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At least 19 records

Kelvin-Helmholtz instability as one of the key features for fast and efficient emulsification by hydrodynamic cavitation

The paper investigates the oil–water emulsification process inside a micro-venturi channel. More specifically, the possible influence of Kelvin-Helmholtz instability on the emulsification process. High-speed visualizations were conducted inside a square venturi constriction with throat dimensions of 450 µm by 450 µm, both under visible light and X-Rays. We show that cavity shedding caused by the instability results in the formation of several cavity vortices. Their rotation causes the deformation of the oil stream into a distinct wave-like shape, combined with fragmentation into larger drops due to cavitation bubble collapse. Later on, the cavity collapse further disperses the larger drops into a finer emulsion. Thus, it turns out that the Kelvin-Helmholtz instability is similarly characteristic for hydrodynamic cavitation emulsification inside a microchannel as is the Rayleigh-Taylor instability for acoustically driven emulsion formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reversible Emulsions from Polyoxometalate–Polymer: A Robust Strategy to Cyclic Emulsion Catalysis and High-Internal-Phase Emulsion Materials

Reversible Pickering emulsions, achieved by switchable, interfacially active colloidal particles, that enable on-demand emulsification/demulsification or phase inversion, hold substantial promise for biphasic catalysis, emulsion polymerization, cutting fluids, and crude oil pipeline transportation. However, particles with such a responsive behavior usually require complex chemical syntheses and surface modifications, limiting their extensive use. Herein, we report a simple route to generate emulsions that can be controlled and reversibly undergo phase inversion. The emulsions are prepared and stabilized by the interfacial assembly of polyoxometalate (POM)–polymer, where their electrostatic interaction at the interface is dynamic. The wettability of the POMs that dictates the emulsion type can be readily regulated by tuning the number of polymer chains bound to POMs, which, in turn, can be controlled by varying the concentrations of both components and the water/oil ratio. In addition, the number of polymer chains anchored to the POMs can be varied by controlling the number of negative charges on the POMs through an in situ redox reaction. As such, a reversible inversion of the emulsions can be triggered by switching between exposure to ultraviolet light and the introduction of oxygen. Combining the functions of POM itself, a cyclic interfacial catalysis system was realized. Inversion of the emulsion also affords a pathway to high-internal-phase emulsions. Finally, the diversity of the POMs, the polymers, and the responsive switching groups open numerous new, simple strategies for designing a wide range of responsive soft matter for cargo loading, controlled release, and delivery in biomedical and engineering applications without time-consuming particle syntheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics of oil–water interface at the beginning of the ultrasonic emulsification process

A lot of effort has been dedicated in recent years towards understanding the basics of cavitation induced emulsification, mainly in the form of single cavitation bubbles. Regarding bulk acoustic emulsification, a lot less research has been done. In our here presented work we utilize advanced high-speed observation techniques in visible light and X-Rays to build upon that knowledge and advance the understanding of bulk emulsion preparation. During research we discovered that emulsion formation has an acute impact on the behavior of the interface and more importantly on its position relative to the horn, hence their interdependence must be carefully studied. We did this by observing bulk emulsification with 2 cameras simultaneously and corroborating these measurements with observation under X-Rays. Since the ultrasonic horns location also influences interface behavior, we shifted its initial position to different locations nearer to and further away from the oil–water interface in both phases. We found that a few millimeters distance between the horn and interface is not enough for fine emulsion formation, but that they must be completely adjacent to each other, with the horn being located inside the oil–water interface. We also observed some previously undiscovered phenomena, such as the splitting of the interface to preserve continuous emulsion formation, climbing of the interface up the horn and circular interface protrusions towards the horn forming vertical emulsion streams. Interestingly, no visible W/O emulsion was ever formed during our experiments, only O/W regardless of initial horn position.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Amphiphilic Polyphosphazene for Fluorocarbon Emulsion Stabilization

High internal phase emulsions (HIPEs) have been of great interest for fabricating fluorinated porous polymers having controlled pore structures and excellent physicochemical properties. However, it remains a challenge to prepare stable fluorocarbon HIPEs, due to the lack of suitable surfactants. By randomly grating hydrophilic and fluorophilic side chains to polyphosphazene (PPZ), a comb-like amphiphilic PPZ surfactant with biodegradability is designed and synthesized for stabilizing water/fluorocarbon oil-based emulsions. The hydrophilic–lipophilic balance of PPZs can be controlled by tuning the grating ratio of the two side chains, leading to the preparation of stable water-in-oil HIPEs and oil-in-water emulsions, and the production of fluorinated porous polymers and particles by polymerizing the oil phase. Finally, these fluorinated porous polymers show excellent thermal stability and, due to the hydrophobicity and porous structure, applications in the field of oil/water separation can be achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Role of Interfaces and Charge for Chemical Reactivity in Microdroplets

A wide variety of reactions are reported to be dramatically accelerated in aqueous microdroplets, making them a promising platform for environmentally clean chemical synthesis. However, to fully utilize the microdroplets for accelerating chemical reactions requires a fundamental understanding of how microdroplet chemistry differs from that of a homogeneous phase. Here, in this work, we provide our perspective on recent progress to this end, both experimentally and theoretically. We begin by reviewing the many ways in which microdroplets can be prepared, creating water/hydrophobic interfaces that have been frequently implicated in microdroplet reactivity due to preferential surface adsorption of solutes, persistent electric fields, and their acidity or basicity. These features of the interface interplay with specific mechanisms proposed for microdroplet reactivity, including partial solvation, possible gas phase channels, and the presence of highly reactive intermediates. We especially highlight the role of droplet charge and associated electric fields, which appears to be key to understanding how certain reactions, like the formation of hydrogen peroxide and reduced transition metal complexes, are thermodynamically possible in microdroplets. Lastly, we emphasize opportunities for theoretical advances and suggest experiments that would greatly enhance our understanding of this fascinating subject.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Encapsulation of Wastes Using Adapted Geopolymer Formulations - 20272

A geopolymer formulation characterized by a low initial viscosity, suitable to immobilise a wide range of waste types such as oils, chemicals and solid waste, is introduced and characterized. The role of the specific surface area of magnesium oxide additions to the reference formulation is presented. Moreover, its capability to encapsulate different volume fractions of oil via the preparation of oil in activator solution emulsions is introduced. Lastly, the effect of oil incorporation on the density, the mechanical strength and the leaching properties of the compositions is presented and discussed. (authors)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facile design of renewable lignin copolymers by photoinitiated RAFT polymerization as Pickering emulsion stabilizers

As the richest aromatic renewable resource, lignin has attracted significant attention for fabricating various materials. However, due to lignin's structural complexity, an effective and facile structural modification strategy remains a substantial challenge. Herein, we have successfully applied photoinitiated reversible addition–fragmentation chain transfer (RAFT) as a versatile tool to synthesize amphiphilic lignin copolymers with lignin derivatives as the macroinitiator. The experimental and density functional theory analysis systematically investigated the photopolymerization kinetics, proving excellent control over molecular weights. Additionally, 1 H NMR and FT-IR analyses confirmed the well-designed structures. Moreover, the structures of copolymers were tunable by simple variations of monomer structures. Finally, the self-assembly of the synthesized copolymers into nanoparticles was explored, together with the potential applications as Pickering emulsion stabilizers. Finally, we believe that this work will offer a facile and green approach to synthesize lignin-based novel copolymers and further expand its applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Suspended Membrane Evaporators Integrating Environmental and Solar Evaporation for Oily Wastewater Purification

Solar-driven evaporation is promising in oily wastewater treatment, in particular for emulsions, but conventional evaporators suffer from pore blocking by residual oil or contamination by volatile oil compounds in the condensed water. In the current research, we develop a suspended membrane evaporator integrating solar evaporation with oil-in-water emulsion separation. The heating and evaporating interface is separated from the rejecting interface to avoid oil escape and improve heat management. A temperature gradient forms on the membrane surface that can promote evaporation performance by combining both solar and environmental evaporation. Such an evaporator achieves a maximum evaporation rate of 1.645 kg/(m 2 ·h) as well as an apparent evaporation efficiency of 111.9%. Moreover, the superhydrophilic and superoleophobic membrane shows excellent oil repellence and emulsion rejection, which can achieve an oil removal efficiency above 98.8% in oil-in-water emulsion separation, and high evaporation rate recovery in cycling tests. Furthermore, a scaled-up membrane evaporator array produces ~8 kg/(m 2 ·d) of clean water from oily wastewater in outdoor experiments, further demonstrating the strong purification performance of this evaporator in oily wastewater treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of phospholipids and triacylglycerols in intravenous lipid emulsions

Intravenous lipid emulsions (ILEs) are used for parenteral nutrition, providing a vital source of essential fatty acids and concentrated energy for patients who are unable to absorb nutrients via the digestive track. They are commonly used to treat local and non-local anesthetic toxicity, and lipophilic drug overdose. ILE are composed of natural lipids, and the composition of these natural lipids can be varied based on their source. The lipids are susceptible to hydrolytic degradation with time, resulting various lipid degradation products such as Lysophosphatidylcholines (LPs), affecting the actual composition of nutrients in the formulation. As a result, the identification and quantification of lipid components, including degradation products, in ILEs are crucial in quality control. In this study, lipids from different batches of ILE Intralipid® 20%, were separated and identified using a UHPLC-ESI-QTOF system and SimLipid® high throughput lipid identification software. Out of 47 lipids identified, 34 were phospholipids (PLs) and the others were triacylglycerols (TAGs). Most of the phospholipids detected were phosphatidylcholines (PC) and Lysophosphatidylcholines (LPC). A total of 9 LPCs, 18 PCs, 6 phosphoethanolamines (PEs), and 1 sphingomyelin (SM) were identified. The LPCs concentration changed with the manufacturing date and storage time. Furthermore, this UHPLC method enabled the identification and quantification of lipids and their decomposition products in complex ILE emulsion mixtures on a single 20-minute chromatographic run.

60 APPLIED LIFE SCIENCES↗

Learning New Techniques for Remediation of Contaminated Sites

The project emphasizes NASA's Missions of understanding and protecting our home planet as well as of inspiring the next generation of explorers. The project fellow worked as part of a team on the development of new emulsion-based technologies for the removal of Contaminants from soil, sediment, and groundwater media with the scientists in charge of the emulsion-based technologies. Hands-on chemistry formulation and analyses using a GCM, as well as field sampling was done. The fellow was tidy immersed in lab and fieldwork, as well as, training sessions to qualify her to do the required work. The principal outcome of the project is the motivation to create collaboration links between major research university (UCF) and an emerging research university (UT).

Lipsett-Ruiz, Teresa↗

Synthesis and characterization of polylactic acid microspheres via emulsion-based processing

Polylactic acid (PLA) microspheres are primarily used in drug delivery applications and rarely manufactured commercially. In encapsulation, the drug encapsulation and microsphere synthesis process happen simultaneously. Simultaneous synthesis necessitates conditions that ensure the drugs to be encapsulated remain viable in the synthesis process. Here, in the present work, solid pure PLA microspheres are prepared using a repeatable centrifugal mixing method to create a single emulsion system. A planetary thinky mixer is used to achieve centrifugal mixing. PLA acts as the dispersed phase of the emulsion, whereas Polyvinyl alcohol (emulsifier) dissolved in deionized water serves as the bulk phase. The emulsions are stirred for about 4 min at 2000 rpm. Microspheres prepared by mechanical mixing are compared with microspheres prepared by centrifugal mixing. The microspheres prepared by centrifugal mixing proved to be narrower and closer to a normal distribution with a mean size (D x 50) of 30 microns. The size distribution of planetary mixed microspheres did not change from one batch to another.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanolignin-based high internal phase emulsions for efficient protection of curcumin against UV degradation

As an emulsifier, lignin exhibits excellent UV resistance on drug-loaded emulsion systems for drug delivery. However, due to the structural variation and complexity of lignins from various origins, their UV shielding performance varies with the techniques for lignin extraction, which impacts properties and the protection efficiency of lignin-based HIPEs (high internal phase emulsions). In this work, lignin nanoparticles, prepared from three lignin preparations of Eucalyptus, were used in HIPEs delivery systems to protect curcumin from degradation by UV radiation. Structures of the lignin preparations were characterized using 2D HSQC (heteronuclear single-quantum coherence) NMR (nuclear magnetic resonance), 31 P NMR, and GPC (gel permeation chromatography). The residual curcumin level after 36h UV exposure in the nanolignin-based HIPEs was over 72%, much higher than that (< 10% after 24 h UV exposure) in the oil phase without lignin, indicating that the nanolignin-based HIPEs with enhanced UV shielding ability protect curcumin better. Of the three lignin preparations, AL (alkali lignin), with the lowest molecular weight, highest contents of phenolic hydroxyl and carboxyl groups, and highest S/G ratio, displayed the best anti-UV radiation ability and the most uniform nanoparticle size.

59 BASIC BIOLOGICAL SCIENCES↗

3D Structure of Oil Droplets in Hardened Geopolymer Emulsions: Impact of Various Commercial Liquid Oils - 20184

Cement-based solidification/stabilization (S/S) is a widely applied technique for the immobilization of inorganic hazardous constituents. However, S/S is considered less compatible for organic liquid waste (OLW) because organic compounds may inhibit binder hydration. Geopolymers (i.e. alumino-silicate materials) are an alternative for applications in which Portland cements are inappropriate. In a previous work, we proposed a direct immobilization of organic liquid waste in a geopolymer binder (GEOIL composite). We demonstrated the feasibility for producing various composites on model system (hexadecane) and on a hydraulic oil, which are dispersed in the geopolymer binder as droplets (10-50 μm typical size). In nuclear facilities, legacy waste based on organic liquids are currently stored. Many of them have been used for various applications in the nuclear industry (lubrication, cutting, analysis, liquid/liquid extraction..) with very wide chemical compositions. In this study, we study the influence of various commercial organic oils immobilized in hardened geopolymer emulsions by X-ray micro-tomography. Image analysis make it possible to determine the 3D spatial and size distributions of oil droplets in geopolymer emulsions. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Can Li: A Career in Catalysis

Prof. Can Li is distinguished for his seminal achievements in fundamental and applied researches in catalysis, especially in advancing the characterization of catalysts and catalytic reactions related to solar energy conversion and fine chemical synthesis. The scope of his research is wide ranging, and he is leading some of the fields. This account highlights his major scientific achievements in advancing the fundamental sciences of characterizing catalysts and understanding the mechanisms of catalytic reactions by developing in situ spectroscopic techniques (e.g., infrared (IR), ultraviolet (UV), Raman, space- and time-resolved spectroscopies and photoelectric imaging), and applying the obtained knowledge in the rational design and synthesis of catalysts for practical applications in photocatalytic, electrocatalytic and photoelectrocatalytic water splitting and CO 2 reduction, chiral synthesis in nanoreactors and ultradeep desulfurization of fuels, and fine chemical synthesis. In particular, his demonstration of the kiloton scale solar fuel production project will be introduced as a successful model for converting fundamental science into practical and impactful applications to convert CO 2 and water into solar fuels. This account also highlights his services to the catalysis communities and international collaborations for promoting catalysis science worldwide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗