Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Parameter Identifiability”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 973 records · Page 54

Manifold learning for coarse-graining atomistic simulations: Application to amorphous solids

In this work, we introduce a generalized machine learning framework to probabilistically parameterize upper-scale models in the form of nonlinear PDEs consistent with a continuum theory, based on coarse-grained atomistic simulation data of mechanical deformation and flow processes. The proposed framework utilizes a hypothesized coarse-graining methodology with manifold learning and surrogate-based optimization techniques. Coarse-grained high-dimensional data describing quantities of interest of the multiscale models are projected onto a nonlinear manifold whose geometric and topological structure is exploited for measuring behavioral discrepancies in the form of manifold distances. A surrogate model is constructed using Gaussian process regression to identify a mapping between stochastic parameters and distances. Derivative-free optimization is employed to adaptively identify a unique set of parameters of the upper-scale model capable of rapidly reproducing the system's behavior while maintaining consistency with coarse-grained atomic-level simulations. The proposed method is applied to learn the parameters of the shear transformation zone (STZ) theory of plasticity that describes plastic deformation in amorphous solids as well as coarse-graining parameters needed to translate between atomistic and continuum representations. We show that the methodology is able to successfully link coarse-grained microscale simulations to macroscale observables and achieve a high-level of parity between the models across scales.

36 MATERIALS SCIENCE↗

Parametric Sensitivity and Uncertainty Quantification in the Version 1 of E3SM Atmosphere Model Based on Short Perturbed Parameter Ensemble Simulations

Abstract The atmospheric component of Energy Exascale Earth System Model version 1 has included many new features in the physics parameterizations compared to its predecessors. Potential complex nonlinear interactions among the new features create a significant challenge for understanding the model behaviors and parameter tuning. Using the one‐at‐a‐time method, the benefit of tuning one parameter may offset the benefit of tuning another parameter, or improvement in one target variable may lead to degradation in another target variable. To better understand the Energy Exascale Earth System Model version 1 model behaviors and physics, we conducted a large number of short simulations (three days) in which 18 parameters carefully selected from parameterizations of deep convection, shallow convection, and cloud macrophysics and microphysics were perturbed simultaneously using the Latin hypercube sampling method. From the perturbed parameter ensemble simulations and use of different skill score functions, we identified the most sensitive parameters, quantified how the model responds to changes of the parameters for both global mean and spatial distribution, and estimated the maximum likelihood of model parameter space for a number of important fidelity metrics. Comparison of the parametric sensitivity using simulations of two different lengths suggests that perturbed parameter ensemble using short simulations has some bearing on understanding parametric sensitivity of longer simulations. Results from this analysis provide a more comprehensive picture of the Energy Exascale Earth System Model version 1 behavior. The difficulty in reducing biases in multiple variables simultaneously highlights the need of characterizing model structural uncertainty (so‐called embedded errors) to inform future development efforts.

54 ENVIRONMENTAL SCIENCES↗

Effect of Temperature and Deformation Rate on the Tensile Mechanical Properties of Polyimide Films

In order to study the structure-property relationships of different processed oriented polyimide films, the mechanical properties will be identified by using tensile tester Instron 4505 and structural information such as the 3-dimensional birefringence molecular symmetry axis and 3-dimensional refractive indices will be determined by using wave guide coupling techniques. The monoaxial drawing techniques utilized in this research are very useful for improving the tensile mechanical properties of aromatic polyimide films. In order to obtain high modulus/high strength polyimide films the following two techniques have been employed, cold drawing in which polyimide films are drawn at room temperature at different cross head speeds and hot drawing in which polyimide films are drawn at different temperatures and cross head speeds. In the hot drawing process the polyimide films are drawn at different temperatures until the glass transition temperature (Tg) is reached by using the environmental chamber. All of the mechanical and optical property parameters will be identified for each sample processed by both cold and hot drawing techniques.

Moghazy, Samir F.↗

Impact of media and antifoam selection on monoclonal antibody production and quality using a high throughput micro-bioreactor system

Monoclonal antibody production in commercial scale cell culture bioprocessing requires a thorough understanding of the engineering process and components used throughout manufacturing. It is important to identify high impact components early on during the lifecycle of a biotechnology-derived product. While cell culture media selection is of obvious importance to the health and productivity of mammalian bioreactor operations, other components such as antifoam selection can also play an important role in bioreactor cell culture. Silicone polymer-based antifoams were known to have negative impacts on cell health, production, and downstream filtration and purification operations. High throughput screening in micro-scale bioreactors provides an efficient strategy to identify initial operating parameters. Here, we utilized a micro-scale parallel bioreactor system to study an IgG1 producing CHO cell line, to screen Dynamis, ProCHO5, PowerCHO2, EX-Cell Advanced, and OptiCHO media, and 204, C, EX-Cell, SE-15, and Y-30 antifoams and their impacts on IgG1 production, cell growth, aggregation, and process control. This study found ProCHO5, EX-Cell Advanced, and PowerCHO2 media supported strong cellular growth profiles, with an IVCD of 25-35 3 106 cells-d/ mL, while maintaining specific antibody production (Qp> 2 pg/cell-d) for our model cell line and a monomer percentage above 94%. Antifoams C, EX-Cell, and SE-15 were capable of providing adequate control of foaming while antifoam 204 and Y-30 noticeably stunted cellular growth. This work highlights the utility of high throughput micro bioreactors and the importance of identifying both positive and negative impacts of media and antifoam selection on a model IgG1 producing CHO cell line.

59 BASIC BIOLOGICAL SCIENCES↗

Hot Raman amplification

A parameter regime is identified for Raman amplification at high temperatures, where deleterious laser–plasma instabilities that limit current amplification experiments are avoided, yet sufficient gain for an effective power amplifier is attained. Furthermore, calculations and kinetic simulations show that even at high temperatures, an amplifier is able to satisfy the criteria set forth to present a proof-of-principle system scalable to high powers, where energy transfer efficiencies are ≥30%, intensity gains are ≥10, and output intensities are ≥100× the pump intensity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Enabling Bipolar Membrane Manufacturing Using Microscopy

Bipolar membranes (BPMs) used for water treatment suffer from interface instabilities, causing premature failure and decreased performance. Recent research has highlighted the impacts of membrane morphology on mechanical behavior and performance. Improved material performance of thin film membranes requires enhanced transport properties coupled with better control of the mechanical characteristics to avoid premature failure of the film. Thus, morphology is a key parameter when developing and evaluating novel membrane materials. Microscopy offers unique advantages for nano-scale characterization of thin film membrane interfaces and morphologies. In this study, the interface junction of BPMs was evaluated using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). BPMs were fabricated using (1) hot pressing lamination, (2) bench-scale solution casting, and (3) roll-to-roll sequential casting (R2R). Both commercial and in-house fabricated ion exchange membranes were used in the BPMs. The BPMs were comprised of a cation exchange membrane and an anion exchange membrane with a catalyst layer sandwiched in between. Cross sectional SEM and EDX images of the membrane interface junction were compared among the different fabrication techniques and materials. The bench cast catalyst layers were nonuniform compared to the R2R and hot pressed membranes, demonstrating the importance of precise catalyst application conditions. Different thicknesses of the BPMs and individual membrane layers revealed that polymer solution concentration needs to be optimized during manufacturing. This work shows that microscopy can identify key processing parameters that affect BPM interface junction quality at the microscale to enable manufacturing of high performance BPMs.

36 MATERIALS SCIENCE↗

Enabling Roll-to-Roll Manufacturing of Bipolar Membranes Using Microscopy

Bipolar membranes (BPMs) used for water treatment suffer from interface instabilities, causing premature failure and decreased performance. Recent research has highlighted the impacts of membrane morphology on mechanical behavior and performance. Improved material performance of thin film membranes requires enhanced transport properties coupled with better control of the mechanical characteristics to avoid premature failure of the film. Thus, morphology is a key parameter when developing and evaluating novel membrane materials. Microscopy offers unique advantages for nano-scale characterization of thin film membrane interfaces and morphologies. In this study, the interface junction of BPMs was evaluated using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). BPMs were fabricated using (1) hot pressing lamination, (2) bench-scale solution casting, and (3) roll-to-roll sequential casting (R2R). Both commercial and in-house fabricated ion exchange membranes were used in the BPMs. The BPMs were comprised of a cation exchange membrane and an anion exchange membrane with a catalyst layer sandwiched in between. Cross sectional SEM and EDX images of the membrane interface junction were compared among the different fabrication techniques and materials. The bench cast catalyst layers were nonuniform compared to the R2R and hot pressed membranes, demonstrating the importance of precise catalyst application conditions. Different thicknesses of the BPMs and individual membrane layers revealed that polymer solution concentration needs to be optimized during manufacturing. This work shows that microscopy can identify key processing parameters that affect BPM interface junction quality at the microscale to enable manufacturing of high performance BPMs.

36 MATERIALS SCIENCE↗

Mitigating Abnormal Grain Growth for Friction Stir Welded Al-Li 2195 Spun Formed Domes

Formability and abnormal grain growth (AGG) are the two major issues that have been encountered for Al alloy spun formed dome development using friction stir welded blanks. Material properties that have significant influence on the formability include forming range and strain hardening exponent. In this study, tensile tests were performed for two 2195 friction stir weld parameter sets at 400 F to study the effects of post weld anneal on the forming range and strain hardening exponent. It was found that the formability can be enhanced by applying a newly developed post weld anneal to heat treat the friction stir welded panels. This new post weld anneal leads to a higher forming range and much improved strain hardening exponent. AGG in the weld nugget is known to cause a significant reduction of ductility and fracture toughness. This study also investigated how AGG may be influenced by the heating rate to the solution heat treatment temperature. After post-weld annealing, friction stir welds were strained to 15% and 39% by compression at 400 F before they were subjected to SHT at 950 F for 1 hour. Salt bath SHT is very effective in reducing the grain size as it helps arrest the onset of AGG and promote normal recrystallization and grain growth. However, heat treating a 18 ft dome using a salt bath is not practical. Efforts are continuing at Marshall Space Flight Center to identify the welding parameters and heat treating parameters that can help mitigate the AGG in the friction stir welds.

Chen, Po-Shou↗

Maximum likelihood identification and optimal input design for identifying aircraft stability and control derivatives

A new method of extracting aircraft stability and control derivatives from flight test data is developed based on the maximum likelihood cirterion. It is shown that this new method is capable of processing data from both linear and nonlinear models, both with and without process noise and includes output error and equation error methods as special cases. The first application of this method to flight test data is reported for lateral maneuvers of the HL-10 and M2/F3 lifting bodies, including the extraction of stability and control derivatives in the presence of wind gusts. All the problems encountered in this identification study are discussed. Several different methods (including a priori weighting, parameter fixing and constrained parameter values) for dealing with identifiability and uniqueness problems are introduced and the results given. The method for the design of optimal inputs for identifying the parameters of linear dynamic systems is also given. The criterion used for the optimization is the sensitivity of the system output to the unknown parameters. Several simple examples are first given and then the results of an extensive stability and control dervative identification simulation for a C-8 aircraft are detailed.

Stepner, D. E.↗

ON THE CLUSTER PHYSICS OF SUNYAEV-ZEL'DOVICH AND X-RAY SURVEYS. I. THE INFLUENCE OF FEEDBACK, NON-THERMAL PRESSURE, AND CLUSTER SHAPES ON Y-M SCALING RELATIONS

The utility of large Sunyaev-Zel'dovich (SZ) surveys for determining cosmological parameters from cluster abundances is limited by the theoretical uncertainties in the integrated SZ-flux-to-mass relation, Y-M. We explore how non-thermal pressure and the anisotropic shape of the gas distribution of the intracluster medium (ICM) impacts Y-M scaling using a suite of smoothed particle hydrodynamic simulations of the cosmic web. We contrast results for models with different treatments of entropy injection and transport, varying radiative cooling, star formation and accompanying supernova feedback, cosmic rays, and energetic feedback from active galactic nuclei (AGNs). We find that the gas kinetic-to-thermal pressure ratio, P {sub kin}/P {sub th}, from internal bulk motions depends on the cluster mass, and increases in the outer-cluster due to enhanced substructure, as does the asphericity of the ICM gas. With only a {approx}5%-10% correction to projected (observable) ellipticities, we can infer the three-dimensional ellipticities. Our simulated Y-M slope roughly follows the self-similar prediction, except for a steepening due to a deficit of gas in lower mass clusters at low redshift in our AGN feedback simulations. AGN feedback enhances the overall Y-M scatter, from {approx}11% to {approx}13% (z = 0) and to {approx}15% (z = 1), a reflection of the accretion history variations due to cluster merging. If we split the cluster system into lower, middle, and upper bands of both P {sub kin}/P {sub th} and long-to-short axis ratio, we find a {approx}10% effect on Y-M. Identifying observable second parameters related to internal bulk flows and anisotropy for cluster selection to minimize Y-M scatter in a 'fundamental plane' would allow tighter cosmological parameter constraints.

79 ASTRONOMY AND ASTROPHYSICS↗

Experimental analysis of thread movement in bolted connections due to vibrations

This is the final report of research project NAS8-39131 #33 sponsored by NASA's George C. Marshall Space Flight Center (MSFC) and carried out by the Civil Engineering Department of Auburn University (Auburn, Alabama) and personnel of MSFC. The objective of this study was to identify the main design parameters contributing to the loosening of bolts due to vibration and to identify their relative importance and degree of contribution to bolt loosening. Vibration testing was conducted on a shaketable with a controlled-random input in the dynamic testing laboratory of the Structural Test Division of MSFC. Test specimens which contained one test bolt were vibrated for a fixed amount of time and a percentage of pre-load loss was measured. Each specimen tested implemented some combination of eleven design parameters as dictated by the design of experiment methodology employed. The eleven design parameters were: bolt size (diameter), lubrication on bolt, hole tolerance, initial pre-load, nut locking device, grip length, thread pitch, lubrication between mating materials, class of fit, joint configuration, and mass of configuration. These parameters were chosen for this experiment because they are believed to be the design parameters having the greatest impact on bolt loosening. Two values of each design parameter were used and each combination of parameters tested was subjected to two different directions of vibration and two different g-levels of vibration. One replication was made for each test to gain some indication of experimental error and repeatability and to give some degree of statistical credibility to the data, resulting in a total of 96 tests being performed. The results of the investigation indicated that nut locking devices, joint configuration, fastener size, and mass of configuration were significant in bolt loosening due to vibration. The results of this test can be utilized to further research the complex problem of bolt loosening due to vibration.

Ramsey, G. ED↗

Selection Effects in Identifying Magnetic Clouds and the Importance of the Closest Approach Parameter

This study is motivated by the unusually low number of magnetic clouds (MCs) that are strictly identified within interplanetary coronal mass ejections (ICMEs), as observed at 1 AU; this is usually estimated to be around 30% or lower. But a looser definition of MCs may significantly increase this percentage. Another motivation is the unexpected shape of the occurrence distribution of the observers' "closest approach distances" (measured from a MC's axis, and called CA) which drops off somewhat rapidly as |CA| (in % of MC radius) approaches 100%, based on earlier studies. We suggest, for various geometrical and physical reasons, that the |CA|-distribution should be somewhere between a uniform one and the one actually observed, and therefore the 30% estimate should be higher. So we ask, When there is a failure to identify a MC within an ICME, is it occasionally due to a large |CA| passage, making MC identification more difficult, i.e., is it due to an event selection effect? In attempting to answer this question we examine WIND data to obtain an accurate distribution of the number of MCs vs. |CA| distance, whether the event is ICME-related or not, where initially a large number of cases (N=98) are considered. This gives a frequence distribution that is far from uniform, confirming earlier studies. This along with the fact that there are many ICME identification-parameters that do not depend on |CA| suggest that, indeed an MC event selection effect may explain at least part of the low ratio of (No. MCs)/(No. ICMEs). We also show that there is an acceptable geometrical and physical consistency in the relationships for both average "normalized" magnetic field intensity change and field direction change vs. |CA| within a MC, suggesting that our estimates of |CA|, B(sub 0) (magnetic field intensity on the axis), and choice of a proper "cloud coordinate" system (all needed in the analysis) are acceptably accurate. Therefore the MC fitting model (Lepping et al., 1990) is adequate, on average, for our analysis. However, this selection effect is not likely to completely answer our original question, on the unexpected ratio of MCs to ICMEs, so we must look for other factors, such as peculiarities of CME birth conditions. As a by-product of this analysis, we determine that the first order structural effects within a MC due to its interaction with the solar wind, plus the MC's usual expansion at 1 AU (i.e., the non-force free components of the MC's field) are, on average, weakly dependent on radial distance from the MC's axis; that is, in the outer reaches of a typical MC the non-force free effects show up, but even there they are rather weak. Finally, we show that it is not likely that a MC's size distribution statistically controls the occurrence distribution of the estimated |CA|s.

Lepping, R. P.↗

BEYONDPLANCK XI. Bayesian CMB analysis with sample-based end-to-end error propagation

We present posterior sample-based cosmic microwave background (CMB) constraints from Planck LFI and WMAP observations as derived through global end-to-end Bayesian processing within the BeyondPlanck framework. We first use these samples to study correlations between CMB, foreground, and instrumental parameters, and we identify a particularly strong degeneracy between CMB temperature fluctuations and free-free emission on intermediate angular scales (400 ≲ ℓ ≲ 600), which is mitigated through model reduction, masking, and resampling. We compare our posterior-based CMB results with previous Planck products, and find generally good agreement, although with notably higher noise due to our exclusion of HFI data. We find a best-fit CMB dipole amplitude of 3362.7 ± 1.4 µK, in excellent agreement with previous Planck results. The quoted dipole uncertainty is derived directly from the sampled posterior distribution, and does not involve any ad hoc contributions for Planck instrumental systematic effects. Similarly, we find a temperature quadrupole amplitude of ${σ}_{2}^{TT}$ = 229 ± 97 µK 2 , which is in good agreement with previous results in terms of the amplitude, but the uncertainty is an order of magnitude larger than the naive diagonal Fisher uncertainty. Relatedly, we find lower evidence for a possible alignment between the quadrupole and octopole than previously reported due to a much larger scatter in the individual quadrupole coefficients, caused both by marginalizing over a more complete set of systematic effects, but also by our more conservative analysis mask required to mitigate the free-free degeneracy. For higher multipoles, we find that the angular temperature power spectrum is generally in good agreement with both Planck and WMAP. At the same time, we note that this is the first time the sample-based asymptotically exact Blackwell-Rao estimator has been successfully established for multipoles up to ℓ ≤ 600, and it now accounts for the majority of the cosmologically important information. Overall, this analysis demonstrates the unique capabilities of the Bayesian approach with respect to end-to-end systematic uncertainty propagation, and we believe it can and should play an important role in the analysis of future CMB experiments. Cosmological parameter constraints are presented in a companion paper.

79 ASTRONOMY AND ASTROPHYSICS↗

Wavelet and Deep-Learning-Based Approach for Generation System Problematic Parameters Identification and Calibration

Accurate models of generation systems are critical for maintaining reliable and secure grid operations. In this paper, a novel and systematic approach is proposed to identify and calibrate the generation system problematic parameters using continuous wavelet transform (CWT) and advanced deep-learning technology. The phasor measurement unit (PMU) data are used through “event playback” to check whether the parameter calibration is required, and if yes, a group of suspicious parameters will be identified as the primary problematic parameter candidates (PPCs). These primary PPCs are randomly perturbed to generate the event playback simulation data, which are used by the CWT and convolutional neural networks (CNNs) to further narrow down the primary PPCs into a smaller set of candidates. Then, the identified candidates are perturbed again to generate massive event playback simulation data for training a parameter calibration neural network. Here, we designed a multi-output neural network structure to find the mappings between the perturbed parameters and the simulation data using both CNN and long short-term memory (LSTM) models. Finally, the well-trained and tested CNN-LSTM model is used to estimate the accurate value of the suspicious parameters with actual PMU measurements. The proposed CNN-LSTM network can accurately and reliably estimate the generation-system problematic parameters, and has better performance when compared to other machine-learning methods, such as the multilayer perceptron network and the conditional variational autoencoder method. The accuracy and effectiveness of the proposed approach have been validated through simulation and real-world data.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Understanding the eco-geomorphologic feedback of coastal marsh under sea level rise: vegetation dynamic representations, processes interaction, and parametric sensitivity

A growing number of coastal eco-geomorphologic modeling studies have been conducted to understand coastal marsh evolution under sea-level rise (SLR). Although these models quantify marsh topographic change as a function of sedimentation and erosion, their representations of vegetation dynamics that control organic sedimentation differ. How vegetation dynamic schemes contribute to simulation outcomes is not well quantified. Additionally, the sensitivity of modeling outcomes to parameter selection in the available formulations has not been rigorously tested to date, especially under the influence of an accelerating SLR. In this paper, we used a coastal eco-geomorphologic model with different vegetation dynamic schemes to investigate the eco-geomorphologic feedbacks of coastal marshes and parametric sensitivity under SLR scenarios. We found that marsh platform relief increased with sea level rise rate. The simulations with different vegetation schemes exhibited different spatial-temporal variations in elevation and biomass. The nonlinear Spartina scheme presented the most resilient prediction with generally the highest marsh accretion and vegetation biomass, and the least elevation relief under SLR. But the linear Spartina scheme predicts the lowest unvegetated-vegetated ratio. We also found that vegetation-related parameters and sediment diffusivity, which were not well measured or discussed in previous studies, were identified as some of the most critical parameters. Additionally, the model sensitivity to vegetation-related parameters increased with SLR rates. The identified most sensitive parameters may inform how to appropriately choose modeling representations of key processes and parameters for different coastal marsh landscapes under SLR, and demonstrate the importance of future field measurements of these key parameters.

58 GEOSCIENCES↗

Global Sensitivity Analysis and Estimation of Model Error, Toward Uncertainty Quantification in Scramjet Computations

The development of scramjet engines is an important research area for advancing hypersonic and orbital flights. Progress toward optimal engine designs requires accurate flow simulations together with uncertainty quantification. However, performing uncertainty quantification for scramjet simulations is challenging due to the large number of uncertain parameters involved and the high computational cost of flow simulations. These difficulties are addressed in this paper by developing practical uncertainty quantification algorithms and computational methods, and deploying them in the current study to large-eddy simulations of a jet in crossflow inside a simplified HIFiRE Direct Connect Rig scramjet combustor. First, global sensitivity analysis is conducted to identify influential uncertain input parameters, which can help reduce the system’s stochastic dimension. Second, because models of different fidelity are used in the overall uncertainty quantification assessment, a framework for quantifying and propagating the uncertainty due to model error is presented. In conclusion, these methods are demonstrated on a nonreacting jet-in-crossflow test problem in a simplified scramjet geometry, with parameter space up to 24 dimensions, using static and dynamic treatments of the turbulence subgrid model, and with two-dimensional and three-dimensional geometries.

33 ADVANCED PROPULSION SYSTEMS↗

Effect of Ring‐Fusion on Miscibility and Domain Purity: Key Factors Determining the Performance of PDI‐Based Nonfullerene Organic Solar Cells

Abstract Compared to the rapid development of nonfullerene organic solar cells (OSCs) based on the state‐of‐the‐art indacenodithiophene (IDT)‐based small molecule acceptors (SMAs), the progress for perylene diimide (PDI)‐based electron acceptors has lagged behind owing to the lack of understanding on the structure–morphology–performance relationship of PDI SMAs. Given the ease of synthesis for PDIs and their high intrinsic electron mobility, it is crucial to identify key material parameters that influence the polymer:PDI blend morphology and to develop rational approaches for molecular design toward high‐performance PDI‐based SMAs. In this study, three pairs of PDI‐based SMAs with and without ring‐fusion are investigated and it is found that ring‐fusion and domain purity are the key structural and morphological factors determining the fill factors (FFs) and efficiencies of PDI‐based nonfullerene OSCs. This data shows that nonfullerene OSCs based on the ring‐fused PDI‐based SMAs exhibit much higher average domain purity and thus increased charge mobilities, which lead to enhanced FFs compared to those solar cells based on nonfused PDIs. This is explained by higher Florry Huggins interaction parameters as observed by melting point depression measurements. This study suggests that increasing repulsive molecular interactions to lower the miscibility between the polymer donor and PDI acceptor is the key to improve the FF and performance of PDI‐based devices.

Hu, Huawei↗

Advancing Insights into Electrochemical Pre‐Treatments of Supported Nanoparticle Electrocatalysts by Combining a Design of Experiments Strategy with In Situ Characterization

Activation, break-in, and/or pre-treatment protocols are generally applied to energy conversion devices before regular operation to reach stable performance. There remains much to understand about the relationships among physical properties, performance, and electrochemical pre-treatments. Here, a design-of-experiments (DoE) strategy is employed to address this gap by demonstrating the influence of five pre-treatment parameters for carbon-supported Pt-nanoparticle catalysts on the electrocatalytic oxygen reduction reaction (ORR). A subset of pre-treatments, developed using a central composite design, are tested in a flow cell combined with an inductively-coupled plasma mass spectrometer (on-line ICP-MS). The DoE-based approach facilitates comprehensive insights from two orders of magnitude fewer experiments than a conventional grid search. The coupled on-line ICP-MS setup enables effective catalysis and real-time catalyst dissolution data. Leveraging insights from DoE for on-line ICP-MS and additional characterization, a model is built between the degradation of a multi-dimensional supported Pt surface, its performance, and applied electrochemical parameters. These investigations identify surface modifications, such as oxidation, and subsequent restructuring of Pt during pre-treatment as a primary cause of performance deterioration during ORR. By combining DoE with advanced characterization techniques, a powerful approach is demonstrated to gain a mechanistic understanding of pre-treatment protocols that can be broadly adapted to various reaction chemistries.

Platinum↗