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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Effects of various parameters of different porous transport layers in proton exchange membrane water electrolysis

Porous transport layers (PTLs) play an important role in proton exchange membrane water electrolysis (PEMWE) cells. The PTL facilitates water and gas transport, as well as thermal and electrical conduction, and is required to sustain good contact with adjacent components. It is expected that using PTLs with variations in material properties such as structure, composition, thickness and wettability results in performance changes of the PEMWE. Here, a general mathematical PEMWE model is developed that separates and analyzes the contributions of ohmic, activation, diffusion and Nernst potentials. For model validation, three inherently different anode PTL structures (carbon paper, sintered titanium particles, and titanium felt) are operated over a range of conditions. Additionally, the effects of PTL wettability were used to verify the model using Polytetrafluoroethylene (PTFE) treated Toray papers with PTFE loading ranging from 0% to 20%. The modeling results of both PTFE treated and untreated materials show good agreement with the experimental data. Mass transport or diffusion loss is the primary reason for performance differences between PTFE treated and untreated PTLs. Sintered titanium PTLs with thicknesses above 1 mm suffer from up to 33% increased ohmic losses without indicating any obvious changes in activation and diffusion losses when compared to untreated PTLs. The losses of the cell increase when using PTFE treated Toray paper. Individual contributions are quantified and assigned to increased ohmic, activation, and diffusion losses. In conclusion, the proposed model offers insights into the overpotential contributions of a PEMWE. It is a useful tool for predicting performance of various PTL materials and can be applied for PTL development and optimization efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The Effect of Proton Conductivity of Fe–N–C–Based Cathode on PEM Fuel cell Performance

A model–based impedance spectroscopy is used to determine proton conductivity, oxygen transport parameter, double layer capacitance and oxygen reduction reaction (ORR) Tafel slope in the Fe–N–C cathode catalyst layer (CCL) of a PEM fuel cell. Experimental spectra of two cells differing by the membrane thickness only are processed using a physics–based model for PEMFC impedance. The spectra have been measured in the range of current densities from 25 to 800 mA cm -2 . The ORR Tafel slope of both the cells shows almost linear growth with the current density. In one of the cells, the CCL proton conductivity σp strongly decays at the current density of 100 mA cm -2 ; this decay is accompanied by the step growth of the double layer capacitance. Other minor variations of proton conductivity and double layer capacitance with the cell current occur also in a counterphase; presumed origin of this effect is discussed. The oxygen diffusion coefficient in the cathode exhibits explosive growth with the cell current. We attribute this effect to formation of temperature and pressure gradients in the CCL due to strongly non–uniform distribution of ORR rate in the electrode.

25 ENERGY STORAGE↗
DOE OSTI2026

Porin-Inspired Ionomers with sub-nm Gated Ion Channels for High Ion Conductivity and Selectivity (Final Project Report (2026))

The physiological functions of living systems heavily rely on biological ion channels, whose malfunction can lead to disease. These channels enable selective and regulated transport of water, ions, or small molecules across membranes. Analogously, ionomers used in energy conversion and storage technologies govern ion transport within membrane separators and catalyst binder layers. This DOE Office of Science Early CAREER project aimed to achieve molecular-level control over ionic conductivity and ion permselectivity by translating the functionalities of biological, gated ion channels into a novel class of ion-conducting polymers (ionomers) incorporating macrocyclic calix[4]arene-based repeat units. The overarching goal was to establish fundamental design principles and elucidate proton conduction mechanisms through strategic design of macrocyclic calix[4]arene-containing ionomers, with close relevance to energy conversion and storage devices, including proton exchange membrane fuel cells (PEMFCs). The project leveraged sub-nm-sized macrocyclic pores to facilitate exceptionally fast ion transport (beneficial to addressing sluggish ORR kinetics of PEMFC electrodes) and achieve functionalities of ionic diodes under applied electrochemical fields, beneficial for selective transport/separation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

An overview of bipolar plates in proton exchange membrane fuel cells

Bipolar plates are a crucial component of proton exchange membrane fuel cells. They are responsible for transporting reactant gases, carrying the current from the membrane electrode assembly to the end plates, providing heat and water management, and separating the individual cells. However, these plates also contribute to 80% of the fuel cell’s weight, 50% of its volume, and 40% of its cost, posing a barrier to the commercialization of fuel cells. This paper provides a comprehensive review of the materials and manufacturing processes used in the fabrication of bipolar plates as well as recent research conducted on the improvement of bipolar plate weight, volume, and cost through material selection and manufacturing methods. Additive manufacturing is highlighted in this work as an innovative manufacturing method to produce bipolar plates. Novel contributions in this paper include a detailed explanation of traditional manufacturing processes for metallic and graphitic-polymer bipolar plates as well as a cost comparison between additive and traditional manufacturing processes.

08 HYDROGEN↗
DOE OSTI2024

Thermodynamic Modeling of Point Defects in Triple Conducting Perovskite Ba 0.95 La 0.05 FeO 3- $_δ$ with Incorporation of the Hydride Defect Formation Reaction for Solid Oxide Cells

Distinct from the proton defect, the hydride defect species may be present in certain perovskite materials in reducing environments such as in fuel electrodes of solid oxide cells (SOCs) or on the reducing side of ceramic membranes. A generalized defect thermodynamic model was developed for the triple-conducting perovskites (La,Ba)Fe 1-x M x O 3-δ (M = Y and Zr) to allow inclusion of the hydride defect formation reaction in addition to the other three main defect reactions, namely, the oxygen vacancy formation, hydration, and charge disproportionation reactions. This comprehensive defect model also allows the incorporation of polynomial functional forms of oxygen nonstoichiometry δ to describe the defect reaction energies and entropies and to enable refinements of the defect reaction equilibrium constants in the defect thermodynamic analysis. As a first step, the developed model is applied to the Ba 0.95 La 0.05 FeO 3-δ material as an illustrative system to obtain its Brouwer diagrams with both the proton and hydride defects in relevant SOC conditions, particularly for more reducing environments. In conclusion, the results provide direct guidance on the influence of electronic and ionic defect concentrations upon thermodynamic properties and ultimately on the performance of Ba 0.95 La 0.05 FeO 3-δ and potentially other (La,Ba)Fe 1-x M x O 3-δ perovskite materials involved in SOC applications.

25 ENERGY STORAGE↗
DOE OSTI2020

Synergistically integrated phosphonated poly(pentafluorostyrene) for fuel cells

Modern electrochemical energy conversion devices require more advanced proton conductors for their broad applications. Phosphonated polymers have been proposed as anhydrous proton conductors for fuel cells. However, the anhydride formation of phosphonic acid functional groups lowers proton conductivity and this prevents the use of phosphonated polymers in fuel cell applications. Here, we report a poly(2,3,5,6-tetrafluorostyrene-4-phosphonic acid) that does not undergo anhydride formation and thus maintains protonic conductivity above 200 °C. We use the phosphonated polymer in fuel cell electrodes with an ion-pair coordinated membrane in a membrane electrode assembly. We find that this synergistically integrated fuel cell reached peak power densities of 1,130 mW cm -2 at 160 °C and 1,740 mW cm -2 at 240 °C under H2/O2 conditions, substantially outperforming polybenzimidazole- and metal phosphate-based fuel cells. Our result indicates a pathway towards using phosphonated polymers in high-performance fuel cells under hot and dry operating conditions.

25 ENERGY STORAGE↗
DOE OSTI2022

Modeling ammonia-fueled co-flow dual-channel protonic-ceramic fuel cells

This paper reports the model development for a dual-channel protonic-ceramic fuel cell (PCFC) operating on ammonia fuel. The model considers the coupled interactions of several physical and chemical processes, including three-dimensional heat conduction within the bipolar plates and the membrane-electrode assembly (MEA), one-dimensional flow within the fuel and air channels, detailed heterogeneous catalytic reactions within the porous composite anode structure, Butler–Volmer representation of the charge-transfer chemistry, and Nernst–Planck transport of three charged defects (protons, oxygen vacancies, and small polarons) within the dense electrolyte membrane. The membrane-electrode assembly is composed of a Ni-BCZYYb (BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ ) anode, a BCZYYb electrolyte membrane, and a BCFZY (BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ ) cathode. Chemical and physical parameters for the MEA model are established using previously published button-cell data. One aspect of the study is to investigate the partial ammonia decomposition upstream of the fuel cell. Such fuel cracking increases the H 2 content of the fuel entering the PCFC, which may have benefits. However, endothermic ammonia pyrolysis within the composite anode structure assists with thermal control of the cell. The dual-channel model can be considered as the unit cell of a full fuel-cell stack.

25 ENERGY STORAGE↗
DOE OSTI2022

Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.

impedance↗
DOE OSTI2024

How Low Can You Go? Nanoscale Membranes for Efficient Water Electrolysis

Motivated by the need to lower the cost of hydrogen (H 2 ) production by water electrolysis, significant research efforts are focused on making proton (H + ) exchange membrane (PEM) water electrolyzers more efficient and capable of operating at higher current densities. These aims can be met by making H + -conducting membranes thinner, which has the effect of lowering ohmic drops across the membrane that represent the largest efficiency loss at high current densities (>2 A cm –2 ). However, decreasing membrane thickness below 50 μm is not trivial due to trade-offs between membrane resistance, H 2 crossover (safety), membrane degradation, and manufacturing throughput. Furthermore, descriptions of key processes, limitations, and trade-offs that arise in thin membranes are provided that can be used to guide the design of ultrathin (i.e., submicron thick), low-resistance membrane materials that have the potential to transform the field of clean H 2 production.

08 HYDROGEN↗
DOE OSTI2021

Characterization of a Sulfonated Poly(Ionic Liquid) Block Copolymer as an Ionomer for Proton Exchange Membrane Fuel Cells using Rotating Disk Electrode

Ionic liquid (IL) additives to both traditional and advanced oxygen reduction reaction (ORR) electrocatalysts have yielded remarkable improvements in catalyst performance and durability. However, incorporating ILs or IL-modified catalysts into the electrodes of a proton exchange membrane fuel cell (PEMFC) membrane electrode assembly (MEA) has proven to be challenging. Sulfonated poly(ionic liquid) block copolymers (S-PILBCP) present an opportunity to incorporate IL functionality directly into the ionomer, orthogonal to protonic conductivity. Here, we use a rotating disc electrode (RDE) to characterize the interface between a S-PILBCP and Pt catalyst in comparison to Nafion. Catalyst thin films prepared with S-PILBCP show an 80% improvement in the ORR activity over those containing Nafion. Thin films of S-PILBCP also show a significantly reduced degree of poisoning sulfonate adsorption on a Pt(111) surface in comparison to Nafion. Furthermore, these half-cell results provide useful insights that help to highlight the source of the impact of the S-PILBCP on PEMFC MEA performance.

25 ENERGY STORAGE↗
DOE OSTI2024

Constitutive model development of aluminum alloy 1100 for elevated temperature forming process

Commercially pure aluminum alloy, AA1100, presents good electrical and thermal conductivity, high formability, and low cost. Those favorable characteristics have the potential to enable bipolar plates with improved economics and enhanced performance compared to current stainless steel bipolar plates for proton exchange membrane fuel cells. An accurate constitutive model is essential to develop and optimize processing parameters and effectively control the forming process. Here, the objective of this work is to develop a constitutive model of AA1100 that is able to simulate stress-strain relation, formed geometry, and predict the onset of fracture strain to avoid forming failure. Initially, a set of tensile tests at temperature between 300 and 500°C and strain rate between 0.005 and 1.0/s were conducted to examine the deformation behavior. Then, a set of damage-based unified visco-plastic constitutive equations is proposed and calibrated based on the results of stress-strain data. A genetic algorithm optimization method is applied to search for best fitting material constants in constitutive equations. The proposed model shows good predictability of both the stress-strain relation and fracture strain at low strain rate and high temperature conditions. The accuracy of proposed model is also evaluated statistically. A comparison of the proposed model with three popular models (Arrhenius-type mode, Johnson-Cook model and Zerilli-Armstrong model) was made. The proposed model shows the best experimental agreement with correlation coefficient of 0.96 in contrast to 0.25, 0.38 and 0.75 for the popular models, respectively. The proposed model can help to optimize the elevated temperature forming process and guide die design to enable optimal geometric features in the formed components.

08 HYDROGEN↗
DOE OSTI2020

Role of phosphate source in improving the proton conductivity of tin pyrophosphate and its composite electrolytes

Metal pyrophosphates (MPPs) in general, and tin pyrophosphate (TPP) in particular, have received significant interest in the last decade due to their potential as proton conductors for electrolyte application in intermediate temperature (IT)-fuel cells. However, for MPP based electrolytes, despite high reported proton conductivities, achieving good fuel cell performance and high open circuit voltage (OCV) remains a challenge with synthesis methods playing a crucial role in determining the final proton conductivity. Here we report the role of phosphate precursor in determining the TPP proton conductivity by examining five different precursors: (1) phosphoric acid (TPP-PA), (2) ammonium hydroxide + phosphoric acid (TPP-NH 4 OH), (3) diammonium phosphate (TPP-DAP), (4) tetramethylammonium sulphate + phosphoric acid (TPP-TMAP), and (5) tetrabutylammonium phosphate (TPP-TBAP), where a maximum conductivity of 88 mS cm -1 at 200 °C was obtained for TPP prepared from the TBAP precursor. TPP prepared from all of the different precursors formed the crystalline cubic Pa-3 with combining macron] phase after sintering at 650 °C for 2.5 hours. Furthermore, TPP-TBAP/Nafion® composite membranes prepared with a 90 : 10 ratio exhibited an OCV of 0.98 V and produced a maximum peak power density (PPD) of 630 mW cm -2 at an operating temperature of 220 °C. Our results demonstrate the significant impact of the TPP precursor on proton conductivity and fuel cell performance.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Technology Assessment for Producing Propellant From Lunar Water

Introduction: The presence of water ice in permanently shadowed regions (PSRs) on the lunar surface may enable a sustained human presence on the Moon with minimal need for consumables. One of the most valuable uses of lunar water is to produce rocket propellant. A sustained human presence on the Moon will re-quire frequent launches from the lunar surface, and each launch will require tons of propellant. However, many other volatiles are likely to be present in the areas where lunar water is stable1. Producing propellant from lunar water in-situ will require the separation and purification of water before it can be electrolyzed into oxygen and hydrogen gas. The Resource Exploration and Science of OUR Cosmic Environment (RESOURCE) project, funded by the Solar System Exploration Research Virtual Institute (SSERVI) program, includes a task to demonstrate the end-to-end process of water extraction, capture, purification and electrolysis to produce pure/dry oxygen gas sourced from an icy regolith mixture. Water Purification: The requirements for water purity are driven by the type of water electrolyzer used. For example, the water electrolyzer currently used on the International Space Station is based on proton ex-change membrane (PEM) technology. PEM-based electrolyzers require water to be ultrapure and deionized (>10 MegaOhm-cm) so that electrical conductivity is limited to the membranes themselves, where electrical current is used to convert H2O into H2 and O2.. A practical first step toward purifying water that is sourced from a lunar PSR is to use freeze distillation to separate water from other volatiles2. A sub-micronic filter can also be used to ensure that a minimal amount of dust is present in any lunar water that is captured. The combination of freeze distillation and sub-micronic filtration will result in relatively pure water but would require a deionization step if being fed into a PEM electrolyzer. Water Electrolysis: An alternative to PEM electrolysis is to use a Solid Oxide Electrolyzer (SOE). This technology operates at a much higher operating temperature (~800oC) and has a limited pressure range but does not require water to be ultrapure and deionized. Another advantage of SOE technology is that it produces pure dry oxygen gas without the need of an additional drying step. PEM electrolyzers produce humid oxygen gas and the humidity must be removed prior to liquefaction. Assessment: In order to compare PEM and SOE technologies side-by-side, they must be compared at a system level that includes water purification and gas drying steps. Engineers at the Johnson Space Center up-dated and utilized a detailed In-Situ Resource Utilization (ISRU) system model to compare and select the best option for the RESOURCE project which will conclude with a laboratory demonstration of the process of producing pure/dry oxygen from an icy regolith mixture in 2025.

A.J. Paz↗
NASA NTRSDate not supplied

Technology Assessment for Producing Propellant From Lunar Water

Introduction: The presence of water ice in permanently shadowed regions (PSRs) on the lunar surface may enable a sustained human presence on the Moon with minimal need for consumables. One of the most valuable uses of lunar water is to produce rocket propellant. A sustained human presence on the Moon will re-quire frequent launches from the lunar surface, and each launch will require tons of propellant. However, many other volatiles are likely to be present in the areas where lunar water is stable1. Producing propellant from lunar water in-situ will require the separation and purification of water before it can be electrolyzed into oxygen and hydrogen gas. The Resource Exploration and Science of OUR Cosmic Environment (RESOURCE) project, funded by the Solar System Exploration Research Virtual Institute (SSERVI) program, includes a task to demonstrate the end-to-end process of water extraction, capture, purification and electrolysis to produce pure/dry oxygen gas sourced from an icy regolith mixture. Water Purification: The requirements for water purity are driven by the type of water electrolyzer used. For example, the water electrolyzer currently used on the International Space Station is based on proton ex-change membrane (PEM) technology. PEM-based electrolyzers require water to be ultrapure and deionized (>10 MegaOhm-cm) so that electrical conductivity is limited to the membranes themselves, where electrical current is used to convert H2O into H2 and O2.. A practical first step toward purifying water that is sourced from a lunar PSR is to use freeze distillation to separate water from other volatiles2. A sub-micronic filter can also be used to ensure that a minimal amount of dust is present in any lunar water that is captured. The combination of freeze distillation and sub-micronic filtration will result in relatively pure water but would require a deionization step if being fed into a PEM electrolyzer. Water Electrolysis: An alternative to PEM electrolysis is to use a Solid Oxide Electrolyzer (SOE). This technology operates at a much higher operating temperature (~800oC) and has a limited pressure range but does not require water to be ultrapure and deionized. Another advantage of SOE technology is that it produces pure dry oxygen gas without the need of an additional drying step. PEM electrolyzers produce humid oxygen gas and the humidity must be removed prior to liquefaction. Assessment: In order to compare PEM and SOE technologies side-by-side, they must be compared at a system level that includes water purification and gas drying steps. Engineers at the Johnson Space Center up-dated and utilized a detailed In-Situ Resource Utilization (ISRU) system model to compare and select the best option for the RESOURCE project which will conclude with a laboratory demonstration of the process of producing pure/dry oxygen from an icy regolith mixture in 2025.

ISRU↗
DOE OSTI2022

Intermediate-Temperature Proton Exchange Membranes Based on Cerium Ultraphosphate Composited with Polybenzimidazole

This paper reports the rational fabrication and structural, thermal, mechanical and electrochemical characterization of a new type of intermediate-temperature (IT) polymer-inorganic composite (PIC) proton exchange membranes (PEMs) that are made of cerium ultraphosphate (CeP 5 O 14 —CUP) as the solid-state proton conductor composited with a high-temperature (HT) polybenzimidazole (PBI) as the polymeric binder. Here, flexible PBI-CUP PIC membranes with the thickness of ~135 μ m and CUP mass fraction of up to 75% were prepared by solution-casting without additional acid-doping (e.g., phosphoric acid). The proton conductivity of the fabricated IT-PIC-PEMs was up to 5.80 × 10 –2 S cm –1 as measured from a prototype IT PEM fuel cell (PEMFC) operated at 200 °C in the humidified hydrogen and air environment. This type of IT-PIC-PEMs also demonstrated sufficient mechanical strength and flexibility, excellent thermal stability (up to 350 °C), and very good durability of the proton conductivity (within the test duration of 500 h). The present experimental study shows the promising future of the IT-PIC-PEMs for applications in various IT electrochemical processes including IT-PEMFCs, IT-electrolyzers, etc.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Perovskite Catalysts for Pure-Water-Fed Anion-Exchange-Membrane Electrolyzer Anodes: Co-design of Electrically Conductive Nanoparticle Cores and Active Surfaces

Anion-exchange-membrane water electrolyzers (AEMWEs) are a possible low-capital-expense, efficient, and scalable hydrogen-production technology with inexpensive hardware, earth-abundant catalysts, and pure water. However, pure-water-fed AEMWEs remain at an early stage of development and suffer from inferior performance compared with proton-exchange-membrane water electrolyzers (PEMWEs). One challenge is to develop effective non-platinum-group-metal (non-PGM) anode catalysts and electrodes in pure-water-fed AEMWEs. We show how LaNiO3-based perovskite oxides can be tuned by cosubstitution on both A- and B-sites to simultaneously maintain high metallic electrical conductivity along with a degree of surface reconstruction to expose a stable Co-based active catalyst. The optimized perovskite, Sr0.1La0.9Co0.5Ni0.5O3, yielded pure-water AEMWEs operating at 1.97 V at 2.0 A cm-2 at 70 °C with a pure-water feed, thus illustrating the utility of the catalyst design principles.

Zhai, Tingting↗
DOE OSTI2024

Surface Functionalization of Carbon Black for PEM Fuel Cell Electrodes

Abstract Carbon‐based materials are extensively used in fuel cell applications due to their crucial role in maintaining high performance. Particularly, carbon black (CB) stands out as a preferred electrode material for fuel cells, owing to its high electrical conductivity and large surface area. This review focuses on the functionalization of CB and its use as a support for Pt‐based catalysts in proton exchange membrane fuel cells. Functionalization strategies include oxidation, covalent functionalization, as well as polymer grafting or impregnation. Various approaches to functionalize the CB surface are discussed that effectively tailor the surface properties of electrodes, leading to improved fuel cell performance. The improvements are seen in enhanced dispersibility of catalyst particles, better ionomer distribution, increased catalyst stability, and reduced carbon corrosion. This review provides an overview of various modifications applied to CB to enhance their structural and electrochemical properties, thereby boosting fuel cell performance.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS2003

Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.

Irvin, Jennifer A.↗