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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 1,513 records · Page 84
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Strong Fermi-level pinning at metal contacts to halide perovskites

The performance of halide perovskite-based electronic and optoelectronic devices is often related to interfacial charge transport. To shed light on the underlying physical and chemical properties of CH 3 NH 3 PbI 3 (MAPbI 3 ) in direct contact with common electrodes Al, Ti, Cr, Ag, and Au, the evolution of interfacial properties and Fermi level pinning is systematically studied. Given a unique experimental facility, pristine interfaces without any exposure to ambient air were prepared. We observe aggregation of substantial amounts of metallic lead (Pb 0 ) at the metal/MAPbI 3 interface, resulting from the interfacial reaction between the deposited metal and iodine ions from MAPbI 3 . It is found that the Schottky barrier height at the metal/MAPbI 3 interface is independent of the metal work function due to strong Fermi level pinning, possibly due to the metallic Pb 0 aggregates, which act as interfacial trap sites. The charge neutrality level of MAPbI 3 is consistent with the energy level of Pb 0 -related defects, indicating that Pb 0 interfacial trap states can be nonradiative recombination sites. Here this work underlines that control of chemical bonding at interfaces is a key factor for designing future halide perovskite-based devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electrolyte clusters as hydrogen sponges: diffusion Monte Carlo simulations

Here, we carry out Diffusion Monte Carlo simulations of up to five hydrogen molecules aggregated with two Stockmayer clusters that solvate a single lithium ion. The first one contains six point dipole solvent particles with parameters tuned to emulate nitromethane. The second cluster is a relative large system investigated recently [G. DiEmma, S. Kalette, and E. Curotto, Chem. Phys. Lett. 2019, 725, 80–86]. In both cases we find that the aggregated hydrogen molecules perturb significantly the ground state of the host cluster and form a distorted tetrahedral cage around the Li + ion. The fifth hydrogen molecule is absorbed by the larger Stockmayer cluster while remaining in the proximity of the solvated charge.

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

Customized metallodielectric colloids and their behavior in dielectrophoretic fields

A synthetic strategy for fabricating colloidal particles with spatially segregated amine-functionalized lobes enables regioselective coating with gold to afford metallodielectric particles with a variety of shapes and lobe sizes. This approach can produce either dissymmetric dumbbell-shaped two-lobed Au-TPM particles (Au-T) or dissymmetric or symmetric three-lobed particles with gold coating on one (Au-T-T and T-Au-T) or two lobes (Au-T-Au). Dielectrophoretic (DEP) forces exerted by an AC field confined between two opposing electrodes generate aggregates ranging from 1D chains to 2D close-packed lattices, depending on the particle shape and lobe arrangement. Furthermore, the aggregate structures reflect the lowest energy configurations resulting from the induced dipole moments created in particle lobes within the confined electric field.

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

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT–TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H–C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π–π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm −1 . More importantly, thermally annealed TPT–TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10 −2 cm 2 V −1 s −1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.

Chemistry↗
DOE OSTI2025

Polymer nanoparticle photocatalysts realized in non-aqueous solvents

Colloidal organic nanoparticles (oNPs) have emerged as a promising category of photocatalyst, thanks to their long-lived surface-bound charges, electronic tunability, and strong absorption in the visible spectrum. Our previous research has established a direct correlation between charge generation in oNPs and their photocatalytic activity, highlighting their effectiveness as a framework for stable, long-lived free carriers. However, oNPs have been restricted to use only in aqueous environments as a result of being synthesized via either nano-emulsion or nano-precipitation procedures. Herein, we present a method for transferring oNP photocatalysts from water into polar non-aqueous solvents while retaining their long-term colloidal stability. We observed that the polymer chains in the solvent-transferred oNPs rearrange from a predominantly H-aggregate structure in water to a combination of H- and J-aggregate characteristics in N,N-dimethylformamide, suggesting a dynamic rearrangement in response to the new solvent environment. Importantly, transient absorption and time-resolved microwave conductivity measurements confirm that the solvent-transferred oNPs maintain their ability to generate free charges at an internal heterojunction. This development opens unique opportunities for eventually leveraging light-generated, long-lived electrons and holes in synthetic redox chemistry across diverse solvent environments, a direction that will be explored in future studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Stochastic Optimization with Risk Aversion for Virtual Power Plant Operations: A Rolling Horizon Control

While the concept of aggregating and controlling renewable distributed energy resources (DERs) to provide grid services is not new, increasing policy support of DER market participation has driven research and development in algorithms to pool DERs for economically viable market participation. Sandia National Laboratories recently undertook a three-year research program to create the components of a real-world virtual power plant (VPP) that can simultaneously participate in multiple markets. Our research extends current state-of-the-art rolling horizon control through the application of stochastic programming with risk aversion at various time resolutions. Our rolling horizon control consists of (1) day-ahead optimization to produce an hourly aggregate schedule for the VPP operator and (2) sub-hourly optimization for real-time dispatch of each VPP subresource. Both optimization routines leverage a two-stage stochastic program (SP) with risk aversion, and integrate the most up-to-date forecasts to generate probabilistic scenarios in real operating time. Our results demonstrate the benefits to the VPP operator of constructing a stochastic solution regardless of the weather. In more extreme weather, applying risk optimization strategies can dramatically increase the financial viability of the VPP. As a result, the methodologies presented here can be further tailored for optimal control of any VPP asset fleet and its operational requirements.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2025

Leveraging the Run 3 experience for the evolution of the ATLAS software-based readout towards HL-LHC

The High-Luminosity Large Hadron Collider (HL-LHC), scheduled to start operating in 2030, aims to increase the instantaneous luminosity by a factor of 10 compared to the LHC. To match this increase, the ATLAS experiment has been implementing a major upgrade program divided into two phases. The first phase (Phase-I), completed in 2022, introduced new trigger and detector systems that have been used during the Run 3 data taking period which began in July 2022. These systems have been used in conjunction with the new Data Acquisition (DAQ) Readout system, based on a software application called Software Readout Driver (SW ROD). SW ROD receives and aggregates data from the front-end electronics via the Front-End Link eXchange (FELIX) system and passes aggregated data fragments to the High-Level Trigger (HLT) system. During Run 3, SW ROD operates in parallel with the legacy Readout System (ROS) at an input rate of 100 kHz. For the Phase-II, the legacy ROS will be completely replaced with a new system based on the next generation of FELIX and an evolution of the SW ROD application called Data Handler. Data Handler has the same functional requirements as SW ROD but must be able to operate at an input rate of 1 MHz. To facilitate this evolution the SW ROD has been implemented using plugin architecture. This contribution presents the design and implementation of the SW ROD application for Run 3, along with the strategy for its evolution to the Phase-II Readout system. It discusses the lessons learned during Run 3 and describes the challenges that have been addressed to accomplish the demanding performance requirements of HL-LHC.

Kolos, Serguei [Univ. of California, Irvine, CA (U↗
DOE OSTI2019

Simulating the Fracture of Notched Mortar Beams through Extended Finite-Element Method and Peridynamics

This paper simulates fracture in notched mortar beams under three-point bending using extended finite element method (XFEM) and peridynamics. A three-phase microstructure (i.e., cement paste, aggregates, and paste-aggregate interface) is used for constitutive modeling of the mortar to obtain the elastic properties for simulation. In the XFEM approach, the simulated homogenized elastic modulus is used along with the total fracture energy of the cement mortar in a damage model to predict the fracture response of the mortar including crack propagation and its fracture parameters (Mode I stress intensity factor, K IC and critical crack tip opening displacement, CTOD C ). The damage model incorporates a maximum principal stress-based damage initiation criteria and a traction-separation law for damage evolution. In the peridynamics approach, a bond-based model involving a prototype microelastic brittle (PMB) material model is used. The elastic properties and fracture energy release rates are used as inputs in the PMB model, along with the choice of peridynamic horizon size. Comparison with experimental fracture properties ( K IC , CTOD C ) as well as crack propagation paths from digital image correlation show that both the approaches yield satisfactory results, particularly for K IC and crack extension. Furthermore, both these methods can be adopted for fracture simulation of cement-based materials.

42 ENGINEERING↗
DOE OSTI2018

Enhanced scattering induced by electrostatic correlations in concentrated solutions of salt-free dipolar and ionic polymers

Here, we present a generalized theory for studying the static monomer density-density correlation function (structure factor) in concentrated solutions and melts of dipolar as well as ionic polymers. The theory captures effects of electrostatic fluctuations on the structure factor and provides insights into the origin of experimentally observed enhanced scattering at ultralow wavevectors in salt-free ionic polymers. It is shown that the enhanced scattering can originate from a coupling between the fluctuations of electric polarization and monomer density. Local and non-local effects of the polarization resulting from finite sized permanent dipoles and ion-pairs in dipolar and charge regulating ionic polymers, respectively, are considered. Theoretical calculations reveal that, similar to the salt-free ionic polymers, the structure factor for dipolar polymers can also exhibit a peak at a finite wavevector and enhanced scattering at ultralow wavevectors. Although consideration of dipolar interactions leads to attractive interactions between monomers, the enhanced scattering at ultralow wavevectors is predicted solely on the basis of the electrostatics of weakly inhomogeneous dipolar and ionic polymers without considering the effects of any aggregates or phase separation. Thus, we conclude that neither aggregation nor phase separation is necessary for observing the enhanced scattering at ultralow wavevectors in salt-free dipolar and ionic polymers. For charge regulating ionic polymers, it is shown that electrostatic interactions between charged monomers get screened with a screening length, which depends not only on the concentration of “free” counterions and coions, but also on the concentration of “adsorbed” ions on the polymer chains. Qualitative comparisons with the experimental scattering curves for ionic and dipolar polymer melts are presented using the theory developed in this work.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Vibrational probe of the origin of singlet exciton fission in TIPS-pentacene solutions

We use native vibrational modes of the model singlet fission chromophore 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) to examine the origins of singlet fission in solution between molecules that are not tethered by a covalent linkage. We use the C—H stretch modes of TIPS side groups of TIPS-Pn to demonstrate that singlet fission does not occur by diffusive encounter of independent molecules in solution. Instead, TIPS-Pn molecules aggregate in solution through their TIPS side groups. This aggregation breaks the symmetry of the TIPS-Pn molecules and enables the formation of triplets to be probed through the formally symmetry forbidden symmetric alkyne stretch mode of the TIPS side groups. The alkyne stretch modes of TIPS-Pn are sensitive to the electronic excited states present during the singlet fission reaction and provide unique signatures of the formation of triplets following the initial separation of triplet pair intermediates. These findings highlight the opportunity to leverage structural information from vibrational modes to better understand intermolecular interactions that lead to singlet fission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Viscous flow properties and hydrodynamic diameter of phenothiazine-based redox-active molecules in different supporting salt environments

We report viscous flow properties of a redox-active organic molecule, N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT), a candidate for non-aqueous redox flow batteries, and two of its radical cation salts. A microfluidic viscometer enabled the use of small sample volumes in determining viscosity as a function of shear rate and concentration in the non-aqueous solvent, acetonitrile, both with and without supporting salts. All solutions tested show Newtonian behavior over shear rates of up to 30 000 s−1, which was rationalized by scaling arguments for the diffusion-based relaxation time of a single MEEPT molecule without aggregation. Neat MEEPT is flowable but with a large viscosity (412 mPa⋅s at room temperature), which is ∼1000 times larger than that of acetonitrile. MEEPT solutions in acetonitrile have low viscosities; at concentrations up to 0.5 M, the viscosity increases by less than a factor of two. From concentration-dependent viscosity measurements, molecular information was inferred from intrinsic viscosity (hydrodynamic diameter) and the Huggins coefficient (interactions). Model fit credibility was assessed using the Bayesian Information Criterion. It is found that the MEEPT and its charged cations are “flowable” and do not flocculate at concentrations up to 0.5 M. MEEPT has a hydrodynamic diameter of around 8.5 Å, which is almost insensitive to supporting salt and state of charge. This size is comparable to molecular dimensions of single molecules obtained from optimized structures using density functional theory calculations. The results suggest that MEEPT is a promising candidate for redox flow batteries in terms of its viscous flow properties.

Wang, Yilin (ORCID:0000000316102995)↗
DOE OSTI2020

Determining population densities in bimodal micellar solutions using contrast-variation small angle neutron scattering

Self-assembly of amphiphilic polymers in water is of fundamental and practical importance. Significant amounts of free unimers and associated micellar aggregates often coexist over a wide range of phase regions. The thermodynamic and kinetic properties of the microphase separation are closely related to the relative population density of unimers and micelles. Although the scattering technique has been employed to identify the structure of micellar aggregates as well as their time-evolution, the determination of the population ratio of micelles to unimers remains a challenging problem due to their difference in scattering power. In this work, using small-angle neutron scattering (SANS), we present a comprehensive structural study of amphiphilic n-dodecyl-PNIPAm polymers, which shows a bimodal size distribution in water. By adjusting the deuterium/hydrogen ratio of water, the intra-micellar polymer and water distributions are obtained from the SANS spectra. The micellar size and number density are further determined, and the population densities of micelles and unimers are calculated to quantitatively address the degree of micellization at different temperatures. Our method can be used to provide an in-depth insight into the solution properties of microphase separation, which are present in many amphiphilic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Vibronic exciton model for low bandgap donor–acceptor polymers

In this study, a vibronic exciton model is introduced to describe the excited state band structure and associated absorption spectra of low bandgap donor–acceptor conjugated polymers. The Hamiltonian is represented in a diabatic basis consisting of Frenkel-like donor and acceptor fragment excitations as well as charge-transfer (CT) excitations between neighboring fragments. States are coupled to each other through electron and hole transfer as well as Coulombically, through interacting fragment transition dipole moments. Local vibronic coupling involving the prominent aromatic-quinoidal vibrational mode, which is responsible for pronounced vibronic progressions in most conjugated oligomers and polymers, is also included. The DAD repeat unit is shown to behave like a J-aggregate trimer, driven by both the sizable in-phase electron and hole transfer integrals between donor and acceptor fragments as well as negative Coulomb coupling between donor and acceptor fragment excitations. The J-aggregate behavior is enhanced in the polymer limit through inter-repeat unit coupling, with the 0–0 vibronic peak significantly enhanced in the lowest-energy near-IR band. In addition, the radiative rate is enhanced by the number of coherently connected repeat units. The near-IR band is shown to possess roughly equal admixtures of CT and Frenkel-like excitations. Applications are made to the polymer PffBT4T-2DT, with the simulated absorption spectrum quantitatively capturing the salient features of the measured spectrum.

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

Polyvinyl acetate-based polymer host for optical and far-infrared spectroscopy of individualized nanoparticles

Preparation techniques for producing films of individualized solution-dispersed nanoparticles (NPs) for optical spectroscopy are frequently technically challenging and tailored for a specific NP system. In this work, we present a rapid, easy, and economical technique for producing polyvinyl acetate (PVAc)-based NP-polymer films on the order of 100’s of micrometers thick that exhibit high uniformity, low aggregation, excellent optical transparency, and low terahertz absorption. In addition, we find that these films are robust at cryogenic temperatures and have a high laser damage threshold of 0.3 TW cm –2 , which make them suitable for pulsed laser measurements. We show that free-standing, flexible, PVAc films can incorporate both one-dimensional single-wall carbon nanotubes (SWCNTs) and zero-dimensional Au NPs. Using absorbance, Raman scattering, and photoluminescence excitation spectroscopy, we observe that SWCNT individualization is maintained, and minimized polymer strain imposed, when the nanotubes are transitioned from the solution to the polymer host. This PVAc-based polymer host presents researchers with a straightforward method for producing free-standing and flexible NP films with low aggregation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dependent scattering and fractal microstructure determine the transparency of aerogel monoliths

This study reveals how dependent scattering and microstructure significantly affect electromagnetic wave propagation through aerogel monoliths, contributing to their transparency. Light scattering by particle ensembles is considered “dependent” when the scattering properties rely not only on particle size and optical constants but also on their spatial distribution, typically occurring when the average interparticle distance is small in comparison with the wavelength of incident radiation. Addressing dependent scattering requires solving Maxwell’s equations for complex heterogeneous structures, which is computationally demanding and usually limited to sample thicknesses on the same scale as the wavelength. This study combines computer-generated ambigel microstructures of fractal aggregates of polydisperse nanoparticles and the radiative transfer with reciprocal transaction method to predict the transmittance of thick ambigel slabs. Transmittance measurements of ambiently dried aerogel monoliths (ambigels) with porosities from about 50% to 90% closely matched the predicted values for their digital twins. However, ignoring dependent scattering or particle aggregation led to inaccurate predictions. This study validated the computational framework, and its findings offer insights for designing photonic metamaterials and analyzing their interactions with electromagnetic waves.

Yalcin, Refet A. (ORCID:0000000339973494)↗
DOE OSTI2019

Laser formation of luminescence bubble microstructures in polymer films

The results of laser-induced formation of luminescent structures on the surface of poly-2.2’-n-oxydiphenylene-5.5’-bis-benzimidazole films, obtained by the coating method from a formic acid solution, are presented. The structures are formed using cw 405-nm laser radiation with intensities of 10{sup 2} – 10{sup 4} W cm{sup –2}. It is shown (using methods of optical, atomic-force, and electron microscopy) that the structures formed on the surface are microbubble foam-like aggregations. Their formation is modelled as a sequence of the following processes: release of formic acid molecules, their condensation on matrix defects in the surface layer, and explosive boiling as a result of heating this layer of polymer film by the laser beam. The luminescence of these structures is due to the weakening of the concentration quenching from closely spaced luminescence centres in benzimidazole cycles during their emergence to the surface and the increase in the distance between them due to the extension on bubble aggregates on the surface. (interaction of laser radiation with matter. laser plasma)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗