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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8

Intercalation of Ca into a Highly Defective Manganese Oxide at Room Temperature

The utilization of oxide frameworks as intercalation cathodes for non-aqueous Ca-ion batteries potentially unlocks a new energy storage system that delivers high energy density. However, the slow kinetics of Ca 2+ in oxide electrodes strongly handicaps their activity and reversibility at room temperature. Here, nanocrystals of layered MnO x containing a high concentration of atomic defects and lattice water are shown to have remarkable electrochemical activity towards Ca 2+ , amounting to a capacity of ~130 mAh/g at room temperature. Multimodal characterization revealed the notable degree of intercalation by probing the structural, compositional and redox changes undertaken by the defective MnO x nanocrystals. The results suggest that the existence of atomic defects and lattice water played a role in improving Ca 2+ diffusivity in the oxide. These outcomes reaffirm the prospects for functional Ca-ion batteries using oxide cathodes under moderate conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Speed in Information Processing with a Computer Driven Visual Display in a Real-time Digital Simulation

Information transfer between the operator and computer-generated display systems is an area where the human factors engineer discovers little useful design data relating human performance to system effectiveness. This study utilized a computer-driven, cathode-ray-tube graphic display to quantify human response speed in a sequential information processing task. The performance criteria was response time to sixteen cell elements of a square matrix display. A stimulus signal instruction specified selected cell locations by both row and column identification. An equal probable number code, from one to four, was assigned at random to the sixteen cells of the matrix and correspondingly required one of four, matched keyed-response alternatives. The display format corresponded to a sequence of diagnostic system maintenance events, that enable the operator to verify prime system status, engage backup redundancy for failed subsystem components, and exercise alternate decision-making judgements. The experimental task bypassed the skilled decision-making element and computer processing time, in order to determine a lower bound on the basic response speed for given stimulus/response hardware arrangement.

Kyle, R. G.↗

Effect of Polymer Electrode Morphology on Performance of a Lithium/Polypyrrole Battery

A variety of conducting polymer batteries were described in the recent literature. In this work, a Li/Polypyrrole secondary battery is described. The effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase is explored. A method of preparing conducting polymers was developed which yields high surface area per unit volume of electrode material. A porous membrane is used as a template in which to electrochemically polymerize pyrrole, then the membrane is dissolved, leaving the polymer in a fibrillar form. Conventionally, the polymer is electrochemically polymerized as a dense polymer film on a smooth Pt disk electrode. Previous work has shown that when the polymer is electrochemically polymerized in fribrillar form, charge transport rates are faster and charge capacities are greater than for dense, conventionally grown films containing the same amount of polymer. The purpose is to expand previous work by further investigating the possibilities of the optimization of transport rates in polypyrrole films by controlling the morphology of the films. The utility of fibrillar polypyrrole as a cathode material in a lithium/polymer secondary battery is then assessed. The performance of the fibrillar battery is compared to the performance of an analogous battery which employed a conventionally grown polypyrrole film. The study includes a comparison of cyclic voltammetry, shape of charge/discharge curves, discharge time and voltage, cycle life, coulombic efficiencies, charge capacities, energy densities, and energy efficiencies.

Nicholson, Marjorie Anne↗

Design and Preliminary Performance Testing of Electronegative Gas Plasma Thruster

In classical gridded electrostatic ion thrusters, positively charged ions are generated from a plasma discharge of noble gas propellant and accelerated to provide thrust. To maintain overall charge balance on the propulsion system, a separate electron source is required to neutralize the ion beam as it exits the thruster. However, if high-electronegativity propellant gases (e.g., sulfur hexafluoride) are instead used, a plasma discharge can result consisting of both positively and negatively charged ions. Extracting such electronegative plasma species for thrust generation (e.g., with time-varying, bipolar ion optics) would eliminate the need for a separate neutralizer cathode subsystem. In addition for thrusters utilizing a RF plasma discharge, further simplification of the ion thruster power system may be possible by also using the RF power supply to bias the ion optics. Recently, the PEGASES (Plasma propulsion with Electronegative gases) thruster prototype successfully demonstrated proof-of-concept operations in alternatively accelerating positively and negatively charged ions from a RF discharge of a mixture of argon and sulfur hexafluoride.i In collaboration with NASA Marshall Space Flight Center (MSFC), the Georgia Institute of Technology High-Power Electric Propulsion Laboratory (HPEPL) is applying the lessons learned from PEGASES design and testing to develop a new thruster prototype. This prototype will incorporate design improvements and undergo gridless operational testing and diagnostics checkout at HPEPL in April 2014. Performance mapping with ion optics will be conducted at NASA MSFC starting in May 2014. The proposed paper discusses the design and preliminary performance testing of this electronegative gas plasma thruster prototype.

Liu, Thomas M.↗

Solid-state Architecture Batteries for Enhanced Rechargeability and Safety (SABERS) for Extended Deep Space Applications

Extended duration deep space missions as well as permanent space habitats face numerous technical challenges, key among them is energy generation and energy storage. There are considerable monetary and technical barriers to the generation of power in space. Therefore, it is important to store and be able to access power in an efficient and safe manner over a large number of cycles. Energy storage and in particular, batteries, are vital to the operation of next-generation extraterrestrial shuttles, rovers, habitats and extravehicular activity (EVA) space suits. The performance metrics for extended duration space missions are at least 2 times greater than those set for terrestrial applications such as electric automobiles. Furthermore, safety is essential for operation of space missions particularly involving astronauts such as shuttles, habitats and EVA space suits. Preliminary systems level analysis has indicated that there are five key properties which must be optimized for successful implementation of battery systems. Those five key criteria are: safety, energy density, power, packaging design and scalability. Current state-of-the-art (SOA) lithium-ion batteries can meet or exceed the requirements for certain space applications in the areas of power and scalability, yet are insufficient in the key performance criteria of energy, safety and packaging design. The SABERS concept proposes a battery that meets all five key performance criteria through development of a solid-state architecture battery utilizing high capacity sulfur-selenium cathode and lithium metal anode. The combination of sulfur and selenium offers a balanced energy-to-power density ratio, which can be tailored to the specific application by altering the stoichiometric ratios of sulfur to selenium. This hybrid cathode will be developed by implementing NASA patented holey graphene technology as a highly conductive, ultra-lightweight electrode scaffold. A solid-state electrolyte will be used as a safe, non-flammable replacement to the highly flammable liquid organic electrolytes currently used in SOA lithium-ion batteries. This solid-state lithium-sulfur/selenium cell will be designed into a serial stacking configuration to enable dense packaging of the battery cells. The serial stacking configuration is termed a bipolar stack, which has the advantages of reducing overall cell weight, simplifying the interfaced connections for the cell, and minimizing the cooling requirements for the cell. Lastly, optimization of battery components will occur through a robust and rigorous combination of various computational modeling techniques covering multiple length scales. The expected result will be a fully solid-state battery with operational temperatures up to 150 °C which provides the required energy density, discharge rates, and inherent safety to meet the strict space mission performance criteria. In particular, the wide operational temperature window is required for the large temperature ranges which are experienced across a broad range of potential space missions. This presentation will show initial results that demonstrate the SABERS team has developed a composite carbon-sulfur cathode which exceeds 1100 Wh/kg at a discharge rate of 0.4C, and 804 Wh/kg at a discharge rate of 1C. Additionally, this presentation will show the SABERS team multiscale computational modeling approach and has produced a novel particle dynamics method called Solid Electrolyte Sphere Approximation Model (SESAM). SESAM is on the 1-10 µm scale and provides electromechanical and grain interactions for predictive design guidelines for the experimental team to follow.

Urban Air Mobility (UAM) Vehicles↗

Collapse of LiNi 1– x–y Co x Mn y O 2 Lattice at Deep Charge Irrespective of Nickel Content in Lithium-Ion Batteries

Volume variation and the associated mechanical fracture of electrode materials upon Li extraction/insertion are a main cause limiting lifetime performance of lithium-ion batteries. For LiNi 1-x-y Co x Mn y O 2 (NCM) cathodes, abrupt anisotropic collapse of the layered lattice structure at deep charge is generally considered characteristic to high Ni content and can be effectively suppressed by elemental substitution. Herein, we demonstrate the lattice collapse is a universal phenomenon almost entirely dependent on Li utilization, and not Ni content, of NCM cathodes upon delithiation. With Li removal nearing 80 mol%, very similar c-axis lattice shrinkage of around 5% occurs concurrently for NCMs synthesized in-house regardless of nickel content (90, 70, 50, or 33 mol%); meanwhile, the a-axis lattice contracts for high-Ni NCM, but it expands for low-Ni NCM. We further reveal Co-Mn co-substitution in NCM barely, if at all, affects several key structural aspects governing the lattice distortion upon delithiation. Finally, our results highlight the importance of evaluating true implications of compositional tuning on high-Ni layered oxide cathode materials to maximize their charge-storage capacities for next-generation high-energy Li-ion batteries.

25 ENERGY STORAGE↗

Multi-species electrolyte migration kinetics with directed flow

Here, this paper investigates an electrochemical process designed to control mixing kinetics in liquid electrolytes. The process utilizes an electrochemical cell with anode and cathode chambers connected by a channel without a membrane. This configuration depletes multiple electroactive species in the cathode chamber while selectively replenishing them in the anode chamber. A key application is the removal of impurity species from the cathode chamber electrolyte and the selective replenishment of primary electroactive species in the anode chamber. Aqueous cell experiments were conducted to validate the theoretical model, and simulations were performed for molten salt electrolytes. This approach minimizes waste by reducing the need for additional electrolyte supplies and extends the utilization of anion species, contributing to environmentally sustainable electrochemical materials processing.

Electrochemical Process↗

Jet transport flight operations using cockpit display of traffic information during instrument meteorological conditions: Simulation evaluation

A simulation study was undertaken to evaluate flight operations using cockpit display of traffic information (CDTI) in a conventional jet transport aircraft. Eight two-person airline flight crews participated as test subjects flying simulated terminal area approach and departure operations under instrument meteorological conditions (IMC). A fixed-base cockpit simulator configured with a full complement of conventional electromechanical instrumentation to permit full workload operations was utilized. Traffic information was displayed on a color cathode-ray tube (CRT) mounted above the throttle quadrant in the typical weather radar location. A transparent touchpanel overlay was utilized for pilot interface with the display. Air traffic control (ATC) simulation included an experienced controller and full partyline radio environment for evaluation of pilot-controlled self-separation and traffic situation monitoring tasks. Results of the study revealed the CDTI to be well received by the test subjects as a useful system which could be incorporated into an existing jet transport cockpit. Crew coordination and consistent operating procedures were identified as important considerations in operational implementation of traffic displays. Cockpit workload was increased with active CDTI tasks. However, all test subjects rated the increase to be acceptable.

Williams, David H.↗

High-performance room-temperature sodium–sulfur battery enabled by electrocatalytic sodium polysulfides full conversion

Room-temperature sodium–sulfur (RT-Na–S) batteries are highly desirable for grid-scale stationary energy storage due to their low cost; however, short cycling stability caused by the incomplete conversion of sodium polysulfides is a major issue for their application. Herein, we introduce an effective sulfiphilic host, gold nanodots decorated on hierarchical N-doped carbon microspheres (CN/Au/S), to achieve completely reversible conversion reactions in the S cathode by electrocatalyzing the low-kinetics conversion of Na 2 S 4 into NaS 2 (discharge process) or S (charge process). Besides, gold nanodots and N-doped carbon can increase the conductivity of the S cathode and provide strong polar–polar adsorption of sodium polysulfides to alleviate the shuttling effects. When serving as the cathode, the CN/Au/S composite can realize enhanced sulfur utilization, excellent cycling stability, and outstanding rate capability. This work deepens our understanding of the catalytic effect of gold atoms on sulfur molecules, opening a new avenue for cathode design and development of advanced RT-Na–S batteries.

25 ENERGY STORAGE↗

Computationally Guided Design of Multiple Impurities Tolerant Cathode for Solid Oxide Fuel Cell Applications

Solid oxide fuel cells (SOFCs) have been recognized as promising candidates in the demand of reducing the dependence on fossil fuels, which is one of the solutions to the threat of global warming. It was reported that the direct chemical-to-electrical energy conversion in SOFCs comes with negligible emission of greenhouse gases and up to 60% working efficiency. SOFC has unique advantages over traditional power generation technologies and other types of fuel cells due to the use of relatively inexpensive materials, low sensitivity to poisoning impurities in fuels, relatively high conversion efficiency, and fuel flexibility (like carbon-based fuels). However, during the SOFC operation, the cathode is exposed to intrinsic and extrinsic airborne contaminants at high temperatures (600–900°C), leading to their reaction with electrode materials, irreversible chemical and structural changes, and electrochemical performance degradation. of which CO2, SO2, Cr6+ and H2O are known to be concerns. Thus, developing a comprehensive understanding of the multiple impurities poisoning of SOFC cathodes in the presence of single or multiple impurities is necessary to address the long-term degradation of the SOFC cathode systems at operating conditions. An integrated computational and experimental approach has been utilized in the current work aiming at the comprehensive investigation of the cathode materials under single or multiple impurities poisoning effects, understanding the multiple impurities poisoning mechanism(s), and improving the long-term durability of the SOFC cathodes to develop better performing impurity-tolerant cathode materials. We first examined the agreement between the simulation approach and the experimental observations at various atmospheric and temperature conditions to confirm the reliability of CALPHAD for poisoning simulations in these cathodes. Then, using this approach, we investigated the accelerated testing protocol, which has become the standard method for conducting impurity poisoning experiments involving these cathode materials. We found our simulation approach is able to predict in which systems, i.e., cathode material and treatment environment, the accelerated testing protocols reflect actual operating conditions. Finally, in-depth simulations were done for these three candidate cathodes under different experimental conditions and suggested directions toward alternative cathode materials that have superior impurity tolerance.

36 MATERIALS SCIENCE↗

Two-layer cathode architecture for high-energy density and high-power density solid state batteries

Solid state batteries with high-energy density and high-power density require the development of thick and energy dense cathodes. Structured cathode electrodes with a double-layer configuration were enabled using a freeze tape casting technique. A bottom dense layer was utilized to enhance the energy density whereas a top porous layer with vertically aligned walls was utilized to enhance the power density. The porous structure of the power layer was achieved by ice templating this layer on top of the densified energy layer of the cathode. This configuration was found to better utilize the active material of the cathodes and was optimized using numerical simulation and computer modeling. Cells with Li metal anode and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) at approximately 5 and 20 mg/cm 2 were cycled at 70 °C at different C-rates. Poly(ethylene oxide) (PEO) with lithium bis-trifluoromethanesulfonimide (LiTFSI) was used for the catholyte and the solid-state electrolyte. The structured cathodes exhibited more than double capacity values as well as better Coulombic efficiency compared to non-structured (single-layer) thick cathodes. In conclusion, synchrotron X-ray tomography and scanning electron microscopy were used to characterize the microstructure of the cathodes.

25 ENERGY STORAGE↗

Structure–performance relationships of lithium-ion battery cathodes revealed by contrast-variation small-angle neutron scattering

Lithium-ion battery cathodes are porous composites of active material, conductive carbon, and polymer binder. Controlling the cathode microstructure is key to achieving high energy density and cycling stability. Current characterization techniques lack the nanoscale resolution over representative volumes necessary to relate cathode microstructure to cycling performance. To address this challenge, we utilize contrast-variation small-angle neutron scattering to quantify the chemical and structural features of cathodes wet by dimethyl carbonate, representing a relevant solvent environment. Using neutron scattering measurements, we identify an expansion in carbon and polymer structures that arises after calendering and wetting with solvent. Further, we deconvolute the carbon and binder phases to obtain the solvent-accessible carbon black surface area, which we correlate to diminished capacity retention driven by electrolyte decomposition on exposed carbon. This technique provides nanoscale insight into composite cathode microstructures and resulting cycling performance, promising future applications to a broad range of porous materials that exist in energy storage systems.

25 ENERGY STORAGE↗

Coupling of multiscale imaging analysis and computational modeling for understanding thick cathode degradation mechanisms

Here, using a thick NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) electrode as an example, we present a macro- to nanoscale 2D and 3D imaging analysis approach coupled with 4D (space + time) computational modeling to probe its degradation mechanism in a lithium-ion battery cell. Particle cracking increases and contact loss between particles and carbon-binder domain are observed to correlate with the cell degradation. This study unravels that the reaction heterogeneity within the thick cathode caused by the unbalanced electron conduction is the main cause of the battery degradation over cycling. The increased heterogeneity in the system will entail more cathode regions where the degree of active material utilization is uneven, leading to higher probabilities of particle cracking. These findings shed light on the crucial role of the electronic and ionic transportation networks in the performance deterioration of the thick cathode. They also provide guidance for cathode architecture optimization and performance improvement.

25 ENERGY STORAGE↗

Freestanding vanadium nitride nanowire membrane as an efficient, carbon-free gas diffusion cathode for Li–CO 2 batteries

A freestanding vanadium nitride nanowire (VN-NW) membrane is employed as a carbon-free gas diffusion cathode (GDC) for high-performance Li–CO 2 batteries. Li–CO 2 cells built with the VN-NW GDC exhibit excellent electrochemical performance, achieving 100 discharge/charge cycles with an ultralow round-trip overpotential of <1 V. The VN-NW GDC also delivers vastly improved capacity and rate capability compared to a conventional multiwalled carbon nanotube GDC. The morphology of the discharge products (Li 2 CO 3 + C) is greatly improved with the VN-NW GDC compared to the carbon-based cathode, allowing for facile decomposition on charge. Furthermore, the absence of carbon in the VN-NW GDC allows for easy characterization of the discharge products with a variety of techniques, including transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The impressive performance of the hierarchically structured VN-NW GDC in Li–CO 2 batteries justifies further investigation into noble metal-free and carbon-free materials for gas diffusion cathodes.

25 ENERGY STORAGE↗

Highly Loaded Sulfur Cathode, Coated Separator and Gel Electrolyte for High Rate Li-Sulfur Batteries

As one of DOE Battery 500 Seedling projects, Cornell University and EIC Labs investigated and developed i) highly loaded sulfur cathodes (> 3 mg/cm 2 ), ii) hybrid separators, and iii) gel ceramic electrolytes (GCE) to mitigate the low rate capability, shuttling effect and limited cycle life in high performance Li-Sulfur batteries. Scalable nanomanufacturing processes such as air-controlled electrospray (ACES) and gas-assisted electrospinning (GAES) have been utilized to develop directly deposited electrodes and polymer/ceramic hybrid separators. First, in the development of highly loaded cathodes, alternating layers of sulfur impregnated mesoporous carbon and graphene were fabricated via ACES and the resulting layered cathodes and coated separators exhibit higher capacity and capacity retention (about 1,000 mAh/g capacity with less than 0.02% fade/cycles) than single layer cathode or cathode prepared by conventional slurry cast. Alternating layer approach via ACES has been applied to high loading systems (3 - 5 mg S/cm 2 ), demonstrating the potential to increase sulfur utilization and capacity retention. We have also incorporated iron oxides (Fe 3 O 4 ) into S/mesoporous carbon/graphene cathodes to enhance sulfur utilization and mitigation of polysulfide shuttling. and the effect of Fe 3 O 4 in mesoporous carbon and Gr is highly pronounced at high C rates of 1C and 2C cycling performance. To further improve the cathodes at high rates, graphene nanoribbons (GNR) which can promote ion transport were incorporated in the cathode, resulting in 550 mAh/g at 5C/5C rates. Hybrid Li-ion/Li-S cathodes has also been explored to better engage unreacted polysulfides during charge/discharge. S/LFP hybrid cathodes offer higher sulfur utilization and enhanced rate capability, as well as higher areal loading. This study suggests inclusion of iron phosphide (Fe2P) which can chemically interact with polysulfides can further enhance sulfur utilization and mitigation of soluble polysulfides at high rates. Secondly, in the development of hybrid separators, we first employed graphene coating on the commercial polyolefin separators, which exhibits higher capability, better capacity retention and enhanced rate capability. To improve the rate capability with enhanced safety features such as thermal stability and nonflammability, we developed polymer/ceramic hybrids based on thermally stable polyimide (PI) and room temperature curable ceramic precursors such as organopolysilazane (OPSZ) or polysilsesquioxanes (PSSQ), which exhibit no shrinkages up to 300 ºC and non-flammability. To improve mechanical properties and electrochemical stability, polybenzimidazole (PBI) and alumina have been incorporated in polymer/ceramic hybrid separator, replacing PI and OPSZ/PSSQ, respectively. Finally, the gel ceramic electrolyte (GCE) based on ceramic cross linkers have been applied to make Li-S cells even safer and also to mitigate the polysulfide shuttling further. The resulting gel ceramic electrolyte offers improved capacity retention and rate capability, and also effectively mitigates polysulfide shuttling which was also confirmed by modeling. Inclusion of high ion conducting additives into GCE together with polymer/ceramic hybrid separators exhibit the higher ionic conductivity than liquid electrolyte with commercial polyolefin separator. We demonstrated that the developed highly loaded sulfur cathodes, polymer/ceramic hybrid separators and gel ceramic electrolyte can effectively mitigate the low rate capability, shuttling effect and limited cycle life in high performance Li-Sulfur batteries with improved safety.

25 ENERGY STORAGE↗

Understanding Operando Water Management in Hydroxide‐Exchange‐Membrane Fuel Cells

The water balance in hydroxide-exchange-membrane fuel cells (HEMFCs) is a key challenge for improved performance and durability, intimately linked with the various interfaces and coupled phenomena. For every 4 electrons produced, 4 water molecules are generated in the anode and 2 consumed in the cathode, while electroosmosis transports water across the HEM from the cathode to the anode. Consequently, a concentration gradient drives water back, from anode to cathode. Ineffective water management could lead to cathode dry-out, limiting reaction rate and causing ionomer degradation, or to anode flooding. To address these concerns, it is critical to measure the water transport operando . Herein, a home-built water-flux station is used to measure total water flux during cell operation with different inlet relative humidities and back pressures. Increasing the HEM thickness fourfold decreases the water flux at high current density, and utilizing microporous layers on both the anode and cathode decreases the water flux from the anode to the cathode. However, the most significant variable in changing the water flux was found by increasing the anode back pressure. Furthermore, humidity cycling significantly changed electrochemical performance without affecting the overall water fluxes. These findings can be translated to other devices utilizing an HEM.

AEMFC↗

Methodologies for Design, Characterization and Testing of Electrolytes that Enable Extreme Fast Charging of Lithium-ion Cells

Selection, testing and validation of electrolyte candidates for Li-ion cells are discussed, based on a 10-minute target for extreme fast charge (XFC). A combination of modeling and laboratory measurements create a timely and synergistic approach to identifying candidate electrolyte formulations. Multi-solvent systems provide a balanced set of properties, wherein lower molecular-weight solvents offer reduced viscosity, increased species diffusivity, and mitigation of concentration polarization at high charge rates. Carefully selected formulations can exhibit peak conductivity and usable conductivity range of two to three times that of the baseline EC-EMC (3:7, wt.) + LiPF 6 . Candidates are also chosen based on stability and longevity within the cell environment. Lab testing coincides with property predictions from the Advanced Electrolyte Model (AEM) and a macro-scale cell model. Furthermore, cell testing utilized coin and pouch cells having NMC532 or NMC811 cathodes with graphite electrodes. Results indicate combinations of low-molecular weight solvents are key for fast-charge electrolytes as they extend the useful conductivity range to both low and higher salt concentrations, and possess higher self-diffusivities compared to conventional solvents. This reduces impacts from concentration polarization. The choice of electrolyte also influences the tendency for lithium metal deposition at the anode, as showcased by experimental and modeling results herein.

25 ENERGY STORAGE↗

High reliability cathode heaters for ion thrusters

A number of space missions were proposed which utilize 30-cm mercury bombardment ion thrusters and also require a large number of thruster restarts. A test program was carried out to determine thermal cycle life of several different cathode heater designs. Plasma/flame sprayed heaters and swaged type heaters were tested. Four of the five plasma/flame sprayed heaters tested failed in a comparatively short time. Four tantalum swaged heaters that were brazed to the tantalum cathode tube were successfully tested and met the goals that were set at the start of the test.

Mueller, L. A.↗