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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Strong polaronic effect in a superatomic two-dimensional semiconductor

Crystalline solids assembled from superatomic building blocks are attractive functional materials due to their hierarchical structure, multifunctionality, and tunability. An interesting example is Re 6 Se 8 Cl 2 , in which the Re 6 Se 8 building blocks are covalently linked into two-dimensional (2D) sheets that are stacked into a layered van der Waals solid. It is an indirect gap semiconductor that, when heavily doped, becomes a superconductor at low temperatures. Given the finite electronic bandwidths (300–400 meV), carrier properties in this material are expected to be strongly influenced by coupling to phonons. Here, we apply angle-resolved photoemission spectroscopy to probe the valence band edge (VBE) of Re 6 Se 8 Cl 2 . We find that dispersion of the VBE is a strong function of temperature. The bandwidth is W = 120 ± 30 meV at 70 K and decreases by one order of magnitude to W ~ 10 ± 20 meV as temperature is increased to 300 K. This observation reveals the dominant polaronic effects in Re 6 Se 8 Cl 2 , consistent with the Holstein polaron model commonly used to describe molecular solids.

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

Exploring the effects of molecular beam epitaxy growth characteristics on the temperature performance of state-of-the-art terahertz quantum cascade lasers

This study conducts a comparative analysis, using non-equilibrium Green’s functions (NEGF), of two state-of-the-art two-well (TW) Terahertz Quantum Cascade Lasers (THz QCLs) supporting clean 3-level systems. The devices have nearly identical parameters and the NEGF calculations with an abrupt-interface roughness height of 0.12 nm predict a maximum operating temperature (T max ) of ~ 250 K for both devices. However, experimentally, one device reaches a T max of ~ 250 K and the other a T max of only ~ 134 K. Both devices were fabricated and measured under identical conditions in the same laboratory, with high quality processes as verified by reference devices. The main difference between the two devices is that they were grown in different MBE reactors. Our NEGF-based analysis considered all parameters related to MBE growth, including the maximum estimated variation in aluminum content, growth rate, doping density, background doping, and abrupt-interface roughness height. From our NEGF calculations it is evident that the sole parameter to which a drastic drop in T max could be attributed is the abrupt-interface roughness height. We can also learn from the simulations that both devices exhibit high-quality interfaces, with one having an abrupt-interface roughness height of approximately an atomic layer and the other approximately a monolayer. However, these small differences in interface sharpness are the cause of the large performance discrepancy. This underscores the sensitivity of device performance to interface roughness and emphasizes its strategic role in achieving higher operating temperatures for THz QCLs. We suggest Atom Probe Tomography (APT) as a path to analyze and measure the (graded)-interfaces roughness (IFR) parameters for THz QCLs, and subsequently as a design tool for higher performance THz QCLs, as was done for mid-IR QCLs. Our study not only addresses challenges faced by other groups in reproducing the record T max of ~ 250 K and ~ 261 K but also proposes a systematic pathway for further improving the temperature performance of THz QCLs beyond the state-of-the-art.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Spectroscopic evidence of spin-state excitation in d-electron correlated semiconductor FeSb 2

Iron antimonide (FeSb 2 ) has been investigated for decades due to its puzzling electronic properties. It undergoes the temperature-controlled transition from an insulator to an ill-defined metal, with a cross-over from diamagnetism to paramagnetism. Extensive efforts have been made to uncover the underlying mechanism, but a consensus has yet to be reached. While macroscopic transport and magnetic measurements can be explained by different theoretical proposals, the essential spectroscopic evidence required to distinguish the physical origin is missing. In this paper, through the use of X-ray absorption spectroscopy and atomic multiplet simulations, we have observed the mixed spin states of 3d 6 configuration in FeSb 2 . Furthermore, we reveal that the enhancement of the conductivity, whether induced by temperature or doping, is characterized by populating the high-spin state from the low-spin state. Our work constitutes vital spectroscopic evidence that the electrical/magnetical transition in FeSb 2 is directly associated with the spin-state excitation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Oxygen Electrocatalysis on Mixed-Metal Oxides/Oxyhydroxides: From Fundamentals to Membrane Electrolyzer Technology

Catalyzing the oxygen evolution reaction (OER) is important for key energy-storage technologies, particularly water electrolysis and photoelectrolysis for hydrogen fuel production. Under neutral-to-alkaline conditions, first-row transition-metal oxides/(oxy)hydroxides are the fastest-known OER catalysts and have been the subject of intense study for the past decade. Critical to their high performance is the intentional or accidental addition of Fe to Ni/Co oxides that convert to layered (oxy)hydroxide structures during the OER. Unraveling the role that Fe plays in the catalysis and the molecular identity of the true “active site” has proved challenging, however, due to the dynamics of the host structure and absorbed Fe sites as well as the diversity of local structures in these disordered active phases. In this Account, we highlight our work to understand the role of Fe in Ni/Co (oxy)hydroxide OER catalysts. We first discuss how we characterize the intrinsic activity of the first-row transition-metal (oxy)hydroxide catalysts as thin films by accounting for the contributions of the catalyst-layer thickness (mass loading) and electrical conductivity as well as the underlying substrate’s chemical interactions with the catalyst and the presence of Fe species in the electrolyte. We show how Fe-doped Ni/Co (oxy)hydroxides restructure during catalysis, absorb/desorb Fe, and in some cases degrade or regenerate their activity during electrochemical testing. We highlight the relevant techniques and procedures that allowed us to better understand the role of Fe in activating other first-row transition metals for OER. We find several modes of Fe incorporation in Ni/Co (oxy)hydroxides and show how those modes correlate with activity and durability. We also discuss how this understanding informs the incorporation of earth-abundant transition-metal OER catalysts in anion-exchange-membrane water electrolyzers (AEMWE) that provide a locally basic anode environment but run on pure water and have advantages over the more-developed proton-exchange-membrane water electrolyzers (PEMWE) that use platinum-group-metal (PGM) catalysts. We outline the key issues of introducing Fe-doped Ni/Co (oxy)hydroxide catalysts at the anode of the AEMWE, such as the oxidative processes triggered by Fe species traveling through the polymer membrane, pH-gradient effects on the catalyst stability, and possibly limited catalyst utilization in the compressed stack configuration. We also suggest possible mitigation strategies for these issues. Lastly, we summarize remaining challenges including the long-term stability of Fe-doped Ni/Co (oxy)hydroxides under OER conditions and the lack of accurate models of the dynamic active surface that hinder our understanding of, and thus ability to design, these catalysts.

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

Bioderived Radical Polymers for Sustainable Energy Storage Materials

Organic mixed ionic and electronic conductors have emerged as promising materials for next-generation energy applications, and a variety of molecular designs have been implemented to push performance to higher levels. Importantly, nonconjugated redox-active radical polymers capable of charge transport offer benefits such as ready synthesis in large quantities and the capability to separate thermomechanical and electrochemical behaviors. This affords more freedom with respect to macromolecular backbone design; thus, the resultant materials properties make this class of polymers appealing alternatives for energy storage. However, these radical polymers often still rely on petrochemically derived polymer backbones. Here, we demonstrate the polymerization of the bioderived terpene β-myrcene and its functionalization by attaching stable radical pendant groups capable of mixed electronic and ionic conduction. The electrochemical enhancement of these materials was substantial as the addition of carbon black and doping of lithium salts electronic conductivities of ~60 S cm -1 were achieved for the composite systems. The addition of the lithium salts proved fruitful as the electric and ionic conductivities of the radical polymers surpassed 10 -4 S cm -1 at elevated temperatures when both lithium hexafluorophosphate and lithium chloride, a more bio and environmentally friendly material, where introduced to the system. Finally, these findings demonstrate a bioderived alternative for an organic mixed conductor serving as both potential cathode and polymer electrolyte for a more sustainable alternative for energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2022

Single-molecule magnet Mn 12 on GaAs-supported graphene: Gate field effects from first principles

In this work, we study gate field effects on the Mn 12 O 12 (COOH) 16 (H 2 O) 4 | graphene | GaAs heterostructure via first-principles calculations. We find that under moderate doping levels electrons can be added to but not taken from the single-molecule magnet Mn 12 O 12 (COOH) 16 (H 2 O) 4 (Mn 12 ). The magnetic anisotropy energy (MAE) of Mn 12 decreases as the electron doping level increases, due to electron transfer from graphene to Mn 12 and change in the band alignment between Mn 12 and graphene. At an electron doping level of -5.00×10 13 cm -2 , the MAE decreases by about 18% compared with zero doping. The band alignment between graphene and GaAs is more sensitive to electron doping than to hole doping, since the valence band of GaAs is close to the Fermi level. The GaAs substrate induces a small band gap in the supported graphene under zero gate field and a nearly strain-free configuration. Finally, we propose a vertical tunnel junction for probing the gate dependence of MAE via electron transport measurements.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Massive Suppression of Proximity Pairing in Topological ( Bi 1 - x Sb x ) 2 Te 3 Films on Niobium

Interfacing bulk conducting topological Bi 2 Se 3 films with s-wave superconductors initiates strong superconducting order in the nontrivial surface states. Yet, bulk insulating topological (Bi 1-x Sb x ) 2 Te 3 films on bulk Nb instead exhibit a giant attenuation of surface superconductivity, even for films only two-layers thick. This massive suppression of proximity pairing is shown by ultrahigh-resolution band mappings and by contrasting quantified superconducting gaps with those of heavily n-doped topological Bi 2 Se 3 /Nb. The results underscore the limitations of using superconducting proximity effects to realize topological superconductivity in nearly intrinsic systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Applications of Nickelate perovskites for neuromorphic computing from electronic structure and Machine Learning

While the limit of Moore's law is presently being reached with current microelectronic technologies, we need to develop new paradigms that overcome this limitation. In that respect, neuromorphic computing is a concept that emulates the neural behavior and response of the human brain, and it has been recognized as a promising alternative approach. In this research project, we will perform multi-fidelity scale bridging to explore the potential use of materials with metal to insulator transition for neuromorphic applications. In particular, rare earth nickelates are promising for such purposes, as the transition in these materials is quite sensitive to a broad set of different external stimuli. Our multi-fidelity approach will bridge the high-fidelity electronic structure calculations with classical potentials. We will bridge dynamical mean field theory with a classical atomistic representation via a deep learning force field. The neural network is trained with energies, charges, and forces obtained by accurate electronic structure theories based on Dynamical Mean Field Theory. The configurational space is generated from known crystal phases, ab initio molecular dynamics with exchange-correlation functionals corrected with the Hubbard model, disordered phases with different concentrations of oxygen vacancies, and nonsymmetrical positions and induced strain by grain interfaces or contact with a substrate. Strategies to train the model with a reduced number of training examples are obtained from active learning methods, and new structures for improving the learning process are generated by using machine learning autoencoders. This classical potential will be validated through a diversity of electronic structure methods and represents an important step to combine the flexibility and accuracy of first-principles with the speed of classical potentials. The generated multi-fidelity surrogate model will be used to understand the role of strain, oxygen vacancies, proton doping, the variation of the crystal phase, substrate effects, vibrational effects as the octahedral rotation, grain boundaries and defect effects on the response of a Metal to Insulator Transition (MIT) in correlated materials. Long time and large-scale simulations will help understand the role of different stimuli to control the hysteresis of the MIT, as it has been experimentally suggested. Selected configurations will be analyzed with higher-level theories to provide an accurate electronic description and to study how the orbitals and charges are rearranged under different conditions.

36 MATERIALS SCIENCE↗
NASA NTRS2006

2.4 Micrometer Cutoff Wavelength AlGaAsSb/InGaAsSb Phototransistors

We report the first AlGaAsSb/InGaAsSb phototransistors with a cutoff wavelength (50% of peak responsivity) of 2.4 micrometers operating in a broad range of temperatures. These devices are also the first AlGaAsSb/InGaAsSb heterojunction phototransistors (HPT) grown by molecular beam epitaxy (MBE). This work is a continuation of a preceding study, which was carried out using LPE (liquid phase epitaxy)-grown AlGaAsSb/InGaAsSb/GaSb heterostructures. Although the LPE-related work resulted in the fabrication of an HPT with excellent parameters [1-4], the room temperature cutoff wavelength of these devices (approximately 2.15 micrometers) was determined by fundamental limitations implied by the close-to-equilibrium growth from Al-In-Ga-As-Sb melts. As the MBE technique is free from the above limitations, AlGaAsSb/InGaAsSb/GaSb heterostructures for HPT with a narrower bandgap of the InGaAsSb base and collector - and hence sensitivity at longer wavelengths (lambda) - were grown in this work. Moreover, MBE - compared to LPE - provides better control over doping levels, composition and width of the AlGaAsSb and InGaAsSb layers, compositional and doping profiles, especially with regard to abrupt heterojunctions. The new MBE-grown HPT exhibited both high responsivity R (up to 2334 A/W for lambda=2.05 micrometers at -20 deg C.) and specific detectivity D* (up to 2.1 x 10(exp 11) cmHz(exp 1/2)/W for lambda=2.05 micrometers at -20 deg C).

Sulima, O. V.↗
DOE OSTI2020

Tunable exciton binding energy in 2D hybrid layered perovskites through donor–acceptor interactions within the organic layer

The strength of electrostatic interactions within semiconductors strongly affects their performance in optoelectronic devices. An important target is the tuning of a material’s exciton binding energy—the energy binding an electron–hole pair through the electrostatic Coulomb force—independent of its electronic band gap. Here, we report on the doping of a family of two-dimensional hybrid perovskites, in which inorganic lead halide sheets alternate with naphthalene-based organic layers, with tetrachloro-1,2-benzoquinone (TCBQ). For four out of seven n = 1 perovskites, the incorporation of the electron-accepting TCBQ dopant into the organic sublattice containing the electron-donating naphthalene species enabled the tuning of the materials’ 1s exciton binding energy. The naphthalene–TCBQ electron donor–acceptor interactions increased the electrostatic screening of the exciton, in turn lowering its binding energy relative to the undoped perovskite—by almost 50% in one system. Structural and optical characterization showed that the inorganic lattice is not significantly perturbed even though the layer-to-layer spacing increases upon molecular dopant incorporation.

36 MATERIALS SCIENCE↗
NASA NTRS1977

A high pressure modulated molecular beam mass spectrometric sampling system

The current state of understanding of free-jet high pressure sampling is critically reviewed and modifications of certain theoretical and empirical considerations are presented. A high pressure, free-jet expansion, modulated molecular beam, mass spectrometric sampling apparatus was constructed and this apparatus is described in detail. Experimental studies have demonstrated that the apparatus can be used to sample high temperature systems at pressures up to one atmosphere. Condensible high temperature gaseous species have been routinely sampled and the mass spectrometric detector has provided direct identification of sampled species. System sensitivity is better than one tenth of a part per million. Experimental results obtained with argon and nitrogen beams are presented and compared to theoretical predictions. These results and the respective comparison are taken to indicate acceptable performance of the sampling apparatus. Results are also given for two groups of experiments related to hot corrosion studies. The formation of gaseous sodium sulfate in doped methane-oxygen flames was characterized and the oxidative vaporization of metals was studied in an atmospheric pressure flowing gas system to which gaseous salt partial pressures were added.

Stearns, C. A.↗
DOE OSTI2021

Molecular beam epitaxy of PdO on MgO (001)

PdO, widely used in catalysis in powder form for decades, has been predicted recently to be a Dirac semimetal. Synthesis of high-quality single crystals of this material is thus of great interest. Here, by using ozone-assisted molecular beam epitaxy, PdO thin films were grown on a MgO (001) substrate. X-ray diffraction and transmission electron microscopy indicate the film is a / b axis oriented, with the c axis lying in plane. Fully oxygenated PdO films have a low density of holelike carriers, and are insulating at the lowest temperatures. Our density functional theory calculations using the Heyd-Scuseria-Ernzerhof exchange-correlation functional suggest a ~1.0 eV band gap at the M point, where the gap can be reduced by tensile strain along the c axis and the bands begin to invert when the tensile strain is as high as 18%. Although tensile strain of this magnitude is experimentally not viable using epitaxy, electrons can be doped by oxygen reduction. Finally, our results emphasize the need for careful consideration of electron correlation effects and stoichiometry in ab initio modeling of topological semimetals involving transition metal oxides.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Fast Growth of Ga2O3 on Highly Offcut (100)-Oriented Substrates

Beta-Ga2O3 has emerged as a leading candidate for next-generation power electronics, radio frequency (RF) switches, and extreme environment electronics due to a wide band gap (4.6 - 4.9 eV), high dopability (approximately 40 meV activation energy for an isolated silicon donor), and melt growth characteristics resulting in commercially available 4-inch substrates and commercial demonstrations of 6-inch substrates by multiple techniques. The (100) surface of Ga2O3 is highly desirable from a device and epitaxy standpoint - bulk growth of (100) material is more scalable than (010), the surface is nearly lattice-matched to p-type partner NiO, and Al2O3 incorporates at higher concentrations without phase separation. More importantly, the impact ionization coefficients along the [100] direction are low, leading to the highest possible critical fields. This is advantageous compared to the current state of the art, (001), due to reduced surface defects and increased possible breakdown voltage. However, the epitaxial growth rate on (100) surfaces is less than 10% of other faces due to weak bonding and favorable desorption, and on-axis (100) growth easily forms twin domains. Recent demonstrations have shown growth rate improvements from 0.4 nm/min to 1.5 nm/min by growing on (100) wafers that are offcut 6 degrees in the -c direction. These films show step-flow growth from (20-1) step-edges and high electron mobility due to suppressed twins. Despite these exciting results, offcuts greater than 6 degrees have not been explored due to the waste associated with grinding and polishing large offcuts. In this talk we will discuss the molecular beam epitaxy (MBE) growth and properties of Beta-Ga2O3 grown on (100) substrates offcut in the -c direction up to 13.4 degrees. These large offcuts are enabled by edge-fed film-defined growth (EFG) where the offcut is grown into the surface by pulling the crystal through the EFG die with the seed crystal rotated by the desired offcut angle. We will demonstrate that 13.4 degrees offcut substrates still exhibit a terraced (100) surface, and that a >10x increase (>5 nm/min) in growth rate is achieved. As previously reported on lower offcuts, we observe reversal of substrate twin domains around the (001) direction at the substrate-epilayer interface. We will discuss electrical properties including record-low (by MBE) unintentional doping densities of < 5E15 cm-3 and critical breakdown field in Schottky barrier diodes comparable with state-of-the-art (001) Ga2O3 without edge termination.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Charge Transfer Screening and Energy Level Alignment at Complex Organic–Inorganic Interfaces: A Tractable Ab Initio GW Approach

Complex organic–inorganic interfaces are important for device and sensing applications. Charge transfer doping is prevalent in such applications and can affect the interfacial energy level alignments (ELA), which are determined by many-body interactions. We develop an approximate ab initio many-body GW approach that can capture many-body interactions due to interfacial charge transfer. The approach uses significantly less resources than a regular GW calculation but gives excellent agreement with benchmark GW calculations on an F4TCNQ/graphene interface. We find that many-body interactions due to charge transfer screening result in gate-tunable F4TCNQ HOMO–LUMO gaps. We further predict the ELA of a large system of experimental interest—4,4'-bis(dimethylamino)bipyridine (DMAP-OED) on monolayer MoS 2 , where charge transfer screening results in an ~1 eV reduction of the molecular HOMO–LUMO gap. Comparison with a two-dimensional electron gas model reveals the importance of explicitly considering the intraband transitions in determining the charge transfer screening in organic–inorganic interface systems.

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

Epitaxy of Beta-Ga2O3 on Highly-Offcut (Greater than 10 Degrees) Substrates

Beta-Ga2O3 has emerged as a leading candidate for next-generation power electronics, radio frequency (RF) switches, and extreme environment electronics due to a wide band gap (4.6 - 4.9 eV), high dopability (approximately 40 meV activation energy for an isolated silicon donor), and melt growth characteristics resulting in commercially available 4-inch substrates and commercial demonstrations of 6-inch substrates by multiple techniques. The (100) surface of Ga2O3 is highly desirable from a device and epitaxy standpoint - bulk growth of (100) material is more scalable than (010), the surface is nearly lattice-matched to p-type partner NiO, and Al2O3 incorporates at higher concentrations without phase separation. However, the epitaxial growth rate on (100) surfaces is less than 10% of other faces due to weak bonding and favorable desorption. Recent demonstrations have shown growth rate improvements from 0.4 nm/min to 1.5 nm/min by growing on (100) wafers that are offcut 6 degrees in the -c direction.1 These films show step-flow growth from (-201) step-edges and high electron mobility. Despite these exciting results, offcuts greater than 6 degrees have not been explored due to the waste associated with grinding and polishing large offcuts. In this talk we will discuss the molecular beam epitaxy (MBE) growth and properties of Beta-Ga2O3 grown on (100) substrates offcut in the -c direction up to 13.4 degrees. These large offcuts are enabled by edge-fed film-defined growth (EFG) where the offcut is grown into the surface by pulling the crystal through the EFG die with the seed crystal rotated by the desired offcut angle. We will demonstrate that 13.4 degrees offcut substrates still exhibit a terraced (100) surface, and that a >10x increase (4.8 nm/min) in growth rate is achieved. As previously reported on lower offcuts, we observe 100% reversal of substrate twin domains around the (001) direction at the substrate-epilayer interface. We will discuss electrical properties including record-low (by MBE) unintentional doping densities of < 5E15 cm-3.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Yttrium Contenting Compositionally Complex Medium-Entropy Li-Garnet Electrolyte with Improved Ionic Conductivity

The compositionally complex medium/high-entropy design concept can greatly expand the categories and affect the properties of the materials. With such a designing concept, a medium-entropy Li-garnet electrolyte with appropriate yttrium content (formula Li 6.6 La 3 ZrNb 0.3 Ta 0.3 Hf 0.3 Y 0.1 O 12 ) shows a record-high ionic conductivity of ∼5.7 × 10 –4 S/cm, the highest reported for any single-site substituted high/medium-entropy Li-garnet. The assembled Li metal symmetric cells also show stable long-term cycling (0.1 mA/cm 2 for over 200 h). Neutron powder diffraction and Rietveld refinement results indicate that a competing conduction mechanism between (1) occupancy on high mobility of 96h sites and (2) the associated site vacancies and the bond length requires an appropriate content of Y for enhanced ionic conductivity. Li-ion hopping through the bottleneck can also contribute to the conductivity. Finally, density functional theory and Born–Oppenheimer molecular dynamics simulations also indicate the high mobility and number of hopping transitions of Li ions, contributing to the high ionic conductivity.

Li-garnet↗
DOE OSTI2020

Thiolate‐Protected Single‐Atom Alloy Nanoclusters: Correlation between Electronic Properties and Catalytic Activities

Abstract Due to their interesting chemical and optical properties, metal nanoclusters are used in various catalytic reactions and in energy conversion. By incorporating thiolate‐protecting ligands, their size and composition can be tuned. Doping these nanoclusters to form single‐atom alloy (SAA) nanoclusters is shown to further enhance these properties as a result from the synergy between the dopant and host atoms. In addition to their optical and chemical properties, SAA nanoclusters also have interesting electronic properties. However, these properties are often underdiscussed when studying SAA nanoclusters. This review provides an overview of representative studies done on the in‐depth understanding of the electronic properties and catalytic activities of Ag‐based and Au‐based thiolate‐protected SAA nanoclusters. The use of density functional theory (DFT), X‐ray absorption spectroscopy, and X‐ray photoelectron spectroscopy are employed to correlate the changes in charge states of thiolate‐protected SAA nanoclusters with their superior catalytic activity versus monometallic nanoclusters. DFT, UV–vis spectroscopy, and voltammetric methods link the changes in molecular energy levels of thiolate‐protected SAA nanoclusters to their enhanced catalytic performance over monometallic nanoclusters.

Walsh, Andrew G.↗
DOE OSTI2024

Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate

The linear viscoelastic response, LVR, of a hydrated polyelectrolyte complex coacervate, PEC, was evaluated over a range of frequencies, temperatures, and salt concentrations. The PEC was a nearly stoichiometric blend of a quaternary ammonium poly([3-(methacrylamido)propyl]trimethylammonium chloride), PMAPTAC, and poly(2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt), PAMPS, an aliphatic sulfonate, selected because they remain fully charged over the conditions of use. Narrow molecular weight distribution polyelectrolytes were prepared using fractionation techniques. A partially deuterated version of PMAPTAC was incorporated to determine its coil radius of gyration, R g , within PECs using small-angle neutron scattering. Chain dimensions were determined to be Gaussian with a Kuhn length of 2.37 nm, which remained constant from 25 to 65 °C. The LVR for a series of matched molecular weight PECs, mostly above the entanglement threshold, exhibited crossovers of modulus versus frequency classically attributed to the reptation time, relaxation between entanglements, and the relaxation of a Kuhn length of units (the “monomer” time). The scaling for zero shear viscosity, η 0 , versus chain length, N, was η 0 ~ N 3.1 , in agreement with “sticky reptation” theory. The lifetime and activation energy, E p , of a pair between polyanion and polycation repeat units, Pol + Pol – , were determined from diffusion coefficients of salt ions within the PEC. The activation energy for LVR of salt-free PECs was 2E p , showing that the key mechanism limiting the dynamics of undoped PECs is pair exchange. An FTIR technique was used to distinguish whether SCN– acts as a counterion or a co-ion within PECs. Doping of PECs with NaSCN breaks Pol + Pol – pairing efficiently, which decreases effective cross-linking and decreases viscosity. Finally, an equation was derived that quantitatively predicts this effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗