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At least 1,225 records · Page 68

Improved ceramic slip casting technique

A primary concern in modern fluid dynamics research is the experimental verification of computational aerothermodynamic codes. This research requires high precision and detail in the test model employed. Ceramic materials are used for these models because of their low heat conductivity and their survivability at high temperatures. To fabricate such models, slip casting techniques were developed to provide net-form, precision casting capability for high-purity ceramic materials in aqueous solutions. In previous slip casting techniques, block, or flask molds made of plaster-of-paris were used to draw liquid from the slip material. Upon setting, parts were removed from the flask mold and cured in a kiln at high temperatures. Casting detail was usually limited with this technique -- detailed parts were frequently damaged upon separation from the flask mold, as the molded parts are extremely delicate in the uncured state, and the flask mold is inflexible. Ceramic surfaces were also marred by 'parting lines' caused by mold separation. This adversely affected the aerodynamic surface quality of the model as well. (Parting lines are invariably necessary on or near the leading edges of wings, nosetips, and fins for mold separation. These areas are also critical for flow boundary layer control.) Parting agents used in the casting process also affected surface quality. These agents eventually soaked into the mold, the model, or flaked off when releasing the case model. Different materials were tried, such as oils, paraffin, and even an algae. The algae released best, but some of it remained on the model and imparted an uneven texture and discoloration on the model surface when cured. According to the present invention, a wax pattern for a shell mold is provided, and an aqueous mixture of a calcium sulfate-bonded investment material is applied as a coating to the wax pattern. The coated wax pattern is then dried, followed by curing to vaporize the wax pattern and leave a shell mold of the calcium sulfate-bonded investment material. The shell mold is cooled to room temperature, and a ceramic slip is poured therein. After a ceramic shell of desired thickness has set up in the shell mold, excess ceramic slip is poured out. While still wet, the shell mold is peeled from the ceramic shell to expose any delicate or detailed parts, after which the ceramic shell is cured to provide a complete, detailed, precision ceramic article without parting lines.

Buck, Gregory M.↗

Unleashing the capacity of Rhodococcus for converting lignin into lipids

Bioconversion of bioresources/wastes (e.g., lignin, chemical pulping byproducts) represents a promising approach for developing a bioeconomy to help address growing energy and materials demands. Rhodococcus, a promising microbial strain, utilizes numerous carbon sources to produce lipids, which are precursors for synthesizing biodiesel and aviation fuels. However, compared to chemical conversion, bioconversion involves living cells, which is a more complex system that needs further understanding and upgrading. Various wastes amenable to bioconversion are reviewed herein to highlight the potential of Rhodococci for producing lipid-derived bioproducts. In light of the abundant availability of these substrates, Rhodococcus’ metabolic pathways converting them to lipids are analyzed from a “beginning-to-end” view. Based on an in-depth understanding of microbial metabolic routes, genetic modifications of Rhodococcus by employing emerging tools (e.g., multiplex genome editing, biosensors, and genome-scale metabolic models) are presented for promoting the bioconversion. Co-solvent enhanced lignocellulose fractionation (CELF) strategy facilitates the generation of a lignin-derived aromatic stream suitable for the Rhodococcus’ utilization. Novel alkali sterilization (AS) and elimination of thermal sterilization (ETS) approaches can significantly enhance the bioaccessibility of lignin and its derived aromatics in aqueous fermentation media, which promotes lipid titer significantly. In order to achieve value-added utilization of lignin, biodiesel and aviation fuel synthesis from lignin and lipids are further discussed. In conclusion, the possible directions for unleashing the capacity of Rhodococcus through synergistically modifying microbial strains, substrates, and fermentation processes are proposed toward a sustainable biological lignin valorization.

09 BIOMASS FUELS↗

Surface Zeta Potential of ALD-Grown Metal-Oxide Films

Membranes are among the most promising technologies for energy-efficient and highly selective separations, and the surface-charge property of membranes plays a critical role in their broad applications. Atomic layer deposition (ALD) can deposit materials uniformly and with high precision and controllability on arbitrarily complex and large substrates, which renders it a promising method to tune the electrostatics of water/solid interfaces. However, a systematic study of surface-charge properties of ALD-grown films in aqueous environments is still lacking. In this work, 17 ALD-grown metal-oxide films are synthesized, and a comprehensive study of their water stability, wetting properties, and surface-charge properties is provided. Furthermore, this work represents a resource guide for researchers and ultimately for materials and process engineers, seeking to tailor interfacial charge properties of membranes and other porous water treatment components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Membranes for Lithium Recovery From Conventional and Unconventional Sources

Lithium has been deemed a critical mineral of national importance that finds uses in a wide range of applications, and its demand has been rising significantly in recent years. The urgency of meeting this demand requires lithium extraction from various aqueous sources such as continental brines, geothermal brines, seawater, produced water, and battery waste. While direct lithium extraction (DLE) technologies such as adsorption, ion exchange, and solvent extraction have emerged as possible solutions, membrane technologies are also being investigated for various sources and at different stages of the recovery process. Here, we analyze the application of membranes for pretreatment of lithium source waters, bring management, lithium/magnesium separation, lithium/sodium separation, and lithium hydroxide conversion, and evaluate performance metrics for critical lithium separations from the literature. We explore the potential of membranes at every stage of the recovery process and describe their current status and future prospects. We describe hypothetical process trains with integrated membrane technologies for each source type and address their feasibility and challenges. The potential energy and water impacts of membrane-integrated and conventional DLE processes are also critically considered alongside performance and selectivity metrics, and this is illustrated using examples and calculated from published technical reports. This paper thus provides a comprehensive overview of the application of membranes along every stage of the lithium recovery process, emphasizing the versatility and potential of membrane technologies for critical mineral recovery.

36 MATERIALS SCIENCE↗

Spectroscopic Online Monitoring: Using a Multi-Track Visible Spectrometer to Facilitate a Mass Balance Study in a Simulated TALSPEAK Process

Nuclear energy is a promising low-carbon energy candidate to meet the increased demand for green energy, where the integration of fuel recycling can have significant benefits for material usage and waste reduction. Utilizing in situ monitoring tools can provide ample opportunities to better control and safeguard nuclear material recycle processes while also offering knowledge and insight into real-time solution properties. The simultaneous measurement of analytical targets in multiple process locations can enable real-time mass balance and material accountancy calculations. This is demonstrated here with a mass balance study of Nd 3+ on countercurrent aqueous/organic metal extraction within a single centrifugal contactor. The Nd 3+ concentration was simultaneously monitored at the inlets and outlets of both aqueous and organic phases using a visible absorbance detector that allowed for the simultaneous measurement of up to six locations. The Nd 3+ concentration was calculated by using chemical data science algorithms, where model training sets were collected on a single track of the detector. The discussion includes addressing the challenges of using a model collected on a single track and applying it as a model across the other tracks on the detector. Each track of the detector corresponds to one measurement location on the contactor. The difference in the integrated moles of Nd 3+ between the inlet and outlet at the end of the experiment was near zero, indicating that the mass balance of this experiment was maintained. Overall, the online spectroscopic monitoring was able to follow changing solution conditions and accurately measure the concentration of Nd 3+ in different locations within the contactor system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supercritical Treatment Technology for Water Purification (Annual Final Report)

This project continued the development of the Supercritical Water Extraction – Enhanced Targeted Recovery (SWEETR™) technology, a novel desalination process for treating hypersaline brines. The overall objective is to demonstrate the technical and economic feasibility of an innovative, energy efficient, and robust supercritical desalination technology to treat hypersaline solutions and separating saltwater into a pure water stream and valuable recovered solids, resulting in zero liquid discharge (ZLD). The proposed technology, focuses on innovative methods of applying supercritical water to treat highly concentrated brine solutions without incurring a high energy penalty. Integrating the technology with solar energy reduces the energy cost for the system. The results obtained during the proof-of-concept testing demonstrate that the SWEETR™ concept is technically feasible and that supercritical water treatment is a viable option with strong merit for treating high salinity waters. The strategic design of the system provides the opportunity to localize the supercritical zone, which helps reduce the overall energy cost associated with the desalination process. The process can be tuned to remove only the amount of salts required to make the treated water “fit for purpose”, providing further opportunities to minimize energy costs. The ability to destroy organic compounds associated with the water while simultaneously being able to desalinate makes SWEETR™ uniquely fitted for treating aqueous streams such as produced water from oil and gas extraction which contain small amounts of organics. Such mixed contaminant streams pose an extreme challenge for other treatment options. Future work will further develop the SWEETR™ technology to take it from the bench-scale to the pilot-scale, and ready the technology for commercial application.

04 OIL SHALES AND TAR SANDS↗

PDADMAC/PSS Oligoelectrolyte Multilayers: Internal Structure and Hydration Properties at Early Growth Stages from Atomistic Simulations

We analyze the internal structure and hydration properties of poly(diallyl dimethyl ammonium chloride)/poly(styrene sulfonate sodium salt) oligoelectrolyte multilayers at early stages of their layer-by-layer growth process. Our study is based on large-scale molecular dynamics simulations with atomistic resolution that we presented recently [Sánchez et al., Soft Matter 2019, 15, 9437], in which we produced the first four deposition cycles of a multilayer obtained by alternate exposure of a flat silica substrate to aqueous electrolyte solutions of such polymers at 0.1M of NaCl. In contrast to any previous work, here we perform a local structural analysis that allows us to determine the dependence of the multilayer properties on the distance to the substrate. We prove that the large accumulation of water and ions next to the substrate observed in previous overall measurements actually decreases the degree of intrinsic charge compensation, but this remains as the main mechanism within the interface region. We show that the range of influence of the substrate reaches approximately 3 nm, whereas the structure of the outer region is rather independent from the position. This detailed characterization is essential for the development of accurate mesoscale models able to reach length and time scales of technological interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microcapsules and Methods for Making

This invention relates to methods for forming multi-lamellar microcapsules of both hydrophilic and hydrophobic immiscible liquid phases using several polymer/solvent systems. Liquid-Liquid diffusion and spontaneous emulsification are controlled by properly timed sequence exposures of immiscible phases in aqueous vehicles dispersed in hydrocarbon solvents containing small quantities of oil, co-surfactants, and glycerides. Water-in-oil and oil-in-water microcapsules are formed containing selected combinations of several types of drugs, co-encapsulated within fluid compartments inside the microcapsule. Commercial applications of the process and the resultant product relate to drug therapy for treating medical conditions such as cancer, circulatory conditions, and other conditions in which pharmaceuticals are advantageously targeted to specific organs, or delivered in combination with other pharmaceuticals. Small microcapsules may be delivered intravenously to diseased organs or clotted vessels. The use of multiple drugs within the same microcapsule structure provides advantages for applications such as chemoembolization treatments and may be used to deliver both chemotherapeutic drugs, against tumor cells, and an immuno-adjuvant or immunological stimulant to enhance the patient's immune response. Active forms of urokinase and other enzymes may be delivered without dilution to the local site of an embolism for dissolving the embolism. Thus, the invention has several potentially valuable commercial applications related to pharmaceutical and medical applications.

Morrison, Dennis R.↗

Coordinated Isotopic and Mineral Characterization of Highly Fractionated 18O-Rich Silicates in the Queen Alexandra Range 99177 CR3 Chondrite

Carbonaceous chondrites contain a mixture of solar system condensates, pre-solar grains, and primitive organic matter. Each of these materials record conditions and processes in different regions of the solar nebula, on the meteorite parent body, and beyond the solar system. Oxygen isotopic studies of meteorite components can trace interactions of distinct oxygen isotopic reservoirs in the early solar system and secondary alteration processes. The O isotopic compositions of the earliest solar system condensates fall along a carbonaceous chondrite anhydrous mineral (CCAM) line of slope approximately 1 in a plot of delta 17O against delta 18O. This trend is attributed to mixing of material from 16O-poor and 16O-rich reservoirs. Secondary processing can induce mass-dependent fractionation of the O isotopes, shifting these compositions along a line of slope approximately 0.52. Substantial mass-dependent fractionation of O isotopes has been observed in secondary minerals in CAIs, calcite, and FUN inclusions. These fractionations were caused by significant thermal or aqueous alteration. We recently reported the identification of four silicate grains with extremely fractionated O isotopic ratios (delta 18O equals 37 - 55 per mille) in the minimally altered CR3 chondrite QUE 99177. TEM analysis of one grain indicates it is a nebular condensate that did not experience substantial alteration. The history of these grains is thus distinct from those of the aforementioned fractionated materials. To constrain the origin of the silicate grains, we conducted further Mg and Fe isotopic studies and TEM analyses of two grains.

Nguyen, A. N.↗

Bulk Oxygen Isotope Composition of Aggregate Samples From Asteroid Bennu Returned By OSIRIS-REx

On 24 September 2023, the OSIRIS-REx spacecraft delivered to Earth material collected from the surface of the B-type asteroid Bennu. During its ~2.5-year encounter with the asteroid, OSIRIS-REx made many important discoveries, including establishing its extremely primitive chemical composition, the presence of at least two lithologies, and evidence of fluid flow on its parent asteroid. One of the driving hypotheses of the Sample Analysis Plan is that Bennu’s dominant lithologies are comparable to the most aqueously altered carbonaceous chondrites. Oxygen three-isotope analysis is a powerful tool for defining the relationship between different meteorite groups and can be used to understand the nature of the returned Bennu samples. The O isotope signatures reflect the materials that parent asteroids accreted from and the geological processes that operated during asteroidal evolution. Aggregate samples of particles (typically <500 μm) likely sampled many different larger stones and boulders, and their composition may therefore represent the average composition of Bennu. Fractionation of the sample, e.g. comparison of aliquots of finer material with coarser particles within the aggregate samples, offers the opportunity to identify different isotopic reservoirs within the returned material. The average O isotope composition will also provide a baseline from which to identify and characterize any exogenous clasts present in the sample.

I. A. Franchi↗

Is Water a Universal Solvent for Life?

There are strong reasons to believe that the laws, principles and constraints of physics and chemistry are universal. It is much less clear how this universality translates into our understanding of the origins of life. Conventionally, discussions of this topic focus on chemistry that must be sufficiently rich to seed life. Although this is clearly a prerequisite for the emergence of living systems, I propose to focus instead on self-organization of matter into functional structures capable of reproduction, evolution and responding to environmental changes. In biology, most essential functions are largely mediated by noncovalent interactions (interactions that do not involve making or breaking chemical bonds). Forming chemical bonds is only a small part of what living systems do. There are specific implications of this point of view for universality. I will concentrate on one of these implications. Strength of non-covalent interactions must be properly tuned. If they were too weak, the system would exhibit undesired, uncontrolled response to natural fluctuations of physical and chemical parameters. If they were too strong kinetics of biological processes would be slow and energetics costly. This balance, however, is not a natural property of complex chemical systems. Instead, it has to be achieved with the aid of an appropriate solvent for life. In particular, potential solvents for life must be characterized by a high dielectric constant to ensure solubility of polar species and sufficient flexibility of biological structures stabilized by electrostatic interactions. Among these solvents, water exhibits a remarkable trait that it also promotes solvophobic (hydrophobic) interactions between non-polar species, typically manifested by a tendency of these species to aggregate and minimize their contacts with the aqueous solvent. Hydrophobic interactions are responsible, at least in part, for many self-organization phenomena in biological systems, such as the formation of cellular boundary structures or protein folding. Strengths of electrostatic and hydrophobic interactions are similar and can be balanced over a wide range of temperatures, which considerably increases the repertoire of interactions that can be used to modulate biological functions. Some properties of water, e.g. its chemical activity against polymerization reactions, are considered as unfavorable to life. In actuality, this might be a favorable trait because life requires a balance between constructive and destructive processes. For example, molecules synthesized in response to specific conditions must be degraded once these conditions change. Otherwise regulation of biological processes would be virtually impossible. Water might not be the only liquid with favorable properties for supporting life. It has been proposed that formamide, which might be present elsewhere in the universe in sufficient quantities to warrant interest, could be a potential alternative to water for the origin of life. However, this will remain highly hypothetical until it is demonstrated in further studies on its physical, chemical and biological properties it is capable of mediating self-organization of matter and providing proper balance between different types of non-covalent interactions.

Pohorill, Andrew↗

Layered Sediments, Rampart Craters, and Potential Fluvio-Lacustrine Activity in S.W. Arabia Terra, Mars: Support for a History of Aqueous Conditions

Arabia Terra is a unique area on Mars in that it is the only major, equatorial region characterized by high abundances of near-surface water (as measured by gamma ray and neutron spectroscopy). Vernal Crater is a 55 km-diameter structure in southwest Arabia Terra, centered at 6 N, 355.5 E. The crater includes layered sediments, potential remnants of fluvio-lacustrine activity, and indications of aeolian processes. Regional considerations, along with new THEMIS and MOC data, are being assessed to gain insight into the significance of the geomorphic units within Vernal Crater and the geologic history of SW Arabia Terra.

Oehler, D. Z.↗

Elucidation of Design Criteria for V‐based Redox Mediators: Structure‐Function Relationships that Dictate Rates of Heterogeneous Electron Transfer

Redox mediators are attractive solutions for addressing the stringent kinetic stipulations required for efficient energy conversion processes. In this work, we compare the electrochemical properties of four vanadium complexes, namely [V(acac) 3 ], [V 6 O 7 (OMe) 12 ], [ n Bu 4 N] 3 [V 6 O 13 (TRIS NO2 ) 2 ], and [ n Bu 4 N] 5 [V 18 O 46 (NO 3 )] in non-aqueous solutions on glassy carbon electrodes. The goal of this study is to investigate the electron transfer kinetics and diffusivity of these compounds under identical experimental conditions to develop an understanding of structure-function relationships that dictate the physicochemical properties of vanadium oxide assemblies. Complex selection was dictated by two criteria – (1) nuclearity of the transition metal complexes (2) distribution of electron density in the native electronic configuration. In conclusion, our analyses establish that electronic communication between metal centers significantly impacts charge transfer kinetics of these vanadium-based compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 : Insights from First-Principles

The transformations of complex metal oxides in aqueous settings must be studied to form a chemical understanding of how technologically relevant nanomaterials impact the environment upon disposal. Owing to the inherent heterogeneity and structural complexity of the ternary intercalation material Li(Ni x Mn y Co 1-x-y )O 2 (NMC), the mechanisms of chemical processes at the solid–water interfac e are challenging to model. Here, density functional theory (DFT) + solvent ion methodology is used to study the energetics of stepwise release of two surface metals following unique pathways. Further, the study spans different combinations of metal removal and also considers unique patterns of defects formed by modeling the NMC surface in supercells. The approach here also considers the equilibration of the surface with the surroundings between successive metal removals. A key finding is that a second metal removal prefers to proceed at a metal lattice site adjacent to the initial defect, and this is attributed in part to how the resulting slab with two metal vacancies maintains the most antiferromagnetic couplings between the remaining Ni/Mn.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward Lithium Recovery Using Modular (and Membraneless) Phase Separation and Extraction (MPSE) Technology with Ionic Liquid (IL) Solvents: Effect of Coatings

In this work, a single-channel slope-plate Modular and Membrane-less Phase Separation and Extraction (MPSE) device was fabricated using 3D printing. The slope-plate was designed with an insertable glass slide to enable surface modification with coatings. Self-assembled monolayers (SAMs) and perfluoropolyether (Zdol) coatings were applied to tailor surface wettability and enhance phase separation. Using a model biphasic system of water and hexadecane, both coatings significantly improved the separation efficiency compared to the uncoated device by promoting selective wetting. Building on these results, lithium extraction from a simulated saline solution was investigated using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf₂]) as the ionic liquid (IL) extractant. The IL effectively extracted Li⁺ from the aqueous phase in bulk extraction, demonstrating its potential for lithium recovery. However, the low interfacial tension between the IL and aqueous phases posed challenges for phase separation. The application of SAM and Zdol coatings effectively mitigated this issue. Overall, integrating tailored surface chemistry with the slope-plate MPSE design shows great promise as an efficient and scalable platform for studying liquid–liquid separation and optimizing ionic liquid–based extraction processes for lithium recovery from saline sources.

3D printing↗

The radiolysis of tryptophan and leucine with P-32 beta-radiation

The paper extends earlier experiments on the radiolysis of DL-tryptophan using P-32 beta-radiation to longer reaction times, observing complete destruction of tryptophan by secondary, nonradiolytic processes. In addition DL-leucine is irradiated with P-32 beta-irradiation at -196 C, leading to radiolyses to the extents of about 20-30%, but observing no concomitant asymmetric bias. The complete absence of asymmetric bias in the present and earlier (Bonner et al., 1979) radiolyses of aqueous tryptophan at -25 C and the present radiolyses of water-free leucine at -196 C using P-32 beta-radiation and its accompanying bremsstrahlung leave it an open question whether or not the Vester-Ulbricht beta-decay/bremsstrahlung mechanism for the origin of optical activity is a viable one.

Blair, N. E.↗

Small Business Innovations

Under a Small Business Innovation Research (SBIR) contract to Kennedy Space Center, EIC Laboratories invented a Raman Spectrograph with fiber optic sampling for space applications such as sensing hazardous fuel vapors and making on-board rapid analyses of chemicals and minerals. Raman spectroscopy is a laser-based measurement technique that provides through a unique vibrational spectrum a molecular 'fingerprint,' and can function in aqueous environments. EIC combined optical fiber technology with Raman methods to develop sensors that can be operated at a distance from the spectrographic analysis instruments and the laser excitation source. EIC refined and commercialized the technology to create the Fiber Optic Raman Spectrograph and the RamanProbe. Commercial applications range from process control to monitoring hazardous materials.

Source record↗

Upcycling of Waste Plastics into Carboxylic Acids for Biodegradable Surfactants

This work outlines a process for producing high‐purity (>95%) carboxylate surfactants from post‐consumer recycled high‐density polyethylene (PCR‐HDPE). The approach involves the thermal depolymerization of PCR‐HDPE via pyrolysis, followed by fractional distillation to isolate C9–C14 olefins. These olefins undergo hydroformylation using cobalt carbonyl catalysts to generate aldehydes, which are subsequently oxidized to carboxylic acids using Pinnick oxidation under mild aqueous‐phase conditions. Neutralization of the resulting carboxylic acids with sodium hydroxide produces plastic‐derived carboxylate surfactants (PDCs) in the form of sodium carboxylates. Subsequent purification steps ensure surfactant‐grade purity and enable accurate assessment of physicochemical properties. The resulting PDCs are evaluated for critical micelle concentration (CMC), foamability, surface tension reduction, and calcium ion tolerance, demonstrating competitive behavior with conventional anionic carboxylate surfactants. This route provides a sustainable alternative for surfactant production, reducing reliance on fossil‐derived feedstocks and valorizing plastic waste streams through chemical upcycling.

Biodegradable surfactants↗