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At least 397 records · Page 22

Applying NIR and MIR spectroscopy for C and soil property prediction in northern cold-region ecosystems. Which approach works better?

Here, developing reliable predictions of soil attributes is necessary to understand northern cold-region climate-soil feedback. Calibration models using near-infrared (NIR) and mid-infrared (MIR) spectroscopy were developed to predict eight commonly measured soil properties for 119 soil samples representing a range of vegetation types, parent materials, and soil types spanning >23° of latitude from southeast Alaska to the Canadian high Arctic. In order to obtain a more accurate prediction, this study compared the performance of linear and non-linear calibration techniques, including lasso regression (Lasso), support vector machine (SVM), random forest (RF) and classic partial least squares (PLS) to predict different soil properties of these soils. Comparing the four models, we noticed that their performance was quite similar for MIR overall, while NIR achieved better results with a PLS model for our dataset. PLS coupled with MIR showed a better performance for soil parameters, such as total organic carbon (TOC), total nitrogen (TN), cation exchange capacity (CEC) and clay (R-squared of 0.9, 0.81, 0.80, and 0.84) when compared with NIR (R-squared of 0.85, 0.72, 0.81 and 0.68). However, using either MIR or NIR spectroscopy, PLS predictions for bulk density (BD) and sand content were not accurate. The variable importance analysis based on the PLS model successfully estimated the relative contribution of wavelengths influencing soil property predictions most. Overall, TOC, TN, CEC and clay mineral predictions are closely related to the occurrence of specific spectral bands in the MIR region. For example, wavelengths at 2978 and 1761 cm -1 for TOC and TN, as well as at 3064 cm -1 for CEC, were selected as the most influential predictor variables. We demonstrated that MIR spectroscopy is a powerful tool for more extensive monitoring in soils of the northern cold climate region; however, NIR could be utilized for rapid estimates when the highest accuracy is not essential.

54 ENVIRONMENTAL SCIENCES↗

Effects of Microstructural Composition, Porosity, and Microcracks on the Elastic Moduli of Nuclear Graphites

The elastic responses of nuclear graphite not only depend on the graphitic content itself but are largely dictated by the microstructural constitution of the material. The types of raw materials combined with the manufacturing processes used to produce the graphite yield the microstructural content that primarily includes graphite filler, graphitized pitch binder, and voids/defects that typically occupy approximately 20% of the volume. Among these microstructural components, porosity and microcracking (considered to be part of voids/defects) heavily influence the overall properties of the material, including the elastic moduli. It is widely accepted that the primary effect of oxidation is to increase porosity, but the related effect on the moduli cannot be explained satisfactorily by simply noting changes to porosity. Models describing the elastic moduli of porous, polycrystalline graphite materials have been developed to interpret experimental determinations of Young's modulus and shear modulus in oxidized graphites. Beyond porosity, the moduli are heavily influenced by microcracks, and their effects can be assessed using physical property models based on orientation distribution coefficients and microcrack-modified, single-crystal moduli to represent the combined effects of crystallite orientation and microcracking. This work demonstrates how most modulus measurements in nuclear graphites can be understood using relatively simple models that describe the effects of porosity and microcracking. We also present directions to be pursued to account for microstructure-related effects that occur as a result of neutron irradiation.

Spicer, James B.↗

Analysis of Element Size and Element Type on SS304L Material Model Performance

Finite element solutions are only valid if the information inputted into the models is a valid assumption. This is why it is important to determine if the model behaves as expected especially in the material response. Material models that consider deformation in the elastic and plastic regions are desirable. As a material deforms plastically, hardening will occur until the ultimate strength is reached due to the reduction of the cross sectional area in a uniaxial tensile test environment. A phenomenological approximation of this behavior which is known as power law hardening (plh) can be expressed as σ = σ y + K $ϵ^{n}_{p}$ where K and n are empirically determined constants, and σ y is the proportional limit of the material. The first objective of this study is to verify the behavior for a calibrated plh material model for selective deviatoric hexahedral elements when applied to a different material stock. The Sierra SM input for this calibrated model can be found in the appendix. The second objective of this study is to determine the differences in failure characteristics for considerably large shell elements versus that of fine hexahedral elements.

36 MATERIALS SCIENCE↗

Materials for foam type insulation

An internal foam fabrication is one of the concepts being considered for cryogenic insulation on the hydrogen tanks of the shuttle vehicle. The three-dimensional polyurethane used on the S-4 B tanks failed to meet the higher temperature requirements of the shuttle vehicle, however, and other foams under consideration include polyisocyanurates, polyphenylene oxides, polyimides, and polybenzimidazoles. Improved adhesive systems for attaching the foams to the interior tank wall are under study.

Hill, W. E.↗

Improved Superconducting Magnetic Rotary Bearings

Improved magnetic rotary bearings designed by exploiting properties of type-II superconducting materials. Depending on design and application, bearing provides fixed or adjustable compensation for lateral vector component of weight or other lateral load on rotor. Allows applied magnetic field to penetrate partially in clusters of field lines, with concomitant establishment of undamped circulating electrical currents within material. Type-II superconductors have critical magnetic fields and critical temperatures greater than type-I superconductors.

Flom, Yury↗

The Effect of Dose Rate on Composite Durability When Exposed to a Simulated Long-Term Lunar Radiation Environment

Human exploration of space beyond low Earth orbit (LEO) requires a safe living and working environment for crew. Composite materials are one type of material being investigated by NASA as a multi-functional structural approach to habitats for long-term use in space or on planetary surfaces with limited magnetic fields and atmosphere. These materials provide high strength with the potential for decreased weight and increased radiation protection of crew and electronics when compared with conventional aluminum structures. However, these materials have not been evaluated in a harsh radiation environment, as would be experienced outside of LEO or on a planetary surface. Thus, NASA has been investigating the durability of select composite materials in a long-term radiation environment. Previously, NASA exposed composite samples to a simulated, accelerated 30-year radiation treatment and tensile stresses similar to those of a habitat pressure vessel. The results showed evidence of potential surface oxidation and enhanced cross-linking of the matrix. As a follow-on study, we performed the same accelerated exposure alongside an exposure with a decreased dose rate. The slower dose ]rate is comparable to a realistic scenario, although still accelerated. Strain measurements were collected during exposure and showed that with a fastdose rate, the strain decreased with time, but with a slow ]dose rate, the strain increased with time. After the radiation exposures, samples were characterized via tensile tests, flexure tests, Fourier Transform Infrared Spectroscopy (FTIR), and Differential Scanning Calorimetry (DSC). The results of these tests will be discussed.

Rojdev, Kristina↗

MISSE Results Used for RF Plasma Ground Testing-To-Space-Exposure Correlation for Coated Kapton

The ability to predict the durability of materials in the low Earth orbit (LEO) environment by exposing them in ground-based facilities is important because one can achieve test results sooner, expose more types of materials, and do it much more cost effectively than to test them in flight. However, flight experiments to determine the durability of groups or classes of materials that behave similarly are needed in order to provide correlations of how much time in ground-based facilities represents certain durations in LEO for the material type of interest. An experiment was designed and flown on the Materials International Space Station Experiment (MISSE) 2 (3.95 yr in LEO) and MISSE 4 (1.04 yr in LEO) in order to develop this type of correlation between ground-based RF plasma exposure and LEO exposure for coated Kapton. The experiment consisted of a sample of Kapton H (DuPont) polyimide coated with 1300 of silicon dioxide by Sheldahl, Inc. The samples were exposed to atomic oxygen in a radio frequency (RF) generated atomic oxygen plasma. Mass change was measured for the samples and then the same samples were exposed in flight on MISSE and the mass change was again recorded post-flight. After documentation, the samples were exposed again in the ground-based RF plasma in order to determine if the erosion would be the same as it had been in the same facility pre-flight which would indicate whether or not the sample had been damaged during flight and if the defects on the surface were those that were there preflight. The slopes of the mass change versus fluence plots were then used to develop a correlation factor that can be used to help predict the durability of coated Kapton in ground-based isotropic atomic oxygen plasma systems. This paper describes the experiment and presents the correlation factor results.

Miller, Sharon K. R.↗

Yb14MnSb11 as a High-Efficiency Thermoelectric Material

Yb14MnSb11 has been found to be wellsuited for use as a p-type thermoelectric material in applications that involve hotside temperatures in the approximate range of 1,200 to 1,300 K. The figure of merit that characterizes the thermal-to-electric power-conversion efficiency is greater for this material than for SiGe, which, until now, has been regarded as the state-of-the art high-temperature ptype thermoelectric material. Moreover, relative to SiGe, Yb14MnSb11 is better suited to incorporation into a segmented thermoelectric leg that includes the moderate-temperature p-type thermoelectric material CeFe4Sb12 and possibly other, lower-temperature p-type thermoelectric materials. Interest in Yb14MnSb11 as a candidate high-temperature thermoelectric material was prompted in part by its unique electronic properties and complex crystalline structure, which place it in a class somewhere between (1) a class of semiconducting valence compounds known in the art as Zintl compounds and (2) the class of intermetallic compounds. From the perspective of chemistry, this classification of Yb14MnSb11 provides a first indication of a potentially rich library of compounds, the thermoelectric properties of which can be easily optimized. The concepts of the thermoelectric figure of merit and the thermoelectric compatibility factor are discussed in Compatibility of Segments of Thermo - electric Generators (NPO-30798), which appears on page 55. The traditional thermoelectric figure of merit, Z, is defined by the equation Z = alpha sup 2/rho K, where alpha is the Seebeck coefficient, rho is the electrical resistivity, and k is the thermal conductivity.

Snyder, G. Jeffrey↗

Thermal property measurements on lunar material returned by Apollo 11 and 12 missions.

Measurement of thermal diffusivity on Apollo 11 type A and type C samples in the temperature range between 150 and 440 K under atmospheric pressure. Thermal diffusivity of type C material is lower and less temperature-dependent than type A material. Both types of samples exhibit lower thermal diffusivities than nonporous terrestrial basalt. The rate of heat generation of Apollo 11 and 12 samples was calculated from the concentrations of radioactive elements: potassium, thorium, and uranium. Apollo 11 crystalline rocks show an average rate of heat generation which is not significantly different from terrestrial basalt. The Th/U ratio does not differ greatly from chondritic and terrestrial averages.

Horai, K.-I.↗

Materials data handbook: Stainless steel type 301

A summary of the materials property information for stainless steel type 301 is presented. The scope of the information includes physical and mechanical properties at cryogenic, ambient, and elevated temperatures. Information on material procurement, metallurgy of the alloy, corrosion, environmental effects, fabrication, and bonding is developed.

Muraca, R. F.↗

Multimodal Analysis of Reaction Pathways of Cathode Materials for Lithium Ion Batteries

Conversion mechanism in lithium ion batteries provides higher capacity than intercalation mechanism since multiple numbers of electrons and lithium ions are associated. However, poor cycling stability, large voltage hysteresis, and low energy efficiency have been great challenges of conversion reaction. To address those issues, conversion-type electrode materials have been reformed via doping or substituting other elements. For example, iron fluorides (FeF 2 , FeF 3 ) have modified as iron oxyfluorides (FeF 1-x O x ), showing enhanced long-term stability. Furthermore, co-substituted (both anion and cation substituted) Fe 0.9 Co 0.1 OF (FeCoOF) was demonstrated excellent cycling stability. (capacity of 350 mAh g -1 at a current of 500 mA g -1 for 1000 cycles). Substituting anion and cation in iron fluoride has been suggested as an effective method to achieve better reversibility but understanding of lithiation reactions in co-substituted FeCoOF is not clear. This work takes advantage of ex-situ/ in-situ synchrotron X-ray based techniques and transmission electron microscopy to elucidate structural changes with lithium ion, which may provide fundamental insights into modifying conversion-type materials. Figure 1 presents discharge-charge curves and pair distribution function patterns acquired at each potential. As lithium ions were inserted, structural changes were noticed both at short-range and long-range. However, long-range ordering was nearly maintained even at 1 V, indicating absence of conversion reaction. Figure 2 shows lithiation induced structural evolution of a single FeCoOF nanorod observed in real time. As lithiation proceeds, the width of nanorods shows a stepwise increase, particularly A in figure 2d, which may indicate multiple steps of lithiation occur. Considering that conversion reaction takes place around 2 V in FeF 3 , co-substitution Co and O into iron fluoride may change thermodynamic features of lithiation reactions by lowering the initiation potential for conversion reaction. Instead, phase transformations occur at long-range order, which may help maintaining structural integrity during operation, eventually, achieving cycling stability.

25 ENERGY STORAGE↗

Reliability of two sintered silicon nitride materials

Two types of sintered silicon nitride were evaluated in terms of reliability: an experimental high pressure nitrogen sintered material and a commercial material. The results show wide variations in strength for both materials. The Weibull moduli were 5.5, 8.9, and 11 for the experimental material at room temperature, 1200, and 1370 C, respectively. The commercial material showed Weibull moduli of 9.0, 8.6, and 8.9 at these respective temperatures. No correlation between strength and flaw size was noted for the experimental material. The applicability of the Weibull and Griffith theories to processing defects on the order of 100 microns or less in size are discussed.

Mieskowski, D. M.↗

Asymmetric Reaction Pathways of Conversion-Type Electrodes for Lithium-Ion Batteries

Metal oxides have been actively explored as promising conversion-type electrode materials for lithium ion batteries due to high deliverable capacity but still notorious for poor cyclability, capacity fading, voltage hysteresis, etc. Yet, the fundamental reason for the undesirable properties of metal oxides behind the repetitive conversion process is still obscure. In this work, we take advantage of synchrotron X-ray techniques as well as transmission electron microscopy to monitor the structural changes during both conversion (lithiation) and reconversion (delithiation) reactions. Difference in diffusion rates of lithium and metal plays a decisive role in determining the reaction pathway. We find lithium accommodation and extraction occur via different reaction routes: lithiation follows a kinetically driven way while delithiation adopts a route close to the thermodynamic ground state path. Thermodynamic structural evolution features the formation of an intermediate phase of Li-Metal (M)-O, suggesting lithium removal accompanies with the Li/M ionic exchange and rearrangement of oxygen framework. The slow diffusion of metal ions and the high kinetic and energy barrier for dissociating the intermediate phase are mainly responsible for uncompleted reconversion reaction, evidenced by remaining Li-M-O phase at the end of charge. Imperfect reconversion reaction eventually limits the utilization of lithium ions over the repeated cycling. Furthermore, this work sheds light on structural changes occurring at metal oxides during both conversion and reconversion processes, which is strongly linked with the performances of conversion-type materials in applications.

25 ENERGY STORAGE↗

An Overview of NASA's Current Materials Development Efforts for Mars EDL

Current roadmaps point to landing heavy masses (cargo, followed by manned vehicles) on Mars in the 2030's and the existing entry, descent and landing (EDL) technology will not be sufficient to facilitate such missions. In 2009 the Exploration Technology Development Program (ETDP) established the Entry, Descent and Landing Technology Development Project (EDL TDP), to be managed programmatically at Langley Research Center (LaRC) and technically a Ames Research Center (ARC). The purpose of the project is to further the technologies required to land heavy (approximately 40 metric ton) masses on Mars to facilitate exploration. The EDL TDP contains three technical elements. They are: 1) Thermal Protection Systems (TPS) development 2) Modeling and Tools (MAT) development 3) Supersonic Retropropulsion (SRP) development The primary goals of the EDL TDP TPS element is to design and develop TPS materials capable of withstanding the severe aerothermal loads associated with aerocapture and entry into the Martian atmosphere while significantly decreasing the TPS mass fraction contribution to the entry system. Significant advancements in TPS materials technology are needed in order to enable heavy mass payloads to be successfully landed on the Martian surface for robotic precursors and subsequent human exploration missions. The EDL TDP TPS element is further divided into two different TPS concepts for Mars EDL those being: 1) Rigid TPS for a mid L/D aeroshell with the capability to withstand dual pulsed heating environments as high as 500 W/square cm for aerocapture and 130 W/square cm for entry 2) Flexible TPS for a deployable aerodynamic decelerator with the capability to withstand dual pulsed heating environments as high as 120 W/square cm for aerocapture and 30 W/square cm for entry NASA, along with its vendors, has begun developing and testing materials for each of the deceleration approaches. These include multi-layer rigid ablators and flexible ablative materials. In order to model the response of these types of materials, new and improved modeling techniques will be required. This presentation will outline the types of materials that are under development and illustrate the need for advancement in modeling of ablative materials.

Beck, Robin A.↗

Fermi Level Engineering of Passivation and Electron Transport Materials for p-Type CuBi 2 O 4 Employing a High-Throughput Methodology

Metal oxide semiconductors are promising for solar photochemistry if the issues of excessive charge carrier recombination and material degradation can be resolved, which are both influenced by surface quality and interface chemistry. Coating the semiconductor with an overlayer to passivate surface states is a common remedial strategy but is less desirable than application of a functional coating that can improve carrier extraction and reduce recombination while mitigating corrosion. Here, a data-driven materials science approach utilizing high-throughput methodologies, including inkjet printing and scanning droplet electrochemical cell measurements, is used to create and evaluate multi-element coating libraries to discover new classes of candidate passivation and electron-selective contact materials for p-type CuBi 2 O 4 . The optimized overlayer (Cu 1.5 TiO z ) improves the onset potential by 110 mV, the photocurrent by 2.8×, and the absorbed photon-to-current efficiency by 15.5% compared to non-coated photoelectrodes. It is shown that these enhancements are related to reduced surface recombination through passivation of surface defect states as well as improved carrier extraction efficiency through Fermi level engineering. This work presents a generalizable, high-throughput method to design and optimize passivation materials for a variety of semiconductors, providing a powerful platform for development of high-performance photoelectrodes for incorporation into solar-fuel generation systems.

36 MATERIALS SCIENCE↗