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At least 775 records · Page 43

d -Electron Heavy Fermion Behavior in a Near-Room-Temperature Polar Metallic Ferrimagnet: A Case of Mn 5 SiC

Polycrystalline Mn 5 SiC was synthesized by using a high-temperature solid-state method. Mn 5 SiC adopts a polar space group (Cmc2 1 ) with six crystallographic Mn sites confirmed by X-ray and neutron diffraction, transmission electron microscopy, and second harmonic generation experiments. The complex crystal structure features edge-sharing trigonal prisms and icosahedra, as well as face/edge-sharing pentagonal prisms. Magnetic measurements indicate ferrimagnetic ordering with a transition temperature of 284 K. The ferrimagnetic structure (magnetic space group Cm’c’2 1 ) was further identified by powder neutron diffraction, where collinear Mn spins align along the crystallographic c-axis. The refined magnetic moment for each crystallographic Mn site at 4 K is 1.8(2), −2.42(9), −1.72(8), 0.51(6), 0.50(4), and 1.7(2) μ B . Density functional theory calculations confirm both the metallic behavior and the ferrimagnetic structure observed experimentally and further provide insight into the observed Mn moment dependence across crystallographic sites. The resistivity and specific heat measurements and density functional theory calculations reveal a substantially large Kadowaki–Woods ratio of 5 × 10 –5 μΩ·cm/(mJ/mol) 2 and a many-body renormalization factor of 5.5, indicating the unusual heavy Fermion behavior in such an itinerant magnetic metal.

Messegee, Zachary T. [George Mason University, Fai↗

Influences on Subsurface Plutonium and Americium Migration

Plutonium (Pu) has been released to the environment worldwide, including approximately 1.85 × 1015 Bq (200 kg) of Pu from process waste solutions to unconfined soil structures at the Hanford Site in Washington State. The subsurface mobility of Pu is influenced by complex interactions with sediments, groundwater, and any co-contaminants within the waste stream. Previous investigations at Hanford have shown that Pu exists as discrete PuO 2 particles forming before or after disposal, as secondary solid phases formed from waste interactions with sediments as adsorbed/incorporated species, and/or as dissolved species. In this research, new evidence is presented for the existence of PuO 2 , PuO 2 -Bi 2 O 3 composites, and particles from burnt Pu metal in near-surface sediments where Pu-laden acidic process waste was disposed to sediments. Pu and americium (Am) L3 X-ray absorption spectroscopy and density functional theory suggest that, in larger, more crystalline PuO 2 particles, Am formed from radioactive decay is retained in the Pu IV O 2 structure as Am IV . The Pu and Am that were disposed of in an acidic waste stream have since migrated deeper into the subsurface with detection to at least 37 meters below ground surface. In contrast, Pu deposited near the ground surface from neutral pH waste is found to be homogeneously distributed and relatively immobile. Groundwater extractions performed on contaminated sediments indicate that both Pu and Am are recalcitrant, with Am being fractionally less extractable than Pu on a molar basis. These results suggest that the more mobile fraction of Am has migrated from the near-surface and may be present in the deeper sediments as a different phase than Pu. From these results, it is suggested that Pu and Am deposited from acidic wastes were initially mobile and became significantly less mobile as wastes were neutralized within the soil profile.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Volumetric additive manufacturing of silica glass with microscale computed axial lithography

Glass is increasingly desired as a material for manufacturing complex microscopic geometries, from the micro-optics in compact consumer products to microfluidic systems for chemical synthesis and biological analyses. As the size, geometric, surface roughness, and mechanical strength requirements of glass evolve, conventional processing methods are challenged. We introduce microscale computed axial lithography (micro-CAL) of fused silica components, by tomographically illuminating a photopolymer-silica nanocomposite that is then sintered. We fabricated three-dimensional microfluidics with internal diameters of 150 micrometers, free-form micro-optical elements with a surface roughness of 6 nanometers, and complex high-strength trusses and lattice structures with minimum feature sizes of 50 micrometers. As a high-speed, layer-free digital light manufacturing process, micro-CAL can process nanocomposites with high solids content and high geometric freedom, enabling new device structures and applications.

36 MATERIALS SCIENCE↗

Techno-economic assessment for the production of algal fuels and value-added products: opportunities for high-protein microalgae conversion

Abstract Background Microalgae possess numerous advantages for use as a feedstock in producing renewable fuels and products, with techno-economic analysis (TEA) frequently used to highlight the economic potential and technical challenges of utilizing this biomass in a biorefinery context. However, many historical TEA studies have focused on the conversion of biomass with elevated levels of carbohydrates and lipids and lower levels of protein, incurring substantial burdens on the ability to achieve high cultivation productivity rates relative to nutrient-replete, high-protein biomass. Given a strong dependence of algal biomass production costs on cultivation productivity, further TEA assessment is needed to understand the economic potential for utilizing potentially lower-cost but lower-quality, high-protein microalgae for biorefinery conversion. Results In this work, we conduct rigorous TEA modeling to assess the economic viability of two conceptual technology pathways for processing proteinaceous algae into a suite of fuels and products. One approach, termed mild oxidative treatment and upgrading (MOTU), makes use of a series of thermo-catalytic operations to upgrade solubilized proteins and carbohydrates to hydrocarbon fuels, while another alternative focuses on the biological conversion of those substrates to oxygenated fuels in the form of mixed alcohols (MA). Both pathways rely on the production of polyurethanes from unsaturated fatty acids and valorization of unconverted solids for use as a material for synthesizing bioplastics. The assessment found similar, albeit slightly higher fuel yields and lower costs for the MA pathway, translating to a residual solids selling price of $899/ton for MA versus $1033/ton for MOTU as would be required to support a $2.50/gallon gasoline equivalent (GGE) fuel selling price. A variation of the MA pathway including subsequent upgrading of the mixed alcohols to hydrocarbon fuels (MAU) reflected a required solids selling price of $975/ton. Conclusion The slight advantages observed for the MA pathway are partially attributed to a boundary that stops at oxygenated fuels versus fungible drop-in hydrocarbon fuels through a more complex MOTU configuration, with more comparable results obtained for the MAU scenario. In either case, it was shown that an integrated algal biorefinery can be economical through optimal strategies to utilize and valorize all fractions of the biomass.

09 BIOMASS FUELS↗

Kramers–Kronig relation in attosecond transient absorption spectroscopy

The Kramers–Kronig relation (KKR) has a wide range of applications in extreme ultraviolet (XUV) and x-ray spectroscopy. However, the validity of KKR for many of these applications has not been systematically studied, while it is known to require careful attention in nonlinear and pump–probe experiments in optical domain spectroscopy. Here, we study the validity of KKR in XUV attosecond transient absorption spectroscopy pump–probe measurements both experimentally and theoretically using argon Fano resonances as a case study. Experiments are enabled by a phase-resolved method dubbed Complex Attosecond Transient-absorption Spectroscopy (CATS). Although the estimations based on the rotating-wave approximation suggest that KKR violation could be expected in the studied case, our results validate KKR and provide a solid basis for its application in a broad range of attosecond spectroscopy experiments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

End-to-end optimization for battery materials and molecules by combining graph neural networks and reinforcement learning

The National Renewable Energy Laboratory (NREL), together with the Colorado School of Mines (CSM) and Colorado State University (CSU), has developed a machine learning-enhanced approach to design new battery materials. Currently, such materials are designed in part via numerous expensive high-fidelity computational simulations that predict the performance of a given composition. Even with computational screening tools, the vast landscape of possible molecular or crystal structures exceeds current and future computational capacity. Improving the efficiency by which new materials can be optimized will therefore disrupt the cost, risk, and time required to bring new energy solutions to the marketplace. Predicting the properties of an organic molecule or periodic crystalline material given its structure has grown increasingly common. These approaches leverage large-scale computational and experimental databases and ML approaches such as graph neural networks. The inverse design problem of finding a material that possesses desired properties is substantially more challenging, since enumerating all valid material structures is not feasible. In this project, we leveraged recent success in reinforcement learning to efficiently navigate this high-dimensional search space. Just as algorithms can find the optimal chess moves from nearly limitless options, we train an approach to evolve a simple starting structure into a complex structure that possess the desired properties. Our solution has been demonstrated by applying it to two related design application tasks for short- and long-term energy storage, respectively: (1) the design of solid-state ion conductors and (2) the design of organic redox-active materials. The project has resulted an open-source software library for material design, documented examples of applying the library to both organic and inorganic material optimization, and peer-reviewed publications detailing the data, computational models, and resulting candidate materials.

25 ENERGY STORAGE↗

End-to-End Optimization for Battery Materials and Molecules by Combining Graph Neural Networks and Reinforcement Learning

The National Renewable Energy Laboratory (NREL), together with the Colorado School of Mines (CSM) and Colorado State University (CSU), has developed a machine learning-enhanced approach to the design of new battery materials. Currently, such materials are designed in part via numerous expensive high-fidelity computational simulations that predict the performance of a given composition. Even with computational screening tools, the vast landscape of possible molecular or crystal structures exceeds current and future computational capacity. Improving the efficiency by which new materials can be optimized will therefore disrupt the cost, risk, and time required to bring new energy solutions to the marketplace. Predicting the properties of an organic molecule or periodic crystalline material given its structure has grown increasingly common. These approaches leverage large-scale computational and experimental databases and ML approaches such as graph neural networks. The inverse design problem of finding a material that possesses desired properties is substantially more challenging, since enumerating all valid material structures is not feasible. In this project, we leveraged recent success in reinforcement learning to efficiently navigate this high-dimensional search space. Just as algorithms can find the optimal chess moves from nearly limitless options, we train an approach to evolve a simple starting structure into a complex structure that possess the desired properties. Our solution has been demonstrated by applying it to two related design application tasks for short- and long-term energy storage, respectively: (1) the design of solid-state ion conductors and (2) the design of organic redox-active materials. The project has resulted an open-source software library for material design, documented examples of applying the library to both organic and inorganic material optimization, and peer-reviewed publications detailing the data, computational models, and resulting candidate materials.

25 ENERGY STORAGE↗

Microwave-Assisted Reforming of Tar Model Compound Using the Ni/La-CeO2 Catalyst

Gasification of solid feedstocks like coal, biomass and waste plastic produces syngas as a desired product. However, this process also produces an unwanted byproduct known as tar, which is a sticky compound consisting of a mixture of complex aromatic and polyaromatic hydrocarbons. The tar formed during the gasification process lowers the syngas yields and reduces the gasification efficiency by damaging the reactor. Therefore, it is essential to reduce the amount of tar formed during the gasification process. Catalytic reforming of tars is one way to mitigate tars. The goal of this research is to explore the possibility of microwave-assisted catalytic tar conversion to syngas. However, due to the complexity of the tar, toluene has been used as a model tar compound as it is stable and easy to handle. Ni-La/CeO2 was used as a catalyst for this study, which was synthesized by wet impregnation method. Fresh and spent catalysts were analyzed using various techniques to understand the reaction mechanism. The reaction was performed both under microwave (MW) and conventional (CV) reactor for comparison.

catalysis↗

Realizing the Materials-Designed-To-Environments Promise of Additive Manufacturing Through a Fundamentally Different Approach to Optimization of Nonlinear Solid Mechanics Structures

Additive Manufacturing (AM) is expected to play a large role in the labs-wide goals of accelerating innovation and leading in modern engineering. More specifically, AM is seen as a key enabling technology for increasing the agility of nuclear deterrence and other national security applications involving complex coupled environments. However, the impact of AM on these initiatives has not been as wide-ranging as hoped because – despite its unique qualities – the focus has mostly been on detailed qualification to force AM components into pre-existing performance envelopes. This paradigm fundamentally precludes the novel possibilities afforded by the geometric and material flexibility of AM. In particular, the engineering of small-scale features to undergo buckling and contact can cause large geometric and symmetry changes which provide responsiveness to different environments. Despite almost a decade of observing such behavior, there exists no way to systematically design for AM to exploit it. Our goal for this project was to connect material design to multi-environment component performance by reconceptualizing how to design for AM to exploit the buckling and contact of small-scale features.

36 MATERIALS SCIENCE↗

Multiresolution GPC-Structured Control of a Single-Loop Cold-Flow Chemical Looping Testbed

Chemical looping is a near-zero emission process for generating power from coal. It is based on a multi-phase gas-solid flow and has extremely challenging nonlinear, multi-scale dynamics with jumps, producing large dynamic model uncertainty, which renders traditional robust control techniques, such as linear parameter varying H ∞ design, largely inapplicable. This process complexity is addressed in the present work through the temporal and the spatiotemporal multiresolution modeling along with the corresponding model-based control laws. Namely, the nonlinear autoregressive with exogenous input model structure, nonlinear in the wavelet basis, but linear in parameters, is used to identify the dominant temporal chemical looping process dynamics. The control inputs and the wavelet model parameters are calculated by optimizing a quadratic cost function using a gradient descent method. The respective identification and tracking error convergence of the proposed self-tuning identification and control schemes, the latter using the unconstrained generalized predictive control structure, is separately ascertained through the Lyapunov stability theorem. The rate constraint on the control signal in the temporal control law is then imposed and the control topology is augmented by an additional control loop with self-tuning deadbeat controller which uses the spatiotemporal wavelet riser dynamics representation. The novelty of this work is three-fold: (1) developing the self-tuning controller design methodology that consists in embedding the real-time tunable temporal highly nonlinear, but linearly parametrizable, multiresolution system representations into the classical rate-constrained generalized predictive quadratic optimal control structure, (2) augmenting the temporal multiresolution loop by a more complex spatiotemporal multiresolution self-tuning deadbeat control loop, and (3) demonstrating the effectiveness of the proposed methodology in producing fast recursive real-time algorithms for controlling highly uncertain nonlinear multiscale processes. The latter is shown through the data from the implemented temporal and augmented spatiotemporal solutions of a difficult chemical looping cold flow tracking control problem.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Arsenic (III and V) Removal in Anoxic Environments by Hierarchically Structured Citrate/FeCO 3 Nanocomposites

Novel citrate/FeCO 3 nanocomposites (CF-NCs) were synthesized for effective arsenic (III and V) sorption with constant addition of Fe2+ into HCO 3 - solution in the presence of citrate. This paper is the first report on the formation of CF-NCs, and in this study we investigate the mechanisms of arsenic uptake by the sorbent under anoxic conditions through various solid- and liquid-phase spectroscopic methods, including X-ray absorption spectroscopy. In CF-NCs, citrate was found to be incorporated into the structure of siderite (up to 17.94%) through (Fe 2+ citrate) - complexes. The crystal morphology of rhombohedral siderite was changed into hierarchically nanostructured spherical aggregates composed of several sheet-like crystals, which improved the surface reactivity in the presence of sufficient citrate. Compared to pure siderite (15.2%), enhanced removal of As(III) in the range of 19.3% to 88.2% was observed, depending on the amount of incorporated citrate. The maximum sorption capacities of CF-NCs for As(III) and As(V) were 188.97 and 290.22 mg/g, respectively, which are much higher than those of previously reported siderite-based adsorbents. It was found that arsenic (III and V) sorption on CF-NCs occurred via bidentate corner-sharing surface complexation, predominantly without changes in the arsenic oxidation states. These results suggest that arsenic (III and V) can be attenuated by siderite in anoxic environments, and this attenuation can be even more effective when siderite is modified by incorporation of organic compounds such as citrate.

54 ENVIRONMENTAL SCIENCES↗

Benchmarking and Exploring Parameter Space of the 2-Phase Bubble Tracking Model for Liquid Mercury Target Simulation

High intensity proton pulses strike the Spallation Neutron Source (SNS)’s mercury target to provide bright neutron beams. These strikes deposit extensive energy into the mercury and its steel vessel. Prediction of the resultant loading on the target is difficult when helium gas is intentionally injected into the mercury to reduce the loading and to mitigate the pitting damage on the vessel. A 2-phase material model that incorporates the Rayleigh-Plesset (R-P) model is expected to address this complex multi-physics dynamics problem by including the bubble dynamics in the liquid mercury. We present a study comparing the measured target strains in the SNS target station with the simulation results of the solid mechanics simulation framework. We investigate a wide range of various physical model parameters, including the number of bubble families, bubble size distribution, viscosity, surface tension, etc. to understand their impact on simulation accuracy. Our initial findings reveal that using 8-10 bubble families in the model renders a simulation strain envelope that covers the experimental ones. Further optimization studies are planned to predict the strain response more accurately.

Lin, Lianshan↗

Exploring the Nature of f-Element Soft Donor Interactions Using Electronically Tunable Azolate Ionic Liquids

This project was undertaken to advance the understanding of how f-elements interact with moderately soft donors, a heavily investigated yet open question which is of prime importance in spent nuclear fuel processing and fundamental inorganic chemistry. During the course of the project, based on exciting results, a stretch goal was developed to study the hydrolysis products of transuranic actinide metals, a somewhat understudied field even with its significance in nuclear fuel cycle and impacts in environmental chemistry. The stretch goal was to take our serendipitous discovery of an easy route to isolation of crystalline multinuclear ƒ-element hydrolysis products, and apply it to gaining a mechanistic understanding of Pu(III/IV) colloid formation. The simplicity of our techniques should lend themselves to the remote handling required for study of many transuranic elements. We developed several methodologies using azolium azolate chemistry to overcome ƒ-element hydrolysis problems that prohibit the isolation of ƒ-element soft donor complexes and to build a crystallographic library of ƒ-element N-donor complexes as a means to understand the fundamental differences between actinide and lanthanide interactions with moderately soft donor ligands. Our next major endeavor will be to transfer this chemistry from 4ƒ elements to transuranic elements, particularly in the study of hydrolysis of Pu(III/IV). While our work is fundamental in nature, applications of the knowledge we are generating should be felt in such diverse fields as catalysis, separations in general, nuclear waste remediation specifically, and many other applications in f-element magnetic and luminescent properties. The potential ramifications of the consistent and robust formation of hydrolysis controlled hexanuclear lanthanide structures are enormous, with future uses being catalyst formation, higher-nuclearity structure synthesis using our hexanuclear motif as a fundamental building block, Pu waste remediation, separations, and many other potential applications resulting from characteristic magnetic and luminescent properties of lanthanide polynuclear structures. Three synthetic methodologies (direct mixing with variable stoichiometries, use of volatile solvent, metathesis) were developed starting with 7 acidic and 6 basic azoles to obtain ionic liquids suitable for f-element coordination. Proton transfer by acidic/basic azole combination led to suitable low melting salts and two cocrystals. Acid/base reaction of azoles with soft-donor permanent cations of ([X 4444 ][OH] (where [X 4444 ] + = tetrabutylammonium [N 4444 ] + or tetrabutylphosphonium [P 4444 ] + ) with weakly acidic azoles including imidazole, 1,2,3-triazole, 1,2,4-triazole, 5-aminotetrazole, 4,5-dicyanoimidazole, and 2-amino-4,5-dicyanoimidazole) revealed several suitable low-melting salts. Metathesis reactions of Na(azolate) were conducted by first using weakly acidic azoles including 4,5-dicyanoimidazole, 2-amino-4,5-dicyanoimidazole, 5-aminotetrazole, and 1,2,4-triazole to form sodium or lithium salts using group(I) hydroxides in methanolic solutions. The best results were obtained by reacting the basic and acidic azoles directly in 1:1 or 3:1 ratios at elevated temperatures. Twenty-two azole mixtures were identified which are either low melting solids or room temperature liquids. Each of the low melting solids was confirmed to be a new solid phase, each of which is being further characterized. The liquids and solids are anticipated to be ILs, eutectics, or partially ionized systems, all of which will be suitable for the dissolution of f-element salts. Five new synthetic methodologies were developed to finding suitable crystallization conditions for f-element complexation with the goal of finding simple one pot reaction syntheses and crystallization strategies that could be used under the demanding conditions of transuranic chemistries. These synthetic methods yield many new crystalline phases which were studied by single crystal X-ray diffraction.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Temperature-dependent solid electrolyte interphase reactions drive performance in lithium-mediated nitrogen reduction to ammonia

The solid electrolyte interphase (SEI) is a vital component to control mass transport and selectivity in the lithium-mediated reduction of N 2 to NH 3 (Li-N 2 R). Finding strategies that generate the optimal SEI, a complex network of organic and inorganic species, can potentially improve Li-N 2 R performance. Here, we unravel structure-property relationships of the SEI by correlating its composition with the NH 3 faradaic efficiency (FENH3). By modifying the reaction temperature, we alter electrolyte decomposition reactions and observe changes in the SEI that explain FE NH3 trends between electrolyte solvents. We quantify a complex reaction environment at elevated temperatures where SEI formation is counteracted by etching reactions. This tradeoff leads to temporal fluctuations of FE NH3 , but the maximal FE NH3 can reach up to 40%, the highest value reported for batch cells at ambient pressure, thus far. In conclusion, our work underscores the potential of novel electrolytes that steer SEI selectivity and, ultimately, improve Li-N 2 R performance.

electrocatalytic nitrogen reduction↗

Rationalization of the tensile creep behavior of the Nb45Ta25Ti15Hf15 bcc refractory complex concentrated alloy using Rao-Suzuki screw dislocation glide model

Published experimental tensile creep data for refractory body-centered cubic alloy Nb45Ta25Ti15Hf15 (NTTH) at temperatures ranging from 850–950 °C and applied tensile stresses 50–300 MPa are analyzed using the Rao-Suzuki screw dislocation glide model of solid solution strengthening. It is shown that the experimental creep data as well as transmission electron microscopy observations of post- creep deformation dislocation microstructure are in agreement with the model results. This suggests that the creep deformation of NTTH at 850–950 °C is controlled by screw dislocation glide.

Rao, Satish I↗

Effect of Cr(III) Adsorption on the Dissolution of Boehmite Nanoparticles in Caustic Solution

Incorporation of relatively minor impurity metals onto metal (oxy)hydroxides can strongly impact solubility. In complex highly alkaline multicomponent tank waste such as that at the Hanford Nuclear Reservation, tests indicate that the surface area-normalized dissolution rate of boehmite ($γ$-AlOOH) nanomaterials is at least an order of magnitude lower than that predicted for the pure phase. In this work we examine the dissolution kinetics of boehmite coated by adsorbed Cr(III), which adheres at saturation coverages as sparse chemisorbed monolayer clusters. Using 40 nm boehmite nanoplates as a model system, temperature-dependent dissolution rates of pure versus Cr(III)-adsorbed boehmite showed that the initial rate for the latter is consistently several times lower, with an apparent activation energy 16 kJ·mol -1 higher. Although the surface coverage is only around 50%, solution analytics coupled to multimethod solids characterization reveals a phyicochemical armoring effect by adsorbed Cr(III) that substantially reduces the number of dissolution-active sites on particle surfaces. Such findings could help improve kinetics models of boehmite and/or metal ion adsorbed boehmite nanomaterials, ultimately providing a stronger foundation for the development of more robust complex radioactive liquid waste processing strategies.

54 ENVIRONMENTAL SCIENCES↗

Spectroscopic Evidence of Hyponitrite Radical Intermediate in NO Disproportionation at a MOF-Supported Mononuclear Copper Site

Dianionic hyponitrite (N 2 O 2 2- ) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme-copper oxidases and nitric oxide reductases. In this work, we examine the gas-solid reaction of nitric oxide with the metal–organic framework Cu I -ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N 2 O 2 .- intermediate. These results highlight the advantage provided by site-isolation in metal–organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one-electron couple in these enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid Cylinder Torsion for Large Shear Deformation and Failure of Engineering Materials

Using a thin-walled tube torsion test to characterize a material’s shear response is a well-known technique; however, the thin walled specimen tends to buckle before reaching large shear deformation and failure. An alternative technique is the surface stress method (Nadai 1950; Wu et al. J Test Eval 20:396–402, 1992), which derives a shear stress-strain curve from the torque-angular displacement relationship of a solid cylindrical bar. The solid bar torsion test uniquely stabilizes the deformation which allows us to control and explore very large shear deformation up to failure. However, this method has rarely been considered in the literature, possibly due to the complexity of the analysis and experimental issues such as twist measurement and specimen uniformity.

42 ENGINEERING↗