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DOE OSTI2022

Replicating HCCI-like autoignition behavior: What gasoline surrogate fidelity is needed?

This work seeks to characterize the fidelity needed in a gasoline surrogate with the intent to replicate the complex autoignition behavior exhibited within advanced combustion engines, and specifically Homogeneous Charge Compression Ignition (HCCI). A low-temperature gasoline combustion (LGTC) engine operating in HCCI mode and a rapid compression machine (RCM) are utilized to experimentally quantify fuel reactivity, through autoignition and preliminary heat release characteristics. Fuels considered include a research grade E10 U.S. gasoline (RD5-87), three multi-component surrogates (PACE-1, PACE-8, PACE-20), and a binary surrogate (PRF88.4). Each fuel was studied at lean/HCCI-like conditions covering a wide range of temperatures and pressures that are representative of naturally aspirated to high boost engine operation. Detailed chemical kinetic modeling is also undertaken using a recently updated gasoline surrogate kinetic model to simulate the RCM experiments and to provide chemical insight into surrogate-to-surrogate differences. The LGTC engine experiments demonstrate nearly identical reactivity between PACE-20 and RD5-87 across studied conditions, while faster phasing is seen for both PACE-1 and PACE-8 due to their stronger intermediate- and low-temperature heat release (ITHR/LTHR) at naturally aspirated and boosted conditions, respectively. The RCM experiments reveal typical low-temperature, negative temperature coefficient (NTC) and intermediate-temperature autoignition behaviors at all pressure conditions for RD5-87, which are qualitatively reproduced by all surrogates. Quantitative discrepancies in both autoignition and preliminary heat release are observed for all surrogates, while their ability to replicate RD5-87 autoignition behavior follows the order of PACE-20 > PACE-1 > PACE-8 > PRF88.4. Excellent mapping is obtained between the LGTC engine and the RCM, where the engine pressure-time trajectories can be characterized by the regimes represented by the RCM autoignition isopleths. The kinetic model performs commendably when simulating both autoignition and preliminary heat release of PACE-20, while typically overpredicting ignition delay times for PACE-1, PACE-8 and PRF88.4 at high-pressure and low-temperature/NTC conditions. Sensitivity and rate of production (ROP) analyses highlight surrogate-to-surrogate differences in the governing chemical kinetics where n-pentane initiates rapid OH branching at a faster rate and an earlier timing for PACE-20 than iso-pentane does for PACE-1 and PACE-8, making it computationally more reactive than the other surrogates. The current study highlights the need to include non-standardized properties, such as the lean/HCCI-like autoignition characteristics, in addition to ASTM properties (e.g., RON, MON) as metrics of fuel reactivity and targets to be matched when formulating high-fidelity surrogates that fully capture gasoline advanced combustion behavior such as HCCI-like autoignition.

42 ENGINEERING↗

DOE OSTI2015

Analysis of structure and deformation behavior of AISI 316L tensile specimens from the second operational target module at the Spallation Neutron Source

In an earlier publication, tensile testing was performed on specimens removed from the first two operational targets of the Spallation Neutron Source (SNS). There were several anomalous features in the results. First, some specimens had very large elongations (up to 57%) while others had significantly smaller values. Second, there was a larger than the usual amount of data scatter in the elongation results. Third, the stress-strain diagrams of nominally similar specimens spanned a wide range of behavior ranging from expected irradiation-induced hardening to varying levels of force drop after yield point and indirect signs of "traveling deformation wave" behavior associated with strain-induced martensite formation. To investigate the cause(s) of such variable tensile behavior, several specimens from Target 2, spanning the range of observed tensile behavior, were chosen for detailed microstructural examination using electron backscattering analysis (EBSD). It was also shown that the steel employed in the construction of the target contained an unexpected bimodal grain size distribution, containing very large out-of-specification grains surrounded by necklaces of grains of within-specification sizes. The large grains were frequently comparable to the width of the gauge section of the tensile specimen. Moreover, the propensity to form martensite during deformation was shown to be accelerated by radiation but also to be very sensitive to the relative orientation of the grains with respect to the tensile axis. Specimens having large grains in the gauge that were most favorably oriented for production of martensite strongly exhibited the traveling deformation wave phenomenon, while those specimens with less favorably oriented grains had lesser or no degree of the wave effect, thereby accounting for the larger than expected data scatter.

316L↗

DOE OSTI2016

Oxidation behavior of U-Si compounds in air from 25 to 1000 C

The air oxidation behavior of U 3 Si 2 , USi, and U 3 Si 5 is studied from room temperature to 1000 C. Moreover, the onsets of breakaway oxidation for each compound are identified during synthetic air ramps to 1000 C using thermogravimetric analysis. Isothermal air oxidation tests are performed below and above the breakaway oxidation onset to discern the oxidation kinetic behavior of these candidate accident tolerant fuel forms. Uranium metal is tested in the same manner to provide a reference for the oxidation behavior. We present thermogravimetric, x-ray diffraction, and scanning electron microscopy analysis here along with a discussion of the oxidation behavior of these materials and the impact of the lack of oxidation resistance to their deployment as accident tolerant nuclear fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2017

Determination of gaseous fission product behavior near the cerium dioxide Σ 3 (111)/[1 1 ¯ 0] tilt grain boundary via first-principles study

We present that grain boundaries (GBs) are the most abundant structural defects in nanostructured nuclear fuels and play an important role in determining fission product behavior, which further affects the performance of nuclear fuels. In this work, cerium dioxide (CeO 2 ) is used as a surrogate material for mixed oxide fuels to understand gaseous fission product behavior, specifically Xe. First-principles calculations are employed to comprehensively study the behavior of Xe and trap sites for Xe near the Σ 3 (111)/[1 1 ¯ 0] grain boundary in CeO 2 , which will provide guidance on overall trends for Xe stability and diffusion at grain boundaries vs in the bulk. Significant segregation behavior of trap sites, regardless of charge states, is observed near the GB. This is mainly ascribed to the local atomic structure near the GB, which results in weaker bond strength and more negative segregation energies. For Xe, however, the segregation profile near the GB is different. Our calculations show that, as the size of trap sites increases, the segregation propensity of Xe is reduced. In addition, under hyper-stoichiometric conditions, the solubility of Xe trapped at the GB is significantly higher than that in the bulk, suggesting higher Xe concentration than that in the bulk. The results of this work demonstrate that the diffusion mechanism of Xe in CeO 2 is comparable to that in UO 2 . The diffusion activation energies of Xe atoms in the Σ3GB are lower than that in the bulk CeO 2 . Lastly, these results suggest that the diffusivity of Xe atoms is higher along the GB than that in the bulk, which enhances the aggregation of Xe atoms near the GB.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Creep behavior of an additively manufactured 9Cr steel in the as-built condition

Limited studies have evaluated the creep behavior of additively manufactured (AM) ferritic-martensitic (FM) steels. This work investigated the creep behavior of a 9Cr FM steel fabricated by powder blown directed energy deposition (DED) technique. Here, the creep testing at 550–650 °C and 150 MPa for the specimens along the deposition direction in the as-built condition, together with corresponding microstructural characterization, revealed a threshold temperature between 600 and 625 °C, below which the steel has creep resistance comparable with Grade 91 cross-welds and noticeably greater than 9Cr-1Mo steel. The threshold temperature distinguishes the creep behavior in two regimes differentiated in creep activation energy, creep deformation, and failure mechanism. Unlike the creep rupture surface ~45° from the loading direction when tested above the threshold temperature, the creep rupture for testing below the threshold temperature resembles type IV failure in the cross-welds of ferritic steels. The DED-induced layer structure in the as-built steel played a significant role on the change of creep behavior.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Modification of lithium electrodeposition behavior by variation of electrode distance

Developing a better understanding and control over the lithium electrodeposition behavior will assist with the commercial application of lithium metal anodes for rechargeable batteries. Despite intensive research over the past decade, our understanding of the deposition of lithium is limited. Here a new observation on the effect of distance between the working electrode and the counter electrode for electrochemical lithium deposition behavior is reported. From this fundamental investigation of distance, the high lithium ion concentration regions formed by release of lithium ions from the counter electrode modify the lithium deposition behavior on the working electrode, resulting in the generation of non-uniform lithium dendrites with a thick diversely composed surface film. Alternatively, increasing the distance between the electrodes results in the deposition of a spherical lithium morphology with a thin LiF rich surface film. Here, this fundamental study provides a deeper understanding of correlation between lithium deposition behavior and electrode separation and provides insight to inhibit lithium dendrite formation.

25 ENERGY STORAGE↗

DOE OSTI2018

High-temperature deformation behavior and microstructural characterization of high-Mn bearing titanium-based alloy

Highlights: • The hot deformation behavior of a biomedical low-cost Ti-10Mn alloys was studied. • The flow curves of the alloy display periodic serrations attributed to dynamic strain aging. • Mn alloying increases the activation energy to 243 kJ/mol compared to pure Ti. • The dynamic recovery is more effective than dynamic recrystallization at hot deformation. - Abstract: Ti-Mn alloys exhibit an excellent potential for biomedical applications as well as structural engineering applications, especially in the aerospace industry. In order to control and enhance grain structure during the manufacturing of Ti-Mn alloys and thereby help to enhance mechanical properties such as strength and toughness, we studied the hot-deformation behavior of βTi-10Mn alloys. Isothermal compression tests were conducted in the strain rate range of 0.01–10 s{sup −1} and temperatures in the range of 850–1000 °C using a Gleeble thermomechanical simulator. High-temperature flow stress curves exhibited discontinuous yielding and pronounced periodic serrations without any strain hardening during compression straining of these alloys. Such peculiar behavior of this alloy is due to active dynamic strain aging in its β-bcc structure. Metallographic observations by electron-backscattered diffraction (EBSD) analysis revealed that dynamic recovery (DRV) is more active than continuous dynamic recrystallization (CDRX) when the alloy is deformed at high strain rates, i.e. higher than 1 s{sup −1}. Furthermore, the constitutive behavior of the alloy was modeled and the apparent hot-deformation activation energy of the alloy was estimated to be 243 kJ/mol, which is ~60% higher than the self-diffusion energy in pure titanium.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Low cycle fatigue behavior of AlSi10Mg(Cu) alloy at high temperature

Highlights: • The cyclic stress response of AlSi10Mg(Cu) alloy in LCF regime is temperature-dependent. • Precipitates transitions were observed after high temperature cycle loading. • Changes in the interaction mechanism between dislocations and nanoparticles lead to different cyclic stress responses. - Abstract: Low cycle fatigue (LCF) behavior of AlSi10Mg(Cu) alloy was investigated at 100 °C and 250 °C over a range of strain amplitude from 0.25% to 0.40%. Cycle stress response, hysteresis loops, fatigue life, as well as post-fatigue microstructure were studied in detail. Except 0.25%, the alloy performed cycle hardening behavior at 100 °C and softening behavior at 250 °C at any given strain amplitude, which corresponded well with the observed phenomena in hysteresis loops. At any given temperature, cyclic stress increases while fatigue life decreases with the increasing strain amplitude. The fatigue life of the studied alloy at 100 °C was higher than that at 250 °C under the same strain amplitude. Fractography indicated that most fatigue crack initiated from casting defects. The fatigue crack propagation was mainly characterized by fatigue striations and tear ridges in any conditions. Section inspection shows that the number of cracked eutectic Si increases with decreasing the temperature or increasing strain amplitude. Post-mortem transmission electron microscopy (TEM) investigations indicated that cyclic hardening behavior at 100 °C was due to the pinning effect of coherent precipitates (β″-Mg{sub 2}Si and GP zones). Most of tiny coherency precipitates and clusters transformed to large semi-coherency Q′ and β′-Mg{sub 2}Si precipitates after cyclic loading at 250 °C, leading to the sharp decrease of pinning number and dislocation density, which is a key reason for the cyclic softening. Another factor is that more dislocations can be activated and dislocation climb is easier at higher temperature.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Structure and phase formation behavior and dielectric and magnetic properties of lead iron tantalate-lead zirconate titanate multiferroic ceramics

Highlights: • The multiferroic ceramics consisted of PFT and PZT. • Crystal structure changed from cubic to mixedcubic and tetragonal with increasing PZT content. • Dielectric showed the samples underwent a typical relaxor ferroelectric behavior. • Magnetic properties showed very interesting behavior with square saturated magnetic hysteresis loops. - Abstract: Multiferroic (1 − x)Pb(Fe{sub 0.5}Ta{sub 0.5})O{sub 3}–xPb(Zr{sub 0.53}Ti{sub 0.47})O{sub 3} (or PFT–PZT) ceramics were synthesized by solid-state reaction method. The crystal structure and phase formation of the ceramics were examined by X-ray diffraction (XRD). The local structure surrounding Fe and Ti absorbing atoms was investigated by synchrotron X-ray Absorption Near-Edge Structure (XANES) measurement. Dielectric properties were studied as a function of frequency and temperature using a LCR meter. A vibrating sample magnetometer (VSM) was used to determine the magnetic hysteresis loops. XRD study indicated that the crystal structure of the sample changed from pure cubic to mixed cubic and tetragonal with increasing PZT content. XANES measurements showed that the local structure surrounding Fe and Ti ions was similar. Dielectric study showed that the samples underwent a typical relaxor ferroelectric behavior while the magnetic properties showed very interesting behavior with square saturated magnetic hysteresis loops.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Self-regulating behavior of hybrid membrane systems as demonstrated in an element-scale forward osmosis-reverse osmosis hybrid system

Hybrid membrane systems can be difficult to design due to the requisite flow rate matching between up- and downstream unit operations. In this work, we use a forward osmosis-reverse osmosis (FO-RO) hybrid system to demonstrate how some membrane systems can exhibit self-regulating behavior due to osmotic coupling. This can reduce the need for complex control systems for flow balancing. We show this behavior using a module-scale test bed that can mimic the behavior of larger scale operations. The system shows permeate flow rate near-convergence between the FO and RO modules after startup or when perturbed by a change in RO module pressure. The behavior of this hybrid system demonstrates that some membrane operations can exploit osmotic interdependence, rather than expensive control systems, to achieve steady state operation.

Debottlenecking↗

DOE OSTI2022

A layered 2D computational framework: Theory and applications to nuclear fuel behavior

Nuclear fuel performance computer codes have been developed over the last 50 years to analyze fuel behavior under various operating conditions. Traditionally, these codes used quasi-two-dimensional (also commonly known as 1.5D) representations of the fuel rod, which model the rod using a set of one-dimensional axisymmetric models that represent the behavior at specific axial positions on the rod. Modern fuel performance codes have the ability to investigate full three-dimensional (3D) effects and couple to other physics-based codes for true multiphysics simulations. However, with increasing complexity comes increasing computational costs. Many phenomena of interest involve azimuthally-varying behavior that cannot be represented using the aforementioned quasi-two-dimensional approach, but do not require the use of a full 3D model. To efficiently address these problems, there is a need for a computational framework that provides a compromise between the quasi-two-dimensional and full 3D models. In this paper, we present a new quasi-three-dimensional approach that represents the fuel as a set of 2D planar models that represent the behavior of the fuel cross-section at various axial positions. Presented here are the theory behind the methodology, test cases to illustrate proper implementation, and practical applications of its use in the BISON fuel performance code for a variety of cases in nuclear fuel analysis, such as fuel fracture, axial fuel relocation, and cladding distension and oxidation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

A review of rare earth elements and yttrium in coal ash: Content, modes of occurrences, combustion behavior, and extraction methods

Rare earth elements and yttrium (REY) have attracted considerable attention over the last decade because of their vital roles in clean energy, consumer product, national defense and security applications, among other uses. Due to the retention of REY during coal burning, coal combustion ash is considered as potential alternative sources for REY. Understanding the content, speciation, retention and/or transformation behavior of REY during coal combustion not only expands our knowledge of the combustion behavior of the trace elements in coal, but also provides basis for modeling REY partitioning during coal combustion and for developing economically viable REY recovery technologies. This review makes a critical summary of recent progress in the study of REY in coal ash. The contents and the extraction potentials of REY in coal ash derived from 15 major coal-producing countries worldwide were summarized and evaluated. Various analytical methods for determining REY bulk contents and speciation, together with the solid sample pretreatment, analytical accuracy and precision, advantages and disadvantages were summarized and compared. Modern analytical approaches combined indirect methods (e.g., sequential extraction) shed light on the physical distribution, mineralogy, and the chemical state of REY in coal ash. Three types of REY occurrences in coal ash, including Si-Al glassy association, discrete minerals or compounds, and organic association (bound with unburned carbon) were defined in the review. The glassy association can be further divided into REY minerals closely bound to glass phases and dispersed throughout the glassy structure. REY partitioning in various emission streams, the size distribution, and their enrichment behavior in coal ash were discussed. Additionally, thermal behavior and transformation of various REY forms in coal during combustion process, including organic-associated REY, REY phosphates, REY carbonates, clay-bound REY and among others were summarized. Two possible retention mechanisms of REY by aluminosilicate glass at boiler temperature were proposed: the incorporation of the individual REY phases into the glass as inclusions and the diffusion of REY phases throughout Si-Al glass structures in the melting process. Feed coal mineral types, mineral-mineral associations, boiler conditions, and other factors control the retention process. After coal combustion, the speciation of REY in fly ash may be modified by the reactions of REY phases with flue gas components. Further, an overview of REY transformation mechanisms during coal combustion was deeply discussed. Finally, current extraction techniques for REY recovery from coal combustion ash were introduced. Future outlooks and research problems were also identified.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Relationships between maternally-transferred mercury and hatchling development, behavior, and survival in the American alligator ( Alligator mississippiensis )

Mercury is a toxic and pervasive environmental contaminant that can be transferred from mother to offspring during development. Consequences of maternally-transferred mercury have been observed in vertebrate taxa, including reduced clutch viability, reduced offspring size, and behavioral alterations. These sublethal effects have been assumed to decrease survivorship, though this is seldom assessed. Here, we examined how maternally-transferred mercury interacts with incubation temperature to influence reproductive success, offspring behavior, and subsequent survival in the American alligator (Alligator mississippiensis). We collected nine clutches of eggs from a mercury contaminated reservoir on the Savannah River Site, South Carolina, and incubated eggs at either female- or male-promoting temperatures. Clutch-averaged mercury in egg yolk was high relative to other studies in crocodilians and ranged from 0.248 to 0.554 ppm compared to 0.018–0.052 ppm at a site with low levels of mercury contamination; mercury levels in hatchling blood ranged from 0.090 to 0.490 ppm ($\overline{x}$= 0.240 ppm, n = 158). We found few, mostly negligible correlations between life history traits and mercury but noted a positive relationship with egg mass, possibly mediated by correlated maternal effects such as resource provisioning. Incubation temperature exerted strong effects on hatchling phenotypes, with warmer, male-promoting temperatures producing larger and bolder hatchlings. Presumptive females, produced from cooler incubation temperatures, spent more time in warm areas during behavior trials. Hatchlings were released 10–15 days post-hatch and surveyed over eight months to assess survival. Survivorship was positively correlated with hatchling size and negatively correlated with proportional time spent in warm areas. Presumptive females had much lower survival, and overall survivorship for the eight-month period was 0.185–0.208, depending on the modelling approach. Finally, our study suggests that, within the range of concentrations we observed, incubation temperature has a stronger effect on offspring behavior and survival than maternally-transferred mercury pollution in American alligators.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2017

Morphological and behavioral responses of zebrafish after 24 h of ketamine embryonic exposure

Ketamine, one anesthetic used as an illicit drug, has been detected both in freshwater and marine ecosystems. However, knowledge of its impact on aquatic life is still limited. This study aimed to test its effects in zebrafish embryos by analyzing its time- and dose-dependent developmental toxicity and long-term behavioral changes. The 24 h-LC{sub 50} was calculated from percent survival using probit analysis. Based on the 24 h-LC{sub 50} (94.4 mg L{sup −1}), embryos (2 hour post-fertilization - hpf) were divided into four groups, including control, and exposed for 24 h to ketamine concentrations of 50, 70 or 90 mg L{sup −1}. Developmental parameters were evaluated on the course of the experimental period, and anatomical abnormalities and locomotor deficits were analyzed at 144 hpf. Although the portion of ketamine transferred into the embryo was higher in the lowest exposed group (about 0.056 ± 0.020 pmol per embryo), the results showed that endpoints such as increased mortality, edema, heart rate alterations, malformation and abnormal growth rates were significantly affected. At 144 hpf, the developmental abnormalities included thoracic and trunk abnormalities in the groups exposed to 70 and 90 mg L{sup −1}. Defects in cartilage (alcian blue) and bone (calcein) elements also corroborated the craniofacial anomalies observed. A significant up-regulation of the development-related gene nog3 was detected by qRT-PCR at 8 hpf. Early exposure to ketamine also resulted in long-term behavioral changes, such as an increase in thigmotaxis and disruption of avoidance behavior at 144 hpf. Altogether, this study provides new evidence on the ketamine teratogenic potential, indicating a possible pharmacological impact of ketamine in aquatic environments. - Highlights: • 24 h exposure to ketamine increases mortality. • Morphological changes were observed after exposure. • Exposure to ketamine leads to severe craniofacial anomalies. • Developmental gene expression changes in response to ketamine. • Developmental ketamine exposure produces lasting behavioral changes.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2019

Evacuation decision behavior for no-notice emergency events

No-notice emergency events refer to unpredictable disasters such as earthquakes, chemical spills, or terrorist attacks, where it is impracticable to forewarn the public about their occurrence and design evacuation plans for them. This calls for an in-depth investigation of people’s evacuation behavior and identifying the most influential factors in their evacuation planning process to develop policy-sensitive pre-disaster plans for such events. As a response to this need, this study investigates individuals’ evacuation decision behavior in the context of no-notice emergency events. Since it is highly expected that people will have heterogenous decision behavior in such situations, we first apply a clustering algorithm to classify them into three maximally homogeneous clusters. Then, cluster-specific multivariate ordered probit models are developed to estimate the likelihood of selecting any of the three options of ignoring the situation, seeking shelter at the place, and evacuating to a safe place. The model estimation results indicate that a wide spectrum of factors affect the evacuation decision including individuals’ socio-economic attributes, disaster characteristics, built-environment factors, and government evacuation order. Further, variations of estimated coefficients across the population clusters highlight the significant dissimilarities in decision behavior of their associated members.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2026

Sliding friction and wear behavior of nuclear graphite in high temperature inert environment: Influence of contact load, speed and temperature

Repeated dynamic interactions of graphitic components in pebble-bed gas-cooled nuclear reactors can cause abrasive wear-induced pebble surface damage, generate hazardous fine graphite debris, and alter fuel circulation dynamics due to changes in friction behavior. Comprehensive tribological characterization of nuclear graphitic materials in conditions relevant to reactor operation is needed to assess reactor long-term safety and performance. This work reports sliding friction and wear behavior of self-mated nuclear graphite ET-10 at various elevated temperatures (650 °C and 750 °C), sliding speeds (1 and 10 mm/s) and contact loads (20 and 40 N) in a controlled argon environment. The results revealed nonmonotonic frictional behavior with a higher running-in coefficient of friction (COF) followed by a lower steady-state COF, as a result of transition from two-body abrasion to three-body abrasion along with formation of a tribofilm. A key finding of this work is the sensitivity of the running-in COF to experimental conditions; maximum running-in values were lower at either elevated temperature (0.52–0.54) or reduced sliding speed (0.51–0.54). Conversely, the steady-state COF remained invariant at approximately 0.3 across all tested parameters. Transmission electron microscopy revealed a 0.5–2.0 μm thick nanocrystalline tribofilm that was thought to be formed by the compaction of the graphitic wear debris on the contact surface during the sliding process. The nanocrystalline nature of the tribofilm was further confirmed by Raman spectroscopy. As a result, the combination of tribological testing and morphological characterization provided a mechanistic understanding of the frictional behavior of nuclear graphite upon sliding.

Friction↗

DOE OSTI2022

Emerging Electrochemical Techniques for Probing Site Behavior in Single-Atom Electrocatalysts

Single-atom catalysts (SACs) have aroused tremendous interest over the past decade, particularly in the community of energy and environment-related electrocatalysis. A rapidly growing number of recent publications have recognized it as a promising candidate with maximum atomic utilization, distinct activity, and selectivity in comparison to bulk catalysts and nanocatalysts. However, the complexity of localized coordination environments and the dispersion of isolated sites lead to significant difficulties when it comes to gaining insight into the intrinsic behavior of electrocatalytic reactions. Furthermore, the low metal loadings of most SACs make conventional ensemble measurements less likely to be accurate on the subnanoscale. Thus, it remains challenging to probe the activity and properties of individual atomic sites by available commercial instruments and analytical methods. In spite of this, continuing efforts have lately focused on the development of advanced measurement methodologies, which are very useful to the fundamental understanding of SACs. There have recently been a number of in situ/operando techniques applied to SACs, such as electron microscopy, spectroscopy, and other analysis methods, which support relevant functions to identify the active sites and reaction intermediates and to investigate the dynamic behavior of localized structures of the catalytic sites. This Account aims to present recent electrochemical probing techniques which can be used to identify single-atomic catalytic sites within solid supports. First, we describe the basic principles of molecular probe methods for the study and analysis of electrocatalytic site behavior. In particular, the in situ probing technique enabled by surface interrogation scanning electrochemical microscopy (SISECM) can measure the active site density and kinetic rate with high resolution. An alternative electrochemical probing technique is further demonstrated on the basis of single-entity electrochemistry, which allows the unique electrochemical imaging of the size and catalytic rate of single atoms, molecules, and clusters. Next, the merits and limitations of different electrochemical techniques are then discussed, along with perspectives for future prospects. Apart from this, we further showcase the powerful capability of emerging electrochemical probing techniques for determining significant effects and properties of SACs for various electrocatalytic reactions, including oxygen reduction and evolution, hydrogen evolution, and nitrate reduction. Overall, electrochemical techniques with atomic resolution have greatly increased opportunities for observing, measuring, and understanding the surface and interface chemistry during energy conversion. In the future, it is anticipated that the development of electrochemical probing techniques will be advanced with innovative perspectives on the behavior and features of SACs. We hope that this Account can contribute in several ways to promoting the fundamental knowledge and technical progress of emerging electrochemical measurements for studying SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Interfacial Phenomena and Mechanical Behavior of Polyetheretherketone/Polybenzimidazole Blend under Hygrothermal Environment

Demands for engineering applications of high performance polymers, such as the polyaryletherketone families, have grown significantly in recent years. Fundamental knowledge on the mechanical behavior of such polymers, especially under harsh environments, is still lacking. In this study, the mechanical behavior and interfacial phenomena of a blend of polybenzimidazole (PBI) particles having sizes of about 50 μm and polyetheretherketone (PEEK) matrix at 50:50 weight ratio was characterized. PBI and PEEK are known to be incompatible with each other in the dry state. The possible influence of hygrothermal exposure on interfacial bonding between PEEK and PBI has been systematically studied. Under dry conditions, the PEEK matrix dominates the dynamic mechanical behavior, indicating no noticeable viscoelastic coupling between the two phases. After being exposed to hygrothermal conditions, the T g of the PEEK phase in the blend shifts to a lower temperature by as much as 26 °C. The extent of this shift is much greater than what is observed for neat PEEK alone under the same condition. Nanomechanical property mapping results indicate that the interfacial region is broadened after 288 °C hot water immersion treatment. The above finding strongly suggests the hygrothermal conditioning promotes apparent compatibility between PEEK and PBI. Likewise, the fracture behavior of the blend provides direct evidence that the interfacial adhesion is greater than the cohesive strength of either phase after water immersion. In the meantime, it is found that both fracture toughness and tensile strength of the blend are improved by water absorption at 60 °C, at the expense of a minor reduction in Young’s modulus. However, if the blend is exposed to hot water at 288 °C, all of the mechanical properties will deteriorate significantly. In conclusion, the possible causes of the mechanical property deterioration in the PEEK/PBI blend after hygrothermal treatment are discussed.

36 MATERIALS SCIENCE↗