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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.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Cross-Linker Selection Controls Glass Transition Elevation or Reduction in Dynamic Covalently Bonded Polymer Networks

Introducing cross-links is a powerful approach to improve polymeric material performance relevant to controlling viscoelasticity, thermal and creep resistance, degradability, and efficient membrane separations. The chemically specific glass transition temperature T g is of fundamental importance in determining the time scales of key dynamical processes and physical state of the material in such applications. Here, we study experimentally how the introduction of relatively large cross-linking molecules in slowly exchanging dynamic bond-forming polymers (vitrimers) impacts vitrification for diverse polymer chemistries and a wide range of cross-link fractions. We find T g can increase, decrease, or even remain essentially unchanged, in qualitative contrast to the generic elevation of T g in traditional permanent polymer networks. We formulate an effective terpolymer network model to understand this rich behavior, which emerges as a consequence of a competition between pure cross-linking and generalized plasticization effects. The latter is associated with the tunable cross-linker size and intrinsic dynamic mobility that can offset slowing down due to traditional permanent cross-linking constraints. Here, a new strategy for functional polymer network design is suggested based on adjusting the relative importance of the two competing physical effects, which potentially can significantly enhance energy savings in applications while retaining other intrinsic properties germane to advanced materials performance.

Copolymers↗
DOE OSTI2026

Understanding the Influence of Chain Architecture on the Transport Quantities of Polymer Electrolytes with Covalently Bonded Anions

Here, we use a combination of experiments and coarse-grained molecular dynamics simulations to elucidate the structure–property relationships in polymer electrolytes obtained by the copolymerization of poly(vinyl ethylene carbonate─lithium styrene bis(trifluoromethanesulfonyl)imide) or p(VEC-LiSTFSI). Experiments show that the conductivity reduces with increasing anion (i.e., STFSI) fraction on the chain, and the cation transference number (t + ) is found to be dependent on the anion fraction. Furthermore, a significant fraction of unpolymerized VEC monomers are observed. Since it is inherently difficult to experimentally control the chain architecture and the amount of unpolymerized VEC in these systems, we perform coarse-grained molecular dynamics simulations on model polymer systems with different chain architectures to mimic the plausible experimental systems. Specifically, we look at the differences in transference numbers arising from (i) a random copolymer of VEC and STFSI monomers; (ii) a blend of VEC-STFSI copolymer with VEC monomers; and (iii) a ternary blend of the VEC homopolymer, STFSI homopolymers, and VEC monomers. The ternary blend model demonstrates the closest resemblance with the experimental transference numbers and diffusivities. The lithium diffusivity obtained from the coarse-grained models with VEC monomers (plasticizers) is about 1.5 times that of the model without VEC monomers, showing that the plasticizing effect of VEC monomers is modest. We rationalize the experimental observations based on aggregate and cluster analyses obtained from molecular simulations. This work reveals that polymer electrolyte chain architecture and plasticizers can critically influence the transport properties, and these parameters should be considered when designing single ion conducting polymeric electrolytes.

cluster distribution↗
DOE OSTI2023

Conventional High-Temperature Superconductivity in Metallic, Covalently Bonded, Binary-Guest C–B Clathrates

Inspired by the synthesis of XB 3 C 3 (X = Sr, La) compounds in the bipartite sodalite clathrate structure, density functional theory (DFT) calculations are performed on members of this family containing up to two different metal atoms. A DFT chemical pressure analysis on systems with X = Mg, Ca, Sr, Ba reveals that the size of the metal cation, which can be tuned to stabilize the B–C framework, is key for their ambient-pressure dynamic stability. High-throughput density functional theory calculations on 105 Pm$\bar{3}$ symmetry XYB 6 C 6 binary-guest compounds (where X, Y are electropositive metal atoms) find 22 that are dynamically stable at 1 atm, expanding the number of potentially synthesizable phases by 19 (18 metals and 1 insulator). Here, the density of states at the Fermi level and superconducting critical temperature, T c , can be tuned by changing the average oxidation state of the metal atoms, with T c being highest for an average valence of +1.5. KPbB 6 C 6 , with an ambient-pressure Eliashberg T c of 88 K, is predicted to possess the highest T c among the studied Pm$\bar{3}$n XB 3 C 3 or Pm$\bar{3}$XYB 6 C 6 phases, and calculations suggest it may be synthesized using high-pressure high-temperature techniques and then quenched to ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Machine learning the metastable phase diagram of covalently bonded carbon

Abstract Conventional phase diagram generation involves experimentation to provide an initial estimate of the set of thermodynamically accessible phases and their boundaries, followed by use of phenomenological models to interpolate between the available experimental data points and extrapolate to experimentally inaccessible regions. Such an approach, combined with high throughput first-principles calculations and data-mining techniques, has led to exhaustive thermodynamic databases (e.g. compatible with the CALPHAD method), albeit focused on the reduced set of phases observed at distinct thermodynamic equilibria. In contrast, materials during their synthesis, operation, or processing, may not reach their thermodynamic equilibrium state but, instead, remain trapped in a local (metastable) free energy minimum, which may exhibit desirable properties. Here, we introduce an automated workflow that integrates first-principles physics and atomistic simulations with machine learning (ML), and high-performance computing to allow rapid exploration of the metastable phases to construct “metastable” phase diagrams for materials far-from-equilibrium. Using carbon as a prototypical system, we demonstrate automated metastable phase diagram construction to map hundreds of metastable states ranging from near equilibrium to far-from-equilibrium (400 meV/atom). We incorporate the free energy calculations into a neural-network-based learning of the equations of state that allows for efficient construction of metastable phase diagrams. We use the metastable phase diagram and identify domains of relative stability and synthesizability of metastable materials. High temperature high pressure experiments using a diamond anvil cell on graphite sample coupled with high-resolution transmission electron microscopy (HRTEM) confirm our metastable phase predictions. In particular, we identify the previously ambiguous structure of n -diamond as a cubic-analog of diaphite-like lonsdaelite phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Erratum: “Breaking covalent bonds in the context of the many-body expansion (MBE). I. The purported ‘first row anomaly’ in XH n (X = C, Si, Ge, Sn; n = 1–4)” [J. Chem. Phys. 156, 244303 (2022)]

We have noted typographical errors in TABLE V of J. Chem. Phys. 156, 244303 (2022). Specifically, the values of the angles φ HχH for the XH 2 species in both the ( 3 B 1 ) and ( 1 A 1 ) states were incorrectly reported as half of the correct values. Additionally, the values of the same angles for the XH 3 and XH 4 species were reported correctly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Covalent bonding of polycations to small polymeric particles

Process produces small spherical polymeric particles which have polycations bound to them. In emulsion form, particles present large positively charged surface which is available to absorb polyanions. This properly can be used in removing heparin from blood or bile acids from the digestive tract. Other anions, such as DNA and RNA, can also be removed from aqueous solutions.

Rembaum, A.↗
NASA NTRS1984

Covalent bonding effect on the mean excitation energy of H2 with the local plasma model

Chemical bonding is taken into account explicitly in the determination of the mean excitation energy (I) for stopping power of H2 with the local plasma approximation by employing molecular electronic wave functions for H2 for the first time. This procedure leads to a new value for IH2 that is higher than all accepted experimental and theoretical values.

Kamaratos, E.↗
DOE OSTI2021

Methods of making non-covalently bonded carbon-titania nanocomposite thin films and applications of the same

In one aspect of the invention, a dye sensitized solar cell has a counter-electrode including carbon-titania nanocomposite thin films made by forming a carbon-based ink; forming a titania (TiO 2 ) solution; blade-coating a mechanical mixture of the carbon-based ink and the titania solution onto a substrate; and annealing the blade-coated substrate at a first temperature for a first period of time to obtain the carbon-based titania nanocomposite thin films. In certain embodiments, the carbon-based titania nanocomposite thin films may include solvent-exfoliated graphene titania (SEG-TiO 2 ) nanocomposite thin films, or single walled carbon nanotube titania (SWCNT-TiO 2 ) nanocomposite thin films.

Liang, Yu Teng↗
NASA NTRS2008

Preparation and Properties of Nanocomposites from Pristine and Modified SWCNTs of Comparable Average Aspect Ratios

Low color, flexible, space-durable polyimide films with inherent and robust electrical conductivity to dissipate electrostatic charge (ESC) have been under investigation as part of a materials development activity for future NASA space missions. The use of single-walled carbon nanotubes (SWCNTs) is one means to achieving this goal. Even though the concentration of SWCNTs needed to achieve ESC dissipation is typically low, it is dependent upon purity, size, dispersion, and functionalization. In this study, SWCNTs prepared by the electric arc discharge method were used to synthesize nanocomposites using the LaRC(TradeMark) CP2 backbone as the matrix. Pristine and functionalized SWCNTs were mixed with an alkoxysilane terminated amide acid of LaRC(TradeMark) CP2 and the soluble imide form of the polymer and the resultant nanocomposites evaluated for mechanical, thermal, and electrical properties. Due to the preparative conditions for the pristine and functionalized SWCNTs, the average aspect ratio for both was comparable. This permitted the assessment of SWCNT functionalization with respect to various interactions (e.g. van der Waals, hydrogen bonding, covalent bond formation, etc.) with the matrix and the macroscopic effects upon nanocomposite properties. The results of this study are described herein.

Smith, Joseph G.↗
NASA NTRSDate not supplied

Fracture Prediction of Epoxy Resin using Morse Bond Potential Embedded in GAFF using Molecular Dynamics Simulations

A generic method is developed to investigate the fracture behavior of an epoxy resin using atomistic molecular (MD) dynamics simulations. The epoxy system consisted of the stoichiometric mixture of tetra-/tri-functional epoxies and di-functional hardener molecules and was cured with a step-growth crosslinking algorithm. A hybrid force field (hFF) in which Morse bond function were added in second generation-general Amber Force Field (GAFF2) was used to capture bond breaking of the crosslinked epoxy system under uniaxial deformation. The Morse bond parameters for covalent bonds in the crosslinked backbone were fit to dissociation curves computed by CASPT2/6-311+G**. After the systems in various crosslink densities were obtained and equilibrated, the full length of stress-strain (𝜎-𝜀) curve was produced including initial elastic regime, yielding, plastic flow, strain hardening, and progressive failure. We found that the hFF was effective in studying the dissociation of crosslinked polymers and understanding the failure mechanism. In the results, the hFF delivered the same elastic property obtained from the unmodified force field GAFF. The stress-strain curve, however, began to be distinct in the plastic regime due to broken covalent bonds capable of altering the tensile behavior. Once the stress reached maximum, it progressively decreased until the ultimate failure (𝜎=0). Since hFF employed the existing GAFF functions with including a minimal change of its bond potential, this approach is easier to perform and computationally more efficient for unveiling the fracture behavior of polymer materials at the molecular level than other approaches with reactive force fields. We expect this approach will be utilized to accelerate the material-by-design process for thermosets by incorporate data from molecular models.

Changwoon Jang↗
DOE OSTI2026

Cs X Si 15 P 21 ( X = Sn or Pb): Polar Noncentrosymmetric Si–P Frameworks Stabilized by Covalent X –P Bonding

Metal silicon phosphides composed of earth-abundant Si and P tend to exhibit semiconducting properties and adopt diverse crystal structures with relatively small additions of structure-directing elements. The potential of silicon phosphide materials in nonlinear optical applications has been hindered by the inability to systematically produce noncentrosymmetric structures with such a flexible framework. Here, in this work, two isostructural compounds with a novel noncentrosymmetric structure were made possible by the inclusion of elements with stereochemically active lone pairs (Sn 2+ and Pb 2+ ). The structures were determined through single-crystal and synchrotron powder X-ray diffraction. Analysis of chemical bonding in real space through the electron localization function revealed stereochemically active Pb 2+ and Sn 2+ species in a trigonal pyramidal coordination with {Pb/Sn}–P bonds. Such covalent bonding between Pb and P is quite uncommon in extended solids and has been reported in a few rare instances. Band structure calculations and linear optical measurements confirm the semiconducting nature of Cs X Si 15 P 21 ( X = Sn or Pb). The synthesis was optimized to yield high-purity polycrystalline samples. The nonlinear optical properties show promising second-harmonic generation (SHG) coefficients from the Kurtz–Perry method. First-principles calculations of the nonlinear optical properties support the experimentally determined SHG values and provide moderate values of birefringence, suggesting Cs X Si 15 P 21 could be phase-matchable and practical nonlinear optical materials in the mid-IR region.

crystal structure↗
DOE OSTI2023

A constitutive model for elastomers tailored by ionic bonds and entanglements

Over the past decade or two, the concept has emerged of using multiple types of weak interactions simultaneously to enhance the mechanical properties of elastomers. These weak interactions include physical entanglements, hydrogen bonds, metal-coordination bonds, dynamic covalent bonds, and ionic bonds. The combination of entanglements and ionic bonding has been minimally explored and is particularly exciting because of the broad application space for polyelectrolytes. In this work, a constitutive model framework is developed to describe the response of elastomers with both ionic bonds and entanglements. Here we formulate a micromechanical model that couples together chain stretching, ionic bond slipping, and entanglement evolution. The ionic bonds provide toughness by enabling plastic deformation in comparison to covalently crosslinked material and add strength compared to a linear polymer. Evolution of the entanglement density is taken as a key mechanism that can govern stiffness, toughness, and self-recovery in elastomers. The model is used to match bulk polyelectrolytes with different fractions of ionic components under a variety of loading histories. The variations in material parameters are then used to help understand the relative importance of different governing mechanisms in the bulk polymers. We show that the theoretical framework can explain our experimental uniaxial tensile experimental results for polyelectrolytes. This model can help to design better material with high stiffness and toughness. We expect that our model can be extended to explain the mechanical behavior of other polyelectrolytes and other soft materials with a wide range of dynamic bonds.

42 ENGINEERING↗
DOE OSTI2026

Harnessing the Spin-Flip Radiative Lifetimes of Optically Addressable Molecular Qubits

Optically addressable molecular qubits based on spin-flip (SF) emissive transitions are promising candidates for quantum technologies due to their sharp luminescence lines and tunable optical-spin interfaces. Yet, the microscopic mechanisms controlling the spin-flip radiative lifetime of SF emitters, a key property for efficient spin readout, remain largely unexplored. Here, we present a computational study of several Cr 4+ and Mo 4+ pseudotetrahedral molecular qubits, and we identify chemical and structural features that influence the transition dipole moment associated with the SF emission, which, in turn, governs the SF radiative lifetime. We find that the magnitude of the dipole moment is governed by the multireference character of the spin-flip excited-state wave function, which can be modulated by tuning the energy separation between the d orbitals of the metal and the spin-pairing energy. Both parameters are sensitive to molecular symmetry, metal–ligand bond covalency, and bond anisotropy and leave room for modulation via ligand and metal design, as well as applied strain, which is relevant for sensing applications. Our findings provide a mechanistic framework for understanding and tuning the spin-flip radiative behavior of molecular qubits and SF emitters that may guide future advances in quantum information science.

molecular qubits↗
DOE OSTI2020

Polyester functional graphenic materials as a mechanically enhanced scaffold for tissue regeneration

Traditional metal implants such as titanium, cobalt, and chromium have found wide utility in medicine; however, these come with a risk of toxicity. To overcome metal-related toxicity and enable degradability, polyesters including polycaprolactone (PCL), polylactic acid (PLA), and polyglycolic acid (PGA) show promise for the replacement of various biomedical applications of metals due to their accepted biocompatibility and FDA approval. However, polyesters are less stiff than their metallic counterparts, limiting their application to non-load bearing injury sites, such as fixation hardware for fingers. To improve mechanical properties, graphene oxide (GO)-polyester composites are a promising class of biodegradable scaffolds. Initial reports of these composites are encouraging, but mechanical properties still fall short. Traditional composites rely on non-covalent association between GO and the polyesters, which often leads to failure at the interface and weakens the overall strength of the material. Herein, we present a strategy for attachment of these FDA-approved polyesters onto a derivative of GO using a robust covalent bond. By covalently functionalizing the graphenic backbone with polyesters and without metal catalysts, we create functional graphenic materials (FGMs) to not only simultaneously retain biodegradability and compatibility, but also mechanically strengthen PCL, PLA, and PGA; we observed an average increase in the Young's modulus of over 140% compared to the graphenic backbone. These polyester-functionalized FGMs are a promising platform technology for tissue implants.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1985

Transition metal oxides - CrO, MoO, NiO, PdO, AgO

The transition-metal oxides are quite ionic; Mulliken population analyses for several oxides give a negative charge of about 0.7 electrons for oxygen. When the transition-metal d shell is only partially filled, the orbitals are involved in covalent bonds with O; both two-electron bonding (2)-antibonding (0) and one-electron bonding (2)-antibonding (1) bonds are formed. These covalent bonds occur in addition to the ionic bonding. There is d-sigma-O2 p sigma repulsion, and this repulsion is reduced when the d-sigma electron is promoted into an orbital which has dominantly 4sp-sigma character and is polarized away from O.

Bauschlicher, C. W., Jr.↗
DOE OSTI2024

Gas-Phase Coordination of Phosphine-Chalcogenides to the Uranyl Cation

It is generally believed that actinides exhibit an increased covalency in bonding to soft-donor atoms such as nitrogen and sulfur compared to the lanthanides. The explanation is that the greater spatial extent of the 5f orbitals in the actinides compared to the 4f orbitals in the lanthanides accounts for this behavior. However, recent computational studies on lanthanide and actinide complexes with sulfur-donor atom ligands suggest that while calculated metrics of bond covalency could increase for actinide complexes with sulfur ligands, the overall stability of the complexes decreased. While many studies of actinide covalency were conducted in the condensed phases, this work investigates the intrinsic interaction between actinides and soft-donor ligands compared with oxygen in the gas phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗