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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.

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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

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↗
DOE OSTI2021

A new hypothesis for air loss in cement systems containing fly ash

Although there are many benefits gained from incorporating fly ash into concrete, carbon contamination in the fly ash has been shown to interfere with the efficacy of organic additives in an unpredictable manner. This work uses surface tension measurements to quantify the adsorption of air-entraining agents (AEA) onto cement and fly ash. Both the adsorption capacity of the adsorbents and the adsorption isotherms indicate that the fly ash particles, rather than the carbon itself, dominate adsorption in a carbon-contaminated ash in cement pore solution. We propose that adsorption onto fly ash particles and cement actually improve air entrainment via Pickering stabilization. While the carbon is still expected to contribute to air loss via hydrophobic adsorption of the surfactants, we suggest that the primary way in which the carbon interferes is by shielding surfactant-coated fly ash particles from participating in air development and Pickering stabilization during mixing.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Nanostructural and rheological transitions of pH-responsive supramolecular systems involving a zwitterionic amphiphile and a triamine

Supramolecular aqueous complexes of a synthesized zwitterionic surfactant, 2-(dimethyl(octadecyl)ammonio)acetate (stearyl betaine) and diethylenetriamine, have been found to display pH-tunable rheological properties without the need for a co-surfactant. For this supramolecular system, the dynamically changing interplay among the constituents is responsible for the rich phase behavior including hollow nanotubules, bilayers, and vesicles. A further hypothesis is that hollow nanotubular structure is highly desirable for achieving chain entanglement geometries with reduced mesh size. The rheological properties of the suspension were measured using a rotational rheometer. An analysis using zero-shear viscosities at various temperatures as well as differential scanning calorimetry(DSC) helped shed light on thermodynamic and phase transitions taking place. The morphology of the suspension was analyzed by using a combination of small angle x-ray scattering(SAXS) and atomic force microscopy(AFM). Large steady-shear viscosities (up to ~160 Pa.s) and viscoelastic behavior was observed in acidic conditions which diminished upon increasing the pH. A novel analysis consisting of measured thermodynamic quantities such as activation energy(E a ) and enthalpy of transition(ΔH T ) further allude to the rich pH-sensitive nanoarchitecture of the system. Rather than commonly observed wormlike micelles, hollow nanotubules, as long as 1.6 µm were observed at pH 4 which disintegrated to bilayer sheets and vesicles upon increasing pH. Finally, gaining a comprehensive understanding from all the results, a transition mechanism between different suspension architectures was proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Direct Observation of Liquid Crystal Droplet Configurational Transitions using Optical Tweezers

Liquid crystals (LCs) are easily influenced by external interactions, particularly at interfaces. When rod-like LC molecules are confined to spherical droplets, they experience a competition between interfacial tension and elastic deformations. The configuration of LCs inside a droplet can be controlled using surfactants that influence the interfacial orientation of the LC molecules in the oil-phase of an oil in water emulsion. Here, we used the surfactant sodium dodecyl sulfate (SDS) to manipulate the orientation of 5CB molecules in a polydisperse emulsion and examined the configuration of the droplets as a function of SDS concentration. We triggered pronounced morphological transitions by altering the SDS concentration while observing an individual LC droplet held in place using an optical tweezer. We compared the experimental configuration changes to predictions from simulations. Finally, we observed a hysteresis in the SDS concentration that induced the morphological transition from radial to bipolar and back as well as a fluctuations in the configuration during the transition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Supramolecular Effects of Alkyl Sulfonates in Silver Nanocrystal Synthesis

While cationic surfactants such as hexadecyltrimethylammonium bromide (CTAB) are ubiquitous in the synthesis of noble metal nanocrystals, anionic surfactants are rarely used. This work explores the addition of sodium alkyl sulfonates with chain lengths ranging from one to eight carbons to a silver nanoplatelet reaction. Short-chain sulfonates comprised of one to four carbons show little effect on the nanocrystal synthesis, but alkyl sulfonates comprised of five or more carbons at concentrations above 1 mM have a pronounced effect on the absorbance of the nanocrystals, causing a blueshift in the wavelength of maximum absorbance (λ max ) from approximately 800 to 400 nm as the sulfonate concentration is increased to 7 mM. Higher concentrations of sulfonate result in a subsequent red-shift of the peak. Investigation into the possible formation mechanisms responsible for this synthetic control revealed the absence of sulfonate micelles under the reaction conditions. Instead, we hypothesize that sulfonate bilayers are nucleated around the silver nanocrystals at concentrations below the critical micelle concentration and interact with either the citrate ligands or the silver surface to influence nanocrystal morphology, and thus absorbance. Strikingly, the addition of long-chain alkyl sulfonates to already-synthesized nanocrystals results in similar changes to the nanocrystal absorbance that occur within seconds, providing further support for the proposal that these effects are related to the surface chemistry of the nanocrystals, which appear to be highly dynamic.

alkyls↗
DOE OSTI2021

Characterisation of nano-assemblies inside mesopores using neutron scattering

Adsorption of molecular and nanoscale matter in mesoporous materials is important in filtration and chromatography as well as membrane processes. However, the morphology and distribution of self-assembled structures of adsorbate formed within nanoconfined environments is largely unknown. Small Angle Neutron Scattering (SANS) with porous matrix matching the neutron scattering length density of the solvent has the potential to provide detailed information on the self-assemblies formed in pore spaces. However, analysis of such SANS profiles remains a challenge. In this study, we extend the SANS analysis method previously developed by Findenegg and co-workers to include interparticle correlations, providing a qualitative characterisation of the adsorption state of surfactants and nanoparticles in the cylindrical pores of silica nanomaterials. We find that the pore filling fraction and the self-assembled state of the adsorbate governs the scattering profile. We apply the model to two materials namely, triethyleneglycol monohexyl ether (C 6 E 3 ) surfactant and gold nanoparticles adsorbed in SBA-15 mesoporous silica. In contrast to the C 6 E 3 system, Bragg scattering dominates the diffuse scattering in gold nanoparticle system, which we attribute to the immobile internal structure of the nanoparticles. In conclusion, this new SANS analysis method has potential to elucidate structures of soft matter nanoassemblies inside mesopores.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Surface-active antibiotic production as a multifunctional adaptation for postfire microorganisms

Abstract Wildfires affect soils in multiple ways, leading to numerous challenges for colonizing microorganisms. Although it is thought that fire-adapted microorganisms lie at the forefront of postfire ecosystem recovery, the specific strategies that these organisms use to thrive in burned soils remain largely unknown. Through bioactivity screening of bacterial isolates from burned soils, we discovered that several Paraburkholderia spp. isolates produced a set of unusual rhamnolipid surfactants with a natural methyl ester modification. These rhamnolipid methyl esters (RLMEs) exhibited enhanced antimicrobial activity against other postfire microbial isolates, including pyrophilous Pyronema fungi and Amycolatopsis bacteria, compared to the typical rhamnolipids made by organisms such as Pseudomonas spp. RLMEs also showed enhanced surfactant properties and facilitated bacterial motility on agar surfaces. In vitro assays further demonstrated that RLMEs improved aqueous solubilization of polycyclic aromatic hydrocarbons, which are potential carbon sources found in char. Identification of the rhamnolipid biosynthesis genes in the postfire isolate, Paraburkholderia kirstenboschensis str. F3, led to the discovery of rhlM, whose gene product is responsible for the unique methylation of rhamnolipid substrates. RhlM is the first characterized bacterial representative of a large class of integral membrane methyltransferases that are widespread in bacteria. These results indicate multiple roles for RLMEs in the postfire lifestyle of Paraburkholderia isolates, including enhanced dispersal, solubilization of potential nutrients, and inhibition of competitors. Our findings shed new light on the chemical adaptations that bacteria employ to navigate, grow, and outcompete other soil community members in postfire environments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Effect of Silica and Mixing Time on Microstructures of Porous Polymer Composite by Emulsion Templating

Porous polymer composite with tailored porosity is applied in the myriads of areas such as energy storage, oil/water absorption, bioengineering, and advanced areas of material science. The emulsion templating technology is one of the most popular methods for synthesizing porous polymer composite. It involves solidifying a two-phase mixture of porogen and polymer, then removing porogen to create pores within the continuous emulsion phase by polymerization or curing. The surfactant plays a pivotal role in accomplishing a stable emulsion, a key factor in designing the internal porous structure. This study highlights the effect of silica filler and mixing time on pore morphology, i.e., shape, size, and distribution. on polydimethylsiloxane (PDMS) porous structure utilizing the water-in-oil emulsion templating method. Span® 80 is used as a surfactant to reduce the surface tension between water, silica, and PDMS and simultaneously create a strong foaming effect. Different weight concentrations of silica (1-10 wt%) were chosen while keeping the internal phase, i.e., water (50 wt%) constant. The designed porous structures were further characterized through scanning electron microscopy (SEM). Porous composite specimens fabricated with higher silica content and mixing time consistently exhibit smaller pore sizes than specimens fabricated with lower mixing time and silica content. A breakthrough of pore morphology is seen at silica content higher than 5wt% at 1 min mixing, however, pore morphology drastically changes when mixing time increases from 1 min to 6 min. Variation of finer mixing time beyond 1 min shows stepwise changes in pore morphology from a large single-phase porous structure to a bi-modal porous structure which eventually become a smaller single-mode porous structure. Thus, the emulsion templating technique, in combination with different filler content and mixing time, will effectively aid in designing engineered porous polymer composite with varying stiffness and pore morphology.

Porous polymer, Emulsion templating, Surfactant, P↗
DOE OSTI2025

Shape‐Evolving Structured Liquids

Migration, division, and reconfiguration - functions essential to living systems - are driven by active processes. Developing synthetic mimics is an outstanding challenge. Lipid bilayers that bound natural systems are locally deformed by active species, e.g., microtubules, but the resulting non-equilibrium shapes relax when active species motion ceases, and the shape changes lack immediate control. A fully synthetic system is described, driven by active particles encapsulated by a reconfigurable nanoparticle-surfactant membrane that undergoes shape fluctuations reminiscent of living cells. These shape changes are preserved after particle activity stops. Surfactant concentration tunes the interfacial tension over three orders of magnitude, making on-demand shape evolution possible. Directional migration, division, and reconfiguration across multiple scales are possible, leading to a new class of biomimetic, reconfigurable, and responsive materials, paving the way for autonomous synthetic machines.

Kim, Paul Y↗
DOE OSTI2023

Relaxing Wrinkles in Jammed Interfacial Assemblies

Abstract Dynamic covalent bonding has emerged as a mean by which stresses in a network can be relaxed. Here, the strength of the bonding of ligands to nanoparticles at the interface between two immiscible liquids affect the same results in jammed assemblies of nanoparticle surfactants. Beyond a critical degree of overcrowding induced by the compression of jammed interfacial assemblies, the bonding of ligands to nanoparticles (NPs) can be broken, resulting in a desorption of the NPs from the interface. This reduces the areal density of nanoparticle surfactants at the interface, allowing the assemblies to relax, not to a fluid state but rather another jammed state. The relaxation of the wrinkles caused by the compression reflects the tendency of these assemblies to eliminate areas of high curvature, favoring a more planar geometry. This enabled the generation of giant vesicular and multivesicular structures from these assemblies.

Xie, Ganhua↗
DOE OSTI2023

Dynamic Oscillation and Motion of Oil‐in‐Water Emulsion Droplets

Abstract The interplay of interfacial tensions on droplets results in a range of self‐powered motions that mimic those of living systems and serve as a tunable model to understand their complex non‐equilibrium behavior. Spontaneous shape deformations and oscillations are crucial features observed in nature but difficult to incorporate in synthetic artificial systems. Here, we report sessile oil‐in‐water emulsions that exhibit rapid oscillating behavior. The oscillations depend on the nature and concentration of the surfactant, the chemical composition of the oil, and the wettability of the solid substrate. The rapid changes in the contact angle per oscillation are observed using side‐view optical microscopy. We propose that the changes in the interfacial tension of the oil droplets is due to the partitioning of the surfactant into the oil phase and the movement of self‐emulsified oil out of the parent droplets giving rise to the rhythmic variation in droplet contact‐line. The ability to control and understand droplet oscillation can help model similar oscillations in out‐of‐equilibrium systems in nature and reproduce biomimetic behavior in artificial systems for various applications, such as microfluidic lab‐on‐a‐chip and adaptive materials.

Krishna Mani, Sanjana↗
DOE OSTI2023

Dynamic Oscillation and Motion of Oil‐in‐Water Emulsion Droplets

The interplay of interfacial tensions on droplets results in a range of self‐powered motions that mimic those of living systems and serve as a tunable model to understand their complex non‐equilibrium behavior. Spontaneous shape deformations and oscillations are crucial features observed in nature but difficult to incorporate in synthetic artificial systems. Here, we report sessile oil‐in‐water emulsions that exhibit rapid oscillating behavior. The oscillations depend on the nature and concentration of the surfactant, the chemical composition of the oil, and the wettability of the solid substrate. The rapid changes in the contact angle per oscillation are observed using side‐view optical microscopy. We propose that the changes in the interfacial tension of the oil droplets is due to the partitioning of the surfactant into the oil phase and the movement of self‐emulsified oil out of the parent droplets giving rise to the rhythmic variation in droplet contact‐line. The ability to control and understand droplet oscillation can help model similar oscillations in out‐of‐equilibrium systems in nature and reproduce biomimetic behavior in artificial systems for various applications, such as microfluidic lab‐on‐a‐chip and adaptive materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Corn stover‐derived porous carbon for asymmetric supercapacitors

In this investigation, hydrothermal liquefaction‐derived hydrochar from pulverized corn stover (avg. particle size 1.12 mm and ash content 6.75 wt%) is chemically activated with aqueous KOH in the presence of Pluronic F127 surfactant and thermally treated further up to 800°C to generate porous carbon (POC) with higher specific surface area and porosity. POC obtained under different processing conditions is thoroughly characterized by Brunauer‐Emmett‐Teller surface area analyzer, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. Metallic impurity present in POC is characterized by inductively coupled plasma mass spectrometry. Higher specific surface area POC is observed with the use of the surfactant during the activation process. Fully characterized POC is used with (Mn, Ti)‐mixed oxide electrode to fabricate asymmetric supercapacitor (ASC). Specific capacitance of ASC is measured by cyclic voltammetry (CV) technique using Gamry G‐300 potentiostat/galvanostat/ZRA. CV plots are obtained with different voltage scan rates whereas galvanostatic charge‐discharge plots are studied by varying the current density. Renewable corn stover‐derived POC prepared using Pluronic F127/KOH activation method is found to be highly suitable as an electrode material because of higher capacitance and electrochemical stability over 100 charging‐discharging cycles.

25 ENERGY STORAGE↗
DOE OSTI2022

Bioremediation of heavy oily sludge: a microcosms study

Oily sludge is a residue from the petroleum industry composed of a mixture of sand, water, metals, and high content of hydrocarbons (HCs). The heavy oily sludge used in this study originated from Colombian crude oil with high density and low American Petroleum Institute (API) gravity. The residual waste from heavy oil processing was subject to thermal and centrifugal extraction, resulting in heavy oily sludge with very high density and viscosity. Biodegradation of the total petroleum hydrocarbons (TPH) was tested in microcosms using several bioremediation approaches, including: biostimulation with bulking agents and nutrients, the surfactant Tween 80, and bioaugmentation. Select HC degrading bacteria were isolated based on their ability to grow and produce clear zones on different HCs. Degradation of TPH in the microcosms was monitored gravimetrically and with gas chromatography (GC). The TPH removal in all treatments ranged between 2 and 67%, regardless of the addition of microbial consortiums, amendments, or surfactants within the tested parameters. The results of this study demonstrated that bioremediation of heavy oily sludge presents greater challenges to achieve regulatory requirements. Additional physicochemical treatments analysis to remediate this recalcitrant material may be required to achieve a desirable degradation rate.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Research on oxygen solubility in aqueous amine solvents with common additives used for CO 2 chemical absorption

Oxidative degradation in amine based post-combustion carbon capture (PCCC) leads to solvent losses and decreased solvent performance. Oxygen (O 2 ) in the flue gas is dissolved into the aqueous solvent and can reactively degrade the amine component. Advanced aqueous amine solvents are designed to contain additional surfactant and anti-foam additives as well as two types of corrosion inhibitors. These additives contribute to improve the solvent performance while reducing foaming and corrosion of expensive equipment. This work examines the impact of these additives on oxygen solubility (or dissolved oxygen - DO) in various aqueous amines used in PCCC including ethanolamine (MEA), 1-amino-2-propanol (A2P), 2-amino-1-propanol (2A1P), 2-(methylamino)-ethanol (NMEA), 2-(ethylamine)-ethanol (2EAE), diethanolamine (DEA), methyl-diethanolamine (MDEA), dimethylethanolamine (DMEA), piperazine (PZ), 1,2-ethyldiamine (EDA), and 1,6 hexadiamine (HDA). Further, the impact of carbon loading on oxygen solubility with and without these additives was also examined. The surfactant and anti-foam additives had minimal impact on DO for all the solvents investigated. The two anticorrosion additives had opposite effects in the measured DO, 2- mercaptobenzothiazole (MBT) decreased the DO concentration, and sodium metavanadate showed an increase. These results indicate that several of these common additives can be expected to minimally affect DO related oxidative degradation in these advance amine solvents.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Peeling back the layers: Investigating the effects of polyelectrolyte layering on surface structure and stability of oil-in-water nanoemulsions

Layer-by-layer deposition of polyelectrolytes is a useful technique for modifying surface functionalities. For drug delivery systems, alternating layers of biopolymers coat nanoemulsions, which house and protect the cargo until the time and destination of delivery. In this report we investigate molecular factors contributing to the stability and interfacial properties of nanoemulsions prepared by a co-adsorption of polymers poly(styrene sulfonate) and polyethylenimine (PEI), and surfactant dodecyltrimethylammonium bromide. We hypothesize the interplay between electrosteric and hydrophobic effects upon multi-polymer co-adsorption contributes to both macroscopic and molecular-level interfacial properties of nanoemulsions. To probe interfacial layering properties, we use vibrational sum frequency scattering spectroscopy with ζ -potential measurements to determine the adsorptive behavior and molecular conformational arrangement of the polymer layers. Complementing these interfacial studies are dynamic light scattering experiments measuring the nanoemulsion size distribution and polydispersity index over a 30-day period. Our light scattering, ζ -potential, and spectroscopic results of the nanoemulsion surface show that the duration of droplet stability and the degree of molecular orientation of adsorbed polymers can be tuned by surfactant concentration, PEI concentration, and pH. These results illustrate how molecular surface properties of multi-polymer coated nanoemulsions contribute to synergistic effects and droplet stability, enabling advancements in applications surrounding biopharmaceuticals, cosmetics, and food sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Stoichiometric metal nitration based novel green synthesis of mesoporous metal oxides and their enhanced heterogeneity

Here, in this work, a general and novel method for the green synthesis of mesoporous metal oxides via stoichiometric metal nitration has been demonstrated. Pluronic surfactants and their effect on synthesis procedures in terms of surface area have been experimentally studied in detail. Contrary to the traditional synthesis procedure, water has been utilized as the solvent and in several cases, such as tin oxide, manganese oxide, aluminum oxide, antimony oxide, zinc oxide, cobalt oxide, copper oxide, yttrium oxide, lanthanum oxide, and silver either the highest or comparable surface areas have been successfully synthesized. Through XRD, and TEM, all materials were observed to be crystalline except silver and magnesium oxide. SEM shows that with an increase in surfactant molar mass agglomeration decreases. Ammonia chemisorption on acidic materials gives quantitative amounts of ammonia chemical bonding with catalysts, whereas carbon dioxide chemisorption gives a quantitative value of CO 2 chemical binding with basic sites. As high as 1901.8 μmol/g and 994.6 μmol/g ammonia chemisorption values for oxides of vanadium and tin were achieved. Amphoteric materials give both acidic and basic enhanced adsorption. Finally, all synthesized materials are studied under organic catalytic transformations. Benzyl bromide is theoretically more active compared with benzylamine and benzyl alcohol which was also experimentally shown through the conversion.

36 MATERIALS SCIENCE↗