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Potential Dependent Mn Oxidation and Its Role in Passivation of Ni 38 Fe 20 Cr 22 Mn 10 Co 10 Multi-Principal Element Alloy Using Multi-Element Resolved Atomic Emission Spectroelectrochemistry
The identity of passivating oxides on multi-principal element alloys is of great interest as their optimization offers the potential for exceptional corrosion resistance in aqueous solutions over a broad range of potential and pH. This study focuses on a non-equiatomic Ni 38 Fe 20 Cr 22 Mn 10 Co 10 solid solution alloy and tracks the fate of each alloying element during linear sweep voltammetry, low and intermediate potential holds in the passive potential domain as well as during open circuit relaxation after anodic polarization in slightly acidified Cl − solution. Ni dissolves at all potentials investigated in this work, Fe and Co are incorporated into oxides or hydroxides in low concentrations whilst Cr and Mn are enriched at passive potentials. At low passivating potentials, Mn(II) dissolves and is incorporated in minor amounts in oxides containing large concentrations of Cr(III). Considerable enrichment in Mn(II)-species occurs relative to Cr(III) in the oxide at 0.1 V vs SCE. Electrochemical impedance spectroscopy suggests the presence of layered oxides with marginal passivation at high Mn(II) levels. The formation of these oxides depends on a combination of thermodynamic and kinetic factors as well as the sequence of passivation.
Element redistributions during early stages of oxidation in a Ni38Cr22Fe20Mn10Co10 multi-principal element alloy
Element redistributions after initial gaseous oxidation of a Ni38Cr22Fe20Mn10Co10 (at%) multi-principle element alloy at 120°C and 300°C is captured via psuedo in situ atom probe tomography. All cations contribute to the oxide in both conditions, consisting of a Cr-rich inner oxide and Fe, Mn, Co and Ni-rich outer oxide. At the lower temperature, Ni tends to be trapped at the outer/inner oxide interface, while Ni enriches at the oxide/metal interface at higher temperature in tandem with Cr metal depletion. These observations confirm oxidation of complex alloys involves the formation of metastable, multi-layered oxide films, with a distinct tendency for solute trapping.
Assessment of SPAR elements and formulation of some basic 2-D and 3-D elements for use with testbed generic element processor
The initial Computational Structural Mechanics (CSM) Testbed was based on Level 13 of the SPAR finite element computer program. Until recently, the element library of the Testbed has been limited to those elements in Level 13 of SPAR. The development of a generic element processor has enabled element researchers to develop, implement and assess element formulations with relative ease. An assessment of new elements as well as the existing SPAR Level 13 elements has revealed some definite shortcomings with the SPAR Level 13 2-D and 3-D elements. The SPAR S81 solid element does not pass the patch test problem proposed by MacNeal-Harder. These deficiencies are identified here. The 2-D elements, however, seem to perform well taking into account the limitations imposed by the theory used to formulate them, (i.e., thin plates only). Common deficiencies of the 2-D and 3-D elements in SPAR have to do with their adaptability to the nonlinear analysis utilities developed by Lockheed Palo Alto Research Lab. Also, the EFIL format of the SPAR element data does not conform to the standard format of the Testbed.
Updating finite element dynamic models using an element-by-element sensitivity methodology
A sensitivity-based methodology for improving the finite element model of a given structure using test modal data and a few sensors is presented. The proposed method searches for both the location and sources of the mass and stiffness errors and does not interfere with the theory behind the finite element model while correcting these errors. The updating algorithm is derived from the unconstrained minimization of the squared L sub 2 norms of the modal dynamic residuals via an iterative two-step staggered procedure. At each iteration, the measured mode shapes are first expanded assuming that the model is error free, then the model parameters are corrected assuming that the expanded mode shapes are exact. The numerical algorithm is implemented in an element-by-element fashion and is capable of 'zooming' on the detected error locations. Several simulation examples which demonstate the potential of the proposed methodology are discussed.
Plumbojarosite Remediation of Soil Affects Lead Speciation and Elemental Interactions in Soil and in Mice Tissues
Lead (Pb) contamination of soils is of global concern due to the devastating impacts of Pb exposure in children. Because early-life exposure to Pb has long-lasting health effects, reducing exposure in children is a critical public health goal that has intensified research on the conversion of soil Pb to low bioavailability phases. Recently, plumbojarosite (PLJ) conversion of highly available soil Pb was found to decrease Pb relative bioavailability (RBA <10%). However, there is sparse information concerning interactions between Pb and other elements when contaminated soil, pre- and post-remediation, is ingested and moves through the gastrointestinal tract (GIT). Addressing this may inform drivers of effective chemical remediation strategies. In this study, we utilize bulk and micro-focused Pb X-ray absorption spectroscopy to probe elemental interactions and Pb speciation in mouse diet, cecum, and feces samples following ingestion of contaminated soils pre- and post-PLJ treatment. RBA of treated soils was less than 1% with PLJ phases transiting the GIT with little absorption. In contrast, Pb associated with organics was predominantly found in the cecum. These results are consistent with transit of insoluble PLJ to feces following ingestion. The expanded understanding of Pb interactions during GIT transit complements our knowledge of elemental interactions with Pb that occur at higher levels of biological organization.
Augmented weak forms and element-by-element preconditioners: Efficient iterative strategies for structural finite elements. A preliminary study
A weak formulation in structural analysis that provides well conditioned matrices suitable for iterative solutions is presented. A mixed formulation ensures the proper representation of the problem and the constitutive relations are added in a penalized form. The problem is solved by a double conjugate gradient algorithm combined with an element by element approximate factorization procedure. The double conjugate gradient strategy resembles Uzawa's variable-length type algorithms the main difference is the presence of quadratic terms in the mixed variables. In the case of shear deformable beams these terms ensure that the proper finite thickness solution is obtained.
Element-by-element and implicit-explicit finite element formulations for computational fluid dynamics
Preconditioner algorithms to reduce the computational effort in FEM analyses of large-scale fluid-dynamics problems are presented. A general model problem is constructed on the basis of the convection-diffusion equation and the two-dimensional vorticity/stream-function formulation of the Navier-Stokes equations; this problem is then analyzed using element-by-element, implicit-explicit, and adaptive implicit-explicit approximation schemes. Numerical results for the two-dimensional advection and rigid-body rotation of a cosine hill, flow past a circular cylinder, and driven cavity flow are presented in extensive graphs and shown to be in good agreement with those obtained using implicit methods.
A General Procedure to Formulate 3D Elements for Finite Element Applications
This paper presents a general procedure to formulate and implement 3D elements of arbitrary order in meshes with multiple element types. This procedure includes obtaining shape functions and integration quadrature and establishing an approach for checking the generated element’s compatibility with adjacent elements’ surfaces. This procedure was implemented in Matlab, using its symbolic and graphics toolbox, and complied as a GUI interface named ShapeGen3D to provide finite element users with a tool to tailor elements according to their analysis needs. ShapeGen3D also outputs files with the element formulation needed to enable users to implement the generated elements in other programming languages or through user elements in commercial finite element software. Currently, finite element (FE) users are limited to employing element formulation available in the literature, commercial software, or existing element libraries. Thus, the developed procedure implemented in ShapeGen3D offers FEM users the possibility to employ elements beyond those readily available. The procedure was tested by generating the formulation for a brick element, a brick transition element, and higher-order hexahedron and tetrahedron elements that can be used in a spectral finite element analysis. The formulation obtained for the 20-node element was in perfect agreement with the formulation available in the literature. In addition, the results showed that the interpolation condition was met for all the generated elements, which provides confidence in the implementation of the process. Researchers and educators can use this procedure to efficiently develop and illustrate three-dimensional elements.
Comparison of Single-Element and Multi-Element Oxygen/RP-1 Oxidizer-Rich Staged-Combustion Injector Hot-Fire Test Results
As part of the Combustion Stability Tool Development project funded by the Air Force Space and Missile Systems Center, the NASA Marshall Space Flight Center designed, fabricated, assembled and hot-fire tested an oxygen/hydrocarbon propellant multi-element integrated test article that included an oxidizer-rich oxygen/hydrocarbon propellant preburner and a staged-combustion main injector. Also as part of this project, the Air Force Research Laboratory fabricated single-element main injectors of the same designs as used in the NASA multi-element injectors, and tested them in a staged-combustion integrated test article that used an oxidizer-rich oxygen/hydrogen propellant preburner. Final results of the multi-element and single-element staged-combustion main injector test programs are described in companion papers at this JANNAF meeting. The design, development, and preliminary test results of these main injectors have also been described in previous JANNAF papers. The main injector element designs were all based on relatively conventional gas-centered swirl coaxial injector element configurations such as used in Russian RD-170 and NK-33 engines, and planned for use in future U.S.-built experimental engine systems such as the Hydrocarbon Boost program demonstration engine. Four different elements were tested in both the multi-element and single-element main injectors, at similar combustion chamber pressures, chamber contraction ratios, and mixture ratios. Variations of the element features included recess depth, fuel gap width, and the presence of the sleeve separating the swirling fuel flow from the axial oxidizer flow. This paper compares the hydraulics, combustion performance, stability, and compatibility characteristics of the single-element and multi-element injectors operated at similar conditions. The single-element hardware is shown to have captured a significant level of the operability of the multi-element hardware.
Controlling the corrosion resistance of multi-principal element alloys
Multi-principal element alloys (MPEAs) offer the possibility of many degrees of freedom in the choice of alloying elements to produce either single phase solid solutions or more complex multiphase microstructures. Large ranges of material properties have been observed for MPEAs and mastery of the selection of elements and their compositions can enable novel combinations of properties not possible in traditional alloys. From the aqueous corrosion perspective, optimization of phase stability, control of heterogeneities, passive film identity and its protectiveness, as well as substrate properties such as metal-metal bond strength and activation energy associated with dissolution, can all be controlling factors governed by alloy composition and structure. These factors can mediate the electrochemical reactions controlling spontaneous corrosion. The quest for superior properties based on well-informed element choice is suggested as a path forward guiding MPEA formulations for corrosion performance. However, gaps in fundamental knowledge exist regarding (a) the specific functions of each element, (b) the behavior of elements in unusual combinations, and (c) the formation of complex protective oxides. These issues currently hold back progress in optimization of corrosion properties.
A 2-D Interface Element for Coupled Analysis of Independently Modeled 3-D Finite Element Subdomains
Over the past few years, the development of the interface technology has provided an analysis framework for embedding detailed finite element models within finite element models which are less refined. This development has enabled the use of cascading substructure domains without the constraint of coincident nodes along substructure boundaries. The approach used for the interface element is based on an alternate variational principle often used in deriving hybrid finite elements. The resulting system of equations exhibits a high degree of sparsity but gives rise to a non-positive definite system which causes difficulties with many of the equation solvers in general-purpose finite element codes. Hence the global system of equations is generally solved using, a decomposition procedure with pivoting. The research reported to-date for the interface element includes the one-dimensional line interface element and two-dimensional surface interface element. Several large-scale simulations, including geometrically nonlinear problems, have been reported using the one-dimensional interface element technology; however, only limited applications are available for the surface interface element. In the applications reported to-date, the geometry of the interfaced domains exactly match each other even though the spatial discretization within each domain may be different. As such, the spatial modeling of each domain, the interface elements and the assembled system is still laborious. The present research is focused on developing a rapid modeling procedure based on a parametric interface representation of independently defined subdomains which are also independently discretized.
Core-Mantle Partitioning of Volatile Siderophile Elements and the Origin of Volatile Elements in the Earth
There are currently several hypotheses on the origin of volatile siderophile elements in the Earth. One hypothesis is that they were added during Earth s accretion and core formation and mobilized into the metallic core [1], others claim multiple stage origin [2], while some hypothesize that volatiles were added after the core already formed [3]. Several volatile siderophile elements are depleted in Earth s mantle relative to the chondrites, something which continues to puzzle many scientists. This depletion is likely due to a combination of volatility and core formation. The Earth s core is composed of Fe and some lighter constituents, although the abundances of these lighter elements are unknown [4]. Si is one of these potential light elements [5] although few studies have analyzed the effect of Si on metal-silicate partitioning, in particular the volatile elements. As, In, Ge, and Sb are trace volatile siderophile elements which are depleted in the mantle but have yet to be extensively studied. The metal-silicate partition coefficients of these elements will be measured to determine the effect of Si. Partition coefficients depend on temperature, pressure, oxygen fugacity, and metal and silicate composition and can constrain the concentrations of volatile, siderophile elements found in the mantle. Reported here are the results from 13 experiments examining the partitioning of As, In, Ge, and Sb between metallic and silicate liquid. These experiments will examine the effect of temperature, and metal-composition (i.e., Si content) on these elements in or-der to gain a greater understanding of the core-mantle separation which occurred during the Earth s early stages. The data can then be applied to the origin of volatile elements in the Earth.
Survey and development of finite elements for nonlinear structural analysis. Volume 1: Handbook for nonlinear finite elements
A survey of research efforts in the area of geometrically nonlinear finite elements is presented. The survey is intended to serve as a guide in the choice of nonlinear elements for specific problems, and as background to provide directions for new element developments. The elements are presented in a handbook format and are separated by type as beams, plates (or shallow shells), shells, and other elements. Within a given type, the elements are identified by the assumed displacement shapes and the forms of the nonlinear strain equations. Solution procedures are not discussed except when a particular element formulation poses special problems or capabilities in this regard. The main goal of the format is to provide quick access to a wide variety of element types, in a consistent presentation format, and to facilitate comparison and evaluation of different elements with regard to features, probable accuracy, and complexity.
Survey and development of finite elements for nonlinear structural analysis. Volume 2: Nonlinear shell finite elements
The development of two new shell finite elements for applications to large deflection problems is considered. The elements in question are doubly curved and of triangular and quadrilateral planform. They are restricted to small strains of elastic materials, and can accommodate large rotations. The elements described, which are based on relatively simple linear elements, make use of a new displacement function approach specifically designed for strongly nonlinear problems. The displacement function development for nonlinear applications is based on certain beam element formulations, and the strain-displacement equations are of a shallow shell type. Additional terms were included in these equations in an attempt to avoid the large errors characteristic of shallow shell elements in certain types of problems. An incremental nonlinear solution procedure specifically adopted to the element formulation was developed. The solution procedure is of combined incremental and total Lagrangian type, and uses a new updating scheme. A computer program was written to evaluate the developed formulations. This program can accommodate small element groups in arbitrary arrangements. Two simple programs were successfully solved. The results indicate that this new type of element has definite promise and should be a fruitful area for further research.
Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon
Depletions of siderophile elements in mantles have placed constraints on the conditions on core segregation and differentiation in bodies such as Earth, Earth's Moon, Mars, and asteroid 4 Vesta. Among the siderophile elements there are a sub-set that are also volatile (volatile siderophile elements or VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd), and thus can help to constrain the origin of volatile elements in these bodies, and in particular the Earth and Moon. One of the fundamental observations of the geochemistry of the Moon is the overall depletion of volatile elements relative to the Earth, but a satisfactory explanation has remained elusive. Hypotheses for Earth include addition during accretion and core formation and mobilized into the metallic core, multiple stage origin, or addition after the core formed. Any explanation for volatile elements in the Earth's mantle must also be linked to an explanation of these elements in the lunar mantle. New metal-silicate partitioning data will be applied to the origin of volatile elements in both the Earth and Moon, and will evaluate theories for exogenous versus endogenous origin of volatile elements.
A Six-Node Curved Triangular Element and a Four-Node Quadrilateral Element for Analysis of Laminated Composite Aerospace Structures
Mathematical development and some computed results are presented for Mindlin plate and shell elements, suitable for analysis of laminated composite and sandwich structures. These elements use the conventional 3 (plate) or 5 (shell) nodal degrees of freedom, have no communicable mechanisms, have no spurious shear energy (no shear locking), have no spurious membrane energy (no membrane locking) and do not require arbitrary reduction of out-of-plane shear moduli or under-integration. Artificial out-of-plane rotational stiffnesses are added at the element level to avoid convergence problems or singularity due to flat spots in shells. This report discusses a 6-node curved triangular element and a 4-node quadrilateral element. Findings show that in regular rectangular meshes, the Martin-Breiner 6-node triangular curved shell (MB6) is approximately equivalent to the conventional 8-node quadrilateral with integration. The 4-node quadrilateral (MB4) has very good accuracy for a 4-node element, and may be preferred in vibration analysis because of narrower bandwidth. The mathematical developments used in these elements, those discussed in the seven appendices, have been applied to elements with 3, 4, 6, and 10 nodes and can be applied to other nodal configurations.
Local Heat Flux Measurements with Single and Small Multi-element Coaxial Element-Injectors
To support NASA's Vision for Space Exploration mission, the NASA Marshall Space Flight Center conducted a program in 2005 to improve the capability to predict local thermal compatibility and heat transfer in liquid propellant rocket engine combustion devices. The ultimate objective was to predict and hence reduce the local peak heat flux due to injector design, resulting in a significant improvement in overall engine reliability and durability. Such analyses are applicable to combustion devices in booster, upper stage, and in-space engines with regeneratively cooled chamber walls, as well as in small thrust chambers with few elements in the injector. In this program, single and three-element injectors were hot-fire tested with liquid oxygen and gaseous hydrogen propellants at The Pennsylvania State University Cryogenic Combustor Laboratory from May to August 2005. Local heat fluxes were measured in a 1-inch internal diameter heat sink combustion chamber using Medtherm coaxial thermocouples and Gardon heat flux gauges, Injector configurations were tested with both shear coaxial elements and swirl coaxial elements. Both a straight and a scarfed single element swirl injector were tested. This paper includes general descriptions of the experimental hardware, instrumentation, and results of the hot-fire testing for three coaxial shear and swirl elements. Detailed geometry and test results the for shear coax elements has already been published. Detailed test result for the remaining 6 swirl coax element for the will be published in a future JANNAF presentation to provide well-defined data sets for development and model validation.