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Bottlebrush Polymers at Liquid Interfaces: Assembly Dynamics, Mechanical Properties, and All-Liquid Printed Constructs
Bottlebrush polymer surfactants (BPSs), formed by the interfacial interactions between bottlebrush polymers (BPs) with poly(acrylic acid) side chains dissolved in an aqueous phase and amine-functionalized ligands dissolved in the oil phase, assemble and bind strongly to the fluid-fluid interface. The ratio between N BB (backbone degree of polymerization) and N SC (side chain degree of polymerization) defines the initial assembly kinetics, interface packing efficiency, and stress relaxation. The equilibrium interfacial tension (γ) increases when N BB < N SC , but decreases when N BB $\gg$ N SC , correlating to a pronounced change in the effective shape of the BPs from being spherical to worm-like structures. The apparent surface coverage (ASC), i.e., the interfacial packing efficiency, decreases as N BB increases. The dripping-to-jetting transition of an injected polymer solution, as well as fluorescence recovery after photobleaching experiments, revealed faster initial assembly kinetics for BPs with higher N BB . Furhter, Euler buckling of BPS assemblies with different N BB values was used to characterize the stress relaxation behavior and bending modulus. The stress relaxation behavior was directly related to the ASC, reflecting the strong influence of macromolecular shape on packing efficiency. The bending modulus of BPSs decreases for N BB < N SC , but increased when N BB $\gg$ N SC , showing the effect of molecular architecture and multisite anchoring. All-liquid printed constructs with lower N BB BPs yielded more stable structured liquids, underscoring the importance of macromolecular packing efficiency at fluid interfaces. Overall, this work elucidates fundamental relationships between nanoscopic structures and macroscopic properties associated with various bottlebrush polymer architectures, which translate to the stabilization of all-fluidic printed constructs.
Structural and dynamic mechanisms for coupled folding and tRNA recognition of a translational T-box riboswitch
T-box riboswitches are unique riboregulators where gene regulation is mediated through interactions between two highly structured RNAs. Despite extensive structural insights, how RNA-RNA interactions drive the folding and structural transitions of T-box to achieve functional conformations remains unclear. Here, by combining SAXS, single-molecule FRET and computational modeling, we elaborate the folding energy landscape of a translational T-box aptamer consisting of stems I, II and IIA/B, which Mg 2+ -induced global folding and tRNA binding are cooperatively coupled. smFRET measurements reveal that high Mg 2+ stabilizes IIA/B and its stacking on II, which drives the pre-docking of I and II into a competent conformation, subsequent tRNA binding promotes docking of I and II to form a high-affinity tRNA binding groove, of which the essentiality of IIA/B and S-turn in II is substantiated with mutational analysis. We highlight a delicate balance among Mg 2+ , the intra- and intermolecular RNA-RNA interactions in modulating RNA folding and function.
Superposition of dynamic mechanical properties in the glassy state
Glassy state beta transition temperatures in cured epoxy resins, showing diglycidyl ether of bisphenol A /DGEBA/ dependence
A comparison of some static and dynamic mechanical properties of 18 x 5.5 and 49 x 17 type 7 aircraft tires as measured by three test facilities
The properties were measured during static, slow rolling, and high-speed tests, and comparisons were made between data as acquired on indoor drum dynamometers and on an outdoor test track. In addition, mechanical properties were also obtained from scale model tires and compared with corresponding properties from full-size tires. While the tests covered a wide range of tire properties, results seem to indicate that speed effects are not large, scale models may be used for obtaining some but not all tire properties, and that predictive equations developed in NASA TR R-64 are still useful in estimating most mechanical properties.
Investigation of the equatorial orographic-dynamic mechanism applying the bounded derivative method
A system of equations which describe the motion of a barotropic fluid in the presence of bottom topography are presented. The mathematical expression for orography is developed and the bounded derivative initialization method is applied to suppress gravitational oscillations. A stationary orographic trough is simulated. The geopotential and zonal motion have maximum deviation from the mean state at the top of the mountain. Regarding meridional speed, outflow occurs on the windward slope and inflow on the leeward slope. Divergence of order (10(-6)s(-1) is found on the windward slope while convergence of the same order of magnitude resides on the leeward slope. This outcome may have interesting implications regarding real climatology occurring over the equatorial regions of continental land masses.
Carboxyl-terminated butadiene-acrylonitrile-modified epoxy resin and its graphite fiber-reinforced composite - Morphology and dynamic mechanical properties
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An investigation of the equatorial orographic-dynamic mechanism
A barotropic model over an equatorial beta-plane is used to investigate the response when a uniform zonal current crosses an isolated hypothetical mountain centered at the equator. The bounded derivative initialization method is applied to suppress gravity-inertia motions. A quasi-stationary trough is generated at the top of the orography. Its intensity is greater in the easterly case than in the westerly case of the initial zonal current. A diagnostic equation is derived to interpret this difference in the solution. The quasi-stationary orographic divergence field which is positive on the windward slope and negative on the leeward slope (for both easterly and westerly cases of the initial zonal current) is responsible for maintaining the trough. The difference in the intensity of the trough is due to the contribution of the beta-u effect, which changes sign with the direction of the initial zonal flow.
Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanism in Stratospheric Models
We proposed model-data intercomparison studies for UARS data. In the past three months, we have been working on constructing analysis tools to diagnose the UARS data. The 'Trajectory mapping' technique, which was developed by Morris (1994), is adaptable to generate synoptic maps of trace gas data from asynoptic observations. An in-house trajectory model (kinematic methods following Merrill et al., 1986 and Pickering et al., 1994) has been developed in AER under contract with NASA/ACMAP and the trajectory mapping tool has been applied to analyze UARS measurement.
Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanism in Stratospheric Models
UARS data sets provide global coverage for the distributions of trace gases, which gives us an excellent chance to utilize the data set for model-data intercomparison studies. In the past three months, we have been working on the comparisons of the UARS data between 1992 (a half year after the Pinatubo eruption) and 1993 (one and a half year after the eruption) in an attempt to see how the Pinatubo volcanic eruption may have impacted stratospheric chemistry.
Dynamic Mechanical Characterization of Thin Film Polymer Nanocomposites
Many new materials are being produced for aerospace applications with the objective of maximizing certain ideal properties without sacrificing others. Polymer composites in various forms and configurations are being developed in an effort to provide lighter weight construction and better thermal and electrical properties and still maintain adequate strength and stability. To this end, thin film polymer nanocomposites, synthesized for the purpose of influencing electrical conductivity using metal oxide particles as filler without incurring losses in mechanical properties, were examined to determine elastic modulus and degree of dispersion of particles. The effects of various metal oxides on these properties will be discussed.
Verification of a 2 kWe Closed-Brayton-Cycle Power Conversion System Mechanical Dynamics Model
Vibration test data from an operating 2 kWe closed-Brayton-cycle (CBC) power conversion system (PCS) located at the NASA Glenn Research Center was used for a comparison with a dynamic disturbance model of the same unit. This effort was performed to show that a dynamic disturbance model of a CBC PCS can be developed that can accurately predict the torque and vibration disturbance fields of such class of rotating machinery. The ability to accurately predict these disturbance fields is required before such hardware can be confidently integrated onto a spacecraft mission. Accurate predictions of CBC disturbance fields will be used for spacecraft control/structure interaction analyses and for understanding the vibration disturbances affecting the scientific instrumentation onboard. This paper discusses how test cell data measurements for the 2 kWe CBC PCS were obtained, the development of a dynamic disturbance model used to predict the transient torque and steady state vibration fields of the same unit, and a comparison of the two sets of data.
Hybrid Gear Preliminary Results-Application of Composites to Dynamic Mechanical Components
Composite spur gears were fabricated and then tested at NASA Glenn Research Center. The composite material served as the web of the gear between the gear teeth and a metallic hub for mounting to the torque-applying shaft. The composite web was bonded only to the inner and outer hexagonal features that were machined from an initially all-metallic aerospace quality spur gear. The Hybrid Gear was tested against an all-steel gear and against a mating Hybrid Gear. As a result of the composite to metal fabrication process used, the concentricity of the gears were reduced from their initial high-precision value. Regardless of the concentricity error, the hybrid gears operated successfully for over 300 million cycles at 10000 rpm and 490 in.*lbs torque. Although the design was not optimized for weight, the composite gears were found to be 20% lighter than the all-steel gears. Free vibration modes and vibration/noise tests were also conduct to compare the vibration and damping characteristic of the Hybrid Gear to all-steel gears. The initial results indicate that this type of hybrid design may have a dramatic effect on drive system weight without sacrificing strength.
Evaluation of Nanomaterial Approaches to Damping in Epoxy Resin and Carbon Fiber/Epoxy Composite Structures by Dynamic Mechanical Analysis
Vibration mitigation in composite structures has been demonstrated through widely varying methods which include both active and passive damping. Recently, nanomaterials have been investigated as a viable approach to composite vibration damping due to the large surface available to generate energy dissipation through friction. This work evaluates the influence of dispersed nanoparticles on the damping ratio of an epoxy matrix. Limited benefit was observed through dispersion methods, however nanoparticle application as a coating resulting in up to a three-fold increase in damping.
Dynamic Mechanisms Associated with the Structure and Evolution of Roll Vortices and Coherent Turbulence in the Hurricane Boundary Layer: A Large Eddy Simulation During the Landfall of Hurricane Harvey
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Unraveling the convoluted and dynamic interphasial mechanisms on Li metal anode
Accurate understanding of the chemistry of solid-electrolyte interphase (SEI) is key to developing new electrolytes for high-energy batteries using lithium metal (Li-0) anodes(1). SEI is generally believed to be formed by the reactions between Li-0 and electrolyte(2,3). However, our new study shows this is not the whole story. Through synchrotron-based X-ray diffraction and pair distribution function analysis, we reveal a much more convoluted formation mechanism of SEI, which receives considerable contributions from electrolyte, cathode, moisture and native surface species on Li-0, with highly dynamic nature during cycling. Using isotope labelling, we traced the origin of LiH to electrolyte solvent, moisture and a new source: the native surface species (LiOH) on pristine Li-0. When lithium accessibility is very limited as in the case of anode-free cells, LiOH develops into plate-shaped large crystals during cycling. Alternatively, when the lithium source is abundant, as in the case of Li||NMC811 cells, LiOH reacts with Li-0 to form LiH and Li2O. While the desired anion-derived LiF-rich SEI is typically found in the concentrated electrolytes or their derivatives, we found it can also be formed in low-concentration electrolyte via the crosstalk effect, emphasizing the importance of formation cycle protocol and opening up opportunities for low-cost electrolyte development.
Viscosity-Controlled Thiol–Ene Reaction and Its Impact on Mechanical Response of Dynamic Networks
The impact of curing conditions on the final properties of thioester-thiol-based dynamic polymer networks was systematically investigated. Despite identical monomer and cross-linker compositions, networks synthesized in the absence of solvent exhibited significantly higher shear moduli and longer relaxation times compared to those cured in solvent. These differences arise from viscosity-controlled photoinitiated thiol–ene reactions, where reduced chain mobility under solvent-free conditions suppresses termination between two polymer radicals, leading to higher reaction conversion. Fourier Transform Infrared (FTIR) spectroscopy and solid-state NMR (ssNMR) spectroscopy confirmed a greater degree of “click” reaction completion in higher viscosity environments. Control experiments revealed that prolonged radical lifetimes and suppressed termination reactions under solvent-free curing conditions contribute to these variations. Here, this study highlights the crucial role of processing conditions in determining cross-link density and, consequently, the dynamic mechanical behavior of polymer networks. It demonstrates that, beyond polymer chemistry, dynamic cross-linker design, and phase separation, curing conditions serve as a key design parameter for tailoring material performance to specific applications.
Solute/twin boundary interaction as a new atomic-scale mechanism for dynamic strain aging
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