Search NASA⌕ Search

SEARCH · Search NASA

Results for “cyclohexane”

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

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

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Measurement of isosteric heat of gas adsorption and Brunauer–Emmett–Teller (BET) surface area using a quartz crystal microbalance

The study of gas adsorption on a solid surface evaluates the affinity between sorbate gas and sorbent substrate and factors that contribute to this. This report presents a test platform for adsorption experiments of various gases on various solid surfaces. Controlled environmental conditions enable investigations in materials surface science and increase the consistency among adsorption data. The system utilizes a quartz crystal microbalance to perform gravimetric analysis of deposition and adsorption, enabling investigation of the interaction of gaseous molecules with solid surfaces. In this study, a quartz crystal microbalance as gas adsorption detector was integrated with an environmental chamber to create a versatile tool for gas adsorption experiments on thin films. Experimental operation of this apparatus was demonstrated via acquisition of the adsorption isotherms of cyclohexane vapor on a gold surface at 55 and 70 °C. The result indicated International Union of Pure and Applied Chemistry Type II adsorption. Consequentially, application of the Brunauer–Emmett–Teller model to the isotherm data subject to predefined criteria for linear region selection yielded a surface area of the sorbent of 0.53 cm2 at 55 °C. From the monolayer region of the isotherms, the isosteric heat of adsorption of the cyclohexane vapor on gold was calculated to be 37 kJ mol-1.

47 OTHER INSTRUMENTATION↗
NASA NTRS1988

Structure of a fluid interface near the critical point

The structure of the liquid-liquid interface of three very different mixtures (carbon disulfide + methanol, methanol + cyclohexane + deuterated cyclohexane, and nitrobenzene + n-decane) has been studied using ellipsometry in the reduced temperature range between 0.0009 and 0.042. Although the elliptical thickness varies by an order of magnitude between these mixtures, the data from all three mixtures can be scaled to the same universal constant by a combined mean-field plus capillary-wave model of the interface. The universal constant determined experimentally is significantly less than the theoretical value.

Schmidt, James W.↗
NASA NTRS1993

Loading and testing a light scattering cell with a binary fluid mixture near its critical composition

Critical phenomena has been the subject of physics research for many years. However, only in recent years has the research effort become intense. The current intensity has caused the study of critical phenomena to be grouped into a previous older era and a present contemporary era. Turbidity cell filling with methanol cyclohexane is one of the first steps toward a further understanding of critical phenomena. Work performed during the research period is outlined. During this period, research was spent developing apparatus and techniques that will make it possible to study critical phenomena through turbidity measurements on methanol cyclohexane. Topics covered range from the orientation of turbidity cell parts for assembly to the filling apparatus and procedure used when th cell is built. The last section will briefly cover some of the observations made when viewing the cell in a controlled water bath. However, before mention is made of the specifics of the summer research, a short introduction to critical phenomena and turbidity and how they relate to this experiment is provided.

Jacobs, Donald T.↗
DOE OSTI2024

Molecular Precision Engineering for Efficient Binary Organic Photovoltaics through Energy Level and Fibrillar Structure Modulation

Adjusting the energy levels and fibrillar morphology is paramount to enhancing the power conversion efficiency (PCE) of organic solar cells (OSCs). In the present study, an increase in the open-circuit voltage (VOC) is facilitated through the elongation of the alkyl chain within AQx (namely AQx-8), aiming to decrease the free volume ratio (FVR). This reduction in FVR attenuates electron-phonon coupling, thereby augmenting emission efficiency and diminishing the non-radiative energy loss (ΔEnr). To further refine the energy levels and morphological characteristics, the external undecyl chain of AQx-8 is substituted with a shorter carbon chain and cyclohexane noted for its considerable steric hindrance (AQx-H). Additionally, this alteration significantly mitigates intermolecular aggregation, expands the bandgap, and elevates the lowest unoccupied molecular orbital (LUMO) energy level, culminating in an elevated VOC of 0.923 V in devices based on AQx-H. Morphological analysis reveals that blends based on AQx-H exhibit an enhanced multi-length-scale fibrillar structure, which is conducive to exciton dissociation and charge transport, thereby contributing to a high fill factor (FF) nearing 80%. Consequently, this study reports one of the highest binary PCEs documented, standing at 19.5% (with certification at 19.0%).

14 SOLAR ENERGY↗
DOE OSTI2022

Demonstration of VOC Fenceline Sensors and Canister Grab Sampling near Chemical Facilities in Louisville, Kentucky

Experimental fenceline sensor pods (SPods) fitted with 30 s duration canister grab sampling (CGS) systems were deployed at a site near chemical facilities in Louisville, KY, from 4 June 2018 to 5 January 2020. The objective of the study was to better understand lower cost 10.6 eV photoionization detector (PID)-based volatile organic compound (VOC) sensors and investigate their utility for near-source emissions detection applications. Prototype SPods containing PID sensor elements from two different manufacturers yielded between 78% and 86% valid data over the study, producing a dataset of over 120,000 collocated pair fenceline measurements averaged into 5-min datapoints. Ten-second time-resolved SPod data from an elevated fenceline sensor signal day are presented, illustrating source emission detections from the direction of a facility 500 m west of the monitoring site. An SPod-triggered CGS acquired in the emission plume on this day contained elevated concentrations of 1,3-butadiene and cyclohexane (36 parts per billion by volume (ppbv) and 637 ppbv, respectively), compounds known to be emitted by this facility. Elevated concentrations of these compounds were observed in a subset of the 61 manual and triggered CGS grab samples acquired during the study, with winds from the west. Using novel wind-resolved visualization and normalization approaches described herein, the collocated pair SPod datasets exhibited similarity in emission source signature. With winds from the west, approximately 50% of SPod readings were above our defined theoretical detection limit indicating persistent measurable VOC signal at this site. Overall, this 19-month study demonstrated reasonable prototype SPod operational performance indicating that improved commercial forms of lower cost PID sensors could be useful for select VOC fenceline monitoring applications.

1,3-butadiene↗
DOE OSTI2022

C−H Activation of Inert Arenes using a Photochemically Activated Guanidinato‐Magnesium(I) Compound

Abstract UV irradiation of solutions of a guanidinate coordinated dimagnesium(I) compound, [{(Priso)Mg} 2 ] 3 (Priso=[(DipN) 2 CNPr i 2 ] − , Dip=2,6‐diisopropylphenyl), in either benzene, toluene, the three isomers of xylene, or mesitylene, leads to facile activation of an aromatic C−H bond of the solvent in all cases, and formation of aryl/hydride bridged magnesium(II) products, [{(Priso)Mg} 2 (μ‐H)(μ‐Ar)] 4 – 9 . In contrast to similar reactions reported for β‐diketiminate coordinated counterparts of 3 , these C−H activations proceed with little regioselectivity, though they are considerably faster. Reaction of 3 with an excess of the pyridine, p ‐NC 5 H 4 Bu t (py Bu t ), gave [(Priso)Mg(py Bu t H)(py Bu t ) 2 ] 10 , presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(py Bu t ⋅)(py Bu t ) 2 ] 11 , which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C−H activations. One of these involves photochemical cleavage of the Mg−Mg bond of 3 , generating magnesium(I) doublet radicals, (Priso)Mg⋅. These then doubly reduce the arene substrate to give “Birch‐like” products, which subsequently rearrange via C−H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of 3 leads to an intramolecular aliphatic C−H activation process and formation of an alkyl‐bridged magnesium(II) species, [{Mg(μ‐Priso −H )} 2 ] 12 . Furthermore, irradiation of a 1 : 1 mixture of 3 and the β‐diketiminato dimagnesium(I) compound, [{( Dip Nacnac)Mg} 2 ] ( Dip Nacnac=[HC(MeCNDip) 2 ] − ), effects a “scrambling” reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg−Mg( Dip Nacnac)] 13 . Finally, the EPR spectrum (77 K) of a glassed solution of UV irradiated 3 is dominated by a broad featureless signal, indicating the presence of a doublet radical species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Microwave synthesis of single-phase nanoparticles made of multi-principal element alloys

In this work, metal nanoparticles of multi-principal element alloys (MPEA) with a single crystalline phase have been synthesized by flash heating/cooling of nanosized metals encapsulated in micelle vesicles dispersed in an oil phase (e.g., cyclohexane). Flash heating is realized by selective absorption of a microwave pulse in metals to rapidly heat metals into uniform melts. The oil phase barely absorbs microwave and maintains the low temperature, which can rapidly quench the high-temperature metal melts to enable the flash cooling process. The precursor ions of four metals, including Au, Pt, Pd, and Cu, can be simultaneously reduced by hydrazine in the aqueous solution encapsulated in the micelle vesicles. The resulting metals efficiently absorb microwave energy to locally reach a temperature high enough to melt themselves into a uniform mixture. The duration of microwave pulse is crucial to ensure the reduced metals mix uniformly, while the temperature of oil phase is still low to rapidly quench the metals and freeze the single-phase crystalline lattices in alloy nanoparticles. The microwave-enabled flash heating/cooling provides a new method to synthesize single-phase MPEA nanoparticles of many metal combinations when the appropriate water-in-oil micelle systems and the appropriate reduction reactions of metal precursors are available.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Engineered $\mathrm{Ru}$ on $\mathrm{HY}$ zeolite catalyst for continuous and selective hydrodeoxygenation of lignin phenolics to cycloalkanes under moderate conditions

Here we report a continuous selective hydrodeoxygenation (HDO) process of guaiacol conversion to cycloalkanes under 180 °C/1 MPa, which results in improved HDO chemistry for lignin-based jet fuel production. The incipient wetness impregnation method was modified to prepare an HY zeolite-supported Ru catalyst with better metal dispersion and acid site uniformity, which overcomes the low conversion and selectivity of previous literature. The modified catalyst (Ru-HY-60-MI) was tested in a continuous fixed bed reactor, resulting in increased HDO conversion of guaiacol to cycloalkanes compared to the unmodified catalyst. Pressure, temperature, and weight hourly space velocity-dependent tests validate guaiacol HDO over Ru-HY-60-MI catalyzed ring hydrogenation of guaiacol to 2-methoxycyclohexanol, acid-catalyzed demethoxylation and dehydration to cyclohexene, and further hydrogenation of cyclohexene to cyclohexane. These experiments enable exploring a continuous HDO process, demonstrate effectiveness for other ß-ß and a-O-4 lignin representatives and real lignin bio-oil, and pave the way towards commercialization of lignin-based jet fuel

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

A one-pot synthesis of high-density biofuels through bifunctional mesoporous zeolite-encapsulated Pd catalysts

Developing a powerful bifunctional catalyst for tandem reactions is essential to the future carbon neutrality by reducing the energy consumption in chemical industries. Herein, mesoporous zeolite-encapsulated palladium (Pd) nanoparticles (Pd@meso-ZSM-5) synthesized via emulsification-demulsification followed by a dry-gel transformation method were demonstrated to have a remarkable catalytic performance for a one-pot multiple tandem reaction of cyclic ketones (cyclopentanone, cyclohexanone) to bicyclic alkanes (bicyclopentane, bicyclohexane). Compared with supported catalysts (Pd/meso-ZSM-5) and microporous zeolite-encapsulated catalysts (Pd@ZSM-5) with a primary product of monocyclic alkane (cyclopentane, cyclohexane), Pd@meso-ZSM-5 shows much higher catalytic efficiency for the bicyclic alkanes synthesis, which was previously unattainable in the conventional two-step synthesis route. Controlled experiments and detailed characterizations show that mesoporosity provides sufficient space for the generation and diffusion of large molecular intermediates, and the intimate acid-Pd interface promotes the conversion of intermediates. As a result, this work proposes a design strategy for a mesoporous zeolite-encapsulated metal catalyst, which efficiently provides cooperative acid-hydrogenation catalysis.

09 BIOMASS FUELS↗
DOE OSTI2026

Advancing technologies for lignin-based jet fuel production in aqueous phase

Integrating lignin into a cellulosic ethanol plant for the co-production of lignin-based jet fuel (LJF) in aqueous phase offers a significant opportunity to boost operational efficiency, economic viability, carbon conversion, and the overall sustainability of biofuel and chemical production. LJF is lignin-structure-based jet fuel blendstocks primarily composed of alkyl-substituted mono-, bi-, and tri-cyclohexanes. It exhibits high energy density, potential for low emissions, and favourable blend characteristics that comply with drop-in specifications. An overview of lignin feedstock, catalytic processes, LJF chemical compositions, fuel properties tests, and techno-economic analysis (TEA) and life cycle assessment (LCA) indicate that (1) the reactivity of lignin plays a crucial role in its structure transformation to LJF molecules; (2) catalytic processing of lignin to LJF can occur through a simultaneous depolymerization and hydrodeoxygenation process, bypassing the intermediate step of producing and upgrading lignin-derived oil; (3) LJF's uniqueness molecules making it more promising for high energy content and low emission jet fuel properties for next generation sustainable aviation fuel (SAF); and (4) TEA and LCA demonstrate that LJF is not only potentially cost-effective but also offers favourable carbon footprint compared to other SAFs. In conclusion, this review highlights the most recent advancements in LJF technology, along with the challenges and opportunities that lie ahead in fulfilling its potential.

09 BIOMASS FUELS↗
DOE OSTI2022

Thermodynamic modeling of adsorption at the liquid-solid interface

Adsorptive separation techniques are significantly energy efficient in comparison to conventional thermal separation techniques such as distillation. Despite extensive research and development activities undertaken for mixed-gas adsorption, the use of adsorption techniques for the separation of multicomponent liquid mixtures is still limited. A major barrier is the lack of accurate adsorption thermodynamic models, which form the scientific foundation of process simulation of such systems, making the translation to industrial scale challenging. In this work, we have rigorously computed the surface excess of adsorption for six binary liquid mixtures on silica gel at 303 K using the frameworks of the generalized Langmuir isotherm (gL) and the adsorbed solution theory (AST). The six binary liquid mixtures were formed by the pair-wise combinations of four components: benzene, 1,2-dichloroethane, cyclohexane, and n-heptane. We have based our calculations by considering simultaneous equilibria of three phases: saturated vapor phase, bulk liquid phase, and adsorbed phase. Further, the composition of the corresponding saturated vapor phase was estimated by the Nonrandom Two-Liquid activity coefficient model and experimental vapor-liquid equilibria data. The activity coefficients of the adsorbed phase, the central issue of multicomponent adsorption thermodynamics, were calculated using the adsorption Nonrandom Two-Liquid activity coefficient model. Devoid of simplifying assumptions, gL and AST provide rigorous thermodynamic frameworks for adsorption equilibria of multicomponent liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Influence of interfacial responses of Berea Sandstone in low-salinity waterflooding environments

Wetting conditions and fluid-fluid interfacial properties are essential to understanding oil recovery in the context of low-salinity and smart waterflooding. Many have deemed wettability alteration to be the dominant interaction, while some highlight the importance of fluid-fluid interactions. In some rock-fluid systems, benefits from the use of additives can arise to favor hydrocarbon production. Understanding the balance between the fluid-fluid and rock-fluid interactions when utilizing additives is crucial to evaluate benefits in improved efficiency. Ultimately, this understanding will shed light on recovery mechanisms. Regarding oil recovery, previous studies indicate that the injection of a naphthenic acid (NA) blend dissolved in an injection brine improves oil recovery in Berea Sandstone, particularly under low-salinity conditions. Interfacial rheology results for the brine-oil interface correlated well with the recovery response. This observation was speculated to serve as a potential improved recovery mechanism through oil-trapping suppression. However, the said studies did not evaluate potentially concurrent rock wettability alteration during recovery or the initial wetting condition. The purpose of this work is to determine the production behavior in systems with NAs, namely NA-10 (3-Cyclohexanepropinoic acid), NA-14 (Cyclopentane carboxylic acid), NA-18 (Cyclohexane carboxylic acid), and NA-mix (Naphthenic acid mixture), at different initial wetting conditions under spontaneous imbibition. In addition, we tested the NAs ability to alter wettability in Berea Sandstone and determine each “additive’s” capacity to improve recovery. Here, time-domain nuclear magnetic resonance (TD-NMR), contact angle, and Amott cell tests, i.e. spontaneous imbibition, were used to analyze the influence of the selected naphthenic acids on oil displacement under different initial wetting conditions. Our results indicate that individual naphthenic acids indeed have potential as additives in low-salinity waterflooding for oil-wet systems while negatively impacting recovery in water-wet systems. However, results suggest that the evolution of the interfacial properties and wettability conditions are equally important on the recovery behavior.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

A comparison of computational models for predicting yield sooting index

Sooting propensity, a measurement of how much particulate matter is produced when a fuel is burned, is a property of significant interest among researchers who are striving to discover the next generation of cleaner, more efficient fuels and fuel additives. Many compounds are not viable as fuels and/or fuel additives, and as a result, designing cleaner-burning biofuels using only experimental techniques is inefficient. Predictive models have been instrumental in reducing this inherent difficulty, providing researchers with a tool to preemptively screen compounds before production and testing. The present work compares the accuracies and interpretabilities of existing models used to predict a particular measure of sooting propensity, Yield Sooting Index (YSI). These models include artificial neural networks, graph neural networks, and multivariate equations. A novel equation for predicting YSI based on atom path count and bond order is proposed, which can highlight key structural components that contribute to YSI. It was found that artificial neural networks slightly outperform graph neural networks and greatly outperform multivariate equations in blind (test set) prediction accuracy; however, graph neural networks and multivariate equations provide significantly more interpretability as to how compound structure relates to YSI. Predictions of YSI are compared to experimental measurements for previously un-tested compounds with cetane numbers comparable to diesel fuel (50-60) (butyl decanoate, ethyl decanoate, 1,4-bis(ethenoxymethyl)cyclohexane, and 5-heptyloxolan-2-one), and it was found that these compounds produce significantly less soot compared to diesel fuel.

09 BIOMASS FUELS↗
DOE OSTI2020

Pressure-Induced Superconductivity in the Wide-Band-Gap Semiconductor Cu 2 Br 2 Se 6 with a Robust Framework

We report pressure-induced superconductivity in a ternary and nonmagnetic Cu-containing semiconductor, Cu 2 Br 2 Se 6 , with a wide band gap of 1.89 eV, in which the Cu and Br atoms generate infinite 2, helical chains along the c-axis and are linked by the cyclohexane-like Se 6 rings to form a three-dimensional framework. We find that this framework is remarkably robust under compression, and the ambient-pressure phase survives at least to our experimental limit of 32.1 GPa. Concurrent semiconductor-to-metal transition and superconductivity are observed above 21.0 GPa. The superconducting temperature monotonically increases from 4.0 to 6.7 K at 40.0 GPa. Furthermore, first-principles calculations show that the emergence of superconductivity is associated with the formation of weak multicentered bonds that involve the increase in coordination of the Cu atoms and a subset of the Se atoms. The observation of superconductivity in this type of nonmagnetic transition-metal-based material will inspire the exploration of related new superconductors under pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Predicting Small Molecule Transfer Free Energies by Combining Molecular Dynamics Simulations and Deep Learning

Accurately predicting small molecule partitioning and hydrophobicity is critical in the drug discovery process. There are many heterogeneous chemical environments within a cell and entire human body. For example, drugs must be able to cross the hydrophobic cellular membrane to reach their intracellular targets, and hydrophobicity is an important driving force for drug–protein binding. Atomistic molecular dynamics (MD) simulations are routinely used to calculate free energies of small molecules binding to proteins, crossing lipid membranes, and solvation but are computationally expensive. Machine learning (ML) and empirical methods are also used throughout drug discovery but rely on experimental data, limiting the domain of applicability. We present atomistic MD simulations calculating 15,000 small molecule free energies of transfer from water to cyclohexane. This large data set is used to train ML models that predict the free energies of transfer. We show that a spatial graph neural network model achieves the highest accuracy, followed closely by a 3D-convolutional neural network, and shallow learning based on the chemical fingerprint is significantly less accurate. A mean absolute error of ~4 kJ/mol compared to the MD calculations was achieved for our best ML model. We also show that including data from the MD simulation improves the predictions, tests the transferability of each model to a diverse set of molecules, and show multitask learning improves the predictions. This work provides insight into the hydrophobicity of small molecules and ML cheminformatics modeling, and our data set will be useful for designing and testing future ML cheminformatics methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗