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At least 469 records · Page 26

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DOE OSTI2020

Densification of non-radioactive porous siliceous particles loaded with cesium potassium copper hexacyanoferrate by spark plasma sintering

In the development of a conditioning process for cesium-bearing sorbents from the decontamination of aqueous waste streams, the treatment of a granular material composed of (Cs,K) 2 CuFe(CN) 6 loaded onto mesoporous silica particles has been investigated in an additive-free two-step conditioning process involving (i) calcination at 1000 °C to remove volatile species and (ii) densification by spark plasma sintering. A 92.0 % dense pellet was obtained after 10 min sintering at 850 °C under 100 MPa. Density and microstructural measurements indicate that densification is first driven by the viscous flow of a vitreous phase containing Cs, formed during calcination. Additionally, the density of the sample then increases further during sintering by grain boundary diffusion. However, a limited but non negligible part of cesium is lost during densification.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Data for 3-Hydroxypropionic Acid Recovery from Fermentation Broth through Novel Downstream Processing: Technoeconomic Analysis

This study develops and validates a simplified, fully solvent-free downstream processing (DSP) strategy for high-purity recovery of 3-hydroxypropionic acid (3-HP) from real fermentation broth containing 62.3 g/L of 3-HP. Optimized activated carbon treatment achieved 98% color removal, while Amberlite IRA-67 was operated at pH 4.5 and 30 °C to minimize product loss. This is the first integrated demonstration of a fully solvent-free DSP enabling recovery of bio-based 3-HP as both a solid sodium salt and a concentrated aqueous solution, supported by techno-economic analysis. At lab scale, the process achieved 77.3% recovery of sodium 3-HP with 83.2% (w/w) purity and produced a 30% (w/v) aqueous solution. Techno-economic analysis yielded minimum selling prices of $0.551/kg for the solution and $0.892/kg for the salt, both below target thresholds for cost-competitive bio-acrylic acid production. Overall, these results demonstrate an efficient, scalable, and economically viable industrial pathway for 3-HP recovery.

Bioproducts↗

NASA NTRS1976

Candidate space processing techniques for biomaterials other than preparative electrophoresis

The advantages of performing the partition and countercurrent distribution (CCD) of cells in phase separated aqueous polymer systems under reduced gravity were assessed. Other possible applications considered for the space processing program include the freezing front separation of cells, adsorption of cells at the air-water interface, and the macrophage electrophoretic mobility test for cancer.

Brooks, D. E.↗

DOE OSTI2023

Aqueous Interfaces in Chemical Separations

Chemical separations play a vital role in refinery and reprocessing of critical materials, such as platinum group metals, rare earths, and actinides. The choice of separation system─whether it is liquid–liquid extraction (LLE), sorbents, or membranes─depends on specific needs and applications. In almost all separation processes, the desired metal ions adsorb or transfer across an aqueous interface, such as the solid/liquid interface in sorbents or oil/water interfaces in LLE. Despite these separation technologies being extensively used for decades, our understanding of the molecular-scale mechanisms governing ion adsorption and transport at interfaces remains limited. This knowledge gap presents a significant challenge in meeting the increasing demands for these critical materials due to their growing use in advanced technologies. Fortunately, recent advancements in surface-specific experimental and computational techniques offer promising avenues to bridge this gap and facilitate the development of next-generation separation systems. Interestingly, unanswered questions regarding interfacial phenomena in chemical separations hold great relevance to various fields, including energy storage, geochemistry, and atmospheric chemistry. Therefore, the model interfacial systems developed for studying chemical separations, such as amphiphilic molecules assembled at a solid/water, air/water, or oil/water interface, may have far-reaching implications, extending beyond separations and opening doors to addressing a wide range of scientific inquiries. This perspective discusses recent interfacial studies elucidating amphiphile–ion interactions in chemical separations of metal ions. Finally, these studies provide direct, molecular-scale information about solute and solvent behavior at aqueous interfaces, including multivalent and complex ions in highly concentrated solutions, which play key roles in LLE of critical materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

The Dopamine Assisted Synthesis of MoO3/Carbon Electrodes With Enhanced Capacitance in Aqueous Electrolyte

A capacitance increase phenomenon is observed for MoO 3 electrodes synthesized via a sol-gel process in the presence of dopamine hydrochloride (Dopa HCl) as compared to α-MoO 3 electrodes in 5M ZnCl 2 aqueous electrolyte. The synthesis approach is based on a hydrogen peroxide-initiated sol-gel reaction to which the Dopa HCl is added. The powder precursor (Dopa) x MoO y , is isolated from the metastable gel using freeze-drying. Hydrothermal treatment (HT) of the precursor results in the formation of MoO 3 accompanied by carbonization of the organic molecules; designated as HT-MoO 3 /C. HT of the precipitate formed in the absence of dopamine in the reaction produced α-MoO 3 , which was used as a reference material in this study (α-MoO 3 -ref). Scanning electron microscopy (SEM) images show a nanobelt morphology for both HT-MoO 3 /C and α-MoO 3 -ref powders, but with distinct differences in the shape of the nanobelts. The presence of carbonaceous content in the structure of HT-MoO 3 /C is confirmed by FTIR and Raman spectroscopy measurements. X-ray diffraction (XRD) and Rietveld refinement analysis demonstrate the presence of α-MoO 3 and h-MoO 3 phases in the structure of HT-MoO 3 /C. The increased specific capacitance delivered by the HT-MoO 3 /C electrode as compared to the α-MoO 3 -ref electrode in 5M ZnCl 2 electrolyte in a −0.25–0.70 V vs. Ag/AgCl potential window triggered a more detailed study in an expanded potential window. In the 5M ZnCl 2 electrolyte at a scan rate of 2 mV s −1 , the HT-MoO 3 /C electrode shows a second cycle capacitance of 347.6 F g −1 . The higher electrochemical performance of the HT-MoO 3 /C electrode can be attributed to the presence of carbon in its structure, which can facilitate electron transport. Our study provides a new route for further development of metal oxides for energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRSDate not supplied

Potential Discovery of Amphibole in Miller Range (MIL) 090292 via Raman Spectroscopy

Ungrouped carbonaceous chondrites have the potential to provide insights into processes on their parent bodies that may not be accessible through studying established groups. Miller Range (MIL) 090292 is an extensively aqueously altered ungrouped carbonaceous chondrite, which provides the potential to reveal new information about alteration processes on carbonaceous chondrite-like asteroids. The meteorite MIL090292 was initially classified as a CR1 chondrite. It experienced heavy aqueous alteration and, texturally, the meteorite is highly brecciated. MIL 090292 was reclassified as a C1 ungrouped chondrite after it was found that the Δ17O values of its magnetite grains do not plot along the CR mixing line. Furthermore, there is a lack of calcium carbonate grains in the sample, which are common in aqueously altered CRs –calcium is found in andradite and hedenbergite (which are not found in CRs) and phosphates. However, beyond this basic mineralogical information, there is a lack of knowledge about the petrogenetic history of the meteorite or its parent body.

Meteorite↗

DOE OSTI2025

Cesium exhibits different mesoscale segregation and ion pairing than lithium, sodium, or potassium in concentrated alkaline aqueous nitrite solutions

Understanding ion pairing in concentrated alkaline electrolytes facilitates the prediction and control of chemical processes in nuclear waste. While sodium is the dominant alkali metal in such systems, cesium often exhibits distinct bulk behavior relative to lighter alkali cations. Aqueous mixtures of cesium hydroxide and sodium nitrite were compared to alkali hydroxide analogs using small-angle x-ray scattering, revealing that cesium disrupts the sodium nitrite electrolyte structure, forming cesium-rich domains. This mesoscale segregation contrasts with the near-ideal mixing observed in other mixed hydroxide–nitrite systems. Raman spectroscopy indicates cesium–nitrite ion pairing, evidenced by vibrational shifts distinct from those associated with sodium. Multinuclear magnetic resonance spectroscopy further supports cesium–nitrite and cesium–hydroxide association, revealing a distinct local environment for nitrite in cesium-containing solutions. Together, these findings show that cesium promotes a unique solution structure dominated by specific ion pairing within segregated domains. This structural organization may influence radical generation pathways in high-ionic-strength alkaline media relevant to nuclear waste processing and management.

Nienhuis, Emily T. [Pacific Northwest National Lab↗

DOE OSTI2025

Probing air-water interfaces of dibutyl phosphoric acid (HDBP) aqueous solutions using vibrational sum frequency generation (vSFG) spectroscopy

Liquid-liquid extraction is a separation technique implemented in a wide variety of areas, achieving particular success in both the nuclear and biomedical fields. In this work, vibrational sum frequency generation spectroscopy (VSFG) and surface tension measurements were used to investigate the adsorption of dibutyl phosphate (DBP) at air-aqueous interfaces to simulate liquid-liquid systems relevant to the Plutonium Uranium Redox Extraction (PUREX) Process. The objective of this work is to establish qualitative relationships between changes in the bulk aqueous phase concentrations of DBP and its concentration and structure at air-liquid interface as probed with VSFG. Nitric acid concentration and solution ionic strength were varied to examine their effect on the interfacial DBP.. Introduction of DBP into neat water resulted in reduction of the VSFG spectral intensity in the dangling O-H region (3680 – 3800 cm -1 ) but large increase in the H-bonded O-H stretch frequency region (3000 – 3500 cm-1) and the appearance of the CH 3 symmetric stretch and CH 3 Fermi resonance peaks at ~ 2880 and 2945 cm -1 , respectively, indicating DBP at the air-water interface. The intensity of the C-H strecth peaks increased as DBP concentration increased from 0.24 to 32 mM, accompanied by a decreasing surface tension values. At fixed DBP concentration, the addition of either or both of HNO 3 and NaNO 3 to an ionic strength of 1 M or 3 M led to significant reduction of the O-H VSFG peaks and enhancement of the C-H peaks. The origins of these experimental observations are attributed to both the increased HDBP molecules partitioning and adsorption to the interface and the protonation of the interfacial DBP- molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Static and Dynamic Gradient Based Directional Transportation of Neutral Molecules in Swollen Polymer Films

Abstract Materials which selectively transport molecules offer powerful opportunities for concentrating and separating chemical agents. Here, utilizing static and dynamic chemical gradients, transport of molecules within swollen crosslinked polymers is demonstrated. Using an ≈200 μm static hydroxyl to hexyl gradient, the neutral ambipolar nerve agent surrogate diethyl (cyanomethyl)phosphonate (DECP) is directionally transported and concentrated 60‐fold within 4 hours. To accelerate transport kinetics, a dynamic gradient (a “travelling wave”) is utilized. Here, the non‐polar dye pyrene was transported. The dynamic gradient is generated by an ion exchange process triggered by the localized introduction of an aqueous NaCl solution, which converts the gel from hydrophobic to hydrophilic. As the hydrophilic region expands, associated water enters the gel, and pyrene is pushed ahead of the expansion front. The dynamic gradient provides about 10‐fold faster transport kinetics than the static gradient.

Ali, Mohammad A.↗

DOE OSTI2022

Static and Dynamic Gradient Based Directional Transportation of Neutral Molecules in Swollen Polymer Films

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Beta-Amino Carboxylate (BAC) non-aqueous physical solvents for enhanced CO2 separations in pre-combustion carbon capture, industrial CO 2 capture, and biogas upgrading processes

Novel beta-amino carboxylate (BAC) solvents have been synthesized and tested to efficiently capture carbon dioxide (CO 2 ) from process gas streams with CO 2 partial pressure intermediate between pre-combustion and post-combustion capture. The BAC solvents have molecular structures characterized by alkyl-substituted amides or esters containing a secondary amine functional group on the second carbon from the carbonyl carbon (referred to as the beta “β” carbon). The ester or amide functional group combined with optimal steric crowding around the amine nitrogen by proximate alkyl groups are tailored to modify the strength of CO 2 binding in the solvent. The solvents possess high CO 2 solubilities and high gas selectivity including good CO 2 /H 2 O selectivity and can be utilized for CO 2 absorption over a range of partial pressures. Due to low volatility, many of the solvents can be operated at or above ambient temperature which eliminates solvent chilling and allows regeneration using low grade waste heat. These novel solvents offer an opportunity for efficient carbon capture for a range of applications including biogas upgrading, hydrogen production, and pre-combustion carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Direct Conversion of Biomass Carbohydrates to Platform Chemicals: 5-Hydroxymethylfurfural (HMF) and Furfural

5-hydroxymethylfurfural (HMF) and furfural are promising platform molecules which can be converted to fuel intermediates and hydrocarbon fuels. Herein, one-step, direct conversion of the carbohydrates in never treated biomass to HMF and furfural in a microwave reactor was investigated. The influence of reaction temperature, time, feedstock, addition of Lewis and Bronsted acids, solvent and solvent to aqueous ratio were studied to find the optimum process conditions to maximize the yields of furfurals. The reaction conditions of 200 degrees C for 5 min with 33 mM HCl and 8 mM AlCl 3 using a dioxane/water (4:1) miscible solvent system were found to be the most conducive for direct dehydration of the glucan and hemicelluloses present in untreated poplar wood to furfural and HMF in yields of 91 and 69%, respectively. Furfural could be easily produced in yields greater than 80%, and once formed, it was found to be stable under the various process conditions explored. In contrast, HMF yields varied with both reaction time and temperature, as it readily underwent rehydration to levulinic acid in yields approaching 25-30% at increased reaction severity. The additions of both Bronsted (HCl) and Lewis (AlCl 3 ) acids in catalytic amounts, i.e., 33 and 8 mM, respectively, were required to maximize the yield of furfurals. Reactions were also performed on other feedstocks (corn stover, switchgrass, loblolly pine, and pure cellulose) to investigate the effect of feedstock type on furfurals yields. Results showed that HMF and furfural yields were primarily dependent on hexosan and pentosan loading regardless of the type of feedstock. In addition, biomass physical features, such as crystallinity or the presence of other biomass constituents, such as lignin, had little influence on furfurals yields.

09 BIOMASS FUELS↗

DOE OSTI2023

Polymer-Grafted Cellulose Nanofibrils with Enhanced Interfacial Compatibility for Stronger Poly(lactic acid) Composites

Cellulose nanofibrils (CNFs) are a promising reinforcement for biodegradable composite matrices such as poly(lactic acid) (PLA), but they require commercially scalable drying methods that preserve their fibrillar morphology along with improved interfacial interactions with polymer matrices. In this work, a water-based grafting-through polymerization scheme to modify CNFs improved spray drying behavior and reinforcement capacity in PLA composites. All polymer modifications yielded CNFs with a more fibrillar morphology after spray drying, increasing specific surface area by up to 490% compared to unmodified CNFs, values similar to conventional freeze drying. Polymer-grafted CNFs in PLA composites improved the tensile strength by 16% at 20 wt % loading and stiffness by 22% at a 10 wt % loading with two different graft-polymer chemistries compared to unmodified CNF composites. Surface energy heterogeneity measurements of the reinforcements and PLA matrix were employed to understand the improvements in composite properties. Polymer modifications lowered the total surface energy of the CNFs, and calculated ratios of work of adhesion to work of cohesion suggested improved interfacial compatibility for four of the modified CNFs with PLA. Rheological oscillatory shear studies of the composites correlated solid-like melt behavior, as demonstrated by storage moduli dominance, with higher tensile strength. Thermal analysis of the composites revealed that excessive plasticization by the poly(oligoethylene glycol methyl ether methacrylate)-grafted sample potentially offset mechanical property improvements imparted by the more fibrillar morphology. This work provides an opportunity for large-scale manufacturing of CNF/PLA composites via an entirely aqueous modification scheme and industrially relevant spray drying process.

36 MATERIALS SCIENCE↗

DOE OSTI2023

DEHP− extractant binding to trivalent lanthanide Er3+: Fast binding accompanied by concerted angular motions of hydration water

Solvent extraction of trivalent rare earth metal ions by organophosphorus extractants proceeds via binding of phosphoric acid headgroups to the metal ion. Water molecules in the tightly bound first hydration shell of the metal ions must be displaced by oxygen atoms from phosphoric acid headgroups. Here, we use classical molecular dynamics simulations to explore the event in which a fully hydrated Er3+ binds to its first phosphoric acid headgroup. Approach of the headgroup into the region between the first and second hydration shells leads to a fast ejection of a water molecule that is accompanied by reordering of the hydration water molecules, including discretization of their angular positions and collective rotation about the metal ion. The water molecule ejected from the first shell is located diametrically opposite from the binding oxygen. Headgroup binding places a headgroup oxygen closer to Er3+ than its first hydration shell and creates a loosely bound water that subsequently exchanges between the first shell and its environment. This second exchange of water also occurs at discrete angular positions. This geometrical aspect of binding may be of relevance to understanding the binding and transport of ion–extractant complexes that are expected to occur at the organic–aqueous liquid–liquid interface used in solvent extraction processes.

Chemistry↗

NASA NTRS1992

Design of multisample, multistep phase partitioning apparatus for use on Space Shuttle Spacelab, and Spacelab missions

Traditional separation techniques are inadequate for many new bioprocessing challenges. Innovative separation methods such as aqueous two phase partitioning are needed to perpetuate bioprocess commercialization. Aqueous two phase polymer partitioning systems provide a process for separating biological materials when combined with microgravity. An innovative space qualified apparatus developed for carrying out separations by partitioning in immiscible polymer systems under mirogravity conditions is described. The apparatus offers an innovative approach to low gravity bioseparations in general and phase partitioning in particular. These capabilities support NASA's interest in serving the biotechnology research community and providing quantitative data in the gravity dependent components of separation processes.

Deuser, Mark S.↗

NASA NTRS1998

Development of a High Resolution-High Sensitivity Ion Microprobe Facility for Cosmochemical Applications

NASA NAGW-4112 has supported development of the CAMECA ims 1270 ion microprobe at UCLA for applications in cosmochemistry. The instrument has been brought to an operational status and techniques developed for accurate, precise microbeam analysis of oxygen isotope ratios in polished thin-sections. We made the first oxygen isotopic (delta(18)O and delta(17)O) measurements of rare mafic silicates in the most chemically primitive meteorites, the a chondrites (Leshin et al., 1997). The results have implications for both high temperature processing in the nebula and low-T aqueous alteration on the CI asteroid. We have performed measurements of oxygen isotopic compositions of magnetite and co-existing olivine from carbonaceous (Choi et al., 1997) and unequilibrated ordinary chondrites (Choi et al., in press). This work has identified a significant new oxygen isotope reservoir in the early solar system: water characterized by a very high Delta(17)) value of approx. 5 % per thousand. We have determined the spatial distributions of oxygen isotopic anomalies in all major mineral phases of a type B CAI from Allende. We have also studied an unusual fractionated CAI from Leoville and made the first oxygen isotopic measurements in rare CAIs from ordinary chondrites.

McKeegan, Kevin D.↗

NASA NTRS2005

Olivine and Carbonate Globules in ALH84001: A Terrestrial Analog, and Implications for Water on Mars

Carbonate globules in ALH84001 are associated with small olivine grains an unexpected finding because the olivines equilibrated at high T while the carbonate is chemically zoned and unequilibrated. A possible explanation comes from a terrestrial analog on Spitsbergen (Norway), where some carbonate globules grew in cavities left by aqueous dissolution of olivine. For ALH84001, the same process may have acted, with larger olivines dissolved out and smaller ones shielded inside orthopyroxene. Carbonate would have been deposited in holes where the olivine had been. Later shocks crushed remaining void space, and mobilized feldspathic glass around the carbonates.

Treiman, A. H.↗

NASA NTRS2006

Distillation Kinetics of Solid Mixtures of Hydrogen Peroxide and Water and the Isolation of Pure Hydrogen Peroxide in Ultrahigh Vacuum

We present results of the growth of thin films of crystalline H2O2 and H2O2.2H2O (dihydrate) in ultrahigh vacuum by distilling an aqueous solution of hydrogen peroxide. We traced the process using infrared reflectance spectroscopy, mass loss on a quartz crystal microbalance, and in a few cases ultraviolet-visible reflectance. We find that the different crystalline phases-water, dihydrate, and hydrogen peroxide-have very different sublimation rates, making distillation efficient to isolate the less volatile component, crystalline H2O2.

Teolis, B. D.↗