ABSTRACT
Clay slurries are both ubiquitous and essential in the oil exploration industry, and are most commonly employed as drilling fluids. Due to its natural abundance, bentonite clay is often the de facto choice for these materials. Understanding and predicting the mechanical response of these fluids is critical for safe and efficient drilling operations. However, rheological modeling of bentonite clay suspensions is complicated by the fact that thermally-driven microscopic arrangements of particle aggregates lead to a continual evolution of the viscoelastic properties and the yield stress of the suspension with time. Ergodic relations fundamental to linear viscoelastic theory, such as the Boltzmann superposition principle, do not hold in this scenario of 'rheological aging'. We present an approach for modeling the linear viscoelastic response of aging bentonite suspensions across a range of temperatures that is based on the transformation from laboratory time to an effective 'material time' domain in which time-translation invariance holds, and the typical relations of non-aging linear viscoelastic theory apply. In particular, we model the constitutive relationship between stress and strain-rate in the bentonite suspensions as fractional Maxwell gels with constant relaxation dynamics in the material time domain, in parallel with a non-aging Newtonian viscous contribution to the total stress. This approach is supported by experimental measurements of the stress relaxation and rapid time-resolved measurements of the linear viscoelastic properties performed using optimized exponential chirps. This data is then reduced to master curves in the material domain using time-age-time superposition to obtain best fits of the model parameters over a range of operating temperatures.
ABSTRACT
Petroleum well drilling fluids are one of the most significant constituents in the subterranean drilling processes to meet an increasing global demand for oil and gas. Drilling fluids experience exceptional wellbore conditions, e.g. high temperature and high pressure that adversely affect the rheology of these fluids. Gas and oil well drilling operations have to adjourn due to changes in fluid rheology, since the drilling fluids may lose their effectiveness to suspend heavy particles and to carry drilled cuttings to the surface. The rheological properties of drilling fluids can be controlled by employing viscosifiers that should have exceptional stability in downhole environments. Here, we have developed next-generation viscosifiers-organically modified magnesium silicates (MSils)-for reservoir drilling fluids where organic functionalities are directly linked through the Si-C bond, unlike the industry's traditional viscosifier, organoclay, that has electrostatic linkages. The successful formation of covalently-linked hexadecyl and phenyl functionalized magnesium silicates (MSil-C16 and MSil-Ph) were confirmed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). Identical drilling fluid formulations were designed for comparison using MSils and a commercial viscosifier. The rheological properties of fluids were measured at ambient conditions as well as at high temperatures (up to 150 °C) and high pressure (70 MPa). Owing to strong covalent linkages, drilling fluids that were formulated with MSils showed a 19.3% increase in yield point (YP) and a 31% decrease in apparent viscosity (AV) at 150 °C under 70 MPa pressure, as compared to drilling fluids that were formulated with traditional organoclay. The higher yield point and lower apparent viscosity are known to facilitate and increased drilling rate of penetration of the fluids and an enhanced equivalent circulation density (ECD), the dynamic density condition, for efficient oil and gas wells drilling procedures.
ABSTRACT
The selective oxidation of styrene on clean and modified Ag(100) surfaces has been studied by synchrotron fast XPS and temperature-programmed reaction spectroscopy. By following the time dependence of surface species, it is unequivocally demonstrated that the necessary and sufficient conditions for epoxide formation are oxygen adatoms and pi-adsorbed alkene molecules. Increased oxygen coverage and coadsorbed Cs have pronounced and opposite effects on epoxidation selectivity, consistent with the view that the valence charge density on O(a) is pivotal in determining this property. Submonolayer quantities of Cs nitrate generated in situ open a new, low-temperature ultraselective, epoxidation pathway thought to involve direct oxygen transfer from the oxyanion to the alkene.
