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Adapting Nuclear Forensics from Light Water to Molten Salt Reactors: A Survey of Emerging Needs

Rising interest in molten salt reactors for commercial power production presents an opportunity to evaluate the techniques used to characterize materials of nuclear forensic interest. Since extensive research has been performed to identify and develop signatures of light water reactor (LWR) materials (e.g. uranium ore concentrates and uranium dioxide fuel pellets), we use this as a basis to explore possibilities for molten salt signature development. Through this comparative method, nuclear forensic signatures used today to identify the provenance of nuclear materials found out of regulatory control are adapted to molten salt reactor (MSR) fuel cycle materials. Radiological, elemental composition, isotopic composition, and model age signatures will likely not need large adaptations before being applied to MSR materials but may need to expand to be applicable to both thorium- and uranium-fueled systems. The liquid nature of molten salt fuel may erase signatures related to production and irradiation history that are informative for typical LWR materials. However, it may also lead to opportunities for new signatures, such as cooling rate–controlled morphology. Targets identified for further research include radiological attributes of fuel salts; elemental, chemical, and isotopic analysis of salts with differing production routes; morphological effects of various thermodynamic environments; and relevant fuel cycle radiochronometers. Additionally, the comparative nature of the proposed signatures implies a need for MSR-relevant databases and the production of salt standard reference materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Cyclic Oxidation Testing and Modelling: A NASA Lewis Perspective

The Materials Division of the NASA Lewis Research Center has been heavily involved in the cyclic oxidation of high temperature materials for 30 years. Cyclic furnace and burner rig apparati have been developed, refined, and replicated to provide a large scale facility capable of evaluating many materials by a standard technique. Material behavior is characterized by weight change data obtained throughout the test, which has been modelled in a step-wise process of scale growth and spallation. This model and a coupled diffusion model have successfully described cyclic behavior for a number of systems and have provided insights regarding life prediction and variations in the spalling process. Performance ranking and mechanistic studies are discussed primarily for superalloys and coating alloys. Similar cyclic oxidation studies have been performed on steels, intermetallic compounds, thermal barrier coatings, ceramics, and ceramic composites. The most common oxidation test was performed in air at temperatures ranging from 800 deg. to 1600 C, for times up to 10000 h, and for cycle durations of 0.1 to 1000 h. Less controlled, but important, test parameters are the cooling temperature and humidity level. Heating and cooling rates are not likely to affect scale spallation. Broad experience has usually allowed for considerable focus and simplification of these test parameters, while still revealing the principal aspects of material behavior and performance. Extensive testing has been performed to statistically model the compositional effects of experimental alloys and to construct a comprehensive database of complex commercial alloys.

Smialek, J. L.

Fe-Ti-Cr-Oxides in Martian Meteorite EETA79001 Studied by Point-counting Procedure Using Raman Spectroscopy

Fe-Ti-Cr-Oxide minerals contain much information about rock petrogenesis and alteration. Among the most important in the petrology of common intrusive and extrusive rocks are those of the FeO-TiO2-Cr2O3 compositional system chromite, ulv spinel-magnetite, and ilmenite-hematite. These minerals retain memories of oxygen fugacity. Their exsolution into companion mineral pairs give constraints on formation temperature and cooling rate. Laser Raman spectroscopy is anticipated to be a powerful technique for characterization of materials on the surface of Mars. A Mars Microbeam Raman Spectrometer (MMRS) is under development. It combines a micro sized laser beam and an automatic point-counting mechanism, and so can detect minor minerals or weak Raman-scattering phases such as Fe- Ti-Cr-oxides in mixtures (rocks & soils), and provide information on grain size and mineral mode. Most Fe-Ti-Cr-oxides produce weaker Raman signals than those from oxyanionic minerals, e.g. carbonates, sulfates, phosphates, and silicates, partly because most of them are intrinsically weaker Raman scatters, and partly because their dark colors limit the penetration depth of the excitation laser beam (visible wavelength) and of the Raman radiation produced. The purpose of this study is to show how well the Fe-Ti-Cr-oxides can be characterized by on-surface planetary exploration using Raman spectroscopy. We studied the basic Raman features of common examples of these minerals using well-characterized individual mineral grains. The knowledge gained was then used to study the Fe-Ti-Cr-oxides in Martian meteorite EETA79001, especially effects of compositional and structural variations on their Raman features.

Wang, Alian

Near-Infrared (NIR) Raman Spectroscopy of Precambrian Carbonate Stromatolites with Post-Depositional Organic Inclusions

Raman spectroscopy has promising potential for future Mars missions as a non-contact detection technique for characterizing organic material and mineralogy. Such a capability will be useful for selecting samples for detailed analysis on a rover and for selecting samples for return to Earth. Stromatolites are important evidence for the earliest life on Earth and are promising targets for Mars investigations. Although constructed by microorganisms, stromatolites are organo-sedimentary structures that can be large enough to be discovered and investigated by a Mars rover. In this paper, we report the Raman spectroscopic investigations of the carbonate mineralogy and organic layering in a Precambrian (;1.5 Gyr old) stromatolite from the Crystal Spring Formation of Southern California. Ultraviolet (UV: 266 nm), visible (514 nm, 633 nm), and near-infrared (NIR: 785 nm, 1064 nm) Raman spectra are presented. We conclude that 1064 nm excitation is the optimal excitation wavelength for avoiding intrinsic fluorescence and detecting organic carbon within the carbonate matrix. Our results confirm that NIR Raman spectroscopy has important applications for future Mars missions.

Tanaka, Zuki

Large Scale and Multi-Alloy Rocket Engine Component Development using Various Metal Additive Manufacturing Techniques

The NASA Marshall Space Flight Center (MSFC) has been involved with various forms of metallic additive manufacturing (AM) for use in liquid rocket engine component design, development, and testing since 2010. These AM techniques have been demonstrated to significantly reduce hardware cost, shorten fabrication schedules, increase reliability by reducing the number of joints, and improve hardware performance by allowing fabrication of designs not feasible by conventional means. The focus at the NASA MSFC for these metal additive manufacturing techniques include laser powder-bed fusion (L-PBF), blown powder directed energy deposition (DED), arc-based deposition, and Laser Wire Direct Closeout (LWDC). A variety of components have been evaluated and tested including thrust chamber injectors, injector components such as faceplates, regeneratively-cooled combustion chambers, regeneratively-cooled nozzles, gas generator and preburner hardware, and augmented spark igniters. To support these component applications in harsh environments, NASA has advanced a variety of “standard” additive manufacturing alloys such as those in the superalloy-family and also evolved new alloys including GRCop-84, GRCop-42, NASA HR-1, and JBK-75. The purpose of this presentation is to discuss the various component programs at the NASA MSFC using AM to develop, fabricate, and test combustion devices hardware and the evolution of the new additive alloys. One of these projects that will be highlighted is Rapid Analysis and Manufacturing Propulsion Technology (RAMPT), which includes new process development for large scale AM components, multi-metallic AM components, including unique component designs using additive manufacturing. Additional information will be provided on the development of other components, hot-fire testing, post-processing of AM techniques including surface enhancements (polishing) techniques, material and process characterization, future development programs, and dissemination of data to industry partners.

Additive Manufacturing

Large Scale and Multi-Alloy Rocket Engine Component Development using Various Metal Additive Manufacturing Techniques

The NASA Marshall Space Flight Center (MSFC) has been involved with various forms of metallic additive manufacturing (AM) for use in liquid rocket engine component design, development, and testing since 2010. These AM techniques have been demonstrated to significantly reduce hardware cost, shorten fabrication schedules, increase reliability by reducing the number of joints, and improve hardware performance by allowing fabrication of designs not feasible by conventional means. The focus at the NASA MSFC for these metal additive manufacturing techniques include laser powder-bed fusion (L-PBF), blown powder directed energy deposition (DED), arc-based deposition, and Laser Wire Direct Closeout (LWDC). A variety of components have been evaluated and tested including thrust chamber injectors, injector components such as faceplates, regeneratively-cooled combustion chambers, regeneratively-cooled nozzles, gas generator and preburner hardware, and augmented spark igniters. To support these component applications in harsh environments, NASA has advanced a variety of “standard” additive manufacturing alloys such as those in the superalloy-family and also evolved new alloys including GRCop-84, GRCop-42, NASA HR-1, and JBK-75. The purpose of this presentation is to discuss the various component programs at the NASA MSFC using AM to develop, fabricate, and test combustion devices hardware and the evolution of the new additive alloys. One of these projects that will be highlighted is Rapid Analysis and Manufacturing Propulsion Technology (RAMPT), which includes new process development for large scale AM components, multi-metallic AM components, including unique component designs using additive manufacturing. Additional information will be provided on the development of other components, hot-fire testing, post-processing of AM techniques including surface enhancements (polishing) techniques, material and process characterization, future development programs, and dissemination of data to industry partners.

Additive Manufacturing

Component Applications using Metal Additive Manufacturing Techniques and Materials for Rocket Propulsion

The NASA Marshall Space Flight Center (MSFC) has been involved with various forms of metallic additive manufacturing for use in liquid rocket engine component design, development, and testing since 2010. These AM techniques have been demonstrated to significantly reduce hardware cost, shorten fabrication schedules, increase reliability by reducing the number of joints, and improve hardware performance by allowing fabrication of designs not feasible by conventional means. The focus at the NASA MSFC for these metal additive manufacturing techniques include laser powder-bed fusion (L-PBF), blown powder directed energy deposition (DED) and arc-based deposition. A variety of components have been evaluated and tested including thrust chamber injectors, injector components such as faceplates, regeneratively-cooled combustion chambers, regeneratively-cooled nozzles, gas generator and preburner hardware, and augmented spark igniters. To support these component applications in harsh environments, NASA has advanced a variety of “standard” additive manufacturing alloys such as those in the superalloy-family and also evolved new alloys including GRCop-84, GRCop-42, NASA HR-1, and JBK-75. The purpose of this presentation is to discuss the various programs at the NASA MSFC using AM to develop, fabricate, and test combustion devices hardware and the evolution of the new additive alloys. Additional information will be provided on the development of multi-metallic additive manufacturing, post-processing of AM techniques including surface enhancements (polishing) techniques, material and process characterization, future development programs, and dissemination of data to industry partners.

Additive Manufacturing

Thermal and Chemical Characterization of Composite Materials. MSFC Center Director's Discretionary Fund Final Report, Project No. ED36-18

The purpose of this research effort was to: (1) provide a concise and well-defined property profile of current and developing composite materials using thermal and chemical characterization techniques and (2) optimize analytical testing requirements of materials. This effort applied a diverse array of methodologies to ascertain composite material properties. Often, a single method of technique will provide useful, but nonetheless incomplete, information on material composition and/or behavior. To more completely understand and predict material properties, a broad-based analytical approach is required. By developing a database of information comprised of both thermal and chemical properties, material behavior under varying conditions may be better understood. THis is even more important in the aerospace community, where new composite materials and those in the development stage have little reference data. For example, Fourier transform infrared (FTIR) spectroscopy spectral databases available for identification of vapor phase spectra, such as those generated during experiments, generally refer to well-defined chemical compounds. Because this method renders a unique thermal decomposition spectral pattern, even larger, more diverse databases, such as those found in solid and liquid phase FTIR spectroscopy libraries, cannot be used. By combining this and other available methodologies, a database specifically for new materials and materials being developed at Marshall Space Flight Center can be generated . In addition, characterizing materials using this approach will be extremely useful in the verification of materials and identification of anomalies in NASA-wide investigations.

Stanley, D. C.

Nanomechanical Characterization of Additive Manufactured GRCop-42 Alloy Developed by Directed Energy Deposition Methods

Propulsion applications such as combustion chambers and nozzles for liquid rocket engines require the use of unique materials with superior mechanical and thermal properties. GRCop-42(Cu-4 wt.% Cr-2 wt.% Nb) is one such candidate material developed by NASA and is now being manufactured using additive manufacturing (AM) techniques. AM offers a unique processing environment different from traditional metal fabrication processes. This study characterized the mechanical and structural properties of as-deposited and heat-treated GRCop-42manufactured with Blown Powder Directed Energy Deposition (BPD)based on preliminary testing. The materials were characterized using several techniques including surface profiling by laser microscopy, mechanical stiffness by instrumented indentation, crystal structure, residual stress measurements using XRD and residual XRD, and chemical composition and microstructural evaluation using SEM with EBSD. The results of the study are compared using the BPD techniques for samples in the as-deposited and heat-treated conditions.

GRCop-42

Electro-optic network analyzer

The bandwidth of frequency domain measurement methods of electrical signals has usually been far greater than the bandwidth of time domain methods. The primary limits of the time domain approach have been the 20 to 30 GHz bandwidth limit for electronic waveform acquisition instrumentation, and the lack of usable electrical pulse generators for excitation of a test device. The bandwidth of frequency domain network analysis appears to have reached a plateau of between 100 to 200 GHz, while time domain measurement have improved markedly in both bandwidth and sensitivity with the introduction of the pulsed laser based electro-optic sampling approach. Network analysis or the measurement of device scattering parameters provides information necessary to the design of electronic network such as high frequency amplifiers, mixers, and phase shifter. The bandwidth of frequency domain network analysis is currently being exceeded by the next generations of high frequency transistors and devices. Thus the electro-optic approach is a natural means of extending network analysis into the range above 100 GHz by employing time domain methods. In this approach, a suitable electrical excitation pulse is generated and propagated along a transmission line toward a test device. In the picosecond domain, laser driven photoconductive switches provide a unique method of generating electrical transients. Several materials were studied for generating short electrical pulses using photoconductive switches. The various semiconductive materials tested for photoconductive switching, and the electro-optic measurement technique used to characterize the material performance are described.

Jackson, Todd A.

Proton Conducting Neuromorphic Materials and Devices

Neuromorphic computing and artificial intelligence hardware generally aims to emulate features found in biological neural circuit components and to enable the development of energy-efficient machines. In the biological brain, ionic currents and temporal concentration gradients control information flow and storage. It is therefore of interest to examine materials and devices for neuromorphic computing wherein ionic and electronic currents can propagate. Protons being mobile under an external electric field offers a compelling avenue for facilitating biological functionalities in artificial synapses and neurons. In this review, we first highlight the interesting biological analog of protons as neurotransmitters in various animals. We then discuss the experimental approaches and mechanisms of proton doping in various classes of inorganic and organic proton-conducting materials for the advancement of neuromorphic architectures. Since hydrogen is among the lightest of elements, characterization in a solid matrix requires advanced techniques. We review powerful synchrotron-based spectroscopic techniques for characterizing hydrogen doping in various materials as well as complementary scattering techniques to detect hydrogen. First-principles calculations are then discussed as they help provide an understanding of proton migration and electronic structure modification. Outstanding scientific challenges to further our understanding of proton doping and its use in emerging neuromorphic electronics are pointed out.

36 MATERIALS SCIENCE

Physical interpretation and development of ultrasonic nondestructive evaluation techniques applied to the quantitative characterization of textile composite materials

The development and implementation of advanced ultrasonic nondestructive evaluation methods applied to the characterization of composite materials requires a better understanding of the physics underlying the interaction of ultrasound with the material. The purpose of this investigation is to identify and characterize the features of complex, three dimensional materials that limit the ability of ultrasound to detect flaws in this broad class of emerging materials. In order to explore the interaction of ultrasound with such complex media, we investigate the characteristics of ultrasonic fields which have propagated through samples with complex geometries and/or internal architecture. We focus on the physics that underlies the detection of flaws in such materials.

Miller, James G.

Physical interpretation and development of ultrasonic nondestructive evaluation techniques applied to the quantitative characterization of textile composite materials

In this Progress Report, we describe our current research activities concerning the development and implementation of advanced ultrasonic nondestructive evaluation methods applied to the characterization of stitched composite materials and bonded aluminum plate specimens. One purpose of this investigation is to identify and characterize specific features of polar backscatter interrogation which enhance the ability of ultrasound to detect flaws in a stitched composite laminate. Another focus is to explore the feasibility of implementing medical linear array imaging technology as a viable ultrasonic-based nondestructive evaluation method to inspect and characterize bonded aluminum lap joints. As an approach to implementing quantitative ultrasonic inspection methods to both of these materials, we focus on the physics that underlies the detection of flaws in such materials.

Miller, James G.

Physical interpretation and development of ultrasonic nondestructive evaluation techniques applied to the quantitative characterization of textile composite materials

In this Progress Report, we describe our continuing research activities concerning the development and implementation of advanced ultrasonic nondestructive evaluation methods applied to the inspection and characterization of complex composite structures. We explore the feasibility of implementing medical linear array imaging technology as a viable ultrasonic-based nondestructive evaluation method to inspect and characterize complex materials. As an initial step toward the application of linear array imaging technology to the interrogation of a wide range of complex composite structures, we present images obtained using an unmodified medical ultrasonic imaging system of two epoxy-bonded aluminum plate specimens, each with intentionally disbonded regions. These images are compared with corresponding conventional ultrasonic contact transducer measurements in order to assess whether these images can detect disbonded regions and provide information regarding the nature of the disbonded region. We present a description of a standoff/delay fixture which has been designed, constructed, and implemented on a Hewlett-Packard SONOS 1500 medical imaging system. This standoff/delay fixture, when attached to a 7.5 MHz linear array probe, greatly enhances our ability to interrogate flat plate specimens. The final section of this Progress Report describes a woven composite plate specimen that has been specially machined to include intentional flaws. This woven composite specimen will allow us to assess the feasibility of applying linear array imaging technology to the inspection and characterization of complex textile composite materials. We anticipate the results of this on-going investigation may provide a step toward the development of a rapid, real-time, and portable method of ultrasonic inspection and characterization based on linear array technology.

Miller, James G.

Physical interpretation and development of ultrasonic nondestructive evaluation techniques applied to the quantitative characterization of textile composite materials

In this Progress Report, the author describes the continuing research to explore the feasibility of implementing medical linear array imaging technology as a viable ultrasonic-based nondestructive evaluation method to inspect and characterize complex materials. Images obtained using an unmodified medical ultrasonic imaging system of a bonded aluminum plate sample with a simulated disbond region are presented. The disbond region was produced by adhering a piece of plain white paper to a piece of cellophane tape and applying the paper-tape combination to one of the aluminum plates. Because the area under the paper was not adhesively bonded to the aluminum plate, this arrangement more closely simulates a disbond. Images are also presented for an aluminum plate sample with an epoxy strip adhered to one side to help provide information for the interpretation of the images of the bonded aluminum plate sample containing the disbond region. These images are compared with corresponding conventional ultrasonic contact transducer measurements in order to provide information regarding the nature of the disbonded region. The results of this on-going investigation may provide a step toward the development of a rapid, real-time, and portable method of ultrasonic inspection and characterization based on linear array technology. In Section 2 of this Progress Report, the preparation of the aluminum plate specimens is described. Section 3 describes the method of linear array imaging. Sections 4 and 5 present the linear array images and results from contact transducer measurements, respectively. A discussion of the results are presented in Section 6.

Miller, James G.

Ultrasonic Nondestructive Evaluation Techniques Applied to the Quantitative Characterization of Textile Composite Materials

In this Progress Report, we describe our further development of advanced ultrasonic nondestructive evaluation methods applied to the characterization of anisotropic materials. We present images obtained from experimental measurements of ultrasonic diffraction patterns transmitted through water only and transmitted through water and a thin woven composite. All images of diffraction patterns have been included on the accompanying CD-ROM in the JPEG format and Adobe TM Portable Document Format (PDF), in addition to the inclusion of hardcopies of the images contained in this report. In our previous semi-annual Progress Report (NAG 1-1848, December, 1996), we proposed a simple model to simulate the effect of a thin woven composite on an insonifying ultrasonic pressure field. This initial approach provided an avenue to begin development of a robust measurement method for nondestructive evaluation of anisotropic materials. In this Progress Report, we extend that work by performing experimental measurements on a single layer of a five-harness biaxial woven composite to investigate how a thin, yet architecturally complex, material interacts with the insonifying ultrasonic field. In Section 2 of this Progress Report we describe the experimental arrangement and methods for data acquisition of the ultrasonic diffraction patterns upon transmission through a thin woven composite. We also briefly describe the thin composite specimen investigated. Section 3 details the analysis of the experimental data followed by the experimental results in Section 4. Finally, a discussion of the observations and conclusions is found in Section 5.

Miller, James G.

Ultrasonic Nondestructive Evaluation Techniques Applied to the Quantitative Characterization of Textile Composite Materials

In this Progress Report, we describe our recent developments of advanced ultrasonic nondestructive evaluation methods applied to the characterization of anisotropic materials. We present images obtained from experimental measurements of ultrasonic diffraction patterns for a thin woven composite in an immersion setup. In addition, we compare apparent signal loss measurements of the thin woven composite for phase-sensitive and phase-insensitive detection methods. All images of diffraction patterns have been included on the accompanying CD-ROM in the Adobe(Trademark) Portable Document Format (PDF). Due to the extensive amount of data, however, hardcopies of only a small representative selection of the images are included within the printed report. This Progress Report presents experimental results that support successful implementation of single element as well as one and two-dimensional ultrasonic array technologies for the inspection of textile composite structures. In our previous reports, we have addressed issues regarding beam profiles of ultrasonic pressure fields transmitted through a water reference path and transmitted through a thin woven composite sample path. Furthermore, we presented experimental results of the effect of a thin woven composite on the magnitude of an insonifying ultrasonic pressure field. In addition to the study of ultrasonic beam profiles, we consider issues relevant to the application of single-element, one-dimensional, and two-dimensional array technologies towards probing the mechanical properties of advanced engineering composites and structures. We provide comparisons between phase-sensitive and phase-insensitive detection methods for determination of textile composite structure parameters. We also compare phase-sensitive and phase-insensitive - - ---- ----- apparent signal loss measurements in an effort to study the phenomenon of phase cancellation at the face of a finite-aperture single-element receiver. Furthermore, in this Progress Report we extend our work on ultrasonic beam profile issues through investigation of the phase fronts of the pressure field. In Section H of this Progress Report we briefly describe the experimental arrangement and methods for data acquisition of the ultrasonic diffraction patterns upon transmission through a thin woven composite. Section III details the analysis of the experimental data followed by the experimental results in Section IV. Finally, a discussion of the observations and conclusions is found in Section V.

Miller, James G.