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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

Thermal and evolved gas analyzer

The Thermal and Evolved Gas Analyzer (TEGA) instrument will perform calorimetry and evolved gas analysis on soil samples collected from the Martian surface. TEGA is one of three instruments, along with a robotic arm, that form the Mars Volatile and Climate Survey (MVACS) payload. The other instruments are a stereo surface imager, built by Peter Smith of the University of Arizona and a meteorological station, built by JPL. The MVACS lander will investigate a Martian landing site at approximately 70 deg south latitude. Launch will take place from Kennedy Space Center in January, 1999. The TEGA project started in February, 1996. In the intervening 24 months, a flight instrument concept has been designed, prototyped, built as an engineering model and flight model, and tested. The instrument performs laboratory-quality differential-scanning calorimetry (DSC) over the temperature range of Mars ambient to 1400K. Low-temperature volatiles (water and carbon dioxide ices) and the carbonates will be analyzed in this temperature range. Carbonates melt and evolve carbon dioxide at temperatures above 600 C. Evolved oxygen (down to a concentration of 1 ppm) is detected, and C02 and water vapor and the isotopic variations of C02 and water vapor are detected and their concentrations measured. The isotopic composition provides important tests of the theory of solar system formation.

Williams, M. S.↗
NASA NTRS1997

Development of Large Area Emulsion Chamber Methods with a Super Conducting Magnet for Observation of Cosmic Ray Nuclei from 1 GeV to 1,000 TeV (Emulsion Techniques)

The research developed the fundamental techniques of the emulsion chamber methods that permit measurements of the composition and energy spectra of cosmic rays at energies ranging from 1 GeV/n to over 1,000 TeV/n. The research program consisted of exploring new principles and techniques in measuring very high energy cosmic nuclei with large-area emulsion chambers for high statistics experiments. These tasks have been accomplished and their use was essential in successful analysis of the balloon-borne emulsion chamber experiments up to 10(exp 14) eV. It also provided the fundamental technologies for designing large-area detectors that are aimed at measuring the composition at above 1015 eV region. The latter is now partially succeeded by a NASA Mission Concept, Advanced Cosmic Composition Experiments on the Space Station (ACCESS). The cosmic ray group at the University of Alabama in Huntsville has performed technological R & D as well as contributing to the Japanese-American-Emulsion-Chamber-Experiments (JACEE) Collaboration with the regular data analysis. While primary research support for other institutions' efforts in the JACEE experiments came from NSF and DOE, primary support for the University of Alabama in Huntsville was this contract. Supplemental tasks to standardize the data base and hardware upgrades (automatized microscope) had this institutions cooperation. Investigation of new techniques in this program consisted of development of a fast calorimetry, magnetic/scattering selection of high momentum tracks for a pairmeter, and high statistics momentum measurements for low energy nuclei (E < 1 TeV/n). The highest energy calorimetry and a pairmeter have been considered as strawman instruments by the GOAL (Galactic Origin and Acceleration Limit) proposal of the NASA Cosmic Ray Working Group for long- duration balloon flights. We accomplished the objectives of the GOAL program with three circumpolar, Antarctic JACEE balloon flights during 1992 - 1994.

Takahashi, Yoshiyuki↗
NASA NTRS1999

Microcalorimetric Measurements of Hydrogen Peroxide Stability

Recent interest in propellants with nontoxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because hydrogen peroxide is sensitive to contaminants and materials interactions, stability and shelf life are issues. A relatively new, ultrasensitive heat measurement technique, isothermal microcalorimetry, is being used at the White Sands Test Facility to monitor the decomposition of hydrogen peroxide at near ambient temperatures. Isothermal microcalorimetry measures the beat flow from a reaction vessel into a surrounding heat sink. In these applications, microcalorimetry is approximately 1,000 times more sensitive than accelerating rate calorimetry or differential scanning calorimetry for measuring thermal events. Experimental procedures have been developed for the microcalorimetric measurement of the ultra-small beat effects caused by incompatible interactions of hydrogen peroxide. The decomposition rates of hydrogen peroxide at the picomole/sec/gram level have been measured showing the effects of stabilizers and peroxide concentration. Typical measurements are carried out at 40 C over a 24-hour period, This paper describes a method for the conversion of the heat flow measurements to chemical reaction rates based on thermochemical considerations. The reaction rates are used in a study of the effects of stabilizer levels on the decomposition of propellant grade hydrogen peroxide.

Davis, Dennis D.↗
NASA NTRS2000

Radioprotective Thiolamines WR-1065 and WR-33278 Selectively Denature Nonhistone Nuclear Proteins

Differential scanning calorimetry was used to study the interactions of nuclei isolated from Chinese hamster V79 cells with the radioprotector WR-1065, other thiol compounds, and polyamines. Differential scanning calorimetry monitors denaturation of macromolecules and resolves the major nuclear components (e.g. constrained and relaxed DNA, nucleosome core, and nuclear matrix) of intact nuclei on the basis of thermal stability. WR-1065 treatment (0.5-10 mM) of isolated nuclei led to the irreversible denaturation of nuclear proteins, a fraction of which are nuclear matrix proteins. Denaturation of 50% of the total nonhistone nuclear protein content of isolated nuclei occurred after exposure to 4.7 mM WR-1065 for 20 min at 23 C. In addition, a 22% increase in the insoluble protein content of nuclei isolated from V79 cells that had been treated with 4 mM WR-1065 for 30 min at 37 C was observed, indicating that WR-1065-induced protein denaturation occurs not only in isolated nuclei but also in the nuclei of intact cells. From the extent of the increase in insoluble protein in the nucleus, protein denaturation by WR-1065 is expected to contribute to drug toxicity at concentrations greater than approximately 4 mM. WR-33278, the disulfide form of WR1065, was approximately twice as effective as the free thiol at denaturing nuclear proteins. The proposed mechanism for nucleoprotein denaturation is through direct interactions with protein cysteine groups with the formation of destabilizing protein-WR-1065 disulfides. In comparison to its effect on nuclear proteins in isolated nuclei, WR-1065 had only a very small effect on non-nuclear proteins of whole cells, isolated nuclear matrix, or the thiol-rich Ca (2+) ATPase of sarcoplasmic reticulum, indicating that WR-1065 can effectively denature protein only inside an intact nucleus, probably due to the increased concentration of the positively charged drug in the vicinity of DNA.

Booth, Valerie K.↗
NASA NTRS2003

Design and Performance Tests of Ultra-Compact Calorimeters for High Energy Astrophysics

This R&D project had two goals: a) the study of general-application ultra-compact calorimetry technologies for use in High Energy Astrophysics and, b) contribute to the design of an efficient calorimeter for the ACCESS mission. The direct measurement of galactic cosmic ray fluxes is performed from space or from balloon-borne detectors. Detectors used in those studies are limited in size and, specially, in weight. Since galactic cosmic ray fluxes are very small, detectors with high geometrical acceptances and long exposures are usually required for collecting enough statistics. We have studied calorimeter techniques that could produce large geometrical acceptance per unit of mass (G/w) and that may be used to study galactic cosmic rays at intermediate energies (knee energies).-The most important asset for detection of primary cosmic rays at and about the knee is large acceptance. To construct a large acceptance calorimeter (this term is used here in its most general accepted meaning of calorimeter as a device to measure particle energies ) the detector needs to be verv liaht or verv shallow . We studied two possible technologies to built compact calorimeters: the use of lead-tungstate crystals (PWO) and the use of sampling calorimetry using scintillating fibers embedded in a matrix of powder tungsten. For a very light detector, we considered the possibility of using Optical Transition Radiation (OTR) to measure the energy (and perhaps also direction and identity) of VHE cosmic rays.

Salgado, Carlos W.↗
NASA NTRS2005

Flammability of Epoxy Resins Containing Phosphorus

As part of a program to develop fire-resistant exterior composite structures for future subsonic commercial and general aviation aircraft, flame-retardant epoxy resins are under investigation. Epoxies and their curing agents (aromatic diamines) containing phosphorus were synthesized and used to prepare epoxy formulations. Phosphorus was incorporated within the backbone of the epoxy resin and not used as an additive. The resulting cured neat epoxy formulations were characterized by thermogravimetric analysis, propane torch test, elemental analysis, microscale combustion calorimetry, and fire calorimetry. Several formulations showed excellent flame retardation with phosphorous contents as low as 1.5% by weight. The fracture toughness and compressive strength of several cured formulations showed no detrimental effect due to phosphorus content. The chemistry and properties of these new epoxy formulations are discussed.

Flammability studies↗
NASA NTRS1996

Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition reactions of FORP compositions used in this study were unremarkable, Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant-system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid MMH and liquid NTO in a confined space. The test hardware was constructed with pressure- and temperature-measurement devices to determine if the expected fuel oxidizer reaction would result in increased energy release when FORP, FORP constituents, or propellant-system corrosion products were present. These tests demonstrated that FORP, MMHN, AN, or Inconel corrosion products can induce a mixture of MMH and NTO to produce component-damaging energies. The simulation-test program was not extensive enough to provide statistical probabilities for these events but did show that such events can occur. Damaging events required FORP or metal salts to be present at the initial mixing of MMH and NTO. Based on the results of these studies, it is suggested that removal or mitigation of a buildup of these materials may decrease the incidence of these high-energy, potentially damaging events.

Source record↗
NASA NTRS2017

Partitioning of F and Cl Between Apatite and a Synthetic Shergottite Liquid (QUE 94201) at 4 Gpa from 1300 TO 1500 C

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (Xsite), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to accurately determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multicomponent silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al., recently reported that the exchange coefficients vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing, and McCubbin et al. reported substantial deviations in the Cl-F exchange Kd along the F-Cl apatite join that could be explained by the preferential incorporation of F into apatite. In the present study, we assess the effect of apatite crystal chemistry on F-Cl exchange equilibria between apatite and melt at 4 GPa over the temperature range of 1300-1500 C. The goal of these experiments is to assess the variation in the Ap-melt Cl-F exchange Kd over a broad range of F:Cl ratios in apatite. The results of these experiments could be used to understand at what composition apatite shifts from a hexagonal unit cell with space group P63/m to a unit cell with monoclinic symmetry within space group P21/b. We anticipate that this transition occurs at >70% chlorapatite based on solution calorimetry data.

McCubbin, F. M.↗
NASA NTRS2016

Below Ambient and Cryogenic Thermal Testing

Methods and apparatus for the testing of below-ambient temperature thermal insulation systems have been developed based on boiloff calorimetry. Boiloff calorimetry provides a direct measure of heat flow for below-ambient temperature conditions. The effective thermal conductivity (ke) and heat flux (q) of a test specimen are calculated for a fixed environmental condition (warm boundary temperature; cold boundary temperature; ambient or vacuum pressure). Through its heat of vaporization, liquid nitrogen (LN2) serves as the energy meter. Different apparatus have been built for flat-plate, cylindrical, and pipeline test specimens. Boundary temperatures can range from 353 K down to 77 K (80 C to -196 C). By interposing different insulation layers on the cold boundary, the cryogenic boiloff method is suitable for a wide range of below-ambient temperature applications. A cylindrical apparatus, Cryostat-100, as well as the pipeline test apparatus, Cryostat-P100, are thermally guarded and directly measure absolute thermal performance in watts. Pipe insulation systems can be mechanical, double-walled, or vacuum-jacketed including materials such as foams, cellular glass, aerogel blankets, clam-shell panels, and multilayer insulation. Two test pipelines, 12-meter-long, are mounted between two cold box assemblies. The test pipeline diameter is from 25-mm to 76-mm while the maximum outside diameter including insulation is up to 204-mm. The cold pipe tester design and test methods are discussed, as well as results for select thermal insulation materials. Progress toward a comparative type, bench-top cold pipe tester (Cryostat-P200) is also discussed.

Fesmire, James E.↗
NASA NTRS2019

Thermochemistry of Protective Coatings and Molten Silicate Debris

The durability of gas-turbine engine components can be significantly affected by the ingestion of siliceous particles, which can melt at high temperature and corrode protective coatings that are essential for long life requirements. The silicate debris consists mainly of CaO-MgO-Al2O3-SiO2 (CMAS) and is usually ingested by aircraft engines during and after take-off, sticking to their hot surfaces and resulting in the formation of calcium rare-earth silicate oxyapatites. The thermochemistry of coatings and their reaction products with molten silicate debris are crucial to understand in order to improve the durability of gas-turbine engines. Here we discuss results of high temperature drop solution calorimetry, drop-and-catch calorimetry (DnC) and differential thermal analysis (DTA) techniques for the thermodynamic properties of both thermal barrier coatings (TBCs) and environmental barrier coatings (EBCs) and their reaction with CMAS compositions. The enthalpies of solution of Y2Si2O7, Yb2Si2O7, 31YSZ, and 16RESZ based coatings and the oxyapatite are moderately positive. However, oxyapatite formation is only favorable over coating dissolution in terms of enthalpy for 7YSZ. The enthalpies of mixing between the coatings and the molten silicate are less exothermic for Yb2Si2O7 and CaYb4Si3O13 than for 7YSZ, indicating lower energetic stability of the latter against molten silicate corrosion. We also report for the first time the calorimetric measurements of the enthalpies of formation of rare-earth silicate based EBC coatings and oxyapatites (rare-earth, RE = Y, Yb, Gd, Dy, Er, Nd and Sm).

Costa, Gustavo↗
NASA NTRS2020

Calorimetric Measurements of the Thermodynamic Properties of RE-Silicate Coating Materials

Thermodynamic quantities of coatings materials and siliceous debris-induced corrosion products are crucial to understand in order to develop mitigation strategies necessary to improve the durability of gas-turbine engines. Siliceous induced corrosion can occur when debris consisting mainly of CaO-MgO-Al2O3-SiO2 (CMAS) is ingested by aircraft engines during and after take-off, which sticks to hot surfaces and forms calcium rare-earth silicate oxyapatites. In this work, high-temperature oxide melt drop solution calorimetry (HT drop solution calorimetry) was used to obtain the enthalpies of formation for RE silicate (RE2Si2O7, RE2SiO5 where RE = Yb, Er, Y, Dy, Nd, Lu and Gd) environmental barrier coatings (EBCs) and the calcium RE silicate oxyapatite Ca2RE8(SiO4)6O2 (RE = Yb, Er, Y, Dy, Nd, Gd and Sm) corrosion products. Trends in the enthalpy of formation as a function of the ionic potential of the rare-earth cations in their related crystallographic sites are discussed.

Costa, Gustavo↗
NASA NTRSDate not supplied

Battery Failure Databank

The Battery Failure Databank contains thermal runaway results gathered from nearly 300 small format fractional thermal runaway calorimetry (S-FTRC) experiments. A majority of these experiments were conducted at synchrotron facilities where high-speed x-ray videography was conducted of the cell while tested inside of the S-FTRC. The databank is a two-component system which consists of a Microsoft ExcelTM spreadsheet which provides S-FTRC results in tabular format and a radiographic video library containing the high-speed x-ray videos. Overall, the databank provides thermal results from S-FTRC experiments conducted on a mixture of commercially available lithium-ion (Li-ion) cells and specialized Li-ion test cells with varying cell format (18650, 21700, and D-cell) and trigger mechanism (heaters, heaters plus internal short circuiting device, and nail penetration). The radiography video component provides insight into the initiation and propagation of TR in the cells, in addition to consequences of TR measured by the FTRC. Fractions of mass ejected for the cell types are separated into regimes based on the different failure modes of the cells, such as purely venting, partial ejection, and total ejection. With knowledge of the rate and characterization of the internal degradation of the cells during TR, and the amounts of mass ejected and unrecovered, the extent of TR, and therefore the mitigation of TR, is revealed relative to cell types and failure modes.

Lithium-ion battery↗
DOE OSTI2024

Understanding the stability of a plastic‐degrading Rieske iron oxidoreductase system

Abstract Rieske oxygenases (ROs) are a diverse metalloenzyme class with growing potential in bioconversion and synthetic applications. We postulated that ROs are nonetheless underutilized because they are unstable. Terephthalate dioxygenase (TPA DO PDB ID 7Q05 ) is a structurally characterized heterohexameric α 3 β 3 RO that, with its cognate reductase (TPA RED ), catalyzes the first intracellular step of bacterial polyethylene terephthalate plastic bioconversion. Here, we showed that the heterologously expressed TPA DO /TPA RED system exhibits only ~300 total turnovers at its optimal pH and temperature. We investigated the thermal stability of the system and the unfolding pathway of TPA DO through a combination of biochemical and biophysical approaches. The system's activity is thermally limited by a melting temperature ( T m ) of 39.9°C for the monomeric TPA RED , while the independent T m of TPA DO is 50.8°C. Differential scanning calorimetry revealed a two‐step thermal decomposition pathway for TPA DO with T m values of 47.6 and 58.0°C (Δ H = 210 and 509 kcal mol −1 , respectively) for each step. Temperature‐dependent small‐angle x‐ray scattering and dynamic light scattering both detected heat‐induced dissociation of TPA DO subunits at 53.8°C, followed by higher‐temperature loss of tertiary structure that coincided with protein aggregation. The computed enthalpies of dissociation for the monomer interfaces were most congruent with a decomposition pathway initiated by β‐β interface dissociation, a pattern predicted to be widespread in ROs. As a strategy for enhancing TPA DO stability, we propose prioritizing the re‐engineering of the β subunit interfaces, with subsequent targeted improvements of the subunits.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Kinetics of amorphous defect phases measured through ultrafast nanocalorimetry

Recognition of the role of extended defects on local phase transitions has led to the conceptualization of the defect phase, localized thermodynamically stable interfacial states that have since been applied in a myriad of material systems to realize significant enhancements in material properties. Here, we explore the kinetics of grain boundary confined amorphous defect phases, utilizing the high temperature and scanning rates afforded by ultrafast differential scanning calorimetry to apply targeted annealing/quenching treatments at high rates capable of capturing the kinetic behavior. Four Al-based nanocrystalline alloys, including two binary systems, Al–Ni and Al–Y, and two ternary systems, Al–Mg–Y and Al–Ni–Y, are selected to probe the materials design space (enthalpy of mixing, enthalpy of segregation, chemical complexity) for amorphous defect phase formation and stability, with correlative transmission electron microscopy applied to link phase evolution and grain stability to nanocalorimetry signatures. A series of targeted isothermal annealing heat treatments is utilized to construct a Time–Temperature-Transformation curve for the Al–Ni system, from which a critical cooling rate of 2400 °C/s was determined for the grain boundary confined disordered-to-ordered transition. Finally, a thermal profile consisting of 1000 repeated annealing sequences was created to quantify the recovery of the amorphous defect phase following sequential annealing treatments, with results indicating remarkable microstructural stability after annealing at temperatures above 90% of the melting temperature. This work contributes to a deeper understanding of grain boundary localized thermodynamics and kinetics, with potential implications for the design and optimization of advanced materials with enhanced stability and performance.

Amorphous defect phases↗
DOE OSTI2025

High-temperature stability and thermal expansion behavior of equi-atomic refractory multi-principal element alloys based on MoNbTi system for Gen IV reactor applications

The present study investigates the thermal stability and thermal expansion behavior of seven equi-atomic refractory multi-principal element alloys (MPEAs) based on the MoNbTi ternary system composed of low neutron absorption cross section elements. Through an integrated approach utilizing in-situ high-temperature X-ray diffraction (HT-XRD) in conjunction with differential scanning calorimetry (DSC), dilatometry and ageing heat treatment, the thermal stability of the MPEAs was comprehensively analyzed. In-situ HT-XRD experiment confirmed the stability of the room temperature phases up to 1000 °C with no peaks observed corresponding to additional phases in the HT-XRD patterns at 500, 800 and 1100 °C. DSC thermograms showed the absence of peaks up to 1000 °C, while peaks and valleys corresponding to exothermic and endothermic events were observed above 1000 °C. Coefficient of thermal expansion (CTE) derived from second order polynomial fitting of linear thermal expansion data from the dilatometry experiment showed linear increment up to 1000 °C for all the alloys except those containing Zr. The Cr containing alloys exhibited notably higher CTE values, particularly the Al containing alloy exhibited the highest value. Ageing heat treatment at 800 and 1000 °C for 96 h and subsequent microstructural analysis revealed significant precipitation of secondary phases in MoNbTiZr, MoNbTiZrV and MoNbTiCrAl. In conclusion, a substantial increase in hardness was observed in MoNbTiZr and MoNbTiCrAl due to secondary phase precipitation, while the other alloys maintained hardness values comparable to their as-cast and homogenized states.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Probing thermodynamics of radiogenic helium and defects in $δ$-plutonium alloys and interactions with adsorbed environmental gases

Differential scanning calorimetry coupled with simultaneous evolved gas analysis (DSC-EGA) on aged δ-Pu samples shows that most radiogenic helium remains trapped within the Pu matrix at temperatures very close to, or slightly above, the melting temperature. Our results indicate that helium release from 50-year-old δ-Pu occurs as a burst just below the melting temperature (>0.994 T m ), with subsequent pressure oscillations as temperature increases. Subordinate quantities of H 2 were also released along with helium. Here, the helium emission tails off and ceases above ~720 – 750°C. In a δ-Pu alloy aged 6 years, the initial helium burst occurs slightly above melting (~1.015 – 1.042 T m ), with a discrete, larger helium spike occurring between 670 and 686°C. The proximity of helium release to the liquidus transition presented challenges in the deconvolution of overlapping process enthalpies, the liquidus endotherm, and the exotherm resulting from bubble collapse, annealing and gas expulsion. Helium’s strong affinity for vacancy binding in a 2He-vac configuration is predicted by Density Functional Theory (DFT) modeling. The measured stored energy associated with the He release events in a 50-year-old δ alloy is on the order of ~ 10–11 J/g, which is significantly higher than stored energies measured in the sub-solidus regimes (~2 J/g) that are related to the solid-state annealing of processing- and radiation-induced defects. This implies that aged δ Pu alloys have a remarkable resilience to accommodate the lattice strain produced by the internal pressure of the helium bubbles and provides further insight into the thermodynamic behavior of aged δ Pu.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Structural basis of heme scavenging by the ChtA and HtaA hemophores in Corynebacterium diphtheriae

Corynebacterium diphtheriae causes diphtheria, a potentially fatal infectious disease that damages tissues in the upper respiratory tract. In order to proliferate, this pathogen acquires the essential nutrient iron from heme (iron-protoporphyrin IX) primarily found in human hemoglobin (Hb). C. diphtheriae secretes ChtA and HtaA hemophore proteins that bind ferric heme (hemin) via conserved region (CR) domains. Here, we demonstrate that their CR domains scavenge hemin after it is spontaneously released from Hb, and define the structural basis of hemin binding to ChtA and the N-terminal CR domain from HtaA by determining X-ray crystal structures of their protein-hemin complexes. Resonance Raman and electron paramagnetic resonance experiments demonstrate that the CR domains from ChtA and HtaA engage in pentacoordinate hemin binding through a conserved iron-tyrosyl linkage, though variations in their hemin pockets alter the way they stabilize the axial tyrosine and mask hemin’s metal. The importance of these interactions is probed using isothermal titration calorimetry experiments, which represent the first quantitative assessment of CR-hemin affinity and reveal that ChtA binds hemin via an enthalpically driven process. Hemin partitioning experiments using native mass spectrometry demonstrate that the cohort of CR domains within C. diphtheriae ’s hemin-uptake system have dissociation constants for hemin between 0.8 and 22 nM, raising the possibility that affinity differences contribute to the directional flow of hemin into the cell. Collectively, the results of this work provide insight into how C. diphtheriae and other pathogenic and commensal corynebacterium species utilize CR domains to scavenge iron rich hemin from their environment.

Corynebacterium diphtheriae↗
DOE OSTI2025

A critical analysis of U-Pu-Zr phase transitions using calorimetric, microstructural, and phase equilibria data

Metallic fuels consisting primarily of uranium, plutonium, and zirconium (U-Pu-Zr) are a leading material candidate for fast-spectrum nuclear reactors. Early demonstration programs proved the principle of safe and efficient fast reactor operation, however there is still considerable uncertainty regarding the phase equilibria and microstructural evolution across the ternary composition space. Quantitative phase formation and identification measurements are scarce and often incomplete, with studies reporting either phase transition temperatures or phase identification data, but not both from the same specimens. In this study, we critically compared experimental and calculated phase transition data and correlated with the microstructure and phase characterization data of as-cast and annealed U-Pu-Zr alloys. Differential scanning calorimetry (DSC) was used to measure phase transitions in the subsolidus regions (723−948 K) of three ternary U-Pu-Zr alloys with similar plutonium concentrations but various U/Zr ratios. Due to sluggish kinetics and narrow ranges of phase stability, complex peaks required the use of a Frazier-Suzuki peak fitting algorithm to deconvolute and calculate transition peak temperatures and enthalpies. We also identified trends of phase transition behavior by critically comparing our DSC data with previous phase transition measurements as well as historical and calculated phase equilibrium diagrams. In conclusion, this provides a critical approach for benchmarking and assessing the quality of new U-Pu-Zr phase equilibria data prior to its incorporation into nuclear material databases.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗