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At least 667 records · Page 37

ZBLAN Viscosity Instrumentation

The past year's contribution from Dr. Kaukler's experimental effort consists of these 5 parts: a) Construction and proof-of-concept testing of a novel shearing plate viscometer designed to produce small shear rates and operate at elevated temperatures; b) Preparing nonlinear polymeric materials to serve as standards of nonlinear Theological behavior; c) Measurements and evaluation of above materials for nonlinear rheometric behavior at room temperature using commercial spinning cone and plate viscometers available in the lab; d) Preparing specimens from various forms of pitch for quantitative comparative testing in a Dynamic Mechanical Analyzer, Thermal Mechanical Analyzer; and Archeological Analyzer; e) Arranging to have sets of pitch specimens tested using the various instruments listed above, from different manufacturers, to form a baseline of the viscosity variation with temperature using the different test modes offered by these instruments by compiling the data collected from the various test results. Our focus in this project is the shear thinning behavior of ZBLAN glass over a wide range of temperature. Experimentally, there are no standard techniques to perform such measurements on glasses, particularly at elevated temperatures. Literature reviews to date have shown that shear thinning in certain glasses appears to occur, but no data is available for ZBLAN glass. The best techniques to find shear thinning behavior require the application of very low rates of shear. In addition, because the onset of the thinning behavior occurs at an unknown elevated temperature, the instruments used in this study must provide controlled low rates of shear and do so for temperatures approaching 600 C. In this regard, a novel shearing parallel plate viscometer was designed and a prototype built and tested.

Kaukler, William↗

Chemoviscosity modeling for thermosetting resin systems, part 3

A new analytical model for simulating chemoviscosity resin has been formulated. The model is developed by modifying the well established Williams-Landel-Ferry (WLF) theory in polymer rheology for thermoplastic materials. By introducing a relationship between the glass transition temperature (T sub g (t)) and the degree of cure alpha(t) of the resin system under cure, the WLF theory can be modified to account for the factor of reaction time. Temperature-dependent functions of the modified WLF theory parameters C sub 1 (T) and C sub 2 (T) were determined from the isothermal cure data. Theoretical predictions of the model for the resin under dynamic heating cure cycles were shown to compare favorably with the experimental data. This work represents a progress toward establishing a chemoviscosity model which is capable of not only describing viscosity profiles accurately under various cure cycles, but also correlating viscosity data to the changes of physical properties associated with the structural transformations of the thermosetting resin systems during cure.

Hou, T. H.↗

Estimation of the viscosities of silicate liquids at high pressure from measurements of oxygen diffusivity

The dynamics and evolution of a magma ocean depend significantly on the structure and physical properties of silicate liquids at high pressure. Viscosity is particularly important because of its effect on the dynamics of convection and crystal setting. Traditionally, the viscosities of silicate liquids have been measured at high pressure by falling sphere viscometry but, due to some limitations of this technique, few measurements have been made at pressures exceeding 2.5 GPa. An alternative approach, which has previously been proven up to 2 GPa, is to use high pressure measurements of oxygen self-diffusivity (D) to estimate viscosity (eta) from the Eyring relationship eta = kT/D lambda (where k is the Boltzmann constant, T is absolute temperature, and lambda is the diffusive jump distance). We have performed preliminary experiments on Na2Si4O9 liquid in order to explore the feasibility of this method up to pressures in excess of 10 GPa. Diffusion couples were prepared from glass starting materials with one half of the sample enriched in O-18 and the other half containing the natural abundance (0.2 wt percent). Diffusion experiments were performed at 1600 to 1800 C at pressures in the range of 2.5 to 10 GPa for times up to 6 minutes using a 1200 ton multianvil apparatus. Oxygen diffusivities were derived from the resulting O-18 concentration profiles, which were analyzed using an ion microprobe. At 1800 C, oxygen diffusivities increase continuously from 1 x 10(exp -10) m(exp -2) s(exp -1) at 2.5 Gpa to 5 x 10(exp -10) m(exp -2) s(exp -1) at 10 GPa. From the Eyring relationship, the viscosity of Na2SiO9 liquid is predicted to decrease by approx. 0.7 log units over this pressure range at 1800 C. These trends, which can be related to changes in the structure of the liquid at high pressure, are in agreement with results of molecular dynamics calculations. These results suggest that it should be possible to estimate the viscosities of silicate liquids up to at least 15 GPa and 2200 C by this method.

Rubie, D. C.↗

Cation-Diffusive Carbon Interlayers Stabilize Na Metal and Double the Current in Na-S Redox-Flow Batteries for Grid-Scale Energy Storage

The sodium-sulfur nonaqueous redox-flow batteries (Na-S NARFBs) using earth-abundant elements are highly attractive due to the low material cost and improved energy density for grid-scale energy storage. However, the low current performance, poor Na0/Na+ redox kinetics, and Na dendrite growth pose severe challenges. We introduce cation-diffusive layers (CDLs): thin and Na+ affinitive interlayers at the Na anode that direct Na+ transport and stabilize Na deposition. Benchmarking three archetypal materials—carbon paper (CP), glass microfiber paper (GF), and foam—across Na-Na and Na-Cu, and Na-S cells identifies CP as the optimum. CP reduces symmetric cell overpotential by more than 70%, achieves 98% Na plating-stripping efficiency, and doubles the Na-S cell current density from 0.5 to 1.0 mA cm−2 without sacrificing capacity or efficiency. Ex situ electrochemical and SEM/XPS analysis, combined with molecular dynamics (MD) studies, reveal that electron-rich carbon fibers disperse supporting salt aggregates, enrich near-surface Na+ density, and create ion transport pathways for fast Na0/Na+ exchange while mitigating membrane degradation. Because of the ion-centric mechanism, CDLs can be generalized to other metal-anode designs. Further, this work establishes CDL design rules—cationic affinity and appropriate micro/nanostructure—as a simple, scalable route to high-current, durable metal-anode flow batteries.

Wu, Wenda [ORNL] (ORCID:000900033307687X)↗

Degradation of Insulating Glass Units: Thermal Performance, Measurements and Energy Impacts

Insulating glass unit (IGU) degradation has been studied extensively. However, there is limited understanding of how present durability evaluation standards relate to product lifetime. Furthermore, there is debate on how to quantify performance of installed windows over time to better understand degradation processes. More knowledge on these topics is required to link durability evaluation to product lifetime projections based on energy performance. Energy models provide helpful estimations of total annual building energy consumption. However, most models are based on “as installed” performance of envelope components and fail to account for performance degradation. This can lead to an underestimation of building lifetime energy consumption. A better understanding of the relationship between durability and energy performance can inform integration of degradation dynamics into energy modeling software. This will improve lifetime building energy consumption estimations as well as inform appropriate retrofit strategies and timing. This paper reviews current durability literature, various standards for window performance ratings and weathering methods, existing in situ IGU energy performance measurement techniques, and whole-building energy effects. The challenges and disparities among various studies are analyzed and discussed. The authors hope that further work in this area will lead to the development of improved in situ test methods to assess IGU degradation in the field and link this knowledge to improved energy performance modeling approaches.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Dynamics of the iron spins in superconducting YBa2(Cu(1-x)Fe(x))O7

The dynamics of the iron spins in YBa2(Cu(1-x)Fe(x))3O7 alloys (0 = to or less than 0.12) was studied by the means of inelastic neutron scattering. Measurements were performed using the time of flight technique with an excellent resolution of 50 micro eV, in a temperature range of 1.8 to 300 K. The doped samples show an elastic and a quasielastic intensity strongly varying with temperature. A spin glass like freezing is revealed at low temperature by a sudden decrease of the quasielastic intensity, an increase of the elastic or resolution limited intensity and a minimum in the quasielastic width. The freezing temperature corresponds to the one already determinated by a magnetic splitting in Mossbauer experiments. Above freezing, the occurrence of superconductivity slightly modifies the characteristics of the spin relaxation in the paramagnetic state, as shown by measurements in two x = 0.06 samples. In the whole temperature range of measurement, the dependence of the quasielastic intensity with the scattering vector q, mainly reflects the variation of the Iron form factor, which shows that the spins are almost uncorrelated.

Mirebeau, I.↗

Rb-Sr and Sm-Nd Isotopic Studies of Lunar Green and Orange Glasses

Lunar volcanic glassy beads have been considered as quenched basaltic magmas derived directly from deep lunar mantle during fire-fountaining eruptions [1]. Since these sub-mm size glassy melt droplets were cooled in a hot gaseous medium during free flight [2], they have not been subject to mineral fractionations. Thus, they represent primary magmas and are the best samples for the investigation of the lunar mantle. Previously, we presented preliminary Rb- Sr and Sm-Nd isotopic results for green and orange glassy samples from green glass clod 15426,63 and orange soil 74220,44, respectively [3]. Using these isotopic data, initial Sr-87/Sr-86 and Nd ratios for these pristine mare glass sources can be calculated from their respective crystallization ages previously determined by other age-dating techniques. These isotopic data were used to evaluate the mineralogy of the mantle sources. In this report, we analyzed additional glassy samples in order to further characterize isotopic signatures of their source regions. Also, we'll postulate a relationship between these two major mare basalt source mineralogies in the context of lunar magma ocean dynamics.

Shih, C.-Y.↗

Drop dynamics in space and interference with acoustic field (M-15)

The objective of the experiment is to study contactless positioning of liquid drops, excitation of capillary waves on the surface of acoustically levitated liquid drops, and deformation of liquid drops by means of acoustic radiation pressure. Contactless positioning technologies are very important in space materials processing because the melt is processed without contacting the wall of a crucible which can easily contaminate the melt specifically for high melting temperatures and chemically reactive materials. Among the contactless positioning technologies, an acoustic technology is especially important for materials unsusceptible to electromagnetic fields such as glasses and ceramics. The shape of a levitated liquid drop in the weightless condition is determined by its surface tension and the internal and external pressure distribution. If the surface temperature is constant and there exist neither internal nor external pressure perturbations, the levitated liquid drop forms a shape of perfect sphere. If temperature gradients on the surface and internal or external pressure perturbations exist, the liquid drop forms various modes of shapes with proper vibrations. A rotating liquid drop was specifically studied not only as a classical problem of theoretical mechanics to describe the shapes of the planets of the solar system, as well as their arrangement, but it is also more a contemporary problem of modern non-linear mechanics. In the experiment, we are expecting to observe various shapes of a liquid drop such as cocoon, tri-lobed, tetropod, multi-lobed, and doughnut.

Yamanaka, Tatsuo↗

Thermo-mechanical deterioration and molecular degradation of 3D-printed methacrylate-based polymer in various chemical environments

The advancement of additive manufacturing (AM) has accelerated the development of stereolithographic (SLA) photo-curable resins, particularly methacrylate-based polymers, due to the ability to their high-resolution, robust mechanical properties, and suitability. However, their long-term performance in chemical environments remains poorly understood. This study investigates the extent and mechanisms of degradation on an SLA-printed methacrylate-based polymer subjected to various chemicals, including polar and non-polar solvents, as well as strongly acidic aqueous solutions over a 12-week accelerated aging period. A comprehensive analytical approach incorporating swelling kinetics, surface morphology, tensile and dynamic mechanical analysis (DMA), Fourier-transform infrared (FTIR) spectroscopy, and mass spectrometry (MS) was employed to characterize chemical absorption, structural integrity, and leached products. Results reveal that degradation severity is governed by both the polarity and reactivity of the chemical environment. Notably, exposure to 6 mol L -1 HNO₃ induced the most severe deterioration, with over threefold higher swelling compared to other media, and significant reductions in tensile strength, tensile modulus, and glass transition temperature (T g ). In contrast, specimens aged in non-polar solvents (xylene and dodecane) exhibited negligible chemical interaction and retained mechanical performance. FTIR and MS analyses identified acid-catalyzed hydrolysis of ester groups as prominent degradation pathways in acidic media, while diffusion-controlled plasticization prevailed in polar solvents. Furthermore, this study provides valuable insights into the chemical stability of SLA-printed polymers and develops predictive degradation profiles that are crucial for designing durable polymer systems for advanced industrial use.

36 MATERIALS SCIENCE↗

Segmental relaxation of sequence defined polymers

For this work, the dynamical behavior of sequence defined polymers, P(C n EG 4 ), was studied using dielectric spectroscopy showing one segmental relaxation in addition to a secondary relaxation. In case of segmental relaxation, the relaxation times strongly depend on the molecular weight at low temperatures, while at higher temperatures, unlike to linear homo polymers, this effect levels out. With increasing length of C-units, the segmental relaxation accelerates. This is also reflected in the glass transition temperature, extracted from dielectric spectroscopy. With increasing length of C-units the glass transition temperature decreases, compatible with the accelerated segmental relaxation.

36 MATERIALS SCIENCE↗

Dynamic dielectric analysis for nondestructive cure monitoring and process control

Dynamic dielectric analysis (DDA) is an effective in situ NDE method that can monitor the reaction status in thermosets and the phase changes in thermoplastics, including slow reactions occuring late in the cure cycle and recrystallization during annealing. The effects of moisture and resin history on reaction rate can also be determined, as can ionic and dipolar contributions. The ionic mobility parameter is noted to be an excellent monitor of viscosity above the glass transition temperature. The ability of DDA to monitor cure rate variations in a thick section during autoclaving has been demonstrated.

Kranbuehl, D. E.↗

Tissue Photolithography

Tissue lithography will enable physicians and researchers to obtain macromolecules with high purity (greater than 90 percent) from desired cells in conventionally processed, clinical tissues by simply annotating the desired cells on a computer screen. After identifying the desired cells, a suitable lithography mask will be generated to protect the contents of the desired cells while allowing destruction of all undesired cells by irradiation with ultraviolet light. The DNA from the protected cells can be used in a number of downstream applications including DNA sequencing. The purity (i.e., macromolecules isolated form specific cell types) of such specimens will greatly enhance the value and information of downstream applications. In this method, the specific cells are isolated on a microscope slide using photolithography, which will be faster, more specific, and less expensive than current methods. It relies on the fact that many biological molecules such as DNA are photosensitive and can be destroyed by ultraviolet irradiation. Therefore, it is possible to protect the contents of desired cells, yet destroy undesired cells. This approach leverages the technologies of the microelectronics industry, which can make features smaller than 1 micrometer with photolithography. A variety of ways has been created to achieve identification of the desired cell, and also to designate the other cells for destruction. This can be accomplished through chrome masks, direct laser writing, and also active masking using dynamic arrays. Image recognition is envisioned as one method for identifying cell nuclei and cell membranes. The pathologist can identify the cells of interest using a microscopic computerized image of the slide, and appropriate custom software. In one of the approaches described in this work, the software converts the selection into a digital mask that can be fed into a direct laser writer, e.g. the Heidelberg DWL66. Such a machine uses a metalized glass plate (with chrome metallization) on which there is a thin layer of photoresist. The laser transfers the digital mask onto the photoresist by direct writing, with typical best resolution of 2 micrometers. The plate is then developed to remove the exposed photoresist, which leaves the exposed areas susceptible to chemical chrome etch. The etch removes the unprotected chrome. The rest of the photoresist is then removed, by either ultraviolet organic solvent or over-development. The remaining chrome pattern is quickly oxidized by atmospheric exposure (typically within 30 seconds). The ready chrome mask is now applied to the tissue slide and aligned manually, or using automatic software and pre-designed alignment marks. The slide plate sandwich is then exposed to UV to destroy the DNA of the unwanted cells. The slide and plate are separated and the slide is processed in a standard way to prepare for polymerase chain reaction (PCR) and potential identification of cancer sequences.

Wade, Lawrence A.↗

Chain dynamics of alternating polymers P(C n EG 4 )

Alternating or sequence defined polymers attract the attention of an increasing number of researchers recently. Due to their different blocks, they are very customizable and material properties can be tuned. In this publication, we present dynamical studies with focus on polymer dynamics, investigated by rheology and fast field cycling (FFC) NMR. The molecular weight dependencies of the relaxation time and zero-shear viscosity could hint to entanglement effects; however, the spectral shape of the viscoelastic data resembles the polymer dynamics of unentangled melts. Furthermore, taking both techniques into account, i.e. rheology and FFC NMR leads to the conclusion that the relaxation spectra of the alternating polymer are similar to those of linear polymers.

36 MATERIALS SCIENCE↗

Gas transport characteristics of supramolecular networks of metal-coordinated highly branched Poly(ethylene oxide)

Model systems are developed and investigated to better understand the effect of polyether-metal ion interactions on gas separation characteristics. These systems help answer current questions raised by the substantial body of research on metal-organic frameworks (MOFs) dispersed in polyethers to improve gas separation performance, where favorable interactions between the metal centers and polyethers are preferred to improve interfacial compatibility. Specifically, we investigate CO 2 /gas transport properties of supramolecular networks comprising cross-linked poly(ethylene oxide) (XLPEO) and dissociable salts, including LiClO 4 , Ni(BF 4 ) 2 , and Cu(BF 4 ) 2 . Increasing the salt content increases the glass transition temperature (T g ) and generally decreases gas diffusivity and permeability, which can be successfully described using a T g -integrated free volume model with an expression similar to the Vogel-Tammann-Fulcher (VTF) equation. Surprisingly, low loadings of LiClO 4 and Cu(BF 4 ) 2 (2 mass% or less) can increase gas permeability by 30%–70% without affecting the CO 2 /gas selectivity. This increase correlates with polyether-metal ion dynamics as measured by dielectric spectroscopy. Understanding how interaction-mediated dynamics affect gas transport will be instrumental to designing MOF-based mixed matrix materials for gas separations.

36 MATERIALS SCIENCE↗

Perovskite-Derived Cs 2 SnCl 6 –Silica Composites as Advanced Waste Forms for Chloride Salt Wastes

Advanced materials and processes are required to separate halides and fission products from complex salt waste streams associated with the chemical reprocessing of used nuclear fuels and molten salt reactor technologies for immobilization into chemically durable waste forms. Here, in this work, we explore an innovative concept using metal-halide perovskites as advanced host phases to incorporate Cs and Cl with very high waste loadings. Wet chemistry-synthesized Cs 2 SnCl 6 powders from CsCl salt solutions are successfully encapsulated into a silica matrix to form a composite using low-temperature spark plasma sintering with tunable Cs and Cl loadings up to 31 wt.% and 26 wt.%, respectively. Chemical durability testing of the composite waste forms by semi-dynamic leaching experiments demonstrates that incongruent leaching mechanism dominated. The metal-halide perovskite-silica composite waste forms display exceptional chemical durability with the long-term release rates of Cs and Cl comparable to or outperforming the state-of-the-art waste form materials but with significantly higher waste loadings. The scalable synthesis of the metal-halide perovskite from wet-chemistry processes opens up new opportunities in designing perovskite-glass composite waste forms for salt wastes with very high waste loadings and exceptional chemical durability for the sustainable development of advanced fuel cycles and next-generation reactor technologies.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Pseudogap in electron-doped cuprates: Strong correlation leading to band splitting

The pseudogap phenomena have been a long-standing mystery of the cuprate high-temperature superconductors. The pseudogap in the electron-doped cuprates has been attributed to band folding due to antiferromagnetic (AFM) long-range order or short-range correlation. We performed an angle-resolved photoemission spectroscopy study of the electron-doped cuprates Pr 1.3−x La 0.7 Ce x CuO 4 showing spin-glass, disordered AFM behaviors, and superconductivity at low temperatures and, by measurements with fine momentum cuts, found that the gap opens on the unfolded Fermi surface rather than the AFM Brillouin zone boundary. The gap did not show a node, following the full symmetry of the Brillouin zone, and its magnitude decreased from the zone-diagonal to (π,0) directions, opposite to the hole-doped case. These observations were reproduced by cluster dynamical-mean-field-theory calculation, which took into account electron correlation precisely within a (CuO 2 ) 4 cluster. In conclusion, the present experimental and theoretical results are consistent with the mechanism that electron or hole doping into a Mott insulator creates an in-gap band that is separated from the upper or lower Hubbard band by the pseudogap.

74 ATOMIC AND MOLECULAR PHYSICS↗

Cross-Effects in Microgravity Flows

Film growth by chemical/physical vapor deposition is a process of considerable interest in microgravity experiments. The absence of natural convection should allow better control of film growth processes but, in highly non-isothermal ampoules, thermal slip (creep) can become a matter of significant concern. The reported research is a theoretical and experimental investigation of the flow of gas/vapor mixtures under non-continuum conditions. The Boltzmann equation has been solved for a monatomic gas under non-condensing conditions and the various phenomenological coefficients have been computed. Computations for realistic potentials as well as for velocity and creep slip have been completed and the creep slip has been found to be dependent on the type of gas confirming the accuracy of previous variational results. The variational technique has been extended and planar flows calculated via the Burnett solutions. Velocity, diffusion and creep slips have been computed for gas mixtures and previously unknown dependencies of the creep slip on the mixture properties have been observed. Also for gas mixtures, an integral representation of the linearized Boltzmann operator has been developed for use in numerical and variational calculations for all intermolecular force laws. Two, two-bulb capillary systems have been designed, built and tested for the measurements of cross-flows; one of glass for isothermal measurements and one of stainless steel for non-isothermal measurements. Extensive data have been collected for Ar-He and N2-He mixtures at a variety of pressures and mole ratios. Viscosity, velocity slip coefficients and tangential momentum accommodation coefficients have been obtained from measurements with a spinning rotor gauge via a new theory that has been formulated for the spinning rotor gauge in the slip regime. The FIDAP fluid dynamics code has been applied to condensing flows in ampoules in the continuum regime and agreement obtained with the earlier work of Duval.

Loyalka, Sudarshan K.↗

Honeycomb Core Permeability Under Mechanical Loads

A method for characterizing the air permeability of sandwich core materials as a function of applied shear stress was developed. The core material for the test specimens was either Hexcel HRP-3/16-8.0 and or DuPont Korex-1/8-4.5 and was nominally one-half inch thick and six inches square. The facesheets where made of Hercules' AS4/8552 graphite/epoxy (Gr/Ep) composites and were nominally 0.059-in. thick. Cytec's Metalbond 1515-3M epoxy film adhesive was used for co-curing the facesheets to the core. The permeability of the specimens during both static (tension) and dynamic (reversed and non-reversed) shear loads were measured. The permeability was measured as the rate of air flow through the core from a circular 1-in2 area of the core exposed to an air pressure of 10.0 psig. In both the static and dynamic testing, the Korex core experienced sudden increases in core permeability corresponding to a core catastrophic failure, while the URP core experienced a gradual increase in the permeability prior to core failure. The Korex core failed at lower loads than the HRP core both in the transverse and ribbon directions.

Glass, David E.↗