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At least 343 records · Page 19

Directing the adsorption and assembly of laponite nano-discs at oil–water interfaces

Achieving tunable controls on the adsorption and self-assembly of nanoscale building blocks at immiscible fluid interfaces is essential for synthesizing advanced materials, stabilizing emulsions, and the sustainable storage and recovery of fluids. Although extensive efforts have been directed toward resolving the assembly of spherical nanoparticles at water–hydrocarbon interfaces, 2D nanoparticles have received far less attention. In this study, we developed novel controls to direct the adsorption and assembly of 2D laponite nano-discs (diameter = ∼30 nm and thickness = ∼1 nm) at water–heptane interfaces using traces of sodium dodecyl sulfate (SDS) surfactant, demonstrated by advanced in situ small-angle X-ray scattering, atomic force microscopy, spinning drop tensiometer measurements and molecular dynamics simulations. The results show that SDS surfactant displaces the adsorbed laponite nano-discs from the interface toward the aqueous phase. The extent of this displacement increases with SDS concentration such that high SDS concentrations convert laponite-rich interfaces to SDS-rich interfaces free of laponite nano-discs. This transformation is associated with significant alterations in the rheological and nanomechanical properties of the host interface. In this context, reduction in interfacial tension and interfacial stiffness and an increase in the interfacial deformation is observed on increasing the SDS concentration from 0 to 0.1 wt%. The displacement of laponite nano-discs from the interface is driven by strong electrostatic interactions between the hydrophilic SDS group and interfacial water molecules. These studies unlock new insights into the adsorption and assembly of 2D nanoscale particles at water–hydrocarbons interfaces that are relevant for various applications related to energy and environmental science and engineering.

interfacial tension↗

Probing specific ion effects at air-aqueous dibutyl phosphate interfaces using vibrational sum frequency generation spectroscopy

Molecular properties at air–liquid and liquid–liquid interface hold the key to many processes involving molecular transport across phase boundaries from aerosol formation to carbon cycling and material separation using solvent extraction techniques. Using dibutyl phosphate (DBP) as a representative for partially aqueous soluble surfactants, the specific ion effect (SIE) of the Hofmeister series cations Cs + , Na + , Li + , and Mg 2+ on the partition and interaction between surfactant molecules and water molecules in the air–aqueous interface are investigated using vibrational sum frequency generation spectroscopy and surface tension measurements. In the presence of 1 mM and 1M bulk aqueous phase ionic strength salt concentrations, fundamental qualitative relationships are observed for the salting out of DBP relative to bulk aqueous phase nitrate salt concentrations and the specific cations species. At 1 mM ionic strength, the interfacial charge and hence the interfacial potential modulates the electrostatic interactions; in particular, the counter cations partially screen the negatively charged interface induced by the DBP in a direct Hofmeister order. At 1M ionic strength, the electric field at the interface or interfacial potential is effectively neutralized, and the counter cations promote the partitioning of DBP to the interface depending on their specific interaction with the DBP head group and metal ion hydration properties. The present results lay a foundation to study SIEs of heavier metals on hydrophobic-aqueous DBP interfaces.

Louie, Christina [Washington State University, Pul↗

Challenges to magnetic doping of thin films of the Dirac semimetal Cd 3 As 2

Magnetic doping of topological quantum materials provides an attractive route for studying the effects of time-reversal symmetry breaking. Thus motivated, we explore the introduction of the transition metal Mn into thin films of the Dirac semimetal Cd 3 A s2 during growth by molecular beam epitaxy. Scanning transmission electron microscopy measurements show the formation of a Mn-rich phase at the top surface of Mn-doped Cd 3 A s2 thin films grown using both uniform doping and delta doping. This suggests that Mn acts as a surfactant during epitaxial growth of Cd 3 A s2 , resulting in phase separation. Magnetometry measurements of such samples indicate a ferromagnetic phase with out-of-plane magnetic anisotropy. Electrical magneto-transport measurements of these films as a function of temperature, magnetic field, and chemical potential reveal a lower carrier density and higher electron mobility compared with pristine Cd 3 A s2 films grown under similar conditions. This suggests that the surfactant effect might also serve to remove impurities from the bulk of the film. Further, we observe robust quantum transport (Shubnikov-de Haas oscillations and an incipient integer quantum Hall effect) in very thin (7 nm) Cd 3 A s2 films despite being in direct contact with a structurally disordered surface ferromagnetic overlayer.

36 MATERIALS SCIENCE↗

Boron nitride on SiC(0001)

Here, in the field of van der Waals heterostructures, the twist angle between stacked two-dimensional layers has been identified to be of utmost importance for the properties of the heterostructures. In this context, we previously reported the growth of a single layer of unconventionally oriented epitaxial graphene that forms in a surfactant atmosphere [F. C. Bocquet et al., Phys. Rev. Lett. 125, 106102 (2020)]. The resulting G-R0° layer is aligned with the SiC lattice, and hence represents an important milestone towards high-quality twisted bilayer graphene, a frequently investigated model system in this field. Here, we focus on the surface structures obtained in the same surfactant atmosphere, but at lower preparation temperatures at which a boron nitride template layer forms on SiC(0001). In a comprehensive study based on complementary experimental and theoretical techniques, we find—in contrast to the literature—that this template layer is a hexagonal B x N y layer, but not high-quality hBN. It is aligned with the SiC lattice and gradually replaced by low-quality graphene in the 0° orientation of the B x N y template layer upon annealing.

36 MATERIALS SCIENCE↗

A Study of Ferrocene Diffusion in Toluene/Tween 20/1-Butanol/Water Microemulsions for Redox Flow Battery Applications

Redox flow batteries (RFBs) possess multiple advantages as a flexible energy storage solution. However, RFB researchers are still facing many challenges in finding an appropriate electrolyte. Microemulsions have recently been proposed as a promising alternative RFB electrolyte because of their ability to accommodate organic redox species with fast electron transfer rates that are not soluble in aqueous phase, while still offering the high conductivity of an aqueous salt electrolyte. In this work, we focused on understanding the transport of ferrocene (Fc) in a toluene/Tween 20/1-butanol/water model microemulsion and studied the compositional influence on Fc diffusion. The results show that Fc redistributes among the oil, surfactant, and water microenvironments, and the corresponding diffusion and partition coefficients are quantified. Thus, a tortuous path diffusion model is proposed to describe the mass transport of Fc to an electrode surface. Diffusion coefficients are also obtained by pulsed-field gradient nuclear magnetic resonance (PFG NMR), while the values for Fc diffusion are substantially higher than those from electrochemical measurements, suggesting that they measure samples in different ways. The current contributions from each microenvironment indicate that the Fc permeability is much higher in the oil, even though the electron transfer reaction is likely occurring in the surfactant.

25 ENERGY STORAGE↗

EMC3 regulates trafficking and pulmonary toxicity of the SFTPC I73T mutation associated with interstitial lung disease

The most common mutation in surfactant protein C gene (SFTPC), SFTPC I73T , causes interstitial lung disease with few therapeutic options. We previously demonstrated that EMC3, an important component of the multiprotein endoplasmic reticulum membrane complex (EMC), is required for surfactant homeostasis in alveolar type 2 epithelial (AT2) cells at birth. In the present study, we investigated the role of EMC3 in the control of SFTPC I73T metabolism and its associated alveolar dysfunction. Using a knock-in mouse model phenocopying the I73T mutation, we demonstrated that conditional deletion of Emc3 in AT2 cells rescued alveolar remodeling/simplification defects in neonatal and adult mice. Proteomic analysis revealed that Emc3 depletion reversed the disruption of vesicle trafficking pathways and rescued the mitochondrial dysfunction associated with I73T mutation. Affinity mass spectrometry analysis identified potential EMC3 interacting proteins in lung AT2 cells, including Valosin Containing Protein (VCP) and its interactors. Treatment of Sftpc I73T knock-in mice and SFTPC I73T expressing iAT2 cells derived from SFTPC I73T patient-specific iPSCs with the specific VCP inhibitor CB5083 restored alveolar structure and SFTPC I73T trafficking respectively. Taken together, the present work identifies the EMC complex and VCP in the metabolism of the disease-associated SFTPC I73T mutant, providing novel therapeutical targets for SFTPC I73T -associated interstitial lung disease.

60 APPLIED LIFE SCIENCES↗

Foam Fracturing Study for Stimulation Development of Enhanced Geothermal Systems

This is a final technical report for the project: Foam Fracturing Study for Stimulation Development of Enhanced Geothermal Systems (EGS). The goal is to demonstrate the feasibility of foam fracturing in EGS applications. The project, led by Oak Ridge National Laboratory (ORNL), was conducted in collaboration with Temple University. The report describes the research activities with Task 1 at ORNL: foam fracturing testing system development and experimental study on foam fracturing, and Task 2 at Temple University: foam testing and foam characterization. Main findings are: 1. A foam fracturing test system has been developed at ORNL, which can be used to perform foam fracturing under pressure up to 6,000 psi. The system monitors foam density during fracturing online and is capable of testing materials in both monotonic and cyclic (up to 50 Hz) injections. 2. Foam fracturing tests were carried out on Charcoal black granite specimens with a blind borehole to the middle length. Two diameters of blind borehole were tested; G2 series: 9.53 mm and G3 series: 4.76 mm. N2-in-water foam was used with AOS as a surfactant. 3. There was a hole-size effect on fracture initiation pressure. The effect is smaller in the case of foam, which was influenced by the high penetrability of gas in foam. Breakdown pressure showed a behavior just as that of fracture pressure; namely an increased value for small hole samples, while the effect in water fracture was more impressive than in foam fracture. 4. Water mass was reduced in foam fracturing within similar range of breakdown pressures. In G2 series, it was decreased from 10.44 g for water fracturing to 5.17 g, representing more than 50% water reduction. Therefore, there is the potential to reduce water use in EGS stimulation through foam fracturing. 5. Use of cyclic injection has the potential to reduce the breakdown pressure and seismicity in EGS application. Experiments using 4-s cycle period found that specimens can be fractured with a low number of cycles. The fatigue pressure was approximately 64 - 77% of monotonic breakdown pressure for water fracturing and 58 - 94% of the breakdown pressure for foam fracturing. 6. A foam stability testing system has been developed that can test foam at 220 Deg C to 2,000 psi. Tested components of candidate foams included two gases: N2 and CO2; 4 surfactants: AOS, SDS, NP-40 and CTAC; 5 stabilizing agents: guar, bentonite clay, borate salt, silica NPs, and GO. 7. N2 and AOS provided the most stable performance over the tested ranges. Furthermore, the AOS foam with stabilizing agents of guar and borate salt (crosslinker) offered the highest half-life of 20 minutes at 200 Deg C and 1,000 psi. 8. Arrhenius equation and modified power law have been demonstrated to fit well the half-time vs. temperature and pressure data, respectively. These relations can be useful to provide the suggestion for future foam stability study. This submission contains the supporting data developed during the project: 1) A final technical report 2) Granite fracturing data in monotonic and cyclic injections with water and N2 foam Foam performance data in various temperatures and pressures, including half-time, is submitted separately.

15 GEOTHERMAL ENERGY↗

Literature Data on Foam Fracturing Fluid

At the beginning of this project, the Temple team spent significant effort to collect data relevant to foam fracturing. More than 40 articles/reports were found in the open literature that reported the properties of aqueous foams under various testing conditions. The foam properties included viscosity and stability in terms of half-life, while were influenced by the foam quality, shear rate, temperature, pressure, as well as surfactants and additives used in making the foam base solutions. As a result, more than 1100 data points were collected, which are included in a master worksheet named "Literature data on Foam Fracturing Fluid". These data points are organized based on following parameters: 1. Literature source, including authors and publication year 2. Gaseous phase (e.g. CO2, N2) 3. Liquid phase (e.g. tap water, DI water, salt water) 4. Surfactants and their concentrations 6. Additives 7. Foam quality 8. Pressure 9. Temperature 10. Viscosity 11. Foam stability, which was characterized by its half-life: Half-life Foam study data base with data analysis was completed and a webpage is designed hosted on public server at https://surfactant-dashboard.herokuapp.com

15 GEOTHERMAL ENERGY↗

Experimental Images and Videos of Foam Stability (Half-life)

The experimental data obtained in this project is the thermal stability data of various foams measured using the setup established at Temple University during this study. The setup is installed with a portable digital camera which can take images and videos of foam evolution at a given pressure and temperature condition. Consequently, the half-life data was recorded from the images/videos, which are used as a measure of the thermal stability for foams. Over the 3 years of this project, four different surfactants and five different stabilizing agents were studied. The surfactants are, Alfa Olefin Sulfonate (AOS), Sodium Dodecyl Sulphate (SDS), Tergitol (NP-40), and Cetyltrimethylammonium chloride (CTAC). The stabilizing agents are, guar gum, bentonite clay, crosslinking agents, silicon dioxide nanoparticles (60 to 70nm), and graphene oxide dispersions. Foam stability was evaluated at different temperatures between 100C and 200cC, while the foam generation pressure varied between atmospheric pressure (14.7 psi) and 1000 psi. The images are saved as .jpg file and videos are saved as .avi files.

15 GEOTHERMAL ENERGY↗

Dynamic Behavior of Natural Seep Vents: Analysis of Field and Laboratory Observations and Modeling (Final Scientific/Technical Report)

In this project, we have analyzed data collected by the U.S. Department of Energy (DOE), National Energy Technology Laboratory (NETL) in a high pressure water tunnel (HPWT) and data from two research cruises to natural seeps in the Gulf of Mexico to adapt and validate a numerical model to predict the dynamics of natural seeps in the deep oceans. The HPWT data include video observations of the shrinkage rate of individual methane and natural gas bubbles under simulated deep-water conditions. Field data were collected during two cruises by the Gulf Integrated Spill Research (GISR) Consortium led by Texas A&M University and funded by the Gulf of Mexico Research Initiative (GoMRI). These data included in situ observations from a remotely operated vehicle (ROV) of gas bubbles at two natural seep sites in the Gulf and acoustic observations of the natural seep bubble flares in the ocean water column. The acoustic data were from multibeam echosounders, one mounted in a forward-looking orientation on the ROV and another mounted down-looking in the haul of the ship. All of these laboratory and field data were focused on the dynamics of natural gas bubbles at temperatures and pressures favorable for clathrate hydrate formation between the gas and water. Our analyses of this data focused on understanding the mechanisms responsible for gas bubble dissolution within the hydrate stability zone (HSZ) of the oceans. Ice-like hydrate shells may form on the bubble-water interface under these conditions, and it was unknown how this might affect the mass transfer of gas into the ocean. We were able to extract bubble shrinkage rates from the HPWT datasets. Using this data we determined that mass transfer coefficients with and without a hydrate shell match empirical values for bubbles in contaminated systems (so-called dirty bubbles contaminated by naturally occurring surfactants). We also showed that free gas, and not gas hydrate, is the dominant dissolving phase when the hydrate sub-cooling is below 11 degree Celsius (temperature difference between hydrate the hydrate formation temperature and ambient temperator) or the pressure is reducing as bubbles rise through the ocean water column. Using this mass transfer model, our numerical model of bubble dissolution matched the over 200 HPWT experiments with an average error of 10% for predicting the bubble size at the end of an experiment. From field data in the literature, we also observed that gas bubbles dissolve faster when they are initially released, following mass transfer coefficients for so-called clean-bubbles (those not yet contaminated by surfactants). Shortly after release within the HSZ, a hydrate shell forms on the bubble-water interface, and the mass transfer reduces to rates matching those of dirty bubbles. We correlated this transition time from clean to dirty bubble behavior with the initial bubble surface area and the hydrate sub-cooling. With this model for hydrate formation time and using the mass transfer coefficients deduced from the HPWT data, we validated our numerical model for predicting the rise heights of natural seep flares in the oceans. Flare heights are commonly observed in haul-mounted acoustic multibeam data. The numerical model predicts bubbles to rise high in the ocean water column owing to the slower mass transfer rates for dirty bubbles that accompany the majority of their rise time. We found that the numerical model predictions matched the observed flare heights within 5% to 10% accuracy when we compared the rise heights of the largest bubbles released from the seafloor with the bubbles acoustically visible in the multibeam data. Bubbles become acoustically transparent as they shrink to sizes of order 1 mm in diameter for the multibeam frequencies used in the field. The forward-looking multibeam on the ROV also provided data on the lateral spreading of bubbles in natural seep flares. Our analysis of this data showed that spreading follows a diffusion process, with the effective diffusivity correlating with the wobbling length scale of these ellipsoidal bubbles. When we apply this diffusivity in a random displacement model of bubble spreading, our numerical simulations match closely the lateral spread observed by the M3 in the ocean water column. Finally, we compared the seep model predictions for the acoustic properties of these natural seep plumes with that observed by the acoustic instruments in the field. The M3 and EM 302 observations were converted to relative values of target strength using a calibration we obtained in the laboratory for the M3 and using an algorithm from the manufacturer for the EM 302. Comparing the numerical seep model to these data, we obtain good agreement over the whole height of rise of these bubble flares. This further validates the numerical model. Overall, our validated seep model captures the key dynamics of gas bubbles released from natural seeps in the oceans and helps to predict the fate of methane in the water column.

03 NATURAL GAS↗

Engineered Water for Improved Oil Recovery from Fractured Reservoirs (Final Scientific/Technical Report)

The goal of this proposal is to field test the novel technology of engineered water (modifying ionic composition and/or adding surfactants or nanoparticles) injection to improve oil recovery from the carbonate matrix in fractured reservoirs. Carbonate reservoirs tend to be oil-wet/mixed-wet due to positively charged carbonate mineral surfaces and negatively charged acidic/asphaltic components in the oil. Many carbonate reservoirs are also highly fractured. Water injection does not work efficiently in fractured oil-wet reservoirs because water does not imbibe into the matrix. The water composition can be engineered with ionic modification, surfactants and nanoparticles which can change the wettability of carbonate rocks towards more water-wet conditions which can imbibe water into the matrix and push the oil into the fractures. The engineered water can also lower interfacial tension and minimize capillary forces so that gravity can push the oil up and out of the matrix. Wettability alteration also increases water relative permeability which can also improve oil recovery in non-fractured carbonate reservoirs. This technology, if successful, can be a game changer for West Texas carbonates.

02 PETROLEUM↗

EOR in Shale Resources

This work provides an overview of the research conducted at NETL and the University of Pittsburgh related to improving the perfornace of CO2 huff-and-puff enhanced oil recovery (EOR) in fractured shale and fractured tight formations. CO2-soluble wettability-altering surfactants will be dissolved in high pressure CO2 during the "huff" stages in an attempt to shift the wettability of shale surfaces away from oil-wet toward CO2-wet. Such a change should promote additinal oil recovery during the depressurization of the formation that occurs during the "puff" stages. Surfactant soubility in CO2, CO2-oil IFT, CO2-rock-oil contact angle, and core-scale huff and puff oil recovery results are presented.

Enick, Robert↗

Neonatal respiratory support strategies—short and long-term respiratory outcomes

Mechanical ventilation (MV), although life-saving, is associated with chronic respiratory morbidity in both preterm and term born infants. New ventilation modes have been developed with the aim of minimising lung injury. These include invasive and non-invasive respiratory support strategies, techniques for less invasive surfactant administration (LISA) and closed-loop automated oxygen control (CLAC) systems. Increasingly, newborn infants with signs of respiratory distress are stabilised on continuous positive airway pressure (CPAP) and receive LISA. Early CPAP when compared to mechanical ventilation reduced the incidence of BPD and respiratory morbidity at 18 to 22 months corrected age. Nasal intermittent positive pressure ventilation reduced treatment failure rates compared to CPAP, but not bronchopulmonary dysplasia (BPD). LISA compared with intubation and surfactant delivery reduced BPD, but there is no evidence from randomised trials regarding long-term respiratory and neurodevelopmental outcomes. Synchronisation of positive pressure inflations with the infant's respiratory efforts used with volume targeting should be applied for infants requiring intubation as this strategy reduces BPD. A large RCT with long term follow up data demonstrated that prophylactic high frequency oscillatory ventilation (HFOV) improved respiratory and functional outcomes at school age, but those effects were not maintained after puberty. CLAC systems appear promising, but their effect on long term clinical outcomes has not yet been explored in randomised trials. Further studies are required to determine the role of newer ventilation modes such as neurally adjusted ventilator assist (NAVA). All such respiratory support strategies should be tested in randomised controlled trials powered to assess long-term outcomes.

Kaltsogianni, Ourania↗

Progress of Gas Injection EOR Surveillance in the Bakken Unconventional Play—Technical Review and Machine Learning Study

Although considerable laboratory and modeling activities were performed to investigate the enhanced oil recovery (EOR) mechanisms and potential in unconventional reservoirs, only limited research has been reported to investigate actual EOR implementations and their surveillance in fields. Eleven EOR pilot tests that used CO2, rich gas, surfactant, water, etc., have been conducted in the Bakken unconventional play since 2008. Gas injection was involved in eight of these pilots with huff ‘n’ puff, flooding, and injectivity operations. Surveillance data, including daily production/injection rates, bottomhole injection pressure, gas composition, well logs, and tracer testing, were collected from these tests to generate time-series plots or analytics that can inform operators of downhole conditions. A technical review showed that pressure buildup, conformance issues, and timely gas breakthrough detection were some of the main challenges because of the interconnected fractures between injection and offset wells. The latest operation of co-injecting gas, water, and surfactant through the same injection well showed that these challenges could be mitigated by careful EOR design and continuous reservoir monitoring. Reservoir simulation and machine learning were then conducted for operators to rapidly predict EOR performance and take control actions to improve EOR outcomes in unconventional reservoirs.

Energy & Fuels↗

Wash water solids removal system study

During wash water purification, surfactants tend to precipitate and foul the RO membranes, causing water flux decline and loss of salt rejection. The use of 165 to 190 ppm ferric chloride and optionally 0.25 to 1.0 ppm polymeric flocculate precipitates 92 to 96 percent of the surfactant from an Olive Leaf Soap based wash water. Crossflow filtration and pressure filtration yield good soap rejection at high water flux rates. Post-treatment of the chemically pretreated and filtered wash water with activated charcoal removes the residual soap down to an undetectable level.

Source record↗

The foaming of lavas

Foaming is of great practical and theoretical significance for volcanic processes on the earth, the moon, and perhaps the meteorite parent bodies. The theory of foams agrees with steelmaking experience to indicate that their presence depends on the existence of solutes in the lavas which reduce the surface tension, and are not saturated. These solutes concentrate at the surface, and are called surfactants. The surfactant responsible for the formation of volcanic ash was not identified; it appears to be related to the oxygen partial pressure above the lava. This fact may explain why lunar and meteoritic melts are not observed to foam. Experimental studies are needed to clarify the process.

Okeefe, J. A.↗

The effect of surface contamination on thermocapillary flow in a two-dimensional slot

In an analysis of the effect of insoluble surfactants on the steady capillary flow in a shallow slot, the problem is formulated as a two-dimensional channel heated differentially from the side, with a free surface on which an insoluble surface species is adsorbed. The vertical boundaries are considered to be isothermal and impenetrable and the lower horizontal boundary to be insulated and impenetrable. Lubrication theory and matched asymptotic expansions are used to reduce the problem to a single nonlinear integral-algebraic equation. For small elasticity E, the surface velocity is nearly constant, with the result that, for small Pe, the surface concentration is nearly uniform while, for large Pe, it develops a boundary layer near the stagnation point at the cold wall, resulting in high local surface concentrations. Condensed surfactant layers will form only with E much less than one and Pe much greater than one.

Homsy, G. M.↗