Search NASA⌕ Search

SEARCH · Search NASA

Results for “MICROEMULSIONS”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

High coercivity sized controlled cobalt–gold core–shell nano-crystals prepared by reverse microemulsion

Graphical abstract: - Highlights: • Calculating the crystallinity percentage and percentage of phases presented in Co–Au core–shell nanoparticles. • Magnetic properties of four groups nanogarin: 5, 10, 15, 20 nm. • Single domain ferromagnetic materials with high coercivity at room temperature. • Intrinsic blocking temperature measured in zero field cooled-warmed (ZFC-W). - Abstract: Size-controlled cobalt–gold core–shell nanoparticles were synthesized via the reverse-micelle microemulsion method. In order to control the size of the nanoparticles, the nucleation and growth process were performed within a confined space by adjusting the water to surfactant ratio of reverse micelles solution during synthesis. The crystallinity percentage and percentage of phases presented in Co–Au core–shell nanoparticles were calculated using X-ray diffraction data. The results from transmission electron microscopy provide direct evidence for core–shell structure nanomaterials. Magnetic properties of the samples were investigated using a vibrating sample magnetometer. The as-prepared samples showed significant coercivity at room temperature. The intrinsic blocking temperature was experimentally deduced from zero-field-cooled warmed (ZFC-W) curves by a simple method without employing an external magnetic field. The B-field dependence temperature data of Co–Au nanoparticles exhibited an intrinsic blocking temperature at 45 K. Annealing these samples at 400 °C caused an increase in particle size, crystallinity percentage and further enhanced their magnetic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Microemulsions as Emerging Electrolytes: The Correlation of Structure to Electrochemical Response

We describe the structural studies of microemulsions (μEs) prepared from water, toluene, butanol, and polysorbate 20 (PS20) that we recently used as electrolytes. Small-angle neutron scattering was used to monitor the development of the bicontinuous system as a function of the water-to-surfactant mass ratio on a constant oil-to-surfactant dilution line, revealing how the domain size, correlation length, amphiphilicity factor, and bending moduli change with composition. Kratky and Porod analyses are also employed, providing further structural detail of the scattering domains. Here, we demonstrate that controlling the water-to-surfactant ratio with a constant oil-to-surfactant dilution affects the bicontinuous phase, reveals a sizeable compositional region with structural similarities, and provides insight into the correlation of structure to physical properties. Voltammetric results are presented to examine how the evolution of the bicontinuous structure formed in a μE prepared from water, toluene, butanol, and PS20 contributes to the electrochemical response. These findings, therefore, provide essential information that will guide the formulation of μEs as electrolytes for energy storage.

25 ENERGY STORAGE↗
DOE OSTI2014

Dynamics of microemulsions bridged with hydrophobically end-capped star polymers studied by neutron spin-echo

The mesoscopic dynamical properties of oil-in-water microemulsions (MEs) bridged with telechelic polymers of different number of arms and with different lengths of hydrophobic stickers were studied with neutron spin-echo (NSE) probing the dynamics in the size range of individual ME droplets. These results then were compared to those of dynamicic light scattering (DLS) which allow to investigate the dynamics on a much larger length scale. Studies were performed as a function of the polymer concentration, number of polymer arms, and length of the hydrophobic end-group. In general it is observed that the polymer bridging has a rather small influence on the local dynamics, despite the fact that the polymer addition leads to an increase of viscosity by several orders of magnitude. In contrast to results from rheology and DLS, where the dynamics on much larger length and time scales are observed, NSE shows that the linear polymer is more efficient in arresting the motion of individual ME droplets. This finding can be explained by a simple simulation, merely by the fact that the interconnection of droplets becomes more efficient with a decreasing number of arms. This means that the dynamics observed on the short and on the longer length scale depend in an opposite way on the number of arms and hydrophobic stickers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Form fluctuations of polymer loaded spherical microemulsions studied by neutron scattering and dielectric spectroscopy

We investigate the structure and shell dynamics of the droplet phase in water/AOT/octane microemulsions with polyethyleneglycol (M{sub W} = 1500) molecules loaded in the droplets. Size and polydispersity of the droplets is determined with small angle X-ray scattering and small angle neutron scattering experiments. Shell fluctuations are measured with neutron spin echo spectroscopy and related to the dynamic percolation seen in dielectric spectroscopy. Shell fluctuations are found to be well described by the bending modulus of the shell and the viscosities inside and outside the droplets. Addition of the polymer decreases the modulus for small droplets. For large droplets the opposite is found as percolation temperature shifts to higher values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Recording-media-related morphology and magnetic properties of crystalline CoPt{sub 3} and CoPt{sub 3}-Au core-shell nanoparticles synthesized via reverse microemulsion

A comparative experimental study of the magnetic properties of CoPt{sub 3} and CoPt{sub 3}/Au nanoparticles as well as a detailed study of the structural properties of the samples by X-ray diffraction, Transmission electron microscopy, and vibrating sample magnetometer is presented in this work. In addition, the effect of particle size on the structure and magnetic properties of nanoparticles prepared by microemulsion is studied. The correlation between particle size, crystallinity, and magnetization was studied as well. CoPt nanoparticles have been studied intensively over the last decade because of their increased magnetic anisotropy in the ordered phase that can be interesting for high density magnetic recording. A significant high coercivity for as-prepared CoPt{sub 3} and CoPt{sub 3}-Au nanoparticles was obtained at room temperature and enhanced after annealing. The focused aim of our study is to obtain high coercivity at room temperature that follows the Curie-Weiss law. This indicates an interacting system in which the nanoparticles behave like single domain ferromagnetic materials in the particle size range of 8 to 35 nm. In addition, the interaction increases by cooling the samples to low temperature around 15 K. Temperature dependence 1/M graph was obtained to investigate the behavior of nanoparticles at low temperature and shows the best fit with Curie-Weis mode.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Organic nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP

Unlike inorganic nanoparticles, organic nanoparticles (oNPs) offer the advantage of “interior tailorability,” thereby enabling the controlled variation of physicochemical characteristics and functionalities, for example, by incorporation of diverse functional small molecules. In this study, a unique inimer-based microemulsion approach is presented to realize oNPs with enhanced control of chemical and mechanical properties by deliberate variation of the degree of hyperbranching or cross-linking. The use of anionic cosurfactants led to oNPs with superior uniformity. Benefitting from the high initiator concentration from inimer and preserved chain-end functionality during atom transfer radical polymerization (ATRP), the capability of oNPs as a multifunctional macroinitiator for the subsequent surface-initiated ATRP was demonstrated. This facilitated the synthesis of densely tethered poly(methyl methacrylate) brush oNPs. Detailed analysis revealed that exceptionally high grafting densities (~1 nm −2 ) were attributable to multilayer surface grafting from oNPs due to the hyperbranched macromolecular architecture. The ability to control functional attributes along with elastic properties renders this “bottom-up” synthetic strategy of macroinitiator-type oNPs a unique platform for realizing functional materials with a broad spectrum of applications.

ATRP↗
DOE OSTI2016

Microemulsions and Aggregation Formation in Extraction Processes for Used Nuclear Fuel: Thermodynamic and Structural Studies

Advanced nuclear fuel cycles rely on successful chemical separation of various elements in the used fuel. Numerous solvent extraction (SX) processes have been developed for the recovery and purification of metal ions from this used material. However, the predictability of process operations has been challenged by the lack of a fundamental understanding of the chemical interactions in several of these separation systems. For example, gaps in the thermodynamic description of the mechanism and the complexes formed will make predictions very challenging. Recent studies of certain extraction systems under development and a number of more established SX processes have suggested that aggregate formation in the organic phase results in a transformation of its selectivity and efficiency. Aggregation phenomena have consistently been interfering in SX process development, and have, over the years, become synonymous with an undesirable effect that must be prevented. This multiyear, multicollaborative research effort was carried out to study solvation and self-organization in non-aqueous solutions at conditions promoting aggregation phenomena. Our approach to this challenging topic was to investigate extraction systems comprising more than one extraction reagent where synergy of the metal ion could be observed. These systems were probed for the existence of stable microemulsions in the organic phase, and a number of high-end characterization tools were employed to elucidate the role of the aggregates in metal ion extraction. The ultimate goal was to find connections between synergy of metal ion extraction and reverse micellar formation. Our main accomplishment for this project was the expansion of the understanding of metal ion complexation in the extraction system combining tributyl phosphate (TBP) and dibutyl phosphoric acid (HDBP). We have found that for this system no direct correlation exists for the metal ion extraction and the formation of aggregates, meaning that the metal ion is not solubilized in a reverse micelle core. Rather we have found solid evidence that the metal ions are extracted and coordinated by the organic ligands as suggested by classic SX theories. However, we have challenged the existence of mixed complexes that have been suggested to exist in this particular extraction system. Most importantly we have generated a wealth of information and trained students on important lab techniques and strengthened the collaboration between the DOE national laboratories and US educational institution involved in this work.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2019

Characterization of Fe{sub 3}O{sub 4}/γ-Fe{sub 2}O{sub 3}@ SiO{sub 2} Core-Shell Structure Composite Magnetic Fluid by Microemulsion Method

Fe{sub 3}O{sub 4}/γ-Fe{sub 2}O{sub 3}@SiO{sub 2} composite magnetic fluids were prepared successfully by microemulsion method in this study. Fe{sub 3}O{sub 4} magnetic nanoparticles (Nps) were successfully converted to Fe{sub 3}O{sub 4}/γ-Fe{sub 2}O{sub 3} magnetic Nps by low-temperature low-vacuum oxidation method (LTLV oxidation method), and then coated with silica by the modified Stöber method. The core-shell structure composite magnetic Nps were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), and transmission electron microscopy (TEM). The results show that the size of Fe{sub 3}O{sub 4}/γ-Fe{sub 2}O{sub 3} particles was about 13 nm and that of SiO{sub 2} coating was about 3 nm, and the saturation magnetization of Fe{sub 3}O{sub 4}/γ-Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4}/γ-Fe{sub 2}O{sub 3}@SiO{sub 2} Nps was 59.12 A m{sup 2}/kg and 35.84 A m{sup 2}/kg, respectively. And the saturation magnetization of Fe{sub 3}O{sub 4}/γ-Fe{sub 2}O{sub 3}@SiO{sub 2} magnetic fluid was 22.91 A m{sup 2}/kg.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Effect of Protein Incorporation on the Nanostructure of the Bicontinuous Microemulsion Phase of Winsor-III Systems: A Small-Angle Neutron Scattering Study

Small-angle neutron scattering (SANS) analysis using the Teubner₋Strey model has been employed to evaluate the effect of protein incorporation into the middle, bicontinuous microemulsion (BμE) phase of Winsor-III (W III ) systems formed by an aerosol-OT (AOT)/alkyl ethoxylate mixed surfactant system to understand better the extraction of proteins into and out of BμEs and to study the effect of proteins on a system that serves as a biomimetic analog of cell membranes. Under conditions of high salinity, the incorporation of positively charged proteins cytochrome c, lysozyme, and α-chymotrypsin, near their solubilization limit in the BμEs promoted the release of water and oil from the BμEs, a decrease in the quasi-periodic repeat distance (d), an increase in ordering (a decrease in the amphiphilicity factor, f a ) for the surfactant monolayers, and a decrease in the surface area per surfactant headgroup, suggesting that the proteins affected the self-assembly of components in the BμE phase and produced Debye shielding of AOTs sulfonate headgroup. For W III systems possessing lower salinity, cytochrome c reduced the efficiency of surfactant in the BμE phase, noted by increases in d and f a , suggesting that the enzyme and AOT underwent ion pairing. We find that the results of this study demonstrate the importance of ionic strength to modulate proteinsurfactant interactions, which in turn will control the release of proteins encapsulated in the BμEs, relevant to W III -based protein extraction and controlled release from BμE delivery systems, and demonstrate the utility of BμEs as a model system to understand the effect of proteins on biomembranes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Observation of a structural gradient in Winsor-III microemulsion systems

Here, we demonstrate here for the first time via small-angle neutron scattering (SANS) that the middle, bicontinuous microemulsion (BμE) phase of Winsor-III systems undergoes a gradual change of structure and composition in the vertical direction, contrary to the commonly held belief of uniform structure and composition. A vertical stage was deployed to enable precise alignment of a custom-designed rectangular cell containing the W III system with respect to the neutron beam, allowing for several different vertical positions to be analyzed. For the water/AOT/CK-2,13 (two-tailed alkyl ethoxylate containing a 1,3-dioxolane linkage)/heptane Winsor-III system, the quasi-periodic repeat distance ( d ) and correlation length (ξ), obtained from the Teubner–Strey model applied to the SANS data, decreased and the surface area per volume of the surfactant monolayer ( via Porod analysis) increased in the downward direction, trends that reflect an increase of surfactant concentration, consistent with the ultralow interfacial tension that often occurs for the lower liquid–liquid interface of many W III systems. The water/sodium dodecyl sulfate (SDS)/1-pentanol/dodecane system shared the same trend with regard to d as observed for AOT/CK-2,13. In contrast, for SDS/pentanol, ξ increased and the amphiphilicity factor ( f a ) decreased in the downward direction, trends consistent with a decrease of cosurfactant (pentanol) concentration in the downward direction. Non-uniformity in the vertical direction has implications in the transport of solutes between W III phases during the extractive purification of proteins or the removal of heavy metals and pollutants from wastewater, or the deposition of BμEs onto hydrophilic vs. hydrophobic surfaces as thin coatings.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Correlation Between Microscopic Current Fluctuations Observed at Ultra-Microelectrodes and Macroscopic Bulk Electrolysis Performance in Redox-Active Microemulsions

Microemulsions (μEs) have been proposed as redox flow battery (RFB) electrolytes that maximize ionic conductivity and charge capacity by synergizing two immiscible phases. However, charge transfer during electrolysis in μEs is poorly understood. Here, we show that ultramicroelectrode electrolysis of ferrocene-loaded μEs –20%, 60%, and 90% water - reveals stochastic current fluctuations. These are differentiated in the scanning electrochemical microscopy (SECM) geometry, where power spectral density analysis showed distinct changes in the frequency contributions. SECM in the substrate generation-tip collection mode showed that fluctuations arise under mass-transfer control. Significant differences in the diffusion coefficient of ferrocene species were deducted from SECM approach curves, suggesting phase transfer behavior. Using bulk electrolysis, we calculated the charge accessibility and cycling behavior in the μEs. A decrease in the stochastic behavior of the μEs seems to correlate to a higher accessibility and cycling performance, with the 90% water μE displaying the best reversibility and the 60% the lowest. Altogether, these results suggest that Marangoni-type convection driven by concentration gradients and/or μE restructuring during charge transfer play a role in the electrochemical performance of μEs. This presents opportunities for screening and diagnosing the performance of these emerging RFB electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2026

Structuring, stochastic behavior, and charge storage capacity of redox-active microemulsions formulated with mixtures of toluene and ionic liquid as oil phase

Oil/water microemulsions (µEs) are promising electrolytes for redox flow batteries (RFBs) as they simultaneously improve charge capacity and ionic conductivity. Here, we report the successful formulation of bicontinuous µEs where the oil phase is a solution of trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid in toluene with redox-active ferrocene. We examined the effect of supporting electrolyte anion (NO 3 – , Cl – , ClO 4 – ) on the structure, reactivity, transport, and electrolytic performance of redox-active µEs. Neutron scattering and nuclear magnetic resonance showed that the domain size increased as Cl – > NO 3 – > ClO 4 – while the ferrocene diffusion coefficient increased as NO 3 – > Cl – > ClO 4 – . Scanning electrochemical microscopy indicated anion-dependent current fluctuations during electrolysis, with ClO 4 – exhibiting the least high-frequency oscillations, which correlate to the highest charge and discharge capacity and reversibility. All ionic liquid containing systems improved the performance of toluene-based µEs, highlighting new design principles for these electrolytes.

diffusion↗
DOE OSTI2020

Enhanced Corneal Penetration of a Poorly Permeable Drug Using Bioadhesive Multiple Microemulsion Technology

Corneal penetration is a key rate limiting step in the bioavailability of topical ophthalmic formulations that incorporate poorly permeable drugs. Recent advances have greatly aided the ocular delivery of such drugs using colloidal drug delivery systems. Ribavirin, a poorly permeable BCS class-III drug, was incorporated in bioadhesive multiple W/O/W microemulsion (ME) to improve its corneal permeability. The drug-loaded ME was evaluated regarding its physical stability, droplet size, PDI, zeta potential, ultrastructure, viscosity, bioadhesion, in vitro release, transcorneal permeability, cytotoxicity, safety and ocular tolerance. Our ME possessed excellent physical stability, as it successfully passed several cycles of centrifugation and freeze–thaw tests. The formulation has a transparent appearance due to its tiny droplet size (10 nm). TEM confirmed ME droplet size and revealed its multilayered structure. In spite of the high aqueous solubility and the low permeability of ribavirin, this unique formulation was capable of sustaining its release for up to 24 h and improving its corneal permeability by 3-fold. The in vitro safety of our ME was proved by its high percentage cell viability, while its in vivo safety was confirmed by the absence of any sign of toxicity or irritation after either a single dose or 14 days of daily dosing. Our ME could serve as a vehicle for enhanced ocular delivery of drugs with different physicochemical properties, including those with low permeability.

Ibrahim, Mohamed Moustafa↗
NASA NTRS1987

Quantitative characterization of the viscosity of a microemulsion

The viscosity of the three-component microemulsion water/decane/AOT has been measured as a function of temperature and droplet volume fraction. At temperatures well below the phase-separation temperature the viscosity is described by treating the droplets as hard spheres suspended in decane. Upon approaching the two-phase region from low temperature, there is a large (as much as a factor of four) smooth increase of the viscosity which may be related to the percolation-like transition observed in the electrical conductivity. This increase in viscosity is not completely consistent with either a naive electroviscous model or a simple clustering model. The divergence of the viscosity near the critical point (39 C) is superimposed upon the smooth increase. The magnitude and temperature dependence of the critical divergence are similar to that seen near the critical points of binary liquid mixtures.

Berg, Robert F.↗
NASA NTRS1993

Microemulsion characterization by the use of a noninvasive backscatter fiber optic probe

This paper demonstrates the utility of a noninvasive backscatter fiber optic probe for dynamic light-scattering characterization of a microemulsion comprising sodium dodecyl sulfate/1-butanol/ brine/heptane. The fiber probe, comprising two optical fibers precisely positioned in a stainless steel body, is a miniaturized and efficient self-beating dynamic light-scattering system. Accuracy of particle size estimation is better than +/- 2 percent.

Ansari, Rafat R.↗