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Evidence of coexisting microemulsion droplets in oil-in-water emulsions revealed by 2D DOSY 1H NMR
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Capillary condensation and gelling of microemulsions with clay additives
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Acoustic activation of water-in-oil microemulsions for controlled salt dissolution
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Reverse Microemulsion Synthesis of Sulfur/Graphene Composite for Lithium/Sulfur Batteries
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Mixing oil and water with ionic liquids: bicontinuous microemulsions under confinement
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Enhanced reactivity at the oil–water interface accelerates the synthesis of zymonic acid in microemulsions
Chemical reactions in microscale compartments, such as aerosols and emulsions, can exhibit significantly faster reaction rates relative to macroscale containers. This enhancement in chemistry is often due to the elevated importance of surfaces as reaction vessels are reduced to picoliter volumes. While most studies have focused on the air-water interface of droplets, there are comparably fewer studies of reactions in micron-scale aqueous solutions encapsulated by oil. Here we investigate the condensation reaction of pyruvic acid (PA) to form zymonic acid (ZA) and water. Using microfluidics and optical trapping, chemical kinetics are measured in monodisperse micron-sized emulsion droplets in situ via Raman spectroscopy. Relative to a macroscopic bulk solution, which exhibits little to no reaction over many days, we find efficient production of ZA over the same time period. A kinetic model is developed to elucidate the role of the interface in accelerating the microdroplet reaction kinetics. After quantifying the surface partitioning of PA from interfacial tension measurements, the rate coefficient for the condensation reaction at the oil-water interface is determined to be 1.8 × 10-2 M-1 s-1. This rate coefficient is estimated to be 105 larger than the reaction rate in bulk aqueous solutions. Compared to previous studies of accelerated ZA formation at the air-water interface on nanodroplets, we find that the reaction at the oil-water interface is 20 times more efficient. Despite this difference, the overall ZA formation rate in emulsions is significantly slower than in the same-sized aerosols, which arises from the weaker partitioning of PA to the oil-aqueous relative to air-water interface. These results highlight the interplay between interfacial partitioning and reactivity in accelerating chemistry in microcompartments and provides new insights into how interfacial composition influences condensation reactions.
Surfactant Effects in Porous Electrodes for Microemulsion Redox Flow Batteries
The effect of surfactant additives on electrochemical behavior in porous electrodes was investigated using vanadium redox flow battery half-cells and the dependence of volumetric kinetics and mass transport on electrolyte, surfactant, and electrode type was explored. Without surfactant added, carbon paper electrodes demonstrated greater kinetics and transport compared to carbon felt, for a given electrolyte. Additionally, posolyte kinetics are greater than negolyte kinetics by one to three orders of magnitude, depending on the electrode type. Addition of surfactant increased electrode wettability and possibly electrochemical surface area. However, this was accompanied by a decrease in volumetric mass transport, due to stronger electrolyte-electrode interactions. The presence of sodium dodecyl sulfate (SDS) influenced posolyte and negolyte kinetics differently. Kinetics showed a dependence on electrode type and surfactant. On carbon felt, volumetric kinetics decreased for both posolyte and negolyte with SDS addition. On carbon paper, SDS decreased volumetric kinetics for the posolyte but increased (>2X) kinetics for the negolyte! This kinetic enhancement depends on surfactant chemistry: cetyltrimethylammonium bromide, a cationic surfactant, failed to increase kinetics. Furthermore, SDS did not increase areal specific resistance. Furthermore, these findings show the superior performance of carbon paper compared to carbon felt and suggest SDS as a possible VRFB negolyte additive.
Highly-Efficient Microemulsion-Based Absorption Chillers for HVAC Application
Air conditioning is a necessity to achieve a comfortable, habitable home or office for many places in US. However, vapor compression air conditioners are largely made with chlorofluorocarbon refrigerants, or CFCs, which create problems for a world grappling with climate change. In addition, vapor compression air conditioners are driven by electricity. Cooling and heating represent one-third of building electrical energy consumption in US. An absorption chiller is different to vapor compression chillers or air conditioners because it doesn’t use conventional refrigerants, like CFC. Instead, they may use water as the refrigerant which is mixed with safe and nontoxic absorbents. The research performed in this project advanced the understanding of absorption cooling technology and its application in HVAC. Various technologies were explored to improve the performance of the desorber and absorber components in the absorption chillers.
Non-toxic microemulsions polishing for potassium dihydrogen phosphate (KDP) optic
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Spontaneous emulsification induced by nanoparticle surfactants
Microemulsions, mixtures of oil, water, and surfactant, are thermodynamically stable. Unlike conventional emulsions, microemulsions form spontaneously, have a monodisperse droplet size that can be controlled by adjusting the surfactant concentration, and do not degrade with time. To make microemulsions, a judicious choice of surfactant molecules must be made, which significantly limits their potential use. Nanoparticle surfactants, on the other hand, are a promising alternative because the surface chemistry needed to make them bind to a liquid-liquid interface is both well flexible and understood. Here, we derive a thermodynamic model predicting the conditions in which nanoparticle surfactants drive spontaneous emulsification that agrees quantitatively with experiments using Noria nanoparticles. This new class of microemulsions inherits the mechanical, chemical, and optical properties of the nanoparticles used to form them, leading to novel applications.
Etching of water-sensitive optics with water-in-oil emulsions
In one inventive concept, a method for etching an optic includes obtaining a microemulsion, where the microemulsion includes a continuous oil phase, a surfactant system comprising at least one surfactant, and water, submerging at least a portion of the optic in the microemulsion, and agitating by ultrasonication the microemulsion for etching the optic submerged therein.
Development and characterization of acrylated palm oil nanoparticles using ionizing radiation
In this study, the utilization of radiation crosslinking methods which are known as intermolecular and intramolecular crosslinking for the formation of nanoparticles of Acrylated Palm Oil (APO) in the microemulsion system that also consists of Pluronic F-127 (PF-127) surfactant was demonstrated. This microemulsion system was subjected to the ionizing radiation i.e. gamma irradiation at different doses to form the crosslinked APO nanoparticles. The effects of radiation doses on the size of APO nanoparticles were investigated using the Dynamic Light Scattering (DLS) method and their images were viewed using the Transmission Electron Microcrospy (TEM). The Fourier Transform Infra-Red (FTIR) spectroscopy was used to characterize the chemical structure and the crosslinking conversion of carbon-carbon double bond (-C = C-) of the APO nanoparticles after irradiation. As a result, the size of the APO nanoparticle decreased when the irradiation dose increased. Reduce in size might be due to the effect of intramolecular crosslinking reaction of the APO nanoparticles during irradiation process. Meanwhile, the intramolecular -C C- crosslinking conversion percentage was increased at doses below 1kGy before decreasing at the higher dose that might due to the intermolecular crosslinking of the macromolecules. This study showed that radiation crosslinking methods of polymerization and crosslinking in the microemulsion were found to be promising for the synthesis of nanoparticles.
Long wavelength undulations dominate dynamics in large surfactant membrane patches
In this study, by exposing microemulsions to small (80 nm diameter) and large (500 nm) disk shaped clay particles we were able to show the presence of long wavelength undulations that only occur for large membrane patches. A combination of small angle neutron scattering (SANS) and neutron spin echo (NSE) experiments have been applied to study microemulsions. These, consisting of D 2 O, d-decane and the surfactant C 10 E 4 , were used in connection with Laponite (small) and Nanofil (large) clay. To our knowledge our experiments show for the first time that the clay platelets induce lamellar ordering adjacent to the clay discs in the otherwise bicontinuous microemulsion. This is due to the fact that in purely structural investigations, radial averaging smears out the signature of the lamellar phase. For thermodynamically fluctuating membranes near interfaces the theory of Seifert predicts a cross-over of the dispersion relationship from k 2 to a k 3 -dependence. Lastly, with the correlation length of the membrane patches being confined by the dimension of the clay platelets we were able to show that this in fact takes place but is only present for the larger Nanofil particles.
AC electrokinetic manipulation of selenium nanoparticles for potential nanosensor applications
Highlights: ► Se nanoparticles were synthesized using a reverse-microemulsion process. ► AC osmotic fluid flow repulses the particles from electrode edges. ► Dielectrophoretic force attracts the particles to electrode edges. ► Dielectrophoresis electrode showed non-ohmic behavior. ► The device can potentially be used as a nanosensor. - Abstract: We report the AC electrokinetic behavior of selenium (Se) nanoparticles for electrical characterization and possible application as micro/nano devices. selenium Se nanoparticles were successfully synthesized using a reverse-microemulsion process and investigated structurally using X-ray diffraction and transmission electron microscope. Interdigitated castellated ITO and non-castellated platinum electrodes were employed for manipulation of suspended materials in the fluid. Using ITO electrodes at low frequency limits resulted in deposition of Se particles on electrode surface. When Se particles exposed to platinum electrodes in the 10 Hz–1 kHz range and V {sub p−p}> 8, AC osmotic fluid flow repulses the particles from electrode edges. However, in 10 kHz–10 MHz range and V {sub p−p}> 5, dielectrophoretic force attracts the particles to electrode edges. As the Se particle concentration increased, the trapped Se particles were aligned along the electric field line and bridged the electrode gap. The device was characterized and can potentially be useful in making micro/nano electronic devices.
Effect of Eu–Ni substitution on electrical and dielectric properties of Co–Sr–Y-type hexagonal ferrite
Graphical abstract: - Highlights: • Single phase nanostructured Sr{sub 2}Co{sub 2−x}Ni{sub x} Eu{sub y}Fe{sub 12−y}O{sub 22} were synthesized by the microemulsion method. • The materials show semiconducting behavior. • The high resistivity makes these materials useful for high frequency applications. • The Curie temperature decreases with the substituents. - Abstract: Single phase nanostructured Eu–Ni substituted Y-type hexaferrites with nominal composition Sr{sub 2}Co{sub 2−x}Ni{sub x} Eu{sub y}Fe{sub 12−y}O{sub 22} (x = 0.0–1, y = 0.0–0.1) were synthesized by the normal microemulsion method. X-ray diffraction (XRD) technique was employed for phase analysis and indexing of each pattern corroborates that well defined Y-type crystalline phase is formed. It is observed that DC resistivity enhanced which is accredited to room temperature resistivity differences of dopant and host ions. The hopping of electrons and jumping of holes are responsible for conduction below Curie temperature (T{sub C}), whereas above Curie temperature is due to polaron hopping. The decrease in T{sub C} may be due to the fact that Eu–Fe interactions on the B sites are weaker than Fe–Fe interaction. The dispersion in the dielectric constant ε′(f) favor the occurrence of peaks in the tan δ(f). The extraordinary values of resistivity and small dielectric loss make these materials pre-eminent contestant for high frequency applications.