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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Influence of Surface and Structural Variations in Donor–Acceptor–Donor Sensitizers on Photoelectrocatalytic Water Splitting

Conjugated organic chromophores composed of linked donor (D) and acceptor (A) moieties have attracted considerable attention for photoelectrochemical applications. In this work, we compare the optoelectronic properties and photoelectrochemical performance of two D–A–D structural isomers with thiophene-X-carboxylic acid (X denotes 3 and 2 positions) derivatives and 2,1,3-benzothiadiazole as the D and A moieties, respectively. 5,5′-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-3-carboxylic acid), BTD1, and 5,5′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxylic acid), BTD2, were employed in the study to understand how structural isomers affect surface attachments within chromophore–catalyst assemblies and their influence on charge-transfer dynamics. Crystal structures revealed that varying the position of the −COOH anchoring group causes the molecules to either contort out of a plane (BTD1) or adopt a near-perfect planar conformation (BTD2). BTD1 and BTD2 were co-loaded with either a water oxidation catalyst, [Ru(2,6-bis(1-methylbenzimidazol-2-yl)pyridine)-(4,4′-((HO) 2 OPCH 2 )2-2,2′-bipyridine)(OH 2 )] 2 , RuCt 2+ , or proton reduction catalyst [Ni(P 2 Ph N 2 C 6 H 4 CH 2 PO 3 H 2 ) 2 ] 2+ , NiCt 2+ , on oxide electrodes to facilitate photodriven water splitting reactions. Emission quenching measurements indicate that both BTD1 and BTD2 inject electrons into n-type SnO 2 |TiO 2 electrodes and holes into p-type NiO semiconductors from their respective excited states at high efficiencies >60%. Photocurrent densities of chromophore–catalyst assemblies obtained using linear sweep voltammetry (LSV) show that BTD2-sensitized photoanodes generate significantly more photocurrent than BTD1-sensitized electrodes; however, both exhibit similar performances at the photocathode. Photoelectrocatyltic measurements demonstrate that both BTD1 and BTD2 performed similarly, generating Faradaic efficiencies of 39 and 38% at the anode or 61 and 79% at the cathode. Transient absorption measurements suggest that the differences between the LSV and photoelectrocatalytic measurements result from the differences in quantum yields of the photogenerated redox equivalents, which is also a reflection of the varying metal oxide surface conformation. Our findings suggest that BTD2 should be investigated further in photocathodic studies since it has the structural advantage of being incorporated into diverse types of chromophore–catalyst assemblies.

Chromophores↗
DOE OSTI2024

EGS Reservoir Modeling for Developing Geothermal District Heating at Cornell University: Preprint

Cornell University is pursuing development of an enhanced geothermal system (EGS) for providing heating to its main campus in Upstate New York. A ~10,000 ft (~3 km) deep vertical observation well ("CUBO") was drilled in 2022 to characterize the subsurface using wellbore logging, borehole imaging, fluid sampling, mini-frac tests, coring and drill cutting analysis. Down-hole temperatures measured at 3 km depth are about 80 degrees C, sufficiently high for direct-use heating. The well drilled through generally low porosity and low permeability Paleozoic sedimentary formations and into metamorphic basement rock, encountered at about 9,400 ft depth. Leveraging subsurface data obtained through CUBO, we investigated technical feasibility and design requirements of a doublet well system with horizontal laterals connected to a fracture network created through hydraulic fracturing. The EGS reservoir is sized to provide a nominal heat output in the range 5 to 10 MWth of continuous heating over a 15 year-lifetime with limited thermal drawdown. We applied the Gringarten Multiple parallel fracture model, the Cornell Discrete Fracture Simulator FOXFEM and the commercial simulator ResFrac to estimate required heat transfer area and design a potential hydraulic stimulation treatment. Reservoir simulations indicate that, depending on fluid flow rate and injection temperature, 2 to 3 km2 of effective fracture heat transfer area is required to supply the target heat output of 5 to 10 MWth over 15 years.

district heating↗
DOE OSTI2025

EGS Reservoir Modeling for Developing Geothermal District Heating at Cornell University

Cornell University is pursuing development of an enhanced geothermal system (EGS) for providing heating to its main campus in Upstate New York. A ~10,000 ft (~3 km) deep vertical observation well ('CUBO') was drilled in 2022 to characterize the subsurface using wellbore logging, borehole imaging, fluid sampling, mini-frac tests, coring and drill cutting analysis. Down-hole temperatures measured at 3 km depth are about 80 degrees C, sufficiently high for direct-use heating. The well drilled through generally low porosity and low permeability Paleozoic sedimentary formations and into metamorphic basement rock, encountered at about 9,400 ft depth. Leveraging subsurface data obtained through CUBO, we investigated technical feasibility and design requirements of a doublet well system with horizontal laterals connected to a fracture network created through hydraulic fracturing. The EGS reservoir is sized to provide a nominal heat output in the range 5 to 10 MWth of continuous heating over a 15 year-lifetime with limited thermal drawdown. We applied the Gringarten Multiple parallel fracture model, the Cornell Discrete Fracture Simulator FOXFEM and the commercial simulator ResFrac to estimate required heat transfer area and design a potential hydraulic stimulation treatment. Reservoir simulations indicate that, depending on fluid flow rate and injection temperature, 2 to 3 km2 of effective fracture heat transfer area is required to supply the target heat output of 5 to 10 MWth over 15 years.

district heating↗
DOE OSTI2020

Revisiting the first Sandia Fracture Challenge with transient deformation heating and strain localization considerations

In this study, we present a systematic experimental study and accompanying theoretical analysis of the dependence of ductile fracture on strain localization, strain hardening rates, deformation-induced thermal softening, and transient heat conduction under spatially uniform as well as spatially heterogeneous deformation. Spatially uniform cases are studied via standard dogbone shaped specimens subject to uniaxial tension. Spatially heterogeneous deformation is studied via the so-called Sandia Fracture Challenge (SFC) specimen, which is a standard compact tension specimen modified with three machined holes in front of a blunt notch. We utilize the same precipitation hardened martensitic stainless steel used in the first SFC experiments, i.e. 15-5 PH with an H1075 heat treatment. We also study 15-5 PH in Condition A and with the H900 heat treatment, each of which has a different hardening behavior and ductility. We find that the ductility does not correlate with the deformation to first crack initiation in the SFC specimen. Instead, hardening rates are better correlated. Moreover, a re-examination finds that an accurate calibration of the hardening rates is strongly correlated with accurate blind predictions of ductile fracture in the SFC specimens. Given that thermal softening can greatly affect hardening rates, we provided a thermographic analysis of deformation-induced heating and transient heat transfer in both the dogbone shaped samples and the SFC specimens. Transient heating in stainless steels is found to have first-order effects on the strain at the onset of necking, strain to fracture, as well as strain localization and ductile fracture in complex geometries even under so-called quasi-static loading rates.

42 ENGINEERING↗
DOE OSTI2022

An asymmetric electron-scattering photosphere around optical tidal disruption events

We report a star crossing the tidal radius of a supermassive black hole will be spectacularly ripped apart with an accompanying burst of radiation. A few tens of such tidal disruption events have now been identified in optical wavelengths, but the exact origin of the strong optical emission remains inconclusive. Here we report polarimetric observations of three tidal disruption events. The continuum polarization appears independent of wavelength, while emission lines are partially depolarized. These signatures are consistent with photons being scattered and polarized in an envelope of free electrons. An almost axisymmetric photosphere viewed from different angles is in broad agreement with the data, but there is also evidence for deviations from axial symmetry before the peak of the flare and significant time evolution at early times, compatible with the rapid formation of an accretion disk. By combining a super-Eddington accretion model with a radiative transfer code, we simulate the polarization degree as a function of disk mass and viewing angle and we show that the predicted levels are compatible with the observations for extended reprocessing envelopes of ~1,000 gravitational radii. Spectropolarimetry therefore constitutes a new observational test for tidal disruption event models, and opens an important new line of exploration in the study of tidal disruption events.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Simulated impact of fill tube geometry on recent high-yield implosions at the National Ignition Facility

Inertial confinement fusion capsules fielded at the National Ignition Facility are filled with deuterium and tritium fuel by means of a fill tube. The fill tube introduces a low-density pathway into the fuel region of the capsule that allows high Z contaminant to invade the hot spot during the course of the implosion. A recent series of nominally identical high-yield implosions on the NIF has exhibited significant variability in performance. We evaluate the impact of the fill tube in these implosions computationally to determine whether variations in fill tube geometry could have contributed to this variability. The main contrast between the fill tube geometry in the six shots was the outer diameter of the capsule bore hole, a conical hole into which the fill tube is inserted. In our simulations, the geometry of the bore hole can play a significant role in the development of nonlinear flows seeded by the fill tube. Additionally, we find that the amount of space between the bore hole and the fill tube is the primary factor that determines the amount of contaminant jetted into the hot spot by the fill tube and, in turn, the level of yield reduction due to the fill tube in our simulations. As a consequence, some capsules with 5 μm fill tubes are predicted to outperform capsules with 2 μm fill tubes. We also find that micrometer-scale changes to bore hole size can impact fusion yields by up to four times near the ignition threshold. Nevertheless, simulation trends do not reproduce experimental yield trends, suggesting that the fill tube geometry was not the primary factor contributing to the observed variability in performance and that the fill tube could be masking sensitivity to other asymmetries such as other micrometer-scale capsule defects like voids that were not included in our simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Enthalpy-uphill exciton dissociation in organic/2D heterostructures promotes free carrier generation

Despite the large binding energy of charge transfer (CT) excitons in type-II organic/2D heterostructures, it has been demonstrated that free carriers can be generated from CT excitons with a long lifetime. Using a model fluorinated zine phthalocyanine (F 8 ZnPc)/monolayer-WS 2 interface, we find that CT excitons can dissociate spontaneously into free carriers despite it being an enthalpy-uphill process. Specifically, it is observed that CT excitons can gain an energy of 250 meV in 50 ps and dissociate into free carriers without any applied electric field. This observation is surprising because excited electrons typically lose energy to the environment and relax to lower energy states. Here, we hypothesize that this abnormal enthalpy-uphill CT exciton dissociation process is driven by entropy gain. Kinetically, the entropic driving force can also reduce the rate for the reverse process – the conversion of free electron–hole pairs back to CT excitons. Hence, this mechanism can potentially explain the very long carrier lifetime observed in organic/2D heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Infinite-layer nickelates as Ni-e $g$ Hund’s metals

The recent and exciting discovery of superconductivity in the hole-doped infinite-layer nickelate Nd 1-$δ$ Sr $δ$ NiO 2 draws strong attention to correlated quantum materials. From a theoretical viewpoint, this class of unconventional superconducting materials provides an opportunity to unveil a physics hidden in correlated quantum materials. Here we study the temperature and doping dependence of the local spectrum as well as the charge, spin and orbital susceptibilities from first principles. By using ab initio LQSGW+DMFT methodology, we show that onsite Hund’s coupling in Ni-$d$ orbitals gives rise to multiple signatures of Hund’s metallic phase in Ni-e $g$ orbitals. The proposed picture of the nickelates as an e $g$ (two orbital) Hund’s metal differs from the picture of the Fe-based superconductors as a five orbital Hund’s metal as well as the picture of the cuprates as doped charge transfer insulators. Our finding uncovers a new class of the Hund’s metals and has potential implications for the broad range of correlated two orbital systems away from half-filling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Triphenylamine/benzothiadiazole-based compounds for non-doped orange and red fluorescent OLEDs with high efficiencies and low efficiency roll-off

Long-wavelength materials are key for development of pure-color and white organic light-emitting devices (OLEDs). An organic molecule, combining hybridized local electron and charge-transfer (HLCT) states and aggregation-induced emission (AIE), not only breaks the 5% external quantum efficiency (EQE) limit but also overcomes emission quenching. Herein, we designed and synthesized four novel donor–acceptor compounds of TBAN, TBT, TBAT, and TABAT using triphenylamine (TPA) as the donor, benzothiadiazole (BT) as the acceptor, and anthracene (AN) as a bridge. We found that the emission peaks of TBAN, TBT, TBAT and TABAT are located at 596, 615, 580 and 546 nm, respectively. We successfully applied them to non-doped OLEDs, and the resulting devices exhibited excellent performance. For example, the optimal TBAN-based OLEDs showed a maximum luminance of 74 820 cd m –2 , a current efficiency of 12.1 cd A –1 and a maximum EQE of 5.7% with low roll-off. Additionally, the device with TBAN as both the emitter and hole-transport material also exhibited high efficiency that is comparable to that of an NPB-based device. Furthermore, this work demonstrates that it is feasible to obtain excellent orange and red emitters by employing BT- and TPA-based D–A architectures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Gamma Rays from Fast Black-hole Winds

We study massive black holes at the centers of galaxies that can launch powerful wide-angle winds that, if sustained over time, can unbind the gas from the stellar bulges of galaxies. These winds may be responsible for the observed scaling relation between the masses of the central black holes and the velocity dispersion of stars in galactic bulges. Propagating through the galaxy, the wind should interact with the interstellar medium creating a strong shock, similar to those observed in supernovae explosions, which is able to accelerate charged particles to high energies. In this work we use data from the Fermi Large Area Telescope to search for the γ-ray emission from galaxies with an ultrafast outflow (UFO): a fast (v ~0.1 c), highly ionized outflow, detected in absorption at hard X-rays in several nearby active galactic nuclei (AGN). Adopting a sensitive stacking analysis we are able to detect the average γ-ray emission from these galaxies and exclude that it is due to processes other than UFOs. Moreover, our analysis shows that the γ-ray luminosity scales with the AGN bolometric luminosity and that these outflows transfer ~0.04% of their mechanical power to γ-rays. Interpreting the observed γ-ray emission as produced by cosmic rays (CRs) accelerated at the shock front, we find that the γ-ray emission may attest to the onset of the wind–host interaction and that these outflows can energize charged particles up to the transition region between galactic and extragalactic CRs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

The possible disappearance of a massive star in the low-metallicity galaxy PHL 293B

ABSTRACT We investigate a suspected very massive star in one of the most metal-poor dwarf galaxies, PHL 293B. Excitingly, we find the sudden disappearance of the stellar signatures from our 2019 spectra, in particular the broad H lines with P Cygni profiles that have been associated with a massive luminous blue variable (LBV) star. Such features are absent from our spectra obtained in 2019 with the Echelle Spectrograph for Rocky Exoplanet- and Stable Spectroscopic Observation and X-shooter instruments of the European Southern Observatory’s Very Large Telescope. We compute radiative transfer models using cmfgen, which fit the observed spectrum of the LBV and are consistent with ground-based and archival Hubble Space Telescope photometry. Our models show that during 2001–2011, the LBV had a luminosity L* = 2.5–3.5 × 106 L⊙, a mass-loss rate $\dot{M} = 0.005{-}0.020 ~{\rm M}_{\odot }$ yr−1, a wind velocity of 1000 km s−1, and effective and stellar temperatures of Teff = 6000–6800 and T* = 9500–15 000 K. These stellar properties indicate an eruptive state. We consider two main hypotheses for the absence of the broad emission components from the spectra obtained since 2011. One possibility is that we are seeing the end of an LBV eruption of a surviving star, with a mild drop in luminosity, a shift to hotter effective temperatures, and some dust obscuration. Alternatively, the LBV could have collapsed to a massive black hole without the production of a bright supernova.

Allan, Andrew P.↗
DOE OSTI2022

Joule heating in bad and slow metals

Heat supplied to a metal is absorbed by the electrons and then transferred to the lattice. In conventional metals energy is released to the lattice by phonons emitted from the Lindhard continuum. However in a 'bad' metal, with short mean free path, the low energy Lindhard continuum is destroyed. To describe energy transfer to the lattice in these cases we obtain a general Kubo formula for the energy relaxation rate in terms of the electronic density spectral weight \text{lm} \, G^R_{nn}(\omega_{k},k) lm G n n R ( ω k , k ) evaluated on the phonon dispersion \omega_k ω k . We apply our Kubo formula to the high temperature Hubbard model, using recent data from quantum Monte Carlo and experiments in ultracold atoms to characterize \text{lm} \, G^R_{nn}(\omega_{k},k) lm G n n R ( ω k , k ) . We furthermore use recent data from electron energy-loss spectroscopy to estimate the energy relaxation rate of the cuprate strange metal to a high energy optical phonon. As a second, distinct, application of our formalism we consider 'slow' metals. These are defined to have Fermi velocity less than the sound velocity, so that particle-hole pairs are kinematically unable to emit phonons. We obtain an expression for the energy relaxation rate of a slow metal in terms of the optical conductivity.

36 MATERIALS SCIENCE↗
DOE OSTI2022

[Presentation Slides] Code-to-Code Benchmark Study for Thermal Stress Modeling and Preliminary Analysis of the High-temperature Single Heat-Pipe Experiment

In the heat-pipe-cooled microreactor, heat pipes remove heat from the reactor core as a passive heat-transfer device, so the fluid circulation is not required for cooling, which can substantially simplify the overall reactor design. However, given the extremely high temperatures in the core region and potentially large temperature gradients across the structure materials, thermal stresses need to be well-analyzed to ensure structural integrity during normal operations and accident scenarios. This presentation slides discuss finite element method-based thermal-stress analysis for the high-temperature single heat-pipe test article in the Single Primary Heat Extraction and Removal Emulator (SPHERE) facility at Idaho National Laboratory (INL), using two commercial software packages, Abaqus and Star-CCM+. A code-to-code benchmark study was performed to crosscheck the model setup and capability of each code and to gain preliminary insights into the potential thermal stress concerns from the current experimental setup. It is observed the significant thermal stresses happen at the inner surface of the heat pipe hole surrounded by electric heaters where the largest temperature gradients appear. The temperature fields have good agreements between Abaqus and Star-CCM+, while the induced thermal stresses show modest deviations probably due to differences of meshing engines used in these two codes. It is found that the local maximum thermal stresses may reach close to the ultimate tensile strength and yield strength of structural material depending on the heater power. Ultimately, the coupled thermal-structural analysis will help guide the current experimental plan and ensure the facility safety for future experimental study.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Photoexcitation of Fe 3 O Nodes in MOF Drives Water Oxidation at pH=1 When Ru Catalyst Is Present

Abstract Artificial photosynthesis strives to convert the energy of sunlight into sustainable, eco‐friendly solar fuels. However, systems with light‐driven water oxidation reaction (WOR) at pH=1 are rare. Broadly used [Ru(bpy) 3 ] 2+ (bpy=2,2’‐bipyridine) photosensitizer has a fixed +1.23 V potential which is insufficient to drive most water oxidation catalysts (WOCs) in acid, while Fe 2 O 3 , featuring the highly oxidizing holes, is not stable at low pH. Here, the key examples of Fe‐based metal–organic framework (MOF) water oxidation photoelectrocatalysts active at pH=1 are presented. Fe‐MIL‐126 and Fe MOF‐dcbpy structures were formed with 4,4’‐biphenyl dicarboxylate (bpdc), 2,2’‐bipyridine‐5,5’‐dicarboxylate (dcbpy) linkers and their mixtures. Presence of dcbpy linkers allows integration of metal‐based catalysts via coordination to 2,2’‐bipyridine fragments. Fe‐based MOFs were doped with Ru‐based precursors to achieve highly active MOFs bearing [Ru(bpy)(dcbpy)(H 2 O) 2 ] 2+ WOC. Materials were analyzed with X‐ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra‐red (FTIR) spectroscopy, resonance Raman, X‐ray absorption spectroscopy, fs optical pump‐probe, electron paramagnetic resonance (EPR), diffuse reflectance and electric conductivity measurements and were modeled by band structure calculations. It is shown that under reaction conditions, Fe III and Ru III oxidation states are present, indicating rate‐limiting electron transfer in MOF. Fe 3 O nodes emerge as photosensitizers able to drive prolonged O 2 evolution in acid. Further developments are possible via MOF's linker modification for enhanced light absorption, electrical conductivity, reduced MOF solubility in acid, Ru‐WOC modification for faster WOC catalysis, or Ru‐WOC substitution to 3d metal‐based systems. The findings give further insight for development of light‐driven water splitting systems based on Earth‐abundant metals.

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

Salt Vessel-Sample Generator Interface

The goal of the salt sampling program at Argonne is to develop and deploy automated molten salt sampling approaches for interfacing relevant unit operations with salt analysis to improve the timeliness and accuracy of sampling-based accountancy measurements. One technology under development is a vacuum sampler loop module. In this system, molten salt is drawn from a process vessel through a heated sampling line and into a charge vessel. Next, one or more samples are split from the volume in the charge vessel and the remaining salt is returned to the process. The vacuum sampler loop module is being developed to interface with other sample processing and analysis modules to enable rapid at-line sample characterization. The main purpose of the vacuum sampling loop module is to enable the collection of samples that are more representative of the bulk salt by replacing traditional point samplers (i.e., dip probes) with a sampling approach that captures a larger cross section of salt. Additionally, the vacuum sampling approach eliminates the risk of dross contamination of samples and avoids the use of moving parts in the salt. Two methods of interfacing the vacuum sampling loop with a precision pneumatic sample generator were investigated in FY21. This report covers the testing of fluidic coupling between the two modules. Two iterations of the fluidically coupled modules were tested. The first iteration system coupled the two modules using a freeze valve to seal the vacuum sampler during filling and to control flow into the pneumatic sample generator. While this integrated system functioned as intended, some changes were implemented to make the system more robust and better suited to remote deployment. Specifically, the system was made to be more modular and active control of the vacuum filling operation was replaced with a passive control mechanism. For passive filling, the salt charge vessel was vented to a small gas tank that was at negative pressure, causing salt to be drawn into the vessel until the force of the fluid head was in equilibrium with the gas pressure. The passive control system performed well and will be used in future iterations. Another change in the second system was a newly configured pneumatic sample generator in which sample ejection occurred through a hole in the reservoir’s stainless-steel side wall instead of through a non-wetted sapphire orifice on the bottom. This alternate configuration may be better suited for near-process deployment because it enables on-line orifice maintenance and an orifice bypass drain back to the process. A third change in the second iteration system was the transition to a two-chamber charge vessel which split off a fraction of the sampled salt as a liquid aliquot. The goal was to create a buffer mechanism that would allow reproducible aliquoting of samples, independently of variability in the charge vessel fill height. While the two-chamber design was functional, the sample size reproducibility was below target values. To improve reproducibility and overcome many of the impediments to remote deployment of the vacuum sampling loop module, separate work was conducted to replace the two-chamber liquid aliquoting mechanism with aliquoting into single-use sample tubes. Solid salt transfer in the sample tubes will replace fluidic coupling for integrating the vacuum sampler with downstream modules. Because the proposed operations can all be executed with simple overhead actuation mechanisms or other existing hot-cell technology, there will be no need for large investments in novel hot cell sample handling technologies using this alternate approach. As such, near-term deployment of the vacuum sampling technology will be achievable. This new approach for automated coupling of sample tubes with down-stream modules is covered in a separate FY21 report, and a remotely operated version of the vacuum sampler loop module with the tube aliquoting feature is planned for FY22.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Plasmonic Ag nanocomposite phosphate glasses produced via γ-ray irradiation as reduction route

This paper reports on the impact of γ-ray irradiation (10, 100 kGy) on melt-quenched Ag + -doped phosphate glass and the effects of subsequent thermal processing leading to the production of plasmonic Ag nanocomposites. The γ-irradiated glasses were characterized alongside the pristine by differential scanning calorimetry (DSC), Raman spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, optical absorption, and photoluminescence (PL) spectroscopy. DSC characterization showed consistent glass transition temperatures (T g ) before and after γ-irradiation whereas the crystallization temperatures tended to decrease with increasing γ-ray dose. However, a lack of alteration of the glass network structure was supported by Raman spectroscopy. Room temperature EPR spectra clearly showed the formation of phosphorus oxygen hole center (POHC) defects in the undoped host, in addition to another doublet likely associated with a P 3 defect. The presence of paramagnetic silver species encompassing Ag 2+ and 107/109 Ag 0 atoms was also indicated in the silver-activated glass together with POHC defects. Optical absorption spectra were also consistent with the presence of various radiation-induced centers. Further analyzing the glass absorption edge via Tauc plots suggested the formation of electron center (EC) defects in γ-irradiated samples wherein the silver-doped glass exhibited decreasing band gap energies with increasing γ-ray dose. The PL characterization showed the silver-related radio-PL effect was induced exhibiting broad band emission with two maxima around 500 and 625 nm stemming from various molecular Ag$^{x+}_{n}$ clusters. Emission decay analyses revealed that the longer wavelength emission exhibited slower decay. The highest radiation dose of 100 kGy however resulted in weaker emission and faster decay kinetics attributed to energy transfer between the luminescent silver species and POHC defects. Finally subjecting the γ-irradiated Ag-doped glasses to heat treatment near the T g at 490 °C led to the development of the surface plasmon resonance of Ag nanoparticles (NPs) and the vanishing of the Ag$^{x+}_{n}$ clusters luminescence. In conclusion, the presence of the matrix-related EC defects was deemed accountable for the thermally induced reduction and consequent precipitation of Ag NPs making the plasmonic glasses attractive for photonic applications such as nonlinear optics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Boride-Carbon Hybrid Technology to Produce Ultra-Wear and Corrosion Resistant Surfaces for Applications in Harsh Conditions (Final Technical Report)

Engineered functional surfaces play an important role to enable new products and manufacturing processes that can endure harsh service conditions such as high impact and contact loads, highly abrasive wear, extreme temperatures, and corrosive environments. Engineered surfaces can also be instrumental to improving the efficient use of energy by reducing frictional losses and extending service life. The main objective of this project was to develop a hybrid surface engineering technology that combines the advantages of a novel ultrafast boriding process with the next generation of superhard carbon coatings. The hypothesis was that this hybrid process will offer an unprecedented combination of wear and corrosion resistance, low frictional losses and affordability for treated parts so that it can be utilized in many applications. During this project, a duplex process was developed that combines the advantages of ultra-fast electrochemical boriding with those of hard tetrahedral amorphous carbon coatings. Both technologies can be combined to form a hybrid technology that is characterized by low friction and wear properties combined with corrosion and fatigue resistance. Good adhesion of both layers to each other was one main goal of this project, that has been achieved with HF1 adhesion through the Rockwell-C adhesion test. In this project, the mechanical properties of the hybrid coating were modeled through a finite-element analysis approach. We can conclude that the FEA model resembles the actual samples and be utilized to predict mechanical behavior under impacts. Based on this model, application-oriented load conditions can be simulated for optimal layer design regarding thickness and mechanical properties. To exemplify, one conclusion that can be drawn from the nanoindentation model is a boride layer thickness of 50 µm is sufficient to effectively support the carbon coating on the identified AISI 1045 low carbon steel substrate material. The duplex treatment yields wear rates as low as 6 x 10 -8 mm 3 N -1 m -1 and a coefficient of friction of 0.14 when tested against a steel counter face in a ball-on-disk test setup. On the other hand, the wear rate of the only-borided AISI 1045 steel was 5 x 10 -5 mm 3 N -1 m -1 , about three orders of magnitude higher than the duplex coating. At the same time, duplex treated samples experience corrosion resistance, which could not be achieved with single-layer carbon coatings. The developed surface treatment withstands a 3-hour exposure to 15% HCl, while the only carbon coated counter sample shows severe delamination of the coating due to pin hole corrosion. The boride layer is chemically stable and pin hole free because it is formed through an electrochemical process under high current densities (700 mA/cm 2 ) and high temperature. Additionally, the hybrid coating led to at least 3x increase in fatigue strength of the steel substrate, which exceeds the target performance of 30% improvement. There are numerous potential applications for the duplex coatings. A representative application is bearing ball coatings for off-shore windmills. Compared to currently employed surface technologies in this field, the initial costs of applying our technology might be higher due to more process steps but the performance benefits lead to an increased life time of treated parts, which will lower the maintenance and replacement costs in the long-term. To validate the technology for this specific application, the team is currently investigating the process of white etching crack initiation of the duplex coating in collaboration with ANL. Overall, this project successfully validated that the boride-carbon hybrid technology can withstand harsh conditions. One possible approach to commercialization under consideration is to transfer the technology to a startup or an existing coatings company.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Facets control charge separation during photoelectrochemical water oxidation with strontium titanate (SrTiO 3 ) single crystals

The photocatalytic overall water splitting reaction provides a pathway to hydrogen fuel from sunlight. Photocatalysts must achieve the reaction without the application of an external bias, which requires an effective charge separation mechanism. Photolabeling studies and electrostatic simulations for the well-known CoOOH/Al:SrTiO 3 /Rh/Cr 2 O 3 photocatalyst suggest that charge separation is driven by work function differences at the (100) and (110) facets of SrTiO 3 , which are electron and hole selective, respectively. Here we use hydrogen annealed SrTiO 3–x single crystals to obtain the first quantitative assessment of the charge separation ability of the (100), or (110), or (111) facets during oxygen evolution. Under UV illumination (60 mW cm –2 ), the crystals exhibit variable water oxidation photocurrents (0.34, 0.82, 1.36 mA cm –2 at 1.23 V versus RHE) and photovoltage values of 1.40, 1.52 and 1.52 V for (100), (110), and (111) SrTiO 3–x , respectively. A surface photovoltage increase in that same order (0.31 V < 0.57 V < 0.67 V) is confirmed independently with vibrating Kelvin probe surface photovoltage spectroscopy (VKP-SPV) under 375 nm (1.91 mW cm –2 ) illumination. Mott Schottky measurements in aqueous K 3/4 [Fe(CN) 6 ] reveal facet-dependent flatband positions of –0.58, –0.71, and –0.74 V RHE for the (100), (110), and (111) crystals respectively. This confirms that the photoelectrochemical water oxidation performance of SrTiO 3–x crystals is controlled by the work function of each facet, which determines the electron transfer barrier height of the respective solid–liquid junctions. After correcting for differences in electron donor concentrations, barriers are found to increase in the order (100) < (111) < (110) and differ by as much as 0.16 eV, similar to an earlier prediction. Altogehter, these results explain the charge separation mechanism in SrTiO 3 photocatalysts and highlight the need for faceted semiconductor crystals as light absorbers in particle-based photocatalysts.

08 HYDROGEN↗