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Development of advanced material composites for use as internal insulation for LH2 tanks (gas layer concept)

A program is described that was conducted to develop an internal insulation system for potential application to the liquid hydrogen tanks of a reusable booster, where the tanks would be subjected to repeated high temperatures. The design of the internal insulation is based on a unique gas layer concept, in which capillary or surface tension effects are used to maintain a stable gas layer, within a cellular core structure, between the tank wall and the contained liquid hydrogen. Specific objectives were to select materials for insulation systems that would be compatible with wall temperatures of 350 F and 650 F during reentry into the earth's atmosphere, and to fabricate and test insulation systems under conditions simulating the operating environment. A materials test program was conducted to evaluate the properties of candidate materials at elevated temperatures and at the temperature of liquid hydrogen, and to determine the compatibility of the materials with a hydrogen atmosphere at the appropriate elevated temperature. The materials that were finally selected included Kapton polyimide films, silicone adhesives, fiber glass batting, and in the case of the 350 F system, Teflon film.

Gille, J. P.↗

Phase Retrieval Implementation for the WFIRST Coronagraph Development Testbed

The Wide-Field Infrared Survey Telescope (WFIRST) is a 2.4m diameter space telescope NASA program. The payload will include two instruments, including a coronagraph instrument (CGI). The CGI will be the first active, high-contrast stellar coronagraph in space intended for imaging, discovery, and spectral characterization of exoplanets and debris discs. The CGI designs under development use deformable mirrors (DM) to create a point spread function (PSF) with a dark region around the obscured star object. Each DM consists of an array of actuators, and each actuator causes a local displacement to a thin, mirror-coated, glass face sheet. The actuator displacements are designed to create the PSF. Typically, phase retrieval is used to set the DM actuator displacements to their designed pattern, and then the actuators are further modified by an iterative control loop to correct for system non-idealities. To observe an exoplanet near the star object, the contrast in the annular region must be better than 10^8 (10^9 after post processing) relative to the unobstructed image of the star [1,2]. The coronagraph testbed at Jet Propulsion Laboratory is used to test coronagraph design and control algorithms. The optical system (Fig. 1) is maintained in a vacuum tank so that the PSF is stable for long integration times. Phase retrieval is an important tool for the testbed and serves several purposes, in addition to setting initial DM actuator displacements. Other uses include evaluation of systematic wavefront error introduced by system components, and alignment of the DMs and pupil masks. For example, the location of specific DM actuators relative to the Lyot mask can be determined by displacing the actuator, then measuring the location of the phase disturbance in the pupil plane with phase retrieval. In the next section we further describe the optical train of the testbed and the collection of source and pupil images available as inputs for phase retrieval, as well as one phase retrieval algorithm employed. Section 3 shows example phase retrieval results.

Marx, David↗

Thermally stable and self-healable lignin-based polyester

The increased use of plastics and the associated environmental impact has catalyzed research on the development of bio-derived polymers. Bio-based polyesters have gained increased attention due to the abundance of their starting materials and ease of processing. Lignin is naturally occurring in biomass with rich carbon content, whose functionality and rigidity make it an ideal bio-derived candidate for bio-based polyesters. Herein, a lignin-based polyester with good thermal stability and self-repairability was synthesized from carboxylated lignin and epoxidized soybean oil. The synthesized lignin/epoxidized soybean oil (ESO) vitrimer was brittle such that its mechanical performance could not be recorded. However, when polyethylene glycol (PEG) was incorporated as a plasticizer, polymer samples exhibited acceptable ductility. From thermomechanical analysis of the synthesized polyesters, the plasticizer did not impair thermal stability of polymers, but greatly enhanced mechanical properties. Notably, all samples exhibited stability at high temperatures, and good glass transition temperatures (51.0 ± 0.9–78.0 ± 1.2 °C). The highest tensile strength (3.983 ± 0.1 MPa) and storage modulus (1463.67 ± 12.6 MPa) were recorded for the polyester containing 6 % w/w PEG. Moreover, the polymer samples exhibited self-healing capability at 180 °C. This work expands on valorization of lignin through the synthesis of bio-derived materials.

36 MATERIALS SCIENCE↗

Overview of the Fiber System for the Dark Energy Spectroscopic Instrument

The Dark Energy Spectroscopic Instrument (DESI) is a revolutionary instrument designed for precise measurements of cosmic distances and the investigation of dark energy. DESI utilizes 5000 optical fibers to simultaneously measure the spectra of distant objects and aims to measure 40 million galaxies and quasars in a 5 yr survey. One of the critical challenges to DESI's success was ensuring that the fiber system was not only highly efficient but also delivered a highly stable beam enabling more reliable sky subtraction for measurements of faint objects. We achieved this stability by minimizing the stress on the fiber system during the manufacture and operation of the telescope and fiber positioning robots. We installed the DESI fiber system on the 4 m Mayall telescope with ≥99% of fibers intact, and the instrument has delivered superb optical performance throughout the initial years of the DESI survey, including ≥90% average throughput when injected with a focal ratio of ~f/3.9 as delivered by the primary focus corrector, excluding fiber absorption losses. The design of DESI required multiple innovations to achieve these requirements, such as cleaved fibers bonded with a UV-curing epoxy to glass ferrules in the focal plane and fusion splicing instead of physical connectors. In this paper, we describe the development, delivery, and installation of the fiber system, the innovations that made the state-of-the-art performance possible, and the key lessons learned that could benefit future projects.

79 ASTRONOMY AND ASTROPHYSICS↗

Optimized Carbon Fiber Intermediate Development to Enable High-Volume Manufacturing of Lightweight Automotive Composites

The ongoing pursuit of improved fuel economy and reduced greenhouse gas emissions has resulted in sustained interest for lightweight materials technologies. In this context, carbon fiber composites have captured the imagination of automotive engineers due to the potential to achieve substantial mass reduction when compared to traditional steel construction. That stated, the use of carbon fiber composites in automotive has been limited for the most part to premium supercars and other derivative platforms. In these cases, manufacturing costs are less of an obstacle to implementation, and the performance benefits of carbon fiber have enabled production of structures offering more than 50% weight savings. In practice, translating these low-volume demonstrations onto high-volume vehicle platforms has remained challenging. This can be attributed to several factors, with the absence of suitable high throughput production methodologies being a key impediment. To date, structural, crash critical components have relied upon manufacturing techniques born out of the aerospace industry. This has created a disconnect between automotive production systems that are accustomed to manufacturing multiple parts per minute and the aerospace technologies that have cycle times in the order of hours. Consequently, the focus of this project is the development of manufacturing process technology for carbon fiber composites that can support a mainstream vehicle program at an assumed throughput of 100,000 vehicles per year. In practice, this translates to a part-to-part cycle time of less than 3 minutes. Project participation included contributions from a broad range of academic, industrial and national lab partners. The primary scope of work, being the development of new carbon fiber epoxy compounds that are stable at room temperature and suited to high throughput automated processing. For project management, the work streams were divided into six key areas, with the lead organization in parentheses. • Carbon fiber/epoxy materials formulation development and scale up (Dow) • Simulation of discontinuous near isotropic meso-structure intermediates (Purdue) • Simulation of mechanical performance of compression molded components (Purdue) • Meso-Scale morphological analysis and correlation with structural performance (UTK) • Paint and adhesion durability analysis (MSU) • Demonstrator part design, prototype production, and validation testing (Ford). The primary goal at the commencement of the project was development of a chopped carbon fiber sheet molding compound (SMC) that offered a three times improvement in tensile modulus over a comparable glass-based SMC. In addition to meeting mechanical performance targets, the resin kinetics were modified to achieve a processing cycle time of less than 3 minutes. Other critical-to-quality (CTQ) specifications were also stipulated to account for a broad range of materials and processing characteristics. To achieve the above, staff scientists at Dow Chemical created an extensive series of new epoxy blends for testing and validation. Throughout this development, a key challenge was attaining material performance goals without impacting processing behavior and paintability of finished components. The latter required a new internal mold release system being developed by Dow that was designed to complement the kinetics of the rapid cure epoxy. As a complement to work studies at the industrial partners, the teams from academia executed a series of analytical and experimental studies to investigate potential factors influencing CF-SMC performance. Unit cell models were developed to capture the meso-scale representations of the fiber matrix architecture. Results of this analysis and subsequent morphological investigations led to the design of a novel composite derivative comprising carbon fiber platelets embedded in an epoxy matrix; the platelet size and aspect ratio playing significant role in final composite properties. This approach was a departure from previous research in CF-SMC development whereby bulk filamentization or disassembly of the carbon fiber rovings had been considered the most effective means of achieving both fiber wet through and wet-out. As the course of the academia studies progressed, the aspect ratio of the fiber constituents was further optimized before finalizing material attributes and processing conditions. For the purposes of technology validation, the Ford team led a work stream devoted to the design, fabrication and testing of demonstration components. The carbon fiber SMC material has the potential to displace numerous stampings and castings on an automotive structure but ultimately vehicle closure applications were selected to showcase the abilities of the CF-SMC to achieve both mass reduction and business case for large complex structures. Using target properties established by the Dow staff scientists, the complete closure system for a full-size sedan decklid and a mid-size wagon liftgate were engineered. Prototypes for both applications were fabricated using production representative processing methods to allow for physical testing and performance validation of the CF-SMC structures. Following completion of a testing program that concluded with a FMVSS301 55 mph offset rear crash, the CF-SMC formulation was declared by the Ford team to have met all engineering requirements. To summarize, the joint development activities during this project led to significant technical breakthroughs and achievement of all milestones. The result was the development of a novel, tack-free carbon fiber molding compound that is suited to automated processing. This combined room temperature stability, fast cure kinetics, and internal mold release system facilitates cycle times that are conducive to high-volume production. The VORAFUSE M6400 successfully passed technology validation at Ford and is now eligible for consideration on future production commercial vehicle programs.

36 MATERIALS SCIENCE↗

Custom Machines Advance Composite Manufacturing

Here is a brief list of materials that NASA will not be using to construct spacecraft: wood, adobe, fiberglass, bone. While it might be obvious why these materials would not make for safe space travel, they do share a common characteristic with materials that may well be the future foundation of spacecraft design: They all are composites. Formed of two or more unlike materials - such as cellulose and lignin in the case of wood, or glass fibers and plastic resin in the case of fiberglass-composites provide enhanced mechanical and physical properties through the combination of their constituent materials. For this reason, composites are used in everything from buildings, bathtubs, and countertops to boats, racecars, and sports equipment. NASA continually works to develop new materials to enable future space missions - lighter, less expensive materials that can still withstand the extreme demands of space travel. Composites such as carbon fiber materials offer promising solutions in this regard, providing strength and stiffness comparable to metals like aluminum but with less weight, allowing for benefits like better fuel efficiency and simpler propulsion system design. Composites can also be made fatigue tolerant and thermally stable - useful in space where temperatures can swing hundreds of degrees. NASA has recently explored the use of composites for aerospace applications through projects like the Composite Crew Module (CCM), a composite-constructed version of the aluminum-lithium Multipurpose Crew Capsule. The CCM was designed to give NASA engineers a chance to gain valuable experience developing and testing composite aerospace structures.

Source record↗

Metal-Organic Framework Glasses as Rad Contaminant Sequesters and Nuclear Waste Forms

Remediation of Tc remains an unresolved problem at SRS and other DOE sites. The objective of this project was to develop novel metal organic framework (MOF) glasses for radioactive contaminant sequestration and stabilization from aqueous media. During FY20, we synthesized, characterized and evaluated additional cetyltrimethylcimmonium bromide (CTAB)-functionalized and F - , Cl - , I - , CF 3 SO 3 - exchanged MIL-101-Cr samples. MIL-10l-Cr-NO 3 -CTAB was demonstrated to have high ReO 4 - removed capacity (139 mg/g sorbent) from artificial groundwater (AGW). Re chemical specicition and binding mechanism on MIL-101-CTAB were also studied by synchrotron X-ray absorption spectroscopy. ReO 4 - was demonstrated as being in the pore structure with slightly larger Re-O bond distances than those in NciReO 4 and binding with the positively charged sites of CTAB. In addition, a new Ni-TIPA MOF was demonstrated to be very stable, selective and effective for TcO 4 - removed from the SRS tank waste stream (~90% removed). The Ni-TIPA MOF sample containing ReO 4 - was prepared and shipped/planned for vitrification studies by a high-pressure technique. This research may provide a highly applicable platform for solving critical DOE and industrial problems related to nuclear environmental stewardship and nuclear power production.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Understanding and Overcoming Water-induced Interfacial Degradation in Si Modules (Final Technical Report)

Moisture ingress is an established issue for photovoltaic module durability. Durability studies probing moisture effects typically evaluate performance losses at the module level, attributing global power losses to the overall humidity condition of the test environment while leaving local module behavior unknown. This project successfully develops an in situ short-wave infrared probe of moisture content in PV modules with demonstrated detection limits better than 100 ppm in EVA-encapsulated Al-BSF and PERC architectures (66 µg/cm3) and applicability across the range of terrestrial conditions. Combining this optical moisture quantification method (water reflectometry detection, WaRD) with peel testing of interfaces, biased photoluminescence imaging of performance, and first principles computation, we correlate module moisture content and cell performance over the course of accelerated damp heat tests. By performing multi-level humidity and thermal accelerated testing over thousands of hours (0, 65 and 85% RH and 25, 65, and 85°C), we are able to attribute effects of individual environmental stresses and the dependence on module architecture. Using first-principles computational chemistry, we find that the decomposition of EVA to acetic acid (Norrish II) is thermodynamically preferred over a pathway to acetaldehyde (Norrish I), elucidating the underlying chemistry of encapsulant degradation. We also find it is likely that water segregates to the stable interfaces of the cell, especially the SiNx/EVA interface. We find that moisture is strongly correlated with reduction in adhesion at the interfaces of the cells, particularly at Ag fingers. We show uniquely that the peel strength required to delaminate the encapsulant from the front of the cell depends not only on the exposure to a high heat and humid environment, but also to the moisture content during the mechanical testing, indicating an important interaction between when mechanical stresses are faced in terms of the moisture content of the module and its durability. We find that the background sheet resistance (that is, the sheet resistance rise not attributable to finger interruptions or cracks) is substantially higher in the backsheet mini-modules vs glass-glass packages when humidity and temperature are faced. This increase in power loss due to the background resistance increase over time in damp heat in glass-backsheet modules resulted in ~3-4% larger decrease in relative PCE compared to glass-glass modules. In glass-backsheet modules, the effect of the moisture dose alone is comparable or greater than that of the combined temperature and water term, suggesting that glass-backsheet modules are overall more susceptible to moisture induced performance loss. Finally, we show that thin film PV modules are amenable to WaRD measurement, based on the ability to detect moisture in POE encapsulants or in the cell stack itself. The ease of WaRD measurement and its few requirements on the bill of materials should enable broad applicability of this technique for studying the effects of moisture in PV.

14 SOLAR ENERGY↗

Comparison of seal materials for use in Stirling engines

In a dry, reciprocating sliding test, rods of 12 different surface materials rubbed against a glass filled PTFE gas seal. To simulate operation in a Stirling engine a gas (N2) pressure of 1 MPa differential pressure was applied across the seal. Gas leakage rates, rods surface temperatures, changes in the surface finish of the rod, surface hardness of the rod and wear rate of the seals were measured. The rod surface materials that produced the least seal were: plasma sprayed molybdenum (75 Mo 18 Ni 4 Cr), gas nitrided steel, and plasma sprayed aluminum oxide (94 Al2O3 6 TiO2). In contrast to almost all other mating surfaces, the surface roughness of the rods coated with Mo did not decrease during wear. This property is very important for the formation of a PTFE transfer film on the mating surface. The presence of a stable transfer film gives a low PTFE wear rate.

Lundholm, G.↗

High Modulus and High T(sub g) Thermally Stable Polymers from p-Ethynyl-Terminated Rigid-Rod Monomers

Novel p-ethynyl-substituted rigid rod monomers were studied by pressure Differential Scanning Calorimetry (DSC), ThermoGravimetric Analysis (TGA), IsothermoGravimetric Analysis (IGA), and TGA-IR. These monomers, 4,4'-bis(((4-ethynylphenyl)carbonyl)oxy)biphenyl, designated 1, 1,5-bis-(((4-ethynylphenyl)carbonyl)oxy)naphthalene, designated 2, and bis(4-ethynylphenyl)pyromellitimide, designated 3, were polymerized in the solid state. Thermal polymerization in N2 or air produced highly cross-linked resins with polymerization exotherms centered between 212 and 276 C. The (delta)H's of polymerization of these resins in air were found to be double those in N2. When monomers 1 and 2 were heated in air from 23 to 750 C at 10 C/min, the main decomposition product was carbon dioxide, evolving at a maximum rate between 500 and 600 C; water was also detected as a decomposition product. Void-free neat resin moldings, designated lp to 3p, were made by compression molding the monomers and then heating them. The resulting polymers were highly cross-linked, and their glass transition temperatures (T(sub g)) were much higher than their polymerization temperatures. Using ThermoMechanical Analysis (TMA), we found that polymers lp to 3p had T(sub g)'s of 422, 329, and 380 C, respectively. The thermal and thermooxidative stabilities improved when lp to 3p were postcured in N2 (the postcured polymers were designated 1pp to 3pp). The Linear Thermal Expansions (LTE) for lp and 3p were 1% between 23 and 420 C. Using rheological analysis, we could not clearly detect the T(sub g)'s of lp to 3p because their moduli dropped only slightly between 23 and 490 C and the changes in tan beta were very low. Because of high cross-link density, their moduli changed little as the resins went from a glassy to a rubbery state. Their shear storage moduli in air ranged from 0.82 (3p, 3pp) to 1.6 GPa (lpp) at 23 C, from 0.16 (2p) to 0.7GPa(lpp) at 380 C, and from 0.18(lpp)to 0.6GPa(2p) at 490 C. Finally, these novel-p-ethynyl polymers exhibited an excellent combination of high T(sub g), low LTE, and high thermooxidative stability. Most notably, 3pp lost only 3% of its initial weight when it was aged for 500 h at 288 C in air.

Melissaris, Anastasios P.↗

Vortex fluidic regulated phospholipid equilibria involving liposomes down to sub-micelle size assemblies

Conventional channel-based microfluidic platforms have gained prominence in controlling the bottom-up formation of phospholipid based nanostructures including liposomes. However, there are challenges in the production of liposomes from rapidly scalable processes. These have been overcome using a vortex fluidic device (VFD), which is a thin film microfluidic platform rather than channel-based, affording ~110 nm diameter liposomes. The high yielding and high throughput continuous flow process has a 45° tilted rapidly rotating glass tube with an inner hydrophobic surface. Processing is also possible in the confined mode of operation which is effective for labelling pre-VFD-prepared liposomes with fluorophore tags for subsequent mechanistic studies on the fate of liposomes under shear stress in the VFD. In situ small-angle neutron scattering (SANS) established the co-existence of liposomes ~110 nm with small rafts, micelles, distorted micelles, or sub-micelle size assemblies of phospholipid, for increasing rotation speeds. The equilibria between these smaller entities and ~110 nm liposomes for a specific rotational speed of the tube is consistent with the spatial arrangement and dimensionality of topological fluid flow regimes in the VFD. The prevalence for the formation of ~110 nm diameter liposomes establishes that this is typically the most stable structure from the bottom-up self-assembly of the phospholipid and is in accord with dimensions of exosomes.

60 APPLIED LIFE SCIENCES↗

Upstream Ultra-Low Frequency Waves Observed by MESSENGER's Magnetometer: Implications for Particle Acceleration at Mercury's Bow Shock

We perform the first statistical analysis of the main properties of waves observed in the 0.05–0.41 Hz frequency range in the Hermean foreshock by the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) Magnetometer. Although we find similar polarization properties to the “30 second” waves observed at the Earth's foreshock, the normalized wave amplitude (δ B /|B0| ∼0.2) and occurrence rate (∼0.5%) are much smaller. This could be associated with relatively lower backstreaming proton fluxes, the smaller foreshock size and/or less stable solar wind (SW) conditions around Mercury. Furthermore, we estimate that the speed of resonant backstreaming protons in the SW reference frame (likely source for these waves) ranges between 0.95 and 2.6 times the SW speed. The closeness between this range and what is observed at other planetary foreshocks suggests that similar acceleration processes are responsible for this energetic population and might be present in the shocks of exoplanets.

N. Romanelli↗

Comparison of thermionic filament and carbon nanotube field emitter-based electron ionization sources in cycloidal coded aperture mass analyzers

This report compares the coded aperture imaging performance of thermionic filament and carbon nanotube (CNT) field emitter-based electron sources in cycloidal-coded aperture mass spectrometers. The use of spatially coded apertures in mass spectrometry enables miniaturization by improving throughput without sacrificing resolution. CNT-based electron ionization sources for mass spectrometers provide several potential benefits over conventional thermionic emitters, including low voltage and low power consumption, room temperature operation, long lifetime, and ability to emit electrons in a pulsed mode. However, spatiotemporal variation in electron emission from CNTs is a major disadvantage. In this study, electron emission stability and spatiotemporal stability of the coded aperture image were compared for coded aperture cycloidal mass analyzers with either a CNT-based ion source or a thermionic filament-based ion source. We found that the thermionic filament-based ion source produced a significantly more stable coded aperture image than the CNT based ion source. The aperture image fluctuations in the CNT-based source are likely a result of adsorption and desorption of molecules on the CNT surface that cause local work function changes and induce spatiotemporal variation in electron emission and subsequent ion generation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Synergistic foam stabilization and transport improvement in simulated fractures with polyelectrolyte complex nanoparticles: Microscale observation using laser etched glass micromodels

Inaccessibility to direct pore scale observation in hydrocarbon recovery of tight shale formations poses a great challenge to water-energy nexus initiatives and necessitates the use of high throughput technologies to emulate environmentally friendly processes. Herein, we employ a precise glass micromodel fabrication and visualization method to isolate the supercritical CO 2 bubbles surrounded by CO 2 -water lamella prepared in saline produced water stabilized with molecular complexation of zwitterionic surfactants (ZS) and polyelectrolyte complex nanoparticles (PECNP). The Selective Laser Enhanced Etching (SLE) technique was selected for micromodel simulation of high-pressure flow. Two representative designs, (1) fracture/micro-crack network 28 and (2) fracture/matrix were etched on fused silica glass with a laser printing machine and scCO 2 foam was injected to study the foamability, propagation, stability, and fluid loss properties. The highly monodispersed and uniformly distributed array of scCO 2 bubbles were detected in flow of scCO 2 foam in highly saline brine containing ionic complexes of positively charged PECNPs and ZS, whereas foam flow with the lamella containing ZS in fractures offered a noticeably large and polydisperse array of scCO 2 bubbles. scCO 2 bubble motion and deformation were traced, and local description of foam flow was visually examined. The confined array of scCO 2 bubbles stabilized by ZS in microcracks was affected by bubble growth and coalescence, whereas the super-populated array of monodispersed scC O2 bubbles with lamella containing complexes of PECNP and ZS were able to fill the channels with stable configurations within the timeframe of comparative stability measurements. The ability of complex fluid to prevent the formation damage was evaluated through fluid loss visualization in micromodels. Probing scCO 2 foam transport in homogenous porous media revealed smaller volume leak-off for scCO 2 foam containing PECNP-ZS ionic complexes.

04 OIL SHALES AND TAR SANDS↗

Preparation and characterization of poly (arylene ether isoxazole)s by fluoride ion-mediated aromatic nucleophilic displacement reactions

As part of a continuing effort to prepare novel thermally stable high-performance polymers, poly(arylene ether isoxazole)s have been prepared by fluoride ion-catalyzed aromatic nucleophilic substitution reactions with bis(trimethylsiloxyphenyl) isoxazoles and activated bisarylhalides in diphenyl sulfone. Initial investigation involving the preparation of these materials with isoxazole bisphenols and activated bisarylhalides in the presence of potassium carbonate indicated that, under reaction conditions necessary to prepare high-molecular-weight materials, the isoxazole monomer was converted to an enamino ketone. This side reaction was avoided by using fluoride as a base. However, trimethylsilyl ether derivatives of the isoxazole bisphenols were required in these polymerizations for the preparation of high-molecular-weight materials. Moderate to high inherent viscosity eta(sub inh): 0.43-0.87 dl/g) materials with good thermal stability (air: 409-477 C, helium: 435-512 C) can be prepared by the silyl ether method. Glass transition temperatures ranged from 182 to 225 C for polymers with phenyl pendants and from 170 to 214 C for those without. Molecular weight control by 2% endcapping and the incorporation of a phenyl pendant at the 4 position of the isoxazole is necessary to yield polymers soluble in polar aprotic solvents at room temperature. There is evidence, however, indicating the existence of crosslinks between the polymer chains when the silyl ether approach is utilized.

Herbert, C. G.↗

Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement

Core principles of chemistry are ubiquitously invoked to shed light on the nature of molecular level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochemistry, biology, and engineering. A detailed understanding of the physicochemical processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technological applications. This Account provides a perspective on new insights into the thermodynamic and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrices, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ~2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrices are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between melting point depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temperature 2 H wide-line nuclear magnetic resonance (NMR) spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics. In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liquids is nonuniversal and the glass transition temperature T g can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming molecular liquids, glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in T g and a pronounced slowdown of the rotational dynamics of the constituent molecules due to a change in the molecular packing between the bulk and the confined liquid, OTP displays a linear and confining-media-dependent depression of T g with increased confinement that is strongly influenced by the pore-liquid interface characteristics. This Account concludes with a focus on recent experimental evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two melting points for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were observed. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liquids. Finally, while the findings reviewed in this Account provide new insights into thermodynamic and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chemical research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hyperspectral Fluorescence and Reflectance Imaging Instrument

The system is a single hyperspectral imaging instrument that has the unique capability to acquire both fluorescence and reflectance high-spatial-resolution data that is inherently spatially and spectrally registered. Potential uses of this instrument include plant stress monitoring, counterfeit document detection, biomedical imaging, forensic imaging, and general materials identification. Until now, reflectance and fluorescence spectral imaging have been performed by separate instruments. Neither a reflectance spectral image nor a fluorescence spectral image alone yields as much information about a target surface as does a combination of the two modalities. Before this system was developed, to benefit from this combination, analysts needed to perform time-consuming post-processing efforts to co-register the reflective and fluorescence information. With this instrument, the inherent spatial and spectral registration of the reflectance and fluorescence images minimizes the need for this post-processing step. The main challenge for this technology is to detect the fluorescence signal in the presence of a much stronger reflectance signal. To meet this challenge, the instrument modulates artificial light sources from ultraviolet through the visible to the near-infrared part of the spectrum; in this way, both the reflective and fluorescence signals can be measured through differencing processes to optimize fluorescence and reflectance spectra as needed. The main functional components of the instrument are a hyperspectral imager, an illumination system, and an image-plane scanner. The hyperspectral imager is a one-dimensional (line) imaging spectrometer that includes a spectrally dispersive element and a two-dimensional focal plane detector array. The spectral range of the current imaging spectrometer is between 400 to 1,000 nm, and the wavelength resolution is approximately 3 nm. The illumination system consists of narrowband blue, ultraviolet, and other discrete wavelength light-emitting-diode (LED) sources and white-light LED sources designed to produce consistently spatially stable light. White LEDs provide illumination for the measurement of reflectance spectra, while narrowband blue and UV LEDs are used to excite fluorescence. Each spectral type of LED can be turned on or off depending on the specific remote-sensing process being performed. Uniformity of illumination is achieved by using an array of LEDs and/or an integrating sphere or other diffusing surface. The image plane scanner uses a fore optic with a field of view large enough to provide an entire scan line on the image plane. It builds up a two-dimensional image in pushbroom fashion as the target is scanned across the image plane either by moving the object or moving the fore optic. For fluorescence detection, spectral filtering of a narrowband light illumination source is sometimes necessary to minimize the interference of the source spectrum wings with the fluorescence signal. Spectral filtering is achieved with optical interference filters and absorption glasses. This dual spectral imaging capability will enable the optimization of reflective, fluorescence, and fused datasets as well as a cost-effective design for multispectral imaging solutions. This system has been used in plant stress detection studies and in currency analysis.

Ryan, Robert E.↗

Simulation of DWPF Chemical Process Cell Using a Reaction Calorimeter

The Defense Waste Processing Facility (DWPF) converts liquid radioactive waste into glass using a Sludge Receipt Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) in addition to other processes. The SRAT and SME processes can be simulated on a small-scale using the Mettler-Toledo Reaction Calorimeter (RC1). This equipment is able to automate the execution and monitoring of experiments involving nonradioactive chemical simulants. During the chemical processing of sludge in the SRAT process, foam begins to form and can foam over the reaction vessel. The current antifoam used at DWPF creates a risk of increased flammability and has a limited pH range. Usually, mercury is circulated back into the reaction vessel during the SRAT process, making it difficult to remove. To combat foam over, novel antifoams will be tested during the boil-up process using the RC1. To improve mercury extraction, 3D-printed coalescer columns will be tested within the Mercury Water Wash Tank (MWWT) of the RC1. Testing of Simulant Sludge Batch 6 (SB6) was performed to ensure: the sludge would form a stable foam at boiling during full SRAT/SME runs; the antifoam would reduce the amount of foam within the vessel The sludge and a Precipitate Reactor Feed Tank (PRFT) simulant with monosodium titanate (MST) were mixed separately, combined, and then heated to boiling. As shown below, the antifoam used was able to eliminate the foam within the vessel, as expected. The FormLabs Form2 3D Printer can be used to create roughly 3-inch tall and 1-inch diameter columns from clear and ceramic resins. The columns will utilize chemical and physical forces to draw the mercury out of a condensed offgas stream leaving the RC1 reaction vessel. These columns will be tested during full SRAT/SME runs on the basis of how well they are able to collect elemental mercury. In preparation for full-scale runs, the RC1 equipment was assembled onto a custom table and tested with water runs. The software used to control automation, iControl, has a user-friendly interface that allows the experiment to be altered as needed. An example of the data recorded during an experimental run is represented in Figure 1 below. Water runs were utilized as a way to prove if the RC1 system was functioning in the following areas: Boil-up rates, Chemical additions using pumps, Temperature readings, Balance readings, Probe readings, Offgas system, Agitation. Future Plans: Five novel antifoams will be tested during full SRAT/SME runs. The most effective antifoam will be utilized in DWPF's Chemical Process Cell. The design of the Mercury Extraction Coalescer can be further manipulated to increase the extraction of not only elemental mercury, but other heavy metals in environmental remediation processes as well.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗