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DOE OSTI2027

Low thermal budget dopant activation in shallow junctions of implanted Si via Tunable plasma enhanced annealing

Low thermal budget (LTB) annealing has become increasingly critical for shallow junctions as semiconductor devices are scaled down. Plasma Enhanced Annealing (PEA) has emerged as a promising LTB annealing process, however its mechanisms remain unclear. In this study, arsenic and boron implanted silicon wafers were subjected to helium or argon ion bombardment generated by annealing plasmas under controlled ion energies and doses in a home-built annealing reactor. The structural and electrical changes were characterized by four-point probe measurements, secondary ion mass spectrometry, Raman spectroscopy and spectroscopic ellipsometry. A pronounced reduction in sheet resistance, accompanied by a decrease in the damage layer thickness demonstrates the surface selective annealing capability of PEA process. Comparative studies using He and Ar plasmas and related ion bombardment reveal a dependence of activation efficacy on both ion species and the dopant implantation profile. Furthermore, a multi-step annealing mechanism is proposed, consisting of an initial (low dose) structural recovery stage followed by the generation of “extended” defects and concluded at large doses by an enhanced dopant activation. The proposed annealing kinetics are thought to be controlled by ion flux, dose and energy. Finally, these results highlight PEA as an effective, surface-selective, LTB approach for shallow-dopant activation and near surface annealing, and provide mechanistic insights into PEA processes.

dopant activation↗

NASA NTRS2014

Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 microns) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200 C in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a approx. 15.03-15.23Angstroms (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Moessbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation.

Sutter, B.↗

DOE OSTI2020

Performance of U 3 Si 2 in an LWR following a cladding breach during normal operation

High-density fuels have been proposed as a possible replacement for uranium-dioxide as a fuel for light water reactors (LWRs) due to their increased loading of fissionable material. The objectives of this proposal are (1) to increase reactor cycle length and reactor power, and (2) to offset any neutronic penalty associated with advanced cladding systems. Of the high-density fuels under consideration, there is particular interest in triuranium disilicide (U 3 Si 2 ) due to its increased metal density and favorable thermal properties as compared to UO 2 . However, there are concerns regarding the chemical compatibility of U 3 Si 2 with water and steam as used for LWR coolant.This paper summarizes research on fuel-coolant chemical compatibility for UO 2 LWR fuel during a cladding breach and highlights that generally, because of its chemical inertness, UO 2 -coolant reactions are of little consequence to reactor operation. However, the volumetric expansion associated with the reaction of UO 2 and oxygen is a concern for possible conditions encountered during air ingress of dry storage. These same concerns arise for U 3 Si 2 , which exhibits greater volumetric expansion than UO 2 when exposed to water or steam. These reactions ultimately result in increased fuel volume that the cladding must accommodate, as well as additional heat generated as the fuel reacts.The BISON fuel performance code was used to perform a comparative analysis on the behavior of UO 2 and U 3 Si 2 under normal operation. Silicide fuel simulations were then extended to demonstrate how varying thermodynamic and chemical kinetics influence fuel expansion and subsequent cladding performance during a cladding breach. These simulations were further extended to a 3D subsection of a fuel rod to demonstrate the characteristics of the resulting cladding crack.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Long-term thermal aging behavior and strength reduction in a laser powder bed fusion 316H stainless steel

The long-term thermal stability of structural alloys is essential for ensuring the safe and reliable operation of nuclear reactors and other power plants. While extensive research has explored the effects of thermal aging on conventional stainless steels, the behavior of additively manufactured (AM) alloys remains less understood. This study examines the thermal aging response of laser powder bed fusion (LPBF) 316H stainless steel (SS) at temperatures ranging from 550 °C to 750 °C over durations of up to 10,000 h (approximately 1.14 years). Advanced characterization techniques, including electron microscopy and synchrotron X-ray diffraction, were used to investigate dislocation recovery and phase evolution. Based on these findings, a time-temperature-precipitation (TTP) diagram was developed for LPBF 316H SS, revealing a 10- to100-fold acceleration in precipitation kinetics compared to wrought 316H SS. A physics-informed model was calibrated using the short-term experimental data, enabling predictions of average precipitate sizes, volume fractions of M 23 C 6 and Laves phases, and changes in molybdenum solute concentration for aging up to 1 × 10⁶ h (114 years). These microstructural insights were further utilized to estimate yield strength and extrapolate strength reduction factors over the extended aging period. Despite the accelerated aging kinetics, LPBF 316H SS demonstrated superior yield strength retention compared to its wrought counterpart. In conclusion, this study establishes a framework for evaluating long-term performance using short-term experimental data and supports the accelerated qualification of AM materials for high-temperature structural applications.

Laser powder bed fusion↗

DOE OSTI2026

Validation of an integrated modeling framework for investigating 3D plasma responses in tokamak plasmas

As contemporary experimental tokamaks are pushed toward reactor-relevant operation, they provide essential testbeds for demonstrating and exploring ELM control strategies for deployment in future fusion pilot plants. Accurate predictions of full plasma responses are essential to guide and optimize these demonstrations. This paper introduces and validates an integrated modeling framework over a historical range of DIII-D operational space. The integrated modeling framework uses only scalar plasma parameters and optional reference boundary to self-consistently and flexibly scan through tokamak operational space and estimate the corresponding ELM-suppression relevant plasma response over 3D coil phase space. The framework generates tightly converged equilibria that satisfy a target set of plasma parameters (I p , β N , l i ), with kinetic profiles constrained by an EPED(NN)-computed pedestal and empirical core model. The plasma response of these modeled equilibria is calculated with GPEC. Validated against 55 distinct DIII-D equilibria, the framework consistently reproduces experimentally constrained equilibrium pressure, q, and other representative profiles using the time-varying information from only evolving scalar plasma parameters; plasma response validation is performed for the n=3 perturbation. In particular, the plasma response of a DIII-D discharge scanning q 95 in search of ELM suppression windows is quantitatively reproduced. By accurately reproducing experimental equilibria and plasma responses across wide parameter variation, the framework supports potential for synthetic parameter scans in key operational, stability, and plasma response dimensions to investigate RMP ELM-suppression experiments and inform predictive RMP scenario optimization.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2000

Kinetics of the Cl(2)P(J)) + CH4 Reaction: Effects of Secondary Chemistry Below 300 K

Absolute rate data for the Cl(2)P(J) + CH4 yields HCl + CH3 reaction have been obtained from 218 to 298 K by using the discharge-flow resonance fluorescence technique at I Torr total pressure. The result at 298 K is (10.1 +/- 0.6) x 10(exp -14) cu cm/molecule/s. The temperature dependence in Arrhenius form is (6.5 +/- 0.9 ) x 10(exp -12) exp[(-1235 +/- 34 )/T]. The errors given are one standard deviation; overall experimental error is estimated at +/- 15%. Because of the relatively large disagreement among earlier measurements at low temperatures, the results were examined for possible effects of non-Boltzmann spin distribution and vibrational excitation of CH4, secondary chemistry of CH3 radicals, and impurities in the CH4 source. There was no significant change in the observed rate constant when an efficient spin quencher, CF4, was added and estimates indicate that vibrational partitioning in CH4 should be at the ambient reactor temperature before the start of the reaction. The results were also independent of the source of Cl atoms (microwave discharge or thermal decomposition of Cl2) and whether CH4 was purified in-situ. However, the observed rate constant did depend on initial Cl atom concentrations and to a lesser extent on CH4 concentrations. Numerical simulations were used to assess the importance of secondary chemistry over a range of reactant concentrations

Wang, J. J.↗

DOE OSTI2024

Polystyrene Hydrogenolysis to High-Quality Lubricants Using Ni/SiO 2

Pyrolytic and light-activated oxidation processes are leading technologies for utilizing polystyrene (PS) wastes. These approaches exhibit poor selectivities, use complex reactors, and require solvents. Hydrogenolysis is effective for deconstructing polyolefins, but its application to PS feedstocks has been limited. Herein, we demonstrate Ni/SiO 2 catalysts to facilitate PS (M w ≈ 97 kDa) hydrogenolysis to produce lubricant base oils possessing group IV properties, achieving maximum yields of 70% within 6 h at 300 °C and 70 bar of H 2 . Gas, liquid, and oil product yields are stable across reaction conditions, whereas hydrogenation of the PS aromaticity and reduction of the molecular weight benefit from higher temperatures and H 2 pressures. Time-dependent experiments underscore the importance of elevated H 2 pressure, revealing that PS hydrogenolysis occurs sequentially, with aromatic ring hydrogenation preceding degradation of the C–C backbone. Kinetic measurements with 1,2-diphenylethane as a probe molecule demonstrate that ring hydrogenation pis 3 orders of magnitude faster than internal C–C bond cleavage over Ni/SiO 2 . Ni/SiO 2 proves to be effective in the hydrogenolysis of heavier PS polymers and rigid commercial PS products. Conversely, flexibility and foam PS feeds result in Ni/SiO 2 deactivation, attributed to performance additives. Unlike polyolefins, the process produces very little methane and other light hydrocarbons. Furthermore, these findings expand the applicability of hydrogenolysis to PS feedstocks, offering a versatile solution and broadening the range of high-value products from PS to include lubricant base oils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Autoencoder Neural Network for chemically reacting systems

Incorporating detailed chemical kinetic models is critical for accurate simulations of reacting flows. However, detailed models involve a large number of thermochemical (TC) state variables. Solving the governing equations to evolve these TC variables becomes impractical for real-world applications. In this work, we propose an autoencoder (AE) neural network (NN)-based reduced model to accelerate such simulations. The AE NN is first trained to find a low-dimensional latent representation of the TC states. Then, the evolving state of a chemical system can be tracked by solving the equations of the latent variables instead of the original TC equations. We demonstrate the reduced model in a syngas CO/H 2 combustion system, using training data collected from canonical perfectly stirred reactors (PSRs). It is found that the AE model can reduce the dimension of the combustion system from 12 to 2 while maintaining low reconstruction error and excellent elemental mass conservation for the test dataset. In the a posteriori test, the combustion states obtained from solving the two latent equations are compared to those from solving the 12 equations of the full model. The AE reduced method is found to be able to capture the diverse combustion states on the top two branches of the S-curve well including the extinction turning point, but with higher prediction errors for states near the ignition turning point.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1991

Surface reaction and pore diffusion in flow-tube reactors

The interaction of gas diffusion with surface reaction in porous solids is discussed and applied specifically to heterogeneous rate measurements in flow-tube reactors. External diffusion to the outer surface of a reactive solid, internal diffusion within the pores, surface reaction, and laminar flow are considered. A procedure is developed to correct observed surface rate constants for the interaction of these processes. Measured surface areas and bulk densities are used to construct a semiempirical model for porous diffusion in vapor-formed HNO3-H2O ices which are used to simulate polar stratospheric cloud surfaces. The model is tested experimentally by varying the thickness of these ices from about 15 to 120 microns. The results are consistent with the model predictions and show that the HNO3-H2O ices used are highly porous, and the internal surface must be considered in calculating kinetic parameters from observed loss rates. The best fit of the data yields a tortuosity factor of 3.3 +/-1.1 for the ice substrates.

Keyser, Leon F.↗

DOE OSTI2021

A comparative study of internal kink stability in EU DEMO designs with negative and positive triangularity

Abstract Internal kink (IK) instability is investigated for European demonstration fusion reactor (EU DEMO) plasmas in both negative triangularity (NT) and positive triangularity (PT) configurations. For NT plasmas, the IK becomes more unstable as an ideal conformal wall moves away from the plasma boundary, with the mode growth rate saturating at the wall radial location of about b / a = 1.5 , where a is the plasma minor radius and b the wall radial location. The plasma resistivity destabilizes the IK mode. The effect of sub-sonic toroidal plasma flow is sufficiently weak and can thus be ignored for these EU DEMO equilibria. These results are consistent with those for PT plasmas, albeit with larger mode growth rate in the NT configuration. Both perturbative and self-consistent magneto-hydrodynamic (MHD)-kinetic hybrid calculations predict (partial) stabilization of the IK modes in both NT and PT configurations, with inclusion of various kinetic contributions. Precessional drift motion of trapped fusion-born alphas in EU DEMO produces weak stabilization to the IK mode. Stronger stabilization occurs with the toroidal precession of trapped thermal particles (ions and electrons) and the bounce-transit motion of thermal ions. The stabilization is similar between the NT and PT configurations, due to the similarity of the mode eigenfunction (occupying a nearly circular region in the plasma core) despite the sign difference in the triangularity. The non-perturbative MHD-kinetic hybrid model predicts much less stabilization of the mode than the perturbative model, primarily due to the self-consistent determination of the mode eigenvalue in the former. Generally, no significant difference in the IK mode stability is found between the NT and PT plasmas in EU DEMO.

Physics↗

DOE OSTI2022

First-Principles Insights into the Thermocatalytic Cracking of Ammonia-Hydrogen Blends on Fe(110): 1. Thermodynamics

Ammonia (NH 3 ) is being considered as a practical means to transport hydrogen (H 2 ) because of its higher volumetric energy density for the same temperature and pressure. Thermodynamics suggest high temperature is needed to decompose NH 3 to nitrogen (N 2 ) and H 2 . Furthermore, overcoming decomposition kinetic barriers requires a catalyst. Via density functional theory, we study this reaction on a model catalyst: the close-packed (110) facet of α-Fe. Specifically, we predict detailed in-operando temperature- and pressure-dependent surface phase diagrams on this benchmark catalyst that offer insights for the design of optimal NH 3 decomposition catalysts. Here, we explore the equilibrium composition(s) of the Fe(110) surface when exposed to NH 3 –H 2 mixtures. Further, we predict that both N and NH partially cover the Fe(110) surface at 300–400 °C (far above the NH 3 decomposition-formation coexistence temperature at standard partial pressures of 1 bar: ~ 180 °C) and 2–4 bar of total reactor pressure. At the equilibrium N/NH coverage, these species inhibit coadsorption of H, indicating that direct H 2 production may occur. However, from thermodynamics alone, removal of N/NH as N 2 (g) is extremely unfavorable even at these elevated temperatures–effectively deactivating the surface toward further NH 3 decomposition. Thus, catalysts that remain active toward N–H bond breaking but with weakened N binding relative to Fe are needed to enable high-turnover catalytic NH 3 decomposition to release H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 1: Theory and numerical solution procedures

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 1 of a series of three reference publications that describe LENS, provide a detailed guide to its usage, and present many example problems. Part 1 derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved. The accuracy and efficiency of LSENS are examined by means of various test problems, and comparisons with other methods and codes are presented. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

Radhakrishnan, Krishnan↗

NASA NTRS1993

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

Fisher, John W.↗

NASA NTRS2004

Advanced Computational Modeling of Vapor Deposition in a High-pressure Reactor

In search of novel approaches to produce new materials for electro-optic technologies, advances have been achieved in the development of computer models for vapor deposition reactors in space. Numerical simulations are invaluable tools for costly and difficult processes, such as those experiments designed for high pressures and microgravity conditions. Indium nitride is a candidate compound for high-speed laser and photo diodes for optical communication system, as well as for semiconductor lasers operating into the blue and ultraviolet regions. But InN and other nitride compounds exhibit large thermal decomposition at its optimum growth temperature. In addition, epitaxy at lower temperatures and subatmospheric pressures incorporates indium droplets into the InN films. However, surface stabilization data indicate that InN could be grown at 900 K in high nitrogen pressures, and microgravity could provide laminar flow conditions. Numerical models for chemical vapor deposition have been developed, coupling complex chemical kinetics with fluid dynamic properties.

Cardelino, Beatriz H.↗

NASA NTRS2004

Advanced Computational Modeling of Vapor Deposition in a High-Pressure Reactor

Cardelino, Beatriz H.↗

DOE OSTI2024

CatTestHub: A benchmarking database of experimental heterogeneous catalysis for evaluating advanced materials

The ability to quantitatively compare newly evolving catalytic materials and technologies is hindered by the widespread availability of catalytic data collected in a consistent manner. While certain catalytic chemistries have been widely studied across decades of scientific research, quantitative comparisons based on literature information is hindered by variability in reaction conditions, types of reported data, and reporting procedures. Here, we present CatTestHub, an open-access database dedicated to benchmarking experimental heterogeneous catalysis data. Combining systematically reported catalytic activity data for selected probe chemistries, with relevant material characterization and reactor configuration information, the database provides a collection of catalytic benchmarks for distinct classes of active site functionality. Through key choices in data access, availability, and traceability, CatTestHub seeks to balance the fundamental information needs of chemical catalysis and the FAIR data design principles. Details of the database architecture and the means through which to navigate it are presented, highlighting examples of catalytic insights readily drawn from the available benchmarking data. In its current iteration, CatTestHub spans over 250 unique experimental data points, collected over 24 solid catalysts, that facilitated the turnover of 3 distinct catalytic chemistries. Here, a roadmap is presented through which to expand the open-access platform that serves as a community wide benchmark, primarily through continuous addition of kinetic information on select catalytic systems by members of the heterogeneous catalysis community at large.

Benchmark↗

DOE OSTI2024

The quest for safer nuclear fuels

Here, to increase the safety and performance of nuclear reactors, researchers are working on developing ‘accident tolerant’ fuels. Ideally, these fuel pellets will be less susceptible to swelling and be more resistant to extreme heat. This led chemists to develop uranium dioxide (UO 2 ) doped with divalent elements, E 2+ . These dopants can introduce vacancies into the lattice that lead to larger grain sizes, which create longer pathways for fission gasses to migrate out of the grains. In undoped fuel, fission gas build-up at grain boundaries causes the fuel pellet to swell. Therefore, having larger grains that slow fission gas migration into grain boundaries is highly desired. Divalent Cr 2+ ions are a commonly explored dopant for UO 2 fuels. These materials have larger grain sizes while maintaining the dissolution kinetics of undoped UO 2 , making their long-term storage and disposal paths similarly safe. Atomistic models have suggested that Mn 2+ is a conceivable alternative doping material, with the potential to increase the sizes of grains even more than Cr 2+ dopants. As such, experimental studies are required to understand the physical chemistry and reactivity of these potential fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS1988

Kinetics of the reaction OH + HO2 yields H2O + O2 from 254 to 382 K

The discharge-flow resonance fluorescence technique has been used to determine the absolute rate constant for the reaction OH + HO2 yields H2O + O2 from 254 to 382 K at a total pressure of 1 Torr. Pseudo-=first-order conditions were used with HO2 in large excess over OH. The rate constant was obtained directly from observed decays of OH and measured concentrations of HO2. Since the observed rate constant was found to be very sensitive to small background concentrations of O and H atoms, NO2 was used to remove both atom species from the system. With added NO2 the result at 299 K is (1.1 + or - 0.3) x 10 to the -10th cu cm/molecule where the error limits are one standard deviation and include an estimate of overall experimental uncertainty. The temperature dependence expressed in Arrhenius form is (4.8 + or - 0.8) x 10 to the -11th exp (250 + or - 50)/T. The results are independent of the type of reactor surface and the precursor used to produce OH and HO2. The present results agree well with earlier measurements near 1-atm total pressure and suggest that this rate constant exhibits little or no pressure dependence between 1 and 1000 Torr.

Keyser, Leon F.↗