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Iodine Hall Thruster Propellant Feed System for a CubeSat

There has been significant work recently in the development of iodine-fed Hall thrusters for in-space propulsion applications.1 The use of iodine as a propellant provides many advantages over present xenon-gas-fed Hall thruster systems. Iodine is a solid at ambient temperature (no pressurization required) and has no special handling requirements, making it safe for secondary flight opportunities. It has exceptionally high ρI sp (density times specific impulse), making it an enabling technology for small satellite near-term applications and providing system level advantages over mid-term high power electric propulsion options. Iodine provides thrust and efficiency that are comparable to xenonfed Hall thrusters while operating in the same discharge current and voltage regime, making it possible to leverage the development of flight-qualified xenon Hall thruster power processing units for the iodine application. Work at MSFC is presently aimed at designing, integrating, and demonstrating a flight-like iodine feed system suitable for the Hall thruster application. This effort represents a significant advancement in state-of-the-art. Though Iodine thrusters have demonstrated high performance with mission enabling potential, a flight-like feed system has never been demonstrated and iodine compatible components do not yet exist. Presented in this paper is the end-to-end integrated feed system demonstration. The system includes a propellant tank with active feedback-control heating, fill and drain interfaces, latching and proportional flow control valves (PFCV), flow resistors, and flight-like CubeSat power and control electronics. Hardware is integrated into a CubeSat-sized structure, calibrated and tested under vacuum conditions, and operated under under hot-fire conditions using a Busek BHT-200 thruster designed for iodine. Performance of the system is evaluated thorugh accurate measurement of thrust and a calibrated of mass flow rate measurement, which is a function of reservoir temperature/pressure, the flow resistors, and the setting of the PFCV. The calibration is performed using independent flow control monitoring techniques, providing an in situ measure of the flowrate as a function of controllable parameters. The reservoir temperature controls the iodine sublimation rate, providing propellant to ths thruster by pressurizing the propellant feed system to approx.1-2 psi. Control of the temperature and the PFCV are used to maintain reservoir pressure and keep the thruster discharge current constant.

Polzin, Kurt A.↗

Iodine Satellite

The Iodine Satellite (iSat) spacecraft will be the first CubeSat to demonstrate high change in velocity from a primary propulsion system by using Hall thruster technology and iodine as a propellant. The mission will demonstrate CubeSat maneuverability, including plane change, altitude change and change in its closest approach to Earth to ensure atmospheric reentry in less than 90 days. The mission is planned for launch in fall 2017. Hall thruster technology is a type of electric propulsion. Electric propulsion uses electricity, typically from solar panels, to accelerate the propellant. Electric propulsion can accelerate propellant to 10 times higher velocities than traditional chemical propulsion systems, which significantly increases fuel efficiency. To enable the success of the propulsion subsystem, iSat will also demonstrate power management and thermal control capabilities well beyond the current state-of-the-art for spacecraft of its size. This technology is a viable primary propulsion system that can be used on small satellites ranging from about 22 pounds (10 kilograms) to more than 1,000 pounds (450 kilograms). iSat's fuel efficiency is ten times greater and its propulsion per volume is 100 times greater than current cold-gas systems and three times better than the same system operating on xenon. iSat's iodine propulsion system consists of a 200 watt (W) Hall thruster, a cathode, a tank to store solid iodine, a power processing unit (PPU) and the feed system to supply the iodine. This propulsion system is based on a 200 W Hall thruster developed by Busek Co. Inc., which was previously flown using xenon as the propellant. Several improvements have been made to the original system to include a compact PPU, targeting greater than 80 percent reduction in mass and volume of conventional PPU designs. The cathode technology is planned to enable heaterless cathode conditioning, significantly increasing total system efficiency. The feed system has been designed to include iodine compatible control valves with internal heaters and temperature sensors to coincide with the iodine-compatible thruster. A key advantage to using iodine as a propellant is that it may be stored in the tank as an unpressurized solid on the ground and before flight operations. During operations, the tank is heated to vaporize the propellant. Iodine vapor is then routed through custom flow control valves to control mass flow to the thruster and cathode assembly. The thruster then ionizes the vapor and accelerates it via magnetic and electrostatic fields, resulting in high specific impulse, characteristic of a highly efficient propulsion system. The iSat spacecraft is a 12-unit (12U) CubeSat with dimensions of about 8 inches x 8 inches x 12 inches (20 centimeters x 20 centimeters x 30 centimeters). The spacecraft frame will be constructed from aluminum with a finish to prevent iodine-driven corrosion. The iSat spacecraft includes full three-axis control and will leverage heat generated by spacecraft components and radiators for a passive thermal control system. After the CubeSat has successfully detached from its launch vehicle, it will deploy its solar panels, correct for tip-off and maintain attitude control before ground contact. An initial check-out period of two weeks is planned for testing all subsystems. The spacecraft will charge the power system while in sunlight, using momentum wheels and magnetic torque rods to rotate the vehicle to the required attitude.

iSat↗

Iodine Satellite

This project is a collaborative effort to mature an iodine propulsion system while reducing risk and increasing fidelity of a technology demonstration mission concept. 1 The FY 2014 tasks include investments leveraged throughout NASA, from multiple mission directorates, as a partnership with NASA Glenn Research Center (GRC), a NASA Marshall Space Flight Center (MSFC) Technology Investment Project, and an Air Force partnership. Propulsion technology is often a critical enabling technology for space missions. NASA is investing in technologies to enable high value missions with very small and low-cost spacecraft, even CubeSats. However, these small spacecraft currently lack any appreciable propulsion capability. CubeSats are typically deployed and drift without any ability to transfer to higher value orbits, perform orbit maintenance, or deorbit. However, the iodine Hall system can allow the spacecraft to transfer into a higher value science orbit. The iodine satellite (iSAT) will be able to achieve a (Delta)V of >500 m/s with <1 kg of solid iodine propellant, which can be stored in an unpressurized benign state prior to launch. The iSAT propulsion system consists of the 200 W Hall thruster, solid iodine propellant tank, a power processing unit, and the necessary valves and tubing to route the iodine vapor. The propulsion system is led by GRC, with critical hardware provided by the Busek Co. The propellant tank begins with solid iodine unpressurized on the ground and in-flight before operations, which is then heated via tank heaters to a temperature at which solid iodine sublimates to iodine vapor. The vapor is then routed through tubing and custom valves to control mass flow to the thruster and cathode assembly. 2 The thruster then ionizes the vapor and accelerates it via magnetic and electrostatic fields, resulting in thrust with a specific impulse >1,300 s. The iSAT spacecraft, illustrated in figure 1, is currently a 12U CubeSat. The spacecraft chassis will be constructed from aluminum with a finish to prevent iodine-driven corrosion. The iSAT spacecraft includes full three-axis control using wheels, magnetic torque rods, inertial management unit, and a suite of sensors and optics. The spacecraft will leverage heat generated by spacecraft components and radiators for a passive thermal control system.

Dankanich, John↗

Engineering Model Propellant Feed System Development for an Iodine Hall Thruster Demonstration Mission

CUBESATS are relatively new spacecraft platforms that are typically deployed from a launch vehicle as a secondary payload, providing low-cost access to space for a wide range of end-users. These satellites are comprised of building blocks having dimensions of 10x10x10 cu cm and a mass of 1.33 kg (a 1-U size). While providing low-cost access to space, a major operational limitation is the lack of a propulsion system that can fit within a CubeSat and is capable of executing high (Delta)v maneuvers. This makes it difficult to use CubeSats on missions requiring certain types of maneuvers (i.e. formation flying, spacecraft rendezvous). Recently, work has been performed investigating the use of iodine as a propellant for Hall-effect thrusters (HETs) 2 that could subsequently be used to provide a high specific impulse path to CubeSat propulsion. 3, 4 Iodine stores as a dense solid at very low pressures, making it acceptable as a propellant on a secondary payload. It has exceptionally high ρIsp (density times specific impulse), making it an enabling technology for small satellite near-term applications and providing the potential for systems-level advantages over mid-term high power electric propulsion options. Iodine flow can also be thermally regulated, subliming at relatively low temperature (< 100 C) to yield I2 vapor at or below 50 torr. At low power, the measured performance of an iodine-fed HET is very similar to that of a state-of-the-art xenon-fed thruster. Just as importantly, the current-voltage discharge characteristics of low power iodine-fed and xenon-fed thrusters are remarkably similar, potentially reducing development and qualifications costs by making it possible to use an already-qualified xenon-HET PPU in an iodine-fed system. Finally, a cold surface can be installed in a vacuum test chamber on which expended iodine propellant can deposit. In addition, the temperature doesn't have to be extremely cold to maintain a low vapor pressure in the vacuum chamber (it is under 10(exp −6) torr at −75 C), making it possible to 'cryopump' the propellant with lower-cost recirculating refrigerant-based systems as opposed to using liquid nitrogen or low temperature gaseous helium cryopanels. In the present paper, we describe the design and testing of the engineering model propellant feed system for iSAT (see Fig. 1). The feed system is based around an iodine propellant reservoir and two proportional control valves (PFCVs) that meter the iodine flow to the cathode and anode. The flow is split upstream of the PFCVs to both components can be fed from a common reservoir. Testing of the reservoir is reported to demonstrate that the design is capable of delivering the required propellant flow rates to operate the thruster. The tubing and reservoir are fabricated from hastelloy to resist corrosion by the heated gaseous iodine propellant. The reservoir, tubing, and PFCVs are heated to ensure the sublimed propellant will not re-deposit within the feed system. Heating is accomplished through a number of individual zones to control the overall power expended on heating the system and insulation is employed to minimize the amount of power used to heat the system prior to thruster operation.

Polzin, Kurt A.↗

Demonstration of a 600 Watt Hybrid Iodine-Xenon Electric Propulsion System

This paper reviews recent iodine compatible electric propulsion technologies evaluated at the NASA Glenn Research Center. The work culminated in a 1,174-hour hybrid iodine-xenon propulsion system durability demonstration (iodine fed thruster with xenon fed cathode). The test demonstrated that (i) a Hall-effect thruster operates with nearly identical performance whether employing iodine or xenon propellant, (ii) careful selection of propulsion system materials and coatings can result in durable iodine-compatible hardware, and (iii) implementation of appropriate facility improvements and procedures can limit negative impacts of iodine on test hardware and ground support equipment. The work was motivated by advancements in capability of very dense small-spacecraft (<500 kg), but spacecraft still lacking very dense in-space propulsion to provide the large delta-v capabilities (3 to 10 km/s) required for many high-value NASA exploration and science missions. Volume limitations of small-spacecraft not only require dense propulsion systems, but more so dense propellants. NASA identifies xenon and iodine as having both favorable storage densities and propulsive properties to enable many NASA small-spacecraft mission scenarios. While xenon is inert and well-proven in spaceflight applications, iodine has triple the storage density of xenon and stores at low pressures, permitting use of conformal tank designs. Unlike xenon, iodine does raise concerns related to its reactivity with most materials, potential spacecraft-propellant interactions, impact on ground test facilities, and challenges to acceptance test iodine propulsion systems prior to flight. This work begins to address these challenges. This work was conducted under the Advanced In-Space Propulsion (AISP) project funded through the Game Changing Development (GCD) program within NASA's Science Technology Mission Directorate (STMD).

Benavides, G. F.↗

Measurement of Iodine, Iodide, and Iodate in Hanford Tank Waste: Technology Transfer from PNNL to Hanford 222-S Laboratory

This report summarizes the measurement of the inorganic chemical forms of iodine in Hanford tank waste. The Hanford tank wastes have roughly a part per million iodine. Part of the iodine is the long-lived beta emitter 129I, and the rest is stable 127I. Because tank waste iodine is radioactive and radiotoxic, its chemical form must be known so that its behavior in the vitrification process can be reliably known and anticipated in various waste streams (glass, secondary liquid and solid waste, and offgas emissions) at Hanford. Iodine in tank wastes exists in the inorganic chemical forms iodide and iodate (and possibly also periodate) and also as organic forms such as alkyl iodides. The measurement of organic iodides is very different from the measurement of inorganic forms and is outside the scope of this report. The inorganic chemical forms are chemically separated, in sequence, from the raw tank waste using solvent extractions and several redox reactions, then measured by ICP-MS. The inorganic chemical forms of iodine are chemically reactive, and so is the tank waste. The chemistry must be carefully designed to avoid unintended reactions that could convert one form of iodine to another during the analysis, which would skew the data and report iodine in the wrong chemical form. This iodine analysis, developed at PNNL, is being transferred to the DOE 222-S Laboratory on the Hanford Site, in Washington State, for implementation during waste processing operations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Iodine Sorption on AgZ-PAN

The Department of Energy (DOE) Nuclear Fuel Cycle and Supply Chain Program Material Recovery and Waste Form Development (MRWFD) Campaign Off-gas Sigma Team has performed research and development on iodine control and iodine waste forms for the past several years. This research and development has included iodine adsorption tests using a laboratory-scale test system containing multiple-segmented fixed beds of iodine adsorbents. Iodine capture performance has been tested using (a) non-radioactive synthetic gas mixtures blended from air, nitrogen, NO, NO 2 , water, to simulate dissolver off-gas (DOG) and vessel off-gas (VOG) streams from used nuclear fuel aqueous reprocessing, (b) inorganic and organic iodine species, and (c) different sorbents. An initial test of silver-functionalized mordenite in polyacrylonitrile matrix (AgZ-PAN) was conducted to assess if this sorbent, initially designed for selective sorption of Xe that evolves into used fuel reprocessing off-gas streams, could also be a candidate for iodine sorption. This test was conducted using the same deep-bed test system and methodologies used in many prior iodine sorption tests using other sorbents. Diatomic iodine (I2) was used as the target iodide in a gas stream containing air, NO, NO 2 , and moisture designed to simulate an aqueous reprocessing dissolver off-gas (DOG) stream.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Iodine sorption study on the proposed use of Viton A in a shuttle galley water accumulator

The installation of a Viton A accumulator in the Shuttle galley has been proposed to prevent overpressurization of the hot water supply system. A laboratory study has been conducted to determine if there would be any interaction between the Viton A material and the iodine used to disinfect the water. Coupons of Viton A were exposed for 24 hours to aqueous iodine solutions similar in quality to the Shuttle's potable water. Changes in the iodine residual were monitored to determine the rate of iodine sorption by the coupon. Total organic carbon (TOC) was monitored to determine the rate of desorption of organic materials from the Viton A. The same coupons were then soaked in reagent-grade water for 24 hours, and iodine was monitored to determine the rate of iodine desorption. The coupons were again exposed to iodine solutions for 24 hours and iodine and TOC were monitored. No significant change in the iodine sorption rate was detected between the first and second exposures. A triangle taste test indicated at a 1 percent confidence level that the water exposed to Viton A had a different taste which was less acceptable to the panelists.

Gibbons, Randall E.↗

Effect of iodine disinfection products on higher plants

Iodine is used to disinfect potable water on United States spacecraft. Iodinated potable water will likely be used to grow plants in space. Little is known about the effects of iodine disinfection products on plants. Seeds of select higher plants were germinated in water iodinated using the Shuttle Microbial Check Valve, and water to which measured amounts of iodine was added. Percent germination was decreased in seeds of most species germinated in iodinated water. Beans were most affected. Germination rates, determined from germination half-times, were decreased for beans germinated in iodinated water, and water to which iodide was added. Development was retarded and rootlets were conspicuously absent in bean and several other plant species germinated in iodinated water. Iodide alone did not elicit these responses. Clearly iodine disinfection products can affect higher plants. These effects must be carefully considered for plant experimentation and cultivation in space, and in design and testing of closed environmental life support systems.

Janik, D.↗

Recent experiences with iodine water disinfection in Shuttle

Microbial proliferation in the STS potable water system is prevented by maintaining a 2-5 ppm iodine residual. The iodine is added to fuel cell water by an iodinated ion exchange resin in the Microbial Check Valve (MCV). Crew comments indicated excessive iodine in the potable water. To better define the problem, a method of in-flight iodine analysis was developed. Inflight analysis during STS-30 and STS-28 indicated iodine residuals were generally in the 9-13 ppm range. It was determined that the high iodine residual was caused by MCV influent temperatures in excess of 120 F. This is well above the MCV operating range of 65-90 F. The solution to this problem was to develop a resin suitable for the higher temperatures. Since 8 months were required to formulate a MCV resin suitable for the higher temperatures, a temporary solution was necessary. Two additional MCV's were installed on the chilled and ambient water lines leading into the galley to remove the excess iodine. These reduced the iodine residual to 3-4 ppm during STS-33, STS-34, STS-36 and STS-32. A high-temperature resin was formulated and initially flown on STS-31.

Gibbons, Randall E.↗

Computation of iodine species concentrations in water

During an evaluation of the use of iodine as a water disinfectant and the development of methods for measuring various iodine species in water onboard Space Freedom, it became necessary to compute the concentration of the various species based on equilibrium principles alone. Of particular concern was the case when various amounts of iodine, iodide, strong acid, and strong base are added to water. Such solutions can be used to evaluate the performance of various monitoring methods being considered. The authors of this paper present an overview of aqueous iodine chemistry, a set of nonlinear equations which can be used to model the above case, and a computer program for solving this system of equations using the Newton-Raphson method. The program was validated by comparing results over a range of concentrations and pH values with those previously presented by Gottardi for a given pH. Use of this program indicated that there are multiple roots to many cases and selecting an appropriate initial guess is important. Comparison of program results with laboratory results for the case when only iodine is added to water indicates the program gives high pH values for the iodine concentrations normally used for water disinfection. Extending the model to include the effects of iodate formation results in the computer pH values being closer to those observed, but the model with iodate does not agree well for the case in which base is added in addition to iodine to raise the pH. Potential explanations include failure to obtain equilibrium conditions in the lab, inaccuracies in published values for the equilibrium constants, and inadequate model of iodine chemistry and/or the lack of adequate analytical methods for measuring the various iodine species in water.

Schultz, John R.↗

Improvement in Suppression of Pulsed Nd:YAG Laser Light With Iodine Absorption Cells for Filtered Rayleigh Scattering Measurements

Filtered Rayleigh scattering using iodine absorption cells is an effective technique for obtaining density, temperature, and velocity measurements in high speed confined flows. By tuning a single frequency laser to a strong iodine absorption line, stray scattered laser light can be greatly suppressed. For example, the minimum transmission predicted by an iodine absorption model calculation is less than 10(exp -5) at the 18788.44/cm line using a 200 mm absorption cell containing iodine vapor at 0.46 T. Measurements obtained by other researches using a CW Nd:YAG laser agree with the model calculations. However, measurements made by us and by others using Q-switched, injection-seeded, frequency doubled Nd:YAG lasers only show minimum transmission of about 3 x 10(exp -3). This greatly reduces the applicability of the filtered Rayleigh scattering technique using these lasers in experiments having large amounts of stray scattered laser light. The purposes of the present study are to characterize the spectrum of the excess light transmitted by the iodine cell and to make changes to the laser to reduce the transmitted laser light. Transmission data as a function of laser frequency for the iodine absorption line at 18788.44/cm are presented. A planar mirror Fabry-Perot interferometer was used to characterize the frequency spectrum of the light passed through the cell. Measurements taken with the laser tuned to the center of the iodine absorption line show the light transmitted through the iodine cell to have a component with a bandwidth of about 40 GHz. This is probably caused by other modes in the laser that exist in spite of the single frequency injection beam. A second broadband component was also observed, possibly caused by the laser flash lamps or by fluorescence. An intracavity etalon was installed in the laser oscillator cavity to suppress the 40 GHz component. Measurements taken with the etalon tuned to the injection frequency showed a reduction in the transmitted laser light. This improvement allows the iodine cell to block significantly more of the stray laser light in filtered Rayleigh scattering experiments. Examples are given of filtered Rayleigh scattering measurements showing the effect of the etalon on measurements taken in a Mach 3 flow in the NASA Lewis 4 inch by 10 inch supersonic wind tunnel.

Seasholtz, Richard G.↗

Mission and System Advantages of Iodine Hall Thrusters

The exploration of alternative propellants for Hall thrusters continues to be of interest to the community. Investments have been made and continue for the maturation of iodine based Hall thrusters. Iodine testing has shown comparable performance to xenon. However, iodine has a higher storage density and resulting higher ΔV capability for volume constrained systems. Iodine's vapor pressure is low enough to permit low-pressure storage, but high enough to minimize potential adverse spacecraft-thruster interactions. The low vapor pressure also means that iodine does not condense inside the thruster at ordinary operating temperatures. Iodine is safe, it stores at sub-atmospheric pressure, and can be stored unregulated for years on end; whether on the ground or on orbit. Iodine fills a niche for both low power (<1kW) and high power (>10kW) electric propulsion regimes. A range of missions have been evaluated for direct comparison of Iodine and Xenon options. The results show advantages of iodine Hall systems for both small and microsatellite application and for very large exploration class missions.

Dankanich, John W.↗

Gaseous Iodine Sorbents: A Comparison between Ag-Loaded Aerogel and Xerogel Scaffolds

The general properties of aluminosilicate aerogels and xerogels with silver nanoparticles as sorbents for capturing iodine gas [I2(g)] were investigated. The structures, morphologies, compositions, and pore structures of aerogel and xerogel were compared using powder X-ray diffraction (PXRD), scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, as well as specific surface area (SSA) and pore size analyses. The as-made aerogels, xerogels, and heat-treated aerogels were impregnated with Ag by aqueous ion exchange using AgNO3 solutions, and PXRD patterns showed the presence of nanocrystalline Ag0 after Ag-impregnation. Iodine loadings of aerogels and xerogels were 0.33–0.41 g g-1. The Ag-impregnated aerogels without heat-treatment showed an 8 mass% higher iodine loading than Ag-impregnated xerogels and 3 mass% higher than heat-treated Ag-impregnated aerogels. All gels after iodine uptake showed the presence of AgI, indicating chemisorption of iodine to silver. The SSA values of the as-made gels were 419–598 m2 g-1 but decreased significantly to 34–120 m2 g-1 after Ag-impregnation and iodine uptake processes. Overall, changes in physical and chemical properties of aerogels and xerogels after iodine uptake were similar, and the difference in iodine loading capacities of the aerogels and xerogels was not significant while the synthesis process of xerogel is more practical because it does not require supercritical drying.

aerogel, xerogel, iodine capture↗

CI-MBPT line strengths and atomic probabilities for some transitions of neutral iodine

Iodine is a promising alternative to expensive xenon as a propellant for electric propulsion devices. Iodine optical spectroscopy is a valuable diagnostic tool for optimization of the iodine propellant. Recently, some measurements have been conducted with cells containing iodine plasma, and iodine atomic absorption at several wavelengths (911, 906, 206 and 1315 nm) was measured with a Ti:sapphire laser. Motivated by these experiments and future applications, here we have calculated line strengths and atomic probabilities for the transitions between different types of 5s 2 5p 5 , 5s 2 5p 4 6s, 5s 2 5p 4 6p and 5s 2 5p 4 5d states of atomic iodine, using configuration-interaction many-body perturbation theory. Since experimental transition data for atomic iodine are only available for a relatively small number of transitions, we also performed calculations for the bromine atom, to further validate our approach. We found good agreement between our theory and available experimental data for both elements in most cases. Therefore, we believe that our predicted line strengths and transition probabilities are quite reliable and will be useful for iodine spectroscopy.

74 ATOMIC AND MOLECULAR PHYSICS↗

Preliminary Study of Iodine Gas Removal in Sodium Pools

Potential iodine gas release from failed fuel pins is a critical factor in the source term analysis of oxide fuel-loaded sodium fast reactors (SFRs). The accumulated iodine-containing gas mixtures inside pin plenums are expected to be ejected during pin failures and rise through sodium pool, with potential release of gaseous iodine to the cover gas region. Due to its potential radiological impacts, a proper assessment of iodine behavior is necessary for an accurate source term assessment. Throughout the bubble rise trajectory in the sodium pool, iodine gas is continuously removed or transformed at the bubble interface by diffusion, as the combining reaction between the iodine and sodium to form sodium iodide (NaI) is a chemically preferred process. As the final amount of iodine released from the facility is strongly influenced by the removal phenomenon inside the sodium pool, experiments were previously performed by PNC (Power Reactor and Nuclear Fuel Development Corporation) to provide insight into this phenomenon. To assess the accuracy of present methods for predicting iodine gas removal within sodium pools, several candidate approaches, available in source term analysis codes, have been summarized and evaluated in this study. Spherical cap bubbles and spherical bubbles are considered in accordance with the methods adopted in each approach, and different forms of correlations for major parameters have been implemented in accordance with the original adoptions. Based on the summarized results, important aspects to be considered have been derived.

Decontamination↗

Charge Compensation by Iodine Covalent Bonding in Lead Iodide Perovskite Materials

Metal halide perovskite materials (MHPs) are a family of next-generation semiconductors that are enabling low-cost, high-performance solar cells and optoelectronic devices. The most-used halogen in MHPs, iodine, can supplement its octet by covalent bonding resulting in atomic charges intermediate to I− and I0. Here, we examine theoretically stabilized defects of iodine using density functional theory (DFT); defect formation enthalpies and iodine Bader charges which illustrate how MHPs adapt to stoichiometry changes. Experimentally, X-ray photoelectron spectroscopy (XPS) is used to identify perovskite defects and their relative binding energies, and validate the predicted chemical environments of iodine defects. Examining MHP samples with excess iodine compared with near stoichiometric samples, we discern additional spectral intensity in the I 3d5/2 XPS data arising from defects, and support the presence of iodine trimers. I 3d5/2 defect peak areas reveal a ratio of 2:1, matching the number of atoms at the ends and middle of the trimer, whereas their binding energies agree with calculated Bader charges. Results suggest the iodine trimer is the preferred structural motif for incorporation of excess iodine into the perovskite lattice. Understanding these easily formed photoactive defects and how to identify their presence is essential for stabilizing MHPs against photodecomposition.

36 MATERIALS SCIENCE↗

Biological monitoring of iodine, a water disinfectant for long-term space missions

In order to establish guidelines for exposure of astronauts to iodine, used as a water disinfectant in space, we studied the usefulness of hair, saliva, and urine for biological monitoring in humans and in the human hair/nude mouse model. The monitoring of iodine in patients that received 150 mCi of Na131I (carrier-free) showed similar patterns of elimination for blood, saliva, and urine. The mean correlation coefficient (r) between iodine elimination for blood/saliva was 0.99, for blood/urine, 0.95, and for saliva/urine, 0.97. The absolute value of iodine concentrations in urine revealed marked variability, which was corrected by adjusting for creatinine levels. The autoradiographic studies of human hair demonstrated that iodine is rapidly incorporated into external layers of the hair root and can be removed easily during washing. These data were confirmed after iodine exposure using the human hair/nude mouse model. Hair does not provide satisfactory information about exposure due to unstable incorporation of iodine. The most useful medium for biological monitoring of astronauts exposed to high doses of iodine in drinking water is urine, when adjusted for creatinine, and saliva, if quantitative evaluation of flow rate is provided.

NASA Discipline Environmental Health↗