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195 records · Page 11

Compatibility of potential reinforcing ceramics with Ni and Fe aluminides

There is a great deal of interest in the possible utilization of intermetallic compounds in advanced high temperature gas turbine engines. These compounds exhibit a variety of promising properties, including reasonable strength, high melting points, relatively low densities, and good corrosion resistance. However, in general, they also show limited ductilities and toughness, and less than optimum creep strengths at elevated temperatures. In addition, in applications involving advanced gas turbine engines, it is often necessary for candidate materials to have large elastic moduli. The present study is part of a program whose objective is to identify a high temperature fiber reinforced composite. The approach adopted was to fabricate laboratory samples of the combinations of materials considered by Misra, in order to determine the extent to which the thermodynamic calculations can predict phase stability. As many of the ceramic phases considered are not currently available in fiber form, they were added as particulates to the alloy matrices. The ways in which the materials were produced and evaluated are described.

Clark, William A. T.↗

Characterization of radiation-induced damage in high performance polymers by electron paramagnetic resonance imaging spectroscopy

The potential for long-term human activity beyond the Earth's protective magnetosphere is limited in part by the lack of detailed information on the effectiveness and performance of existing structural materials to shield the crew and spacecraft from highly penetrating space radiations. The two radiations of greatest concern are high energy protons emitted during solar flares and galactic cosmic rays which are energetic ions ranging from protons to highly oxidized iron. Although the interactions of such high-energy radiations with matter are not completely understood at this time, the effects of the incident radiation are clearly expected to include the formation of paramagnetic spin centers via ionization and bond-scission reactions in the molecular matrices of structural materials. Since this type of radiation damage is readily characterized by Electron Paramagnetic Resonance (EPR) spectroscopy, the NASA Langley Research Center EPR system was repaired and brought on-line during the 1991 ASEE term. A major goal of the 1992 ASEE term was to adapt the existing core of the LaRC EPR system to meet the requirements for EPR Imaging--a powerful new technique which provides detailed information on the internal structure of materials by mapping the spatial distribution of unpaired spin density in bulk media. Major impetus for this adaptation arises from the fact that information derived from EPRI complements other methods such as scanning electron microscopy which primarily characterize surface phenomena. The modification of the EPR system has been initiated by the construction of specially designed, counterwound Helmholtz coils which will be mounted on the main EPR electromagnet. The specifications of the coils have been set to achieve a static linear magnetic field gradient of 10 gauss/mm/amp along the principal (Z) axis of the Zeeman field. Construction is also in progress of a paramagnetic standard in which the spin distribution is known in all three dimensions. This sample will be used to assess the linearity of the magnetic field gradient and to ensure authentic image reconstruction. A second major task was to secure the computer capability to enable image reconstruction from projection data generated by the magnetic field gradients. To this end, commercially available and public domain software packages which perform inverse Fourier Transform and convoluted (filtered) back projection functions are being integrated into the existing EPR data processing system.

Suleman, Naushadalli K.↗

Alternative ways for formulation of hybrid stress elements

An element stiffness matrix can be derived by the conventional potential energy principle and, indirectly, also by generalized variational principles, such as the Hu-Washizu principle and the Hellinger-Reissner principle. The present investigation has the objective to show an approach which is concerned with the formulation of incompatible elements for solid continuum and for plate bending problems by the Hellinger-Reissner principle. It is found that the resulting scheme is equivalent to that considered by Tong (1982) for the construction of hybrid stress elements. In Tong's scheme the inversion of a large flexibility matrix can be avoided. It is concluded that the introduction of additional internal displacement modes in mixed finite element formulations by the Hellinger-Reissner principle and the Hu-Washizu principle can lead to element stiffness matrices which are equivalent to the assumed stress hybrid method.

Pian, T. H. H.↗

Highly Sensitive Tunable Diode Laser Spectrometers for In Situ Planetary Exploration

This paper describes highly sensitive tunable diode laser spectrometers suitable for in situ planetary exploration. The technology developed at JPL is based on wavelength modulated cavity enhanced absorption spectroscopy. It is capable of sensitively detecting chemical signatures of life through the abundance of biogenic molecules and their isotopic composition, and chemicals such as water necessary for habitats of life. The technology would be suitable for searching for biomarkers, extinct life, potential habitats of extant life, and signatures of ancient climates on Mars; and for detecting biomarkers, prebiotic chemicals and habitats of life in the outer Solar System. It would be useful for prospecting for water on the Moon and asteroids, and characterizing its isotopic composition. Deployment on the Moon could provide ground truth to the recent remote measurements and help to uncover precious records of the early bombardment history of the inner Solar System buried at the shadowed poles, and elucidate the mechanism for the generation of near-surface water in the illuminated regions. The technology would also be useful for detecting other volatile molecules in planetary atmospheres and subsurface reservoirs, isotopic characterization of planetary materials, and searching for signatures of extinct life preserved in solid matrices.

Vasudev, Ram↗

Extreme-Temperature Carbon- and Ceramic-Matrix Composite Nozzle Extensions for Liquid Rocket Engines

The United States (US) National Aeronautics and Space Administration (NASA) and its US industry partners are developing extreme-temperature composite nozzle extensions for a variety of cryogenic liquid rocket engine propulsion systems. Applications under consideration at the NASA Marshall Space Flight Center (MSFC) include launch vehicle (upper stage), in-space, and lunar lander descent/ascent propulsion systems. Composite material systems of interest include carbon-carbon (C-C) and carbon/silicon-carbide (C-SiC) composites, as well as modified versions of such composites (coatings, mixed matrices, oxidation inhibitors, etc.). Missions addressed include access to low Earth orbit, the lunar surface, and more distant destinations. Cryogenic upper-stage and in-space liquid rocket engines are optimized for performance through the use of high area ratio nozzles to fully expand combustion gases to low exit pressures, increasing exhaust velocities. As a result of the large size of such nozzles, and the related engine performance requirements, composite nozzle extensions are being considered to reduce mass impacts. Currently, metallic and foreign composite nozzle extensions used on the Atlas V, Delta IV, Falcon 9, and Ariane 5 launch vehicles represent the state-of-the-art. Such extensions are limited to use at or slightly above 2000°F (1093°C). Materials under development by MSFC and its industry partners have the potential to operate at temperatures up to (or above) 4250°F (2343°C). Marshall Space Flight Center efforts are aimed at (a) further developing the technology and databases needed to enable the use of composite nozzle extensions on cryogenic liquid rocket engines, (b) developing and demonstrating low-cost capabilities for testing and qualifying such nozzle extensions, and (c) advancing the US domestic supply chain for nozzle extensions. Through the Small Business Innovation Research (SBIR) and Small Business Technology Transfer (STTR) Programs, low-level internal MSFC research projects, and teaming arrangements with domestic industry partners, composite material design, development, hot-fire test, and evaluation efforts are progressing. Hot- fire engine tests of subscale hardware have been conducted using oxygen/hydrogen (LOX/H2), oxygen/methane (LOX/CH4), and oxygen/kerosene (LOX/RP-1) propellants. These engine tests at MSFC have enabled the evaluation of both heritage and state-of-the-art material systems, demonstrating the initial capabilities of the extreme temperature materials and their fabrication methods. Recent, ongoing, and potential future work supporting cryogenic propulsion systems development will be presented. The composite nozzle extension technology and test capabilities being developed are intended to support both NASA and US Department of Defense requirements, as well as those of the broader Commercial Space industry.

Valentine, Peter G.↗

Design of intelligent mesoscale periodic array structures utilizing smart hydrogel

Mesoscale Periodic Array Structures (MPAS, also known as crystalline colloidal arrays), composed of aqueous or nonaqueous dispersions of self-assembled submicron colloidal spheres are emerging toward the development of advanced optical devices for technological applications. This is because of their unique optical diffraction properties and the ease with which these intriguing properties can be modulated experimentally. Moreover our recent advancements in this area which include 'locking' the liquid MPAS into solid or semisolid polymer matrices for greater stability with longer life span, and incorporation of CdS quantum dots and laser dyes into colloidal spheres to obtain nonlinear optical (NLO) responses further corroborate the use of MPAS in optical technology. Our long term goal is fabrication of all-optical and electro-optical devices such as spatial light modulators for optical signal processing and flat panel display devices by utilizing intelligent nonlinear periodic array structural materials. Here we show further progress in the design of novel linear MPAS which have the ability to sense and respond to an external source such as temperature. This is achieved by combining the self-assembly properties of polymer colloidal spheres and thermoshrinking properties of smart polymer gels. At selected temperatures the periodic array efficiently Bragg diffracts light and transmits most of the light at other temperatures. Hence these intelligent systems are of potential use as fixed notch filters optical switches or limiters to protect delicate optical sensors from high intensity laser radiation.

Sunkara, H. B.↗

Lightweight, Ultra-High-Temperature, CMC-Lined Carbon/Carbon Structures

Carbon/carbon (C/C) is an established engineering material used extensively in aerospace. The beneficial properties of C/C include high strength, low density, and toughness. Its shortcoming is its limited usability at temperatures higher than the oxidation temperature of carbon . approximately 400 C. Ceramic matrix composites (CMCs) are used instead, but carry a weight penalty. Combining a thin laminate of CMC to a bulk structure of C/C retains all of the benefits of C/C with the high temperature oxidizing environment usability of CMCs. Ultramet demonstrated the feasibility of combining the light weight of C/C composites with the oxidation resistance of zirconium carbide (ZrC) and zirconium- silicon carbide (Zr-Si-C) CMCs in a unique system composed of a C/C primary structure with an integral CMC liner with temperature capability up to 4,200 F (.2,315 C). The system effectively bridged the gap in weight and performance between coated C/C and bulk CMCs. Fabrication was demonstrated through an innovative variant of Ultramet fs rapid, pressureless melt infiltration processing technology. The fully developed material system has strength that is comparable with that of C/C, lower density than Cf/SiC, and ultra-high-temperature oxidation stability. Application of the reinforced ceramic casing to a predominantly C/C structure creates a highly innovative material with the potential to achieve the long-sought goal of long-term, cyclic high-temperature use of C/C in an oxidizing environment. The C/C substructure provided most of the mechanical integrity, and the CMC strengths achieved appeared to be sufficient to allow the CMC to perform its primary function of protecting the C/C. Nozzle extension components were fabricated and successfully hot-fire tested. Test results showed good thermochemical and thermomechanical stability of the CMC, as well as excellent interfacial bonding between the CMC liner and the underlying C/C structure. In particular, hafnium-containing CMCs on C/C were shown to perform well at temperatures exceeding 3,500 F (.1,925 C). The melt-infiltrated CMC-lined C/C composites offered a lower density than Cf/SiC. The melt-infiltrated composites offer greater use temperature than Cf/SiC because of the more refractory ceramic matrices and the C/C substructure provides greater high-temperature strength. The progress made in this work will allow multiple high-temperature components used in oxidizing environments to take advantage of the low density and high strength of C/C combined with the high-temperature oxidation resistance of melt-infiltrated CMCs.

Wright, Matthew J.↗

Flight control synthesis for flexible aircraft using Eigenspace assignment

The use of eigenspace assignment techniques to synthesize flight control systems for flexible aircraft is explored. Eigenspace assignment techniques are used to achieve a specified desired eigenspace, chosen to yield desirable system impulse residue magnitudes for selected system responses. Two of these are investigated. The first directly determines constant measurement feedback gains that will yield a close-loop system eigenspace close to a desired eigenspace. The second technique selects quadratic weighting matrices in a linear quadratic control synthesis that will asymptotically yield the close-loop achievable eigenspace. Finally, the possibility of using either of these techniques with state estimation is explored. Application of the methods to synthesize integrated flight-control and structural-mode-control laws for a large flexible aircraft is demonstrated and results discussed. Eigenspace selection criteria based on design goals are discussed, and for the study case it would appear that a desirable eigenspace can be obtained. In addition, the importance of state-space selection is noted along with problems with reduced-order measurement feedback. Since the full-state control laws may be implemented with dynamic compensation (state estimation), the use of reduced-order measurement feedback is less desirable. This is especially true since no change in the transient response from the pilot's input results if state estimation is used appropriately. The potential is also noted for high actuator bandwidth requirements if the linear quadratic synthesis approach is utilized. Even with the actuator pole location selected, a problem with unmodeled modes is noted due to high bandwidth. Some suggestions for future research include investigating how to choose an eigenspace that will achieve certain desired dynamics and stability robustness, determining how the choice of measurements effects synthesis results, and exploring how the phase relationships between desired eigenvector elements effects the synthesis results.

Davidson, J. B.↗

NASA Lewis Launch Collision Probability Model Developed and Analyzed

There are nearly 10,000 tracked objects orbiting the earth. These objects encompass manned objects, active and decommissioned satellites, spent rocket bodies, and debris. They range from a few centimeters across to the size of the MIR space station. Anytime a new satellite is launched, the launch vehicle with its payload attached passes through an area of space in which these objects orbit. Although the population density of these objects is low, there always is a small but finite probability of collision between the launch vehicle and one or more of these space objects. Even though the probability of collision is very low, for some payloads even this small risk is unacceptable. To mitigate the small risk of collision associated with launching at an arbitrary time within the daily launch window, NASA performs a prelaunch mission assurance Collision Avoidance Analysis (or COLA). For the COLA of the Cassini spacecraft, the NASA Lewis Research Center conducted an in-house development and analysis of a model for launch collision probability. The model allows a minimum clearance criteria to be used with the COLA analysis to ensure an acceptably low probability of collision. If, for any given liftoff time, the nominal launch vehicle trajectory would pass a space object with less than the minimum required clearance, launch would not be attempted at that time. The model assumes that the nominal positions of the orbiting objects and of the launch vehicle can be predicted as a function of time, and therefore, that any tracked object that comes within close proximity of the launch vehicle can be identified. For any such pair, these nominal positions can be used to calculate a nominal miss distance. The actual miss distances may differ substantially from the nominal miss distance, due, in part, to the statistical uncertainty of the knowledge of the objects positions. The model further assumes that these position uncertainties can be described with position covariance matrices. With these, and some additional simplifying assumptions, a closed-form solution for the probability of collision is obtained. This solution provides clear insights into how each of the independent parameters affects the probability of collision. It shows that for a given maximum probability of collision and prior knowledge of the objects position uncertainties and sizes, only knowledge of the nominal closest approach distance is required to make the launch/no launch decision. The model was completed and used for the mission assurance COLA analysis for the Cassini spacecraft, which was launched on a Titan IV/Centaur rocket on October 15, 1997. Although the model was specifically developed for the Cassini mission, it is clearly applicable for other launches as well. The effect of COLA closures on the launch window is shown. The bar represents the entire 140-min launch window on October 15, 1997; the blackened areas represent the loss of launch opportunities due to the potential for a collision with an orbiting object.

Bollenbacher, Gary↗

A Versatile Nonlinear Method for Predictive Modeling

As computational fluid dynamics techniques and tools become widely accepted for realworld practice today, it is intriguing to ask: what areas can it be utilized to its potential in the future. Some promising areas include design optimization and exploration of fluid dynamics phenomena (the concept of numerical wind tunnel), in which both have the common feature where some parameters are varied repeatedly and the computation can be costly. We are especially interested in the need for an accurate and efficient approach for handling these applications: (1) capturing complex nonlinear dynamics inherent in a system under consideration and (2) versatility (robustness) to encompass a range of parametric variations. In our previous paper, we proposed to use first-order Taylor expansion collected at numerous sampling points along a trajectory and assembled together via nonlinear weighting functions. The validity and performance of this approach was demonstrated for a number of problems with a vastly different input functions. In this study, we are especially interested in enhancing the method's accuracy; we extend it to include the second-orer Taylor expansion, which however requires a complicated evaluation of Hessian matrices for a system of equations, like in fluid dynamics. We propose a method to avoid these Hessian matrices, while maintaining the accuracy. Results based on the method are presented to confirm its validity.

nonlinear modeling↗

Fiber Reinforcement Architectures of PMCs on the Hygrothermal-Mechanical Performance for Aeropropulsion Applications

A rigid lightweight sandwich support structure, for the combustor chamber of a new generation liquid propellant rocket engine, was designed and fabricated using Polymer Matric Composite (PMC) facesheet on a Ti honeycomb or Carbon foam core. The facesheet consisted of high stiffness carbon fiber, M40JB, and high temperature Polyimides, such as PMR-11-50 and HFPE-II. Six different fiber architectures; 4HS woven fabric, uni-fabric, woven-uni hybrid, stitched woven fabric, stitched uni-fabric and tri-axial braided structures have been investigated for optimum stiffness-thickness-weight-performance design criteria for the hygrothermal-mechanical propulsion service exposure conditions including rapid heating up to 200 F/sec, maximum operating temperature of 600 F, internal pressure up to 100 psi. An extensive property and performance database including dry-wet mechanical properties at both 25 F and 600 F in various loading modes, thermal and physical properties including blistering onset condition was developed for fiber architecture down-selection and design guidelines. Various optimized process methods including vacuum bag compression molding, solvent assistant RTM (SaRTM), resin film infusion (RFI) were utilized for PMC panel fabrication depending on the architecture type. In the case of stitched woven fabric architecture, the optimal stitch pattern was chosen in terms of stitch density and yarn size, based on both in-plane mechanical properties and blistering performance. Potential reduction of the in-plane properties transverse to the line of stitching was also evaluated. Attempt to correlate the experimental results with theoretical micro-mechanics predictions will be presented.

Shin, Eugene↗

Development of Multifunctional Radiation Shielding Materials for Long Duration Human Exploration Beyond the Low Earth Orbit

One of the major challenges for long duration human exploration beyond the low Earth orbit and sustained human presence on planetary surfaces would be development of materials that would help minimize the radiation exposure to crew and equipment from the interplanetary radiation environment, This radiation environment consists primarily of a continuous flux of galactic cosmic rays (GCR) and transient but intense fluxes of solar energetic particles (SEP). The potential for biological damage by the relatively low percentage of high-energy heavy-ions in the GCR spectrum far outweigh that due to lighter particles because of their ionizing-power and the quality of the resulting biological damage. Although the SEP spectrum does not contain heavy ions and their energy range is much lower than that for GCRs, they however pose serious risks to astronaut health particularly in the event of a bad solar storm The primary purpose of this paper is to discuss our recent efforts in development and evaluation of materials for minimizing the hazards from the interplanetary radiation environment. Traditionally, addition of shielding materials to spacecrafts has invariably resulted in paying a penalty in terms of additional weight. It would therefore be of great benefit if materials could be developed not only with superior shielding effectiveness but also sufficient structural integrity. Such a multifunctional material could then be considered as an integral part of spacecraft structures. Any proposed radiation shielding material for use in outer space should be composed of nuclei that maximize the likelihood of projectile fragmentation while producing the minimum number of target fragments. A modeling based approach will be presented to show that composite materials using hydrogen-rich epoxy matrices reinforced with polyethylene fibers and/or fabrics could effectively meet this requirement. This paper will discuss the fabrication of such a material for a crewed vehicle. Ln addition, the capability of synthesizing radiation shielding materials for habitat structures primarily from Lunar or Martian in-situ resources will also be presented. Such an approach would significantly _reduce the cost associated with transportation of such materials and structures from earth. Results from radiation exposure measurements will be presented demonstrating the shielding effectiveness of the developed materials. Mechanical testing data will be discussed to illustrate that the specific mechanical properties of the developed composites are comparable to structural aluminum based alloys currently used for the space shuttle and space station.

Sen, S.↗

Evolution of the Earth and Origin of Life: The Role of Gas/Fluid Interactions with Rocks

The work under the Cooperative Agreement will be centered on questions of the evolution of Life on the early Earth and possibly on Mars. It is still hotly debated whether the essential organic molecules were delivered to the early Earth from space (by comets, meteorites or interplanetary dust particles) or were generated in situ on Earth. Prior work that has shown that the matrix of igneous minerals is a medium in which progenitors of organic molecules assemble from H2O, C02 and N2 incorporated as minority "impurities" in minerals of igneous rocks during crystallization from H2O/CO2/N2-laden magmas. The underlying processes involve a redox. conversion whereby C, H, and N become chemically reduced, while 0 becomes oxidized to the peroxy state. During Year 02 the work will be divided into three tasks. Task 1: After carboxylic (fatty) acids and N-bearing compounds have been identified, other extractable organic molecules including lipids, oily substances and amino acids will be studied. Dedicated lipid analysis will be combined with gas chromatographic-mass spectroscopic (GCMS) analysis of organic compounds extracted from minerals and rocks. Task 2: Using infrared (IR) spectroscopy, C-H entities that are indicators for the organic progenitors in mineral matrices will be studied. A preliminary heating experiment with MgO single crystals has shown that the C-H entities can be pyrolyzed, causing the IR bands to disappear, but at room temperature the IR bands reappear in a matter of days to weeks. This work will be expanded, both by studying synthetic MgO crystals and olivine crystals from the Earth's upper mantle. The C-H bands will be compared to the published "organic" IR feature of dust in the interstellar medium (ISM) and interplanetary dust particles (IDP). Task 3: A paradox marks the evolution of early Life: Oxygen is highly toxic to primitive life, yet early organisms "learned" to detoxify reactive oxygen species, to utilize oxygen, and even produce it. Why would organisms on the early anaerobic Earth be under evolutionary pressure to evolve defenses against reactive oxygen species? Minerals in igneous rocks are now known to contain peroxy. When such minerals weather, the peroxy hydrolyzes to H2O2. The hypothesis will be tested whether organisms living in intimate contact with rock surfaces are subjected to a constant trickle of H202 and thus under stress to develop strategies to either detoxify the reactive oxygen species or repair the molecular damage that they cause. Understanding these processes is central to the Astrobiology mission. It opens new avenues toward understanding the evolution of early life on Earth, and the potential for aerobic life elsewhere. This Cooperative Agreement also has a strong educational and public outreach component involving high school, undergraduate students, and high school teachers.

Freund, Friedemann↗

Actuator placement for active sound and vibration control of cylinders

Active structural acoustic control is a method in which the control inputs (used to reduce interior noise) are applied directly to a vibrating structural acoustic system. The control concept modeled in this work is the application of in-plane force inputs to piezoceramic patches bonded to the wall of a vibrating cylinder. The cylinder is excited by an exterior noise source -- an acoustic monopole -- located near the outside of the cylinder wall. The goal is to determine the force inputs and sites for the piezoelectric actuators so that (1) the interior noise is effectively damped; (2) the level of vibration of the cylinder shell is not increased; and (3) the power requirements needed to drive the actuators are not excessive. We studied external monopole excitations at two frequencies. A cylinder resonance of 100 Hz, where the interior acoustic field is driven in multiple, off-resonance cylinder cavity modes, and a cylinder resonance of 200 Hz are characterized by both near and off-resonance cylinder vibration modes which couple effectively with a single, dominant, low-order acoustic cavity mode at resonance. Previous work has focused almost exclusively on meeting objective (1) and solving a complex least-squares problem to arrive at an optimal force vector for a given set of actuator sites. In addition, it has been noted that when the cavity mode couples with cylinder vibration modes (our 200 Hz case) control spillover may occur in higher order cylinder shell vibrational modes. How to determine the best set of actuator sites to meet objectives (1)-(3) is the main contribution of our research effort. The selection of the best set of actuator sites from a set of potential sites is done via two metaheuristics -- simulated annealing and tabu search. Each of these metaheuristics partitions the set of potential actuator sites into two disjoint sets: those that are selected to control the noise (on) and those that are not (off). Next, each metaheuristic attempts to improve this initial solution by calculating the change in the objective value when one selected actuator site is turned off and one actuator site that previously was not selected is turned on. All such pairwise exchanges are performed and the exchange that improves the objective the most is made. Eventually the search is unable to improve the objective value and a local optimum (with respect to pairwise exchanges) is reached. Both simulated annealing and tabu search provide mechanisms to escape local optima and allow the search to continue until (hopefully) a global optimum is found. Our experiments with the 100 Hz and 200 Hz cases confirm that both metaheuristics are able to uncover better solutions than those selected based upon engineering judgement alone. In addition, the high quality solutions generated by these metaheuristics, when minimizing interior noise, do not further excite the cylinder shell. Thus, we are able to meet objective (2) without imposing an additional constraint or forming a multiobjective performance measure. An additional observation is that in many cases the amplitude and phase values for several chosen actuator sites were nearly identical. This natural grouping means that fewer control channels are needed and the resulting control system is simpler. Currently no power requirements have been set, so objective (3) cannot be addressed. A set of experiments is planned with a laboratory test article (a cylinder). For these experiments the transfer matrices will be generated experimentally. It is hoped that the predicted performance of the best actuator sites found by our metaheuristics will correlate well with the measured performance.

Kincaid, Rex K.↗

4.32 Billion Year Old Impact Melts at Apollo 14: Dating the Procellarum Basin?

Introduction: Recent work has improved our understanding of lunar crustal structure and basin evolution on the Moon, but its early impact history and implications for solar system dynamics remain poorly established [1,2]. In particular, there is a derth of absolute ages, especially for the period >4.0 Ga, that could be related to basin-forming events. Here we present U-Pb isotopic data for Zr-rich minerals found in impact-melt fragments from Apollo 14 soil sample 14163 that, when combined with previously published data, dates an impact event at 4324±15 Ma. The compositions and ages of these impact-melt fragments provide unique information about the timing of early impact events and the composition of the lunar crust. Results: Fourteen rocklets ranging in size from 1 to 3 mm were extracted from soil 14163. Most are impactmelt rocks with 10-30% clasts of mostly pyroxene and plagioclase (100 to 500 μm) in a crystalline matrix. Textures of the matrix vary from subophitic, formed by intergrowths of 10-20 μm plagioclase and pyroxene crystals, to poikilitic, with plagioclase and pyroxene reaching 20-50 μm size. Some fragments that contain no visible clasts have similar textures are also interpreted as impact-melt rocks. All fragments contain notably large proportions of euhedral to subhedral ilmenite, zircon, apatite/merrillite and less abundant zirconolite and baddeleyite in the melt matrices. These grains often form intricate intergrowths with each other and rock-forming minerals, indicating their crystallization from the melt (Fig. 1). However, some slightly larger (~50 μm) zircon and phosphate grains can be interpreted as relict clasts based on their granular textures and relationships with the surrounding phases (Fig. 1). This implies that zircon and phosphate minerals were present in the target rocks. Some of these grains were profoundly remelted during the impact, which resulted in an oversaturation of the melt in Zr and P and crystallization of new grains of Zrrich minerals and phosphates during melt solidification. The presence of zircon and phosphates indicates that the melts were significantly enriched in KREEP components and ties their provenance to the Procellarum- KREEP Terrane (PKT) [3]. Combined U-Pb zircon data obtained for all fragments form two main clusters on a concordia diagram (Fig. 2), between about 4.3 and 3.9 Ga. Phosphate data mostly concentrate on the younger end of this age range but some analyses are almost as old as the older zircon grains (Fig. 2). Figure 1: Zircon (Zr) and phosphate (Apt; Mer) grains in impact melt fragments from Apollo 14 soil 14161. A-zircon grains crystallized from impact melt; B-phosphate grain inherited from the target; C- granular zircon grains Our interpretation of these data is that all U-rich minerals experienced variable resetting of the U-Pb system, with phosphate, where closure temperature is significantly lower than that in zircon, affected more profoundly by Pb loss than zircon. Our best estimate of the time of formation of zircon and phosphate is based on statistically valid analysis of grains interpreted texturally as grown from the impact melt (Fig. 2). Ten of these analyses define an age of 4324±15 Ma (MSWD=3.0, probability of fit P=0.002). Our best estimate for the time of resetting is obtained by combining data from phosphates that are statistically indistinguishable from 3.9 Ga within the analytical uncertainties. This group is represented by 18 analyses of 15 phosphate grains from different fragments (Fig. 2) and defines an age of 3922±6 Ma (MSWD=1.2, P=0.23). Conversely, a minimum age of the target lithologies, remelted in the impact that produced the rocklets studied here (Fig. 2), can be determined from the five oldest analyses of zircon clasts at 4338±13 Ma (MSWD=1.5, P=0.2), which is indistinguishable from the age of the impact melt within the uncertainties. The obtained ages, combined with textural evidence, imply that the impact melt was formed at 4324±15 Ma, and that it occurred in a zircon-rich target with a minimum age of 4338±13 Ma. Further reworking occurred during a second impact event at 3922±6 Ma. Discussion: The younger age of 3922±6 Ma can be interpreted as the time of the Imbrium impact. The older age of 4324±15 Ma would then be the time of formation of the impact melt, which was then caught in the Imbrium ejecta either at the Apollo 14 landing site or within the target rocks of the Imbrium impact. The presence of abundant accessory phases such as zircons and phosphates is consistent with a substantial KREEP component in the analyzed particles. The current distribution of KREEP on the lunar surface appears to be strongly influenced by Imbrum ejecta [4] so interpretation of the 4.32 Ga age depends in part on assumed structure of the pre-impact crust and distribution of KREEP within the crust. If KREEP was present only in the deep crust at 4.32 Ga, then a basin-scale impact possibly analogous to Imbrium or larger may be necessary to excavate a KREEPy impact melt at this time. However, if KREEPy materials were present closer to the surface perhaps due to redistribution related to Mg-suite magmatism, then smaller impacts might be able to rework KREEPy compositions at shallower depths. The coherence of the data on the particles analysed here suggests a large volume of melt that has been preserved since 4.32 Ga, consistent with a large impact event. Relict zircons and mineral clasts suggests that the igneous crust in the vicinity of this impact was well developed by at least 4.34 Ga, similar to the model age of KREEP and older than the isochron ages of many Mg-suite cumulates [5]. A problem that confronts all lunar sample studies using the current collection is that the pre-Imbrium geology of the PKT (the source of these 4.32 Ga impact melts) is not well constrained. The South Pole-Aitken basin contains regions that are moderately enriched in Th, but its ejecta is Th-poor [6]; therefore these A14 fragments are probably not SPA ejecta. Alternatively, these fragments may represent formation of a hypothesized Procellarum basin [7] although the lack of a clearly defined basin ejecta signature is a potential problem with that interpretation. In any case, they provide a younger limit on the age of lunar differentiation and formation of KREEP within the lunar crust. Figure 2: U-Pb data for zircon and phosphate grains from impact melt fragments. A-all data; B-data used for age calculations. References: [1] Orgel C., Michael G., Fassett C. I., van der Bogert C. H., Riedel C., Kneissl T., and Hiesinger H. (2018) J. Geophys. Res. Planets 123, 748- 762. [2] Evans A. J., Andrews-Hanna J. C., Head J. W., Soderblom J. M., Solomon S. C., and Zuber M. T. (2018) J. Geophys. Planets. 123, 1596-1617. [3] Jolliff, B.L., Gillis, J.J., Haskin, L.A., Korotev, R.L. and Wieczorek, M.A. (2000) J. Geophys. Res: Planets 105, 4197-4216. [4] Haskin L. A. (1998) J. Geophys. Res. Planets 103, 1679-1689. [5] Borg L.E., Gaffney A.M., and Shearer C.K. (2015) MAPS 50, 715-732. [6] Moriarty, D.P., Watkins, R.N., Valencia, S.N., Kendall, J.D., Evans, A.J., Dygert, N. and Petro, N.E. (2021) J. Geophys. Res. Planets 126. [7] Zhu, M.H., Wünnemann, K., Potter, R.W., Kleine, T. and Morbidelli, A. (2019) J. Geophys. Res: Planets 124, 2117-2140

M D Norman↗