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At least 703 records · Page 39

Survivability of Affordable High Temperature Polymer Matrix Composites for Propulsion Engine Components

PMR-type polyimides are regarded as state of the art high temperature polymers, due to their excellent thermo-mechanical properties and thermo-oxidative stability. One of their drawbacks, however is the inability to process them using cost-effective processing methods such as Resin Transfer Molding (RTM) and Resin Film Infusion (RFI). Development of low viscosity, high temperature polymers has been the subject of intense research. Recently, a new generation of low viscosity polyimides were synthesized by the introduction of twisted biphenyl or binapthyl groups into the backbone. This report details the progress for Year 1, which has involved acquiring samples and initiating Phases I and II of the proposed research. Specifically, studies of the process-property relationships of a series of polymers using oligomers based on 2,3,3' ,4'-biphenyltertracarboxylic dianhydride (PBDA) and a mixture of a diamine, BAX and a triamine, 1,3,5-Tris (4-aminophenoxybenzene), TAB, where the amount of TAB was varied have been initiated. The sample containing 10 percent TAB possesses a slightly higher degree of crystalline order versus that of the 20 percent TAB sample, based on x-ray diffraction studies of the b-staged oligomers. Both systems lose all of the crystalline order upon curing, however. The chemorheology has been studied as a function of the TAB content. While the magnitude of the viscosity is essentially the same for both systems, the cure kinetics of the 10 percent TAB system is faster than that for the 20 percent TAB system. The sample exhibits a melting-recrystallization-remelting behavior before the crosslinking commences. Correlation of other kinetic parameters, such as the activation energies for curing, the Tg and mechanical properties to the structure of these systems is underway. Future studies will involve characterization of mechanical and thermal properties of the pure resins and the fabrication of fiber reinforced composites using these materials.

Dean, Derrick↗

Comparison of two methods of performing the Thellier experiment

Two methods for performing the Thellier experiment on paleointensity determinations are compared. The first method is essentially that of Coe (1967) and the second is a slight modification of it. Prepared samples containing different species of magnetic particles are used, and both methods are always performed on the same sample. The study is designed to accent procedural differences between the two methods. It is shown that only the Coe method yields linear PNRM-PTRM (Partial ThermoRemanent Magnetization) plots for single domain and pseudo-single domain particles, because it maintains the symmetry between high-temperature VRM (Viscous Remanent Magnetization) and spontaneous decay, whereas for the modified Coe method the spontaneous decay is enhanced. For multidomain remanence, even the Coe method yields a nonlinear concave-up PNRM-PTRM plot. Paleointensity determinations employing only the ratio NRM/TRM provide no means of evaluating the reliability of the results.

Levi, S.↗

Lessons Learned in Employing Data Analytics to Predict Oxidation Kinetics and Spallation Behavior of High-Temperature NiCr-Based Alloys

Machine learning (ML) can offer many advantages in predicting material properties over traditional materials development methods based solely on limited experimental investigations or physical-based simulations with the capability to reduce development cost, risk, and time. However, so far, limited efforts have been made to predict alloy oxidation kinetics and spallation behavior via ML due to the lack of consistently measured and sufficient experimental data and the inherent complexity in oxidation behavior of multicomponent high-temperature alloys. A previous study reported the ability of ML to predict oxidation kinetics of NiCr-based alloys as a function of alloy composition and operating conditions. Here, the performance of a ML model in predicting rate constants and spallation probability was evaluated in light of the roles of the data distribution of the experimental dataset (data analytics), the alloy composition, the exposure environment and the chosen oxidation approach to extracting kinetic values from the measured mass changes (but using either a simple parabolic law or a statistical cyclic oxidation model). Potential strategies to improve the predictions and enhance the extrapolative capability of the previously trained model will be discussed.

36 MATERIALS SCIENCE↗

Alternative Solid‐State Synthesis Route for Highly Fluorinated Disordered Rock‐Salt Cathode Materials for High‐Energy Lithium‐Ion Batteries

Abstract Fluorination has been identified as a key element for enabling the stable cycling of earth‐abundant manganese‐based disordered rock salt (DRX) cathodes. However, fluorination in the DRX bulk remains a challenge for scalable solid‐state synthesis. In this study, a tailored reaction pathway is proposed to synthesize a highly fluorinated DRX. It is demonstrated for the first time that the unconventional precursors, Li 6 MnO 4 , MnF 2 , and TiO 2 , can avoid the formation of Mn‐based intermediates (such as Li 2 (Mn,Ti)O 3, LiMnO 2 , and Mn 3 O 4 ), which, once formed, persist until the synthesis temperature reaches close to or above that required for fluorine volatility. Therefore, this method can form a highly fluorinated DRX with a composition of Li 1.23 Mn 0.40 Ti 0.37 O 2−y F y ( y = 0.29–0.34) at a low temperature (800 °C) relative to that required for conventional DRX solid‐state reactions (≥900 °C). Li 1.23 Mn 0.40 Ti 0.37 O 2−y F y ( y = 0.29–0.34) delivers a specific capacity above 300 mAh g −1 and a specific energy of 980 Wh kg −1 at 30 °C. Detailed characterization reveals that this DRX phase reversibly utilizes Mn 2+/3+ redox in the low‐voltage region and Mn 3+/4+ redox in the middle‐voltage range, whereas reversible oxygen redox is observed at high potentials.

Avvaru, Venkata Sai↗

Design, Fabrication, and Screening of Environmental‐Thermal Barrier Coatings Prepared by Ultrafast High‐Temperature Sintering

Abstract The demand for more efficient gas turbines relies heavily on the development of new environmental‐thermal barrier coatings (ETBCs). However, there is still uncertainty about which alloys and composites will be used for the next generation of turbine blades, as well as the most promising coating materials. Herein, an ETBCs development strategy is presented by integrating the coating design, synthesis, and screening using an ultrafast high temperature sintering (UHS) technique to accelerate coating improvements. The initial basis for composition selection is their thermal expansion mismatch with the substrate alloys; for which a temperature‐dependent coefficient of thermal expansion database is created. By combining tape casting method with the UHS technique a high‐throughput synthesis of single and multi‐layer coatings are realized with different compositions, layer stacking sequences, and layer thicknesses. To evaluate the coatings, thermal cycling tests from room temperature to 1300 °C are conducted. The approach enabled coatings on objects with complex geometries, multi‐layer ETBCs, and porosity tailoring by using staged UHS that runs with different temperatures and durations. The fast iteration strategy is more cost‐effective for the screening of ETBCs compared to conventional methods and greater throughput which can be further extended for rapid optimization of other materials systems.

Xie, Hua↗

Measurement of Seebeck coefficient using a light pulse

A high-temperature (1900 K) Seebeck coefficient apparatus is described in which small thermal gradients are generated in a sample by light pulses transmitted via light pipes. By employing an analog subtraction circuit, the Seebeck coefficient is displayed directly on an X-Y recorder. This technique presents a convenient, accurate, and rapid method for measuring the Seebeck coefficient in highly doped semiconductors as a function of temperature. The nature of the resulting display (X-Y recording) is a valuable tool in determining validity of the data. A straight line results (i.e., a minimum of hysteresis) only if all potential experimental errors are minimized. Under these conditions, the error of measurements of the Seebeck coefficient is estimated to be less than + or - 1 percent.

Wood, C.↗

Mechanical Properties of T650-35/AFR-PE-4 at Elevated Temperatures for Lightweight Aeroshell Designs

Considerable efforts have been underway to develop multidisciplinary technologies for aeroshell structures that will significantly increase the allowable working temperature for the aeroshell components, and enable the system to operate at higher temperatures while sustaining performance and durability. As part of these efforts, high temperature polymer matrix composites and fabrication technologies are being developed for the primary load bearing structure (heat shield) of the spacecraft. New high-temperature resins and composite material manufacturing techniques are available that have the potential to significantly improve current aeroshell design. In order to qualify a polymer matrix composite (PMC) material as a candidate aeroshell structural material, its performance must be evaluated under realistic environments. Thus, verification testing of lightweight PMC's at aeroshell entry temperatures is needed to ensure that they will perform successfully in high-temperature environments. Towards this end, a test program was developed to characterize the mechanical properties of two candidate material systems, T650-35/AFR-PE-4 and T650-35/RP46. The two candidate high-temperature polyimide resins, AFR-PE-4 and RP46, were developed at the Air Force Research Laboratory and NASA Langley Research Center, respectively. This paper presents experimental methods, strength, and stiffness data of the T650-35/AFR-PE-4 material as a function of elevated temperatures. The properties determined during the research test program herein, included tensile strength, tensile stiffness, Poisson s ratio, compressive strength, compressive stiffness, shear modulus, and shear strength. Unidirectional laminates, a cross-ply laminate and two eight-harness satin (8HS)-weave laminates (4-ply and 10-ply) were tested according to ASTM standard methods at room and elevated temperatures (23, 316, and 343 C). All of the relevant test methods and data reduction schemes are outlined along with mechanical data. These data contribute to a database of material properties for high-temperature polyimide composites that will be used to identify the material characteristics of potential candidate materials for aeroshell structure applications.

Whitley, Karen S.↗

Experimental Performance of a Nonlinear Control Strategy to Regulate Temperature of a High-Temperature Solar Reactor

Abstract Despite the significant potential of solar thermochemical process technology for storing solar energy as solid-state solar fuel, several challenges have made its industrial application difficult. It is important to note that solar energy has a transient nature that causes instability and reduces process efficiency. Therefore, it is crucial to implement a robust control system to regulate the process temperature and tackle the shortage of incoming solar energy during cloudy weather. In our previous works, different model-based control strategies were developed namely a proportional integral derivative controller (PID) with gain scheduling and adaptive model predictive control (MPC). These methods were tested numerically to regulate the temperature inside a high-temperature tubular solar reactor. In this work, the proposed control strategies were experimentally tested under various operation conditions. The controllers were challenged to track different setpoints (500 °C, 1000 °C, and 1450 °C) with different amounts of gas/particle flowrates. Additionally, the flow controller was tested to regulate the reactor temperature under a cloudy weather scenario. The ultimate goal was to produce 5 kg of reduced solar fuel magnesium manganese oxide (MgMn2O4) successfully, and the controllers were able to track the required process temperature and reject disturbances despite the system's strong nonlinearity. The experimental results showed a maximum error in the temperature setpoint of less than 0.5% (6 °C), and the MPC controller demonstrated superior performance in reducing the control effort and rejecting disturbances.

Energy & Fuels↗

Conductor on molded barrel magnet assembly and associated systems and methods

A Conductor on Molded Barrel (COMB) magnet assembly optimized for High Temperature Superconducting (HTS) materials. The magnet assembly comprises a magnetic coil(s) carried by a conductor support structure and configured in cosine-theta geometry. Created using additive manufacturing, the conductor support structure features a continuous cable channel that fittedly carries and positions elongated straight portion(s) of the magnetic coil(s) parallel to a magnetic axis. The conductor support structure may be cylindrically shaped and longitudinally bored, with the continuous cable channel comprising an outer channel portion (distal on the cylinder) and an inner channel portion (proximal on the cylinder). A transition hole that joins the outer channel portion and the inner channel portion allows a single magnetic coil to be wound along both the outer and inner surfaces of the conductor support structure. The conductor support structure may be fabricated as longitudinally-symmetrical halves, and secured for operation using azimuthal and/or midplane shims.

Kashikhin, Vadim V.↗

A capillary-based microfluidic device enables primary high-throughput room-temperature crystallographic screening

A novel capillary-based microfluidic strategy to accelerate the process of small-molecule-compound screening by room-temperature X-ray crystallography using protein crystals is reported. The ultra-thin microfluidic devices are composed of a UV-curable polymer, patterned by cleanroom photolithography, and have nine capillary channels per chip. The chip was designed for ease of sample manipulation, sample stability and minimal X-ray background. 3D-printed frames and cassettes conforming to SBS standards are used to house the capillary chips, providing additional mechanical stability and compatibility with automated liquid- and sample-handling robotics. These devices enable an innovative in situ crystal-soaking screening workflow, akin to high-throughput compound screening, such that quantitative electron density maps sufficient to determine weak binding events are efficiently obtained. This work paves the way for adopting a room-temperature microfluidics-based sample delivery method at synchrotron sources to facilitate high-throughput protein-crystallography-based screening of compounds at high concentration with the aim of discovering novel binding events in an automated manner.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

FaceSheet Push-off Tests to Determine Composite Sandwich Toughness at Cryogenic Temperatures

A new novel test method, associated analysis, and experimental procedures are developed to investigate the toughness of the facesheet-to-core interface of a sandwich material at cryogenic temperatures. The test method is designed to simulate the failure mode associated with facesheet debonding from high levels of gas pressure in the sandwich core. The effects of specimen orientation are considered, and the results of toughness measurements are presented. Comparisons are made between room and liquid nitrogen (-196 C) test temperatures. It was determined that the test method is insensitive to specimen facesheet orientation and strain energy release rate increases with a decrease in the test temperature.

Gates, Thomas S.↗

Space-time dependent thermal conductivity in nonlocal thermal transport

Nonlocal thermal transport is generally described by the Peierls-Boltzmann transport equation (PBE). However, solving the PBE for a general space-time dependent problem remains a challenging task due to the high dimensionality of the integro-differential equation. In this work, we present a direct solution to the space-time dependent PBE with a linearized collision matrix using an eigendecomposition method. We show that there exists a generalized Fourier-type relation that links heat flux to the local temperature, and this constitutive relation defines a thermal conductivity that depends on both time and space. Combining this approach with ab initio calculations of phonon properties, we demonstrate that the space-time dependent thermal conductivity gives rise to an oscillatory response in temperature in a transient grating geometry in high thermal conductivity materials. The present solution method allows us to extend the reach of our computational capability for heat conduction to space-time dependent nondiffusive transport regimes. Here, this capability will not only enable a more accurate interpretation of thermal measurements that observe nonlocal thermal transport, but also enhance our physical understanding of nonlocal thermal transport in high thermal conductivity materials that are promising candidates for nanoscale thermal management applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High temperature electrical property measurements of ceramics

Emerging applications in energy and aerospace systems require high quality data on the high temperature electrical properties of ceramics, particularly oxides, to guide material selection, design, and modeling. This presentation demonstrates the functionality of a specially designed sample fixture that enables electrical measurements to be conducted up to temperatures as high as 1600°C. Utilizing the mismatch in the coefficient of thermal expansion between two materials, a purely mechanical method for establishing electrical contact in the van der Pauw geometry is used to measure the bulk resistivity of ceramic materials. Measurements conducted on a number of common high temperature materials will be presented, including 20 mol % Gd-doped cerium oxide. Measurements are performed using multiple techniques and compared to literature values finding excellent agreement. The approach described in this work enables the van der Pauw method to be applied to many ceramic materials over a wide range of temperatures and environments.

Cann, David P.↗

An efficient reconstruction algorithm for diffusion on triangular grids using the nodal discontinuous Galerkin method

High-energy-density (HED) hydrodynamics studies such as those relevant to inertial confinement fusion and astrophysics require highly disparate densities, temperatures, viscosities, and other diffusion parameters over relatively short spatial scales. This presents a challenge for high-order accurate methods to effectively resolve the hydrodynamics at these scales, particularly in the presence of highly disparate diffusion. A significant volume of engineering and physics applications use an unstructured discontinuous Galerkin (DG) method developed based on the finite element mesh generation and algorithmic framework. This work discusses the application of an affine reconstructed nodal DG method for unstructured grids of triangles. Solving the diffusion terms in the DG method is non-trivial due to the solution representations being piecewise continuous. Hence, the diffusive flux is not defined on the interface of elements. The proposed numerical approach reconstructs a smooth solution in a parallelogram that is enclosed by the quadrilateral formed by two adjacent triangle elements. The interface between these two triangles is the diagonal of the enclosed parallelogram. Similar to triangles, the mapping of parallelograms from a physical domain to a reference domain is an affine mapping, which is necessary for an accurate and efficient implementation of the numerical algorithm. Thus, all computations can still be performed on the reference domain, which promotes efficiency in computation and storage. This reconstruction does not make assumptions on choice of polynomial basis. Reconstructed DG algorithms have previously been developed for modal implementations of the convection–diffusion equations. However, to the best of the authors’ knowledge, this is the first practical guideline that has been proposed for applying the reconstructed algorithm on a nodal discontinuous Galerkin method with a focus on accuracy and efficiency. As a result, the algorithm is demonstrated on a number of benchmark cases as well as a challenging substantive problem in HED hydrodynamics with highly disparate diffusion parameters.

Computational efficiency↗

Crystallographic variant mapping using precession electron diffraction data

In this work, we developed three methods to map crystallographic variants of samples at the nanoscale by analyzing precession electron diffraction data using a high-temperature shape memory alloy and a VO2 thin film on sapphire as the model systems. The three methods are (I) a user-selecting-reference pattern approach, (II) an algorithm-selecting-reference-pattern approach, and (III) a k-means approach. In the first two approaches, Euclidean distance, Cosine, and Structural Similarity (SSIM) algorithms were assessed for the diffraction pattern similarity quantification. We demonstrated that the Euclidean distance and SSIM methods outperform the Cosine algorithm. We further revealed that the random noise in the diffraction data can dramatically affect similarity quantification. Denoising processes could improve the crystallographic mapping quality. With the three methods mentioned above, we were able to map the crystallographic variants in different materials systems, thus enabling fast variant number quantification and clear variant distribution visualization. The advantages and disadvantages of each approach are also discussed. We expect these methods to benefit researchers who work on martensitic materials, in which the variant information is critical to understand their properties and functionalities.

Crystallographic variant mapping↗

Upcycling Polynorbornene Derivatives into Chemically Recyclable Multiblock Linear and Thermoset Plastics

Synthetic polymers have found widespread use, but their ineffective end-of-life treatment is causing a significant environmental and human health crisis. Here, we demonstrate the upcycling of polynorbornene derivatives (pNBEs) through their deconstruction into distinct oligomeric buildings blocks that can be repolymerized into chemically recyclable pNBEs-like multiblock polymers via dehydrogenative polymerization. The resulting materials exhibit diverse mechanical properties, while integrating high melting temperatures (T m as high as 133 °C). Notably, this method could also enable the selective deconstruction of permanently cross-linked polydicyclopentadiene (pDCPD) thermosets into telechelic-OH functionalized oligomers, overcoming the significant challenges posed by their robust network structure in recycling and degradation. The resulting pDCPD oligomers can subsequently be repolymerized with macrodiols to create multiblock thermosets with tunable mechanical properties, including Young's modulus and tensile elongation. After use, upcycled plastics could be effectively deconstructed back to the oligomers for recovery and repolymerization. Overall, this work establishes an approach that can be utilized to upcycle pNBEs into previously inaccessible multiblock thermosets and thermoplastics with full recyclability, and may be generalizable to a range of polymers to shift their end-of-life waste disposal toward sustainable recovery and reuse.

36 MATERIALS SCIENCE↗

Dynamics of High Molecular Weight Cylindrical and Lamellar Block Copolymers with X‐ray Photon Correlation Spectroscopy

Here, the structure and dynamics of polystyrene (PS)-b-poly(ethylene oxide) block copolymers (BCPs) are studied. The BCPs exhibit microphase-separated cylindrical and lamellar morphologies. Structural dynamics are measured with X-ray photon correlation spectroscopy in the small-angle regime. Morphologies and domain sizes are evaluated using small-angle X-ray scattering (SAXS), scanning electron microscopy, and atomic force microscopy. Different solvent processing conditions are investigated. Grain sizes evaluated using SAXS are found to depend on processing only for the rubbery majority BCP. The structural relaxation times are examined as a function of PS volume fraction, temperature, morphology, and structural sizes. Well above the glass transition temperature (T g ) of PS, all samples exhibit stretched autocorrelation decays and diffusive dynamics. Near T g of PS, the dynamics of all samples are anomalous with compressed autocorrelation decays and hyperdiffusive dynamics. This transition occurs at 153 °C or 1.13 T g of PS. In the diffusive regime (at high temperature), structural relaxation times are dependent on the processing method. Near PS T g (at low temperature), structural relaxation times scale with the PS volume fraction. Structural relaxation times do not correlate with grain size, indicating that the out-of-equilibrium state of PS dominates the structural dynamics of these strongly phase-segregated BCPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SCALE inventory and reactivity analysis as part of the Hermes 2021 PSAR review

The readiness of SCALE for comprehensive studies of pebble-bed reactors has been demonstrated through detailed analysis of a fluoride salt–cooled, high-temperature pebble-bed reactor (PB-FHR). The methods developed for pebble-bed reactor modeling in SCALE, particularly for inventory generation, have proven effective in gaining insights into the reactor physics of this advanced reactor. Excellent agreement with another code package has been observed, further highlighting SCALE’s strong performance. The SCALE results supported the US Nuclear Regulatory Commission’s construction permit application review of the Hermes low-power PB-FHR demonstration reactor. A SCALE model of the Hermes reactor was developed at Oak Ridge National Laboratory using information from the Preliminary Safety Analysis Report (PSAR) and supplemented with publicly available data. SCALE reactivity coefficient simulations reproduced PSAR results within 1σ statistical uncertainties. Sensitivity studies emphasized the importance of graphite specifications for accurate keff predictions.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗