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Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

Dingemans, Theodorus J.↗

Gamma-Ray Pulsar Light Curves in Vacuum and Force-Free Geometry

Recent studies have shown that gamma-ray pulsar light curves are very sensitive to the geometry of the pulsar magnetic field. Pulsar magnetic field geometries, such as the retarded vacuum dipole and force-free magnetospheres have distorted polar caps that are offset from the magnetic axis in the direction opposite to rotation. Since this effect is due to the sweepback of field lines near the light cylinder, offset polar caps are a generic property of pulsar magnetospheres and their effects should be included in gamma-ray pulsar light curve modeling. In slot gap models (having two-pole caustic geometry), the offset polar caps cause a strong azimuthal asymmetry of the particle acceleration around the magnetic axis. We have studied the effect of the offset polar caps in both retarded vacuum dipole and force-free geometry on the model high-energy pulse profiles. We find that, compared to the profiles derived from symmetric caps, the flux in the pulse peaks, which are caustics formed along the trailing magnetic field lines, increases significantly relative to the off-peak emission, formed along leading field lines. The enhanced contrast produces improved slot gap model fits to Fermi pulsar light curves like Vela, with vacuum dipole fits being more favorable.

Harding, Alice K.↗

Self-Sealing Wet Chemistry Cell for Field Analysis

In most analytical investigations, there is a need to process complex field samples for the unique detection of analytes, especially when detecting low concentration organic molecules that may identify extraterrestrial life. Wet chemistry based instruments are the techniques of choice for most laboratory- based analysis of organic molecules due to several factors including less fragmentation of fragile biomarkers, and ability to concentrate target species resulting in much lower limits of detection. Development of an automated wet chemistry preparation system that can operate autonomously on Earth and is also designed to operate under Martian ambient conditions will demonstrate the technical feasibility of including wet chemistry on future missions. An Automated Sample Processing System (ASPS) has recently been developed that receives fines, extracts organics through solvent extraction, processes the extract by removing non-organic soluble species, and delivers sample to multiple instruments for analysis (including for non-organic soluble species). The key to this system is a sample cell that can autonomously function under field conditions. As a result, a self-sealing sample cell was developed that can autonomously hermetically seal fines and powder into a container, regardless of orientation of the apparatus. The cap is designed with a beveled edge, which allows the cap to be self-righted as the capping motor engages. Each cap consists of a C-clip lock ring below a crucible O-ring that is placed into a groove cut into the sample cap.

Beegle, Luther W.↗

Large Plant Growth Chambers: Flying Soon on a Space Station near You!

The International Space Station (ISS) now has platforms for conducting research on horticultural plant species, and those capabilities continue to grow. The Veggie vegetable production system will be deployed to the ISS in Spring of 2014 to act as an applied research platform with goals of studying food production in space, providing the crew with a source of fresh food, allowing behavioral health and plant microbiology experimentation, and being a source of recreation and enjoyment for the crew. Veggie was conceived, designed, and constructed by Orbital Technologies Corporation (ORBITEC, Madison, WI). Veggie is the largest plant growth chamber that NASA has flown to date, and is capable of growing a wide array of horticultural crops. It was designed for low energy usage, low launch mass and stowage volume, and minimal crew time requirements. The Veggie flight hardware consists of a light cap containing red (630 nanometers), blue, (455 nanometers) and green (530 nanometers) light emitting diodes. Interfacing with the light cap is an extendable bellows baseplate secured to the light cap via magnetic closures and stabilized with extensible flexible arms. The baseplate contains vents allowing air from the ISS cabin to be pulled through the plant growth area by a fan in the light cap. The baseplate holds a Veggie root mat reservoir that will supply water to plant pillows attached via elastic cords. Plant pillows are packages of growth media and seeds that will be sent to ISS dry and installed and hydrated on orbit. Pillows can be constructed in various sizes for different plant types. Watering will be via passive wicking from the root mat to the pillows. Science procedures will include photography or videography, plant thinning, pollination, harvesting, microbial sampling, water sampling, etcetera. Veggie is one of the ISS flight options currently available for research investigations on plants. The Plant Habitat (PH) is being designed and constructed through a NASA-ORBITEC collaboration, and is scheduled to fly on ISS around 2016. This large plant chamber will control light quality, level, and timing, temperature, CO2, relative humidity, and irrigation, while scrubbing ethylene. Additional monitoring capabilities include leaf temperature sensing and root zone moisture and oxygen sensing. The PH light cap will have red (630 nanometers), blue (450 nanometers), green (525 nanometers), far red (730 nanometers) and broad spectrum white light emitting diodes. There will be several internal cameras to monitor and record plant growth and operations.

Space Biology↗

Physical and Biological Properties of Cobalt- and Copper-Doped Calcium Phosphates as Bone Substitute Materials

Arthritis, osteoporosis, and other bone diseases and defects are common medical issues worldwide. By utilizing ceramic biomaterials as bone substitutes to treat these diseases, bone regeneration can be promoted and toxicity from the substitute material can be limited. Calcium phosphate (CaP) ceramics have become popular as bone substitutes due to their biocompatibility and similarity in composition to natural bone. The purpose of this research was to investigate the physical properties and biological responses of CaP-based bone substitutes, doped with metal ions. Some metal ions are present in natural bone in small amounts, and recent studies show they affect the biological responses of CaPs significantly. Dopants such as magnesium (Mg), strontium (Sr), silicon (Si) and iron (Fe) alter the phase composition, mechanical properties, osteogenesis and angiogenesis properties of CaPs, depending on their concentration and method of addition. In the present study, the effects of cobalt (Co) and copper (Cu) on the physical and biological properties of two main CaP materials, brushite cement (BrC) and tricalcium phosphate (TCP), have been investigated. Different concentrations of dopants in forms of oxide and/or chloride were selected and their effect on phase composition, sintering behavior, density, setting time, compressive strength and in vitro interaction with osteosarcoma and osteoblast cells were studied. Different techniques of sample preparation, challenges during cement preparation and compact sample pressing, sintering, and methods of dopant addition are discussed. The presence of Cu in tricalcium phosphate was found to increase thermal stability of the material and decrease the impact of sintering temperature on porosity. In addition, Cu caused a reduction in expression of inflammatory gene markers by human osteoblast cells and an increased expression at early time points due of osteoinductive markers.The addition of Cu and Co to brushite cement caused an increase in thermal stability of the material, and the addition of Cu caused significant increase in setting time. Small dopant amounts of Co caused decrease in setting time, but higher amounts caused an increase. In addition, Cu dopant in small amounts resulted in an increase of compressive strength. Both Cu and Co led to a decrease in expression of inflammatory gene markers by osteoblast and osteosarcoma cells respectively, and Cu also caused an increase in osteoinductive marker expression. Thus, these results indicate that Cu and Co have a positive impact on the physical, mechanical and biological properties of calcium phosphate biomaterials.

Cummings, Haley V.↗

Changes in the Magnetic Field Topology and the Dayside/Nightside Reconnection Rates in Response to a Solar Wind Dynamic Pressure Front A Case Study

One of the most significant observations associated with a sharp enhancement in solar wind dynamic pressure, SWP, is the poleward expansion of the auroral oval and the closing of the polar cap. The polar cap shrinking over a wide range of magnetic local times (MLTs), in connection with an observed increase in ionospheric convection and the transpolar potential, led to the conclusion that the nightside reconnection rate is significantly enhanced after a pressure front impact. However, this enhanced tail reconnection has never been directly measured. We demonstrate the effect of a solar wind dynamic pressure front on the polar cap closure, and for the first time, measure the enhanced reconnection rate in the magnetotail, for a case occurring during southward background Interplanetary Magnetic Field (IMF) conditions. We use Polar Ultra-Violet Imager (UVI) measurements to detect the location of the open-closed field line boundary, and combine them with Assimilative Mapping of Ionospheric Electrodynamics (AMIE) potentials to calculate the ionospheric electric field along the polar cap boundary, and thus evaluate the variation of the dayside/nightside reconnection rates. We find a strong response of the polar cap boundary at all available MLTs, exhibiting a significant reduction of the open flux content. We also observe an immediate response of the dayside reconnection rate, plus a phased response, delayed by 15–20min, of the nightside reconnection rate. Finally, we provide comparison of the observations with the results of the Open Geospace General Circulation Model (OpenGGCM), elucidating significant agreements and disagreements

A Boudouridis↗

Martian B Storm Genesis and Evolution: Initial Analysis of Thermal Datasets.

Introduction: Dust lifting on Mars likely occurs primarily as a result of the exchange of momentum between the atmosphere and the surface via saltation. During saltation, sand-sized particles are mobilized but do not enter into suspension. When these larger particles fall back to the surface, kinetic energy is transferred to smaller dust particles which are then lofted into suspension in the atmosphere. Depending on the altitude to which dust is lofted, it can have a significant effect on atmospheric temperatures. As a strong absorber and emitter in the infrared, dust can influence atmospheric heating and modify the global circulation and weather on Mars [1,2]. Although dust is present in Mars’ atmosphere throughout the year, the atmosphere is generally dustier during the second half of the year when Mars is near perihelion. Observations reveal that episodic global-scale dust storms and fairly regular regional-scale dust storms are superimposed on a well-defined and highly repeatable seasonal cycle of dust opacity and associated mid-level atmospheric temperature responses. Kass et al. (2016) used 50 Pa temperature observations from MRO/MCS to identify three highly repeatable time periods during which regional dust storms occur, and designated them the “A”, “B” and “C” storms. While “A” and “C” storms have been studied a fair amount to-date, “B” storms have not yet been investigated in detail. This study explores the generation and evolution of the annually recurring regional dust storm known as the “B” storm, which was identified and categorized by Kass et al. (2016) based on 25 km (50 Pa) temperature observations. The B storm is a southern-hemisphere (SH) phenomenon that originates at the cap edge just after perihelion and which reaches peak intensity during the SH summer solstice, Ls 270. It may originate from the cap edge storms that spawn near the edge of the seasonal CO2 cap during retreat, but the mechanisms for B storm genesis have yet to be determined definitively [1]. Methods: We will use observational data sets and a global climate model (GCM) to investigate “B” regional storms. The data analysis component will include the analysis of imagery from MGS/MOC and MRO/MARCI, and spectroscopic data sets of dust and temperatures from MGS/TES and MRO/MCS with the goal of fully characterizing the behavior of these storms. Both MGS and TES provide data well-suited for temperature analysis at 25 km. MCS measures atmospheric temperature, dust extinction, and water ice extinction at 5 km intervals from the surface to about 80 km. TES measured atmospheric temperatures, column dust and water ice opacities, and column water vapor abundances. Measurements made by TES extended from the surface to about 40 km [1]. At the 50 Pa (25 km) level, local dust events usually confined to shallower depths are effectively filtered out of the analysis leaving the regional dust events identifiable by their temperature signatures [1]. Our preliminary analysis makes use of the fact that the brightness temperature at 15 microns (T15 temperature) is a close approximation to observed temperature at 25 km. We first reproduce the zonal mean 50 Pa level temperature plots for MY 29-32 to establish a baseline for our procedures moving forward [1]. Expanding on Kass et al. (2016), we include recent MCS data from MY 33 and 34 as well. Preliminary Analysis: The daytime (3PM) T15 temperatures in Figure 1 indicate: in MY 29, a strong A storm at Ls 240, a B storm at high southern latitudes just after Ls 270, and a C storm at Ls 320; in MY 30, a B storm at Ls 270; in MY 31 & MY 32, a B storm just before Ls 270; in MY 33, a B storm at Ls 270; and in MY 34, a strong A storm in the northern hemisphere at Ls 210, and a B storm around Ls 270 although there is a data gap. For the B storms, each is indicative of lofted dust and resultant warming. The daytime temperature structure illustrates that the B storm occurs annually around Ls 270 and is confined to high southern latitudes. It reaches its peak intensity around SH summer solstice, Ls 270, consistently for all six MY assessed. Since direct solar heating is absent overnight, the nighttime T15 temperatures (Figure 2) are often useful for differentiating the heat signature of direct solar heating from the dynamical response to that heating. However, in the southern polar latitudes at perihelion the sun does not set and direct solar heating remains present throughout the night. Importantly for our study, dust lofted in the B storm experiences this direct heating day and night for the entirety of its lifetime. The B storm expands as far north as -60 latitude and decays in latitudinal extent more gradually than it grows. This feature is less obvious in the nighttime (3AM) T15 temperatures (Figure 2). The temperature signal is stronger at night for MY 30-33. The warm pool is larger in area relative to the background at night in these four cases. This more uniform warming masks the “tail” feature somewhat, such that it is barely noticeable during these years. Unfortunately, gaps in MCS data in MY 29 and 34 prevent confirmation of the tail feature during those years, however, the B storm temperature signature follows a very different pattern than that described for MY 30-33. MY 29 and 34 appear to show smaller centers of warming at night and larger centers of warming during the day. This is in opposition to that previously described for MY 30-33. Conclusions and Future Work: We will continue investigating the heat signatures of B storms by looking at the total column heating as recorded by TES. We will also look at lower altitudes for patterns that may describe the relationship between B storms and the cap edge storms that develop while the seasonal cap is retreating. In the future, we will use GCM simulations to determine the atmospheric and thermo-dynamic conditions associated with these storms.

Courtney Marylou Batterson↗

Computational experiments to characterize bubble formation and movement in waste glass foam layer

Computer simulation experiments are a valuable complement to physical experimentation for systems where there is limited access to quantities of interest. The motivation for this work is to characterize the fluid dynamic and heat transfer processes that affect melt rate of waste slurry during vitrification, which can limit the throughput rate of the melter. Heat transfer to the cold cap from the molten glass below this layer is an important factor determining melt rate. In this study, computational fluid dynamics is used to elucidate the behavior of gas-filled cavities that form underneath the cold cap in a laboratory-scale waste glass melter. The cold cap consists of a reacting feed layer above a foam layer. The cavities are a result of coalesced gases from collapsing primary foam and air from forced convection bubblers. Bubbles in the foam layer move horizontally with the circulation pattern of the melt and escape around the edges of the cold cap to the plenum above. The effects of varying thermophysical properties and foam parameters based on the bounds of high-level waste glass formulations were explored. Using the DAKOTA toolkit, a Latin hypercube space-filling design was used to randomly distribute samples in bins to achieve good coverage over the parameter space with minimal points. Using the results from the set of simulations, a Gaussian process model with a linear trend was used to create response surfaces for several key quantities of interest, including temperatures, temperature gradients, velocities, and foam extent beneath the cold cap.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Implementation of a High-Fidelity Interface Resolving Method in Nek5000

The development and utilization of computational fluid dynamics (CFD) models for large, high-temperature electric melters in the Waste Treatment and Immobilization Plant (WTP) in eastern Washington State have proven to be valuable for various purposes. These models allow for a better understanding of the physio-chemical processes occurring within the melter vessels and can contribute to improving operational efficiency, throughput, and addressing operational issues related to vitrification. The CFD models employed for these melter vessels incorporate multiphase fluid flow and heat transfer simulations in different regions, including the plenum, cold cap, and molten glass regions. As the tank waste and glass formers are introduced into the melter, a reacting batch layer known as the cold cap forms on top of the molten glass. To enhance the melt rate, forced convection bubblers located at the bottom of the melters generate convection currents that help homogenize the molten glass and provide heat to the cold cap. As the bubbles rise through the highly viscous glass, they adopt a spherical-cap shape [1]. Meanwhile, the conversion of the batch to glass generates significant amounts of gases (such as water vapor, carbon dioxide, sulfur dioxide, and NOx) due to thermal decomposition [2]. These gases become trapped between the cold cap and molten glass, forming a foam layer [3]. For modeling multiphase flow in CFD and heat transfer simulations of waste glass melters at different scales, efforts are underway to augment the capabilities of the Nek5000 [4] and NekRS [5] open-source codes [6]. Nek5000/NekRS is a scalable and efficient spectral element code that has been successfully applied to a wide range of fluid dynamics problems. By leveraging the Nek5000/NekRS software, it becomes possible to model the melter systems more affordably and with lower computational requirements compared to currently utilized commercial CFD software. The specific objectives of this ongoing effort include: 1. Implementation of a level set method in Nek5000/NekRS: The level set method is a numerical technique commonly employed in CFD simulations to track and represent the interface between different phases or materials accurately. By incorporating this method into Nek5000/NekRS, the ability to simulate multiphase flows in waste glass melters at a high level of fidelity can be achieved. 2. Demonstration of capability for air bubbling through molten glass: As part of the development process, a specific case of air bubbling through molten glass will be simulated using the augmented Nek5000/NekRS code. This demonstration aims to showcase the ability of the software to accurately capture and analyze the complex phenomena involved in the multiphase flow within waste glass melters. By achieving these objectives, the improved Nek5000/NekRS code will offer a powerful computational tool for simulating and analyzing waste glass melter systems, enabling better understanding, optimization, and troubleshooting of these vitrification processes. The ability to accurately model and simulate multiphase flows has broad relevance across many industries and scientific domains, and the improved functionality can contribute to advancements in various fields beyond waste glass melter simulations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of Silica Particle Size on Nuclear Waste-to-Glass Conversion - 17319

The process for converting nuclear waste-to-glass in an electric melter occurs in the cold cap, a crust of reacting solids floating on the glass pool. As the melter feed (a mixture of the nuclear waste and glass forming and modifying additives) heats up in the cold cap, glass-forming reactions ensue, causing the feed matrix to connect, trapping reaction gases to create a foam layer. The foam layer reduces the rate of melting by separating the reacting feed from the melt pool. The size of the silica particle additives in the melter feed affects melt viscosity and, hence, foam stability. To investigate this effect, seven nuclear waste simulant feeds of a high-level waste were batched as slurries and prepared with dissimilar ranges of silica particle size. Each slurry feed was charged into a laboratory-scale melter (LSM) to produce a cold cap and the propensity of feeds to foam was determined by pressing dried feeds into pellets and monitoring the change of pellet volume in response to heating. Two of these slurries were designed to have dissimilar glass viscosities at 1150 deg. C. In the low temperature region of the cold cap, before the melter feed connects, the feeds without fine silica particles behaved similar to the high viscosity feed as their volume contracted while the feed with silica particles no larger than 5 μm reacted like the low viscosity feed. However, the feed volume similarities reversed as the feed connected and expanded through the foam region of the cold cap. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Nanomaterial-Treated Filters for the Uptake of Heavy Metals from Water Sources

We describe the synthesis and properties of ligand-modified gold nanoparticles (AuNPs) grown on stainless steel wool filters. Their selectivity and efficiency with regards to heavy metal uptake from groundwater and other sources of drinking water found at or near DOE facilities were also investigated. The nanomaterial-treated filters are advantageous because they serve as inactive supports that allow for efficient flow of the contaminated water, and can be easily replaced after heavy metal uptake. They are also comparable to nanomaterials free in solution with regards to the effectiveness of remediation of drinking water. Environmental stewardship is at the forefront of core competencies at SRNS. This includes treatment and remediation of contaminated groundwater. Among contaminants present in water resources, hazardous heavy metals and radioactive contaminants are the main concerns in the DOE complex. With the advent of nanotechnology, new remediation technologies have emerged. AuNPs have unique optical properties and enormous surface areas, making them good candidates for water remediation. They can be functionalized with ligands, e.g. citrate and L-cysteine, allowing them to serve as an excellent platform for environmental stewardship applications. Objectives: 1. Nanomaterial development and characterization Ligand-modified AuNPs: (a) in solution and (b) on stainless steel wool filters 2. Nanomaterial evaluation for efficiency and selectivity of heavy metal uptake, including Cu{sup 2+} and Zn{sup 2+}. Materials and Methods: Chloroauric acid (HAuCl{sub 4}), sodium citrate (reducing and capping agent); Stainless steel wool (SSW) was used as a support and filter; L-cysteine- ligand for surface functionalization; Zinc acetate and copper nitrate: heavy metal ions contaminants. Au NPs were prepared by wet chemistry methods. They were characterized by UV-Vis, Zeta sizer and potential, SEM, EDS and EDS mapping to understand their physico-chemical properties. Results and Discussions: Surface modification of AuNPs with surfactants changes their optical properties. Citrate capped AuNPs demonstrate high loading capacity for both heavy metals. L-cysteine capped AuNPs demonstrate high loading capacity for Zn{sup 2+}. Citrate capped AuNPs have excellent sensitivity towards heavy metal ions (0.05 mM can be detected). L-cysteine capped AuNPs can detect heavy metal ions at low concentrations, making them useful for sensing. Conclusions: AuNPs in solution and on SSW were successfully synthesized and characterized. Two functional sensing and remediation technologies - colorimetric sensor and AuNP-treated filters - were developed through wet chemistry methods. AuNP SSW filters exhibit different characteristics (size, shape, etc.) than AuNPs in solution and are efficient at the uptake of heavy metal ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffraction imaging for seal evaluation using ultra high resolution 3D seismic data

Cap rock is any impermeable or low permeability formation that may trap oil, gas or water, preventing it from migrating to the surface. Evaluation of sealing properties of the cap rock is a critical task for seismic exploration. It is important for oil and gas prospecting as well as for locating reservoirs appropriate for carbon dioxide storage. The latter has been proposed as one solution to global climate change caused by heat-trapping anthropogenic gasses in the atmosphere. A fluid escaped from the reservoir fills voids in the overlying strata thereby causing local changes of acoustic properties. We aim to explore such fluid-saturated areas and thus evaluate sealing properties of underlying cap rocks. We assume that local acoustic impedance changes caused by fluid migration generate seismic diffractions. We isolate diffracted waves from P-Cable seismic data acquired over the area of interest and perform diffraction analysis of the near-surface interval (above 200 m). In the diffraction image obtained, we interpret an extensive system of broad sinuous channels, narrow linear faults, and diffuse fracture networks. In addition, we detect high diffractivity anomalies, which extend vertically and laterally. We note no evidence of these anomalies in a conventional seismic image and associated seismic attribute (similarity and fracture density) volumes. We associate this high diffractivity to a variable pore fluid composition and saturation, which we infer to be due to hydrocarbon migration from the underlying strata. Consequently, we conclude poor seal quality for the underlying cap rocks. During data processing, we test diffraction focusing analysis for velocity model building. In conclusion, this option appears quite valuable for P-Cable data processing because of short offset and limitations of the standard velocity analysis.

58 GEOSCIENCES↗

Demonstration and Evaluation of Hybrid Microalgae Aqueous Conversion Systems for Biofuel Production

As an effort to develop affordable and sustainable energy sources, algae-derived biofuels have attracted considerable interest. As use of individual conversion processes targeting a subset of biochemical components (e.g., extraction and upgrading of lipids) has been shown to be economically unfeasible, there is a recognized need for integrated conversion systems that can valorize algal feedstocks with varying cell compositions. In this study, two hybrid systems (HBD-1, HBD-2) are proposed to enable more efficient conversion of all biomass components (lipids, proteins, carbohydrates) by leveraging two complementary systems: direct hydrothermal liquefaction (DHTL) and combined algal processing (CAP). Demonstrative experiments with Scenedesmus acutus show a 12.2-34.3% increase in fuel yields relative to individual systems (DHTL, CAP). Subsequent modeling efforts reveal substantial improvements stemming from CAP valorization of carbohydrates and lipids and DHTL valorization of proteins and CAP residuals. The maximum biomass-to-fuel conversion efficiencies for lipids/proteins/carbohydrate cell components are 79%/34%/75% (HBD-2), and techno-economic analysis suggests a 3.2-62.1% reduction in minimum fuel selling prices (MFSPs). The increased fuel yields and reduced MFSPs highlight the flexibility of the hybrid systems for biofuel production, revealing advantages of these systems for broader ranges of feedstocks, including ones not traditionally considered for fuel production.

09 BIOMASS FUELS↗

Chiral-selective etching effects on carbon nanotube growth at edge carbon atoms

We report that chemical vapor deposition (CVD) utilizing metal cluster nanoparticle catalysts is commonly used to synthesize carbon nanotubes (CNT), with oxygen-containing species such as water or alcohol included in the feedstock for enhanced yield. However, the etching effect of these additives on the growth mechanism has rarely been investigated, despite evidence suggesting that etching potentially affects the chirality distribution of product CNTs. We used quantum chemical methods to study how water-based etchant radicals (OH and H) may enhance the chiral selectivity during CVD growth using CNT cap models. Chemical reactivities of the caps with the etchant radicals were evaluated using density functional theory (DFT). It was found that the reactivities on the cap edges correlate with the chirality of the caps. Finally, these results suggest that proper selection of etchant species can provide opportunities for selective chirality control of the product CNTs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanisms of Selective Antitumor Action of Cold Atmospheric Plasma-Derived Reactive Oxygen and Nitrogen Species

Transformed cells are subject to elimination through intercellular reactive oxygen/nitrogen species (RONS)-dependent apoptosis-inducing signaling. Tumor progression, therefore, requires expression of membrane-bound catalase. Recent research demonstrates that 1 O 2 can inactivate membrane-bound catalase, thus, inducing the generation of tumor cell-derived secondary 1 O 2 and RONS-dependent apoptosis selectively in tumor cells. Crucially, 1 O 2 signaling can result in self-perpetuating apoptotic signaling from cell-to-cell. It is known that CAP contains 1 O 2 and that certain CAP constituents can generate 1 O 2 in solution. The analysis of model experiments performed with defined RONS implies that CAP-derived 1 O 2 induces the mechanism through which CAP acts selectively against cancer cells in vitro and tumors in vivo. Finally, this hypothesis needs to be tested experimentally in order to establish its validity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Future private car stock in China: current growth pattern and effects of car sales restriction

Car stock projection is essential to evaluating the energy and environmental impacts of private cars in China. Since the private car ownership rate in China has not reached its saturation level, limited and outdated data used in previous studies has resulted in high uncertainties regarding the functions of car ownership and significantly reduced the robustness of the projection of private car stocks. In this work, we estimate China's current growth pattern of private car ownership by analyzing more than 6300 pairs of private car ownership and income data collected from various official statistics at the national, provincial, and city levels in the period of 1997-2017. The dataset covers a much wider per-capita disposable income range than national-level data alone and allows us to make satisfactory projections of private car stocks in China up to 2040. We project that the private car stock in China could reach 403 million in 2040, if the current growth pattern of car ownership continues. Significant discrepancies in private car ownership curves are observed for cities with and without car sales restrictions. Without car sales restrictions, we estimate that the private car stock would be even higher at 455 million by 2040, demonstrating the effectiveness of the current restriction policy in controlling car stocks in China. We further quantify the potential impacts of car sales restrictions on future car stock levels by implementing hypothetical national car sales caps. Results show that, although the private car stocks would still continue to grow before 2030, the stock levels would be stable at ~ 280 and ~ 350 million by 2040 for scenarios of 20 and 25 million sales caps, respectively. The impact of private car stock growth on energy consumption in China is also examined. Pump-to-wheels energy consumption of the private car fleet is projected to be 131, 147, 90, and 113 million tonnes of oil equivalent by 2040 for scenarios of the current growth pattern, no sales restriction, the 20 million sales cap, and the 25 million sales cap, respectively. Analysis reveals that private car sales restriction and vehicle population growth control could be an effective strategy for energy consumption reduction (thus greenhouse gas emission mitigation) in China, although the development of the automotive industry may be restrained.

33 ADVANCED PROPULSION SYSTEMS↗

How does acetonitrile modulate single-walled carbon nanotube diameter during CVD growth?

There is a commercial demand for single-walled carbon nanotubes (SWCNTs) with uniform diameters and ( n, m ) chiralities. Yet, controlling these structural parameters in practice remains a challenge. Recent studies have shown that acetonitrile reversibly modulates SWCNT diameter during chemical vapour deposition (CVD) growth. Here we propose a mechanism to explain this phenomenon using non-equilibrium quantum chemical molecular dynamics simulations. We reveal that acetonitrile-derived radicals actively abstract hydrogen from surface hydrocarbon species as the SWCNT nucleates. This forms hydrogen (iso)-cyanide as a principal chemical product, and decreases the overall surface carbon density during nucleation. By liberating hydrogen, the number of dangling bonds present at the interface of the nucleating carbon structure is increased, which in turn accelerates SWCNT nucleation kinetics. Critically, the number of pentagon rings formed in the SWCNT precursor cap structure increases. Because the nucleation kinetics are much faster than the kinetics of ring defect healing, the pentagons become ‘trapped’ in the growing SWCNT cap structure, and this leads to more highly-curved SWCNT caps. As a result, these more highly-curved caps, combined with the lower surface carbon density and the faster kinetics of nucleation and growth, will ultimately yield narrower-diameter SWCNTs in the presence of acetonitrile.

36 MATERIALS SCIENCE↗

Economic competitiveness of pultruded fiber composites for wind turbine applications

Pultrusion manufacturing of fiber reinforced polymers has been shown to yield some of the highest mechanical properties for unidirectional composites, having a high degree of fiber alignment with consistent performance. Pultrusions offer a low-cost manufacturing approach for producing unidirectional composites with a constant cross-section and are used in many applications, including spar caps of wind turbine blades. However, as an intermediate processing step for wind blades, the additional cost of manufacturing pultrusions must be accompanied by sufficient increases in mechanical performance and system benefits. Wind turbine blades are manufactured using vacuum-assisted resin transfer molding with infused unidirectional fiberglass or carbon pultrusions for the spar cap. Infused fiberglass composites are among the most cost-effective structural materials available and replacing this material in the cost-driven wind industry has proven challenging, where infused fiberglass spar caps are still the predominant material system in use. To evaluate alternative material systems in a pultruded composite form, it is necessary to understand the costs for this additional manufacturing step which are shown to add 33%–55% on top of the material costs. A pultrusion cost model has been developed and used to quantify cost sensitivities to various processing parameters. The mechanical performance for pultruded composites is improved versus resin-infusion manufacturing with a 17% increase in design strength at a constant fiber volume fraction, but also enables higher achievable fiber volume fractions. The cost-specific mechanical performance is compared as a function of processing parameters for pultruded composites to identify the opportunities for alternative material and manufacturing approaches for wind turbine spar caps. Finally, four materials are compared in a representative wind turbine blade model to assess the performance of pultruded carbon fiber systems and pultruded fiberglass relative to infused fiberglass, where the pultruded systems produce lower weight blades with various cost distinctions.

42 ENGINEERING↗