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All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Particulate Titanium Matrix Composites Tested--Show Promise for Space Propulsion Applications

Uniformly distributed particle-strengthened titanium matrix composites (TMCs) can be manufactured at lower cost than many types of continuous-fiber composites. The innovative manufacturing technology combines cold and hot isostatic pressing procedures to produce near-final-shape components. Material stiffness is increased up to 26-percent greater than that of components made with conventional titanium materials at no significant increase in the weight. The improved mechanical performance and low-cost manufacturing capability motivated an independent review to assess the improved properties of ceramic titanium carbide (TiC) particulate-reinforced titanium at elevated temperature. Researchers at the NASA Glenn Research Center creatively designed and executed deformation and durability tests to reveal operating regimes where these materials could lower the cost and weight of space propulsion systems. The program compares the elevated-temperature performance of titanium alloy Ti-6Al-4V matrix material to an alloy containing 10 wt% of TiC particles. Initial experiments showed that at these relatively low particle concentrations the material stiffness of the TMC was improved 20 percent over that of the plain Ti-6Al-4V alloy when tested at 427 C. The proportional limit and ultimate strength of the composite in tension are 21- and 14-percent greater than those of the plain alloy. Compression tests showed that the proportional limit is about 30 percent greater for TMC than for the plain alloy. The enhanced deformation resistance of the TMC was also evident in a series of tensile and compressive stress relaxation tests that were made. Specimens were subjected to tensile or compressive strain amplitudes of 0.75 percent for 24 hr followed by a return to zero strain imposed for 24 hr. The stress relaxation data were normalized with respect to the maximum stress for each case and plotted as a function of time in the following graph. Tensile stresses relaxed 19 percent for the TMC and 25 percent for the plain Ti-6Al-4V alloy. Compressive stresses relaxed 25 percent for the TMC and 39 percent for the plain Ti-6Al-4V alloy. The superior deformation resistance of the TMC extends to a creep rate that is 28-percent slower for the TMC when it is loaded to stress levels that are 26-percent higher than for the plain Ti-6Al-4V alloy.

Lerch, Bradley A.↗
NASA NTRS1997

Immersive cyberspace system

An immersive cyberspace system is presented which provides visual, audible, and vibrational inputs to a subject remaining in neutral immersion, and also provides for subject control input. The immersive cyberspace system includes a relaxation chair and a neutral immersion display hood. The relaxation chair supports a subject positioned thereupon, and places the subject in position which merges a neutral body position, the position a body naturally assumes in zero gravity, with a savasana yoga position. The display hood, which covers the subject's head, is configured to produce light images and sounds. An image projection subsystem provides either external or internal image projection. The display hood includes a projection screen moveably attached to an opaque shroud. A motion base supports the relaxation chair and produces vibrational inputs over a range of about 0-30 Hz. The motion base also produces limited translation and rotational movements of the relaxation chair. These limited translational and rotational movements, when properly coordinated with visual stimuli, constitute motion cues which create sensations of pitch, yaw, and roll movements. Vibration transducers produce vibrational inputs from about 20 Hz to about 150 Hz. An external computer, coupled to various components of the immersive cyberspace system, executes a software program and creates the cyberspace environment. One or more neutral hand posture controllers may be coupled to the external computer system and used to control various aspects of the cyberspace environment, or to enter data during the cyberspace experience.

Park, Brian V.↗
NASA NTRS2009

Performance of the Extravehicular Mobility Unit (EMU): Airlock Coolant Loop Recovery (A/L CLR) Hardware - Phase II

An EMU water processing kit (Airlock Coolant Loop Recovery A/L CLR) was developed as a corrective action to Extravehicular Mobility Unit (EMU) coolant flow disruptions experienced on the International Space Station (ISS) in May of 2004 and thereafter. Conservative schedules for A/L CLR use and component life were initially developed and implemented based on prior analysis results and analytical modeling. The examination of postflight samples and EMU hardware in November of 2006 indicated that the A/L CLR kits were functioning well and had excess capacity that would allow a relaxation of the initially conservative schedules of use and component life. A relaxed use schedule and list of component lives was implemented thereafter. Since the adoption of the relaxed A/L CLR schedules of use and component lives, several A/L CLR kit components, transport loop water samples and sensitive EMU transport loop components have been examined to gage the impact of the relaxed requirements. The intent of this paper is to summarize the findings of that evaluation, and to outline updated schedules for A/L CLR use and component life.

Steele, John↗
NASA NTRS2011

Numerical Prediction of Radiation Measurements Taken in the X2 Facility for Mars and Titan Gas Mixtures

Thermochemical relaxation behind a normal shock in Mars and Titan gas mixtures is simulated using a CFD solver, DPLR, for a hemisphere of 1 m radius; the thermochemical relaxation along the stagnation streamline is considered equivalent to the flow behind a normal shock. Flow simulations are performed for a Titan gas mixture (98% N2, 2% CH4 by volume) for shock speeds of 5.7 and 7.6 km/s and pressures ranging from 20 to 1000 Pa, and a Mars gas mixture (96% CO2, and 4% N2 by volume) for a shock speed of 8.6 km/s and freestream pressure of 13 Pa. For each case, the temperatures and number densities of chemical species obtained from the CFD flow predictions are used as an input to a line-by-line radiation code, NEQAIR. The NEQAIR code is then used to compute the spatial distribution of volumetric radiance starting from the shock front to the point where thermochemical equilibrium is nominally established. Computations of volumetric spectral radiance assume Boltzmann distributions over radiatively linked electronic states of atoms and molecules. The results of these simulations are compared against experimental data acquired in the X2 facility at the University of Queensland, Australia. The experimental measurements were taken over a spectral range of 310-450 nm where the dominant contributor to radiation is the CN violet band system. In almost all cases, the present approach of computing the spatial variation of post-shock volumetric radiance by applying NEQAIR along a stagnation line computed using a high-fidelity flow solver with good spatial resolution of the relaxation zone is shown to replicate trends in measured relaxation of radiance for both Mars and Titan gas mixtures.

Palmer, Grant↗
NASA NTRS2013

Powered Descent Guidance with General Thrust-Pointing Constraints

The Powered Descent Guidance (PDG) algorithm and software for generating Mars pinpoint or precision landing guidance profiles has been enhanced to incorporate thrust-pointing constraints. Pointing constraints would typically be needed for onboard sensor and navigation systems that have specific field-of-view requirements to generate valid ground proximity and terrain-relative state measurements. The original PDG algorithm was designed to enforce both control and state constraints, including maximum and minimum thrust bounds, avoidance of the ground or descent within a glide slope cone, and maximum speed limits. The thrust-bound and thrust-pointing constraints within PDG are non-convex, which in general requires nonlinear optimization methods to generate solutions. The short duration of Mars powered descent requires guaranteed PDG convergence to a solution within a finite time; however, nonlinear optimization methods have no guarantees of convergence to the global optimal or convergence within finite computation time. A lossless convexification developed for the original PDG algorithm relaxed the non-convex thrust bound constraints. This relaxation was theoretically proven to provide valid and optimal solutions for the original, non-convex problem within a convex framework. As with the thrust bound constraint, a relaxation of the thrust-pointing constraint also provides a lossless convexification that ensures the enhanced relaxed PDG algorithm remains convex and retains validity for the original nonconvex problem. The enhanced PDG algorithm provides guidance profiles for pinpoint and precision landing that minimize fuel usage, minimize landing error to the target, and ensure satisfaction of all position and control constraints, including thrust bounds and now thrust-pointing constraints.

Carson, John M., III↗
NASA NTRS2015

Theoretical Studies of Spectroscopic Line Mixing in Remote Sensing Applications

The phenomenon of collisional transfer of intensity due to line mixing has an increasing importance for atmospheric monitoring. From a theoretical point of view, all relevant information about the collisional processes is contained in the relaxation matrix where the diagonal elements give half-widths and shifts, and the off-diagonal elements correspond to line interferences. For simple systems such as those consisting of diatom-atom or diatom-diatom, accurate fully quantum calculations based on interaction potentials are feasible. However, fully quantum calculations become unrealistic for more complex systems. On the other hand, the semi-classical Robert-Bonamy (RB) formalism, which has been widely used to calculate half-widths and shifts for decades, fails in calculating the off-diagonal matrix elements. As a result, in order to simulate atmospheric spectra where the effects from line mixing are important, semi-empirical fitting or scaling laws such as the ECS (Energy-Corrected Sudden) and IOS (Infinite-Order Sudden) models are commonly used. Recently, while scrutinizing the development of the RB formalism, we have found that these authors applied the isolated line approximation in their evaluating matrix elements of the Liouville scattering operator given in exponential form. Since the criterion of this assumption is so stringent, it is not valid for many systems of interest in atmospheric applications. Furthermore, it is this assumption that blocks the possibility to calculate the whole relaxation matrix at all. By eliminating this unjustified application, and accurately evaluating matrix elements of the exponential operators, we have developed a more capable formalism. With this new formalism, we are now able not only to reduce uncertainties for calculated half-widths and shifts, but also to remove a once insurmountable obstacle to calculate the whole relaxation matrix. This implies that we can address the line mixing with the semi-classical theory based on interaction potentials between molecular absorber and molecular perturber. We have applied this formalism to address the line mixing for Raman and infrared spectra of molecules such as N2, C2H2, CO2, NH3, and H2O. By carrying out rigorous calculations, our calculated relaxation matrices are in good agreement with both experimental data and results derived from the ECS model.

Formalism↗
NASA NTRS2019

Quantifying the Influence of Redox Conditions on the Seismic Properties of Olivine

A series of eight olivine specimens were fabricated by hot-pressing at 1200 degrees Celsius and 300 megapascals (MPa). Each hot-pressed specimen was then wrapped in Pt, Ni or NiFe foil to vary oxygen fugacity (fO2), and interrogated via forced torsional oscillation. Mechanical testing was conducted at 10 oscillation periods between 1 and 1000 seconds, at a confining pressure of 200 MPa, during a slow staged-cooling from a maximum temperature of 1200 degrees Celsius to room temperature. After mechanical testing, each specimen was axially sectioned and EBSD (Electron BackScatter Diffraction) was used for the determination of the representative grain size, and grain size distribution of each sample. In addition, each longitudinal section was mapped via FTIR (Fourier Transform InfraRed spectroscopy) to determine the spatial distribution and concentrations of chemically bound and molecular water. Amongst these specimens, chemically bound ‘water’ contents were observed to vary between 0 and 1150 atom ppm (parts per million) H/Si, and molecular water concentrations varied between 0 and 245 atom ppm H/Si. Our forced-oscillation results demonstrate that the measured magnitude of anelastic relaxation within the experimental ‘window’ of oscillation periods is unrelated to the water content. Rather, a relationship was observed between the magnitude of anelastic relaxation and the prevailing redox conditions, which is influenced by the choice of metal sleeving used during the mechanical test. Further, regardless of water content or metal sleeving, each specimen exhibits coupled variations in shear modulus and dissipation within the observational window, indicative of ‘high-temperature background’ behavior, that can be described by a Burgers-type model. During initial fitting of the Burgers models, the unrelaxed shear modulus at a reference temperature of 900 degrees Celsius (G (sub UR)) and the temperature derivative of the unrelaxed shear modulus (dG (sub U)/dT), were treated as adjustable parameters. For all Fe-bearing olivine samples (but not a hydrous and oxidized Fe-free sample) we observe deficits of G (sub UR), and increased values of dG (sub U)/dT, relative to the expected elastic (anharmonic) behavior of Fo90 olivine. This behavior is indicative of anelastic relaxation occurring at shorter periods than observable within the ‘window’ of oscillation periods used in the mechanical test. Moving towards a comprehensive seismologically applicable Burgers model, which includes this newly observed effect of redox conditions on anelastic relaxation, we will present our progress in reconciling truly anharmonic and elastic behavior of Fo (sub 90) olivine with our observed forced-oscillation data.

Cline, Christopher, II↗
NASA NTRS2019

The Influence of Redox Conditions on the Seismic Properties of Polycrystalline Olivine

Eight olivine specimens were fabricated by use of a solgel method and hot-pressing at 1200 degrees Centigrade and 300 megapascals (MPa) inside of welded Pt capsules. Each hot-pressed specimen was then recovered, precision ground, and wrapped in Pt, Ni or NiFe foil to vary oxygen fugacity (fO2) during the subsequent forced torsional oscillation measurements. Mechanical testing was conducted at 10 oscillation periods between 1 and 1000 seconds, at a confining pressure of 200 MPa, during a slow staged-cooling from a maximum temperature of 1200 degrees Centigrade down to room temperature. After mechanical testing, each specimen was axially sectioned and EBSD (Electron BackScatter Diffraction) was used for the determination of the representative grain size, and grain size distribution of each sample. In addition, each longitudinal section was mapped via FTIR (Fourier Transform Infrared Spectroscopy) to determine the spatial distribution and concentrations of chemically bound and molecular water. Amongst these eight specimens, chemically bound ‘water’ contents were observed to vary between 0 and 1150 atom parts per million (ppm) H/Si, and molecular water concentrations varied between 0 and 245 atom ppm H/Si. Our forced-oscillation results demonstrate that the measured magnitude of anelastic relaxation within the experimental ‘window’ of oscillation periods is unrelated to the water content. Rather, a relationship was observed between the magnitude of anelastic relaxation and the prevailing redox conditions, which is influenced by the choice of metal sleeving used during the mechanical test. Further, regardless of water content or metal sleeving, each specimen exhibits coupled variations in shear modulus and dissipation within the observational window, indicative of ‘high-temperature background’ behavior, that can be described by a Burgers-type model. During initial fitting of the Burgers models, the unrelaxed shear modulus at a reference temperature of 900°C (elastic unloading/reloading shear modulus G (sub UR)) and the temperature derivative of the unrelaxed shear modulus (dGU/dT), were treated as adjustable parameters. For all Fe-bearing olivine samples we observe deficits of G (sub UR) and increased values of dGU/dT, relative to the expected elastic (anharmonic) behavior for Fo (Forsterite content percentage) (sub 90) olivine. This behavior is indicative of anelastic relaxation occurring at shorter periods than observable within the ‘window’ of oscillation periods used in the mechanical test. Moving towards a comprehensive and seismologically applicable Burgers model, which includes this newly observed effect of redox conditions on anelastic relaxation, we will present our progress on reconciling truly anharmonic and elastic behavior of Fo (sub 90) olivine with our observed forced-oscillation data.

Cline, C. J., II↗
NASA NTRS2019

Viscoelastic Characterization of Polymers for Deployable Composite Booms

Deployable space structures have been built from thin-walled fiber-reinforced polymer composite materials due to their high specific strength, high specific stiffness, and bistability. However, the inherent viscoelastic behavior of the resin matrix can cause dimensional instability when parts are stored under strain. The extended time of stowage between assembly and deployment in space can result in performance degradation and in the worst case, mission failure. In this study, the viscoelastic properties of candidate commercial polymers for deployable boom structures of solar sails were evaluated. Stress relaxation master curves of the candidate polymers were used to predict the relaxation that would occur in 1 year at room temperature under relatively low strains of ~0.1%. A bismaleimide (BMI) showed less stress relaxation (about 20%) than the baseline Novolac epoxy (about 50%). Carbon fiber composites fabricated with the BMI resin showed a 44% improvement in relaxation compared to the baseline epoxy composite. Other difunctional and tetrafunctional epoxies, thermoplastic, and thermosetting polyimides were also evaluated.

Kang, Jin Ho↗
NASA NTRSDate not supplied

Discrete Rotational Energy for Polyatomic Molecules in Direct Simulation Monte Carlo

The environments experienced by vehicles upon entry into planetary atmospheres generally result in severe aerothermodynamic loading. These flows are characterized by the formation of strong shock waves, behind which high temperatures and non-equilibrium environments are generated, and the accurate prediction of internal energy relaxation and chemical kinetics becomes important. This manuscript focuses on the internal relaxation of the rotational energy of polyatomic molecules. Previous work has described the implementation of a discrete rotational energy model for diatomic molecules (linear rotators). Later, Gimelshein et. al extended this model to include polyatomic molecular internal energies. However, they did not include details on how to generate the particles at equilibrium conditions and centrifugal distortion was not included in their model. The purpose of the present study is to extend the afore-mentioned models to the treatment of discrete rotational energy in polyatomic molecules with the addition of centrifugal distortion. An overview of the background theory needed for the implementation of the model will be given followed by the model itself and verification of the model. For example, sampled versus Boltzmann distributions are compared in Figure 1 for CH3 (oblate rotator – two quantum numbers) and examples of thermal relaxation behavior for linear and non-linear rotators are presented in Figure 2. In addition, comparisons of thermophysical properties will be presented, as well as examples of adiabatic relaxation and application to hypersonic flow.

Rarefied Gas Dynamics↗
DOE OSTI2025

Vortex-Controlled Quasiparticle Multiplication and Self-Growth Dynamics in Superconducting Resonators

Even in the quantum limit, non-equilibrium quasiparticle (QP) populations induce QP poisoning that irreversibly relaxes the quantum state and significantly degrades the coherence of transmon qubits. A particularly detrimental yet previously unexplored mechanism arises from QP multiplication facilitated by vortex trapping in superconducting quantum circuits, where a high-energy QP relaxes by breaking additional Cooper pairs and amplifying the QP population due to the locally reduced excitation gap and enhanced quantum confinement within the vortex core. Here we directly resolve this elusive QP multiplication process by revealing vortex-controlled QP self-generation in a highly nonequilibrium regime preceding the phonon bottleneck of QP relaxation. At sufficiently low fluence, femtosecond-resolved magneto-reflection spectroscopy directly reveals a continuously increasing QP population that is strongly dependent on magnetic-field-tuned vortex density and absent at higher excitation fluences. Quantitative analysis of the emergent QP pre-bottleneck dynamics further reveals that, although the phonon population saturates within $\simeq$10~ps, both free and trapped QPs continue to grow in a self-sustained manner--hallmarks of the long-anticipated QP-vortex interactions in nonequilibrium superconductivity. We estimate a substantial increase of $\sim$34% in QP density at vortex densities of $\sim$ 100 magnetic flux quanta per $\mathrm{μm^{2}}$. Our findings establish a powerful spectroscopic tool for uncovering QP multiplication and reveal vortex-assisted QP relaxation as a critical materials bottleneck whose mitigation will be essential for resolving QP poisoning and enhancing coherence in superconducting qubits.

Park, Joong M. [Ames Lab]↗
DOE OSTI2020

Structural dynamics and rejuvenation during cryogenic cycling in a Zr-based metallic glass

Subjecting metallic glasses repeatedly to liquid nitrogen temperature has become a popular method to homogeneously rejuvenate the material. Here in this paper we reveal the atomic-scale structural dynamics using in-situ x-ray photon correlation spectroscopy (XPCS) during and after cryogenic cycling of a Zr-based metallic glass in two structural states (plate and ribbon). Heterogeneous structural dynamics is observed at 300 K that changes to monotonic aging at 78 K. It is found that cryogenic cycling homogenizes the relaxation time distribution. This effect is much more pronounced in the ribbon, which is the only structural state that rejuvenates upon cycling. We furthermore reveal how fast atomic-scale dynamics is correlated with long-time structural relaxation times irrespective of the structural state, and that the ribbon exhibits unexpected additional fast atomic-scale relaxation in comparison to the plate material. A structural picture emerges that points towards heterogeneities in the fictive temperature as a requirement for cryogenic energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

An efficient computational framework for charge density estimation in twisted bilayer graphene

Electronic properties such as band structure and Fermi velocity in low-angle twisted bilayer graphene (TBG) are intrinsically dependent on the atomic structure. Rigid rotation between individual graphene layers provides an approximate description of the bilayer symmetry. Upon relaxation, in-plane displacement of the atoms in low angle TBG causes a change in the symmetry through the enlargement of the AB stacking regions and the reduction in size of AA and SP stacking regions. However, the effect of this in-plane relaxation on the charge density remains unexplored, because the necessary electronic structure calculations of such large supercells of low twist angle TBG are computationally infeasible. Therefore, we develop a computationally efficient framework that enables the exploration of the charge density symmetry of the low twist angle TBG. This framework is based on the Fourier representation of the charge density which presents high intensity Bragg peaks. Here we find that with the decrease of twist angle, low intensity satellite peaks also become apparent. Our framework incorporates these satellite peaks which reveals transformation of symmetry in the charge density distribution from high to low twist angle TBG. One striking outcome is the demonstration of the electron localization in the AA region of low twist angle TBG. Our framework helps to explain the effect of the atomistic relaxation on the charge density distribution and thus, it provides information about exotic electronic properties of low twist angle TBG at a low computational expense.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Natural gas maximal load delivery for multi-contingency analysis

An increasing dependence on natural gas has amplified existing vulnerabilities to the power grid, including disruptions to gas transmission networks from natural and man-made disasters. To address the operational challenges arising from these disruptions, we, in this study, consider the problem of estimating the steady-state operating capacity of a damaged gas pipeline network while ensuring the maximal delivery of load. Specifically, we formulate the mixed-integer nonconvex maximal load delivery (MLD) problem, which proves difficult to solve on large-scale networks. To address this challenge, we present a relaxation of the MLD problem and use it to determine bounds on the transport capacity of a gas pipeline system. A rigorous computational evaluation over network models ranging in size from 11 to 4,197 junctions shows that the relaxation-based method is suitable for analyzing the impacts of multi-contingency network disruptions, often converging to the optimal solution of the relaxation in less than ten seconds.

03 NATURAL GAS↗
DOE OSTI2022

PyOECP: A flexible open-source software library for estimating and modeling the complex permittivity based on the open-ended coaxial probe (OECP) technique

Here, we present PyOECP, a Python-based flexible open-source software for estimating and modeling the complex permittivity obtained from the open-ended coaxial probe (OECP) technique. The transformation of the measured reflection coefficient to complex permittivity is performed based on three different methods. The software library contains the dielectric spectra of common reference liquids, which can be used to transform the reflection coefficient into the dielectric spectra. Several Python routines that are commonly employed (e.g., SciPy and NumPy) in the field of science and engineering are required only so that the users can alter the software structure depending on their needs. The modeling algorithm exploits the Markov Chain Monte Carlo method for the data regression. The discrete relaxation models can be built by a proper combination of well-known relaxation models. In addition to these models, electrode polarization, a typical measurement artifact for interpreting dielectric spectra, can be incorporated into the modeling algorithm. A continuous relaxation model, which solves the Fredholm integral equation of the first kind (a mathematically ill-posed problem), is also included. This open-source software enables users to freely adjust the physical parameters to obtain physical insight into their materials under test and will be consistently updated for more accurate measurement and interpretation of dielectric spectra in an automated manner. This work describes the theoretical and mathematical background of the software, lays out the workflow, and validates the software functionality based on both synthetic and empirical data included in the software.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Experimental workflow to estimate model parameters for evaluating long term viscoelastic response of CO2 storage caprocks

Understanding the time-dependent behavior of reservoir and sealing formations is critical to assessing risks associated with geological carbon storage since time-dependent deformation strongly influences mechanical responses of some rock types. Many studies have evaluated the risk of CO2 leakage and induced seismicity by assuming poroelastic rheology in sealing formations. Few have considered viscoelastic or other time-dependent responses, where the existing literature adopts 1D models to represent long-term time-dependent responses. This is primarily because to date, the general form of a reasonable 3D time-dependent model for rocks remains unclear. In this paper, we address this unclear issue by proposing a new workflow to select constitutive modeling parameters to evaluate if a 3D viscoelastic model is reasonable using several-hour-long experimental data and a power-law response to extrapolate to the decades-long time frames of interest in geologic carbon storage. To provide experimental data, we conducted multi-level loading/unloading triaxial relaxation tests with four rock types. The experimental results showed that the maximum load relaxation observed is approximately 49%, with some rock types showing as little as 1.4%. Using a simple linear viscoelastic model, parameters were chosen such that a maximum deviation of 1.5 MPa in axial stress and 7 MPa in radial stress was attained with the extrapolated 30-year data. We found that a reasonable parameter range for the normalized elastic modulus is 0.1~2 for rocks with significant time-dependent responses and 0.01~0.06 for those with small time-dependent responses. No matter how significant time-dependent responses are for rocks considered, our results showed that the relaxation time has a general range of 1~10^10 s, whose time scale can be one or two orders higher than a time frame typically envisioned for CO2 injection projects.

Stress relaxation, 3D time-dependent model, viscoe↗
DOE OSTI2020

Thermodynamics–Structure–Dynamics Correlations and Nonuniversal Effects in the Elastically Collective Activated Hopping Theory of Glass-Forming Liquids

We employ the microscopic Elastically Collective Nonlinear Langevin Equation (ECNLE) theory of activated dynamics in combination with crystal-avoiding simulations to study four inter-related questions for metastable monodisperse hard sphere fluids. The first is how significantly improved integral equation theory structural input (Modified-Verlet (MV) closure) changes the dynamical predictions of ECNLE theory. The main consequence is a modest enhancement of the importance of the collective elastic barrier relative to its local cage contribution, which increases the alpha relaxation time and fragility relative to prior results based on the Percus–Yevick closure. Second, ECNLE-MV theory predictions for the alpha time and self-diffusion constant in the metastable regime are quantitatively compared to our new simulations. The small adjustment of a numerical prefactor that enters the collective elastic barrier leads to quantitative agreement over three decades. Third, using the more accurate MV structural input, ECNLE theory is shown to predict thermodynamics–structure–dynamics “correlations” based on various long and short wavelength scalar properties all related to static two-point collective density fluctuations. The logarithm of the alpha relaxation time scales as a power law with these scalar metrics with an exponent that is significantly lower in the less dense noncooperative activated regime compared to the very dense highly cooperative regime. However, the discovered correlation of activated relaxation with a thermodynamic property (dimensionless compressibility) is not causal in ECNLE theory, but rather reflects a strong connection between the local structural quantities that quantify kinetic constraints in the theory with the amplitude of long wavelength density fluctuations. Fourth, the consequences of chemically specific nonuniversalities associated with the onset condition and relative importance of collective elasticity are studied. In conclusion, the predicted thermodynamics–structure–dynamics correlations are found to be robust, albeit with nontrivial shifts of the onset condition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗