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Parameter estimation techniques based on optimizing goodness-of-fit statistics for structural reliability

New methods are presented that utilize the optimization of goodness-of-fit statistics in order to estimate Weibull parameters from failure data. It is assumed that the underlying population is characterized by a three-parameter Weibull distribution. Goodness-of-fit tests are based on the empirical distribution function (EDF). The EDF is a step function, calculated using failure data, and represents an approximation of the cumulative distribution function for the underlying population. Statistics (such as the Kolmogorov-Smirnov statistic and the Anderson-Darling statistic) measure the discrepancy between the EDF and the cumulative distribution function (CDF). These statistics are minimized with respect to the three Weibull parameters. Due to nonlinearities encountered in the minimization process, Powell's numerical optimization procedure is applied to obtain the optimum value of the EDF. Numerical examples show the applicability of these new estimation methods. The results are compared to the estimates obtained with Cooper's nonlinear regression algorithm.

Starlinger, Alois↗

A Stochastic Model of Space-Time Variability of Mesoscale Rainfall: Statistics of Spatial Averages

A characteristic feature of rainfall statistics is that they depend on the space and time scales over which rain data are averaged. A previously developed spectral model of rain statistics that is designed to capture this property, predicts power law scaling behavior for the second moment statistics of area-averaged rain rate on the averaging length scale L as L right arrow 0. In the present work a more efficient method of estimating the model parameters is presented, and used to fit the model to the statistics of area-averaged rain rate derived from gridded radar precipitation data from TOGA COARE. Statistical properties of the data and the model predictions are compared over a wide range of averaging scales. An extension of the spectral model scaling relations to describe the dependence of the average fraction of grid boxes within an area containing nonzero rain (the "rainy area fraction") on the grid scale L is also explored.

Kundu, Prasun K.↗

Statistical Methodologies to Integrate Experimental and Computational Research

Development of advanced algorithms for simulating engine flow paths requires the integration of fundamental experiments with the validation of enhanced mathematical models. In this paper, we provide an overview of statistical methods to strategically and efficiently conduct experiments and computational model refinement. Moreover, the integration of experimental and computational research efforts is emphasized. With a statistical engineering perspective, scientific and engineering expertise is combined with statistical sciences to gain deeper insights into experimental phenomenon and code development performance; supporting the overall research objectives. The particular statistical methods discussed are design of experiments, response surface methodology, and uncertainty analysis and planning. Their application is illustrated with a coaxial free jet experiment and a turbulence model refinement investigation. Our goal is to provide an overview, focusing on concepts rather than practice, to demonstrate the benefits of using statistical methods in research and development, thereby encouraging their broader and more systematic application.

Parker, P. A.↗

Statistical Analysis of Model Data for Operational Space Launch Weather Support at Kennedy Space Center and Cape Canaveral Air Force Station

The 12-km resolution North American Mesoscale (NAM) model (MesoNAM) is used by the 45th Weather Squadron (45 WS) Launch Weather Officers at Kennedy Space Center (KSC) and Cape Canaveral Air Force Station (CCAFS) to support space launch weather operations. The 45 WS tasked the Applied Meteorology Unit to conduct an objective statistics-based analysis of MesoNAM output compared to wind tower mesonet observations and then develop a an operational tool to display the results. The National Centers for Environmental Prediction began running the current version of the MesoNAM in mid-August 2006. The period of record for the dataset was 1 September 2006 - 31 January 2010. The AMU evaluated MesoNAM hourly forecasts from 0 to 84 hours based on model initialization times of 00, 06, 12 and 18 UTC. The MesoNAM forecast winds, temperature and dew point were compared to the observed values of these parameters from the sensors in the KSC/CCAFS wind tower network. The data sets were stratified by model initialization time, month and onshore/offshore flow for each wind tower. Statistics computed included bias (mean difference), standard deviation of the bias, root mean square error (RMSE) and a hypothesis test for bias = O. Twelve wind towers located in close proximity to key launch complexes were used for the statistical analysis with the sensors on the towers positioned at varying heights to include 6 ft, 30 ft, 54 ft, 60 ft, 90 ft, 162 ft, 204 ft and 230 ft depending on the launch vehicle and associated weather launch commit criteria being evaluated. These twelve wind towers support activities for the Space Shuttle (launch and landing), Delta IV, Atlas V and Falcon 9 launch vehicles. For all twelve towers, the results indicate a diurnal signal in the bias of temperature (T) and weaker but discernable diurnal signal in the bias of dewpoint temperature (T(sub d)) in the MesoNAM forecasts. Also, the standard deviation of the bias and RMSE of T, T(sub d), wind speed and wind direction indicated the model error increased with the forecast period all four parameters. The hypothesis testing uses statistics to determine the probability that a given hypothesis is true. The goal of using the hypothesis test was to determine if the model bias of any of the parameters assessed throughout the model forecast period was statistically zero. For th is dataset, if this test produced a value >= -1 .96 or <= 1.96 for a data point, then the bias at that point was effectively zero and the model forecast for that point was considered to have no error. A graphical user interface (GUI) was developed so the 45 WS would have an operational tool at their disposal that would be easy to navigate among the multiple stratifications of information to include tower locations, month, model initialization times, sensor heights and onshore/offshore flow. The AMU developed the GUI using HyperText Markup Language (HTML) so the tool could be used in most popular web browsers with computers running different operating systems such as Microsoft Windows and Linux.

Bauman, William H., III↗

Statistical Mechanics of Turbulent Dynamos

Incompressible magnetohydrodynamic (MHD) turbulence and magnetic dynamos, which occur in magnetofluids with large fluid and magnetic Reynolds numbers, will be discussed. When Reynolds numbers are large and energy decays slowly, the distribution of energy with respect to length scale becomes quasi-stationary and MHD turbulence can be described statistically. In the limit of infinite Reynolds numbers, viscosity and resistivity become zero and if these values are used in the MHD equations ab initio, a model system called ideal MHD turbulence results. This model system is typically confined in simple geometries with some form of homogeneous boundary conditions, allowing for velocity and magnetic field to be represented by orthogonal function expansions. One advantage to this is that the coefficients of the expansions form a set of nonlinearly interacting variables whose behavior can be described by equilibrium statistical mechanics, i.e., by a canonical ensemble theory based on the global invariants (energy, cross helicity and magnetic helicity) of ideal MHD turbulence. Another advantage is that truncated expansions provide a finite dynamical system whose time evolution can be numerically simulated to test the predictions of the associated statistical mechanics. If ensemble predictions are the same as time averages, then the system is said to be ergodic; if not, the system is nonergodic. Although it had been implicitly assumed in the early days of ideal MHD statistical theory development that these finite dynamical systems were ergodic, numerical simulations provided sufficient evidence that they were, in fact, nonergodic. Specifically, while canonical ensemble theory predicted that expansion coefficients would be (i) zero-mean random variables with (ii) energy that decreased with length scale, it was found that although (ii) was correct, (i) was not and the expected ergodicity was broken. The exact cause of this broken ergodicity was explained, after much investigation, by greatly extending the statistical theory of ideal MHD turbulence. The mathematical details of broken ergodicity, in fact, give a quantitative explanation of how coherent structure, dynamic alignment and force-free states appear in turbulent magnetofluids. The relevance of these ideal results to real MHD turbulence occurs because broken ergodicity is most manifest in the ideal case at the largest length scales and it is in these largest scales that a real magnetofluid has the least dissipation, i.e., most closely approaches the behavior of an ideal magnetofluid. Furthermore, the effects grow stronger when cross and magnetic helicities grow large with respect to energy, and this is exactly what occurs with time in a real magnetofluid, where it is called selective decay. The relevance of these results found in ideal MHD turbulence theory to the real world is that they provide at least a qualitative explanation of why confined turbulent magnetofluids, such as the liquid iron that fills the Earth's outer core, produce stationary, large-scale magnetic fields, i.e., the geomagnetic field. These results should also apply to other planets as well as to plasma confinement devices on Earth and in space, and the effects should be manifest if Reynolds numbers are high enough and there is enough time for stationarity to occur, at least approximately. In the presentation, details will be given for both theoretical and numerical results, and references will be provided.

Shebalin, John V.↗

Statistical Aspects of North Atlantic Basin Tropical Cyclones During the Weather Satellite Era, 1960-2013

This Technical Publication (TP) is part 2 of a two-part study of the North Atlantic basin tropical cyclones that occurred during the weather satellite era, 1960-2013. In particular, this TP examines the inferred statistical relationships between 25 tropical cyclone parameters and 9 specific climate-related factors, including the (1) Oceanic Niño Index (ONI), (2) Southern Oscillation Index (SOI), (3) Atlantic Multidecadal Oscillation (AMO) index, (4) Quasi-Biennial Oscillation (QBO) index, (5) North Atlantic Oscillation (NAO) index of the Climate Prediction Center (CPC), (6) NAO index of the Climate Research Unit (CRU), (7) Armagh surface air temperature (ASAT), (8) Global Land-Ocean Temperature Index (GLOTI), and (9) Mauna Loa carbon dioxide (CO2) (MLCO2) index. Part 1 of this two-part study examined the statistical aspects of the 25 tropical cyclone parameters (e.g., frequencies, peak wind speed (PWS), accumulated cyclone energy (ACE), etc.) and provided the results of statistical testing (i.e., runs-testing, the t-statistic for independent samples, and Poisson distributions). Also, the study gave predictions for the frequencies of the number of tropical cyclones (NTC), number of hurricanes (NH), number of major hurricanes (NMH), and number of United States land-falling hurricanes (NUSLFH) expected for the 2014 season, based on the statistics of the overall interval 1960-2013, the subinterval 1995-2013, and whether the year 2014 would be either an El Niño year (ENY) or a non-El Niño year (NENY).

Wilson, Robert M.↗

On the Calculation of Uncertainty Statistics with Error Bounds for CFD Calculations Containing Random Parameters and Fields

This chapter discusses the ongoing development of combined uncertainty and error bound estimates for computational fluid dynamics (CFD) calculations subject to imposed random parameters and random fields. An objective of this work is the construction of computable error bound formulas for output uncertainty statistics that guide CFD practitioners in systematically determining how accurately CFD realizations should be approximated and how accurately uncertainty statistics should be approximated for output quantities of interest. Formal error bounds formulas for moment statistics that properly account for the presence of numerical errors in CFD calculations and numerical quadrature errors in the calculation of moment statistics have been previously presented in [8]. In this past work, hierarchical node-nested dense and sparse tensor product quadratures are used to calculate moment statistics integrals. In the present work, a framework has been developed that exploits the hierarchical structure of these quadratures in order to simplify the calculation of an estimate of the quadrature error needed in error bound formulas. When signed estimates of realization error are available, this signed error may also be used to estimate output quantity of interest probability densities as a means to assess the impact of realization error on these density estimates. Numerical results are presented for CFD problems with uncertainty to demonstrate the capabilities of this framework.

Uncertainty↗

Comparison of Atmospheric Delay Statistics from Deep Space Network Arrays and Nearby Test Interferometers

Several techniques have been explored and demonstrated that allow for greater data return on space-to-ground links. Among these techniques, arraying several smaller diameter dish antennas together is one method used in several arenas. These arrays can achieve larger effective area and gain than are available from a single larger antenna. This technique is routinely used by the NASA Deep Space Network (DSN) at 8.4 GHz where the incoming signals are much weaker than those experienced by the near-Earth satellite community. When considering arraying at much higher frequencies such as 32 GHz deep-space Ka-band, the phase alignment of the individual antenna signals is significantly disrupted by atmospheric turbulence. Since 2012, several downlink array demonstrations have been conducted using 32 GHz carrier signals emitted by the deep space probes Cassini and Kepler. Site test interferometers (STIs) that receive signals from geostationary satellites have been deployed at all three DSN tracking complexes for long-term monitoring of atmospheric delay fluctuations. In a previous DSN array demonstration study involving the Cassini spacecraft, it was shown that statistics of the adjusted STI phase fluctuations matched the statistics of concurrent array demonstration phase fluctuations. These adjustments accounted for differences in antenna separation, elevation angle and spacecraft frequencies. The STI antenna separations were about 200 m and the DSN antenna separations were about 300 m. These adjustments made use of the thick-layer turbulence model that was applicable to the Goldstone desert climate during the summer months for which the data were acquired. In this paper, we report on the results of additional array demonstrations involving the Kepler spacecraft and compare the adjusted STI phase fluctuations with those seen by a nearby two-element array of 34 m diameter antennas tracking Kepler’s 32 GHz signal at the Goldstone, California and Madrid, Spain DSN sites. We also discuss results from a demonstration using an array over a longer 12.5 km baseline. The Cassini and Kepler array demonstrations were found to validate the long term statistics acquired from several years of STI data as well as the models used to adjust the statistics for the conditions of an array. These statistics represent reliable estimates of the phase fluctuations that would be seen by an array tracking a deep space signal after applying appropriate adjustments for a given array configuration, elevation angle profile and observing frequency.

Morabito, David D.↗

Overview and Statistical Analysis of Boundary Layer Clouds and Precipitation Over the Western North Atlantic Ocean

Due to their fast evolution and large natural variability in macro- and microphysical properties, the accurate representation of boundary layer clouds in current climate models remains a challenge. One of the regions with large intermodel spread in the Coupled Model Intercomparison Project Phase 6 ensemble is the western North Atlantic Ocean. Here, statistically representative in situ measurements can help to develop and constrain the parameterization of clouds in global models. To this end, we performed comprehensive measurements of boundary layer clouds, aerosol, trace gases, and radiation in the western North Atlantic Ocean during the NASA Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE) mission. In total, 174 research flights with 574 flight hours for cloud and precipitation measurements were performed with the HU-25 Falcon during three winter (February–March 2020, January–April 2021, and November 2021–March 2022) and three summer seasons (August–September 2020, May–June 2021, and May–June 2022). Here we present a statistical evaluation of 16 140 individual cloud events probed by the fast cloud droplet probe and the two-dimensional stereo cloud probe during 155 research flights in a representative and repetitive flight strategy allowing for robust statistical data analyses. We show that the vertical profiles of distributions of the liquid water content and the cloud droplet effective diameter (ED) increase with altitude in the marine boundary layer. Due to higher updraft speeds, higher cloud droplet number concentrations (N liquid ) were measured in winter compared to summer despite lower cloud condensation nucleus abundance. Flight cloud cover derived from statistical analysis of in situ data is reduced in summer and shows large variability. This seasonal contrast in cloud coverage is consistent with a dominance of a synoptic pattern in winter that favors conditions for the formation of stratiform clouds at the western edge of cyclones (post-cyclonic). In contrast, a dominant summer anticyclone is concomitant with the occurrence of shallow cumulus clouds and lower cloud coverage. The evaluation of boundary layer clouds and precipitation in the N liquid ED phase space sheds light on liquid, mixed-phase, and ice cloud properties and helps to categorize the cloud data. Ice and liquid precipitation, often masked in cloud statistics by a high abundance of liquid clouds, is often observed throughout the cloud. The ACTIVATE in situ cloud measurements provide a wealth of cloud information useful for assessing airborne and satellite remote-sensing products, for global climate and weather model evaluations, and for dedicated process studies that address precipitation and aerosol–cloud interactions.

Aerosol↗

Statistical Approaches for Pebble Bed Reactor Operations and Safeguards

The design of pebble bed reactors (PBRs) and their method of operation align more closely with statistical approaches used in manufacturing and process control than traditional safeguards statistical approaches. The reason is PBRs will employ a nondestructive assay (NDA) measurement (burnup measurement system [BUMS]) that is part of the fuel handling system supporting discharge decisions in addition to the reactor code which monitor performance. The integration of these two approaches provides the opportunity to monitor reactor performance statistically for both operations and safeguards in ways not achievable using other reactor designs. For light water reactors (LWRs), knowledge about reactor code performance in predicting irradiated special nuclear material (SNM) content historically was only achieved from special measurement campaigns or from fuel reprocessing. Conversely, through statistical comparison of the BUMS with the reactor code-predicted values, PBRs can achieve this in real time. The resulting SNM distribution is an indicator of reactor performance because factors such as transit time and path of the pebble fuel through the reactor determine the plutonium production and uranium depletion. By analyzing the predicted and measured values, opportunities exist to adjust operating parameters, fuel design, and other characteristics to optimize performance and fuel utilization. From a safeguards perspective, this approach also provides the information necessary to validate declared values and evaluate whether the reactor is being operated as expected. This paper outlines statistical approaches for PBRs that can be used to support both operations and safeguards.

Ball, Cory↗

Memory access statistics monitoring

Systems, apparatuses, and methods related to memory access statistics monitoring are described. A host is configured to map pages of memory for applications to a number of memory devices coupled thereto. A first memory device comprises a monitoring component configured to monitor access statistics of pages of memory mapped to the first memory device. A second memory device does not include a monitoring component capable of monitoring access statistics of pages of memory mapped thereto. The host is configured to map a portion of pages of memory for an application to the first memory device in order to obtain access statistics corresponding to the portion of pages of memory upon execution of the application despite there being space available on the second memory device and adjust mappings of the pages of memory for the application based on the obtained access statistics corresponding to the portion of pages.

Roberts, David A.↗

On the statistical theory of self-gravitating collisionless dark matter flow

Dark matter, if it exists, accounts for five times as much as the ordinary baryonic matter. Compared to hydrodynamic turbulence, the flow of dark matter might possess the widest presence in our universe. This paper presents a statistical theory for the flow of dark matter that is compared with N-body simulations. By contrast to hydrodynamics of normal fluids, dark matter flow is self-gravitating, long-range, and collisionless with a scale-dependent flow behavior. The peculiar velocity field is of constant divergence nature on small scale and irrotational on large scale. The statistical measures, i.e., correlation, structure, dispersion, and spectrum functions, are modeled on both small and large scales, respectively. Kinematic relations between statistical measures are fully developed for incompressible, constant divergence, and irrotational flow. Incompressible and constant divergence flow share the same kinematic relations for even order correlations. The limiting correlation of velocity $\mathrm{ρ_{L}=1/2}$ on the smallest scale ( r = 0) is a unique feature of collisionless flow (⁠$\mathrm{ρ_{L}=1}$ for incompressible flow). On large scale, transverse velocity correlation has an exponential form $T_{2}∝e^{–r/r_2}$ with a constant comoving scale r 2 =21.3 Mpc/h that may be related to the horizon size at matter–radiation equality. All other correlation, structure, dispersion, and spectrum functions for velocity, density, and potential fields are derived analytically from kinematic relations for irrotational flow. On small scale, longitudinal structure function follows one-fourth law of ${S}_{2}^{1}∝r^{1/4}$. All other statistical measures can be obtained from kinematic relations for constant divergence flow. Vorticity is negatively correlated for scale r between 1 and 7 Mpc/h. Divergence is negatively correlated for r > 30 Mpc/h that leads to a negative density correlation.

79 ASTRONOMY AND ASTROPHYSICS↗

Bias Correction and Statistical Downscaling of Future Solar Irradiance Projections Using the NSRDB

Assessing renewable energy resources under future climate scenarios has been highlighted to understand potential impacts of future climate change in renewable generation on the power sector. Climate model projection has been recognized by the renewable energy community as a useful data set to analyze the impacts of future climate change on renewable resources. However, future climate projections generated from general circulation models (GCMs) contain inherent biases that need to be corrected for accurate analysis of future projections of climate variables. In addition, the coarse spatiotemporal resolution of GCMs needs to be improved for regional climate studies. In this work, we develop statistical methods to downscale future projections of global horizontal irradiance (GHI) in a computationally efficient way. Our approach builds statistical downscaling models that correct bias of climate projection of GHI and downscale the future GHI projection from daily-scale to hourly-scale. The National Solar Radiation Database (NSRDB) is used to calibrate the statistical models and validate the downscaled GHI projections across the contiguous United State (CONUS). Preliminary results show that the statistical approach efficiently downscales climate projections of GHI with a nBIAS of 3%, nMAE of 34 % and nRMSE of 46% calculated against NSRDB for CONUS. This study describes the implemented methodology and initial results as well as future research to create high-resolution climate data sets for solar energy applications.

analytical models↗

To have value, comparisons of high-throughput phenotyping methods need statistical tests of bias and variance

The gap between genomics and phenomics is narrowing. The rate at which it is narrowing, however, is being slowed by improper statistical comparison of methods. Quantification using Pearson’s correlation coefficient ( r ) is commonly used to assess method quality, but it is an often misleading statistic for this purpose as it is unable to provide information about the relative quality of two methods. Using r can both erroneously discount methods that are inherently more precise and validate methods that are less accurate. These errors occur because of logical flaws inherent in the use of r when comparing methods, not as a problem of limited sample size or the unavoidable possibility of a type I error. A popular alternative to using r is to measure the limits of agreement (LOA). However both r and LOA fail to identify which instrument is more or less variable than the other and can lead to incorrect conclusions about method quality. An alternative approach, comparing variances of methods, requires repeated measurements of the same subject, but avoids incorrect conclusions. Variance comparison is arguably the most important component of method validation and, thus, when repeated measurements are possible, variance comparison provides considerable value to these studies. Statistical tests to compare variances presented here are well established, easy to interpret and ubiquitously available. The widespread use of r has potentially led to numerous incorrect conclusions about method quality, hampering development, and the approach described here would be useful to advance high throughput phenotyping methods but can also extend into any branch of science. The adoption of the statistical techniques outlined in this paper will help speed the adoption of new high throughput phenotyping techniques by indicating when one should reject a new method, outright replace an old method or conditionally use a new method.

59 BASIC BIOLOGICAL SCIENCES↗

Preliminary Statistical Maneuver Analysis for A Low-Thrust NRHO to DRO Transfer

To understand practical implications of implementing transfers that leverage multibody dynamics, a statistical analysis is performed on an Earth-Moon Near Rectilinear Halo Orbit (NRHO) to distant retrograde orbit (DRO) transfer using solar electric propulsion. The statistical analysis includes perturbations due to maneu- ver execution and orbit determination error to understand operational character- istics of the transfer such as statistical ∆V and statistical state targeting errors at the final DRO. We explore the need for low-thrust trajectory correction maneuver (TCM) opportunities as well as the delivery accuracy to the final target. Finally, we explore options for long-term-stable target DROs.

low thrust↗

Modeling regional precipitation over the Indus River basin of Pakistan using statistical downscaling

Complex processes govern spatiotemporal distribution of precipitation within the high-mountainous headwater regions (commonly known as the upper Indus basin (UIB)), of the Indus River basin of Pakistan. Reliable precipitation simulations particularly over the UIB present a major scientific challenge due to regional complexity and inadequate observational coverage. Here, we present a statistical downscaling approach to model observed precipitation of the entire Indus basin, with a focus on UIB within available data constraints. Taking advantage of recent high altitude (HA) observatories, we perform precipitation regionalization using K-means cluster analysis to demonstrate effectiveness of low-altitude stations to provide useful precipitation inferences over more uncertain and hydrologically important HA of the UIB. We further employ generalized linear models (GLM) with gamma and Tweedie distributions to identify major dynamic and thermodynamic drivers from a reanalysis dataset within a robust cross-validation framework that explain observed spatiotemporal precipitation patterns across the Indus basin. Final statistical models demonstrate higher predictability to resolve precipitation variability over wetter southern Himalayans and different lower Indus regions, by mainly using different dynamic predictors. The modeling framework also shows an adequate performance over more complex and uncertain trans-Himalayans and the northwestern regions of the UIB, particularly during the seasons dominated by the westerly circulations. However, the cryosphere-dominated trans-Himalayan regions, which largely govern the basin hydrology, require relatively complex models that contain dynamic and thermodynamic circulations. Furthermore, we also analyzed relevant atmospheric circulations during precipitation anomalies over the UIB, to evaluate physical consistency of the statistical models, as an additional measure of reliability. Overall, our results suggest that such circulation-based statistical downscaling has the potential to improve our understanding towards distinct features of the regional-scale precipitation across the upper and lower Indus basin. Additionally, such understanding should help to assess the response of this complex, data-scarce, and climate-sensitive river basin amid future climatic changes, to serve communal and scientific interests.

54 ENVIRONMENTAL SCIENCES↗

Statistical analysis of spatial distribution of pores in metal additive manufacturing

We report mechanical properties of additively manufactured parts are sensitive to the presence of pores form during the manufacturing process. The impact of pores on the mechanical performance has been investigated extensively with respect to different parameters, such as pore volume fraction, shape, and size. However, statistical investigations focusing on the relationships between the spatial distribution of pores and process parameters; and consequently, the performance of the manufactured parts are scattered and limited. Also, these sparse investigations usually suffer from an ambiguous definition of terminologies. For instance, the required criteria to consider a point pattern as complete spatial randomness (CSR) are generally not clarified. Moreover, no numerical formalism is yet developed to show how much the observed spatial results are statistically significant. To address these shortcomings, the statistical definition of CSR in a point pattern and the procedure to quantitatively determine the deviation of a pattern from CSR were discussed. The explained statistical approach was used to investigate the effect of scanning speed parameter on the spatial distribution of gas pores in laser powder bed fusion manufactured stainless steel parts. Furthermore, and to highlight the impact of the spatial distribution of pores on mechanical properties, fatigue performances of parts with clustered and randomly distributed pores were simulated by finite element analysis. It is shown that by reducing the scanning speed, the spatial distribution of gas pores deviated more from CSR, and correspondingly fatigue performance deteriorated.

36 MATERIALS SCIENCE↗

Automated identification and calculation of prompt effects in kinetic mechanisms using statistical models

The kinetics of prompt dissociation involves rovibrationally excited species (generally formed by exothermic reactions) which may dissociate or isomerize prior to thermalization via collisions with the bath gas. Treating such rovibrationally excited species (so-called "hot" species) with standard kinetic phenomenology may result in incorrect macroscopic representation of their reactivity. Here this work presents the first fully automated methodology for the calculation of prompt effects of a chosen species in a kinetic mechanism, including (i) reaction selection; (ii) theoretical calculation of rate constants and prompt branching fractions; and (iii) final rate constant fitting. The energy partition between hot fragments is estimated using a variety of statistical models, including a new physically sound microcanonical statistical model based on the rovibrational density of states of the fragments. The methodology is validated against literature data for the prompt dissociations of HCO and C 3 H 7 radicals. The microcanonical statistical model is in better agreement with trajectory simulations for larger species and is thus applicable for practical systems that typically involve large molecules, for which direct dynamics calculations are impractical. The automated workflow is applied to the evaluation of the effects of prompt dissociation for two isomeric radicals C 4 H 7 1-3 (1-methylallyl) and C 4 H 7 1-4 (3-buten-1-yl). Twelve H-atom abstraction reactions are selected and the corresponding rate constants are computed with first principles theory. The microcanonical statistical model predicts that prompt dissociations of C 4 H 7 1-3 and C 4 H 7 1-4 are already significant at 1000K, resulting in differences of up to an order of magnitude at 2000K with respect to the phenomenological thermal rate constants. To illustrate the effects of prompt dissociation on simulations of experimental data, the calculated prompt rate constants are implemented in both CRECK and C3MechV3.3 kinetic mechanisms. Simulations of experimental flame data illustrate the noticeable impact of prompt dissociation kinetics on the high-temperature combustion reactivity of C 4 H 8 -1 and C 4 H 8 -2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗