Predictive model for the composition dependence of glassy dynamics

The problem of glass relaxation is traditionally known as one of the most challenging problems in condensed matter physics, with important implications for several high‐tech applications of glass. In this study, we present a predictive model for the temperature, thermal history, and composition dependence of glassy relaxation dynamics. Our model enables, for the first time, the quantitative prediction of relaxation behavior for new glass compositions. Using the commercial Corning EAGLE XG^® alkaline earth aluminosilicate glass as a reference, the model gives accurate predictions of the nonequilibrium viscosity for 4 other aluminosilicate glasses, covering both alkali‐free and alkali‐containing compositions, without any free fitting parameters. Using the composition‐dependent nonequilibrium viscosity model, only the measured values of the glass transition temperature and fragility are required to predict the nonequilibrium viscosity as a function of both temperature and thermal history. The range of glass transition temperatures of the 4 verification glasses covers about 200°C, while that of fragility values is about 6. As such, this work gives insights into the structural origin of nonequilibrium viscosity and can enable the future design of glass compositions with tailored relaxation behavior.     

Dynamic viscosity of olive oil as a function of composition and temperature: A first approach

Knowledge of the viscosity of virgin olive oils (VOOs) is of great importance for the design of pilot plants, to determine the time required for the settling of particles at the end of the production chain and from a sensory view point. The dynamic viscosities of French VOOs from four different cultivars (‘Aglandau’, ‘Bouteillan’, ‘Salonenque’ and ‘Tanche’) were studied as a function of their fatty acid and TAG compositions and of the temperature [10–50°C]. These four VOOs had different TAG and fatty acid compositions representative of the range of compositional variations in the main French oils. Their viscosities were similar, although small but measurable differences that depended on their compositions were apparent. All the VOO samples exhibited the same dynamic viscosity pattern over temperature. For a given temperature, the viscosity difference was the greatest between Aglandau and Salonenque oils, Aglandau being the oil with the highest viscosity. The correlation between temperature and viscosity was highlighted by an Arrhenius model for this Newtonian fluid. The Arrhenius activation energy was correlated (R² = 0.993) with the percentage of triolein, the main TAG in olive oil.     

Viscosity of glass‐forming systems

As one of the most important properties of glass‐forming liquids, viscosity has drawn significant attention in both glass manufacturing and fundamental research. We review the recent scientific progress in viscosity of glass‐forming systems, including both the liquid and glassy states. After the Vogel‐Fulcher‐Tammann (VFT) equation was introduced, many more efforts have been made to develop more accurate models to describe the temperature dependence of viscosity. In addition to the VFT equation, we also discuss three other viscosity models, viz., the Adam‐Gibbs, Avramov‐Milchev, and Mauro‐Yue‐Ellison‐Gupta‐Allan models. We compare the four viscosity models in terms of their theoretical underpinnings and ability to fit measured viscosity curves. The concept of fragility and the universality of the high‐temperature viscosity limit are also discussed. Temperature‐dependent constraint theory is introduced in detail as a powerful tool for predicting the composition dependence of viscosity. Some examples of the application of this approach to predict the glass transition temperature and fragility of various glass systems are shown. Topological constraint theory is not only of scientific interest, but also has important industrial applicability. We also discuss the thermal history dependence of viscosity in the glassy state. Some phenomenological models are briefly reviewed, while the main focus is given to the modified Mauro‐Allan‐Potuzak model, which can accurately predict the nonequilibrium viscosity as a function of temperature, thermal history, and composition. The correlation of viscosity with elasticity is described in terms of the shoving model. Some theoretical implications of the various viscosity models are discussed, including the concepts of the Kauzmann paradox and the ideal glass transition. Some of the evidence against the existence of these phenomena are discussed. We also review the link between glass relaxation and viscosity, that is, emphasizing that the viscosity equations presented in this review can also be used to model different types of relaxation effects based on the Maxwell relation.     

New aspects of viscosity effects on the photopolymerization kinetics of the 2,2‐bis[4‐(2‐hydroxymethacryloxypropoxy)phenyl]propane/triethylene glycol dimethacrylate monomer system

The photopolymerization kinetics and viscosity behavior of 11 2,2‐bis[4‐(2‐hydroxymethacryloxypropoxy)phenyl]propane/triethylene glycol dimethacrylate mixtures were investigated. The viscosity was studied at six temperatures (20–70°C), and the activation energies for the viscosity were determined. The excess logarithm viscosities were calculated and found to be negative over the whole composition and temperature ranges; they were fitted to the Redlish–Kister polynomial equation. The kinetic analysis of the photopolymerization was carried out at three polymerization temperatures (20, 40, and 60°C). The results proved the existence of the most reactive composition (reaching the highest value of the maximum polymerization rate), but the ratio of the monomers in this composition, close to equimolar, showed a tendency to change with the polymerization temperature. The viscosities of the most reactive compositions lay in the range of about 0.1–1.2 Pa s, which was narrow in comparison with the range of viscosities of all the compositions used in the kinetic studies (from 3 × 10^?3 to 1.5 × 10³ Pa s). The activation energies for the polymerization rates were calculated and correlated with the viscosity changes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Capillary flow of low‐density polyethylene

The capillary flow of a commercial low‐density polyethylene (LDPE) melt was studied both experimentally and numerically. The excess pressure drop due to entry (Bagley correction), the compressibility, the effect of pressure on viscosity, and the possible slip effects on the capillary data analysis have been examined. Using a series of capillary dies having different diameters, D, and length‐to‐diameter L/D ratios, a full rheological characterization has been carried out, and the experimental data have been fitted both with a viscous model (Carreau‐Yasuda) and a viscoelastic one (the Kaye—Bernstein, Kearsley, Zapas/Papanastasiou, Scriven, Macosko, or K‐BKZ/PSM model). Particular emphasis has been given on the pressure‐dependence of viscosity, with a pressure‐dependent coefficient β_p. For the viscous model, the viscosity is a function of both temperature and pressure. For the viscoelastic K‐BKZ model, the time‐temperature shifting concept has been used for the non‐isothermal calculations, while the time–pressure shifting concept has been used to shift the relaxation moduli for the pressure‐dependence effect. It was found that only the viscoelastic simulations were capable of reproducing the experimental data well, while any viscous modeling always underestimates the pressures, especially at the higher apparent shear rates and L/D ratios. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Development of a mathematical model for studying bioethanol–water separation using hydrophilic polyetherimide membrane

An essentially predictive mathematical model was developed to simulate pervaporation process. The group contribution method UNIFAC was used for calculating the upstream activity coefficients. The diffusion coefficient in the membrane was predicted using free‐volume theory. Free‐volume parameters were determined with viscosity and temperature data, and the binary interaction solvent–polymer parameter was calculated by a group‐contribution lattice‐fluid equation of state (GCLF‐EOS). A simulator named PERVAP was developed applying the mathematical model. Pervaporation process was simulated for separating bioethanol–water through polyetherimide membrane. The simulated results were validated using experimental data of bioethanol/water separation through polyetherimide membrane. The model presented a satisfactory performance compared to experimental data. Related to the simulation of the studied separation, a 99% molar enriched bioethanol stream was obtained with a recovery of 94%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Optimal operation of a membrane reactor network

In this contribution, the operation of a membrane reactor network (MRN) for the oxidative coupling of methane is optimized. Therefore, three reactors, a fixed bed reactor (FBR) and two packed bed‐membrane reactors, are modeled. For the (CPBMR), a two‐dimensional (2‐D) model is presented. This model incorporates radial diffusion and thermal conduction. In addition, two 10 cm long cooling segments for the CPBMR are implemented based on the idea of a fixed cooling temperature positioned outside the reactor shell. The model is discretized using a newly developed 2‐D orthogonal collocation on finite elements with a combination of Hermite for the radial and Lagrangian polynomials for the axial coordinate. Membrane thickness, feed compositions, temperatures at the inlet and for the cooling, diameters, and the amount of inert packing in the reactors are considered as decision variables. The optimization results in C₂ yields of up to 40% with a selectivity in C₂ products of more than 60%. The MRN consisting of an additional packed‐bed membrane reactor with an alternative feeding policy and a FBR shows a lower yield than the individual CPBMR. © 2013 American Institute of Chemical Engineers AIChE J, 60: 170–180, 2014     

Natural gas viscosity estimation using density based models

Accurate value determination of natural gas viscosity plays a key role in its management as it is one of the most important parameters in natural gas engineering calculations. In this study, a comprehensive model is suggested for prediction of natural gas viscosity in a wide range of pressures, temperatures, densities and compositions. The new model can be applicable for gases containing heptane plus and non‐hydrocarbon components. It is validated by the 2011 viscosity data from 18 different gas mixtures. Compared to existing similar models and correlations, its results are quite satisfactory. © 2012 Canadian Society for Chemical Engineering     

Synthesis and dynamic mechanical behavior of glucose‐mediated poly(ethylene glycol/chitosan) membrane

The pH‐dependent chitosan/PEG membrane was prepared by a surface‐mediated process with glucose as a source. Swelling study shows that the glucose‐mediated membrane is more stable in a neutral environment than an acidic one and the stability in all soaking environments generally increases with increasing glucose concentration because of an increase in Schiff's reaction product as demonstrated by a mediated degree analysis. DMA analysis shows that as the glucose concentration increases, the rubber plateau of the glucose‐mediated membrane is prolonged and keeps a higher storage modulus, and the tangent δ peak shifts to a high temperature as the temperature increases. In an isothermal mode, as the glucose concentration increases to 10 wt %, the storage modulus shows a small change in frequency dependence, indicating that the mediating effect is obviously affected by glucose addition. It can also be found that surface‐mediated membrane has a higher complex viscosity than chitosan/PEG membrane at high frequencies. Thus, a new way was found to use glucose to produce stable biomaterial. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 809–820, 2004     

Effect of Coating of Ammonium Perchlorate with Fluorocarbon on Ballistic and Sensitivity Properties of AP/Al/HTPB Propellant

Fluorocarbon polymers are used to enhance thermal stability and electrostatic protection of composite propellant compositions. A precipitation technique has been developed to coat ammonium perchlorate (AP) using a copolymer of hexafluoropropylene and vinylidene fluoride (HFP‐VF) with the help of solvent‐counter solvent method. The coated AP has been used to prepare propellant compositions in different ratio based on hydroxyl terminated polybutadiene (HTPB), aluminium powder along with uncoated AP and studied for viscosity build‐up and visco‐elastic behaviour as well as mechanical, ballistic, thermal and sensitivity properties keeping 86% solid loading. The data on viscosity build‐up indicate that as the percentage of viton coated AP increases end of mix viscosity and viscosity build‐up increase accordingly. The mechanical properties data reveal that tensile strength and percentage elongation are found in increasing order. The burn rate of the composition also increases on higher percentage of HFP‐VF coated AP. The thermal stability of composition increases as the percentage of HFP‐VF coated AP increases. The data on sensitivity indicate that impact sensitivity decreases on increasing the percentage of HFP‐VF coated AP while no change is observed in friction sensitivity value.     

The impact of viscoelastic behavior and viscosity ratio on the phase behavior and morphology of polypropylene/polybutene‐1 blends

In this study, the influence of the viscosity ratio on the rheology, morphology, and interfacial interaction of polypropylene and polybutene‐1 (PB‐1) resins with various melt flow behaviors in the blend are investigated. A droplet‐matrix morphology is observed in the scanning electron microscope images for all formulations and the size of particles increased proportionally by increasing the viscosity ratio. Viscoelastic parameters of blends at various viscosity ratios and compositions are measured by small‐amplitude oscillation rheometry in the linear viscoelastic region. The Cole‐Cole plots showed a nearly semicircular arc for all compositions. This semicircular arc is observed while the viscosity ratio is lower than 1, and the Cole‐Cole plots deviated from the semicircular shape at PB‐1 content higher than 10 wt%. It is emphasized that, in addition to compatibility, the semi‐circularity of Cole‐Cole plots affects the size of the dispersed particles, which is under the influence of the viscosity ratio. It is found that the interfacial tensions of polypropylene and PB‐1 are not significantly different when changing the viscosity ratio and coarsening the morphology. The form relaxation times in the blends with lower viscosity ratios are shorter than the form relaxation times of the blends with higher viscosity ratios. J. VINYL ADDIT. TECHNOL. 21:94–101, 2015. © 2014 Society of Plastics Engineers     

X‐ray tomography of feed‐to‐glass transition of simulated borosilicate waste glasses

High‐level waste feed composition affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a cold cap layer that floats on the molten glass where most feed‐to‐glass reactions occur. Data from X‐ray computed tomography imaging of melting pellets comprised of a simulated high‐aluminum feed reveal the morphology of bubbles, known as the primary foam, for various feed compositions at temperatures between 600°C and 1040°C. These feeds were formulated to make glasses with viscosities ranging from 0.5 to 9.5 Pa s at 1150°C, which was accomplished by changing the SiO₂/(B₂O₃+Na₂O+Li₂O) ratio in the final glass. Pellet dimensions and profile area, average and maximum bubble areas, bubble diameter, and void fraction were evaluated. The feed viscosity strongly affects the onset of the primary foaming and the foam collapse temperature. Despite the decreasing amount of gas‐evolving components (Li₂CO₃, H₃BO₃, and Na₂CO₃), as the feed viscosity increases, the measured foam expansion rate does not decrease. This suggests that the primary foaming is not only affected by changes in the primary melt viscosity but also by the compositional reaction kinetic effects. The temperature‐dependent foam morphological data will be used to inform cold cap model development for a high‐level radioactive waste glass melter.     

Curing kinetics and viscosity change of a two‐part epoxy resin during mold filling in resin‐transfer molding process

The curing kinetics and the resulting viscosity change of a two‐part epoxy/amine resin during the mold‐filling process of resin‐transfer molding (RTM) of composites was investigated. The curing kinetics of the epoxy/amine resin was analyzed in both the dynamic and the isothermal modes with differential scanning calorimetry (DSC). The dynamic viscosity of the resin at the same temperature as in the mold‐filling process was measured. The curing kinetics of the resin was described by a modified Kamal kinetic model, accounting for the autocatalytic and the diffusion‐control effect. An empirical model correlated the resin viscosity with temperature and the degree of cure was obtained. Predictions of the rate of reaction and the resulting viscosity change by the modified Kamal model and by the empirical model agreed well with the experimental data, respectively, over the temperature range 50–80°C and up to the degree of cure α = 0.4, which are suitable for the mold‐filling stage in the RTM process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2139–2148, 2000     

Reversible thermal gelation of soft semi‐crystalline polyethylene microparticles with surface interactions in squalane

The effect of temperature on the steady‐shear viscosity of a soft semi‐crystalline crosslinked‐polyethylene microparticle suspension in squalane was studied using rotational rheometry. The results show a sharp increase in the viscosity of the system occurring at about 86°C. The magnitude of this spike is dependent on the concentration of the suspension and is reproducible over multiple heating and cooling cycles. This phenomenon has been attributed to the melting of the crystalline regions within the particles, causing them to swell by soaking up squalane. The Mooney equation was used to model the viscosity data based on swelling data obtained from separate experiments. The results showed that the model is inadequate for describing the observed phenomenon, suggesting the possibility of additional interactions existing among the particles. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

A comprehensive study of the loss of enzyme activity in a continuous membrane reactor – application to starch hydrolysis

Loss of enzyme activity is a problem associated with enzymatic reactions in continuous recycled membrane reactors (CRMR). It may result from catalyst leakage and also enzyme denaturation due to the effects of pH, temperature, shear effects or adsorption/deposit on membrane. In this study, the relative importance of these various factors has been assessed in order to reduce their adverse effects on starch hydrolysis in a CRMR. The effects of temperature and denaturation by adsorption/deposit on membrane were the most limiting phenomena. Reducing the temperature to overcome thermal denaturation was not a practical solution since this increases viscosity and thereby decreases permeate flux and reactor performance. Insofar that adsorption/deposit of enzymes on the membrane is directly linked to membrane fouling, back‐flushing or regularly purging retentate should reduce this phenomenon by lowering accumulation of high molecular weight products. © 2001 Society of Chemical Industry     

Viscous behavior of PS,PP, and ABS in terms of temperature and pressure‐dependent hole fraction

We have developed a zero‐shear viscous model in terms of temperature‐ and pressure‐dependent hole fraction computed from Simha‐Somcynsky Hole Theory. This model successfully interprets the viscosity data of PS, PP, and ABS as a function of hole fraction for a broad range of temperature and pressure. We have also introduced and discussed a new term: Viscoholibility; the derivative of logarithm of viscosity with respect to hole fraction. When the hole fraction takes highest available value, the viscoholibility approaches asymptotically to a constant value by which the viscosity changes linearly with the hole fraction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of temperature and permeate recovery on energy consumption of a reverse osmosis system

A model permits analysis of the influence of temperature on permeate recovery and energy consumption. The proposed model is based on the following assumptions: (1) membrane morphology is temperature-independent; (2) membrane rejection and other transport characteristics of membranes are position-independent; (3) specific water permeability of membranes was based on exponential dependence of viscosity vs. temperature; (4) temperature-dependence depembrane rejection is assumed to be linear. This allows for analyzing the influence of channel geometry, feed concentration, flow rate and temperature on permeate recovery and energy consumption. Calculated data are included. The solutionpresented can be segmented andbuilt into systems for comprehensive techno-economic evaluation of the RO-based process where temperature-dependence of process characteristics has to be considered.     

Thermodynamic insight into the evolution of medieval glassworking properties

We present differential scanning calorimetry (DSC) analyses of seven French stained glasses from the 13th to 16th centuries. These glasses illustrate the dramatic compositional change from the antique soda‐rich glasses to potash‐ and lime‐rich compositions, resulting in drastic temperature and viscosity increases. We investigate the influence of chemical composition on glass thermal properties: glass‐transition (T_g), crystallization, and melting temperatures. We find that T_g varies from 533°C (soda type) to 638°C±17°C (potash type) to 685°C±5°C (lime type). The viscous slowdown of the melt as a function of the temperature, close to T_g, was modeled using the Vogel‐Tammann‐Fulcher equation. This enables temperature‐viscosity profile calculations, and suggests that recipes have been empirically optimized to reach similar thermoelastic properties suitable for glassmaking despite changing the nature of raw materials.     

Rheokinetic modeling of HTPB–TDI and HTPB–DOA–TDI systems

A study of the effect of temperature on a mixture of polymer and curative in the processing of rocket propellants is reported. Experimental viscosity of a hydroxyl‐terminated polybutadiene–toluene diisocyanate (HTPB–TDI) system was measured using a Brookfield viscometer model DV III. Viscosity showed dependence on temperature as well as time. The viscosity data of the HTPB–TDI system showed a linear relationship with temperature, with a change in slope at 45°C. The time dependence model showed a fourth‐order curve fit, which gave better results over the exponential model fit. The activation energy required for flow of the HTPB–TDI system was found to be 15.5 kJ/mol. Experimental viscosity measurements at various temperatures was also carried out on a hydroxyl‐terminated polybutadiene–dioctyl adipate –toluene diisocyanate (HTPB–DOA–TDI) system. The temperature dependence showed a decrease in viscosity with an increase in temperature up to 60 min, beyond which the viscosity increased. Viscosity showed a linear relation with temperature, with a change in the slope at 50°C instead of at 45°C for HTPB–TDI system. Beyond 50°C the data followed a polynomial model similar to that of the HTPB–TDI system, and the results matched well with the experimental data. The activation energy of the HTPB–DOA–TDI system increased with an increase in the binder weight ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1331–1335, 2003