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At least 163 records · Page 9

Surface science insight note: A linear algebraic approach to elucidate native films on Fe 3 O 4 surface

Standard materials are often used to obtain spectra that can be compared to those from unknown samples. Spectra measured from these known substances are also used as a means of computing sensitivity factors to allow quantification by X-ray photoelectron spectroscopy (XPS) of less well-defined materials. Spectra from known materials also provide line shapes suitable for inclusion in spectral models which, when fitted to spectra, permit the chemical state for a sample to be assessed. Both types of information depend on isolating photoemission signals from the inelastically scattered signal. In this Insight note, technical issues associated with the use of XPS of as received Fe 3 O 4 powder sample surface are discussed. The Insight note is designed to show how linear algebraic techniques applied to data collected from a sample marketed as pure Fe 3 O 4 powder are used to verify that XPS has been performed on chemistry representative of the sample. The methods described in this Insight note can further be utilized in elucidating complex XPS data obtained from thin films formed or evolved during cyclic/non-steady use of complex (electro)catalyst surfaces, especially in the presence of contaminants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contrast- vs. non-contrast enhanced MR data sets for characterization of perianal fistulas

Purpose: To evaluate the diagnostic efficacy between pre- and post-contrast MRI sequences in perianal fistulas using intra-operative findings as the gold standard. Materials and methods: Retrospective analysis of 50 patients with a history of perianal fistula and MRI performed between January 2006 and January 2018 was performed. The inclusion criteria were patients who underwent MRI prior to surgery and had a detailed surgical report available. Pre- and post-contrast MR data sets were evaluated by two radiologists at two-week-intervals, assessed fistula type, internal/external opening, presence of abscess/secondary tracts, and confidence scores. The area under the curve (AUC) was used for comparison the diagnostic ability. The sensitivity and specificity were compared using the McNemar’s test. Results: The confidence scores in detecting perianal fistulas were significantly higher in the post-contrast MR data set (p < 0.003). The post-contrast MR data set had similar ability to classify perianal fistulas as combined T2-DWI and isolated T2 data sets in 49/50 cases. For internal/external opening, the post-contrast MR, combined T2-DWI, and isolated T2 data sets had 100% concordance with intra-operative reports. For perianal abscess, there was no significant difference in sensitivity or AUC value between the isolated T2 or combined T2-DWI data sets and post-contrast MR data set (p > 0.05). All MR data sets correctly identified secondary tracts in all 50 cases. Conclusions: Although contrast-enhanced MR studies can improve a radiologist’s confidence, non-contrast MR studies had similar diagnostic efficacy in identifying perianal fistulas and their complications. Therefore, a non-contrast study may suffice in selected patients such as those with renal impairment.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Comparison of CT methods for determining graft steatosis in living donor liver transplantation

Purpose: To evaluate and compare the diagnostic performance of non-enhanced computed tomography (NECT) and contrast-enhanced CT (CECT) attenuation indices in the assessment of hepatic steatosis by using biopsy as the reference standard. Materials and methods: This retrospective study was approved by our Institutional Review Board. 55 Potential donors who underwent both NECT and triphasic CECT and core liver biopsy, were included the study. Average attenuation measurements that were obtained from multiple regions in liver, spleen, and psoas muscle on both unenhanced and CECT were used for analysis. Hepatic attenuation measurements were analyzed with and without normalization with the spleen and psoas muscle. Linear regression and receiver operating characteristic (ROC) curve analysis were used to evaluate the statistical association between CT indices and steatosis at histology. Results: Linear regression analysis confirmed the strongest correlation between steatosis and normalized measurements of hepatic attenuation with splenic attenuations on hepatic venous phase of CECT scan (R 0.821; R{sup 2} 0.674 and R 0.816; R{sup 2} 0.665, respectively). The use of ROC curve analysis also demonstrated that normalized measurements of hepatic attenuation with splenic attenuations on hepatic venous phase of CECT showed high diagnostic performance regarding the qualitative distinction of steatosis (AUC values greater than 0.9). Conclusion: Attenuation measurements of liver normalized with spleen on hepatic venous phase may be useful in evaluating steatosis in donor candidates with moderate to severe steatosis who are unacceptable for liver donation. In this manner unnecessary liver biopsy may be avoided in those donor candidates.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

A Novel Technique for Endovascular Removal of Large Volume Right Atrial Tumor Thrombus

Venous thromboembolic disease is a significant cause of morbidity and mortality, particularly in the setting of large volume pulmonary embolism. Thrombolytic therapy has been shown to be a successful treatment modality; however, its use somewhat limited due to the risk of hemorrhage and potential for distal embolization in the setting of large mobile thrombi. In patients where either thrombolysis is contraindicated or unsuccessful, and conventional therapies prove inadequate, surgical thrombectomy may be considered. We present a case of percutaneous endovascular extraction of a large mobile mass extending from the inferior vena cava into the right atrium using the Angiovac device, a venovenous bypass system designed for high-volume aspiration of undesired endovascular material. Standard endovascular methods for removal of cancer-associated thrombus, such as catheter-directed lysis, maceration, and exclusion, may prove inadequate in the setting of underlying tumor thrombus. Where conventional endovascular methods either fail or are unsuitable, endovascular thrombectomy with the Angiovac device may be a useful and safe minimally invasive alternative to open resection.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Synthesis and Properties Modified Feather Keratin-Based Motor Oil Sorbing Cryogels with High Oil Holding Capacity

Oleic acid was used to modify keratin extracted from chicken feathers by free radical initiated graft copolymerization. Thereafter, the modified keratin was used for the synthesis of cryogels. The influence of oleic acid modification, the crosslinker content, and the protein concentration on the properties of the cryogels were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, SDS-PAGE, and through oil holding capacity tests. To enhance the sorption properties, the cryogels were crosslinked with glutaraldehyde. Varying protein concentration from 1.27 to 5.09 wt% and glutaraldehyde concentration from 0 to 5 wt% produced cryogels with oil holding capacity ranging from 4.56 to 10.76 g/g. The highest results exceeded the sorption capacity of previously published oleic acid modified woodchips (6.3 g/g) as well as polypropylene (6 g/g), which is the standard material used in industry.

36 MATERIALS SCIENCE↗

Development of a Low-Level Ar-37 Calibration Standard

Argon-37 is an important environmental signature of an underground nuclear explosion. Producing and quantifying low-level 37Ar standards is an important step in the development of sensitive field measurement instruments for use during an On-Site Inspection, a key provision of the Comprehensive Nuclear-Test-Ban Treaty. This paper describes progress at Pacific Northwest National Laboratory (PNNL) in the development of a process to generate and quantify low-level 37Ar standard material, which can then be used to calibrate sensitive field systems at activities consistent with soil background levels. The 37Ar used for our work was generated using a laboratory-scale, high-energy neutron source to irradiate powdered samples of calcium carbonate. Small aliquots of 37Ar were then extracted from the head space of the irradiated samples. The specific activity of the head space samples, mixed with P10 (90% stable argon:10% methane by mole fraction) count gas, is then derived using the accepted Length-Compensated Internal-Source Proportional Counting method. Due to the low activity of the samples, a set of three Ultra-Low Background Proportional-Counters designed and fabricated at PNNL from radio-pure electroformed copper was used to make the measurements in PNNL’s shallow underground counting laboratory. Very low background levels (<10 counts/day) have been observed in the spectral region near the 37Ar emission feature at 2.8 keV. Two separate samples from the same irradiation were measured. The first sample was counted for 12 days beginning 28 days after irradiation, the second sample was counted for 24 days beginning 70 days after irradiation (the half-life of 37Ar is 35.0 days). Both sets of measurements were analyzed and yielded very similar results for the starting activity (~0.1 Bq) and activity concentration (0.15 mBq/ccSTP argon) after P10 count gas was added. A detailed uncertainty model was developed based on the ISO Guide to the Expression of Uncertainty in Measurement. This paper presents a discussion of the measurement analysis, along with assumptions and uncertainty estimates.

Absolute radiation measurement↗

Tritium embrittlement of austenitic stainless-steel tubing at low helium contents

Austenitic stainless steels are the standard materials for containment of hydrogen and tritium because of their resistance to mechanical property degradation in those environments. The mechanical performance of the primary containment material is critical for tritium handling, processing, and storage, thus comprehensive understanding of the processes of tritium embrittlement is an enabling capability for fusion energy. This work describes the investigation of the effects of low levels of tritium-decay-helium ingrowth on 304 L tubes. Long-term aging with tritium leads to high helium contents in austenitic stainless steels and can reduce fracture toughness by 95 %, but the details of behavior at low helium contents are not as well characterized. Here, we present results from tensile testing of tritium pre-charged 304 L tube specimens with a variety of starting microstructures that all contain a low level of helium. The results of the tritium exposed-and-aged materials are compared to previously reported results on similar specimens tested in an unexposed condition as well as the hydrogen precharged condition. Tritium precharging and aging for a short duration resulted in increased yield strengths, ultimate tensile strengths and slightly increased elongation to failure, comparable to higher concentrations of hydrogen precharging.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Quantifying Interobserver Variation in Target Definition in Palliative Radiotherapy

Purpose: To describe the degree of interobserver and intraobserver variability in target and field definition when using three-dimensional (3D) volume- vs. two-dimensional (2D) field-based planning. Methods and Materials: Standardized case scenario and diagnostic imaging for 9 palliative cases (3 bone metastases, 3 palliative lung cancer, and 3 abdominal pelvis soft-tissue disease) were presented to 5 study radiation oncologists. After a decision on what the intended anatomic target should be, observers created two sets of treatment fields, first using a 2D field-based and then a 3D volume-based planning approach. Percent overlap, under-coverage, and over-coverage were used to describe interobserver and intraobserver variations in target definition. Results: The degree of interobserver variation for 2D and 3D planning was similar with a degree of overlap of 76% (range, 56%-85%) and 74% (range, 55%-88%), respectively. When comparing the treatment fields defined by the same observer using the two different planning methods, the mean degree of overlap was 78%; over-coverage, 22%; and under-coverage, 41%. There was statistically significantly more under-coverage when field-based planning was used for bone metastases (33%) vs. other anatomic sites (16%) (p = 0.02). In other words, 2D planning is more likely to result in geographic misses in bone metastases compared with other areas. Conclusions: In palliative radiotherapy clinically significant interobserver and intraobserver variation existed when using both field- and volume-based planning approaches. Strategies that would reduce this variability deserve further investigation.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Risk of Salivary Gland Cancer After Childhood Cancer: A Report From the Childhood Cancer Survivor Study

Purpose: To evaluate effects of radiation therapy, chemotherapy, cigarette smoking, and alcohol consumption on the risk of second primary salivary gland cancer (SGC) in the Childhood Cancer Survivor Study (CCSS). Methods and Materials: Standardized incidence ratios (SIR) and excess absolute risks (EAR) of SGC in the CCSS were calculated using incidence rates from Surveillance, Epidemiology, and End Results population-based cancer registries. Radiation dose to the salivary glands was estimated based on medical records. Poisson regression was used to assess risks with respect to radiation dose, chemotherapy, smoking, and alcohol consumption. Results: During the time period of the study, 23 cases of SGC were diagnosed among 14,135 childhood cancer survivors. The mean age at diagnosis of the first primary cancer was 8.3 years, and the mean age at SGC diagnosis was 24.8 years. The incidence of SGC was 39-fold higher in the cohort than in the general population (SIR = 39.4; 95% CI = 25.4-57.8). The EAR was 9.8 per 100,000 person-years. Risk increased linearly with radiation dose (excess relative risk = 0.36/Gy; 95% CI = 0.06-2.5) and remained elevated after 20 years. There was no significant trend of increasing risk with increasing dose of chemotherapeutic agents, pack-years of cigarette smoking, or alcohol intake. Conclusion: Although the cumulative incidence of SGC was low, childhood cancer survivors treated with radiation experienced significantly increased risk for at least 2 decades after exposure, and risk was positively associated with radiation dose. Results underscore the importance of long-term follow up of childhood cancer survivors for the development of new malignancies.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

LaMnO 3 Dopants for Efficient Thermochemical Water Splitting Identified by Density Functional Theory Calculations

While ceria is the standard material for two-step water splitting, perovskites are emerging as viable alternatives. In this work, based on the orthorhombic LaMnO 3 supercell, we substitute Li Na K Rb Mg Ca Sr Ba on the A-sites (La sites) and Al Ga In Mg Zn on the B-sites (Mn sites) at a concentration of 37.5%. The range of temperature and oxygen partial pressure at which each composition is stable is predicted. For compositions that are stable in relevant temperature and pressure ranges, the oxygen vacancy formation energies are determined for all of the oxygen vacancy site positions available in the computational supercell. Mg, Ca, Sr, and Ba A-site-substituted LaMnO 3 and Al and In B-site-substituted LaMnO 3 meet these two criteria for candidates in solar-thermal water splitting applications. Finally, oxygen vacancy formation energy can also be controlled by adjusting the doping strategy.

08 HYDROGEN↗

Polymer, Additives, and Processing Effects on N95 Filter Performance

The current severe acute respiratory syndrome coronavirus 2 (SARS-COV-2) pandemic has highlighted the need for personal protective equipment, specifically filtering facepiece respirators like N95 masks. While it is common knowledge that polypropylene (PP) is the industry standard material for filtration media, trial and error is often required to identify suitable commercial precursors for filtration media production. This work aims to identify differences between several commercial grades of PP and demonstrate the development of N95 filtration media with the intent that the industry partners can pivot and help address N95 shortages. Three commercial grades of high melt flow index PP were melt blown at Oak Ridge National Laboratory and broadly characterized by several methods including differential scanning calorimetry (DSC), X-ray diffraction (XRD), and neutron scattering. Despite the apparent similarities (high melt flow and isotacticity) between PP feedstocks, the application of corona charging and charge enhancing additives improve each material to widely varying degrees. From the analysis performed here, the most differentiating factor appears to be related to crystallization of the polymer and the resulting electret formation. Materials with higher crystallization onset temperatures, slower crystallization rates, and larger number of crystallites form a stronger electret and are more effective at filtration.

36 MATERIALS SCIENCE↗

Distinct Mechanism of Anti-Corrosion and Swelling-Adhesion Modeling of Low-Dimensional Nylon-Fluoropolymer Composite Coatings

Compared to other polymers, composite coatings with fluoropolymers as the matrix have attracted considerable interest due to their mechanical performance, chemical stability, and low surface energy. Herein, we present an anticorrosion mechanism of fluoropolymer composite coatings achieved by dispersing varying amounts of polyamide 12 (PA-12) particles over a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix. The choice of PVDF-HFP as a coating matrix was driven by its superior processability and mechanical properties over Teflon, while PA-12 afforded swelling capacity, preventing electrolyte permeation, and inhibiting matrix stress crack propagation. The corrosion resistance of the coatings was assessed mainly by potentiodynamic polarization and impedance measurements while being immersed in a NaCl solution. Our electrochemical measurement findings showed that 0.75% w/w PA-12 in the PVDF-HFP matrix significantly enhanced corrosion protection even after 21 days of immersion. Microscopy, dielectric spectroscopy, surface analysis, and mechanical testing (American Society for Testing and Materials standards) corroborated the results. PVDF-HFP coatings containing a minimum percolation threshold of 0.75 wt % PA-12 with 1 mil thickness on mild steel exhibited a remarkable increase in resistance and film adhesion, and a notable corrosion rate decrease. Finite element analysis simulation with a bilinear traction-separation law confirmed the swelling mechanism and adhesion behavior. Finally, this study highlights the potential of nylon particle dispersion in PVDF-HFP matrices as a practical approach to developing advanced anticorrosion coatings with promising practical applications in various industries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quasiparticle Level Alignment for Photocatalytic Interfaces

Electronic level alignment at the interface between an adsorbed molecular layer and a semiconducting substrate determines the activity and efficiency of many photocatalytic materials. Standard density functional theory (DFT)-based methods have proven unable to provide a quantitative description of this level alignment. This requires a proper treatment of the anisotropic screening, necessitating the use of quasiparticle (QP) techniques. However, the computational complexity of QP algorithms has meant a quantitative description of interfacial levels has remained elusive. We provide a systematic study of a prototypical interface, bare and methanol-covered rutile TiO2(110) surfaces, to determine the type of many-body theory required to obtain an accurate description of the level alignment. This is accomplished via a direct comparison with metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), and two-photon photoemission (2PP) spectroscopy. We consider GGA DFT, hybrid DFT, and G0W0, scQPGW1, scQPGW0, and scQPGW QP calculations. Our results demonstrate that G0W0, or our recently introduced scQPGW1 approach, are required to obtain the correct alignment of both the highest occupied and lowest unoccupied interfacial molecular levels (HOMO/LUMO). These calculations set a new standard in the interpretation of electronic structure probe experiments of complex organic molecule/semiconductor interfaces.

Environmental Molecular Sciences Laboratory↗

Spontaneous and strong multi-layer graphene n-doping on soda-lime glass and its application in graphene-semiconductor junctions

Scalable and low-cost doping of graphene could improve technologies in a wide range of fields such as microelectronics, optoelectronics, and energy storage. While achieving strong p-doping is relatively straightforward, non-electrostatic approaches to n-dope graphene, such as chemical doping, have yielded electron densities of 9.5 × 10 12 e/cm 2 or below. Furthermore, chemical doping is susceptible to degradation and can adversely affect intrinsic graphene’s properties. Here we demonstrate strong (1.33 × 10 13 e/cm 2 ), robust, and spontaneous graphene n-doping on a soda-lime-glass substrate via surface-transfer doping from Na without any external chemical, high-temperature, or vacuum processes. Remarkably, the n-doping reaches 2.11 × 10 13 e/cm 2 when graphene is transferred onto a p-type copper indium gallium diselenide (CIGS) semiconductor that itself has been deposited onto soda-lime-glass, via surface-transfer doping from Na atoms that diffuse to the CIGS surface. Using this effect, we demonstrate an n-graphene/p-semiconductor Schottky junction with ideality factor of 1.21 and strong photo-response. As a result, the ability to achieve strong and persistent graphene n-doping on low-cost, industry-standard materials paves the way toward an entirely new class of graphene-based devices such as photodetectors, photovoltaics, sensors, batteries, and supercapacitors.

14 SOLAR ENERGY↗

Low-Temperature, Solution-Processed Molybdenum Oxide Hole-Collection Layer for Organic Photovoltaics

We have utilized a commercially available metal-organic precursor to develop a new, low-temperature, solution-processed molybdenum oxide (MoO{sub x}) hole-collection layer (HCL) for organic photovoltaic (OPV) devices that is compatible with high-throughput roll-to-roll manufacturing. Thermogravimetric analysis indicates complete decomposition of the metal-organic precursor by 115 C in air. Acetonitrile solutions spin-cast in a N{sub 2} atmosphere and annealed in air yield continuous thin films of MoO{sub x}. Ultraviolet, inverse, and X-ray photoemission spectroscopies confirm the formation of MoO{sub x} and, along with Kelvin probe measurements, provide detailed information about the energetics of the MoO{sub x} thin films. Incorporation of these films into conventional architecture bulk heterojunction OPV devices with poly(3-hexylthiophene) and [6,6]-phenyl-C{sub 61} butyric acid methyl ester afford comparable power conversion efficiencies to those obtained with the industry-standard material for hole injection and collection: poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). The MoO{sub x} HCL devices exhibit slightly reduced open circuit voltages and short circuit current densities with respect to the PEDOT:PSS HCL devices, likely due in part to charge recombination at Mo{sup 5+} gap states in the MoO{sub x} HCL, and demonstrate enhanced fill factors due to reduced series resistance in the MoO{sub x} HCL.

14 SOLAR ENERGY↗

Characterization of extreme ultraviolet laser ablation mass spectrometry for actinide trace analysis and nanoscale isotopic imaging

The purpose of this research was to characterize Extreme Ultraviolet Time-of-Flight (EUV TOF) Laser Ablation Mass Spectrometry for high spatial resolution elemental and isotopic analysis. We compare EUV TOF results with Secondary Ionization Mass Spectrometry (SIMS) to orient the EUV TOF method within the overall field of analytical mass spectrometry. Using the well-characterized NIST 61x glasses, we show that the EUV ionization approach produces relatively few molecular ion interferences in comparison to TOF SIMS. We demonstrate that the ratio of element ion to element oxide ion is adjustable with EUV laser pulse energy and that the EUV TOF instrument has a sample utilization efficiency of 0.014%. The EUV TOF system also achieves a lateral resolution of 80 nm and we demonstrate this lateral resolution with isotopic imaging of closely spaced particles or uranium isotopic standard materials.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Shock-wave equation-of-state measurements in fused silica up to 1600 GPa

The properties of silica are important to geophysical and high-pressure equation of state research. The most prevalent crystalline form, α-quartz, has been extensively studied to TPa pressures. Recent experiments with amorphous silica, commonly referred to as fused silica, provided Hugoniot and reflectivity data up to 630 GPa using magnetically-driven aluminum impactors. This article presents measurements of the fused silica Hugoniot over the range from 200 to 1600 GPa using laser-driven shocks with a quartz standard. These results extend the measured Hugoniot of fused silica to higher pressures, but more importantly, in the 200-600 GPa range, the data are very good agreement with those obtained with a different driver and standard material. As a result, a new shock velocity-particle velocity relation is derived to fit the experimental data.

58 GEOSCIENCES↗

Magnetic cooling close to a quantum phase transition—The case of Er{sub 2}Ti{sub 2}O{sub 7}

Magnetic cooling, first introduced in the late twenties of last century, has regained considerable interest recently as a cost-efficient and easy-to-handle alternative to {sup 3}He-based refrigeration techniques. Especially, adiabatic demagnetization of paramagnets—the standard materials for magnetic refrigeration—has become indispensable for the present space applications. To match the growing demand for increasing the efficiency in these applications, a new concept for magnetic cooling based on many-body effects around a quantum-critical-point has been introduced and successfully tested [B. Wolf et al., Proc. Natl. Acad. Sci. U.S.A. 108, 6862 (2011)]. By extending this concept to three-dimensional magnetic systems, we present here the magnetothermal response of the cubic pyrochlore material Er{sub 2}Ti{sub 2}O{sub 7} in the vicinity of its B-induced quantum-critical point which is located around 1.5 T. We discuss performance characteristics such as the range of operation, the efficiency, and the hold time. These figures are compared with those of state-of-the-art paramagnetic coolants and with other quantum-critical systems which differ by the dimensionality of the magnetic interactions and the degree of frustration.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗