the electrochemical noise and corrosion intensity was established on the basis of appropriate treatment of the recorded numerical data and ex situ examination of the specimen surface. The parameter, referred to as EN resistance, allowed relatively simple and rapid evaluation of the corrosion behaviour of the investigated metallic materials.     

Microstructure and rheological properties of polybutadienes

The viscosities, rubbery deformations, densities, and their dependence on temperature have been measured for several series of polybutadienes with molecular weights ranging from 5,000 to 400,000 and differing in proportions of cis and trans structures (cis content from 40 to 95%). On the basis of the viscosity measurements the critical molecular weight M_c has been determined, corresponding to a sharp change in the nature of the viscosity versus molecular weight dependence. Rubbery deformations are displayed pronouncedly in specimens with M > M_c and are closely related to the appearance of non-Newtonian flow. The value of M_c depends on the relative content of cis and trans forms. When M > M_c, the initial viscosity is a parameter sensitive to the microstructure of polybutadienes, so that with at a single molecular weight, depending on the ratio of cis and trans units, the viscosity may vary over a more than tenfold range. The glass transition temperature and activation energy of viscous flow rise regularly with increasing trans content in the polymer chain, these parameters becoming independent of the molecular weight for specimens with M > M_c within a series of polybutadienes of equal microtacticity. Thermomechanical investigations of polybutadienes also made it possible to define more accurately the boundaries of the crystallization region and the dependence of the melting point on the microtacticity. The results obtained are discussed on the basis of modern ideas of polymer structure.     

Structure and rheological properties of PVC melts

The Theological properties of PVC compounds reflect the state of the flow units. The steady state structure which may be found in PVC melts is predicted to depend on the interaction of stresses in simple flow and temperatures for transition from rubberlike solid to liquid state and transition from a liquid state containing crystallite aggregates to a liquid state without crystallite aggregates, called the gel destruction temperature T_d and the dynamic melting temperature T^dyn_m, respectively. The model predictions for T_d and T^dyn_m are compared with experimental data.     

Thermal and rheological properties of gelatin-dextran hydrogels

Hydrogels prepared by crosslinkage of gelatin with dextran dialdehyde have been characterized by dynamic shear oscillation measurements at small strain. Isothermal as well as temperature scan measurements were performed. The results obtained demonstrated that the final polymer network is a result of a chemical gelatin-dextran dialdehyde interaction as well as a gelatin-gelatin (physical association) and a polymer-solvent interaction. This balance is strongly dependent on the composition of the system, the polymer concentration, the storage temperature and the storage time.We found that a short cryogenic treatment at –20°C of physically structured gels, significantly increases the chemical crosslinkage. DSC measurements at low cooling rate confirm these results and demonstrate a chemical reaction enthalpy contribution.This work was supported by the Flemish Institute for Science and Technology (IWT) and the Belgian Government (PAI-III-40).The authors also express their gratitude to Systèmes Bio Industries Benelux for providing free samples of well characterized gelatin.     

Copolymerisation properties of siloxy‐substituted bis(indenyl)zirconocene catalysts: modified rheological behaviour

The combination of the copolymerisation ability and vinyl end group selectivity of siloxy substitution of ethylene‐bridged bis(indenyl)zirconium dichlorides suggest these catalyst as potential ones for the production of polyethylene containing small amounts of long chain branching. The role of the polymerisation conditions with these highly active catalysts can clearly be seen. Furthermore low contents of multiple branches may occur, even though the probability of attaching several macromonomers into one chain is low. The effect on melt rheological behaviour depends on both the amount of long chain branching and the length of the branch. Moreover the position of the siloxy group is very important. Polymers synthesized with catalysts, where the siloxy group is in position 1, give peculiar rheological behaviour resembling cross‐linked networks although the polymers are completely soluble.     

On rheological properties of polydisperse polymers

An investigation has been carried out into the effect of the fractional composition on the rheological (flow and elastic) properties of a system, using mixtures of polybutadienes with narrow molecularweight distribution (MWD). For mixtures of high-molecular-weight components, the initial Newtonian viscosity is determined by the weight-average molecular weight: $\text{η}{}_0\text{～}\text{M}{}^{\mathrm{\alpha }}{}_{\mathrm{<mtext>w</mtext>}}$; when low-molecular weight components are introduced, it is also determined by the MWD moment ratio. The characteristic relaxation time of a system is determined by the z-average molecular weight: , and in the general case α₁ ≠ α. A new model has been proposed to explain the non-Newtonian phenomenon as a consequence of the existence of a molecular-weight distribution. According to this model, as the shear rate increases the high-molecular-weight components gradually (at their critical rates) pass over to the high-elastic state. Therefore, at high shear rates, their contribution to viscous losses of a polydisperse polymer is associated with their behaviour as a viscoelastic filler in a viscous liquid.     

Some rheological properties of molten polypropylene

The following measurements were carried out on the melts of two samples of polypropylene, one with a narrow and one with a broad molecular weight distribution: viscosity in steady shear flow, dynamic storage and loss moduli, total normal thrust in cone-and-plate apparatus, and flow birefringence. The validity of various theoretical interrelations between the measured quantities is checked. The influence of molecular weight distribution is qualitatively discussed.     

Preliminary FTIR study of swelling of oriented polyamide 11 samples

The MIR spectra of oriented films of polyamide 11, swollen with various organic liquids, have been investigated by Fourier transform infrared spectroscopy. The main modifications result from the interaction of the amide groups with polar organic molecules. The vibration modes involving the NH and CO stretchings, i.e. amide A and B and amide I bands, are deeply modified by swelling.     

Viscoelastic and rheological properties of syndiotactic 1,2-polybutadiene

The physicomechanical, viscoelastic, and rheological characteristics of syndiotactic 1,2-polybutadiene were studied and compared with those of the analogs produced in other countries.     

Dynamical and rheological properties of soft colloid suspensions

Soft colloids comprise a wide class of materials, ranging from linear polymers over polymeric assemblies, such as star polymers and dendrimers, to vesicles, capsules, and even cells. Suspensions of such colloids exhibit remarkable responses to imposed flow fields. This is related to their ability to undergo conformational changes and elastic deformations, and the adaptation of their dynamical behavior. The rational design of soft particles for targeted applications or the unraveling of their biological function requires an understanding of the relation between their microscopic properties and their macroscopic response. Here, mesoscale computer simulations provide an invaluable tool to tackle the broad range of length and time scales. In this article, we discuss recent theoretical and simulation results on the rheological behavior of ultrasoft polymeric colloids, vesicles, capsules, and cells. The properties of both, individual particles and semi-dilute suspensions, are addressed.     

Synthesis and rheological properties of cation-exchanged Laponite suspensions

In this paper we report our new approach to synthesize cation-exchanged Laponite suspensions. General observations of the prepared samples indicated that an aqueous suspension of 1 wt.% Laponite retained its free flowing liquid phase characteristics even after aging for several weeks. When bivalent cationic metals (Cu, Co, Ni) were ablated into the suspension, the strong charge of the crystal face was reduced and, on standing, the suspension gelled becoming highly viscous. This sol–gel transition was induced by the formation of a space-filled structure due to both van der Waals and electrostatic bonds between the positively charged rims and negatively charged faces. Rheological properties of such prepared suspensions were measured using a Brookfield DV-II Pro Viscometer with a small sample adapter (SSA18/13RPY). The yield strengths of 2.2 N/m², 3.2 N/m², and 1.7 N/m² were measured for Ni-, Co-, and Cu-modified Laponite suspensions, respectively. These yield strengths are sufficiently high for suspending weighting materials such as barite which requires the gel strength of about 0.5 N/m².     

A model representation of the rheological behaviour of wheat-flour dough

Summary A unit model, consisting of three elastic, three frictional and two viscous elements, is proposed to account for the complex rheological behaviour of flour doughs under tension and during relaxation. Such linear units, however, must form part of a continuous and non-linear spectrum of properties if strain hardening, structural viscosity (shear-rate softening) and other complex modes of behaviour are to be described. Since the purpose of rheological models is to simplify phenomenologically complex behaviour, it is better to devise units consisting of linear components which are associated with a non-linear distribution, rather than to postulate non-linear components of the units.

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Zusammenfassung Ein Modell, aus drei elastischen, drei Friktions- und zwei viskosen Elementen bestehend, wird zur Erkl?rung des komplexen rheologischen Verhaltens von Mehlteigen unter Spannung und w?hrend der Relaxation vorgeschlagen. Die linearen Elemente müssen jedoch ein kontinuierliches nichtlineares Spektrum der Eigenschaften formulieren lassen, wenn Spannungsverfestigung, Strukturviskosit?t (Schergeschwindigkeitserweichen) und andere komplexe Züge des Verhaltens dargestellt werden sollen. Da der Sinn rheologischer Modelle darin besteht, ph?nomenologisch komplexes Verhalten vereinfacht zu formulieren, scheint es besser zu sein, Elemente aus linearen Komponenten zu w?hlen, die auf nichtlineare Weise in ihrer Anordnung verkoppelt werden, als von vornherein nichtlineare Komponenten für das einzelne Element zu postulieren.

     

Experimental determination of rheological properties of polydimethylsiloxane

A series of linear polydimethylsiloxane of different molecular weight and with reduced polydispersity were prepared by partial fractionation of commercial products. The rheological functions, i.e. zero shear viscosity (η₀), first and second normal stress coefficients (Ψ₁₀ and Ψ₂₀), of the materials were experimentally measured by conventional rotational rheometers and by a rotation rod apparatus. The relationships between molecular structure (molecular weight and polydispersity index) and rheological functions are presented and discussed on the basis of equations proposed in the literature. Zero shear viscosity data conform to the well-known dependence on a power 3.5 of molecular weight. However, a consistently stronger influence of molecular weight over Ψ₁₀ and Ψ₂₀ is found. The influence of polydispersity over Ψ₁₀ is also analyzed.     

Entropic effects on the rheological behaviour of n-eicosane and comparison with n-heptadecane

Abstract

The motivation for this study is the review by Timusk and Statt [Rep. Prog. Phys. 62, 61 (1999)] on the pseudogap in high-temperature superconductors. Here, we confront the experimental data they present, plus that of Norman et al. [Nature 392, 157 (1998)] on the Fermi surface in underdoped high-T_c materials with the theoretical asymptotic scenario of precursor r space Boson formation. This reveals no inconsistencies with available observations concerning electron (hole) liquids flowing through such underdoped cuprates with their antiferromagnetic spin fluctuations.     

Thermal and rheological behaviour of some random aromatic polyethersulfone/polyetherethersulfone copolymers

The thermal and rheological behaviour of seven random Cl-ended aromatic PES/PEES copolymers (M_n ≈ 9500 g mol⁻¹), at various PES/PEES repeating unit ratios, was studied. The glass transition temperatures (T_g), determined by DSC experiments, showed a dependence on copolymer composition significantly different from the ideal linear behaviour expected on the basis of Fox equation. Degradations were carried out in the scanning mode, under flowing nitrogen, in the temperature range 35-650 °C and a single degradation stage was observed for all copolymers. The initial decomposition temperatures (T_i) and the half decomposition temperatures (T_1/2) were directly determined by TG curves, while the apparent activation energies of degradation (E_a) were obtained by the Kissinger method. In addition, the complex viscosity (η^∗) of molten copolymers was determined in experimental conditions of linear viscoelasticity. T_i, T_1/2, E_a, and η^∗ values were depending on copolymer composition, showing a trend similar to that of T_g values. The results obtained were discussed and interpreted.