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At least 181 records · Page 10

Probing Boron Vacancy Complexes in h-BN Semi-Bulk Crystals Synthesized by Hydride Vapor Phase Epitaxy

Hexagonal BN (h-BN) has emerged as an important ultrawide bandgap (UWBG) semiconductor (Eg~6 eV). The crystal growth technologies for producing semi-bulk crystals/epilayers in large wafer sizes and understanding of defect properties lag decades behind conventional III-nitride wide bandgap (WBG) semiconductors. Here we report probing of boron vacancy (VB)-related defects in freestanding h-BN semi-bulk wafers synthesized by hydride vapor phase epitaxy (HVPE). A photocurrent excitation spectroscopy (PES) was designed to monitor the transport of photoexcited holes from deep-level acceptors. A dominant transition line at 1.66 eV with a side band near 1.62 eV has been directly observed, which matches well with the calculated energy levels of 1.65 for the VB-H deep acceptor in h-BN. The identification of VB complexes via PES measurement was further corroborated by the temperature-dependent dark resistivity and secondary ion mass spectrometry measurements. The results presented here suggested that it is necessary to focus on the optimization of V/III ratio during HVPE growth to minimize the generation of VB-related defects and to improve the overall material quality of h-BN semi-bulk crystals. The work also provided a better understanding of how VB complexes behave and affect the electronic and optical properties of h-BN.

36 MATERIALS SCIENCE↗

GW190814's Secondary Component with Mass 2.50–2.67 M ⊙ as a Superfast Pulsar

Using Stergioulas's RNS code for investigating fast pulsars with Equation of States (EOSs) on the causality surface (where the speed of sound equals that of light) of the high-density EOS parameter space satisfying all known constraints from both nuclear physics and astrophysics, we show that one possible explanation for the GW190814's secondary component of mass (2.50-2.67) M ⊙ is that it is a super-fast pulsar spinning faster than 971 Hz about 42% below its Kepler frequency. If confirmed, it would be the fastest pulsar with the highest mass observed presently. There is a large and physically allowed EOS parameter space below the causality surface where pulsars heavier than 2.50 M ⊙ are supported if they can rotate even faster with critical frequencies depending strongly on the high-density behavior of nuclear symmetry energy.

79 ASTRONOMY AND ASTROPHYSICS↗

Time at Temperature Experiments on Neutron Irradiated Zircaloy-2 using Conventional & Flash DSC

Dryout events in Boiling Water Reactors (BWRs) are currently treated by NRC regulations as automatic disqualification for continued fuel rod operation, even though this criterion does not account for the rate or duration of power increases, associated changes in material behavior, or the possibility of rewetting. Operational history from Anticipated Operational Occurrences (AOOs) shows that short, transient power excursions often demand only modest heat removal, and industry experience suggests that fuel can briefly enter dryout yet return to safe, stable operation. The lack of detailed understanding of the material response during such events motivates the present series of experiments. This study uses unique and innovative methods to investigate microstructural evolution in irradiated Zircaloy-2 exposed to high temperatures in inert environments. Differential Scanning Calorimetry (DSC) and FlashDSC are combined to build a comprehensive experimental framework capable of identifying the a–ß phase transformation in zirconium and examining defect annealing under steep thermal gradients. FlashDSC enables rapid heating and cooling of Focused Ion Beam (FIB)–prepared large-area lift-outs (LALOs) of irradiated Zircaloy-2 at rates of 1,000 K/s to peak temperatures of 600°C, 750°C, and 900°C. The goal is to determine whether these conditions produce measurable microstructural changes that could influence cladding performance in typical BWR environments. Microstructural characterization includes quantifying dislocation density and assessing secondary phase particle (SPP) size and distribution using Transmission Electron Microscopy (TEM). Ongoing analysis, such as diffraction pattern indexing and 4D STEM processing, will further refine these observations.

36 - MATERIALS SCIENCE↗

Fuel Fabrication Specification Impact Analysis for NBSR LEU Conversion

As part of a national initiative to enhance nuclear security and reduce proliferation risks, significant efforts have been undertaken by the National Nuclear Security Administration Material Management and Minimization Office of Reactor Conversion Program to convert U.S. high performance research reactors (USHPRRs) from the use of highly enriched uranium (HEU) to low-enriched uranium (LEU), including the National Bureau of Standards Reactor (NBSR). The current plan is to procure LEU fuel assemblies from commercial fabricators according to fuel specifications tailored for each USHPRR. The analysis conducted at Brookhaven National Laboratory was part of an effort to identify the sources of uncertainty in the fuel specifications that may impact the performance of the NBSR core after its conversion and, in particular, to assess the range of acceptable tolerance limits from the perspective of core safety and reactor performance. Using the stochastic neutronics code MCNP 6.2, the variations in important NBSR neutronics characteristics were analyzed as a function of the specification parameters independently and in combination. The important NBSR specification parameters analyzed were the fuel isotopic composition, the amount of impurity content in cladding, the fuel plate thickness, and the fuel element 235U mass loading. The range of variation of each specification parameter was based on the technical specification limit or available as-fabricated assay data and uncertainties. The NBSR neutronics characteristics selected for analysis were the reactor reactivity characteristics at equilibrium and the equilibrium fuel cycle length. Results show that with variations in the fabrication parameters of the as-fabricated U-10Mo fuel within the specification limitations, the excess reactivity of the NBSR LEU core remains well below the 15% Δk/k technical specification limit, and the shutdown margin is always significantly greater than the required 0.68% Δk/k. This ensures that the NBSR can be operated safely and reliably shut down for all analyzed cases within the specified fabrication limits after the LEU conversion. In the prototypic case, the fuel cycle length was 1.5 days longer than the targeted 38.5 days. In a credible worst-case scenario, where all low-reactivity parameters were combined, the fuel cycle length was reduced to 35.5 days, which is still considered manageable for reactor operations. Variations in cycle length are primarily driven by changes in 235U loading, with other parameters having secondary effects.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Effects of γ-Irradiation, Cation Size, and Salt Concentration on the Aggregation of Boehmite Nanoplatelets

The effects of radiation on the aggregation of nanoplatelets of aluminum oxyhydroxide (boehmite) in slurries of M 1+ cation nitrates has been observed using tumbler small- and ultra-small-angle neutron scattering. Nitrate solutions of H, Li, Na, K, and Rb at concentrations of 10 -5 , 10 -3 , 10 -1 , 2, and 4 molal were compared to the results for pure H 2 O. Primary aggregates consisting of small stacks of boehmite platelets that form immediately after the boehmite is placed in water are smaller for irradiated boehmite than the pristine material. Here, the primary aggregates for irradiated boehmite also appear to have a rougher surface than those observed for unirradiated materials. Both results are possibly due to breaking of the surface OH species and a neutralization of the surface. At low salt concentrations, the pH of the irradiated boehmite slurries is lower than that of the corresponding pristine material indicating that irradiated boehmite adsorbs fewer protons or more hydroxide onto its surface than the pristine boehmite. Increasing the salt concentration decreases the pH to near neutral at 7 due to screening of the electric double layer at the solid/liquid interface. Irradiation does not seem to affect the size of secondary aggregates formed from the aggregation of primary aggregates or of the overall size of the primary aggregates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of an electric field on liquid helium scintillation produced by fast electrons

The dependence on applied electric field (0–40 kV/cm) of the scintillation light produced by fast electrons and α particles stopped in liquid helium in the temperature range of 0.44 K to 3.12 K is reported. For both types of particles, the reduction in the intensity of the scintillation signal due to the applied field exhibits an apparent temperature dependence. Using an approximate solution of the Debye-Smoluchowski equation, we show that the apparent temperature dependence for electrons can be explained by the time required for geminate pairs to recombine relative to the detector signal integration time. This finding indicates that the spatial distribution of secondary electrons with respect to their geminate partners possesses a heavy, non-Gaussian tail at larger separations and has a dependence on the energy of the primary ionization electron. Here, we discuss the potential application of this result to pulse shape analysis for particle detection and discrimination.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

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↗

Destabilizing high-capacity high entropy hydrides via earth abundant substitutions: From predictions to experimental validation

The vast chemical space of high entropy alloys (HEAs) makes trial-and-error experimental approaches for materials discovery intractable and often necessitates data-driven and/or first principles computational insights to successfully target materials with desired properties. In the context of materials discovery for hydrogen storage applications, a theoretical prediction-experimental validation approach can vastly accelerate the search for substitution strategies to destabilize high-capacity hydrides based on benchmark HEAs, e.g. TiVNbCr alloys. Here, in this study, machine learning predictions, corroborated by density functional theory calculations, predict substantial hydride destabilization with increasing substitution of earth-abundant Fe content in the (TiVNb) 75 Cr 25-x Fe x system. The as-prepared alloys crystallize in a single-phase bcc lattice for limited Fe content x < 7, while larger Fe content favors the formation of a secondary C14 Laves phase intermetallic. Short range order for alloys with x < 7 can be well described by a random distribution of atoms within the bcc lattice without lattice distortion. Hydrogen absorption experiments performed on selected alloys validate the predicted thermodynamic destabilization of the corresponding fcc hydrides and demonstrate promising lifecycle performance through reversible absorption/desorption. This demonstrates the potential of computationally expedited hydride discovery and points to further opportunities for optimizing bcc alloy ↔ fcc hydrides for practical hydrogen storage applications.

36 MATERIALS SCIENCE↗

Understanding Fission Gas Bubble Distribution and Zirconium Redistribution in Neutron-irradiated U-Zr Metallic Fuel Using Machine Learning

U-10wt.% Zr (U-10Zr) based metallic fuel is the leading candidate for next-generation sodium cooled fast reactor in United States. Currently, Idaho National Laboratory (INL) has been the leading national laboratory for research, development, and demonstration (RD&D) on metallic fuel. Advanced post-irradiation characterization will help to understand fuel microstructure and property change during irradiation, benefiting fuel qualification for commercial application. Characterization capabilities ranging from sub-nanometer to micrometer, such as scanning electron microscopy (SEM), focused ion beam (FIB) sampling, transmission electron microscopy (TEM) characterization, and local thermal conductivity microscopy (TCM), have been utilized recently on irradiated U-10Zr fuel samples to gain a better understanding of nuclear fuel microstructure and property evolution inside a reactor. The FIB/SEM coupled with energy dispersive X-ray spectroscopy (EDS) can capture the essential information to achieve better understanding of fuel behaviors. Inside a nuclear reactor, the phase and microstructure of U-10Zr is constantly changing under neutron bombardment. For example, the gaseous fission product atoms have a limited solubility inside fuel matrix and tend to precipitate out in bubble form, which not only contribute to fuel thermal conductivity degradation but also provide a shortcut for movement of fission products, i.e. lanthanides. The resultant deposition of lanthanides at the cladding inner surface will potentially trigger a chemical reaction/interaction between nuclear fuel and cladding at reactor operational conditions, threatening fuel integrity and safety. FIB/SEM coupled with EDS can provide the fission bubble information as well as probe into phase separation or Zr redistribution, which is fundamental to predict the fuel performance. With high velocity image data generating method, such as FIB/SEM, an automatic way to extract the microstructural information quantitively can better serve the needs from post irradiation characterization. A trained machine learning model, named Decision Tree, is employed to generate a bubble classifier and to categorize bubbles into three categories: isolated bubble, connected without lanthanides, and connected with lanthanides bubbles[3]. This work presents a showcase of this approach on six regions of a fuel cross-section along the radial temperature gradient. We obtained distributions of bubble categories and porosity rates along the six regions. Moreover, a secondary phase U-Zr2 was determined and found on regions 5 and 6. The secondary phase fraction was increasing from 15.61% in region 5 to 34.79% in region 6 based on this approach . This quantitative data offers insights into the lanthanide migration and potentially thermal conductivity degradation. This information from machine learning will be fed into fuel design code for better prediction of fuel performance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Integrating Machine-learning-assisted Computer Vision with RICH System

Developments in artificial intelligence have vastly expanded the capabilities of robots. Currently, the Spallation Neutron Source (SNS) beamlines at Oak Ridge National Lab (ORNL) have robotic sample loaders to increase the efficiency of running experiments. However, they require retraining if anything about the situation changes, e.g., where the samples are, and cannot notice if errors occur. So, the viability of using computer vision and machine learning to enhance these sample loaders’ functionality was investigated. In this project, the RICH system with a Dobot CR3 6-axis robot present at the VULCAN beamline assisted by an Intel Realsense D435i camera, a unique camera that enables convenient translation of 2D pixel coordinates to 3D world points, was programmed to load ceramic crucibles into a thermogravimetric analyzer (TGA) furnace. An algorithm was constructed in Python with three major phases planned: (1) obtaining a sample, (2) moving it to the target location, and then (3) bringing the sample back to its original location once the experiment finished. In the first phase, the algorithm would dynamically detect sample locations using ArUco markers to recognize the samples’ general location and a custom-trained yolov5 object detection model to locate the crucibles’ centers. Afterward, the robot would be directed to pick up samples based on the crucibles’ calculated positions. In the second phase, the robot would move the sample to a secondary point, reorient its grip, and place the sample at the target location. In the final phase, the robot would determine whether the sample was intact and would bring it back to its original place if it was or raise an alarm. Using this algorithm, the robot was able to pick up different types of crucibles at varying positions. These results indicate that integrating machine-learning-assisted computer vision with robotic sample loaders can result in effective autonomous detection of samples.

97 MATHEMATICS AND COMPUTING↗

Verification of the DIF3D Software to Support Fast Reactor Analysis

Ongoing design activities at Argonne National Laboratory are requiring a thorough verification of the Argonne Reactor Computation codes be performed. DIF3D is central to this system. The driver for this effort requires the 3D Cartesian, triangular-Z, and hexagonal-Z core geometry options of DIF3D be verified. Previous work identified the DIF3D features required to be verified to support current design activities, features of which are generally applicable to hexagonal-Z fast reactor designs. The scope of this verification effort includes verifying DIF3D’s ability to correctly translate the user’s model in to DIF3D’s preferred format, verifying that options planned for use have the desired effect, and verifying the correctness of the eigenvalue, fixed-source, forward, and adjoint solvers in DIF3D-FD and DIF3D-VARIANT. This manuscript provides the verification tasks and their results with respect to the features needed for current design activities. Since analytic solutions of the neutron diffusion and transport equations are either limited in scope or not possible, multiple tiers of problems unique to each solver and geometry type were implemented. Each of these tiers tests features independent and complementary arguments for why the separate testing of functionalities is acceptable. Finally, this separate testing was also supplemented with a high-level integral check of each the diffusion and transport capabilities and applicable geometries. To accommodate cases which an analytic solution is not feasible, MCNP6.2 was relied upon to provide a higher-order reference solution. This therefore required that the capabilities within MCNP6.2 which were relied upon for this work are also verified in this work. No MCNP discrepancies were noted in this effort. Note that the MCNP6.2 verification included in this work does not stand as a full verification of MCNP6.2, but merely verifies the features used in verifying DIF3D. The verification effort identified no issues that are debilitating or otherwise impactful to design usage of DIF3D, and thus DIF3D version 11.0, release 3012 is considered verified. The types of issues that were identified were predominantly in the areas of: unclear documentation, software bugs which were inconsequential to final results, editing options which were ignored in favor of printing more information than requested, bugs in the outputs of intermediate results, or secondary output binary file information which was not present. While not a bug, this verification report also identified that the algorithm used to evaluate the peak fast flux in a nodal transport solution can be quite unreliable due to the polynomial order used and the location of the peak within the mesh. The authors of the report therefore recommend the usage of the EvaluateFlux software (distributed with ARC) as a more robust alternative.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Analytic evaluation of hydrogen neutron elastic scattering moments with free-gas thermal treatment compared to NJOY

In this article, we present an analytic approach to evaluate Legendre moments of hydrogen neutron elastic scattering differential cross section, with and without free-gas thermal treatment. The results for the zero-th (P 0 ) and first (P 1 ) moments are given and compared against a 138-group cross sections produced by NJOY. An MCNP thin-wire test was employed as an independent verification for our analytic model for the free-gas zero-th moment. Excellent agreement was observed between the analytic result and MCNP prediction. They both suggest that an increased thermal cut-off in NJOY THERMR module is advisable for higher accuracy. Discrepancy was also found between the analytic model and NJOY multi-group cross section for the first order Legendre moments of the differential cross section, which might indicate a numerical anomaly in NJOY.

NJOY↗

Verification of the DIF3D Software to Support Fast Reactor Analysis

Ongoing design activities at Argonne National Laboratory are requiring a thorough verification of the Argonne Reactor Computation codes be performed. DIF3D is central to this system. The driver for this effort requires the 3D Cartesian, triangular-Z, and hexagonal-Z core geometry options of DIF3D be verified. Previous work identified the DIF3D features required to be verified to support current design activities, features of which are generally applicable to hexagonal-Z fast reactor designs. The scope of this verification effort includes verifying DIF3D’s ability to correctly translate the user’s model in to DIF3D’s preferred format, verifying that options planned for use have the desired effect, and verifying the correctness of the eigenvalue, fixed-source, forward, and adjoint solvers in DIF3D-FD and DIF3D-VARIANT. This manuscript provides the verification tasks and their results with respect to the features needed for current design activities. Since analytic solutions of the neutron diffusion and transport equations are either limited in scope or not possible, multiple tiers of problems unique to each solver and geometry type were implemented. Each of these tiers tests features independent and complementary arguments for why the separate testing of functionalities is acceptable. Finally, this separate testing was also supplemented with a high-level integral check of each the diffusion and transport capabilities and applicable geometries. To accommodate cases which an analytic solution is not feasible, MCNP6.2 was relied upon to provide a higher-order reference solution. This therefore required that the capabilities within MCNP6.2 which were relied upon for this work are also verified in this work. No MCNP discrepancies were noted in this effort. Note that the MCNP6.2 verification included in this work does not stand as a full verification of MCNP6.2, but merely verifies the features used in verifying DIF3D. The verification effort identified no issues that are debilitating or otherwise impactful to design usage of DIF3D, and thus DIF3D version 11.0, release 3012 is considered verified. As some additional changes have been made to the ARC software since this point all versions between release 3012 and 3266 can be considered verified as version 3253 was used for all updates in this revision. The types of issues that were identified were predominantly in the areas of: unclear documentation, software bugs which were inconsequential to final results, editing options which were ignored in favor of printing more information than requested, bugs in the outputs of intermediate results, or secondary output binary file information which was not present. While not a bug, this verification report also identified that the algorithm used to evaluate the peak fast flux in a nodal transport solution can be quite unreliable due to the methodology used and the location of the peak within the mesh. The authors of the report therefore recommend the usage of the EvaluateFlux software (distributed with ARC) as a more robust alternative noting that DIF3D will properly notify the user when the peaking values it is providing are potentially incorrect.

97 MATHEMATICS AND COMPUTING↗

Verification of the DIF3D Software to Support Fast Reactor Analysis (Rev. 3)

Ongoing design activities at Argonne National Laboratory are requiring a thorough verification of the Argonne Reactor Computation codes be performed. DIF3D is central to this system. The driver for this effort requires the 3D Cartesian, triangular-Z, and hexagonal-Z core geometry options of DIF3D be verified. Previous work identified the DIF3D features required to be verified to support current design activities, features of which are generally applicable to hexagonal-Z fast reactor designs. The scope of this verification effort includes verifying DIF3D’s ability to correctly translate the user’s model in to DIF3D’s preferred format, verifying that options planned for use have the desired effect, and verifying the correctness of the eigenvalue, fixed-source, forward, and adjoint solvers in DIF3D-FD and DIF3D-VARIANT. This manuscript provides the verification tasks and their results with respect to the features needed for current design activities. Since analytic solutions of the neutron diffusion and transport equations are either limited in scope or not possible, multiple tiers of problems unique to each solver and geometry type were implemented. Each of these tiers tests features independent and complementary arguments for why the separate testing of functionalities is acceptable. Finally, this separate testing was also supplemented with a high-level integral check of each the diffusion and transport capabilities and applicable geometries. To accommodate cases which an analytic solution is not feasible, MCNP6.2 was relied upon to provide a higher-order reference solution. This therefore required that the capabilities within MCNP6.2 which were relied upon for this work are also verified in this work. No MCNP discrepancies were noted in this effort. Note that the MCNP6.2 verification included in this work does not stand as a full verification of MCNP6.2, but merely verifies the features used in verifying DIF3D. The verification effort identified no issues that are debilitating or otherwise impactful to design usage of DIF3D, and thus DIF3D version 11.0, release 3012 is considered verified. As some additional changes have been made to the ARC software since this point all versions between release 3012 and 3266 can be considered verified as version 3253 was used for all updates in this revision. The types of issues that were identified were predominantly in the areas of: unclear documentation, software bugs which were inconsequential to final results, editing options which were ignored in favor of printing more information than requested, bugs in the outputs of intermediate results, or secondary output binary file information which was not present. While not a bug, this verification report also identified that the algorithm used to evaluate the peak fast flux in a nodal transport solution can be quite unreliable due to the methodology used and the location of the peak within the mesh. The authors of the report therefore recommend the usage of the EvaluateFlux software (distributed with ARC) as a more robust alternative noting that DIF3D will properly notify the user when the peaking values it is providing are potentially incorrect.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Thermal processing to modulate surface chemistry and bulk charge distribution in nickel-rich layered lithium positive electrodes

The broader application of nickel-rich layered oxides as positive electrode materials for lithium-ion batteries has been hindered by their high manufacturing cost and inferior cycling stability. Thermal processing, which is integral to electrode materials manufacturing and fundamental in materials science, has not been fully utilized to design advanced positive electrode materials. Herein, we demonstrate the capability of using quenching heat treatment to regulate Li distribution and modulate electronic structure near particle surface. The resulting materials exhibit less parasitic reactions with the electrolyte and an improved charge distribution homogeneity in secondary particles, leading to more stable cycling performance at high voltages (4.5 V vs Li/Li + ). Our synchrotron X-ray analyses reveal the underlying interplay between surface structure and bulk charge distribution in positive electrode materials particles. While strategies used to stabilize positive electrode materials through compositional control, surface modification, and electrolyte engineering have become mature, thermal processing can be advantageous to further improve positive electrode materials manufacturing.

36 MATERIALS SCIENCE↗

Kinetically Controlled Formation of Semi-crystalline Conjugated Polymer Nanostructures

Conjugated polymer (CP) materials that are considered as an attractive choice for various electronic and optoelectronic applications possess highly heterogeneous complex structures that can span several orders of magnitude in length scale. This is due to the intricate coupling effects of weak secondary interactions and entropic forces that determine molecular organization in bulk polymer materials. Understanding the influence of molecular interactions on the emergence and evolution of nano- and microscale structures is of paramount importance to the guided design and development of condensed CP materials. Such understanding is even more critical for the rational design of hierarchical systems away from equilibrium, where weak molecular interactions can guide the system along competing kinetic pathways toward local energy minima and metastable architectures. In this work, we studied a promising concept for accessing various kinetically stabilized semi-crystalline CP nanostructures that are formed in the process of controlled chain-growth Kumada catalyst-transfer polymerization initiated by a small-molecule catalytic species which can exist in equilibrium between free and aggregated states. Specifically, we chose a small-molecule perylenedicarboximide (PDCI) polymerization catalytic initiator which has a strong tendency toward reversible supramolecular assembly–disassembly that can be controlled by temperature. Addition of a thiophene monomer to a solution of the PDCI initiator starts the chain-growth polymerization process, which produces distinct nanoscale semi-crystalline polythiophene structures formed under predominant kinetic control. Furthermore, we demonstrated that, depending on the reaction temperature (which affects the fine balance between the position of PDCI assembly–disassembly equilibrium, rate of polymerization, and solvent–solute interactions for the growing polythiophene chains), a range of kinetically trapped hierarchically organized semi-crystalline CP systems with substantially varying optoelectronic properties could be obtained. In addition to spectroscopic and electron microscopic studies, in order to better reveal the structural aspects of the generated polymer nanoscale systems, we carried out a series of X-ray diffraction and neutron scattering experiments which indicated complex hierarchical organization in these kinetically stabilized CP assembled materials. We expect that this in situ polymerization-based approach can lead to a general way to expand access to various semi-crystalline CP nanostructured materials with broadly tunable electronic and optical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneous fatigue damage in a nickel-based single-crystal superalloy unraveled using correlative 3D X-ray technology

Nickel-based single-crystal (Ni-SX) superalloys under cyclic stress are susceptible to cracking at stress-concentration sites, eventually leading to low-cycle fatigue (LCF) failure. LCF cracks typically originate from intrinsic defects (e.g., voids and carbides) within solidified dendrites. However, systematic quantitative experimental analyses of defect-mediated local damage remain limited. To thoroughly understand the microscopic origins and evolution of LCF damage, correlated 3D mapping of dendrites across various regions is essential. Here, in this study, macroscale micro-computed tomography (μ-CT) was initially used to capture internal interdendritic secondary cracks within bulk DD413 superalloy after LCF testing at 760 °C. Subsequently, a multimodal methodology combining synchrotron 3D microdiffraction (3D-μXRD), high-resolution μ-CT, and electron microscopy was established. This approach allowed precise localization of internal damage zones near interdendritic secondary cracks and detailed mapping of the 3D correlated distributions of dendrites, defects, and residual stress/strain fields within these zones at submicron spatial resolution. Finally, the same approach was applied to specimens subjected to interrupted loading at approximately 40 % of the fatigue life to uncover the early damage states of dendrites. The dendrite cores (DCs) and interdendritic regions (IDs) exhibit microscale heterogeneous mechanical responses: nearly defect-free DCs accumulate local irreversible slip along specific slip systems to generate slip bands, while the IDs containing various defects accommodate local microplasticity through the activation of multiple slip systems around these defects. The local tensile stress near defects in the IDs exceeds that in the DC slip band regions by more than threefold, leading to the generation of local damage zones within the IDs. Chain-like defect distributions facilitate the interconnection of these local zones into a continuous damage region, further elevating the overall tensile stress in the IDs. Additionally, geometrically necessary dislocations alone are insufficient as indicators of LCF damage; both the internal stress state and its magnitude must be considered. These experimental results provide critical data and insights for the development of multi-physics fatigue models.

Localized deformation↗