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First Experience With Real-Time EPID-Based Delivery Verification During IMRT and VMAT Sessions

Purpose: Gantry-mounted megavoltage electronic portal imaging devices (EPIDs) have become ubiquitous on linear accelerators. WatchDog is a novel application of EPIDs, in which the image frames acquired during treatment are used to monitor treatment delivery in real time. We report on the preliminary use of WatchDog in a prospective study of cancer patients undergoing intensity modulated radiation therapy (IMRT) and volumetric modulated arc therapy (VMAT) and identify the challenges of clinical adoption. Methods and Materials: At the time of submission, 28 cancer patients (head and neck, pelvis, and prostate) undergoing fractionated external beam radiation therapy (24 IMRT, 4 VMAT) had ≥1 treatment fraction verified in real time (131 fractions or 881 fields). EPID images acquired continuously during treatment were synchronized and compared with model-generated transit EPID images within a frame time (∼0.1 s). A χ comparison was performed to cumulative frames to gauge the overall delivery quality, and the resulting pass rates were reported graphically during treatment delivery. Every frame acquired (500-1500 per fraction) was saved for postprocessing and analysis. Results: The system reported the mean ± standard deviation in real time χ 91.1% ± 11.5% (83.6% ± 13.2%) for cumulative frame χ analysis with 4%, 4 mm (3%, 3 mm) criteria, global over the integrated image. Conclusions: A real-time EPID-based radiation delivery verification system for IMRT and VMAT has been demonstrated that aims to prevent major mistreatments in radiation therapy.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Robust constrained tension control for high-precision roll-to-roll processes

Tension control is critical for maintaining good product quality in most roll-to-roll (R2R) production systems. Previous work has primarily focused on improving the disturbance rejection performance of tension controllers. Here, a robust linear parameter-varying model predictive control (LPV-MPC) scheme is designed to enhance the tension tracking performance of a pilot R2R system for deposition of materials used in flexible thin film applications. The performance of a tension controller may degrade due to disturbances associated with model uncertainties and the slowly-changing dynamics in R2R systems. We introduce a method that separately treats these two sources of disturbance. The controller utilizes an incremental model to eliminate the errors caused by the mismatch between the nominal model and the actual system. A tube-based MPC formulation combined with scheduled parameters adequately updates models and corrects for the time-varying dynamics. Constraints on the rated motor torque are incorporated in the MPC to maintain the controller reliability and avoid machine failures. We illustrate the operation of our control algorithm through simulation of an actual R2R system. The controller outperforms the benchmarks in terms of fast transient response and offset-free tension tracking. Furthermore, it also demonstrates immunity from variations due to parametric uncertainties.

42 ENGINEERING↗

Linking microstructure to creep behavior in vertically and horizontally built LPBF Haynes 282 compared with wrought material via θ -projection

Laser Powder Bed Fusion (LPBF) has emerged as a promising route for fabricating intricate geometries in high-performance alloys. Haynes 282 (H282) is a strong candidate for applications such as heat exchangers or engines due to its excellent creep strength and thermal stability; however, the long-term creep behavior of LPBF-processed H282 remains poorly understood. In this study, the θ -projection method is used to analyze and extrapolate the creep behavior of vertically built LPBF, horizontally built LPBF, compared to wrought H282 tested at 816 °C. Vertically built LPBF H282 exhibits the lowest minimum creep rate (MCR), while the horizontally built condition shows a higher MCR comparable to that of wrought H282. Despite these differences, both LPBF conditions exhibit significantly shorter rupture life and reduced rupture strain than the wrought material, with the most severe degradation observed in the horizontal builds, consistent with an earlier onset of tertiary creep and accelerated strain-rate evolution. Microstructural characterization reveals that both LPBF and wrought H282 exhibit abundant twin-related boundary character; however, their grain boundary topologies differ markedly. The wrought alloy contains a higher fraction of low-angle grain boundaries and continuous twin lamellae, whereas the LPBF microstructure is characterized by a suppressed low-angle boundary population and fragmented twin-related boundaries embedded within irregular high-angle grain boundary networks. Fractographic analysis further reveals predominantly intergranular cracking in LPBF H282, accompanied by grain-boundary-decorated carbides, Al 2 O 3 inclusions, and high-aspect-ratio pores. These results demonstrate that grain boundary topology, rather than minimum creep rate alone, plays a critical role in governing creep damage accumulation and rupture behavior in LPBF and wrought H282.

Creep↗

Control of Early Flame Kernel Growth by Multi-Wavelength Laser Pulses for Enhanced Ignition

The present contribution examines the impact of plasma dynamics and plasma-driven fluid dynamics on the flame growth of laser ignited mixtures and shows that a new dual-pulse scheme can be used to control the kernel formation process in ways that extend the lean ignition limit. We do this by performing a comparative study between (conventional) single-pulse laser ignition (λ = 1064 nm) and a novel dual-pulse method based on combining an ultraviolet (UV) pre-ionization pulse (λ = 266 nm) with an overlapped near-infrared (NIR) energy addition pulse (λ = 1064 nm). We employ OH* chemiluminescence to visualize the evolution of the early flame kernel. For single-pulse laser ignition at lean conditions, the flame kernel separates through third lobe detachment, corresponding to high strain rates that extinguish the flame. In this work, we investigate the capabilities of the dual-pulse to control the plasma-driven fluid dynamics by adjusting the axial offset of the two focal points. In particular, we find there exists a beam waist offset whereby the resulting vorticity suppresses formation of the third lobe, consequently reducing flame stretch. With this approach, we demonstrate that the dual-pulse method enables reduced flame speeds (at early times), an extended lean limit, increased combustion efficiency, and decreased laser energy requirements.

42 ENGINEERING↗

Relativistic MHD simulations of collision-induced magnetic dissipation in Poynting-flux-dominated jets/outflows

The question of the energy composition of the jets/outflows in high-energy astrophysical systems, e.g. GRBs, AGNs, is taken up first: Matter-flux-dominated (MFD), σ < 1, and/or Poynting-flux-dominated (PFD), σ >1? The standard fireball IS model and dissipative photosphere model are MFD, while the ICMART (Internal-Collision-induced MAgnetic Reconnection and Turbulence) model is PFD. Motivated by ICMART model and other relevant problems, such as “jets in a jet” model of AGNs, the author investigates the models from the EMF energy dissipation efficiency, relativistic outflow generation, and σ evolution points of view, and simulates collisions between high-σ blobs to mimic the situation of the interactions inside the PFD jets/outflows by using a 3D SRMHD code which solves the conservative form of the ideal MHD equations. σ b,f is calculated from the simulation results (threshold = 1). The efficiency obtained from this hybrid method is similar to the efficiency got from the energy evolution of the simulations (35.2%). Efficiency is nearly σ independent, which is also confirmed by the hybrid method. σ b,i - σ b,f provides an interesting linear relationship. Results of several parameter studies of EMF energy dissipation efficiency are shown.

79 ASTRONOMY AND ASTROPHYSICS↗

New Total-Ionizing-Dose Resistant Data Storing Technique for NAND Flash Memory

This paper describes a new non-charge-based data storing technique in NAND flash memory called watermark that encodes read-only data in the form of physical properties of flash memory cells. Unlike traditional charge-based data storing method in flash memory, the proposed technique is resistant to total ionizing dose (TID) effects. To evaluate its resistance to irradiation effects, we analyze data stored in several commercial single-level-cell (SLC) flash memory chips from different vendors and technology nodes. These chips are irradiated using a Co-60 gamma-ray source array for up to 100 krad(Si) at Sandia National Laboratories. Experimental evaluation performed on a flash chip from Samsung shows that the intrinsic bit error rate (BER) of watermark increases from 0.8% for TID = 0 krad(Si) to 1% for TID = 100 krad(Si). Conversely, the BER of charge-based data stored on the same chip increases from 0% at TID = 0 krad(Si) to 1.5% at TID = 100 krad(Si). Overall, the results imply that the proposed technique may potentially offer significant improvements in data integrity relative to traditional charge-based data storage for very high radiation (TID > 100 krad(Si)) environments. These gains in data integrity relative to the charge-based data storage are useful in radiation-prone environments, but they come at the cost of increased write times and higher BERs before irradiation.

36 MATERIALS SCIENCE↗

SU-E-T-647: Quality Assurance of VMAT by Gamma Analysis Dependence On Low-Dose Threshold

Purpose: The AAPM TG-119 instructed institutions to use low-dose threshold (LDT) of 10% or a ROI determined by the jaw when they collected gamma analysis QA data of planar dose distribution. Also, based on a survey by Nelms and Simon, more than 70% of institutions use a LDT between 0% and 10% for gamma analysis. However, there are no clinical data to quantitatively demonstrate the impact of the LDT on the gamma index. Therefore, we performed a gamma analysis with LDTs of 0% to 15% according to both global and local normalization and different acceptance criteria: 3%/3 mm, 2%/2 mm, and 1%/1 mm. Methods: A total of 30 treatment plans—10 head and neck, 10 brain, and 10 prostate cancer cases—were randomly selected from the Varian Eclipse TPS, retrospectively. For the gamma analysis, a predicted portal image was acquired through a portal dose calculation algorithm in the Eclipse TPS, and a measured portal image was obtained using a Varian Clinac iX and an EPID. Then, the gamma analysis was performed using the Portal Dosimetry software. Results: For the global normalization, the gamma passing rate (%GP) decreased as the LDT increased, and all cases of low-dose thresholds exhibited a %GP above 95% for both the 3%/3 mm and 2%/2 mm criteria. However, for local normalization, the %GP increased as LDT increased. The gamma passing rate with LDT of 10% increased by 6.86%, 9.22% and 6.14% compared with the 0% in the case of the head and neck, brain and prostate for 3%/3 mm criteria, respectively. Conclusion: Applying the LDT in the global normalization does not have critical impact to judge patient-specific QA results. However, LDT for the local normalization should be carefully selected because applying the LDT could affect the average of the %GP to increase rapidly.

61 RADIATION PROTECTION AND DOSIMETRY↗

Pre-Ionization Controlled Laser Plasma Formation for Ignition Applications (Final Scientific/Technical Report)

This report consists of three grand funded papers. Abstracts for each follow. 1) In this work, we present experimental and modeling studies of air pre-ionization using ultraviolet (UV) laser pulses and its effect on laser breakdown of an overlapped near-infrared (NIR) pulse. Experimental studies are conducted with a 266 nm beam (fourth harmonic of Nd:YAG) for UV pre-ionization and an overlapped 1064 nm NIR beam (fundamental of Nd:YAG), both having pulse duration of 10 ns. Results show that the UV beam produces a pre-ionized volume which assists in breakdown of the NIR beam, leading to reduction in NIR breakdown threshold by factor of >2. Numerical modeling is performed to examine the ionization and breakdown of both beams. The modeled breakdown threshold of the NIR, including assist by pre-ionization, is in reasonable agreement with the experimental results. 2) The present contribution compares the energy absorption, optical emission, temperature, and fluid dynamics of ultraviolet (UV) λ = 266 nm and near infrared (NIR) λ = 1064 nm nanosecond laser induced plasmas in ambient air. For UV pulses at the conditions studied, energy absorption by the plasmas increases relatively gradually with laser pulse energy starting at delivered energy of E~8 mJ. Corresponding measurements of plasma luminosity show that the absorption of UV radiation does not necessarily result in visible plasma emission. For the NIR induced plasmas, the energy absorption profile is far more abrupt and begins at ~55 mJ. In contrast with UV, the absorption of NIR radiation is always accompanied by intense optical emission. The temperatures of both types of plasma have been measured with Rayleigh scattering thermometry (at times after the Thomson signal sufficiently diminishes). The UV plasmas can attain a wider range of temperatures, including lower temperatures, depending on the pulse energy (e.g., T ~400–2000K for E ~7–35 mJ at Δt = 10 μs after the pulse) while the NIR plasmas show only hotter temperatures (e.g., T ~ 12 000 K for E = 75 mJ at Δt = 10 μs after the pulse) as is consistent with the literature. Differences in the fluid dynamics for UV versus NIR pulses are shown with Schlieren imaging. In this work, the contrast in the UV and NIR plasma threshold behavior is attributed to differing roles of avalanche ionization and multiphoton ionization as is also illustrated by a simple numerical model. 3) The present contribution examines the impact of plasma dynamics and plasma-driven fluid dynamics on the flame growth of laser ignited mixtures and shows that a new dual-pulse scheme can be used to control the kernel formation process in ways that extend the lean ignition limit. We perform a comparative study between (conventional) single-pulse laser ignition (λ = 1064 nm) and a novel dual-pulse method based on combining an ultraviolet (UV) pre-ionization pulse (λ = 266 nm) with an overlapped near-infrared (NIR) energy addition pulse (λ = 1064 nm). We employ OH* chemiluminescence to visualize the evolution of the early flame kernel. For single-pulse laser ignition at lean conditions, the flame kernel separates through third lobe detachment, corresponding to high strain rates that extinguish the flame. In this work, we investigate the capabilities of the dual-pulse to control the plasma-driven fluid dynamics by adjusting the axial offset of the two focal points. In particular, we find there exists a beam waist offset whereby the resulting vorticity suppresses formation of the third lobe, consequently reducing flame stretch. With this approach, we demonstrate that the dual-pulse method enables reduced flame speeds (at early times), an extended lean limit, increased combustion efficiency, and decreased laser energy requirements.

Mechanical engineering↗

CoCoMET v1.0: a unified open-source toolkit for atmospheric object tracking and analysis

Advances in performance and analysis capabilities have accelerated the development of object tracking algorithms for atmospheric research. This has resulted in a growing number of studies using Lagrangian tracking techniques to analyze the evolution of atmospheric phenomena and the underlying processes. However, the increasing complexity and variety of tracking algorithms present a steep learning curve for new users and make it difficult for existing users to compare algorithm performance. We introduce CoCoMET (Community Cloud Model Evaluation Toolkit), an open-source toolkit that addresses these issues. CoCoMET simplifies the process of running multiple tracking algorithms simultaneously and analyzing objects in both model and observational datasets by specifying parameters in a single configuration file. It standardizes input data from different sources into a consistent format and unifies the tracking output across algorithms. CoCoMET enhances the functionality of existing tracking methods by calculating additional properties such as cell growth and dissipation rates, perimeter, surface area, convexity, and irregularity. In addition, CoCoMET includes a novel method for identifying mergers and splits in 2D and 3D tracks and supports the integration of Eulerian/stationary datasets external to the tracking data for process studies. Its potential utility is demonstrated through examples of model intercomparison, model evaluation against observations, and comparisons between tracking algorithms. Designed for open-source environments, CoCoMET will continue to expand with future releases, incorporating more input data types and tracking algorithms.

54 ENVIRONMENTAL SCIENCES↗

Building America Case Study: Sealed Crawl Spaces with Integrated Whole-House Ventilation in a Cold Climate, Ithaca, New York

"9One method of code-compliance for crawlspaces is to seal and insulate the crawlspace, rather than venting to the outdoors. However, codes require mechanical ventilation; either via conditioned supply air from the HVAC system, or a continuous exhaust ventilation strategy. As the CARB's building partner, Ithaca Neighborhood Housing Services, intended to use the unvented crawlspace in a recent development, CARB was interested in investigating a hybrid ventilation method that includes the exhaust air from the crawlspace as a portion of an ASHRAE 62.2 compliant whole-house ventilation strategy. This hybrid ventilation method was evaluated through a series of long-term monitoring tests that observed temperature, humidity, and pressure conditions through the home and crawlspace. Additionally, CARB worked with NREL to perform multi-point tracer gas testing on six separate ventilation strategies - varying portions of 62.2 required flow supplied by the crawlspace fan and an upstairs bathroom fan. The intent of the tracer gas testing was to identify effective Reciprocal Age of Air (RAoA), which is equivalent to the air change rate in well-mixed zones, for each strategy while characterizing localized infiltration rates in several areas of the home.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

α-weighted Transition Rate Matrix Method

Relative effectiveness of an α-weighted Transition Rate Matrix Method (TRMM) as compared to the normally used κ- weighted, for solving reactor transient problem is investigated. An improved Monte Carlo κ-α iteration with delayed neutron is implemented to the OpenMC to generate the fundamental α-eigenfunction to be used as the weighting function in calculating the TRMM forward and adjoint operators. A prompt supercritical transient problem and a deep subcritical transient problem of a two-region slab system are devised to compare the relative performance of the α- and κ-weighted TRMM.

Variansyah, Ilham↗

SU-F-T-279: Impact of Beam Energy Drifts On IMRT Delivery Accuracy

Purpose: According to TG-40 percent-depth-dose (PDD) tolerance is ±2% but TG-142 is ±1%. Now the question is, which one is relevant in IMRT era? The primary objective of this study is to evaluate dosimetric impact of beam-energy-drifts on IMRT-delivery. Methods: Beam-energy drifts were simulated by adjusting Linac’s bending-magnet-current (BMC) followed by tuning the pulse-forming network and adjusting gun-current. PDD change of −0.6% and +1.2% were tested. Planar-dosimetry measurements were performed using an ionization-chamber-array in solid-water phantoms. Study includes 10-head-and-neck and 3-breast cancer patients. en-face beam-deliveries were also tested at 1.3cm and 5.3cm depths. Composite and single-field dose-distributions were compared against the plans to determine %Gamma pass-rates (%GPRs). For plan dose comparisons, changes in %Gamma pass-rates (cPGPRs) were computed/reported to exclude the differences between dose-computation and delivery. Dose distributions of the drifted-energies were compared against their baseline measurements to determine the% GPRs. A Gamma criteria of 3%/3mm was considered for plan-dose comparisons while 3%/1mm used for measured dose intercomparisons. Results: For composite-dose delivery, average cPGPRs were 0.41%±2.48% and −2.54%±3.65% for low-energy (LE) and high-energy (HE) drifts, respectively. For measured dose inter-comparisons, the average%GPRs were 98.4%±2.2% (LE-drift) and 95.8%±4.0 (HE-drift). The average %GPR of 92.6%±4.3% was noted for the worst-case scenario comparing LE-drift to HE-drift. All en-face beams at 5.3 cm depth have cPGPRs within ±4% of the baseline-energy measurements. However, greater variations were noted for 1.3cm depth. Average %GPRs for drifted energies were >99% at 5.3cm and >97% at 1.3cm depths. However, for the worst-case scenario (LE-drift to HE-drift) these numbers dropped to 95.2% at 5.3cm and 93.1% at 1.3cm depths. Conclusion: The dosimetric impact of beam-energy drifts was found to be within clinically acceptable tolerance. However, this study includes a single energy with limited range of PDD change. Further studies are on going and the results will be presented. Received funding from Varian Medical Systems, Palo Alto, CA.

60 APPLIED LIFE SCIENCES↗

Dependence of catalytic properties of Al/Fe{sub 2}O{sub 3} thermites on morphology of Fe{sub 2}O{sub 3} particles in combustion reactions

Three Fe{sub 2}O{sub 3} particle samples with the same crystal structure but different morphologies were prepared by the hydrothermal method and then combined with Al nanoparticles to produce Al/Fe{sub 2}O{sub 3} thermites using ultrasonic mixing. The properties of Fe{sub 2}O{sub 3} and Al/Fe{sub 2}O{sub 3} were studied using a combination of experimental techniques including scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). The influences of the three Al/Fe{sub 2}O{sub 3} thermites on the combustion properties of the AP/HTPB (ammonium perchlorate/hydroxyl-terminated polybutadiene) composite propellant were investigated in comparison to those of Fe{sub 2}O{sub 3}. The results show that the Al/Fe{sub 2}O{sub 3} thermites are better than Fe{sub 2}O{sub 3} in enhancing the combustion performance of AP/HTPB. Furthermore, the surface area, which depends on size and mophology, of Fe{sub 2}O{sub 3} particles was found to play a vital role in improving the burning rate of the thermites-containing propellant formulation, with the smallest particles with the largest surface-to-volume (S/V) ratio performing the best. The enhanced catalytic property of the granular-shape Fe{sub 2}O{sub 3} and the corresponding thermite is attributed to the large specific surface area of Fe{sub 2}O{sub 3}. The different thermal behaviors of these three superthemites were supposed to be attributed to the surface site of Fe{sub 2}O{sub 3} particles. This work provides a better understanding on the catalytic properties of thermites that are important for combustion applications. - Graphical abstract: Effects of Fe{sub 2}O{sub 3} and Al/Fe{sub 2}O{sub 3} have been compared for the first time by analyzing combustion properties of formulations containing them, suggesting their potential application in AP/HTPB composite propellant systems. - Highlights: • Three Fe{sub 2}O{sub 3} particles with different morphologies (polyhedral, oval and granular) were prepared by the hydrothermal method. • Thermal behaviors of thermites Al/Fe{sub 2}O{sub 3} are studied upon DSC data. • Effects of Fe{sub 2}O{sub 3} and Al/Fe{sub 2}O{sub 3} on the combustion properties of the AP/HTPB composite propellant are first investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation and Oxidation Performance of a NiCoCrAlYSiHf + NiAl Composite Coating Deposited by Arc Ion Plating and Magnetron Sputtering Techniques

A NiCoCrAlYSiHf+NiAl composite coating was deposited onto a second-generation single-crystal superalloy René N5 by methods of arc ion plating and magnetron sputtering. After vacuum annealing, the composite coating exhibited a gradient distribution of elements, in which Al was enriched in outer layer and Cr was enriched in inner layer. Compared with conventional NiCoCrAlYSiHf and β-NiAl coatings, the composite coating was evaluated in isothermal and cyclic oxidation tests at 1100 °C in ambient air. The results showed that the oxidation rate of the composite coating was lower than that of NiCoCrAlYSiHf coating. Meanwhile, the extent of interdiffusion between coating and substrate in the composite coating was slighter compared with that in the β-NiAl coating. Microstructure evolutions of the composite coating after annealing and further oxidation test are investigated.

36 MATERIALS SCIENCE↗

Economic evaluation on CO₂-EOR of onshore oil fields in China

Carbon dioxide enhanced oil recovery (CO₂-EOR) and sequestration in depleted oil reservoirs is a plausible option for utilizing anthropogenic CO₂ to increase oil production while storing CO₂ underground. Evaluation of the storage resources and cost of potential CO₂-EOR projects is an essential step before the commencement of large-scale deployment of such activities. In this paper, a hybrid techno-economic evaluation method, including a performance model and cost model for onshore CO₂-EOR projects, has been developed based on previous studies. Total 296 onshore oil fields, accounting for about 70% of total mature onshore oil fields in China, were evaluated by the techno-economic method. The key findings of this study are summarized as follows: (1) deterministic analysis shows there are approximately 1.1 billion tons (7.7 billion barrels) of incremental crude oil and 2.2 billion tons CO₂ storage resource for onshore CO₂-EOR at net positive revenue within the Chinese oil fields reviewed under the given operating strategy and economic assumptions. (2) Sensitivity study highlights that the cumulative oil production and cumulative CO₂ storage resource are very sensitive to crude oil price, CO₂ cost, project lifetime, discount rate and tax policy. High oil price, short project lifetime, low discount rate, low CO₂ cost, and low tax policy can greatly increase the net income of the oil enterprise, incremental oil recovery and CO₂ storage resource. (3) From this techno-economic evaluation, the major barriers to large-scale deployment of CO₂-EOR include complex geological conditions, low API of crude oil, high tax policy, and lack of incentives for the CO₂-EOR project.

02 PETROLEUM↗

Modulating Ce 3+ Sites in Ce-Zr Oxide Nanocatalysts through Protamine Biomineralization for Organophosphate Dephosphorylation

Catalytic is a crucial reaction for environmental detoxication of pesticides and neutralization of various molecules classified as chemical warfare agents. Herein, we report on a series of tunable Ce-Zr-based metal oxides, (Zr a Ce 1–a O x ) prepared using a facile biomineralization technique, as catalysts for organophosphates dephosphorylation. Synchrotron scattering and spectroscopy methods showcase that Zr a Ce 1–a O x catalysts are highly defective and exhibit an abundance of Ce 3+ sites that promote oxygen vacancies needed for enhanced dephosphorylation reactions. The catalytic performance was assessed using a model para-nitrophenyl phosphate reaction and showcases a strong dependence on Zr dopant concentration and subsequent tuning of the Ce 3+ /Ce 4+ ratio. Analysis of synchrotron datasets allowed structure-performance correlations between the Ce 3+ concentration and associated oxygen vacancies, the dephosphorylation rate constant, and Zr concentration to be established, confirming that Ce 3+ as active sites is positively correlated with the rate constant. We envision that similar biomineralization approaches can be used to fabricate Ce 3+ -rich Ce-Zr oxide for environmental application in dephosphorylation and other hydrolysis reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nickel sulfide nanostructures prepared by laser irradiation for efficient electrocatalytic hydrogen evolution reaction and supercapacitors

Rational design and synthesis of transition metal sulfide complex nanostructures are significant for achieving desired materials properties for a variety of applications. Herein, we synthesized nickel sulfide (NiS) nanostructures using laser irradiation in an aqueous solution and under the ambient condition. Crystalline nanostructures with high phase-purity were achieved without further calcination. Other transition metal sulfides, such as CuS and ZnS, were also successfully synthesized using the laser irradiation approach, suggesting the practical application of this method. The hydrogen evolution reaction (HER) measurements show the NiS nanostructures synthesized for 4h (NiS-4h) not only exhibited competitive overpotential (-159 mV vs. RHE at 10 A/g), lower Tafel slope (218 mV/dec) but also delivered long-term stability (14 A/g at -250 mV $vs.$ RHE for 12h). Moreover, the NiS-4h functioned as the electrode for supercapacitor with excellent specific capacitance (3761 F/g at 10 mV/s), reversibility and rate capability (1152 F/g at 100 mV/s). These superb electrochemical performances are attributed to the remarkable value of electrochemically active surface area (ECSA) and synergistic effect of Ni 3+ OOH for HER electrocatalytic activities, while the co-existence of Ni 2+ and Ni 3+ facilitates the rich redox reactions of NiS for supercapacitor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of comprehensive two-dimensional liquid chromatography for investigating aging of plastic bonded explosives

The feasibility of measuring the aging and degradation of PBX 9501 via online two dimensional liquid chromatography (LC × LC) is investigated, and a preliminary instrumental setup and method is developed. Plastic-Bonded eXplosive (PBX) 9501 is nominally composed of 94.9 wt% HMX, 2.5 wt% Estane® 5703 (poly (ester urethane)), 2.5 wt% BDNPA/F (nitroplasticizer), 0.1 wt% Irganox 1010 and PBNA (N-phenyl-naphthylamine) at low concentrations. When exposed to various environmental conditions, PBX 9501 will degrade through different pathways. Because PBX 9501 is composed of both low molecular weight compounds (BDNPA/F, Irganox 1010, PBNA, and potential degradation products) and high molecular weight compounds (Estane® 5703), analysis is normally performed via two independent analyses. Additionally, the low molecular weight species are analyzed via high pressure liquid chromatography (HPLC) and the high molecular weight species via size exclusion chromatography (SEC). While these individual techniques yield information about the aging of PBX 9501, the combination of HPLC and SEC (i.e. HPLC × SEC) can simplify and streamline the analyses while also providing additional chemical information. A simplified sample preparation method is proposed for LC × LC analysis. Various SEC columns and HPLC column selection, flow rate, and gradient ramps were investigated for their application of measuring aged PBX 9501. Lastly, two LC × LC separations of a library standard of PBX 9501 and a sample of aged PBX 9501 are compared.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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