Phenytoin is a known human teratogen with unknown etiology. Several mechanisms have been proposed including disturbances in folate metabolism, induction of embryonic hypoxia following phenytoin-induced bradycardia, free radical formation following re-oxygenation and phenytoin-induced maternal hyperglycemia. Using high frequency ultrasound, we demonstrated that phenytoin induced a dramatic decrease in the heart rate of embryos. This coincided with a moderate transient decrease in maternal heart rate and blood glucose levels. Embryonic heart rate had not fully recovered 24 h later in some embryos despite normal maternal physiological parameters. In a separate study, extent of hypoxia was measured using the marker pimonidazole. Phenytoin-exposed embryos did not demonstrate increased hypoxia compared to control embryos at 2, 4, 8 or 24 h dosing. Together our results show that phenytoin induces malformations as a result of a combination of insults: embryonic bradycardia, maternal bradycardia and maternal hyperglycemia. However, this does not appear to result in measurable embryonic hypoxia in our animal model.

OBJECTIVE:Phenytoin exposure during the first trimester of pregnancy increases the risk of maxillary hypoplasia and cleft lip. The etiology of phenytoin embryopathy is unknown. Interestingly, phenytoin is also known to induce hyperglycemia in humans as well as rats. This study uses a rat model of fetal phenytoin syndrome to examine the role of hyperoxia, hyperglycemia, and arachidonic acid deficiency in the development of cleft lip and maxillary hypoplasia.METHODS:Pregnant rats were dosed with phenytoin during the critical period of lip development (day 11 of pregnancy) with or without supplemental oxygen, insulin, or arachidonic acid. The fetuses from all studies were examined at term.RESULTS:The frequency of cleft lip and maxillary hypoplasia was reduced by treating dams at the time of phenytoin exposure with either increased oxygen or insulin. However, in fetuses from phenytoin-treated dams dosed with arachidonic acid, the incidence of severe lip deformities remained the same although there was an increase in normal and mildly affected fetuses. Interestingly, this occurred in embryos from hyperglycemic dams.SIGNIFICANCE:Together, the results from these experiments suggest phenytoin-induced malformations may be a multifactorial process as malformations were not solely linked to a hyperglycemic state of the dam.

With the aim of elucidating the details of enhanced oil recovery by surfactant solution flooding, we have determined the detailed behavior of model systems consisting of a packed column of calcium carbonate particles as the porous rock, n-decane as the trapped oil, and aqueous solutions of the anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT). The AOT concentration was varied from zero to above the critical aggregation concentration (cac). The salt content of the aqueous solutions was varied to give systems of widely different, post-cac oil-water interfacial tensions. The systems were characterized in detail by measuring the permeability behavior of the packed columns, the adsorption isotherms of AOT from the water to the oil-water interface and to the water-calcium carbonate interface, and oil-water-calcium carbonate contact angles. Measurements of the percent oil recovery by pumping surfactant solutions into calcium carbonate-packed columns initially filled with oil were analyzed in terms of the characterization results. We show that the measured contact angles as a function of AOT concentration are in reasonable agreement with those calculated from values of the surface energy of the calcium carbonate-air surface plus the measured adsorption isotherms. Surfactant adsorption onto the calcium carbonate-water interface causes depletion of its aqueous-phase concentration, and we derive equations which enable the concentration of nonadsorbed surfactant within the packed column to be estimated from measured parameters. The percent oil recovery as a function of the surfactant concentration is determined solely by the oil-water-calcium carbonate contact angle for nonadsorbed surfactant concentrations less than the cac. For surfactant concentrations greater than the cac, additional oil removal occurs by a combination of solubilization and emulsification plus oil mobilization due to the low oil-water interfacial tension and a pumping pressure increase.

Single-phase flows of viscoelastic polymer solutions in both microfluidic devices and rock cores exhibit apparent flow thickening. We demonstrate that this thickening occurs above a critical Deborah number corresponding to the onset of spatio-temporal fluctuations. These fluctuations are observed to occur over a broad range of spatial and temporal scales consistent with elastic turbulence. The fluctuations provide a previously unreported mechanism for enhancing the displacement of a second, capillary trapped, immiscible phase.

Abstract Characterization of polymer flow behavior, using data from laboratory measurements, is an essential step in the development of predictive reservoir simulation models of polymer enhanced oil recovery (EOR). We describe a methodology for calibrating simulation parameters, using detailed observations from multiphase coreflood experiments and taking account of the core geometry and polymer rheology. A series of multiphase brine and polymer floods were performed on an oil-filled sandstone core plug, at different concentrations and at different flow rates. Measured data included pressure drop along the core and oil saturation derived from nuclear magnetic resonance. A fine-scale, three-dimensional simulation grid was designed to capture accurately the geometry of the experimental apparatus, including the coreholder platens for fluid injection and extraction. The simulation input parameters were adjusted to match the experimental results of each coreflood, and sensitivity studies were performed to assess the impact of uncertainties. In the coreflood experiments, different recovery efficiencies were observed, depending on the type of aqueous solution and the injection flow rates. An initial relative permeability model was defined by matching a constant-rate brine flood. Further tests were performed for brine, xanthan, and hydrolyzed polyacrylamide (HPAM) solutions, at incrementally increasing flow rates, and the resulting residual oil saturations were used to define capillary desaturation curves. Experimental data also showed that the apparent polymer solution viscosity at different shear rates differed from the values predicted by conventional rheology. To represent this behavior in the simulator, a new method for estimating the apparent aqueous-phase viscosity during multiphase flow has been developed and validated. At each step in the simulation study, sensitivity studies were used to check the quality of the experimental results, and unexpected behavior was explained or corrected. High accuracy is required when designing EOR processes. In this project, close collaboration between research scientists and simulation experts led to development of innovative workflows to interpret experimental results, build the simulation grid, and characterize the polymer properties.

Viscoelastic polymer solutions exhibit a variety of flow instabilities and in particular, in mixed shear and extensional flow, elastic turbulence. Coincident with the transition to turbulence is additional dissipation that, in porous flow, may be characterised as an increased apparent viscosity. We report elastic turbulence and apparent thickening in the flow of polymer solutions both in rock samples and in microfluidic analogues and we correlate the onset of thickening and turbulence with rheological measurements. Contrary to expectations, the characteristic relaxation time associated with the transition to turbulence is found to be independent of polymer concentration over the range studied (10c* ≲c≲ 100c*). Furthermore, this characteristic time scales with the square of molecular weight. Thus the characteristic time associated with the transition to turbulence is not the linear-viscoelastic timescale usually measured but rather scales as a dilute Rouse time despite being an entangled system.

Viscoelastic polymer solutions flowing through reservoir rocks have been found to improve oil displacement efficiency when the aqueous-phase shear-rate exceeds a critical value. A possible mechanism for this enhanced recovery is elastic turbulence that causes breakup and mobilization of trapped oil ganglia. Here, we apply nuclear magnetic resonance (NMR) pulsed field gradient (PFG) diffusion measurements in a novel way to detect increased motion of disconnected oil ganglia. The data are acquired directly from a three-dimensional (3D) opaque porous structure (sandstone) when viscoelastic fluctuations are expected to be present in the continuous phase. The measured increase in motion of trapped ganglia provides unequivocal evidence of fluctuations in the flowing phase in a fully complex 3D system. This work provides direct evidence of elastic turbulence in a realistic reservoir rock - a measurement that cannot be readily achieved by conventional laboratory methods. We support the NMR data with optical microscopy studies of fluctuating ganglia in simple two-dimensional (2D) microfluidic networks, with consistent apparent rheological behaviour of the aqueous phase, to provide conclusive evidence of elastic turbulence in the 3D structure and hence validate the proposed flow-fluctuation mechanism for enhanced oil recovery.

Abstract A laboratory study on core plugs from a carbonate field confirmed the efficacy of an alkaline surfactant (AS) formulation at reservoir conditions. Continuous monitoring of remaining oil saturation (ROS) in short core plugs using spatially resolved nuclear magnetic resonance (NMR) can provide insights into the processes by which surfactants release post-water-flood remaining oil. In single short plugs, volumetric averages do not correctly quantify remaining oil due to capillary end effects (high remaining oil saturation post water flood observed at the outlet face of the plug), oil banks, and other flow heterogeneities. These effects are all quantifiable by NMR, allowing accurate monitoring of ROS. Here, consistent ROS values are obtained in the laboratory, in single-well pilots, and in single-well chemical-tracer (SWCT) tests. Laboratory core floods with nuclear magnetic resonance (NMR) monitoring at low magnetic fields therefore provide a valuable calibration of the NMR logs, in addition to the direct assessment of ROS. Corroboration across multiple length scales, spatial resolution, and correspondence with preferred logging measurements, all contribute to the value of NMR-monitored core-floods as a complement to field pilot studies.

Surfactant formulations that give rise to ultra-low interfacial tensions are used to enhance the recovery of crude oil by eliminating the trapping effects of capillary forces. The formulations, when mixed with oil, often give microemulsion-type phase behaviour. Depending on the surfactant affinity for oil and water, the microemulsion may exist as water-in-oil (L2), oil-in-water (L1), or bi-continuous (L3). Here, an aqueous formulation of anionic surfactants and butan-2-ol that would give rise to Ll and L3 phase behaviours at different NaC1 concentrations is injected into decane-filled porous media. The displacement processes in rock cores are followed by spatially resolved NMR and in microfluidic models by optical microscopy. Both surfactant formulation types enhance the oil displacement from the core but the L3-forming system shows more complex behaviour, consistent with first the formation and then the displacement of microemulsion phases, which leads to significant enhancements in oil recovery. (C) 2014 Elsevier B.V. All rights reserved.

Thermophoresis is the rectification of Brownian motion induced by the presence of a thermal gradient ∇T, yielding a net drift of colloidal particles along or against the direction of ∇T. The effect is known to depend on the specific interactions between solute and solvent, and quantitative theoretical models are lacking except in a few simple experimental cases. Both the order of magnitude and the temperature dependence of the thermophoretic mobility DT are known to be very similar for a wide class of aqueous colloidal systems, ranging from latex colloids to polymers, surfactant micelles, proteins, and DNA. Here we show that thermoresponsive microgel particles made of poly(N-isopropylacrylamide) (PNIPAM) do not share, in the temperature range around the ϑ-point, these common features. Instead, DT displays an unusually strong temperature dependence, maintaining a linear growth across the collapse transition. This behaviour is not shared by linear PNIPAM chains, for which existing data show DT falling at the transition, with similar values between the expanded coil and collapsed globule states away from the transition point. A possible connection of the observed giant temperature dependence of DT to microgel hydration is suggested.

The viscosity of dilute aqueous dispersions of poly(N-isopropylacrylamide) microgel particles is measured by capillary viscometry. The viscosity increases with particle mass fraction and on reducing temperature, particularly below the volume phase transition temperature (VPTT) of 32 °C. Converting the particle loading to volume fraction via the change in hydrodynamic size, the slope of the viscosity-volume fraction graph exhibits an increasing value beyond that for the equivalent effective hard-sphere size as the particles swell. This increase is due to the porosity of the particles. Two microgel samples of different collapsed size (124 and 59 nm at 50 °C) are investigated and the deviation from hard-sphere behavior is greater for the smaller particles.

The requirements for thickeners are continuously increasing. Very mild formulations, like baby shampoos, which contain generally a low amount of Sodium Laureth Sulfate, and furthermore often contain Sulfosuccinates, are very difficult to thicken. Also PEG-free formulations, which are becoming more and more popular, are difficult to thicken. Special applications like dispenser packs require a special flow behaviour -which can be achieved by specific thickeners. Also in case of suspensions, e.g. of pearlizers, capsules or Zinc Pyrithione, a special flow behaviour is advantageous.