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At least 217 records · Page 12

Thixotropic spectra and Ashby-style charts for thixotropy

There is no universal model for thixotropy, and comparing thixotropic effects between different fluids is a subtle yet challenging problem. We introduce a generalized (model-insensitive) framework for comparing thixotropic properties based on thixotropic spectra. A superposition of exponential stress modes distributed over thixotropic time scales is used to quantify buildup and breakdown times and mode strengths in response to step-change input. This mathematical framework is tested with several experimental step-shear rate data on colloidal suspensions. Low-dimensional metrics based on moments of the distribution reveal characteristic average thixotropic properties, which are visualized on Ashby-style diagrams. This method outlines a framework for describing thixotropy across a diverse range of microstructures, supporting scientific studies as well as material selection for engineering design applications.

Mechanics↗

Experiment of Sea Breeze Convection, Aerosols, Precipitation, and Environment (ESCAPE) C-band Radar Deployment Field Campaign Report

Convective clouds play a critical role in the Earth’s climate system, acting as sinks of total water in the atmospheric column through precipitation, thereby contributing to the atmospheric energy balance. They serve as a primary mechanism for the transfer of heat, moisture, and momentum through the troposphere, significantly impacting the large-scale atmospheric circulation and local environment, and affecting the probability of subsequent cloud formation (e.g., Hartmann et al. 1984, Su et al. 2014, Sherwood et al. 2014). Convective characteristics including convective core size (reflectivity and updraft), cloud lifetime, precipitation intensity, total precipitation amount, precipitation efficiency, and lightning flash rates can be strongly related to environmental factors (e.g., wind shear, humidity). Since cumulus clouds evolve rapidly, their microphysical and dynamical properties and life cycles are challenging to resolve in models, and even in observations (e.g., Fridlind et al. 2017, Ladino et al. 2017).

54 ENVIRONMENTAL SCIENCES↗

Robust Molecular Predictive Methods for Novel Polymer Discovery and Applications

Polymeric materials are ubiquitous in modern society and they play an instrumental role in almost all industries, undoubtedly including the energy and environment sectors. Increased demand of energy and awareness to sustainability both necessitates the development of novel polymers with enhanced properties. Unfortunately, their structural and behavioral complexity render such discovery challenging and impeded. To address this problem, scientists are developing various computational modeling techniques and leveraging their power to depict the relationship between structural characteristics of polymers and their properties (such as rheological behaviors), and use such prediction to guide the design and syntheses of novel polymeric materials with enhanced performances. Unfortunately, predicting the relationships between polymer structure and composition with rheological properties via atomistic modeling is still a major challenge because of the extended time and length scales involved. Studying dynamic shear viscosity and linear viscoelasticity using molecular models requires capabilities that have been elusive, including representation of large molecular weight chains with an effective internal scale capable of describing entanglement, shear-rates that are in the s-1 scale with accurate quantitative stresses, and chemically-realistic combinations of both homogeneous and heterogeneous systems. Motivated by these unmet challenges, the overall technical objective of this DOE-STTR Phase II project is to develop robust molecular predictive methods for advanced polymer discovery and applications and especially for designing and demonstrating the “smart” polymer-based waterflooding enhanced oil recovery (EOR) process. In particular, we apply state-of-the-art molecular modeling methods developed by our academic partner, Materials Stimulation Center (MSC) at California Institute of Technology (Caltech), to facilitate and accelerate the experimental discovery processes. During the Phase I of this project, we had focused on development and demonstration of the molecular modeling methods to describe rheological properties of non-Newtonian polymer fluids, and to improve our fundamental understandings of shear-thickening mechanism and kinetics. In Phase II, we further apply the theoretical models to guide our experimental programs to improve our design of smart rheology modifier (SRM) polymers and their optimization for EOR. Specifically, we have three objectives in the Phase II study: (1) to further improve out computational modeling methods, coupling with the advanced machine learning algorithms; (2) to develop cost-effective and efficient SRM-flooding process suitable for EOR applications under typical reservoir conditions; and (3) to further explore the application of our molecular predictive models for innovative material discovery in other industrial applications. The recent development of our multiscale predictive framework allows the successful prediction of rheological properties from the chemical structure for polymers of experimentally relevant molecular weights, and provides an in-silico machine learning engine for screening novel compositions and structures with optimized non-Newtonian response, required for both shear-thinning and shear-thickening applications. Our framework provides: (1) procedures and tools for systematic coarsening from atomistic models and reverse mapping of coarse-grain models to atomistic, (2) unique ab initio methods to characterize the atomistic origin of colloidal and interfacial interactions and phenomena, (3) systematic structure and composition builders based on practical descriptors that drive rheological changes in polymer melts and diluted polymer mixtures, (4) a rheological properties engine capable of predicting viscosity in the zero-shear limit and under realistic dynamic conditions (for shear-rates commensurate with experiments) for large heterogeneous systems, (5) coarse-grain force fields with improved non-bond descriptions based on accurate quantum mechanics, (6) an in-silico screening machine learning engine that feeds from the systematic model builders to cover the descriptors search space, computes the rheological properties from converged trajectories spanning sub-milliseconds and ranks them for each structure/composition using an automated viscosity-vs-shear rate fitness function that can be tuned for shear-thickening, shear-thinning and other rheological responses.

02 PETROLEUM↗

Effects of Salt on Phase Behavior and Rheological Properties of Alginate–Chitosan Polyelectrolyte Complexes

Oppositely charged polyelectrolytes often form polyelectrolyte complexes (PECs) due to the association through electrostatic interactions. Obtaining PECs using natural, biocompatible polyelectrolytes is of interest in the food, pharmaceutical, and biomedical industries. In this work, PECs were prepared from two biopolymers, positively charged chitosan and negatively charged alginate. We investigate the changes in the structure and properties of PECs by adding sodium chloride (salt doping) to the system. The shear modulus of PECs can be tuned from ~10 to 10 4 Pa by changing the salt concentration. The addition of salt led to a decrease in the water content of the complex phase with increasing shear modulus. However, at a very high salt concentration, the shear modulus of the complex phase decreased but did not lead to the liquid coacervate formation, typical of synthetic polyelectrolytes. This difference in phase behavior has likely been attributed to the hydrophobicity of chitosan and long semiflexible alginate and chitosan chains that restrict the conformational changes. Large amplitude oscillatory shear experiments captured nonlinear responses of PECs. The compositions of the PECs, determined as a function of salt concentration, signify the preferential partitioning of salt into the complex phase. Small-angle X-ray scattering of the salt-doped PECs indicates that the Kuhn length and radius of the alginate–chitosan associated structure qualitatively agree with the captured phase behavior and rheological data. This study provides insights into the structure–property as a function of salt concentration of natural polymer-based PECs necessary for developing functional materials from natural polyelectrolytes.

59 BASIC BIOLOGICAL SCIENCES↗

Shear Assisted Processing and Extrusion (ShAPE) of Aluminum Alloy 7075, 2024, and Al-12.4TM

The most common aluminum alloys utilized in the aerospace industry are 7075 and 2024 due to their high strength-to-weight ratio compared to advanced high strength steels and other aluminum alloys. Despite excellent performance, these aluminum alloys have seen limited use outside of the aerospace industry due in part to high cost. If high-performance aluminum extrusions could be made more cost effectively by eliminating energy intensive process steps typical of conventional extrusion, then numerous opportunities exist for more widespread adoption. A key reason for the high cost of 7075 and 2024 extrusions (25-75% higher than 6061) is their slow extrusion speed. 7075 and 2024 are limited to 2 m/min and 3.5 m/min respectively, in contrast to 6061 which can be extruded at 20–80 m/min. In addition to slow speed, aluminum alloys require numerous thermal treatments throughout the extrusion process including homogenization and pre-heating prior to extrusion, and solution heat treating and artificial aging after extrusion. Each of these steps contribute to the total energy consumed during manufacturing of extruded components. This project investigates the use of ShAPE to improve extrusion speed and reduce, or even eliminate, the typical thermal treatments for high strength aluminum alloys, all while improving material performance. The overarching goal of this project was to demonstrate that Shear Assisted Processing and Extrusion (ShAPE) can manufacture high-performance aluminum alloy tubing with lower manufacturing energy and improved mechanical properties compared to conventional extrusion. Unlike conventional extrusion where the billet is rammed against a stationary die using a strictly linear motion, the ShAPE process superimposes a rotational shear force by spinning the die while the billet is plunged. Compared to conventional linear extrusion, the ShAPE process imparts significantly more strain into the feedstock material, which enables the formation of novel microstructures. These microstructures manifest an array of property and process improvements for extrusion of high-performance aluminum alloys. The following accomplishments were achieved for this project: Extrusion of 7075 at 12.2 meters/min compared to 2 meters/min for conventional extrusion; Elimination of 7075 billet homogenization (430 °C for 20 hours) which is required prior to conventional extrusion; Elimination of 7075 billet pre-heating (400 °C for 1 hour) in a separate furnace which is required prior to conventional extrusion; Achieved 7075-T6with yield strength = 595 MPa, ultimate tensile strength = 531MPa, and elongation = 17.4% for extrusions made from unhomogenized billets. Exceeds the ASTM and ASM standard, and typical industry values; Achieved 7075-T5 (i.e., no solution heat treatment) with yield strength = 588 MPa, ultimate tensile strength = 535 MPa, and elongation = 14.8% for extrusions made from homogenized billets; Extrusion of 2024 at 7.4 meters/min compared to 3.5 meters/min for conventional extrusion; Achieved 2024-T8510 yield strength = 522 MPa, ultimate strength = 510MPa, and elongation = 7.1% for extrusions made from wrought billets. Exceeds the ASTM and ASM standard, and typical industry values; Extrusion of Al-12.4TM high-performance aluminum powder directly into tubing, in a single step, which eliminates process steps typical of powder metallurgy extrusion.

36 MATERIALS SCIENCE↗

Deep Convection Initiation, Growth, and Environments in the Complex Terrain of Central Argentina during CACTI

This study characterizes the wide range of deep convective cloud life cycles and their relationships with ambient environments observed during the Cloud, Aerosol, and Complex Terrain Interactions (CACTI) field campaign near the Sierras de Córdoba (SDC) range in central Argentina. We develop a novel convective cell tracking database for the entire field campaign using C-band polarimetric radar observations. The cell tracking database includes timing, location, area, depth, merge/split information, microphysical properties, collocated satellite-retrieved cloud properties, and sounding-derived environmental conditions. Results show that the SDC exerts a strong control on convection initiation (CI) and growth. CI preferentially occurs east of the SDC ridge during the afternoon, and cells often undergo upscale growth through the evening as they travel eastward toward the plains. Larger and more intense cells tend to occur in more unstable and humid low-level environments, and surface-based cells are stronger than elevated cells. Midtropospheric relative humidity and vertical wind shear also jointly affect the size and depth of the cells. Rapid cell area growth rates exhibit dependence on both large environmental wind shear and low-level moisture. Evolution of convective cell macro- and microphysical properties are strongly influenced by convective available potential energy and low-level humidity, as well as the presence of other cells in their vicinity. This cell tracking database demonstrates a framework that ties measurements from various platforms centering around convective life cycles to facilitate process understanding of factors that control convective evolution.

54 ENVIRONMENTAL SCIENCES↗

LAVA 1.0: A general-purpose python toolkit for calculation of material properties with LAMMPS and VASP

Here, we introduce LAVA, a general-purpose python toolkit to provide user-friendly and high throughput calculations for material properties using both LAMMPS and VASP. It contains a set of classes as well as pre-processing and post-processing functions to prepare, execute and extract information from LAMMPS/VASP simulations. An overview of the program structure is provided. The current version contains modules to calculate elastic and mechanical properties such as lattice constant, cohesive energy, cold curve, elastic constants, bulk and shear modulus, volume conserving/non-conserving deformation path, vacancy/interstitial formation energy, surface energy, stacking fault energy, melting point, radial distribution function, and thermal expansion. These functionalities are demonstrated for different interatomic potentials and DFT calculations in Al.

36 MATERIALS SCIENCE↗

Effects of Cooling Rates on Self-Reinforced Polyethylene Composites via Multiscale Experimental Characterizations

This study investigates cooling rate effects on self-reinforced polyethylene composites (PE-SRCs), focusing on macroscopic thermal and mechanical properties, and micro- to sub-micron morphologies. Unlike conventional fiber-reinforced composites (e.g., carbon and glass fiber based), cooling rate effects on SRCs remain less studied. PE-SRCs were fabricated from ultrahigh molecular weight polyethylene (UHMWPE) fabric and high-density polyethylene (HDPE) matrix with cooling rates from 0.76°C/min to 425°C/min. Tensile properties, including modulus (~9.5 GPa), strength (~360 MPa), and ultimate elongation (~6%), showed no significant cooling rate dependence. However, thermal analysis revealed melting temperature of HDPE matrix decreased from ~130°C to ~126.5°C with total crystallinity reducing from 84% to 75%. Wide-angle X-ray scattering confirmed decreasing crystallinity but at lower values (67%–59%), as thermal analysis might overestimate crystallinity. Small-angle X-ray scattering showed long period decreased from 24.3 to 17.4 nm, attributed to thinner lamellae and closer packing, suggesting limited crystal growth and faster nucleation. While cooling rates alter melting point and crystalline structures of HDPE matrix, these changes do not translate to substantial impact on macroscale mechanical properties of PE-SRCs. This insensitivity might be related to low interfacial shear strength at PE/PE interfaces, enabling process optimization while maintaining mechanical performance.

Cooling rate↗

Improving the Physical Basis for Updraft Dynamics in Deep Convection Parameterizations

This article presents a new deep convective parameterization that determines cloud characteristics based on a specified cloud size distribution. The vertical profiles of cloud properties are determined by analytic equations, which formulate entrainment with an inverse relationship to cloud width. In line with recent studies of large eddy simulations (LES), cloud widths are assumed to be constant with height and vertical mass flux (M) characteristics of the clouds are therefore regulated by the vertical velocity profile. The parameterization is configured to work with existing cloud base M closure formulations, with the closure predicting the total cloud area rather than the cloud base M directly. Analytic formula are also used to connect the vertical wind shear magnitude to the cloud size distribution, wherein larger shear magnitudes result in more numerous large updrafts than weaker shear magnitudes, which is in line with recent research results. The parameterization is compared against 10 deep convective LES with varying thermodynamic and vertical wind shear profiles. Results show dramatic improvements in the prediction of normalized M, detrainment, and the properties of detrained air over the existing Zhang and McFarlane (1995) scheme. In particular, the new model is able to correctly portray the transition from a bottom-heavy M profile in weakly sheared environments, to a top-heavy M profile in strongly sheared environments.

54 ENVIRONMENTAL SCIENCES↗

Evaluating Effects of Shear Processing on 2D Crystalline Materials in 3D Metal Matrices: Atomistic Understanding of High Shear Deformation of Copper Graphene Composites

Composites made of copper and graphene demonstrate high strength, lubricity and enhanced electrical and thermal conductivity compared pure copper. However, manufacturing these composites at bulk volumes for industrial applications has been a big challenge. Shear deformation assisted processing is an effective method for manufacturing materials such as copper-graphene composites demonstrating ultra-fine grain structures and compositional homogeneity. Nevertheless, microstructural evolution of the composites and their property development under such conditions is not clearly understood currently. To rectify this gap in literature, high strain shear deformation of copper coated graphene foils was performed using a tribometer pin in this study. Changes in microstructure of the composite as well as the constituent components under shear deformation was correlated to process conditions. A sharp increase in the coefficient of friction attributed to rupture and smearing of graphene layer into copper substrate was observed during the shear processing. The coefficient of friction of the sheared copper/graphene composite was lower than that of pure copper, suggesting that partially worn graphene is effectively lubricious at the macroscale. A multimodal characterization of the processed region further revealed a shear deformation-induced ultrafine two-phase grain-structure consisting of copper and graphitic domains. Shear deformation reduced the copper grain size from around 50 – 100 µm to ~200 nm on an average and ~2 – 5 nm in some locations. The semicrystalline graphene films were observed to fracture into 10 – 50 µm size flakes. Oxygen enrichment was observed in the processed region. Finally, graphitic domain were identified for the first time in the copper matrix and not just at the grain boundaries providing evidence for a metastable composite microstructure as a result of solid phase processing at room temperature.

36 MATERIALS SCIENCE↗

Effect of Cr and Al on Elastic Constants of FeCrAl Alloys Investigated by Molecular Dynamics Method

The FeCrAl alloy system is recognized as one of the candidate materials for accident-tolerant fuel (ATF) cladding in the nuclear power industry due to its high oxidation resistance under irradiation and high-temperature environments. The concentrations of Cr and Al have a significant effect on elastic properties of the FeCrAl alloy. In this work, elastic constants C 11 , C 12 , C 44 , bulk modulus and shear modulus of FeCrAl alloy were calculated with molecular dynamics methods. We explored compositions with 1–15 wt.% Cr and 1–5 wt.% Al at temperatures from 0 K to 750 K. The results show that the concentrations of Al and Cr have different effects on the elastic constants. When the concentration of Al was fixed, a decrease in bulk modulus and shear modulus with increasing Cr content was observed, consistent with previous experimental results. The dependence of elastic constants on temperature was also the same as in the experiments. Investigations into elastic properties of defect-containing alloys have shown that vacancies, voids, interstitials and Cr-rich precipitations have different effects on elastic properties of FeCrAl alloys. Investigations of elastic properties of defect-containing alloys have shown that vacancies, void, interstitials and Cr-rich precipitations have different effects on elastic properties of FeCrAl alloys. Therefore, the present results indicate that both the Cr and Al concentrations and radiation defects should be considered to develop and apply the FeCrAl alloy in ATF design.

36 MATERIALS SCIENCE↗

Polyelectrolyte complex scaffoldings for photocrosslinked hydrogels

Photocrosslinkable precursors (small molecules or polymers) undergo rapid crosslinking upon photoirradiation, forming covalently crosslinked hydrogels. The spatiotemporally controlled crosslinking, which can be achieved in situ, encourages the utility of photocrosslinked hydrogels in biomedicine as bioadhesives, bioprinting inks, and extracellular matrix mimics. However, the low viscosity of the precursor solutions results in unwanted flows and dilution, leading to handling difficulties and compromised strength of the photocrosslinked hydrogels. Here, we introduce oppositely charged triblock polyelectrolytes as additives for precursor solutions that transform them into self-assembled polyelectrolyte complex (PEC) hydrogels with enhanced shear strength and viscosity, providing interim protection against precursor dilution and mitigating secondary flows. The PEC network also augments the properties of the photocrosslinked hydrogels. Crosslinking of the precursors upon photoirradiation results in the formation of interpenetrating polymer network hydrogels with PEC and covalently-linked networks that exhibit shear moduli exceeding the linear combination of the moduli of the constituent networks and overcome the tensile strength–extensibility tradeoff that restricts the performance of covalently-linked hydrogels. In conclusion, the reinforcement approach is shown to be compatible with four types of photocrosslinkable precursors, does not require any modification of the precursors, and introduces minimal processing steps, paving the way for a broader translation of photocrosslinkable materials for biomedical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermo-hydro-mechanical analysis of subsurface ice-based thermal energy storage

Ice-based thermal energy storage systems are widely utilized for cooling and managing peak electrical demand globally, offering daily or weekly storage capabilities for both individual homes and larger office buildings. However, scaling these systems for district-level cooling or integrating them with renewable energy sources presents challenges, especially in accommodating larger volumes and addressing seasonal storage requirements in densely populated urban areas. This paper proposes a novel solution by evaluating subsurface ice-based thermal energy storage, in which the underground is subjected to seasonal freeze/thaw cycles. However, these cycles may influence ground behavior, affecting pore pressure and inducing ground movement. To systematically investigate these challenges, we enhance the TOUGH-FLAC simulator by integrating water/ice phase change capabilities and updating the effective stress–strain constitutive relation. Both modifications are validated against analytical solutions or experimental data. Through numerical simulations spanning a decade with ten seasonal freeze/thaw cycles, we evaluate the performance and long-term stability of a generic subsurface ice-based thermal energy storage system, considering factors such as ground permeability, freezing pipe spacing, freeze/thaw damage, and glycol solution temperature. The simulations indicate that ice formation induces pore pressure variations that drive seasonal surface heave and settlement, controlled by ground permeability, pipe spacing, and glycol solution temperature, along with tensile and localized shear deformation around freeze pipes. This highlights the need for accurate ground property characterization and geomechanical analysis for subsurface ice-based thermal energy storage.

Ground freezing↗

Preseismic Fault Creep and Elastic Wave Amplitude Precursors Scale With Lab Earthquake Magnitude for the Continuum of Tectonic Failure Modes

Tectonic faults fail in a continuum of modes from slow earthquakes to elastodynamic rupture. Precursory variations in elastic wavespeed and amplitude, interpreted as indicators of imminent failure, have been observed in limited natural settings and lab experiments where they are thought to arise from contact rejuvenation and microcracking within and around the fault zone. However, the physical mechanisms and connections to fault creep are poorly understood. Here we vary loading stiffness during frictional shear to generate a range of slip modes and measure fault zone properties using transmitted elastic waves. We find that elastic wave amplitudes show clear changes before fault failure. The temporal onset of amplitude reduction scales with lab earthquake magnitude and the magnitude of this reduction varies with fault slip. Our data provide clear evidence of precursors to lab earthquakes and suggest that continuous seismic monitoring could be useful for assessing fault state and seismic hazard potential.

58 GEOSCIENCES↗

Calibration and validation of the foundation for a multiphase strength model for tin

In this work, the Common Model of Multi-phase Strength and Equation of State (CMMP) model was applied to tin. Specifically, calibrations of the strength-specific elements of the CMMP foundation were developed with a combination of experiments and theory, and then the model was validated experimentally. The first element of the foundation is a multi-phase analytic treatment of the melt temperature and the shear modulus for the solid phases. These models were parameterized for each phase based on ab initio calculations using the software VASP (Vienna Ab initio Simulations Package) based on density functional theory. The shear modulus model for the ambient phase was validated with ultrasonic sound speed measurements as a function of pressure and temperature. The second element of the foundation is a viscoplastic strength model for the phase, upon which strength for inaccessible higher-pressure phases can be scaled as necessary. The stress–strain response of tin was measured at strain rates of 10 -3 to 3 x 10 3 s -1 and temperatures ranging from 87 to 373 K. The Preston–Tonks–Wallace (PTW) strength model was fit to that data using Bayesian model calibration. For validation, six forward and two reverse Taylor impact experiments were performed at different velocities to measure large plastic deformation of tin at strain rates up to ⁠10 5 s -1 . The PTW model accurately predicted the deformed shapes of the cylinders, with modest discrepancies attributed to the inability of PTW to capture the effects of twinning and dynamic recrystallization. Some material in the simulations of higher velocity Taylor cylinders reached the melting temperature, thus testing the multiphase model because of the presence of a second phase, the liquid. In simulations using a traditional modeling approach, the abrupt reduction of strength upon melt resulted in poor predictions of the deformed shape and non-physical temperatures. With CMMP, the most deformed material points evolved gradually to a mixed solid–liquid but never a fully liquid state, never fully lost strength, stayed at the melt temperature as the latent heat of fusion was absorbed, and predicted the deformed shape well.

36 MATERIALS SCIENCE↗

Evaluation of Hopper Flow Prediction based on Cubical Triaxial Tester Data and FEM

A cubical triaxial tester (CTT) laboratory device was used to collect key bulk flow characteristics of Crumbles® 6mm rotary sheared woody biomass and Crumbles® 2mm rotary sheard corn stover. The flow properties and a CAD model of a hopper and conveyor system to predict the consistency of flow of material from the hopper. Prediction included the likeliness of jamming, bridging, or ratholing. Each material was then loaded into the hopper and the actual bulk flow was measured. Measured flow closely matched the predicted flow.

09 BIOMASS FUELS↗

Coarse-Grained Simulations of Polyrotaxane Hydrogels under Quiescent and Shear Conditions

Cyclodextrin-based polyrotaxanes (PR) form hydrogels in water through cyclodextrin (CD) aggregation and crystallization. These networks can break under shear flows, making them versatile platforms for extrusion-based 3D printing. To optimize the material properties of 3D-printed PR gels, a microscopic understanding of the structural evolution during 3D printing is necessary. Here, we employ coarse-grained (CG) simulations to reveal the PR assembly process at the molecular level. Our simulations reproduce the experimental crystal morphologies of PR at varying concentrations and chain lengths under quiescent conditions. Using nonequilibrium simulations, we show shear flow ruptures crystalline domain connectivity in PR gels and stacks the lamellae in the gradient direction, allowing the materials to flow during 3D printing. After the cessation of flow, the anisotropic crystal alignment and absence of available dangling PR diminish the intercrystal connectivity. The printed materials are therefore mechanically weaker than the pristine hydrogels, in agreement with experimental results. Nonetheless, by relating the microscopic structural evolution with viscoelastic properties of PR gels and solutions, we elucidate how flow conditions and sample composition affect the 3D printing performance of PR hydrogels.

Smith, Cameron D. [Dartmouth College, Hanover, NH ↗

Ultrafast vibrational dynamics of a trigonal planar anionic probe in ionic liquids (ILs): A two-dimensional infrared (2DIR) spectroscopic investigation

A major impediment limiting the widespread application of ionic liquids (ILs) is their high shear viscosity. Incorporation of a tricyanomethanide (TCM - ) anion in ILs leads to low shear viscosity and improvement of several characteristics suitable for large scale applications. However, properties including interactions of TCM - with the local environment and dynamics of TCM - have not been thoroughly investigated. Herein, we have studied the ultrafast dynamics of TCM - in several imidazolium ILs using linear IR and two-dimensional infrared spectroscopy techniques. The spectral diffusion dynamics of the CN stretching modes of TCM - in all ILs exhibit a nonexponential behavior with a short time component of ~2 ps and a long time component spanning ~9 ps to 14 ps. The TCM - vibrational probe reports a significantly faster relaxation of ILs compared to those observed previously using linear vibrational probes, such as thiocyanate and selenocyanate. Our results indicate a rapid relaxation of the local ion-cage structure embedding the vibrational probe in the ILs. The faster relaxation suggests that the lifetime of the local ion-cage structure decreases in the presence of TCM - in the ILs. Linear IR spectroscopic results show that the hydrogen-bonding interaction between TCM - and imidazolium cations in ILs is much weaker. Shorter ion-cage lifetimes together with weaker hydrogen-bonding interactions account for the low shear viscosity of TCM - based ILs compared to commonly used ILs. In addition, this work demonstrates that TCM - can be used as a potential vibrational reporter to study the structure and dynamics of ILs and other molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗