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An investigation of low temperature electronic phase arrest in Sm{sub 0.55}Sr{sub 0.45}MnO{sub 3} phase separated manganite

The temperature dependence of electronic-transport and magneto-transport of polycrystalline Sm{sub 0.55}Sr{sub 0.45}MnO{sub 3} manganite at low temperatures has been investigated in detail. The low temperature resistivity data show a distinct minimum in the resistivity versus temperature plots for all fields. The low temperature resistivity upturn below this minimum has been fitted to an expression, which includes three terms, namely, residual resistivity, inelastic scattering, and electron-electron (e-e) interaction or Kondo effects. It has been found that the dominating mechanism is e-e interaction. The resistivity of the sample shows strong dependence on the magnetic field–temperature history. The electronic-transport property clearly confirms that the electronic phase of the sample gets arrested to a low resistive state during field cooling and cannot return to its original state even after the magnetic field is removed. The magnetoresistance of the sample also shows a strong irreversibility with respect to the sweeping of the magnetic field between its highest positive and negative values. Moreover, the resistivity of the sample is found to be time dependent. All the observed phenomena have been explained through the phase separation scenario and kinetic arrest of electronic phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Portable Automation of Static Chamber Sample Collection for Quantifying Soil Gas Flux

Quantification of soil gas flux using the static chamber method is labor intensive. The number of chambers that can be sampled is limited by the spacing between chambers and the availability of trained research technicians. An automated system for collecting gas samples from chambers in the field would eliminate the need for personnel to return to the chamber during a flux measurement period and would allow a single technician to sample multiple chambers simultaneously. This study describes Chamber Automated Sampling Equipment (FluxCASE) to collect and store chamber headspace gas samples at assigned time points for the measurement of soil gas flux. The FluxCASE design and operation is described, and the accuracy and precision of the FluxCASE system is evaluated. In laboratory measurements of nitrous oxide (N2O), carbon dioxide (CO2), and methane (CH4) concentrations of a standardized gas mixture, coefficients of variation associated with automated and manual sample collection were comparable, indicating no loss of precision. In the field, soil gas fluxes measured from FluxCASEs were in agreement with manual sampling for both N2O and CO2. Slopes of regression equations were 1.01 for CO2 and 0.97 for N2O. The 95% confidence limits of the slopes of the regression lines included the value of one, indicating no bias. Additionally, an expense analysis found a cost recovery ranging from 0.6 to 2.2 yr. Implementing the FluxCASE system is an alternative to improve the efficiency of the static chamber method for measuring soil gas flux while maintaining the accuracy and precision of manual sampling.

Davis, Morgan P.↗

Salt Vessel-Sample Generator Interface

The goal of the salt sampling program at Argonne is to develop and deploy automated molten salt sampling approaches for interfacing relevant unit operations with salt analysis to improve the timeliness and accuracy of sampling-based accountancy measurements. One technology under development is a vacuum sampler loop module. In this system, molten salt is drawn from a process vessel through a heated sampling line and into a charge vessel. Next, one or more samples are split from the volume in the charge vessel and the remaining salt is returned to the process. The vacuum sampler loop module is being developed to interface with other sample processing and analysis modules to enable rapid at-line sample characterization. The main purpose of the vacuum sampling loop module is to enable the collection of samples that are more representative of the bulk salt by replacing traditional point samplers (i.e., dip probes) with a sampling approach that captures a larger cross section of salt. Additionally, the vacuum sampling approach eliminates the risk of dross contamination of samples and avoids the use of moving parts in the salt. Two methods of interfacing the vacuum sampling loop with a precision pneumatic sample generator were investigated in FY21. This report covers the testing of fluidic coupling between the two modules. Two iterations of the fluidically coupled modules were tested. The first iteration system coupled the two modules using a freeze valve to seal the vacuum sampler during filling and to control flow into the pneumatic sample generator. While this integrated system functioned as intended, some changes were implemented to make the system more robust and better suited to remote deployment. Specifically, the system was made to be more modular and active control of the vacuum filling operation was replaced with a passive control mechanism. For passive filling, the salt charge vessel was vented to a small gas tank that was at negative pressure, causing salt to be drawn into the vessel until the force of the fluid head was in equilibrium with the gas pressure. The passive control system performed well and will be used in future iterations. Another change in the second system was a newly configured pneumatic sample generator in which sample ejection occurred through a hole in the reservoir’s stainless-steel side wall instead of through a non-wetted sapphire orifice on the bottom. This alternate configuration may be better suited for near-process deployment because it enables on-line orifice maintenance and an orifice bypass drain back to the process. A third change in the second iteration system was the transition to a two-chamber charge vessel which split off a fraction of the sampled salt as a liquid aliquot. The goal was to create a buffer mechanism that would allow reproducible aliquoting of samples, independently of variability in the charge vessel fill height. While the two-chamber design was functional, the sample size reproducibility was below target values. To improve reproducibility and overcome many of the impediments to remote deployment of the vacuum sampling loop module, separate work was conducted to replace the two-chamber liquid aliquoting mechanism with aliquoting into single-use sample tubes. Solid salt transfer in the sample tubes will replace fluidic coupling for integrating the vacuum sampler with downstream modules. Because the proposed operations can all be executed with simple overhead actuation mechanisms or other existing hot-cell technology, there will be no need for large investments in novel hot cell sample handling technologies using this alternate approach. As such, near-term deployment of the vacuum sampling technology will be achievable. This new approach for automated coupling of sample tubes with down-stream modules is covered in a separate FY21 report, and a remotely operated version of the vacuum sampler loop module with the tube aliquoting feature is planned for FY22.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Alteration of the Cesium-137 soil profile by wild boar rooting after the Fukushima Daiichi Nuclear Power Plant accident

Large amounts of Cesium-137 ( 137 Cs, physical half-life ca. 30 years) were released into the environment from the 2011 Fukushima Daiichi Nuclear Power Plant (FDNPP) accident in Japan. Initially contaminants from the accident were deposited on the surface soil layers in terrestrial ecosystems, but over time vertical migration of 137 Cs has occurred, with most 137 Cs now distributed a few centimeters below the soil surface. Wild boar (Sus scrofa) rooting likely alters the distribution of contaminants in soil profiles. Such impacts may be particularly pronounced in areas contaminated from the FDNPP accident, given the increase in abundance of wild boar in these areas. Our objective was to determine whether rooting by wild boar alters the distribution of 137 Cs contamination within soil profiles through collection of soil cores from control sites and two different types of rooting samples, “new depressions” and “old depressions” within the difficult-to-return zone surrounding the FDNPP. The 137 Cs ratio [activity concentration of 137 Cs at each depth / the maximum activity concentration of 137 Cs in each core sample] rapidly decreased after reaching a peak at the control sites. However, the 137 Cs ratio at all rooted sites decreased more slowly, and 137 Cs was distributed deeper into the soil layers than control sites, across both new and old rooting sites. Moreover, the 137 Cs soil profiles varied greatly among core samples and sampling sites. Furthermore, these results demonstrate that soil disturbance from wild boar rooting can directly influence the distribution of contaminants within soil profiles. However, the extent to which deeper layers are affected by contamination depends on the unique characteristics (i.e., depth of rooting) of each wild boar rooting disturbance. Further studies are needed to examine the effects of long-term rooting on the alteration of 137 Cs in soil profiles.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Demographic and genetic consequences of a steelhead supplementation program

Abstract Objective Supplementation of naturally spawning populations by the addition of hatchery-spawned individuals is commonly conducted for recovery of threatened and endangered populations and to support harvest opportunities. Our objective was to evaluate whether the use of a juvenile captive broodstock and an integrated paradigm could increase returns of steelhead, the anadromous form of Rainbow Trout Oncorhynchus mykiss, while avoiding negative genetic impacts commonly associated with hatchery propagation. Methods We analyzed 291 genetic markers in adult steelhead returning to an integrated population in southwest Washington over the course of 15 years. Reproductive success (RS) of fish spawning in the natural environment was evaluated by origin (hatchery versus natural) and return year. Data were then pooled over years to maximize sample sizes for comparing RS estimates among groups (i.e., estimation of relative reproductive success [RRS]). Result We observed a weak relationship between RS and origin (male p = 0.347; female p = 0.066), but a significant relationship between RS and return year (male p < 0.001, η2 = 0.896; female p ⟨ 0.001, η2 = 0.867) (i.e., hatchery- and natural-origin fish did well or poorly together each year). Estimates of RRS for fish spawned in the hatchery ranged from 2.4 to 6.4, indicating that fish spawned in the hatchery produced more returning adult progeny than did fish allowed to spawn in the natural environment. Estimates of RRS were ⟨1.0 for hatchery-origin fish spawning in the natural environment, but the difference was nonsignificant for males and marginally significant for females. Hatchery-origin fish exhibited reduced genetic diversity as well as evidence of increased temporal population structure. Conclusion We conclude that the program was successful in achieving an increase in adult returns but not in avoiding negative genetic effects on the population and that any lasting impacts of supplementation remain to be determined.

Smith, Christian T. (ORCID:0000000240522669)↗

Removal of Technetium-99 on Ion Exchange Resin - A Case Study at 200 West Pump and Treat - 17303

The 200 West Pump and Treat (P and T), on the U.S. Department of Energy's Hanford Site and operated by CH2M HILL Plateau Remediation Company, has a 9,464 liters per minute capacity designed to capture and treat an 8 km{sup 2} contaminated groundwater plume and reduce the mass of contaminants of concern (COCs) by 95 percent in 25 years. The plume is a complex mix of contaminants including technetium-99 (Tc-99), uranium, carbon tetrachloride, chromium, hexavalent chromium, nitrate, and iodine-129 (I-129). Ion exchange (IX), a common treatment approach for Tc-99 used by many nuclear remediation sites, is used to remove uranium and Tc-99 at 200 West P and T. The IX vessels are arranged in a sequence of three to provide a lead, lag and polish vessel. Tc-99 concentrations are monitored monthly to assure good performance of the system. Performance tracking revealed surprising results. On October 14, 2015, the resin in the lead vessels released Tc-99 at concentrations greater than what was being fed. Although Tc-99 was captured by the downstream lag and polish vessels, the facility staff grabbled with the sudden release of Tc-99 entertaining a variety of scenarios that might result in sudden failure of the IX processes. Subsequent sampling indicated Tc-99 removal began a steady return to normal. The incident raised many questions, chief among them whether the same events could recur and undermine Tc-99 treatment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Counterpart identification and classification for eRASS1 and characterisation of the active galactic nuclei content

Context. Accurately accounting for the Active Galactic Nucleus (AGN) phase in galaxy evolution requires a large, clean AGN sample. This is now possible with SRG/eROSITA, which completed its first all-sky X-ray survey (eRASS1) on June 12, 2020. The public Data Release 1 (DR1, Jan 31, 2024) includes 930,203 sources from the western Galactic hemisphere. Aims. The data enable the selection of a large AGN sample and the discovery of rare sources. However, scientific return depends on accurate characterisation of the X-ray emitters, requiring high-quality multi-wavelength data. This paper presents the identification and classification of optical and infrared counterparts to eRASS1 sources. Methods. Counterparts to eRASS1 X-ray point sources were identified using Gaia DR3, CatWISE2020, and Legacy Survey DR10 (LS10) with the Bayesian NWAY algorithm and trained priors. Sources were classified as Galactic or extragalactic via a machine-learning model combining optical/IR and X-ray properties, trained on a reference sample. For extragalactic LS10 sources, photometric redshifts were computed using CIRCLEZ. Results. Within the LS10 footprint, all 656,614 eROSITA/DR1 sources have at least one possible optical counterpart; ∼570 000 are extragalactic and likely AGN. Half are new detections compared to AllWISE, Gaia, and Quaia AGN catalogues. Gaia and CatWISE2020 counterparts are less reliable, due to the survey’s shallowness and the limited amount of features available to assess the probability of being an X-ray emitter. In the Galactic plane, where the overdensity of stellar sources also increases the chance of associations, using conservative reliability cuts, we identified approximately 18 000 Gaia and 55 000 CatWISE2020 extragalactic sources. Conclusions. We have released three high-quality counterpart catalogues – plus the training and validation sets – as a benchmark for the field. These datasets have many applications, but in particular, they empower researchers to build AGN samples tailored for completeness and purity, accelerating the hunt for the Universe’s most energetic engines.

X-rays: general↗

Automatic detection of impact craters on Al foils from the Stardust interstellar dust collector using convolutional neural networks

NASA's Stardust mission utilized a sample collector composed of aerogel and aluminum foil to return cometary and interstellar particles to Earth. Analysis of the aluminum foil begins with locating craters produced by hypervelocity impacts of cometary and interstellar dust. Interstellar dust craters are typically less than one micrometer in size and are sparsely distributed, making them difficult to find. In this paper, we describe a convolutional neural network based on the VGG16 architecture that achieves high specificity and sensitivity in locating impact craters in the Stardust interstellar collector foils. Finally, we evaluate its implications for current and future analyses of Stardust samples.

79 ASTRONOMY AND ASTROPHYSICS↗

Binary pseudorandom test standard to determine the modulation transfer function of optical microscopes

This work reports on the development of a binary pseudo-random test sample optimized to calibrate the MTF of optical microscopes. The sample consists of a number of 1-D and 2-D patterns, with different minimum sizes of spatial artifacts from 300 nm to 2 microns. We describe the mathematical background, fabrication process, data acquisition and analysis procedure to return spatial frequency based instrument calibration. We show that the developed samples satisfy the characteristics of a test standard: functionality, ease of specification and fabrication, reproducibility, and low sensitivity to manufacturing error. © (2015) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Effect of pH on hydrogen pick-up and corrosion in zircaloy-4

Thermal Desorption Spectroscopy (TDS) has been used to investigate the hydrogen pick-up behaviour in different samples of Zircaloy-4. This includes as-received, cold rolled, hydrogen charged, and autoclave-oxidised in pure water and at an elevated pH (with 50% deuterated water) compared to commercial reactors. A characteristic desorption peak for hydrogen has been found at about 650 Celsius degrees, which is theorised to come from hydrides. Cold rolled samples show the same general shape spectrum as the as-received samples, with more hydrogen detected per unit volume of sample. This suggests more hydrogen is in trapping sites or outward diffusion paths are facilitated by dislocations, since no more hydrogen has been added. The peak broadens towards higher temperature, which indicates that additional dislocations could provide trapping sites with a slightly higher energy than the average in the as-received samples. The hydrogen charged samples form a hydride rim, which contains much more hydrogen than the as-received samples. The peak broadens but on average does not shift. The surface oxide, when present, acts as a barrier to the desorption of hydrogen, until the temperature rises enough for the oxygen to migrate into the bulk. The oxide itself only contains a small amount of hydrogen, as is evidenced when the oxide layer is removed, whereupon the desorption peak returns to the characteristic shape seen in as-received samples. Samples oxidised in pure water exhibit a slightly higher oxidation rate, and pass through kinetic transition much earlier than samples exposed to an elevated pH. Before transition pH has little effect on the hydrogen pick-up. After transition the hydrogen pick-up is much higher in pure water, which implies that the H{sup +} concentration in the environment affects hydrogen pickup at this stage. The elevated pH samples showed peaks for D-H and D{sub 2}, which follow the H{sub 2} peaks. The hydrogen content in these samples increases at around 70% of the time to the first transition. This may correlate with development of through-thickness percolation paths, which could lead to the pH inside cracks being modified to a lower value, increasing the availability of H{sup +} ions. (authors)

36 MATERIALS SCIENCE↗

Crewmember microbiome may influence microbial composition of ISS habitable surfaces

The International Space Station (ISS) is a complex built environment physically isolated from Earth. Assessing the interplay between the microbial community of the ISS and its crew is important for preventing biomedical and structural complications for long term human spaceflight missions. In this study, we describe one crewmember’s microbial profile from body swabs of mouth, nose, ear, skin and saliva that were collected at eight different time points pre-, during and post-flight. Additionally, environmental surface samples from eight different habitable locations in the ISS were collected from two flights. Environmental samples from one flight were collected by the crewmember and samples from the next flight were collected after the crewmember departed. The microbial composition in both environment and crewmember samples was measured using shotgun metagenomic sequencing and processed using the Livermore Metagenomics Analysis Toolkit. Ordination of sample to sample distances showed that of the eight crew body sites analyzed, skin, nostril, and ear samples are more similar in microbial composition to the ISS surfaces than mouth and saliva samples; and that the microbial composition of the crewmember’s skin samples are more closely related to the ISS surface samples collected by the crewmember on the same flight than ISS surface samples collected by other crewmembers on different flights. In these collections, species alpha diversity in saliva samples appears to decrease during flight and rebound after returning to Earth. This is the first study to compare the ISS microbiome to a crewmember’s microbiome via shotgun metagenomic sequencing. We observed that the microbiome of the surfaces inside the ISS resemble those of the crew’s skin. These data support future crew and ISS microbial surveillance efforts and the design of preventive measures to maintain crew habitat onboard spacecraft destined for long term space travel.

59 BASIC BIOLOGICAL SCIENCES↗

Adaptive Sample Preparation and Target Fabrication for High-Throughput Materials Science

High-repetition-rate brilliant and coherent light sources are significantly increasing the rate at which scientific experiments can be performed. An investment in transformative technologies to make samples of condensed matter could enable a paradigm shift for that field or open new exciting frontiers in high-energy density science (HEDS). This will especially be true for dynamic materials in extremes research or HEDS, where the repetition rate for placing samples into extreme environments is increasing and the samples or targets are irreversibly destroyed in each experiment. Research teams that are able to implement solutions to all aspects of the experimental process and enable a paradigm of high-throughput science will have the greatest success and impact. There are two different directions for adaptive samples. One is research when the number of experiments can be greatly increased with increased volume, such as in high energy density science. The other is when flexibility and agility can aid Bayesian optimization computational methods and speed up the discovery process, as with materials science. Conducting a similar equation-of-state (EOS) experiment took three years on the OMEGA laser facility, compared to five days of shifts at the LCLS XFEL. New materials with improved properties have been found by guided optimization of experimental science. Adaptive sample preparation and target fabrication can create a tremendous return on scientific investment. High-throughput enabling precision science is also a desirable goal. To address these issues, we sought a diverse set of innovative participants who had ideas of how to achieve this paradigm shift. We invited 42 researchers from a variety of disciplines and fields to attend a workshop in College Station, Texas, May 14–16, 2019. Many of the participants had never been in the same room before, and most found it very exciting to hear about new and different research. The goal was twofold: to define the challenges, i.e., “what would we like to be able to do and why it is difficult to do so,” and to describe the progress, approaches and capabilities, as well as the vision, “what we could do if we had more support.”

36 MATERIALS SCIENCE↗

Enabling dynamic 3D coherent diffraction imaging via adaptive latent space tuning of generative autoencoders

Abstract Coherent diffraction imaging (CDI) is an advanced non-destructive 3D X-ray imaging technique for measuring a sample’s electron density. The main challenge of CDI is loss of phase information in diffraction intensity measurements, resulting in lengthy iterative reconstruction processes that can return non-unique solutions, which pose challenges for experiments attempting to track dynamic sample evolution through multiple states. As the increased brightness of fourth-generation light sources enables faster sample measurements and drives operando experiments with Bragg CDI, there is a growing need for faster reconstruction techniques that can keep pace. We have developed an adaptive generative autoencoder approach for uniquely tracking a sample’s electron density as it dynamically evolves. Our approach adaptively tunes the low-dimensional latent embedding of a generative autoencoder, enabling a computationally efficient manner to account for time-varying shifting distributions in real-time. Analytic proof of convergence is provided as well as numerical demonstration of sample tracking with noisy measurements.

97 MATHEMATICS AND COMPUTING↗

Neutron Fluence Measurements for the UCF HSIS Experiment in ATR

The University of Central Florida (UCF) experiments were irradiated in the Hydraulic Shuttle Irradiation System (HSIS) of the Advanced Test Reactor (ATR) at Idaho national Laboratory (INL) to study the effects of how low neutron fluence on metallic fuels. Four samples were irradiated for 20 days from 2/20/2014 to 3/12/2014 and four additional samples were irradiated for 2 days from 3/17/2014 to 3/19/2014. All eight of the samples included neutron fluence capsules that were previously prepared at PNNL. After irradiation, the neutron fluence monitors were returned to Pacific Northwest National Laboratory (PNNL) for analysis to determine the neutron fluence that was received by each sample.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Method for high-throughput micro-sampling analysis of electrochemical process salts

A method and apparatus for analyzing molten salt electrolyte. The method includes extracting a sample of a molten salt electrolyte from an electrorefiner or other process vessel or conduit; generating droplets from the sample, where the droplets are at a first temperature; transporting the droplets to detectors, where during transport, the droplets attain a second temperature that is lower than the first temperature; analyzing the droplets at or below the second temperature; and returning the droplets to the process. The apparatus includes a droplet generator; a sample transport mechanism; and at least one detector positioned above the sample transport mechanism.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Macquarie Island Cloud and Radiation Experiment (MICRE) Ice Nucleating Particle Measurements Field Campaign Report

The U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility Macquarie Island Cloud and Radiation Experiment (MICRE) Ice Nucleating Particle Measurements campaign was aligned as a supplemental activity with the second year of the overall MICRE campaign. The purpose of the supplemental campaign was to provide a first-ever annual cycle of ice nucleating particle (INP) measurements at a Southern Ocean (SO) site, toward the investigation/characterization of sources of INPs in the marine boundary layer as being from the production or primary sea spray aerosol (SSA) emissions versus other long-range transport influences. Furthermore, measuring the variability in INPs seasonally in this region, as this may relate to meteorology and ocean biological processes, is expected to help constrain (via parameterizations) numerical model simulations of cloud phase and regional climate. In concert with other SO studies during the time frame of the campaign (March 2017 to March 2018), MICRE sought to evaluate the hypotheses that SSA INPs represent the major INP source in the SO and, due to their generally less efficient INP activation properties compared to terrestrial sources, that they may directly influence the persistence of supercooled clouds in a unique manner for this climatic region. These measurements supplemented the original deployment of primarily radiation measurements provided in the ARM MICRE request and the associated Australian Antarctic Division (AAD) Antarctic Clouds and Radiation Experiment (ACRE). Assistance and collaboration was obtained from the AAD, the Commonwealth Scientific and Industrial Research Organization (CSIRO) and the Australian Bureau of Meteorology (BOM). Follow-up plans will include investigations with their additional aerosol, cloud, and radiative transfer measurements. AAD also saw to the transport to Australia and storage of filters at the end of the campaign. The added effort involved an average of twice-weekly collections (a 48-hour and a 72-hour collection) of pre-sterilized, open-faced, polycarbonate filter samples for post-processing of INP number concentrations and tests to analyze the nature of INP sources. Collections were made by AAD technician Emry Thaggard Crocker after online training from our team. Images of the filter sampler and site are shown in Figure 1. Sampling occurred from an approximate elevation of 4m MSL. Filters were returned frozen to Colorado State University (CSU) at the end of the campaign. Initial processing to obtain INP temperature spectra (0 to -28°C) of the concentrations of INPs active via the immersion freezing mechanism were conducted using the CSU ice spectrometer (IS) instrument systems (Hiranuma et al. 2015; McCluskey et al. 2018). In this method, particles are first removed from filters using ultrapure water while under mechanical agitation. Arrays of the particle suspensions from a portion of filter rinses are then cooled to obtain immersion freezing data per volume of water, and finally are related to sampling volumes to obtain numbers per volume of air following the analysis methods of Vali (1971). A total of 103 filters were collected, including blanks at selected intervals throughout the project. For archival and completion of tasks under this ARM proposal, nearly half of the filter collections (46) were processed for basic temperature spectra, and half of these (23) were also tested for microbial/proteinaceous contributions toward INPs via 95°C pre-treatment of portions of the original suspensions.

Southern Ocean, aerosols, marine clouds, MARCUS ca↗

Impacts of advanced diesel combustion operation and fuel formulation on soot nanostructure and reactivity

Advanced diesel combustion, accomplished via a single pulse fuel injection and high levels of exhaust gas recirculation (referred to as “PCCI”, partially-premixed charge compression ignition), is shown to be a path to reduce oxides of nitrogen and particulate matter simultaneously. This is well established in the literature. Less established is the extent to which such dilute combustion processes influence soot formation and affect soot that is emitted from diesel engines under such combustion modes. This work focuses on characterization of the nanostructure and oxidative reactivity of soot generated by a light-duty turbodiesel engine operating under a PCCI combustion mode, a dilute, low-temperature combustion process. Previous work on a type of PCCI combustion, referred to as high-efficiency clean combustion (HECC), showed soot samples having a fullerenic nanostructure, characterized by high levels of tortuosity of the fringe layers as seen in transmission electron micrograph images and as quantified using an image processing algorithm. Thermogravimetric analysis of the HECC mode soot samples showed that they displayed higher rates of oxidation than soot samples from a conventional diesel combustion mode. The present work returns to PCCI combustion, considering the timing of the main fuel injection, and the effects of operating on fuels rich in n-alkanes, particularly a fuel produced from a low temperature Fischer-Tropsch process (LTFT) and a renewable diesel fuel (RD) produced via hydrodeoxygenation of a plant oil. PCCI combustion conditions yield soot that shows higher reactivity compared to soot from the conventional combustion mode regardless of fuel type. LTFT and RD fuels produce soots with lower reactivity compared to ULSD. Soots produced from PCCI combustion have higher surface oxygen concentration and higher proportion of amorphous carbon. In addition, TEM images show that PCCI soots from all three fuels have smaller primary particle and particle aggregate sizes, and smaller graphene layers. These properties explain the higher reactivity of soot from PCCI combustion. The less reactive soots, which are produced from LTFT and RD fuel under conventional combustion, show internal burning during oxidation. However, soots with higher reactivity which are produced from late injection PCCI combustion and ULSD show shrinking core oxidation, most likely because of their overall amorphous structure.

42 ENGINEERING↗