Primitive chain network simulations for asymmetric star polymers.
For branched polymers, the curvilinear motion of the branch point along the backbone is a significant relaxation source but details of this motion have not been well understood. This study conducts multi-chain sliplink simulations to examine effects of the spatial fluctuation and curvilinear hopping of the branch point on the viscoelastic relaxation. The simulation is based on the primitive chain network model that allows the spatial fluctuations of sliplink and branch point and the chain sliding along the backbone according to the subchain tension, chemical potential gradients, drag force against medium, and random force. The sliplinks are created and∕or disrupted through the motion of chain ends. The curvilinear hopping of the branch point along the backbone is allowed to occur when all sliplinks on a branched arm are lost. The simulations considering the fluctuation and the hopping of the branch point described well the viscoelastic data for symmetric and asymmetric star polymers with a parameter set common to the linear polymer. On the other hand, the simulations without the branch point motion predicted unreasonably slow relaxation for asymmetric star polymers. For asymmetric star polymers, further tests with and without the branch point hopping revealed that the hopping is much less important compared to the branch point fluctuation when the lengths of the short and long backbone arms are not very different and the waiting time for the branch point hopping (time for removal of all sliplinks on the short arm) is larger than the backbone relaxation time. Although this waiting time changes with the hopping condition, the above results suggest a significance of the branch point fluctuation in the actual relaxation of branch polymers.
Linear Viscoelastic Behavior of Symmetric and Asymmetric Star Polymer Solutions
Linear viscoelastic properties of linear and star-branched polymer solutions are investigated experimentally and theoretically. Two series of high molar mass 1,4-polyisoprene linear and three-arm star polymers blended with marginally unentangled linear chains of the same chemistry form the focus of this study. We find that, irrespective of polymer architecture, unentangled linear molecules dilate the entanglement environment in the blends in a manner consistent with expectations for a ϑ-solvent. A tube model analysis used in an earlier study [Lee, J. H.; Fetters, L. J.; Archer, L. A. Macromolecules 2005, 38, 4484], for predicting linear viscoelastic properties of branched melts, is extended to describe relaxation dynamics of entangled star-branched polymer solutions. We find that, by simply rescaling the model parameters to account for ϑ-solvent dilution effects, this model quantitatively describes relaxation dynamics in concentrated star and linear polymer solutions, without adjustable parameters. At low...
Prevention of Barite Sag in Oil-Based Drilling Fluids Using a Mixture of Barite and Ilmenite as Weighting Material
Drilling high-pressure high-temperature (HPHT) wells requires a special fluid formulation that is capable of controlling the high pressure and is stable under the high downhole temperature. Barite-weighted fluids are common for such purpose because of the good properties of barite, its low cost, and its availability. However, solids settlement is a major problem encountered with this type of fluids, especially at elevated downhole temperatures. This phenomenon is known as barite sag, and it is encountered in vertical and directional wells under static or dynamic conditions leading to serious well control issues. This study aims to evaluate the use of barite-ilmenite mixture as a weighting agent to prevent solids sag in oil-based muds at elevated temperatures. Sag test was conducted under static conditions (vertical and inclined) at 350 °F and under dynamic conditions at 120 °F to determine the optimum ilmenite concentration. Afterward, a complete evaluation of the drilling fluid was performed by monitoring density, electrical stability, rheological and viscoelastic properties, and filtration performance to study the impact of adding ilmenite on drilling fluid performance. The results of this study showed that adding ilmenite reduces sag tendency, and only 40 wt.% ilmenite (from the total weighting material) was adequate to eliminate barite sag under both static and dynamic conditions with a sag factor of around 0.51. Adding ilmenite enhanced the rheological and viscoelastic properties and the suspension of solid particles in the drilling fluid, which confirmed sag test results. Adding ilmenite slightly increased the density of the drilling fluid, with a slight decrease in the electrical stability within the acceptable range of field applications. Moreover, a minor improvement in the filtration performance of the drilling fluid and filter cake sealing properties was observed with the combined weighting agent. The findings of this study provide a practical solution to the barite sag issue in oil-based fluids using a combination of barite and ilmenite powder as a weighting agent to drill HPHT oil and gas wells safely and efficiently with such type of fluids.