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At least 73 records · Page 4

Time-dependent THMC properties and microstructural evolution of damaged rocks in excavation damage zone

Modeling coupled thermo-hydro-mechanical-chemical (THMC) processes in host rocks near high-level nuclear waste (HLW) repositories at various time scales is an extremely challenging task. The current study integrates experimental, theoretical, and numerical methods in assessing the evolution of excavation damage zone (EDZ) over time and its implication on the long-term migration of hazardous species. Argillite and rock salt and are the focus of this study. The first part of the report presents a novel time-dependent directional microcrack damage theory for generic brittle rocks. It features detailed statistical description of the microcracks within a damaged solid, permitting a direct upscaling of microscale processes such as crack growth kinetics, crack closure/opening, sliding friction to explain the macroscopic creep, nonlinear elasticity, shear dilation, and loading-unloading hysteresis. This provides a basic platform for describing the anisotropic mechanical and transport properties of damaged rocks during excavation and subsequent THMC loadings. The model is validated and numerically implemented to Finite Element (FE) package ABAQUS through the user-defined material (UMAT) interface and have demonstrated great potential in resolving the time-dependent and anisotropic evolution of damage in the EDZ. The second part of the report presents a multi-scale experimental effort in characterizing the thermal, hydraulic, and mechanical properties of Mancos shale and Avery Island salt. For the Mancos shale, triaxial compression tests are performed at different confining pressures and temperatures to probe its thermomechanical properties relevant to HLW repositories. The obtained stress-strain data are interpreted using the proposed directional damage theory. Post-test specimens are subjected to gas permeability tests to reveal the correlation between permeability and the degree of microcracking. At microscale, temperature-controlled nanoindentation tests are performed and found a linear correlation between fracture toughness and elastic modulus from 25°C to 300°C. For Avery Island salt, we have designed and manufactured a novel relative-humidity controlled uniaxial creep device. Long-term creep tests at low stresses (< 5 MPa) are performed at different levels of relative humidity (RH). Besides confirming the much higher creep rates as one would expect through extrapolating the high-stress creep data, the results reveal that the steady-state creep rate of rock salt is strongly dependent on the ambient RH, an aspect that is often neglected in the literature. Both behaviors can be attributed to the pressure-solution creep mechanism which dominates at low stress and high RH levels. The third part of the report explores a set of numerical strategies in modeling the THMC behavior of porous geomaterials. A fully implicit, monolithic FE solution that can flexibly interface with different material models and coupling mechanisms for THMC problems is developed and verified through the ABAQUS user-defined element (UEL) interface. The scheme is used to study the THM response of a hypothetical HLW storage site with reference to an existing in-situ heater test. Strategies for integrating the UEL and the microcrack UMAT are suggested. Another numerical endeavor of this study is to implement a higher-order asymptotic homogenization method to account for the heterogeneous porous structures. The same method is then extended to perform microstructure-informed thermo-mechanical modeling of generalized continua. The above outcomes of this project provide a strong thrust towards enhancing the fundamental understanding and modeling capability of the long-term evolution of host rocks in EDZ, thus helping achieve the design goal of 1-million-year isolation of high-level nuclear wastes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The effect of polymer grafting on the mechanical properties of PEG-grafted cellulose nanocrystals in poly(lactic acid)

Poly(lactic acid) (PLA) is a commercially available bio-based polymer that is a potential alternative to many commodity petrochemical-based polymers. However, PLA's thermomechanical properties limit its use in many applications. Incorporating polymer-grafted cellulose nanocrystals (CNCs) is one potential route to improving these mechanical properties. One key challenge in using these polymer-grafted nanoparticles is to understand which variables associated with polymer grafting are most important for improving composite properties. In this work, poly(ethylene glycol)-grafted CNCs are used to study the effects of polymer grafting density and molecular weight on the properties of PLA composites. All CNC nanofillers are found to reinforce PLA above the glass transition temperature, but non-grafted CNCs and CNCs grafted with short PEG chains (<2 kg mol –1 ) are found to cause significant embrittlement, generally resulting in less than 3% elongation-at-break. By grafting higher molecular weight PEG (10 kg mol –1 ) onto the CNCs at a grafting density where the polymer chains are predicted to be in the semi-dilute polymer brush conformation (~0.1 chains nm –2 ), embrittlement can be avoided.

36 MATERIALS SCIENCE↗

Handbook on the Material Properties of Yttrium Hydride for High Temperature Moderator Applications

Yttrium hydride is an optimal choice for a high-temperature moderator material in advanced thermal neutron spectrum reactors that require small core volumes. A complete database of the thermomechanical properties of yttrium hydride is not yet available, although it is much needed to understand and predict the moderator performance during service in reactors. This milestone report presents the properties of unirradiated bulk yttrium hydride as a function of hydrogen concentration—including density, crystal structure, specific heat capacity, thermal diffusivity, thermal conductivity, hardness, elastic/shear moduli, Poisson’s ratio, fracture strength, microstructure, and thermal stability. This information provides a baseline measurement for the subsequent neutron irradiation response study of yttrium hydride. The recommended empirical treatment of the data is suggested. In addition, other properties (i.e., hydrogen retention, thermal hydrogen migration, and irradiation response) requiring investigation are discussed. Also included are the Preliminary post-irradiation examination (PIE) data of yttrium hydride irradiated at 600 and 900°C to 0.1 dpa in the High Flux Isotope Reactor (HFIR). The thermophysical properties have insignificant change following this low dpa irradiation for both irradiation temperatures.

36 MATERIALS SCIENCE↗

Composite binder, processing, and particle size effects on mechanical properties of non-hazardous high explosive surrogates

Plastic-bonded explosives (PBX) are polymer matrix composites that are highly loaded with micron-scale explosive crystals. The thermal and mechanical properties of these materials must be well-understood so that appropriate engineering models can be developed, but testing such properties under many scenarios can be hazardous and expensive. A non-hazardous PBX surrogate (“mock”) may be used in place of a PBX in many experiments if the thermomechanical properties are well-matched. Our previous research has shown that 5-iodo-2'-deoxyuridine (IDOX) is a promising crystalline filler material for the explosive cyclotetramethylene-tetranitramine (HMX). In this study, we investigate how the binder composition, variations in the IDOX particle size distribution, and pressing temperature affect the compressive strength and elastic modulus. We observe that while the binder system used in the composite dominates the mechanical response, the particle size distribution and pressing conditions do have a measurable effect on the material compliance and strength.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Effect of Fatty Acid Polyunsaturation on Synthesis and Properties of Emulsion Polymers Based on Plant Oil-Based Acrylic Monomers

This study demonstrated that polymerization behavior of plant oil-based acrylic monomers (POBMs) synthesized in one-step transesterification reaction from naturally rich in oleic acid olive, canola, and high-oleic soybean oils is associated with a varying mass fraction of polyunsaturated fatty acid fragments (linoleic (C18:2) and linolenic (C18:3) acid esters) in plant oil. Using miniemulsion polymerization, a range of stable copolymer latexes was synthesized from 60 wt.% of each POBM and styrene to determine the impact of POBM chemical composition (polyunsaturation) on thermal and mechanical properties of the resulted polymeric materials. The unique composition of each plant oil serves as an experimental tool to determine the effect of polyunsaturated fatty acid fragments on POBM polymerization behavior and thermomechanical properties of crosslinked films made from POBM-based latexes. The obtained results show that increasing polyunsaturation in the copolymers results in an enhanced crosslink density of the latex polymer network which essentially impacts the mechanical properties of the films (both Young’s modulus and toughness). Maximum toughness was observed for crosslinked latex films made from 50 wt.% of each POBM in the monomer feed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Behavior and properties of helium cavities in ductile-phase-toughened tungsten irradiated with He + ions at an elevated temperature

Ductile-phase toughened tungsten (DPT W) composites have demonstrated a great potential for plasma-facing components in fusion power systems. These materials can retain the outstanding thermomechanical properties of W while significantly enhancing the fracture toughness. The DPT W composite in this study consists of W particles (88 wt.%) embedded in a ductile NiFeW (12 wt.%) solution matrix. Irradiation of the composite was performed with 90 keV He + ions to 1.0 × 10 17 He + /cm 2 at 973 K. The He cavities formed in both W and NiFeW phases are examined using convergent-beam scanning transmission electron microscopy (CB-STEM) at an atomic-level resolution. Full-range depth profiles of the He cavity diameters and number densities are analyzed. The results show that the average cavity diameter in NiFeW is ~2.7 times that in W, while the number density is an order of magnitude lower. A quantitative analysis of the He density and pressure in the cavities is also achieved using STEM electron energy loss spectroscopy (STEM-EELS) mapping. The He atoms in the cavities in NiFeW are found to be under-pressurized, while those in similar-sized cavities in W are not detectable. Further, the He energy-loss shift exhibits a linear relationship with the He density in cavities in NiFeW, with the slope comparable to that for martensitic steel.

36 MATERIALS SCIENCE↗

A Modified Embedded-Atom Method Potential for a Quaternary Fe-Cr-Si-Mo Solid Solution Alloy

Ferritic-martensitic steels, such as T91, are candidate materials for high-temperature applications, including superheaters, heat exchangers, and advanced nuclear reactors. Considering these alloys’ wide applications, an atomistic understanding of the underlying mechanisms responsible for their excellent mechano-chemical properties is crucial. Here, we developed a modified embedded-atom method (MEAM) potential for the Fe-Cr-Si-Mo quaternary alloy system—i.e., four major elements of T91—using a multi-objective optimization approach to fit thermomechanical properties reported using density functional theory (DFT) calculations and experimental measurements. Elastic constants calculated using the proposed potential for binary interactions agreed well with ab initio calculations. Furthermore, the computed thermal expansion and self-diffusion coefficients employing this potential are in good agreement with other studies. This potential will offer insightful atomistic knowledge to design alloys for use in harsh environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bayesian Calibration of Nuclear Graphite Property Models Accounting for Model Inadequacy and Impacts on Component Performance

Nuclear-grade structural graphite is extensively utilized in the core designs of various advanced nuclear reactors. In the reactor environment, graphite is subjected to prolonged exposure to extreme conditions, including high temperatures, radiation, and potentially molten salt and oxygen. Such exposure can induce several degradation mechanisms in graphite, including nonuniform volumetric strains caused by irradiation and thermal expansion, leading to stresses that may compromise the performance of graphite components. Assessing component integrity requires accurate models of graphite's thermomechanical response. This report documents the Bayesian calibration of thermomechanical properties for nuclear-grade graphite and their application to graphite component modeling and simulation using the Grizzly code. As part of this work, uncertainty-quantified models were developed for the elastic modulus, coefficient of thermal expansion, irradiation-induced dimensional change, and irradiation-induced creep for graphite grades IG-110, NBG-18, NBG-17, PCEA, and 2114. Using a hierarchical Bayesian approach, multiple experimental data sources were combined to develop Gaussian process models for the properties. Using the Kennedy O'Hagan framework, the uncertainties due to inadequacies in the model and the inherent spread in the experimental data were quantified for three different models. These uncertainty-quantified models, with a model-form correction, were subsequently applied to a coupled-physics simulation of representative graphite components, revealing that the uncertainties have a large impact on the components' deformation.

36 - MATERIALS SCIENCE↗

High Temperature Thick Film Sensor Development Based on Refractory Oxide Semiconductors

Solid-state, high-temperature sensing devices are required for accurate temperature, strain/stress, and failure monitoring for a range of advanced manufacturing, transportation, and military applications. High temperature conditions limit sensing strategies, where typically traditional metal and semiconductor materials are unstable, and the sensing options are limited to optical spectroscopy methods. In addition, strategies to embed the sensors directly within active components and protective thermal refractory are of interest that permit near-environment sensing which is not possible with the traditional electronic materials and components. Rare-earth chromite semiconductors exhibit some properties of interest for high temperature sensing technologies, such as: high microstructure and chemical stability, relatively high electronic conductivity at high temperatures, and relative thermal expansion coefficient matching to refractory thermal protective insulation (such as high-zirconia and -alumina ceramics). In this work, n-type and p-type doped lanthanum chromites compositions were computationally modelled and prepared, and the electrical, thermoelectric, and thermomechanical properties were measured for the obtained material systems. A few compositions were then processed into thick film health and temperature sensors and tested at high temperatures. To establish relative stability under harsh environment conditions, post- mortem microstructure and chemical composition was characterized after extended and cycle testing at high temperatures.

20 FOSSIL-FUELED POWER PLANTS↗

Blending Compostable Plastics for Packaging Applications

Non-sustainable packaging materials (polymers) are a large portion of the increasing amount of plastic waste that become environmental pollutants. While many biodegradable or compostable polymers have been developed in recent years, most fail to compete with the non-sustainable polymers dominating the market, due to lack of certain desired properties, such as thermal (high melt temperature) and mechanical (high ductility) performance. For example, the popular compostable polymer polylactic acid (PLLA) has a high melt temperature but is very brittle. Another polymer, poly(d-valerolactone) (PVL) demonstrates great ductility but has a very low melt temperature. By blending PLLA and PVL, there is an opportunity to create a new biodegradable material with synergistic desired properties for packaging applications. In this study, we produce several (9) physical blends of PVL and PLLA with varying compositions of the two polymers while applying three different materials to make them more compatible (compatibilizers). We test the success of compatibilization by scanning electron microscopy (SEM), mechanic testing (strain at break) and differential scanning calorimetry (melting temperature). Overall, we highlight several promising materials with high compatibility and desired thermomechanical properties for sustainable packaging. Ideally, these materials could help mitigate future plastic pollution in Colorado and beyond.

blending↗

Design of a novel carbon/carbon composite microvascular solar receiver

Solar thermal power tower systems are the primary technology being proposed for solar electricity from thermal energy. Operational limits on these towers are often driven by mechanical properties under significant thermal loads, particularly at the receiver where incoming flux is converted to thermal energy. While the solar receiver’s efficiency is largely driven by its optical properties, thermomechanical stresses on the receiver limits the operational envelope. One pathway to higher efficiency is greater allowable solar fluxes on the receiver but novel materials are required. The present study uses computational fluid dynamics to describe a parametric design space for a microvascular carbon/carbon composite solar receiver as a new material option for high flux solar receivers. Simulations are conducted for different microvascular geometries considering the role of material properties and heat transfer fluids, for the impact on thermal efficiency, and allowable strain. Results show that microscale receiver modules made of the proposed carbon/carbon composite could achieve thermal efficiencies over 90% and full-scale receivers can achieve up to 85% thermal efficiency for the design explored considering realistic strain limits, flux levels, and material properties. These values are highly dependent on the heat transfer fluid pairing, the through plane thermal conductivity of the carbon/carbon composite, the path architecture of the microscale receiver, and the incident solar flux profiles.

14 SOLAR ENERGY↗

Circularity in polymers: addressing performance and sustainability challenges using dynamic covalent chemistries

The circularity of current and future polymeric materials is a major focus of fundamental and applied research, as undesirable end-of-life outcomes and waste accumulation are global problems that impact our society. The recycling or repurposing of thermoplastics and thermosets is an attractive solution to these issues, yet both options are encumbered by poor property retention upon reuse, along with heterogeneities in common waste streams that limit property optimization. Dynamic covalent chemistry, when applied to polymeric materials, enables the targeted design of reversible bonds that can be tailored to specific reprocessing conditions to help address conventional recycling challenges. In this review, we highlight the key features of several dynamic covalent chemistries that can promote closed-loop recyclability and we discuss recent synthetic progress towards incorporating these chemistries into new polymers and existing commodity plastics. Next, we outline how dynamic covalent bonds and polymer network structure influence thermomechanical properties related to application and recyclability, with a focus on predictive physical models that describe network rearrangement. Finally, we examine the potential economic and environmental impacts of dynamic covalent polymeric materials in closed-loop processing using elements derived from techno-economic analysis and life-cycle assessment, including minimum selling prices and greenhouse gas emissions. Throughout each section, we discuss interdisciplinary obstacles that hinder the widespread adoption of dynamic polymers and present opportunities and new directions toward the realization of circularity in polymeric materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetics of Hydrogen Desorption from Yttrium Hydride: The Development of Material Characterization Methods

Yttrium hydride possesses attractive neutronic and thermal properties for moderator applications as a high-temperature moderator material in advanced thermal neutron spectrum reactors that require small core volumes. For safe operation of the nuclear reactors, it is critical to understand the kinetics of H desorption from yttrium hydride at elevated temperatures. In previous studies, the H desorption flux as a function of temperature was measured by thermal desorption spectroscopy. To fully understand the H desorption kinetics, the amount of H within the specimen must be locally evaluated, especially if this uniformity strongly affects the thermomechanical properties and irradiation resistance of the bulk material.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Microscopic Dynamics Controls Coupling and Cluster Formation in Brush Particle Solids

Thermodynamics-based models predict the structure of polymer-grafted nanoparticles (PGNs) as well as their assembly behavior based on geometric parameters such as particle size, degree of polymerization, and density of grafted chains. The role of microscopic polymer dynamics, such as the mobility of repeat units in the melt state, in the evolution of the structure and properties remains unknown. Brillouin light spectroscopy (BLS), due to its capability to concurrently discern the local and global elastic properties of PGN assemblies, enables the probing of microscopic processes, such as brush interdigitation, sensitive to the annealing of the assembly. For poly(methyl methacrylate) (PMMA)-grafted silica (SiO 2 ) PGNs in the dry powder state and annealed above the glass transition temperature, BLS revealed fully reversible local elasticity, indicative of limited interdigitation between adjacent PGNs. This contrasts with polystyrene (PS)−SiO 2 analogs that displayed ready (and irreversible) fusion of brush layers during annealing. The retardation of brush interdigitation in PMMA-grafted systems is surprising, given the similar thermomechanical properties of both polymers, and is rationalized as the consequence of higher friction between PMMA repeats compared to PS. Microscopic dynamics thus has a profound impact on the kinetic path of structure (and property) evolution and thus should be considered during the processing of PGNs into functional hybrid materials.

chemical structure↗

Predicting Hugoniot equation of state in erythritol with ab initio and reactive molecular dynamics

Erythritol has been proposed as an inert surrogate for developing theoretical and computational models to study aging in energetic materials. In this work, we present a comparison of mechanical and shock properties of erythritol computed using the ReaxFF reactive force field and from ab initio calculations employing density functional theory (DFT). We screened eight different ReaxFF parameterizations, of which the CHO parameters developed for hydrocarbon oxidation provide the most accurate predictions of mechanical properties and the crystal structure of erythritol. Further validation of the applicability of this ReaxFF parameterization for modeling erythritol is demonstrated by comparing predictions of the elastic constants, crystal structure, vibrational density of states, and Hugoniot curves against DFT calculations. The ReaxFF predictions are in close agreement with the DFT simulations for the elastic constants and shock Hugoniot when the crystal is loaded along its c axis but show as much as 30% disagreement in the elastic constants in the ab plane and 12% difference in shock pressures when shocked along the a or b crystal axes. Last, we compare thermomechanical properties predicted from classical molecular dynamics with those calculated using the quasi-harmonic approximation and show that quantum mechanical effects produce large discrepancies in the computed values of heat capacity and thermal expansion coefficients compared with classical assumptions. Combining classical molecular dynamics predictions of mechanical behavior with phonon-based calculations of thermal behaviors, we show that predicted shock-induced temperatures for pressures up to 6.5 GPa do not exceed the pressure-dependent melting point of erythritol.

Hu, Jing↗

Mechanically and thermally robust microporous copolymer separators for lithium ion batteries

Next generation, multifunctional separators can enhance energy storage, power, and safety performance of lithium ion batteries but must be simple to fabricate and incorporate with existing roll-to-roll manufacturing. Here, this study presents a strategy to facilely prepare these separators using UV-initiated polymerization-induced phase separation (PIPS), wherein microporous polymer separators are fabricated directly from constituent monomers and ethylene carbonate (EC) porogen. This enables a wide compositional design space as co-monomers with specific chemical functionality can be readily incorporated into the PIPS precursor mixture. Herein, 1,4-butanediol diacrylate (BDDA) was copolymerized with poly(ethylene glycol) diacrylate (PEGDA) to increase the acrylate conversion in the photopolymerization and improve mechanical properties. By tuning the ratio of PEGDA and EC, separators with high porosity (41.3%) and effective ionic conductivity (2.09 mS cm –1 ) were prepared. Inclusion of PEGDA was essential to increasing the elastic modulus to > 345 MPa, which is required for cell assembly by roll-to-roll manufacturing. All separators prepared were shown to enable reversible cycling of lithium metal/LiNi 0.5 Mn 0.3 Co 0.2 O 2 half-cells for 100 cycles. Unlike conventional polyolefin separators, which were shown to melt at 160 °C and shrink by up to 29.8% at elevated temperatures, the PIPS separators possess exceptional, safety-enhancing thermomechanical properties, undergoing no phase transitions or thermal shrinkage.

25 ENERGY STORAGE↗

Organocatalysis in ring opening copolymerization as a means of tailoring molecular weight dispersity and the subsequent impact on physical properties in 4D printable photopolymers

Vat photopolymerization 3D printing has traditionally relied on free radical crosslinking between alkenes to produce non-degradable parts, which may have limited use in the biomedical and clinical spaces. Photopolymer resins containing functionalized degradable polymers, specifically polyesters, are greatly interesting for 3D printing tissue scaffolds and medical devices. Unfortunately, most polyesters produced for these applications have been made using metal-containing catalysts, which are not without risk for medical applications. Organocatalysis is a viable alternative route to achieving the same types of polyesters. Here, ring opening copolymerization (ROCOP) of allyl and cyclohexene-containing polyesters is examined using bipyridine and a guanidine-containing catalyst. The role of the catalysts, initiators, and cocatalysts are examined for bulk, open air ROCOP reactions. Unlike previous efforts with organocatalysis, the examined catalysts here could be used to tailor the dispersity of the polyesters, with ~10 kDa polyesters with dispersity ranging from 1.3 to 2.5 examined for the impact on rheological and thermomechanical properties related to resin/part behavior. The bipyridine catalysts and a thiourea cocatalyst further are shown, through the introduction of new fluorescence emissions of the purified polyesters. As a result, this work demonstrates that tuning the dispersity of polyester photopolymers provides a direct method of tailoring physical and optical properties in 3D/4D printable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of cleavable comonomer structure and crosslinker chemistry on the performance and deconstructability of frontally cured pDCPD composites

Reclaiming undamaged carbon fiber from thermoset composites requires chemical recycling methods that leverage complete deconstruction of the polymer matrix. Cleavable comonomers enable chemical recycling of poly(dicyclopentadiene) (pDCPD) composites, but current systems suffer from reduced glass transition temperature (T g ), limiting application. Here, we investigate the effect of cleavable comonomer loading and cleavable crosslinker chemistry on network formation, thermomechanical properties, and fiber recovery in frontally cured pDCPD composites. All formulations fully deconstructed in acid and recovered fibers ranged from pristine to variably contaminated depending on crosslinker chemistry. Reducing backbone-cleaving comonomer content and introducing cleavable crosslinkers raised composite T g to 126–138 °C compared to 105 °C previously reported in deconstructable pDCPD composites. Although the cleavable crosslinkers increased T g in unreinforced polymers to 150–160 °C, the fiber-reinforced composite T g remained lower due to under-curing and interactions between the crosslinkers and the fiber surface. Increasing polymerization initiator loading improved comonomer conversion and yielded a deconstructable composite with T g = 151 °C, approaching the performance of non-deconstructable pDCPD composites (T g = 161 °C). This work clarifies how cleavable comonomer and crosslinker chemistry governs curing, thermomechanical performance, and reclaimed reinforcement quality, and the results highlight the need for more robust cleavable comonomers to realize multigenerational composite materials without sacrificing thermomechanical performance.

Carbon fibers↗