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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Calcined Polyethyleneimine-Coated Optical Fibers for Distributed pH Monitoring at High Pressures and Temperatures

In the oil and gas, CO2 sequestration, H2 subsurface storage, and geothermal energy sectors, subsurface pH measurements are critical for monitoring the geochemical conditions and estimating potential corrosion rates of wellbore systems. Real-time pH measurements in these conditions are vital for detecting and predicting corrosion deterioration of wellbore components that may jeopardize the safety and continued operation of wellbore systems. Previous tests using metal oxide-based coatings (TiO2) provided strong responses at elevated temperatures and moderate pressure stability but provided poor differentiation between acidic and alkaline solutions. Building off the pH responsiveness of the TiO2 surface and known pH sensitivity of amine-based polymers, a coating based on the secondary amine polymer polyethyleneimine (PEI) was developed. As the polymer itself is highly water soluble and easily removed by aqueous solutions, the sensor coating was treated with a high temperature (500 °C) calcination procedure in air to convert it into a more stable oxidized coating capable of withstanding hot aqueous solutions without dissolving while retaining linear pH sensitivity from pH values between 2 and 11. The sensor performance was measured using optical transmission measurements in solutions of various pHs and using optical backscatter reflectometry for distributed pH sensing demonstration in wellbore-relevant pressures (up to 1,000 psi) and temperatures (80 °C).

Shumski, Alexander↗
NASA NTRS1994

Aqueous Phase Non Enzymatic Chemistry of Cyanide, Formaldehyde and RNH2

It is postulated that amino acids were produced on the early earth from dilute aqueous solution of cyanide, carbonyls and ammonia (the Strecker synthesis RNH2 + R"R""C=O + KCN yields H-N(R)-C(R")(R"")-CO2H. We have studied the products obtained from dilute aqueous solutions of cyanide, formaldehyde (R"=R""=H), ammonia (R=H) and amino acids. Solutions in the pH range from 8 to 10. at room temperature and at reactant concentrations from 0.001 M to 0.3 M have been studied. With R= H product yields were low (less than 3%). Only with R"=R""=H and R represented by the following: CH2CO2H (glycine); CH(CH3)CO2H (alanine); CH(CH2CH3)CO2H (a-amino n=butyric acids); C(CH3)2(CO2H) (a-aminoisobutyric acid); CH(CH(CH3)2)CO2H (valine); and CH(CH2CO2H)CO2H (aspartic acid), were product yields high (greater than 10%). The yields of glycine were larger with R not equal to H. The prebiotic implications of these findings will be discussed.

Lerner, Narcinda R.↗
DOE OSTI2022

Water soluble barrier coatings for washout tooling for a composite layup

A washout tooling for a composite layup is provided. The washout tooling comprises a casting mold having an exterior surface. The casting mold comprises a particulate material and a water-soluble binder. The casting mold is adapted to break down in the presence of an aqueous solution. The washout tooling further comprises a water-soluble coating layer overlying the exterior surface. The water-soluble coating layer is adapted to break down in the presence of an aqueous solution. The washout tooling further comprises a curable composite layer overlying the water-soluble coating layer. The water-soluble coating layer minimizes contact between the particulate material and the curable composite layer.

Saito, Tomonori↗
DOE OSTI2025

Soft X‐Ray Absorption Spectroscopy With a Flat Liquid Jet in Vacuum Using a Table‐Top Laser‐Induced Plasma Source

ABSTRACT In this work, we demonstrate the integration of a flat liquid jet sample delivery system into a compact soft x‐ray absorption spectrometer using a table‐top laser‐induced plasma source. A high‐speed flat liquid sheet is formed by the collision of two cylindrical jets. This micrometer‐thin lamella can ideally be utilized for transmission‐mode soft x‐ray absorption spectroscopy using krypton plasma emission. Detailed analysis of the jet's thickness profile is achieved applying Lambert–Beer's law. Measurements on water, focusing on the oxygen K‐edge, reveal a lamella thickness profile ranging from 500 nm to 1 μm over a length of 3.8 mm. Additionally, we have investigated aqueous solutions of iron salts, capturing near edge x‐ray absorption fine structure spectra over a broad spectral range from the nitrogen K‐edge to the iron L‐edge. Focused analysis on iron species in aqueous solutions enabled us to distinguish quantitatively between the oxidation states of Fe 2+ and Fe 3+ at the iron L‐edge. Our results are compared with measurements obtained under similar conditions at a synchrotron.

Holburg, Jonathan [Department Optics/Short Wavelen↗
DOE OSTI2022

Impacts of Bond Type and Grafting Density on the Thermal, Structural, and Transport Behaviors of Nanoparticle Organic Hybrid Materials–Based Electrolytes

Nanoscale Organic Hybrid Materials (NOHMs) consist of polymers tethered to a nanoparticle surface, and NOHMs formed with an ionic bond between the polymer and nanoparticle have been proposed for electrochemical applications. NOHMs exhibit negligible vapor pressure, chemical tunability, oxidative thermal stability, and high ionic conductivity making them attractive in reactive and separation systems. In this study, NOHMs are synthesized by tethering Jeffamine M2070 (HPE) to SiO 2 nanocores via ionic (NOHM-I-HPE) and covalent (NOHM-C-HPE) bonding to investigate the effect of the bond type on the thermal, structural and transport properties of the tethered HPE. In the neat state, NOHM-C-HPE displays the highest thermal stability in a nitrogen atmosphere, while NOHM-I-HPE is the most stable under oxidative conditions. Small-angle neutron scattering (SANS) reveals the presence of multiple types of HPE polymers in aqueous solutions of NOHM-I-HPE (i.e., tethered, interacting, and free), whereas only tethered HPE is observed in NOHM-C-HPE systems. Moreover, the SANS profiles identify clustering of NOHM-C-HPE in aqueous solutions, but not in the corresponding NOHM-I-HPE solutions, suggesting that the free HPE chains stabilize the dispersion of NOHM-I-HPE. Furthermore, the results of this study elucidate how the bond type and grafting density can be used to tune the properties of NOHMs.

25 ENERGY STORAGE↗
DOE OSTI2021

Methods for nondestructive dispersing of carbon nanomaterials in water

A method termed “superacid-surfactant exchange” (S2E) for the dispersion of carbon nanomaterials in aqueous solutions. This S2E method enables nondestructive dispersion of carbon nanomaterials (including single-walled carbon nanotubes, double-walled carbon nanotubes, multi-wall carbon nanotubes, and graphene) at rapidly and at large scale in aqueous solution without a requirement for expensive or complicated equipment. Dispersed carbon nanotubes obtained from this method feature long length, low defect density, high electrical conductivity, and in the case of semiconducting single-walled carbon nanotubes, bright photoluminescence in the near-infrared.

Wang, Yuhuang↗
DOE OSTI2020

A large molecular cluster with high proton release capacity

We present a single molecular polyoxometalate cluster (K-41[(P2W12Nb6O62)(6){Mn-3(OH)(3)(H2O)(6)}(4){Mn3Na(H2O)(16)}]center dot 26H(2)O) with controllable release of a large number of protons (similar to 40 per molecule) in its aqueous solution upon addition of a base. The deprotonation/protonation process is reversible with the clusters remaining intact. This molecule can also absorb up to 11 protons per cluster when an acid, HCl, was added to its original aqueous solution. To the best of our knowledge, such large proton absorption/release capacity along with excellent stability is unprecedented.

Zhang, Dongdi↗
NASA NTRS1998

Preference for internucleotide linkages as a function of the number of constituents in a mixture

Phosphoimidazolide-activated ribomononucleotides (*pN; see Scheme I) are useful substrates for the nonenzymatic synthesis of oligonucleotides. In the presence of metal ions dilute neutral aqueous solutions of *pN (0.01 M) typically yield only small amounts of dimers and traces of oligomers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate (5'NMP). An earlier investigation of *pN reactions in highly concentrated aqueous solutions (up to 1.4 M) showed, as expected, that the percentage yield of the condensation products increases and the yield of the hydrolysis product correspondingly decreases with *pN concentration (Kanavarioti 1997). Here we report product distributions in reactions with one, two, or three reactive components at the same total nucleotide concentration. *pN used as substrates were the nucleoside 5'-phosphate 2-methylimidazolides, 2-MeImpN, with N = cytidine (C), uridine (U), or guanosine (G). Reactions were conducted as self-condensations, i. e., one nucleotide only, with two components in the three binary U,C, U,G, and C,G mixtures, and with three components in the ternary U,C, G mixture. The products are 5'NMP, 5',5'-pyrophosphate-, 2',5'-, 3', 5'-linked dimers, cyclic dimers, and a small percentage of longer oligomers. The surprising finding was that, under identical conditions, including the same total monomer concentration, the product distribution differs substantially from one reaction to another, most likely due to changing intermolecular interactions depending on the constituents. Even more unexpected was the observed trend according to which reactions of the U,C,G mixture produce the highest yield of internucleotide-linked dimers, whereas the self-condensations produce the least and the reactions with the binary mixtures produce yields that fall in between. What is remarkable is that the approximately two-fold increase in the percentage yield of internucleotide-linked dimers is not due to a concentration effect or a catalyst, but to the increased complexity of the system from a single to two and three components. These observations, perhaps, provide an example of how increased complexity in relatively simple chemical systems leads to organization of the material and consequently to chemical evolution. A possible link between prebiotic chemistry and the postulated RNA world is discussed.

NASA Discipline Exobiology↗
DOE OSTI2023

Accumulation of Antifreeze Proteins on Ice Is Determined by Adsorption

Antifreeze proteins (AFPs) enable the survival of organisms in freezing environments by binding to ice crystals and suppressing their growth. The rate at which AFPs accumulate on ice is determined by an interplay between their diffusion from the aqueous solution and their adsorption to the ice crystal. To interrogate the relative importance of these two processes, we combined fluorescence experiments with reaction–diffusion modeling. We found that as AFPs accumulate on ice, their concentration in the aqueous solution does not develop a gradient but remains equal to its bulk concentration throughout our experiments. Furthermore, these findings led us to conclude that AFP accumulation on ice crystals, which are smaller than 100 μm in radius, is not limited by the diffusion of AFPs, but by the kinetics of AFP adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Effects of Concentration, Salinity and Temperature on the Conformations of Zwitterionic Poly(2-Vinylpyridine- N -Oxide) Chains in Semidilute Solutions Probed by Small-Angle X-Ray and Neutron Scattering

Polyzwitterions, composed of repeating units with equal numbers of anionic and cationic groups, have drawn considerable interest for applications ranging from antimicrobial coatings and antifouling membranes to low-friction interfaces, energy storage media, and actuators. A characteristic feature of many polyzwitterions is the anti-polyelectrolyte effect salt-induced chain expansion in aqueous solution a phenomenon often implicated in their functional behavior. In this study, we investigated the conformational behavior of poly(2-vinylpyridine-N-oxide) (P2VPNO) using smallangle X-ray and neutron scattering (SAXS and SANS). Small-angle X-ray scattering (SAXS) revealed that, in salt-free aqueous solution, P2VPNO adopts an expanded wormlike conformation stabilized by hydration. With increasing concentration, the chains contract due to screening of intrachain excluded-volume interactions, qualitatively consistent with de Gennes’ scaling predictions for neutral polymers. Small-angle neutron scattering (SANS) further demonstrated that P2VPNO exhibits the characteristic anti-polyelectrolyte response to added salt, as observed in many other polyzwitterions. At elevated temperatures, chain flexibility increases, leading to a shorter Kuhn length and reduced radius of gyration. Notably, however, salt-induced chain expansion persists, indicating that the anti-polyelectrolyte effect remains operative under elevated thermal conditions. These findings provide the first experimental evidence of scaling behavior in polyzwitterions, as well as the first observation of their altered antipolyelectrolyte response at elevated temperatures, offering new insights into the solution physics of this important class of polymers.

Conformation↗
NASA NTRS2000

Catalytic Decomposition of Propellant Hydrazines, N-Nitrosodimethylamine, and N-Nitrodimethylamine

Remediation of propellant hydrazine spills, waste treatment, or cleanup of water contaminated with these propellants and/or their oxidation products is a subject of great concern for safety and the environment. Current remediation technologies typically employ oxidative methods, such as chlorination or ozonation. Methylated hydrazines, in particular 1,1-dimethythydrazine (UDMH) and to some degree monomethy1hydrazine (MMH), form N-Nitrosodimethylamine (NDMA) and N-Nitrodimethylamine (DMNM) during oxidation. These compounds are highly toxic and may persist if oxidative conditions are not sufficiently harsh. Since NDMA and DMNM may also be formed from exposure of MMH or UDMH to air, a need exists for a method that will remediate hydrazine, MMH, UDMH, NDMA, and DMNM. In this work, aqueous solutions of propellant hydrazines, NDMA, and DMNM were found to degrade by catalytic reduction with nickel-aluminum (Ni-Al) alloy under basic conditions. The reaction is based upon dissolution of At from Ni-Al alloy in aqueous media to form aluminum ion and hydrogen gas; and the resultant finely divided nickel catalyzes reduction of the hydrazine, nitrosoamine, or nitroamine by the hydrogen produced. Greater than 99 percent of hydrazine, MMH, UDMH, NDMA, and DMNM in aqueous solutions were degraded under laboratory conditions when reacted with Ni-Al alloy. UDMH was identified as an intermediate reduction product of NDMA and DNNM. NDMA and UDMH were identified as intermediate reduction products of DMNM. Control experiments without nickel showed no degradation of hydrazine, MMH or UDMH, while NDMA and DMNM were reduced to UDMH. Spill pillows containing Ni-Al alloy and solid sodium hydroxide were also found effective in absorption and degradation of UDMH. The application of chemical reduction as a means to propellant hydrazines, NDMA, and DMNM spill remediation, waste treatment, and water decontamination appears highly attractive.

Greene, Ben↗
NASA NTRS2007

Hydrogen Peroxide Concentrator

A relatively simple and economical process and apparatus for concentrating hydrogen peroxide from aqueous solution at the point of use have been invented. The heart of the apparatus is a vessel comprising an outer shell containing tubular membranes made of a polymer that is significantly more permeable by water than by hydrogen peroxide. The aqueous solution of hydrogen peroxide to be concentrated is fed through the interstitial spaces between the tubular membranes. An initially dry sweep gas is pumped through the interiors of the tubular membranes. Water diffuses through the membranes and is carried away as water vapor mixed into the sweep gas. Because of the removal of water, the hydrogen peroxide solution flowing from the vessel at the outlet end is more concentrated than that fed into the vessel at the inlet end. The sweep gas can be air, nitrogen, or any other gas that can be conveniently supplied in dry form and does not react chemically with hydrogen peroxide.

Parrish, Clyde F.↗
DOE OSTI2022

Comparison of vapour pressure osmometry, freezing point osmometry and direct membrane osmometry for determining the osmotic pressure of concentrated solutions

Osmometry is the analytical method of measuring osmotic pressure ($π$) and related colligative properties. Accurately measuring $π$ is essential for applications that use osmosis, including drug delivery systems and water filtration methods such as forward osmosis. The three most common forms of directly or indirectly measuring $π$ are vapour pressure osmometry (VPO), freezing point osmometry (FPO), and direct membrane osmometry (DMO). In this report, the performance of VPO, FPO, and DMO are compared for various aqueous solutions, including small molecule and polymer solutes, and potentially more difficult samples such as concentrated, carbonated, or viscous solutions. Furthermore, potential problems with each of the three methods are examined. Good practices can avoid inaccuracies in DMO due to external concentration polarization and solute diffusion through the membrane. Similarly, it is important to be aware of and avoid weaknesses in VPO and FPO in order to obtain reliable results. Even with care, however, the three methods still give different values of $π$ for concentrated aqueous solutions.

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

Solid-state crystallization of metal organic frameworks within mesoporous materials methods and hybrid materials thereof

A method, comprising i) contacting an aqueous solution of an organic ligand salt of the formula A X (L −X ) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula A X (L −X )/MPM, ii) treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula H X (L −X )/MPM, iii) contacting an aqueous solution of a metal precursor of the formula M +y (B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M +y (B) y ][H x (L −x )]/MPM, and iv) at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M +y L −x )/MPM, wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

Minguez, Ignacio Luz↗
NASA NTRS1982

Effects of environment on microhardness of magnesium oxide

Micro-Vickers hardness measurements of magnesium oxide single crystals were conducted in various environments. These environments included air, nitrogen gas, water, mineral oil with or without various additives, and aqueous solutions with various pH values. Indentations were made on the (100) plane with the diagonals of the indentation in the (100) direction. The results indicate that a sulfur containing additve in mineral oil increased hardness, a chlorine containing additive in mineral oil decreased hardness, and aqueous solutions of hydrogen chloride decreased hardness. Other environments were found to have little effect on hardness. Mechanically polished surfaces showed larger indentation creep than did as-cleaved surfaces.

Ishigaki, H.↗
DOE OSTI2024

Insights into the Assembly and Conformation of Nanoparticle Organic Hybrid Materials (NOHMs) in Solution with Varying Grafting Type

Recently, nanoparticle organic hybrid materials (NOHMs) have been considered promising electrolytes for energy storage applications due to their unique combination of properties, which include high thermal stability, negligible vapor pressure, and easy synthesis. However, the structural features of NOHMs in electrochemical systems are not well understood. Hence, we investigate the impact of grafting type (ionic vs covalent) on the structure and performance of NOHMs that consist of a silica core and grafted HPE polymer (Jeffamine M2070) in aqueous solution with and without the presence of the supporting electrolyte (0.1 M KHCO 3 ) using small-angle neutron scattering. Careful analyses of the results indicate that even at low grafting density (0.8 chains nm –2 ) and concentration (1–3 wt %), ionic NOHMs solutions contain a free polymer that may interact with the grafted polymer, altering the assembly of NOHMs in solution. Our investigation also elucidates that the covalent NOHM solutions consist of both aggregated and dispersed NOHMs in the solution. Moreover, the addition of the supporting electrolyte affects the assembly and structure of the polymer in the ionic NOHMs solution significantly, whereas only a slight change in the conformation of the grafted polymer is observed for covalent NOHMs. These conformational changes alter the performance of the NOHMs solution, resulting in a dramatic change in viscosity. Careful analysis shows that this significant alteration of solution viscosity in the ionic NOHMs can be traced back to the presence of the free polymer that interacts with the grafted layer and the attenuation of this interaction between the free and grafted polymers with the addition of salt. Furthermore, these studies elucidate the impact of grafting type on the overall structure, assembly, and performance of functionalized NOHMs in aqueous solution and explicitly correlate the structure and assembly of NOHMs to their transport properties and must be considered when designing functional systems that incorporate NOHMs.

25 ENERGY STORAGE↗
DOE OSTI2024

Prediction of stability constants of metal–ligand complexes by machine learning for the design of ligands with optimal metal ion selectivity

The new LOGKPREDICT program integrates HostDesigner molecular design software with the machine learning (ML) program Chemprop. By supplying HostDesigner with predicted log K values, LOGKPREDICT enhances the computer-aided molecular design process by ranking ligands directly by metal–ligand binding strength. Harnessing reliable experimental data from a historic National Institute of Standards and Technology (NIST) database and data from the International Union of Pure and Applied Chemistry (IUPAC), we train message passing neural net algorithms. The multi-metal NIST-based ML model has a root mean square error (RMSE) of 0.629 ± 0.044 (R 2 of 0.960 ± 0.006), while two versions of lanthanide-only IUPAC-based ML models have, respectively, RMSE of 0.764 ± 0.073 (R 2 of 0.976 ± 0.005) and 0.757 ± 0.071 (R 2 of 0.959 ± 0.007). For relative log K predictions on an out-of-sample set of six ligands, demonstrating metal ion selectivity, the RMSE value reaches a commendably low 0.25. Here we showcase the use of LOGKPREDICT in identifying ligands with high selectivity for lanthanides in aqueous solutions, a finding supported by recent experimental evidence. We also predict new ligands yet to be verified experimentally. Therefore, our ML models implemented through LOGKPREDICT and interfaced with the ligand design software HostDesigner pave the way for designing new ligands with predetermined selectivity for competing metal ions in an aqueous solution.

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

Electric Field’s Dueling Effects through Dehydration and Ion Separation in Driving NaCl Nucleation at Charged Nanoconfined Interfaces

Investigating nucleation in charged nanoconfined environments under electric fields is crucial for many scientific and engineering applications. Here we study the nucleation of NaCl from aqueous solution near charged surfaces using machine-learning-augmented enhanced sampling molecular dynamics simulations. Our simulations successfully drive phase transitions between the liquid and solid phases of NaCl. The solid phase is stabilized under electric fields, particularly at an intermediate surface charge density. We examine which physical characteristics drive the nucleation of NaCl from aqueous solutions and find that the removal of solvent water from Cl– at the solid precursor surface plays a more critical role than the accumulation of ions. Our simulations reveal the competing effects of electric fields on nucleation processes: they facilitate the removal of water, promoting nucleation, but also promote the separation of ion pairs, thereby hindering nucleation. Here, this work provides a framework for studying nucleation processes in nanoconfined environments under electric fields and provides physical insights for the design of electrochemistry materials.

Electric fields↗