Development of a predictive model for polymer/solvent diffusion coefficient calculations

A new calculation procedure for free‐volume parameters is considered in this work by using viscosity prediction methods and the Levenberg‐Marquardt calculation scheme. All parameters used in the Vrentas–Duda free‐volume theory can be estimated from pure component properties. The prediction results are compared with experimental data for some polymer/solvent systems. The diffusion coefficient calculated by Vrentas–Duda theory can be used in the modeling of membrane separation processes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dynamic photorheological analysis of photopolymerizable urethane dimethacrylate resins with varying diluent content and light fluence

The in situ measurement of dynamic changes in viscosity induced by illumination has been performed on a range of photosensitive urethane dimethacrylates (UDMA) evaluating the response at three different illuminations intensities (1, 2, and 5 W cm^?2) and at three different diluent concentrations (15, 30, and 50%), using 1,6‐hexanediol dimethacrylate (HDDMA). The initial viscosity value ranged between 1 and 10 Pa s for the mixtures with final viscosities approaching 1 × 10⁷ Pa s after illumination. The initial rise in viscosity was analyzed using an exponential model with an exponent ranging from 1.0 to 2.5 with time under exposure. Higher conversion rates were observed with both higher intensity and lower HDDMA content. The analytical approach taken here could aid in developing more sophisticated models that consider simultaneous flow and cure advancement in other thermosets. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

KINEMATIC VISCOSITY-TEMPERATURE BEHAVIOR OF HEAVY TBP-FRACTIONS (455°C+) OF ARABIAN CRUDE OILS

A generalized kinematic viscosity-temperature correlation for undefined liquid heavy petroleum fractions has been developed to represent the data for a wide range of temperature from 100°C to 200°C. The correlation is based on the experimental kinematic viscosity data of true boiling point fractions of four Arabian crude oils. The characterization property required for estimation is 50% boiling point. The proposed correlation fits the experimental data with an overall absolute error of 6.1%. Experimental measurements of kinematic viscosity of heavy true boiling point fractions of Arabian crude oils were also obtained in order to develop the proposed correlation.     

Rheological behaviour of processed avocado pulp emulsions

Shear rate vs. shear stress data were obtained on avocado pulp in water emulsions using a concentric cylinder rheometer and fitted to a power law model. Dilution, as volume fraction of water, had a pronounced effect on the apparent viscosity of the pulp emulsions and the Richardson equation, (η_R= exp.( a φ) for the emulsion viscosity fitted the data well. A mean slope coefficient, a , of 4.57 can be used as a first approximation. Enzymatic treatment (40°C, 1 h), is slightly more effective than thermal treatment (65°C, 1 h), in reducing the initial apparent viscosity of the pulp-water emulsions     

High-Pressure (up to 140 MPa) Dynamic Viscosity of the Methane and Toluene System: Measurements and Comparative Study of Some Representative Models

The dynamic viscosity of toluene and methane mixtures containing 25.03, 37.19, 49.95, 64.11, and 95.00 mol% methane has been measured using a falling-body viscometer. The measurements (280 data points) have been performed in the temperature range 293.15 to 373.15 K and at pressures up to 140 MPa. The data have been discussed in the framework of recent representative models (hard-sphere scheme, friction theory, and free-volume model) as well as with simple mixing laws and empirical models (particularly the LBC model and the self-referencing model) used in the literature. This comparative study shows that the average absolute deviation of the models is between 4.9 and 26.8%, and the maximum deviation is between 11.6 and 49.5%.     

Correlation of high-pressure thermal conductivity,viscosity, and diffusion coefficients for n-alkanes

Thermal conductivity, viscosity, and self-diffusion coefficient data for liquid n-alkanes are satisfactorily correlated simultaneously by a method based on the hard-sphere theory of transport properties. Universal curves are developed for the reduced transport properties ^*, ^*, and D ^* as a function of the reduced volume. A consistent set of equations is derived for the characteristic volume and for the parameters R , R , and R _D, introduced to account for the nonsphericity and roughness of the molecules. The temperature range of the above scheme extends from 110 to 370 K, and the pressure range up to 650 MPa.     

Viscosities of nonelectrolyte liquid mixtures. III. Selected binary and quaternary mixtures

This paper is the final in a series of three viscosity and density studies of pure n-alkanes and selected binary and quaternary mixtures. A standard U-tube viscometer was used for viscosity measurements, and a Pyrex flask-type pycnometer was used for density determinations. Results are given here for pure alkane and selected binary mixtures of n-tetradecane + n-octane, for selected quaternary mixtures of n-hexadecane + n-dodecane + n-decane + n-hexane, and for pure and selected quaternary mixtures of n-hexadecane + n-dodecane + n-nonane + n-heptane at 303.16 and 308.16 K. The principle of congruence was tested, as was the Grunberg and Nissan equation, as they have been shown to be useful as prediction techniques for other n-alkane binary mixtures. Comparisons were made between the two groups of quaternary alkane mixtures and the binary n-tetradecane + n-octane mixtures of the same pseudo composition to understand better the dependence of mixture viscosities on the composition parameter.     

On the use of the WLF model in polymers and foods.

The validity of the WLF model with fixed "universal" coefficients was tested against that of the model original form with variable coefficients using published coefficients of polymers and amorphous sugars crystallization and viscosity data. The disagreement between the two versions of the model is particularly large at temperature ranges starting about 20 to 30 degrees K above the glass transition or reference temperature, excluding the former from being a model of general applicability. Because the WLF model mathematical structure entails the existence of an almost linear region near the reference temperature, establishment of its validity as a kinetic model and meaningful determination of its constants requires data spread over an extended temperature range, especially when the experimental results have a scatter.     

Correlation and prediction of dense fluid transport coefficients. I. n-alkanes

Recent accurate measurements of the self-diffusion coefficient for n-hexadecane and n-octane and of the viscosity coefficient for n-heptane, n-nonane, and n-undecane over wide pressure ranges have been used to provide a critical test of a previously described method, based on consideration of hard-sphere theory, for the correlation of transport coefficient data. It is found that changes are required to the universal curve for the reduced viscosity coefficient as a function of reduced volume and, also, to the parameters R _D, R , and R which were introduced to account for effects of nonspherical molecular shape. The scheme now accounts most satisfactorily for the self-diffusion, viscosity, and thermal conductivity coefficient data for all n-alkanes from methane to hexadecane at densities greater than the critical density.     

Viscosities of nonelectrolyte liquid mixtures. I. binary mixtures containing p-dioxane

Viscosity measurements are reported for p-dioxans with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, tetrachloroethane, chloroform, pentachloroethane, and ethyl acetate at 303.15 K. Excess Gibbs energies of activation G ^*E of viscous flow have been calculated with Eyring's theory of absolute reaction rates. The deviations of the viscosities from a linear dependence on the mole fraction and values of G ^*E for binary mixtures have been explained in terms of molecular interactions between unlike pairs. The Prigogine-Flory-Patterson theory has been used to estimate the excess viscosity, ln , and corresponding enthalpy ln _H, entropy ln _S, and free volume ln _v terms for binary mixtures of p-dioxane with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, and chloroform. Estimates of excess viscosities from this theory for p-dioxane with benzene, toluene, and carbon tetrachloride are good, while for the other three mixtures they are poor. The local-composition thermodynamic model of Wei and Rowley estimates the excess viscosity quite well even for p-dioxane mixtures with cyclohexane and n-hexane.