Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Organic material decomposition”

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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Data and scripts associated with a manuscript modeling microbial regulation of priming effects

This data package is associated with the publication “Modeling Microbial Regulatory Feedback in Organic Matter Decomposition Identifies Copiotrophic Traits as Key Drivers of Positive Priming” published as a preprint on BioRXiv by Ahamed et al. (2026); https://doi.org/10.1101/2024.08.11.607483. The package contains MATLAB scripts and saved simulation outputs used to implement a cybernetic model of microbial regulation during complex organic matter (OM) decomposition governing priming effects. It includes models of (i) single microbial functional groups (copiotrophic or oligotrophic degraders) and (ii) binary consortia composed of degraders and non-degraders with contrasting or common growth traits. Simulation results were generated using Monte Carlo analyses, with randomized key model parameters across a range of environmental mixing fractions of complex and labile OM. The dataset was created to provide a transparent and reusable computational framework for systematically exploring how microbial growth traits, metabolic regulation, and community composition influence OM decomposition dynamics and priming effects. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes the variable definitions. This package includes: (1) annotated MATLAB code implementing the system of ordinary differential equations and cybernetic control laws; (2) saved output files containing data (e.g., biomass, substrates, enzyme levels, priming metrics); and (3) scripts for processing saved outputs and regenerating figures. Specifically, the data package contains three main MATLAB scripts: runPrimingModel.m, runPlotData.m, and runPlotSuppFigS1.m, along with this readme and supporting documentation. Users should begin with runPrimingModel.m, which contains the annotated code implementing the system of ordinary differential equations and cybernetic control laws. This script runs the Monte Carlo simulations of microbial OM decomposition and allows users to modify microbial trait definitions, adjust parameter distributions, or define new community configurations. Simulation outputs are automatically saved as .mat files in the folder named SavedData, which stores all pre-generated results included in this package. The second script, runPlotData.m, reads files from the SavedData folder and processes them to regenerate the figures presented in the manuscript. The third script, runPlotSuppFigS1.m, specifically generates Figure S1 in the Supplementary Material of the manuscript. The package also includes the aforementioned files in non-proprietary .txt format. If users intend to use them, they should first save the files in their respective .m or .mat formats prior to execution in MATLAB.

Biomass concentration↗
DOE OSTI2023

Reversibly growing crosslinked polymers with programmable sizes and properties

Growth constitutes a powerful method to post-modulate materials’ structures and functions without compromising their mechanical performance for sustainable use, but the process is irreversible. To address this issue, we here report a growing-degrowing strategy that enables thermosetting materials to either absorb or release components for continuously changing their sizes, shapes, compositions, and a set of properties simultaneously. The strategy is based on the monomer-polymer equilibrium of networks in which supplying or removing small polymerizable components would drive the networks toward expansion or contraction. Using acid-catalyzed equilibration of siloxane as an example, we demonstrate that the size and mechanical properties of the resulting silicone materials can be significantly or finely tuned in both directions of growth and decomposition. The equilibration can be turned off to yield stable products or reactivated again. During the degrowing-growing circle, material structures are selectively varied either uniformly or heterogeneously, by the availability of fillers. Our strategy endows the materials with many appealing capabilities including environment adaptivity, self-healing, and switchability of surface morphologies, shapes, and optical properties. Since monomer-polymer equilibration exists in many polymers, we envision the expansion of the presented strategy to various systems for many applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electrochemical reactivity and passivation of organic electrolytes at spinel MgCrMnO 4 cathode interfaces for rechargeable high voltage magnesium-ion batteries

Magnesium transition metal oxides such as MgCr 2−x Mn x O 4 are promising high-voltage and high-capacity cathode materials for rechargeable magnesium batteries (RMBs). Understanding and improving the chemical and electrochemical stability of the cathode–electrolyte interface (CEI) has been the primary technical emphasis to enable this category of cathode materials, which has been significantly underexplored. Herein, in this study, we focus on investigating the fundamental mechanism of parasitic reactions at the charged surface of the high-voltage MgCrMnO 4 model cathode with different organic electrolytes. The aim is to reveal the underlying effect of anions and solvents responsible for the passivation behavior of the cathode by using three exemplary anions: [(CF 3 SO 2 ) 2 N] − (TFSI − ), Al[OC(CF 3 ) 3 ] 4 − (TPFA − ), and [CB 11 H 12 ] − (MC) and three solvents: diglyme (G2), triglyme (G3), and 3-methoxypropylamine (MPA). High precision leakage current measurements during potentiostatic hold reveal that the electrolyte solvent chemistry has a more profound impact than anion's on the passivation of the MgCrMnO 4 cathode surface during deintercalation of Mg 2+ . X-ray photoelectron spectroscopy exhibits the differences in CEI composition. Amine solvents like MPA show poor passivation due to a higher degree of solvent decomposition, while the thin and anion-derived CEI in glyme-based electrolytes is directly linked with the better passivation behavior on the cathode. Furthermore, we leverage the knowledge from these findings to modify the electrolyte structure by adding a solvent additive, with the goal of reducing the parasitic reaction.

25 ENERGY STORAGE↗
DOE OSTI2020

Density Functional Theory Study of the Adsorption and Dissociation of Copper(I) Acetamidinates on Ni(110): The Effect of the Substrate

In order to assess the role of a metal substrates on the thermal chemistry of adsorbed acetamidinate metalorganic compounds, we have studied the surface chemistry of copper(I)–N,N'-dimethylacetamidinate on Ni(110) using density functional theory and contrasted it with similar calculations we previously carried out on Cu(110). At low coverages, it was found that, in its most stable configuration, the molecular adsorption of copper(I)–N,N'-dimethylacetamidinate dimers occurs with the Cu atoms occupying surface hollow sites. In this work, the ligands reorient away from those metal centers, and the N atoms develop new direct bonds with surface Ni atoms. However, this configuration is not stable and decomposes by losing both ligands to the surface. In the final state, the two ligands bind via their N atoms to Ni sites one lattice space away from the sites where the Cu atoms remain, with their molecular planes perpendicular to that of the surface. This is in contrast with what happens in the case of adsorption on Cu(110), where the Cu atoms from the metalorganic complex still occupy hollow sites but where only one of the ligands breaks away and binds directly to the surface; the other remains on top of the two Cu ions. In terms of the energetics of adsorption and decomposition, the reactions on Ni(110) are much more exothermic than on Cu(110). Further analysis of the distribution of charge within the adsorbates shows a minor reduction of the Cu atoms of the dimer upon interaction with the surface; full reduction to metallic copper is complete only when both ligands have fully migrated to their new Ni surface sites.

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

CHIPFoam Modification to Allow for Modelling SWIFT Foams

SWIFT (Silicon-water in Familiar Template) foams are silicone foams that have a continuous porosity without having any obvious spherical or ellipsoidal pore shapes. Like other foamed rubber, SWIFT foams can experience large reversible deformations. Because of their microstructure, SWIFT foams have a stiffering behavior in compression that is very abrupt compared to most other foamed rubbers. Work by Benedikt reported by Miller showed that fitting compressive test data with the CHIPFoam model in its current form is impractical and inaccurate. This report describes an extension made to CHIPFoam to allow the modeling of SWIFT foams. While the extension allows the modeling of SWIFT foams, it also extends the range of porosity of foams that can be modelled with CHIPFoam to include very high porosity (>99%) foamed rubber. The previous model was unstable for porosities greater than 70%. The changes made to CHIPFoam include the introduction of a critical porosity at which the compressible Danielsson strain energy function that couples volumetric and deviatoric mechanical behavior begins to increase with compression. This new feature also required the introduction of a third term in the multiplicative decomposition of the relative volume, J . The organization of this report is described here. The first section, SWIFT Foam Structure and Mechanical Behavior, describes the structure of SWIFT foams as contrasted to other foamed rubbers. It also contrasts the mechanical behavior of SWIFT foams to other more traditional foamed rubbers. The second section, CHIPFoam Modifications, describes the specific modifications done to be able to modify the delayed rapid compressive stiffening seen in SWIFT foams. The third section, Results, demonstrates the use of the modified model to fit compressive loading response data from a SWIFT foam sample. The fourth section, Conclusions and Further Work, puts the work in perspective and presents likely further work.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Intrinsic Chemical Reactivity of Silicon Electrode Materials: Gas Evolution

In this work, we explore how the chemical reactivity toward an aprotic battery electrolyte changes as a function of lithium salt and silicon surface termination chemistry. The reactions are highly correlated, where one decomposition reaction leads to a subsequent decomposition reaction. We report the data show that the presence of silicon hydrides (SiH$_x$) promotes the formation of CO gas, while surface oxides SiO$_x$ drive the formation of CO 2 . The extent and rate of oxidation depend on the surface basicity of the SiO 2 surface species. The most acidic surfaces seem to hinder CO 2 generation but not the decomposition of the salt. Indeed, the presence of F-containing salts (LiPF 6 and LiTFSI) promotes the reactions between carbonate electrolyte and silicon surfaces. Surfaces with high Li content seem to be the most passivating to gassing reactions, pointing to a pathway to stabilize the interfaces during cell formation and assembly.

25 ENERGY STORAGE↗
DOE OSTI2026

Linking DSC/TGA to Cell Levels: Energetics, Evolved Gases, and Thermal Safety of NMC811‐Graphite Micro‐Cell

Thermochemical characterization of battery materials links intrinsic material properties to decomposition pathways, heat generation, and gas evolution that govern performance and safety. Despite extensive work on NMC811-Graphite, variability across partial configurations and the limited adoption of micro-cell architectures (cathode+anode+electrolyte+separator) hinder robust cell-scale interpretation. Accordingly, this work establishes a bottom-up, component-resolved methodology integrating DSC/TGA, evolved gas analysis (EGA), and in situ XRD to link decomposition pathways and energy release across partial and micro-cell configurations, providing a transferable assessment of safety and stability in emerging chemistries. In separator-free configurations, the gas–solid reaction between cathode-evolved O 2 and anode-leached Li dominates the net heat release (1139 J g −1 ). In contrast, in the micro-cell configuration, the separator hinders O 2 transport and alters the timing and pathways of other reactions, and reduces the net energy release to 618 J g −1 . Energy release was organized into defined temperature windows that provide a framework for a thermodynamic model combining quantified gas evolution with selected decomposition pathways and effective reaction enthalpies to estimate net specific energy release, with agreement between DSC and cell-level tests. Ex situ XPS of heat-treated samples extends post-mortem analysis to thermal-abuse regimes, supporting key pathway elements.

25 ENERGY STORAGE↗
DOE OSTI2022

Plutonium Hybrid Materials: A Platform to Explore Assembly and Metal–Ligand Bonding

In this work, we report the synthesis of five new hybrid materials containing the [PuCl 6 ] 2- anion and charge balancing, non-covalent interaction donating 4-X-pyridinium (X = H, Cl, Br, I) cations. Single crystals of the title compounds were grown and harvested from acidic, chloride-rich, aqueous media and their structures were determined via X-ray diffraction. Compounds 1-4, (4XPyH) 2 [PuCl 6 ] and 5, (4IPyH) 4 [PuCl 6 ] · 2Cl, exhibit two distinct sheet-like structure types. Structurally relevant non-covalent interactions were tabulated from crystallographic data and verified computationally using electrostatic surface potential maps and the quantum theory of atoms in molecules (QTAIM) approach. The strength of the hydrogen and halogen bonds was quantified using Kohn-Sham density functional theory and a hierarchy of acceptor-donor pairings established. In turn, the PuIV-Cl bonds were studied using the QTAIM and natural localized molecular orbital (NLMO) approaches to delineate the underlying bond mechanism and hybrid atomic orbital contributions therein. Energy decomposition (ED) and natural ED analyses were also explored to probe the bond mechanism and, more broadly, explore the efficacy of these techniques in studying these anionic systems. The results of the PuIV-Cl bond analyses were compared across composition via analogous treatments of previously reported [PuO 2 Cl 4 ] 2- and [PuCl 3 (H 2 O) 5 ] molecular units. In summary, our study indicates that the Pu-Cl bonds are predominately ionic, yet exhibit small varying degrees of covalent character that increase from [PuCl 3 (H 2 O) 5 ], [PuO 2 Cl 4 ] 2- , to [PuCl 6 ] 2- , while the participation of the Pu based s/d and f orbitals concurrently decrease and increase, respectively.

transuranic↗
DOE OSTI2024

Synthesis of cerium precursors with alkoxide ligands for degradation to cerium oxide nanoparticles

Lanthanide oxide and sulfide nanoparticles present intriguing theoretical questions regarding their electronic structures, alongside numerous potential applications in material science and catalysis. Although these materials can be formed through hydrolysis, their synthesis via thermolysis is crucial for nanoscale materials and practical applications. This research aims to enhance our understanding of the decomposition mechanisms by focusing on cerium compounds, which are analogous to those studied previously. Currently, our knowledge of the decomposition mechanisms of cerium alkoxide precursors is limited. The objective of this project is to develop a mechanistic understanding of the formation of cerium oxide nanoparticles from cerium alkoxide precursors, employing a variety of techniques. These techniques include collision-induced dissociation in an ion-trap mass spectrometer, nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC), and gas chromatography-mass spectrometry (GC-MS) to investigate the decomposition mechanisms of the synthesized precursors.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2025

Microwave-assisted dehydrogenation of fossil fuels using iron-based alumina nanocomposites

Hydrogen is mainly produced via steam reforming of methane and gasification of coal, with enormous CO 2 emissions in both cases. Microwave-assisted thermocatalytic decomposition (pyrolysis) is of interest as a method for hydrogen production from fossil fuels with no CO 2 emissions. For successful implementation of this technology, it is necessary to develop decomposition catalysts that are also good microwave absorbers and can be produced from inexpensive materials via a robust synthetic route. Recently, iron-based alumina nanocomposites, fabricated by solution combustion synthesis (SCS), have shown promising microwave-absorbing and catalytic properties in the pyrolysis of plastics. The reported project explored the feasibilities of improving such catalysts and using them for the microwave-assisted pyrolysis of liquid fossil fuels, viz., diesel fuel, gasoline, and crude oil. The research focused on how SCS parameters affect the material properties and pyrolysis performance.

02 PETROLEUM↗
DOE OSTI2021

Unraveling Strain Gradient Induced Electromechanical Coupling in Twisted Double Bilayer Graphene Moiré Superlattices

Moiré superlattices of 2D materials with a small twist angle are thought to exhibit appreciable flexoelectric effect, though unambiguous confirmation of their flexoelectricity is challenging due to artifacts associated with commonly used piezoresponse force microscopy (PFM). For example, unexpectedly small phase contrast (≈8°) between opposite flexoelectric polarizations is reported in twisted bilayer graphene (tBG), though theoretically predicted value is 180°. We report a methodology is developed to extract intrinsic moiré flexoelectricity using twisted double bilayer graphene (tDBG) as a model system, probed by lateral PFM. For small twist angle samples, it is found that a vectorial decomposition is essential to recover the small intrinsic flexoelectric response at domain walls from a large background signal. The obtained threefold symmetry of commensurate domains with significant flexoelectric response at domain walls is fully consistent with the theoretical calculations. Incommensurate domains in tDBG with relatively large twist angles can also be observed by this technique. A general strategy is provided here for unraveling intrinsic flexoelectricity in van der Waals moiré superlattices while providing insights into engineered symmetry breaking in centrosymmetric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The overlapping fragment approach for non-orthogonal configuration interaction with fragments

The non-orthogonal configuration interaction with fragments (NOCI-F) approach is extended opening the possibility to study intramolecular processes and materials with covalent or ionic lattices. So far, NOCI-F has been applied to study intermolecular energy and electron transfer employing ensembles of fragments that do not have atoms or bonds in common. The here presented approach divides the target system into two overlapping fragments that share one or more atoms and/or one or more bonds. After the construction of a collection of (multiconfigurational) fragment wave functions in a state specific optimization procedure, the fragment wave functions are combined to form many-electron basis functions for the non-orthogonal configuration interaction of the whole system. The orbitals in the overlapping fragment are defined by a corresponding orbital transformation of the fragment orbitals through a singular value decomposition. The overlapping fragments approach is first illustrated for a model system and then used to highlight some possible applications of NOCI with overlapping fragments. In conclusion, the results of excited state diffusion in transition metal oxide, intramolecular singlet fission and magnetic interactions in organic biradicals and ionic compounds are discussed.

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

Effect of Si Content on Extreme Fast Charging Behavior in Silicon–Graphite Composite Anodes

Commercial Li-ion batteries typically incorporate a small amount of high-capacity silicon (Si)-based materials in the composite graphite-based anode to increase the energy density of the battery. However, very little is known about the effects of Si on the fast-charging behavior of composite anodes. Herein, we examine the effects of the Si/graphite ratio in the composite anode on the fast-charging behavior of full cells. We show that addition of Si increases the rate capability from 1C to 8C and improves the capacity retention in early cycles at 6C due to reduced overpotential in constant current charging cycles. The impacts of Si content on fast-charging aging were identified by Post-Test characterization. Despite realizing benefits of available capacity and reduced Li plating at 6C, silicon–electrolyte interactions lead the time-dependent cell performance to fade quickly in the long term. The Post-Test analysis also revealed the thickening of the electrode and nonuniform distribution of electrolyte decomposition products on the Si-containing anodes, as well as the organic-rich solid electrolyte interphase (SEI), which are the factors behind cell degradation. Our study sheds insight on the advantages and disadvantages of Si/graphite composite anodes when they are used in fast-charging applications and guides further research in the area by designing an optimized composition of Si incorporated in a mature graphite matrix.

25 ENERGY STORAGE↗
DOE OSTI2020

Effect of ionizing radiation on PuO2 and surrogate oxide materials under storage conditions

The stockpile of plutonium separated from used nuclear fuel amounts to many 100s of tonnes. The majority of this plutonium is stored as PuO2 powder packaged in multi-can containers. The conditions during the packaging of reprocessed PuO2 for long term storage are closely controlled to limit water uptake as radiolytic decomposition of any adsorbed water will lead to the formation of both a potentially flammable atmosphere containing molecular hydrogen as well as reactive oxygen species which may be incorporated into the oxide phase. Consequently, the safety case for the long-term storage of PuO2 requires a complete understanding of the fundamental physical, chemical and materials degradation processes occurring at the water-oxide interface inside the storage canisters. This study investigates the effect of ionizing radiation on PuO2 and various surrogate oxides under atmospheres potentially encountered in storage canisters.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Stress- and interface-compatible red phosphorus anode for high-energy and durable sodium-ion batteries

Sodium-ion battery is a promising candidate for energy storage application, but the absence of high-capacity and low-cost anode materials significantly limit their practical specific energy and cost. Red phosphorus (RP) possesses a high theoretical specific capacity but suffers from large volume change, low electronic conductivity and unstable solid-electrolyte interphase (SEI). Herein, a hierarchical micro/nanostructured antimony-doped RP/carbon anode was developed, which demonstrate extraordinary electrochemical performance with high initial Coulombic efficiency of ~90%, high areal (~1.7 mAh cm-2) capacity together with good cycle stability and rate capability. Combined experimental and computational studies consistently revealed that such a unique structural design can dramatically accommodate the mechanical stress and moreover effectively restrain the undesired decomposition of electrolyte solvents regardless of electrolytes formulation, resulting in superior structural integrity and thin/robust SEI formation during cycling. The present finding has offered an alternative strategy for stress management and interface engineering on high-capacity alloying-based anode materials.

Liu, Xiang↗
DOE OSTI2025

Use of Fisher's Ratio assisted multivariate curve resolution- alternating least squares for discovery-based analysis using ultrahigh pressure liquid chromatography-high resolution mass spectrometry

Non-targeted analysis of complex chemical mixtures can be difficult considering the convoluted nature of the matrix and the potential unknown chemical differences between samples or classes of samples. Ultrahigh pressure liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF) is an ideal technique to probe chemical differences for a wide variety of samples. While UHPLC-QTOF can discover minute chemical differences down to low part per billion (ppb) concentrations with a high degree of confidence, the application of high-resolution mass spectrometry can yield massive amounts of information (∼ 10 gb per sample) that cannot be analyzed manually. Therefore, the application of chemometric techniques is mandatory for the interrogation of complex samples. Fisher's ratio (FR) assisted multivariate curve resolution-alternating least squares (MCR-ALS) was used to the discover and identify the chemical differences between two classes of materials: 1) a pond water matrix and 2) the matrix spiked with a pharmaceutical standard mix containing 17 compounds. Thirteen of the seventeen spiked compounds were discovered using FR analysis, and then five were successfully deconvoluted using MCR-ALS wherein the number of curves chosen were automatically determined using singular value decomposition (SVD). In conclusion, the use of an automated FR assisted MCR-ALS will aid in discovering trace levels of chemical components without the need for the researcher to provide potentially biased input which will aid in non-targeted workflow.

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

Solid-source metal-organic MBE for elemental Ir and Ru films

Thin films of elemental metals play a very important role in modern electronic nano-devices as conduction pathways, spacer layers, spin-current generators/detectors, and many other important functionalities. In this work, by exploiting the chemistry of solid metal-organic source precursors, we demonstrate the molecular beam epitaxy synthesis of elemental Ir and Ru metal thin films. The synthesis of these metals is enabled by thermodynamic and kinetic selection of the metal phase as the metal-organic precursor decomposes on the substrate surface. Film growth under different conditions was studied using a combination of in situ and ex situ structural and compositional characterization techniques. The critical role of substrate temperature, oxygen reactivity, and precursor flux in tuning film composition and quality is discussed in the context of precursor adsorption, decomposition, and crystal growth. Computed thermodynamics quantifies the driving force for metal or oxide formation as a function of synthesis conditions and changes in chemical potential. These results indicate that bulk thermodynamics are a plausible origin for the formation of Ir metal at low temperatures, while Ru metal formation is likely mediated by kinetics.

Materials Science↗
DOE OSTI2023

The diversity of aluminum-based drinking water treatment residuals for use in environmental remediation

Drinking water treatment residuals (DWTRs) are complex mixtures of organic and inorganic phases generally disposed of as waste materials. However, their strong sorptive properties could be further exploited to immobilize contaminants. To characterize these materials, we applied a range of analytical techniques to a set of aluminum-based DWTRs. Here we determined surface areas, elemental compositions using CHNS analysis and X-ray fluorescence (XRF), performed thermogravimetric analyses paired with mass spectrometry (TGA-MS), and used synchrotron-based methods: X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Elemental analyses and specific surface area measurements – that vary between 7.23 ± 0.03 and 197.6 ± 0.9 m 2 g –1 – indicate that non-coagulant additives must play an important role in controlling sorption. High resolution powder XRD reveals the presence of only a few crystalline minerals mostly derived from source waters or additives. Fe was detected by XRF in all samples, whereas Mn was present in significant levels in samples with potassium permanganate as additive. The chemical speciation of these elements was characterized by performing spectral decompositions of XAS spectra. The spectral features of Fe are consistent with iron(III) oxides/hydroxides and structural iron in clays. On the other hand, Mn is predominantly present under its reduced form, Mn(II).

54 ENVIRONMENTAL SCIENCES↗