Frequency dependence of intrinsic viscosity of macromolecules with finite internal viscosity

In order to explain the observed nonvanishing limiting value of dynamic intrinsic viscosity of polymer solutions at ω = ∞ one has considered the necklace model with finite resistance to the rate of coil deformation introduced long ago by Cerf for the study of gradient dependence of intrinsic viscosity and streaming birefringence. The calculation need not take into account change of hydrodynamic interaction as a consequence of coil deformation because the experimental data are always either obtained at very low gradient or extrapolated to zero gradient so that in the experiment the macromolecule has the same conformation as in the solution at rest. The model indeed yields a finite [η]′_{ω = ∞} in good agreement with experiments on polystyrene in Aroclor. According to the theory [η]′_{ω = ∞}/[η]₀ decreases with increasing molecular weight as M^?1 and M^?1/2 for the free-draining and impermeable coil, respectively. The absolute limiting value [η]_∞′, therefore turns out to be nearly independent of M, at least for small values of internal viscosity. From the observed value [η]_∞′/[η₀] one can obtain the coefficient of internal viscosity of the macromolecule. The value for polystyrene in Aroclor calculated from dynamic experiments on rather concentrated solutions is close to that derived by Cerf from streaming birefringence observations of polystyrene in a series of solvents of widely differing viscosity.     

Rheological properties of linear and crosslinked polymer blends: Relation between crosslink density and enhancement of elongational viscosity

Strain‐hardening behavior in the elongational viscosity of binary blends composed of a linear polymer and a crosslinked polymer, in which the molecular chains of the linear polymer were incorporated into the network chains of the crosslinked polymer, was studied. Blending the crosslinked polymer characterized as the gel just beyond the sol–gel transition point greatly enhanced the strain‐hardening behavior in the elongational viscosity, even though the amount of the crosslinked polymer was only 0.3 wt %. However, the crosslinked polymer, which was far beyond or below the sol–gel transition point, had little influence on the elongational viscosity as well as the shear viscosity. The stretching of the chain sections between the crosslink points was responsible for the strain‐hardening behavior. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 228–235, 2001     

The influence of internal phase viscosity on the viscosity of concentrated water-in-oil emulsions

Summary The influence of the viscosity of the internal phase on the viscosity of concentrated water-in-oil emulsions has been investigated and found to be negligible. It is indicated that thechemical nature of the dispersed medium may be of importance, however, with particular reference to its relationship to the stabilising agent, and an example of this is given. In liquid suspensions the ratio of the viscosities of the two phases is of importance in the transmission of viscous effects from the continuous to the disperse medium. This is not found to be the case for the emulsions examined, and the significance of the rigid structure of the interfacial film in this respect is discussed.

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Zusammenfassung Der Einflu? der Viskosit?t der inneren Phase auf die Viskosit?t von konzentriertem Wasser-in-?lemulsion wurde untersucht. Er ist vernachl?ssigbar. Dagegen ist die chemische Struktur des dispergierten Mediums wichtig, besonders im Zusammenhang mit dem Stabilisator, wie ein Beispiel zeigt. Da in flüssigen Suspensionen das Verh?ltnis der Viskosit?ten der beiden Phasen für die Berechnung der Viskosit?t der Dispersion aus denen der beiden Medien eine Rolle spielen sollte und dies bei den untersuchten Emulsionen nicht der Fall war, wird eine Wirkung von festen Grenzfl?chenfilmen für eine Erkl?rung diskutiert.

     

A constant shear stress strategy for establishing in situ viscosity models of photoinduced polymerization of acrylamide

In situ viscosity kinetics models for blue light induced radical polymerization of acrylamide (AM) were proposed and established with camphorquinone/4-(dimethylamino)-2-ethylbenzoate/diphenyl iodonium hexafluorophosphateas the photoinitiators. In order to minimize the impact of shear effect on polymer network, a constant shear stress technique of photo-rheometry was proposed to characterize in-situ viscosity behavior of acrylamide solution during the photopolymerization. The effect of various factors, for example, the dosages of initiator, monomer, and light intensities, on viscosity, polymerization and gelation behavior of AM solution was systematically analyzed. The viscosity advancement behavior was shaped by the joint action of the movement, growth and entanglement of molecular chains, and shear orientation. Different power-law kinetic models were found in three curves, time-related viscosity, shear rate-related viscosity and time-related shear rate. Such school of thought on constructing the viscosity advancement model provides a new theory and method of systematical studying on the photorheological theories. Furthermore, a trinitarian theoretical model that represented the access from the microscopic kinetics of free radical polymerization to the movement behavior of polymer chains was successfully established by mapping the photoinduced viscosity kinetics model onto the polymerization and crosslinking kinetics model.     

Yield stress and viscoelastic properties of high internal phase ratio emulsions

 The rheology of high internal phase ratio oil-in-water emulsions was investigated using a controlled-stress rheometer. The dispersed-phase (oil) concentration was varied from 71.24 to 89.61% by volume. Three different types of rheological experiments were conducted for each emulsion, namely: steady shear, oscillatory shear, and creep/recovery experiments. All the emulsions investigated in this study possess a yield stress. The yield-stress values obtained from different rheological experiments for the same emulsion show good agreement with each other. The yield-stress value increases exponentially with an increase in the dispersed-phase concentration. The yield-stress data of this study can be described quite well with the Princen and Kiss equation for high internal phase ratio emulsions provided that the thickness of the interdroplet films is taken into account. For any given emulsion, the storage modulus, measured in the linear viscoelastic region, is found to be constant, independent of the frequency, indicating a solid-like behaviour. The value of the storage modulus increases with an increase in the dispersed-phase concentration. The storage modulus data are interpreted in terms of the Princen and Kiss equation. Received: 23 October 1998 Accepted in revised form: 18 February 1999     

Rheological complexity in simple chain models

Dynamical properties of short freely jointed and freely rotating chains are studied using molecular dynamics simulations. These results are combined with those of previous studies, and the degree of rheological complexity of the two models is assessed. New results are based on an improved analysis procedure of the rotational relaxation of the second Legendre polynomials of the end-to-end vector in terms of the Kohlrausch-Williams-Watts (KWW) function. Increased accuracy permits the variation of the KWW stretching exponent beta to be tracked over a wide range of state points. The smoothness of beta as a function of packing fraction eta is a testimony both to the accuracy of the analytical methods and the appropriateness of (eta(0)-eta) as a measure of the distance to the ideal glass transition at eta(0). Relatively direct comparison is made with experiment by viewing beta as a function of the KWW relaxation time tau(KWW). The simulation results are found to be typical of small molecular glass formers. Several manifestations of rheological complexity are considered. First, the proportionality of alpha-relaxation times is explored by the comparison of translational to rotational motion (i.e., the Debye-Stokes-Einstein relation), of motion on different length scales (i.e., the Stokes-Einstein relation), and of rotational motion at intermediate times to that at long time. Second, the range of time-temperature superposition master curve behavior is assessed. Third, the variation of beta across state points is tracked. Although no particulate model of a liquid is rigorously rheologically simple, we find freely jointed chains closely approximated this idealization, while freely rotating chains display distinctly complex dynamical features.     

Rheological properties of polymer melts

A new method of treating experimental data on the viscous and viscoelastic properties of various polymer melts is suggested. The dependence of the apparent viscosity on the molecular weight, temperature and shear stress can be represented as the product of three independent functions, each of them having a single argument. All three functions are universal, at least in first approximation, and the dependence of the apparent viscosity on the variables indicated is determined by two parameters (glass transition temperature and critical molecular weight), characteristic of each homologous polymer series. The viscoelastic characteristics (dynamic, relaxation, creep, as well as relaxation and retardation spectra) of polymer melts are universal in shape in the linear region and contain only one individual polymer parameter, viz., maximum Newtonian viscosity. It is shown that upon normalization of certain nonlinear characteristics with respect to the maximum Newtonian viscosity, they can also be represented in the universal form.     

Rheological properties of sulfate cellulose

Rheological properties of concentrated aqueous solutions of sulfate cellulose prepared by various sulfation methods were studied. Information on the variation of structure of the concentrated solutions under action of external forces during viscous current depending on sulfate cellulose molecular parameters was obtained.     

Rheological properties of filled polymers

The rheological properties of two model suspensions using a Newtonian polymeric matrix are presented and discussed in light of results presented in the literature. It is shown that particle-particle interactions in concentrated suspensions are responsible for a gel-type behavior at very small strain and strain hardening at a critical strain. Suspensions of concentrated colloidal particles in a Newtonian matrix behave like typical viscoelastic molten polymers, but the properties are strongly dependent on the solids dispersion, and strain at small strain. A simple rheological model is proposed to describe the shear viscosity of these suspensions.     

Rheological properties of alcohol-coal slurries

The rheological properties of coal slurries prepared using lower alcohols of the ethanol-pentanol series as dispersion media are investigated. It is shown that an increase in the length of alcohol hydrocarbon radical leads to a rise in the viscosity and shear stress of the alcohol-coal slurries.     

Rheological properties of ethylene-propylene-diene elastomers

The processing of rubbers comprises a combination of complicated processes which realization almost always requires knowledge of their rheological behavior. The goal of the present work is to describe the rheological behavior of the EPDM vulcanizates via rotational rheometry. The effect of the cross-linking density and plasticizer content on the rheological behavior of the EPDM vulcanizates is described. The viscoelastic characteristics of the samples are defined from the frequency dependences of elasticity modulus G' and loss modulus G".     

Rheological properties of polyacrylamide-based hydrogels

Rheological properties of hydrogels of polyacrylamide-based polyelectrolytes were studied. The dependence of the rheological characteristics of the gels on the content of an organic modifier and parameters of a mechanical action was disclosed. The range of parameters where the hydrogels of modified polyacrylamide demonstrated the highest mechanical strength was determined.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 840–843.Original Russian Text Copyright © 2004 by Shevchenko, Ulrikh, Yakovchenko, Pirogov, Smirnov.     

Rheological properties of doughs with buckwheat and quinoa additives

Rheological properties of doughs prepared from wheat flour with buckwheat and quinoa flour addition (2.5 mass %, 5.0 mass %, 7.5 mass %, and 10 mass %) were investigated using a farinograph and compared with those of standard dough (without addition of pseudocereals). The following characteristics were determined: water absorption capacity, water consumption, dough growth time, level of dough softening, dough stability, mechanical resistance, and dough elasticity. Dough stability showed a linear decrease with the increasing content of pseudocereals. Doughs containing quinoa flour were more stable than those with buckwheat flour addition. Dough growth time was reduced with increasing amounts of buckwheat flour but it was not affected in the case of quinoa flour addition. From the comparison of the studied characteristics it can be concluded that an addition of lower amounts of quinoa (up to 5.0 mass %) to wheat flour will not significantly impair rheological properties of the dough but provides for enhanced nutritional value of the prepared bakery products.     

Topological and symmetry features of internal rotation potetial in molecules with two rotors

The detailed knowledge of the potential energy surface features of a molecule in a given electronic state (within the Born-Oppenheimer approximation), is very interesting both from the spectroscopic and from configurational analysis point of view.The study of the topological and symmetry properties of potential energy can be great help in order to characterize and understand it, especially when the number of internal coordinates increases.In the present work, we show an application of these methods to the study of the internal rotation potential in a molecule with two three-fold tops as ether.     

One parameter friction theory models for viscosity

In this work the friction theory (f-theory) for viscosity modeling is used in conjunction with the SRK, PR and PRSV cubic equations of state in order to develop three one parameter general models for viscosity prediction. The models are considered one parameter models because they only require a characteristic critical velocity, which is a parameter normally not tabulated. The models use these rather simple cubic equations of state as a basis to obtain accurate modeling of the viscosity of fluids for wide ranges of temperature and pressure. The general models presented in this work are based on the viscosity behavior of n-alkanes from methane to n-octadecane. Although best performance is obtained for the considered n-alkanes, a good model performance is also obtained for other systems. Thus, recommended characteristic critical viscosity values for several systems are also reported in this work. However, in the case of n-alkanes, an empirical equation for the characteristic critical viscosity is provided so that no additional parameters are required. In addition, with the use of simple mixing rules, the viscosity of several binary to quaternary n-alkane mixtures can also be predicted with a satisfactory accuracy.     

Rheological properties of nanopowder alumina coated with adsorbed fatty acids

The rheological properties of a nanosized alumina powder coated with fatty acid steric stabilizers of varying chain length were investigated. The storage and loss moduli of the complex modulus were measured to characterize the behavior of the flocculated systems. As chain length increased, there was a transition from an elastic response to fluid behavior. However, the fluid system developed elastic characteristics at relatively low volume fractions of 22%. The length of the steric barrier required to produce the fluid dispersion was estimated to be approximately 2 nm and correlates with attractive interactions on the order of the system thermal energy. Moreover, in the flocculated systems, the storage modulus was found to be higher than reported previously in the literature. These higher values were related to the additional attractive forces due to van der Waals attractions between the hydrocarbon tails of the adsorbed fatty acid layers.     

Rheological properties in cholesteric and blue phases of cholesteryl isostearyl carbonate: viscosity and effect of electric field on the rheology

Rheological property (shear stress versus shear rate) of cholesteryl isostearyl carbonate (CISC) is measured as a function of temperature, finding that, like some other cholesteryl derivatives, CISC has blue phases (BPs) between the cholesteric (Ch) and the isotropic (I) phases. In the Ch and the BP phases, measurements of the electrorheological (ER) effect, of the electric field on the rheology, are made; a slight increase of the viscosity is observed in the BPs and no ER effect in the Ch phase, which is contrasted to the distinct ER effect in the nematic (N) and the smectic A (SmA) phases.