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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Expanding the color palette of bicolor-emitting nanocrystals

Owing to their bright and tunable luminescence spectra, nanocrystals appear as a unique playground for light source design. Displays and lighting require white light sources that combine several narrow lines. As Kasha's rule prevents the emission of hot carriers, blends of multiple nanocrystal populations are currently the obvious strategy for broad-band source design. However, a few reports suggest that bicolor emission can also be obtained from a single particle even under weak excitation if a careful design of the exciton scattering mechanism sufficiently slows down its relaxation pathways. A key challenge remains to maintain quantum confinement for color tunability in the same structure, while simultaneously achieving a large size to leverage the critical, slower exciton diffusion or relaxation down to the ground state. In this work, we demonstrate that 2D nanoplatelets offer an original opportunity for the design of confined and large heterostructures. We demonstrate that bicolor emission is not limited to green–red pair and show that blue–yellow and purple–green emissions can be obtained from CdSe/CdTe/CdSe core/crown/crown and CdSe/CdS core/crown heterostructures, respectively.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Signatures of linearized gravity in atom interferometers: A simplified computational framework

We develop a general framework for calculating the leading-order, general relativistic contributions to the gravitational phase shift in single-photon atom interferometers within the context of linearized gravity. We show that the atom gradiometer observable, which only depends on the atom interferometer propagation phase, can be written in terms of three distinct contributions: the Doppler phase shift, which accounts for the tidal displacement of atoms along the baseline, the Shapiro phase shift, which accounts for the delay in the arrival time of photons at atom-light interaction points, and the Einstein phase shift, which accounts for the gravitational redshift measured by the atoms. For specific atom gradiometer configurations, we derive the signal and response functions for two physically motivated scenarios: (i) transient gravitational waves in the transverse-traceless gauge and, for the first time, in the proper detector frame, and (ii) transient massive objects sourcing weak and slow-varying Newtonian potentials. Here, we find that the Doppler contribution of realistic Newtonian noise sources (e.g., a freight truck or a piece of space debris) at proposed atom gradiometer experiments, such as AION, MAGIS, and AEDGE, can exceed the shot noise level and thus affect physics searches if not properly subtracted. Note: 44 pages including appendices, 4 figures; v2: different formatting, fixed typos, 28 pages including appendices, 5 figures, agrees with published version

Atom interferometry↗
DOE OSTI2021

HD 63021: Chromospheric Activity and Mass Transfer in a Close Binary

Prompted by X-ray detections from multiple surveys, we investigated the A-type star HD 63021 and found that it is a double-lined spectroscopic binary with highly variable emission associated with the primary star. Analysis of our multiepoch spectroscopic observations, the majority of which were carried out on small-aperture telescopes, indicates a very short orbital period of just 2.9 days and a mass ratio M {sub 2}/M {sub 1} of 0.23. The A1 V star is a slow rotator, with a rotational speed of ∼34 km s{sup −1}. Assuming that its mass is 2.3 M {sub ⊙}, the present-day secondary is an evolved star of ∼0.5 M {sub ⊙} that nearly fills its Roche lobe. This secondary star rotates comparatively rapidly at ∼44 km s{sup −1}, and we see evidence that it is chromospherically active. Analysis of a photometric light curve from TESS reveals two strong periods, one at the orbital period for the system and another at half the orbital period. These findings suggest that HD 63021 is a close binary system undergoing mass transfer from the secondary star onto the primary star—in all ways like an Algol eclipsing binary system, except without the eclipse. We discuss the system’s mass transfer, which is not steady but seems to run in fits and bursts, and infer the system’s basic physical properties from an orbital parameter study, the Roche lobe geometry, and its extant X-ray emission.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Laser diagnostics to characterize the in-flame growth of platinum nanoparticles manufactured by the reactive spray deposition technology

Reactive Spray Deposition Technology (RSDT) is an atmospheric pressure, flame-based advanced manufacturing method used to fabricate Membrane Electrode Assemblies (MEAs) for proton exchange fuel cells and water electrolyzers. RSDT combines the flame synthesis of catalyst nanoparticles and their deposition onto the membrane in one step. The properties of the synthesized nanoparticles, such as their Size Distribution Function (SDF), determine the manufactured electrodes’ performance, which can be evaluated when the deposition is complete via ex-situ characterization of the products. Efforts to improve RSDT for manufacturing state-of-the-art MEAs can be significantly enhanced with integrated laser diagnostics that enable in situ measurement of the synthesized catalyst nanoparticles. This paper reports the implementation of laser diagnostics in an RSDT facility and evaluates their potential to assist the manufacturing process. Laser Light Scattering (LS) and Laser-Induced Incandescence (LII) measurements are performed in the oxygen-rich zone of the flame at various distances from the flame fuel jet nozzle downstream of its luminous region. The measurements quantitatively track the evolution in size and volume fraction of platinum-based nanoparticles in two flames that yield different catalytic properties in the manufactured electrodes. The profiles of the measured nanoparticles’ volume fraction along the flame axis can be estimated a priori so that the average nanoparticle sizes can be measured in quasi-real time via LS. Nanoparticles experience an extremely slow growth rate while being convected at distances from 150 nm to 300 nm from the fuel nozzle. Complementary characterizations of the synthesized nanoparticles are performed ex-situ via High-Angle Annular Darkfield Scanning Transmission Electron Microscopy (HAADF-STEM) image analyses of samples collected on grids at a fixed distance from the fuel jet nozzle. Comparing the results from laser and microscopy techniques not only cross-validates the findings but also provides the parameters to infer the bimodal SDF in-situ and yields evidence that the coagulation efficiency of the synthesized nanoparticles has extremely low values in the investigated zone of the flames.

Rayleigh Light Scattering (LS)↗
DOE OSTI2022

Community Structure and Microbial Associations in Sediment-Free Methanotrophic Enrichment Cultures from a Marine Methane Seep

We report Syntrophic consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB) consume large amounts of methane and serve as the foundational microorganisms in marine methane seeps. Despite their importance in the carbon cycle, research on the physiology of ANME-SRB consortia has been hampered by the slow growth and complex physicochemical environment the consortia inhabit. Here, we report successful sediment-free enrichment of ANME-SRB consortia from deep-sea methane seep sediments in the Santa Monica Basin, California. Anoxic Percoll density gradients and size-selective filtration were used to separate ANME-SRB consortia from sediment particles and single cells to accelerate the cultivation process. Over a 3-year period, a subset of the sediment-associated ANME and SRB lineages, predominantly comprised of ANME-2a/2b (“Candidatus Methanocomedenaceae”) and their syntrophic bacterial partners, SEEP-SRB1/2, adapted and grew under defined laboratory conditions. Metagenome-assembled genomes from several enrichments revealed that ANME-2a, SEEP-SRB1, and Methanococcoides in different enrichments from the same inoculum represented distinct species, whereas other coenriched microorganisms were closely related at the species level. This suggests that ANME, SRB, and Methanococcoides are more genetically diverse than other members in methane seeps. Flow cytometry sorting and sequencing of cell aggregates revealed that Methanococcoides, Anaerolineales, and SEEP-SRB1 were overrepresented in multiple ANME-2a cell aggregates relative to the bulk metagenomes, suggesting they were physically associated and possibly interacting. Overall, this study represents a successful case of selective cultivation of anaerobic slow-growing microorganisms from sediments based on their physical characteristics, introducing new opportunities for detailed genomic, physiological, biochemical, and ecological analyses. Biological anaerobic oxidation of methane (AOM) coupled with sulfate reduction represents a large methane sink in global ocean sediments. Methane consumption is carried out by syntrophic archaeal-bacterial consortia and fuels a unique ecosystem, yet the interactions in these slow-growing syntrophic consortia and with other associated community members remain poorly understood. The significance of this study is the establishment of sediment-free enrichment cultures of anaerobic methanotrophic archaea and sulfate-reducing bacteria performing AOM with sulfate using selective cultivation approaches based on size, density, and metabolism. By reconstructing microbial genomes and analyzing community composition of the enrichment cultures and cell aggregates, we shed light on the diversity of microorganisms physically associated with AOM consortia beyond the core syntrophic partners. These enrichment cultures offer simplified model systems to extend our understanding of the diversity of microbial interactions within marine methane seeps.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Structural Diversity and Tunable Emission in Hybrid Organic–Inorganic Copper(I) Bromides

Recently, hybrid organic−inorganic copper(I) metal halides have attracted global attention due to their intriguing optical properties and low-cost solution processability. In this work, we report three hybrid organic−inorganic copper(I) bromides, [TMPA] 2 [Cu 2 Br 4 ], [TMPA] 4 [Cu 6 Br 10 ], and [TMPA] 2 [Cu 4 Br 6 ], synthesized through a slow evaporation method using trimethylphenylammonium (TMPA + ) as the organic cation. By precise control of the CuBr and TMPABr precursors, different copper halide [Cu 2 Br 4 ] 2− , [Cu 6 Br 10 ] 4− , and [Cu 4 Br 6 ] 2− structural units can be obtained. [TMPA] 2 [Cu 2 Br 4 ], [TMPA] 4 [Cu 6 Br 10 ], and [TMPA] 2 [Cu 4 Br 6 ] demonstrate distinct blue, orange, and greenish-yellow light emission, respectively. The first two compounds have zero-dimensional (0D) crystal structures in centrosymmetric triclinic space group P-1 and monoclinic space group P2 1 /n. In contrast, [TMPA] 2 [Cu 4 Br 6 ] features a unique one-dimensional (1D) structure and crystallizes in the centrosymmetric monoclinic space group P2 1 /c. Consequently, the observed greenish-yellow emission of [TMPA] 2 [Cu 4 Br 6 ] is also unique, in contrast to the typical orange-red emission of 0D [Cu 4 Br 6 ]-based compounds. This work provides insights into the design of copper halide light emitters and emphasizes the influence of structural dimensionality on photoluminescence. The tunable optical properties suggest the potential of these materials for multicolor photopatterning, information encryption, and anticounterfeiting applications.

Anions↗
DOE OSTI2020

Light induced electron spin resonance properties of van der Waals CrX 3 (X = Cl, I) crystals

The research on layered van der Waals (vdW) magnets is rapidly progressing owing to exciting fundamental science and potential applications. In bulk crystal form, CrCl 3 is a vdW antiferromagnet with in-plane ferromagnetic ordering below 17 K, and CrI 3 is a vdW ferromagnet below 61 K. In this paper, we report on the electron spin resonance (ESR) properties of CrCl 3 and CrI 3 single crystals upon photo-excitation in the visible range. We noticed remarkable changes in the ESR spectra upon illumination. In the case of CrCl 3 , at 10 K, the ESR signal is shifted from g = 1.492 (dark) to 1.661 (light), the linewidth increased from 376 to 506 Oe, and the signal intensity is reduced by 1.5 times. Most interestingly, the observed change in the signal intensity is reversible when the light is cycled on/off. We observed almost no change in the ESR spectral parameters in the paramagnetic phase (>20 K) upon illumination. Upon photo-excitation of CrI 3 , the ESR signal intensity is reduced by 1.9 times; the g-value increased from 1.956 to 1.990; the linewidth increased from 1170 to 1260 Oe at 60 K. These findings are discussed by taking into account the skin depth, the slow relaxation mechanism, and the appearance of low-symmetry fields at the photo-generated Cr 2+ Jahn–Teller centers. Such an increase in the g-value as a result of photo-generated Cr 2+ ions is further supported by our many-body wavefunction calculations. This work has the potential to extend to monolayer vdWs magnets by combining ESR spectroscopy with optical excitation and detection.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Soft de Sitter Effective Theory

Calculating the quantum evolution of a de Sitter universe on superhorizon scales is notoriously difficult. To address this challenge, we introduce the Soft de Sitter Effective Theory (SdSET). This framework holds for superhorizon modes whose comoving momentum is far below the UV scale, which is set by the inverse comoving horizon. The SdSET is formulated using the same approach that yields the Heavy Quark Effective Theory. The degrees of freedom that capture the long wavelength dynamics are identified with the growing and decaying solutions to the equations of motion. The operator expansion is organized using a power counting scheme, and loops can be regulated while respecting the low energy symmetries. For massive quantum fields in a fixed de Sitter background, power counting implies that all interactions beyond the horizon are irrelevant. Alternatively, if the fields are very light, the leading interactions are at most marginal, and resumming the associated logarithms using (dynamical) renormalization group techniques yields the evolution equation for canonical stochastic inflation. The SdSET is also applicable to models where gravity is dynamical, including inflation. In this case, diffeomorphism invariance ensures that all interactions are irrelevant, trivially implying the all-orders conservation of adiabatic density fluctuations and gravitational waves. We briefly touch on the application to slow-roll eternal inflation by identifying novel relevant operators. This work serves to demystify many aspects of perturbation theory outside the horizon, and has a variety of applications to problems of cosmological interest.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Hierarchical multi-time-scale predictive thermal management and fuel optimization for heavy-duty compression ignition engines

For heavy-duty diesel engines, NO X emissions reduction is strongly constrained by fuel efficiency. This paper presents a hierarchical model predictive controller (H-MPC) for coordinated control of tailpipe NO X emissions and fuel consumption. The H-MPC uses the separation of slow and fast dynamics that exist in the engine and its aftertreatment system. The controller is synthesized with an architecture in which a high-level MPC uses a longer prediction horizon compared to the low-level predictive controller which tracks the high-level controller command and manages the thermal dynamics of the aftertreatment system. Engine load preview enables the high-level controller to estimate the desired catalyst temperature ahead of time and addresses the selective catalytic reduction (SCR) slow thermal dynamics. Calculated by the high-level controller, the intake manifold pressure, and the start of injection (SOI) crank angle is used as reference trajectories in the low-level controller that regulates fast dynamical behaviors such as engine out NO X emissions. Hardware-in-the-loop (HIL) validation of this integrated H-MPC on a rapid prototype controller shows that when the SCR catalyst temperature is above light-off temperature (warmed-up condition), the engine operation is shifted to operate with the best fuel economy since the warmed-up SCR can efficiently reduce the engine-out NO X emissions. Results indicate that up to 0.8% benefit in cycle averaged BSFC along with a 13% reduction in tailpipe NO X compared to a stock engine calibration can be achieved with the coordinated engine and aftertreatment system through H-MPC.

Engineering↗
DOE OSTI2020

Modeling Functional Organic Chemistry in Arctic Rivers: An Idealized Siberian System

Rivers of the Arctic will become ever more important for the global climate, since they carry a majority of continental dissolved organic carbon flux into the rapidly changing polar ocean. Aqueous organics comprise a wide array of functional groups, several of which are likely to impact coastal and open water biophysical properties. Light attenuation, interfacial films, aerosol formation, gas release and momentum exchange can all be cited. We performed Lagrangian kinetic modeling for the evolution of riverine organic chemistry as the molecules in question make their way from the highlands to Arctic outlets. Classes as diverse as the proteins, sugars, lipids, re-condensates, humics, bio-tracers and small volatiles are all included. Our reduced framework constitutes an idealized northward flow driving a major hydrological discharge rate and primarily representing the Russian Lena. Mountainous, high solute and tundra sources are all simulated, and they meet up at several points between soil and delta process reactors. Turnover rates are parameterized beginning with extrapolated coastal values imposed along a limited tributary network, with connections between different terrestrial sub-ecologies. Temporal variation of our total dissolved matter most closely resembles the observations when we focus on the restricted removal and low initial carbon loads, suggesting relatively slow transformation along the water course. Thus, channel combinations and mixing must play a dominant role. Nevertheless, microbial and photochemical losses help determine the final concentrations for most species. Chemical evolution is distinct for the various functionalities, with special contributions from pre- and post-reactivity in soil and delta waters. Several functions are combined linearly to represent the collective chromophoric dissolved matter, characterized here by its absorption. Tributaries carry the signature of lignin phenols to segregate tundra versus taiga sources, and special attention is paid to the early then marine behaviors of low molecular weight volatiles. Heteropolycondensates comprise the largest percentage of reactive carbon in our simulations due to recombination/accumulation, and they tend to be preeminent at the mouth. Outlet concentrations of individual structures such as amino acids and absorbers lie above threshold values for biophysical influence, on the monolayer and light attenuation. The extent of coastal spreading is examined through targeted regional box modeling, relying on salinity and color for calibration. In some cases, plumes reach the scale of peripheral arctic seas, and amplification is expected during upcoming decades. Conclusions are mapped from the Lena to other boreal discharges, and future research questions are outlined regarding the bonding type versus mass release as permafrost degrades. Dynamic aqueous organic coupling is recommended for polar system models, from headwaters to coastal diluent.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Dependence of ion-cyclotron range of frequencies instabilities on species mix and fast-ion distribution: I. Stability

Ion cyclotron emission (ICE) driven by fast ions has the potential to be a reactor relevant diagnostic of confined and escaping fast ions; moreover, controlled experiments in magnetic fusion devices can shed light on similar magnetospheric instabilities below and above the ion cyclotron frequency f ci . Dedicated DIII-D experiments studied instabilities below f ci and at cyclotron harmonics l f ci by injecting thirteen different neutral beam populations into plasmas with different thermal compositions of H, D, and 3He at five different values of toroidal field. High-frequency magnetic loops diagnose mode properties. Each beam type is individually injected for an approximate slowing-down time (~100 ms), resulting in a database of 2529 conditions that are analyzed in frequency bands corresponding to ICE harmonics and < f ci global Alfvén eigenmodes. The sub-cyclotron modes are more unstable at low field and in plasmas with large H concentration. For D injection, first harmonic ICE at f cD is more unstable in hydrogen plasmas but, for H injection, the converse is true (ICE at f cH is more unstable in D), suggesting that thermal same-species ions damp fundamental ICE. ICE stability also depends upon the pitch-angle anisotropy gradient and upon the ‘bump-on-tail’ gradient ∂f/∂v. Although the frequency of unstable ICE in these plasmas always occurs near the central cyclotron frequency, the precise value also depends on the Alfvén speed and beam direction, consistent with the idea that instability occurs for modes that simultaneously satisfy ω ≃ 2πlf ci , the magnetosonic dispersion relation, and the Doppler-shifted resonance condition.

electromagnetic ion cyclotron instabilities↗
DOE OSTI2024

Renormalon cancellation and linear power correction to threshold-like asymptotics of space-like parton correlators

Abstract In this paper, we show that the common hard kernel of double-log-type or threshold-type factorization for certain space-like parton correlators that arise in the context of lattice parton distributions, theheavy-light Sudakov hard kernel, has linear infrared (IR) renormalon. We explicitly demonstrate how this IR renormalon correlates with ultraviolet (UV) renormalons of next-to-leading power operators in two explicit examples: threshold asymptotics of space-like quark-bilinear coefficient functions and transverse momentum dependent (TMD) factorization of quasi wave function amplitude. Theoretically, the pattern of renormalon cancellation complies with general expectations to marginal asymptotics in the UV limit. Practically, this linear renormalon explains the slow convergence of imaginary parts observed in lattice extraction of the Collins-Soper kernel and signals the relevance of next-to-leading power contributions. Fully factorized, fully controlled threshold asymptotic expansion for space-like quark-bilinear coefficient functions in coordinate and moment space has also been proposed.

Physics↗
DOE OSTI2025

Sequential Infiltration Synthesis (SIS) of In 2 O 3 -Based Porous Photoelectrodes for Molecular Sensitization

High-surface-area photoelectrodes are highly desirable for solar energy conversion applications, particularly in systems where surface-bound molecular chromophores are responsible for light absorption. To this end, porous Indium-Zinc-Oxide (IZO) frameworks are fabricated via Sequential Infiltration Synthesis (SIS) into poly(methyl methacrylate) (PMMA) films followed by air annealing. A more complete understanding of the multimetal infiltration process conditions and postannealing temperature allows for precise control of zinc (Zn) incorporation to afford porous, conductive, transparent, and amorphous photoelectrodes. Uniform incorporation of both indium (In) and Zn is found to require extended diethylzinc (DEZ) exposures to compensate for remarkably slow precursor diffusion in the presence of indium oxyhydroxide nuclei. SIS-fabricated IZO photoelectrodes are structurally robust, electrochemically active, and exhibit dye adsorption that suggest practical surface area enhancements greater than 100×. In conclusion, these attributes establish SIS as a rapid, scalable, and reproducible route to photoelectrodes for solar energy conversion and hybrid interface characterization.

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

Probing the dynamics and bottleneck of the key atmospheric SO 2 oxidation reaction by the hydroxyl radical

SO 2 (Sulfur dioxide) is the major precursor to the production of sulfuric acid (H 2 SO 4 ), contributing to acid rain and atmospheric aerosols. Sulfuric acid formed from SO 2 generates light-reflecting sulfate aerosol particles in the atmosphere. This property has prompted recent geoengineering proposals to inject sulfuric acid or its precursors into the Earth’s atmosphere to increase the planetary albedo to counteract global warming. SO 2 oxidation in the atmosphere by the hydroxyl radical HO to form HOSO 2 is a key rate-limiting step in the mechanism for forming acid rain. However, the dynamics of the HO + SO 2 → HOSO 2 reaction and its slow rate in the atmosphere are poorly understood to date. Herein, we use photoelectron spectroscopy of cryogenically cooled HOSO 2 – anion to access the neutral HOSO 2 radical near the transition state of the HO + SO 2 reaction. Spectroscopic and dynamic calculations are conducted on the first ab initio-based full-dimensional potential energy surface to interpret the photoelectron spectra of HOSO 2 – and to probe the dynamics of the HO + SO 2 reaction. In addition to the finding of a unique pre-reaction complex (HO⋯SO 2 ) directly connected to the transition state, dynamic calculations reveal that the accessible phase space for the HO + SO 2 → HOSO 2 reaction is extremely narrow, forming a key reaction bottleneck and slowing the reaction rate in the atmosphere, despite the low reaction barrier. This study underlines the importance of understanding the full multidimensional potential energy surface to elucidate the dynamics of complex bimolecular reactions involving polyatomic reactants.

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

Cavity-enabled enhancement of ultrafast intramolecular vibrational redistribution over pseudorotation

Vibrational strong coupling (VSC) between molecular vibrations and microcavity photons yields a few polaritons (light-matter modes) and many dark modes (with negligible photonic character). Although VSC is reported to alter thermally activated chemical reactions, its mechanisms remain opaque. To elucidate this problem, we followed ultrafast dynamics of a simple unimolecular vibrational energy exchange in iron pentacarbonyl [Fe(CO) 5 ] under VSC, which showed two competing channels: pseudorotation and intramolecular vibrational-energy redistribution (IVR). We found that under polariton excitation, energy exchange was overall accelerated, with IVR becoming faster and pseudorotation being slowed down. However, dark-mode excitation revealed unchanged dynamics compared with those outside of the cavity, with pseudorotation dominating. Thus, despite controversies around thermally activated VSC modified chemistry, our work shows that VSC can indeed alter chemistry through a nonequilibrium preparation of polaritons.

Science & Technology - Other Topics↗
DOE OSTI2023

Inclusion Complexes of a Metastable‐State Photoacid with High Acidity and Chemical Stability

Abstract Metastable‐state merocyanine photoacids (MCHs) have been widely applied to various chemical, material and biomedical areas to drive or control chemical processes with light. In this work, stoichiometry and association constants have been determined for inclusion complexes of a photoacid MCH1 ((E)‐3‐(2‐(2‐hydroxystyryl)‐3,3‐dimethyl‐3H‐indol‐1‐ium‐1‐yl)propane‐1‐sulfonate) withβ‐cyclodextrin (β‐CD), 2‐hydroxypropyl‐β‐CD (HP‐β‐CD),γ‐CD and HP‐γ‐CD by means of UV‐Vis absorption spectroscopic titrations. The inclusion complexes were studied to enhance acidity and chemical stability. Kinetic study showed that CDs stabilized the acidic metastable state and slowed its thermal relaxation. The acidity of the ground and metastable state (pK a GS and pK a MS ) increased upon addition of CDs. The pK a MS of [MCH1 ⋅ (γ‐CD) 2 ] is as low as 0.92 in comparison with 2.24 for MCH1, which is close to the lowest pK a MS values (1.20 and 1.03) reported previously, in which case the MCH1 was structurally modified with alkylammonium side chains. Addition of CDs also significantly enhanced the chemical stability of MCH1 against hydrolysis, which is one of the major concerns for the application of MCHs. In particular, the addition of HP‐β‐CD increased the half‐life of MCH1 in aqueous solution more than four‐fold. Moreover, the quantum chemical calculations confirmed the stoichiometry and analyzed the binding sites and hydrogen bonds of the inclusion complexes.

Chemistry↗
DOE OSTI2025

Understanding ERE and iVOC Metrics for Graded CdSeTe Absorbers

PL-based external radiative efficiency (ERE) and implied open-circuit voltage (iVOC) metrics were introduced for thin-film solar absorbers to better understand the voltage deficit and diagnose losses in solar cells. Traditionally, elevated ERE and iVOC measurements are associated with diminished recombination within the solar device, a rationale heavily reliant on the assumption of a uniform bandgap and high carrier mobilities in the absorber. Recently, very low mobilities in CdSeTe absorbers (< 1 cm2/(V.s)) were measured using the light-induced transient grading technique. In this study, we use a detailed numerical model of iVOC to investigate the possible reasons of elevated iVOC in realistic CdSeTe absorbers with a graded Se profile. In particular, we examine how the bandgap nonuniformity and the reduced hole mobility in graded CdSeTe absorbers affect iVOC measurements. We show that high iVOC may result from inflated quasi-Fermi level splitting in the high-Se region in the front part of a CdSeTe absorber with slow hole transport. We reproduce the experimentally reported 360 mV increase in iVOC-VOC gap with reduced doping using a model with sub-1 cm2/(V.s) hole mobility in the high-Se region. Based on our results, we conclude that the iVOC metric (or ERE metric) should not be used as a sole metric of CdSeTe absorber quality. We discuss possible ways to extract useful information from the iVOC-VOC gap by supplementing the front-side illumination measurements with back-side illumination measurements.

14 SOLAR ENERGY↗
DOE OSTI2025

Structural and Dynamical Insights into the Formation Process of a Cross-Linked Polymer Network in Acrylic Adhesives During Thermal Curing

Many modern adhesives, sealants, and coatings rely on the controlled transition from a liquid to a solid state by forming a three-dimensional cross-linked polymer network, often referred to as curing. The curing process, which is initiated by the mixing of reactive components or an external trigger, defines the structure of a network and further controls the final mechanical properties of cured materials. However, the curing mechanism is not fully understood yet due to the lack of experimental tools capable of directly probing the structure and dynamics of a network over relevant time- and length scales. Here, in this paper, we report the curing process of a commercial two-component methyl methacrylate (MMA) adhesive using in operando X-ray photon correlation spectroscopy (XPCS), a method that closely simulates the target manufacturing environment of the adhesive. The results are then integrated with those obtained by rheology, differential scanning calorimetry (DSC), and transmission electron microscopy to establish the structure–dynamics–process–property relationship. The XPCS results identify four distinct stages in the curing process after the mixing, extrusion, and deposition of the acrylic adhesive: (i) At a cure time (or “aging time”, t age ) of less than 1 min, nanodomains of polymerized MMA are formed within a liquid monomeric MMA matrix. The average size is several nm and remains constant over t age , while the dynamics of the nanodomains are slowed down with t age due to an increase in the viscosity of the MMA matrix. (ii) After t age > 1 min, the size of the nanodomains increases with t age until the gel point (= 6.3 min after mixing as determined by rheology). The dynamics of the nanodomains also increase due to the heat generated by the exothermic reaction. (iii) At the gel point, the nanodomains begin to interconnect each other, resulting in a network structure with a characteristic length of about 100 nm. This characteristic network size does not change for the rest of the curing process up to t age = 500 min. The dynamics of the network structure, however, show a rapid slowing down with t age up to t age ≈ 12 min, corresponding to the onset of vitrification (as determined by rheology). (iv) At t age > 12 min, when the DSC and rheology data can no longer provide meaningful information, the XPCS data show a further slowing down of the network dynamics associated with vitrification. Our results provide rich and complex insights into the physics and material design of thermosets in commercially relevant processes, which are essential for future industrial applications.

36 MATERIALS SCIENCE↗