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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

High-entropy induced a glass-to-glass transition in a metallic glass

Glass-to-glass transitions are useful for us to understand the glass nature, but it remains difficult to tune the metallic glass into significantly different glass states. Here, we have demonstrated that the high-entropy can enhance the degree of disorder in an equiatomic high-entropy metallic glass NbNiZrTiCo and elevate it to a high-energy glass state. An unusual glass-to-glass phase transition is discovered during heating with an enormous heat release even larger than that of the following crystallization at higher temperatures. Dramatic atomic rearrangement with a short- and medium-range ordering is revealed by in-situ synchrotron X-ray diffraction analyses. This glass-to-glass transition leads to a significant improvement in the modulus, hardness, and thermal stability, all of which could promote their applications. Based on the proposed high-entropy effect, two high-entropy metallic glasses are developed and they show similar glass-to-glass transitions. These findings uncover a high-entropy effect in metallic glasses and create a pathway for tuning the glass states and properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Self-Consistent Theory for Structural Relaxation, Dynamic Bond Exchange Times, and the Glass Transition in Polymeric Vitrimers

Here, we formulate a statistical mechanical theory for how dynamic bond exchange influences the activated hopping-driven relaxation of Kuhn segments in dynamically cross-linked networks or vitrimers over a wide range of temperatures and cross-link densities. The key new methodological aspect is to address in a self-consistent manner the dynamic consequences of bond exchange on the Kuhn segmental alpha relaxation, and vice versa. The predicted temperature dependence of the segmental alpha time of vitrimers at high temperatures remains the same as that of permanent networks, but at lower temperatures, a significant acceleration of relaxation occurs due to bond exchanges. From a mechanistic perspective, the vitrimer local cage barrier is very weakly affected by bond exchange, while the collective elastic barrier contribution decreases significantly in the deeply supercooled regime. The vitrimer glass transition temperature is predicted to grow linearly with the square root of the cross-link density, as previously found for permanent networks. Material-specific chemical effects such as cross-linker size relative to that of the normal Kuhn segment or special attraction of a cross-linker with polymers are crudely considered based on model calculations. The theory is quantitatively applied to recent experiments on dry ethylene vitrimers. Good agreements are found including that the bond exchange time follows an Arrhenius law at high enough temperatures but upward non-Arrhenius deviations emerge in the deeply supercooled regime, and a collapsed master curve of the segment alpha time exists over a wide range of cross-link densities and temperatures. Possible extensions to treat dynamic heterogeneity effects and penetrant transport in vitrimers are briefly discussed.

chemical calculations↗
DOE OSTI2022

Comment on Comment on “Anomalous structural recovery in the near glass transition range in a polymer glass: Data revisited in light of temperature variability in vacuum oven‐based experiments”*

Abstract Cangialosi, Alegría, and Colmenero have made a comment on a paper of ours [Polym. Eng. Sci. 2022:1–13], in which we discussed the concern that the enthalpy recovery data reported by Cangialosi and co‐workers [Phys. Rev. Lett. 2013;111(9):095701] for polystyrene aged up to 15 K below glass transition temperature was anomalous and contradicted existing experimental results from the literature over a similar range of aging conditions. Their response shifts the focus away from the raised questions about their experimental results and attempts to invalidate the data that we cited in support of our argument. Here we respond to the comment and add additional analysis that suggests the structural recovery response of glassy materials exhibits smooth behavior over the full range of measurements, up to 7 or 8 logarithmic decades. We do this by referring to the work on the intrinsic isotherm down‐jump and memory responses of poly(vinyl acetate) between 40°C and 15°C over six logarithmic decades by Kovacs [Fortsch. Hochpolym. Fo. 1963;3(1/2):394–508], the small‐strain tensile creep of poly(vinyl chloride) quenched from 90°C to 40°C (approximately 40°C below T g ) over seven logarithmic decades from Struik [Polym Eng. Sci., 1977;17:165–173], and the volume recovery behavior for aging times up to 3 months in a temperature range between 95°C and −50°C by Greiner and Schwarzl [Rheol. Acta. 1984;23(4):378–395]. We also add discussion that an isothermal aging procedure using a vacuum oven is highly vulnerable to temperature errors due to the problem of good temperature control when the heat transfer mechanism is primarily radiative.

Jin, Shuang↗
DOE OSTI2024

Applying machine learning and quantum chemistry to predict the glass transition temperatures of polymers

Glass transition temperature (T g ) is important for understanding the physical and mechanical properties of a polymer material because it relates to the thermal energy required to transition between a hard glassy state and a soft rubbery one. Over the years, various models have been developed for predicting this thermal property from molecular structure to aid in designing novel polymers in selected classes. This work builds on those efforts by utilizing both machine learning (ML) and quantum chemistry (QC) techniques to develop models that can predict T g values from the molecular structure under different data availability scenarios and for a wide variety of polymer types. For the ML model, a graph convolutional network (GCN) was used to map topological polymer features; this model was trained against a dataset of more than 7500 T g values and resulted in a root mean square error (RMSE) of 38.1 °C. The QC-based regression model was trained on 83 T g values and produced an RMSE of 34.5 °C. In conclusion, this work demonstrated that while both model techniques produce accurate predictions and are suitable for different data availability scenarios, the QC-based regression model offered a more interpretable model framework with significantly less training data.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Investigation of experimental signatures of spin glass transition temperature

We present a series of temperature and field-dependent magnetization studies of large single-crystal spin glass samples, focusing on both field-cooled (FC) and zero-field-cooled (ZFC) magnetization studies, as well as ac susceptibility measurements. Using the above experimental techniques we aim to understand the nature of spin glass transition in presence of a field, a key factor in understanding the properties of these systems. Building on previous studies that have explored magnetic signatures indicative of spin glass transitions, our research employs a systematic approach to refine the identification of this transition temperature. Through static and dynamic measurements, we aim to shed light on the open issues regarding the key markers of spin glass transitions, enhancing our understanding of these complex systems.

36 MATERIALS SCIENCE↗
DOE OSTI2026

A finite viscoelastic constitutive model for low to high strain rate response of elastomers with application of strain rate-induced glass transition

Amorphous elastomers exhibit significant rate-stiffening and unique viscous flow characteristics across a wide range of strain rates, often undergoing glass transition above a strain rate threshold. We have developed a thermodynamically-consistent and micromechanically-inspired constitutive model for soft elastomeric materials to capture the rate-dependent stress-strain behavior and hysteresis when subjected to low to high strain rates. Here, our proposed constitutive model encapsulates the viscous flow of materials through molecular motion at low strain rates and local rearrangement and alignment of the molecules trying to overcome the intermolecular resistance at high strain rates, essentially covering the glass transition. We applied our constitutive model to uniaxial compression experiments performed at low and high strain rates for polyborosiloxane (PBS) to identify the material parameters, and subsequently, performed numerical simulations of single and multi-cycle compression, stress relaxation, and small amplitude oscillatory tension-compression. Our analyses indicate that the model predicts higher total energy dissipation with increasing strain rate; however, dissipation associated with molecular relaxation decreases (forming a cusp) because, beyond a crossover strain rate, intermolecular rearrangement and alignment become dominant, which is consistent with the onset of the glass transition. For cyclic loading-unloading, we observed that dissipation over a cycle remains constant at low strain rates but decreases non-monotonically at high strain rates before becoming constant, with the peak stress over the cycle becoming higher, which can be interpreted as more loading being carried elastically by the polymer network as the intermolecular rearrangement process occurs. Additionally, our model was able to predict the qualitative nature of the storage modulus and loss modulus in the limit of small strain over a wide range of frequency sweeps.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Anomalous structural recovery in the near glass transition range in a polymer glass: Data revisited in light of temperature variability in vacuum oven‐based experiments*

Abstract There is considerable interest in data reported by Cangialosi et al. [Cangialosi, D., Boucher, V. M., Alegría, A., & Colmenero, J. (2013). Physical Review Letters , 111 (9), 095701] that purportedly showed unusual irregular responses in the isothermal structural recovery behavior of glasses because the observation challenges the general view of the dynamics being smooth functions of time as observed in extensive dilatometric experiments by Kovacs [Kovacs, A. J. (1964). In Fortschritte der Hochpolymeren‐Forschung , 3 , 394–507. Springer, Berlin, Heidelberg.] in the 1960s. The reported data show an apparent two mechanism structural (enthalpy) recovery at aging temperatures ranging from 6 to 17 K below which is also controversial as it could not be reproduced in work from Koh and Simon [Koh, Y. P., & Simon, S. L. (2013). Macromolecules , 46(14), 5815–5821.] where a second plateau observed in the enthalpy loss curve was not reproduced in nearly 1‐year‐long experiments at 15 K below . Therefore, it is important to determine what might be possible reasons for the apparent non‐smooth relaxations. Here, we examine the possibility that the poor temperature control of a typical vacuum oven could explain the anomalous results. We used the Tool–Narayanaswamy–Moynihan (TNM) model of structural recovery to calculate the effect of typical vacuum oven temperature variation on the structural recovery of polystyrene and find that we can reproduce the reported experimental results. The issue of temperature control using a vacuum oven is discussed, and data from thermocouple measurements of temperature at various locations inside a vacuum oven are shown.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Dataset_for_Molecular_Motion_Below_the_Glass_Transition_A_Solid-State_NMR_Study_of_Siloxane_Polymer_Dynamics Study

This dataset contains solid-state 1H and 13C NMR relaxometry data, differential scanning calorimetry (DSC) data, and size exclusion chromatography (SEC/GPC) data supporting the study of sub-glass-transition (sub-Tg) molecular dynamics in a composition- and sequence-controlled series of diphenyl-substituted polysiloxanes (PDMS, 14Ph, 33Ph, 50Ph, 67Ph, and 100Ph; 0–100% diphenylsiloxane content by mole).All solid-state NMR data were acquired on a 200 MHz Bruker Avance III HD spectrometer using a static 7 mm HX probe or a 4 mm HX probe under 4 kHz magic-angle spinning. Raw Bruker TopSpin experiment folders are included for: (1) variable-temperature 1H lineshape measurements used to determine linewidth (FWHM) as a function of temperature across the glass transition; (2) 1H T1 (saturation recovery with solid-echo detection), probing nanosecond-scale dynamics near the 1H Larmor frequency; (3) 1H T1rho (direct spin-lock, 62.5 kHz), probing microsecond-scale segmental dynamics; (4) 13C-detected Lee–Goldburg cross-polarization 1H T1rho (LGCPH T1rho) for 33Ph and 50Ph, resolving aromatic and aliphatic proton environments; and (5) 13C T1 relaxation for 33Ph and 50Ph. Differential scanning calorimetry data (TA Instruments DSC 25, −150 to +120 °C, up to +300 °C for 100Ph, 10 °C/min) are included for all six compositions and support the glass-transition temperatures in Table 1 and Figure 1. Size exclusion chromatography data (Agilent 1200 Series, PL-Gel 300 mixed-C column, THF mobile phase, polystyrene calibration standards) are included for the three synthesized copolymers (33Ph, 50Ph, 67Ph) and support the number-average molecular weights in Table 1. Processed data include per-composition relaxation-time summaries (Excel), curve-fitting and Bloembergen-Purcell-Pound (BPP) model analysis notebooks (Jupyter/Python), and Igor Pro (.pxp) master files used to generate the manuscript's figures.

Bloembergen-Purcell-Pound theory↗
DOE OSTI2026

Understanding Solvent-Induced Glass Transition in Polymer Thin Films Using Absorption–Desorption Isotherms

The fundamental thermodynamic and mechanical underpinnings of polymer thin films exposed to solvent vapor are critical for the development of advanced nanolithography and high-performance coatings. This work investigates the solvent− polymer interactions of glassy thin films by using the solvent absorption−desorption isotherms. An analogous relationship to the Flory−Fox equation was observed between solvent−induced glass transition, swelling, Flory−Huggins interaction parameter, and molecular weight. Isothermal swelling measurements revealed that the glass transition trends are more robust in the absorption curve compared to desorption, contrary to previous reports. Excess osmotic pressure analysis of the isotherm provides a measure of the degree of physical aging in thin films annealed below the glass transition. This is further validated in the ordering of block copolymer (BCP) films annealed at low solvent activity. In agreement with the thermal analysis, free-surface plasticization effects become the most prominent below 100 nm. However, solvent annealing is largely dependent on solvent mass transport, as made evident by the strong dependence on solvent viscosity. From these observations, four general types of isotherms are identified that graphically capture distinct solvent−polymer interaction regimes. More broadly, these results inform solvent vapor annealing-induced self-assembly, sequential infiltration synthesis, membrane-based separations, adsorptive processes, and swelling-based responsive materials design.

Hendeniya, Nayanathara [Iowa State Univ., Ames, IA↗
DOE OSTI2025

Translational diffusion in supercooled water at and near the glass transition temperature—136 K

The properties of amorphous solid water at and near the calorimetric glass transition temperature, T g , of 136 K have been debated for years. One hypothesis is that water turns into a “true” liquid at T g (i.e., it becomes ergodic) and exhibits all the characteristics of an ergodic liquid, including translational diffusion. A competing hypothesis is that only rotational motion becomes active at T g , while the “real” glass transition in water is at a considerably higher temperature. To address this dispute, we have investigated the diffusive mixing in nanoscale water films, with thicknesses up to ∼100 nm, using infrared (IR) spectroscopy. The experiments used films that were composed of at least 90% H 2 O with D 2 O making up the balance and were conducted under conditions where H/D exchange was essentially eliminated. Because the IR spectra of multilayer D 2 O films (e.g., thicknesses of ∼3–6 nm) embedded within thick H 2 O films are distinct from the spectrum of isolated D 2 O molecules within H 2 O, the diffusive mixing of (initially) isotopically layered water films could be followed as a function of annealing time and temperature. The results show that water films with total thicknesses ranging from ∼20 to 100 nm diffusively mixed prior to crystallization for temperatures between 120 and 144 K. The translational diffusion had an Arrhenius temperature dependence with an activation energy of 40.8 ± 3.5 kJ/mol, which indicates that water at and near T g is a strong liquid. The measured diffusion coefficient at 136 K is 6.25 ± 1.4 × 10 −21 m 2 /s.

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

Inhomogeneous mean-field approach to collective excitations near the superfluid–Mott glass transition

Highlights: • Unconventional collective excitations across the superfluid–Mott glass transition. • Higgs mode localized in superfluid and insulating phases. • Broad uncritical amplitude response function at quantum phase transition. • Goldstone mode delocalizes in the superfluid phase. We develop an inhomogeneous quantum mean-field approach to the behavior of collective excitations across the superfluid–Mott glass quantum phase transition in two dimensions, complementing recent quantum Monte Carlo simulations (Puschmann et al. 2020). In quadratic (Gaussian) approximation, the Goldstone (phase) and Higgs (amplitude) modes completely decouple. Each is described by a disordered Bogoliubov Hamiltonian which can be solved by an inhomogeneous multi-mode Bogoliubov transformation. We find that the Higgs mode is spatially localized in both phases. The corresponding scalar spectral function shows a broad peak that is noncritical in the sense that its peak frequency does not soften but remains nonzero across the quantum phase transition. In contrast, the lowest-energy Goldstone mode delocalizes in the superfluid phase, leading to a zero-frequency spectral peak. We compare these findings to the results of the quantum Monte Carlo simulations. We also relate them to general results on the localization of bosonic excitations, and we discuss the limits and generality of our approach.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Machine learning prediction of glass transition temperature of conjugated polymers from chemical structure

Predicting the glass transition temperature (T g ) is of critical importance as it governs the thermomechanical performance of conjugated polymers (CPs). Here, we report a predictive modeling framework to predict T g of CPs through the integration of machine learning (ML), molecular dynamics (MD) simulations, and experiments. With 154 T g data collected, an ML model is developed by taking simplified “geometry” of six chemical building blocks as molecular features, where side-chain fraction, isolated rings, fused rings, and bridged rings features are identified as the dominant ones for T g . MD simulations further unravel the fundamental roles of those chemical building blocks in dynamical heterogeneity and local mobility of CPs at a molecular level. The developed ML model is demonstrated for its capability of predicting T g of several new high-performance solar cell materials to a good approximation. The established predictive framework facilitates the design and prediction of T g of complex CPs, paving the way for addressing device stability issues that have hampered the field from developing stable organic electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Scaling of Shear Rheology of Concentrated Charged Colloidal Suspensions across Glass Transition

Electrostatic interparticle interactions are a key component in controlling and designing rheological characteristics of concentrated charged colloidal suspensions. Herein, we investigate electroviscous effects on shear rheology using highly charged silica particles. By fixing the volume fraction but varying the salinity, the system undergoes a glass transition as evidenced by the evolution of the yield stress and zero-shear viscosity. We show that the steady shear viscosities obey a critical scaling relation that scales the flow curves into a super- and a sub-critical branch with glass transition salinity serving as the bifurcation point; we also demonstrate an isoviscosity scaling that collapses all isoviscosity lines into a single master curve that exhibits no singularity. Based on each scaling relation, in conjunction with common modeling equations, the quantitative relationships between the shear viscosity, stress, and salinity are established. This study demonstrates a new framework to model the steady shear rheology of concentrated charged colloids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Theory of Ion-Mediated Segmental Localization, Activated Structural Relaxation, and the Glass Transition in Polymerized Ionic Liquids

Here we combine polymer integral equation theory for structural correlations with a force-level theory for activated segmental relaxation to construct a microscopic theory for how ions modify the onset of segmental localization, the polymer alpha relaxation time, and glass transition temperature, T g , in dry polymerized ionic liquids (PolyILs). Our most important findings concerning the behavior of T g are (i) a weak dependence on anion–cation Coulomb attraction strength due to strong decoupling of ion and segmental dynamics, (ii) strong reduction with increasing mobile ion size due to both plasticization effects and weakening of ion-modified monomer caging, and (iii) increase with backbone rigidity and intrachain dynamic cooperativity. We quantitatively estimate T g variations as ion size and polymer static and dynamic rigidity are widely varied. The experimental data of 19 PolyILs are organized into a specific pattern consistent with the theoretical predictions with glass transition temperatures varying over a very wide range (~250 K) as observed experimentally. Based on the theoretical results, suggestions are made concerning the search for high conductivity Li- or Na-based PolyILs based on further lowering of T g via new polymer synthesis. Calculations of the alpha time as a function of packing fraction reveal the dynamic fragility increases for larger mobile ions, a more flexible backbone, and/or a smaller degree of intrachain dynamic cooperativity, as a consequence of the increasing importance of collective elasticity in determining the activation barrier. An analysis of transient segmental localization and a crossover to activated dynamics reveals similar, but not identical, trends as predicted at the laboratory vitrification timescale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Tuneable phase behaviour and glass transition via polymerization-induced phase separation in crosslinked step-growth polymers

We report once limited to chain-growth polymerizations, fine control over polymerization-induced phase separation (PIPS) has recently been demonstrated in rubber-toughened thermoset materials formed through step-growth polymerizations. The domain length scales of these thermoset materials can be elegantly tuned by utilizing a binary mixture of curing agents (CAs) that individually yield disparate morphologies. Importantly, varying the composition of the binary mixture affects characteristics of the materials such as glass transition temperature and tensile behavior. Here, we establish a full phase diagram of PIPS in a rubber-toughened epoxy system tuned by a binary CA mixture to provide a robust framework of phase behaviour. X-Ray scattering in situ and post-PIPS is employed to elucidate the PIPS mechanism whereby an initial polymerization-induced compositional fluctuation causes nanoscale phase separation of rubber and epoxy components prior to local chain crosslinking and potential macrophase separation. We further demonstrate the universality of this approach by alternatively employing binary epoxy or binary rubber mixtures to achieve broad variations in morphology and glass transitions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Stockmayer fluid simulations for viscosity and glass transition temperature of ionic liquids

We develop a Stockmayer fluid model for molecular dynamics simulations of ionic liquids that captures molecular polarization, ionic conductivity, viscosity, and glass transition temperature, using ethylammonium nitrate (EAN) as an example. The ions in EAN are treated as spheres interacting via the Lennard-Jones potential with an embedded point charge and a permanent dipole moment. We show that our simulation results for EAN are consistent with experimental data and then explore the effects of the molecular parameters on the viscosity of ionic liquids. Our results indicate that viscosity monotonically increases with ionic charge and dipole moment but non-monotonically changes with ionic diameter (or molar volume). This non-monotonic trend arises from the competition among the electrostatic interactions, molecular packing, and size asymmetry between the cation and anion. In conclusion, our model also shows that long-lived ion pairs result in higher viscosities.

Coarse-grained simulations↗
DOE OSTI2021

Effect of Microstructure on Chain Flexibility and Glass Transition Temperature of Polybenzofulvene

Polybenzofulvene (PBF) is a polydiene with a very high glass transition temperature (T g ), which makes it a potential candidate for use as the hard block for high-temperature thermoplastic elastomer applications. The T g s of polydienes are known to be related to chain flexibility. However, no studies have been reported that correlate the chain flexibility to the microstructure of PBF. Herein, we present a study of solution properties of linear PBFs with narrow molecular weight dispersity and having 1,2-addition ranging from 23% to 99%. The materials were prepared by living anionic polymerization under different conditions. Specifically, the chain flexibility as defined by the Flory's characteristic ratio, , and dependence of chain flexibility on microstructure by combined measurements of intrinsic viscosity and molecular weight using triple-detector size exclusion chromatography (SEC) is studied. The persistence lengths (l p ) and chain diameters (d B ) were also estimated using the touched-bead wormlike chain model. To the best of our knowledge, the characteristic ratio of PBF is found to be the highest of all polydienes that have been reported so far.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Consistent and reproducible computation of the glass transition temperature from molecular dynamics simulations

In many fields, from semiconductors for opto-electronic applications to ionic liquids (ILs) for separations, the glass transition temperature (Tg) of a material is a useful gauge for its potential use in practical settings. As a result, there is a great deal of interest in predicting Tg using molecular simulations. However, the uncertainty and variation in the trend shift method, a common approach in simulations to predict Tg, can be high. This is due to the need for human intervention in defining a fitting range for linear fits of density with temperature assumed for the liquid and glass phases across the simulated cooling. The definition of such fitting ranges then defines the estimate for the Tg as the intersection of linear fits. We eliminate this need for human intervention by leveraging the Shapiro–Wilk normality test and proposing an algorithm to define the fitting ranges and, consequently, Tg. Through this integration, we incorporate into our automated methodology that residuals must be normally distributed around zero for any fit, a requirement that must be met for any regression problem. Consequently, fitting ranges for realizing linear fits for each phase are statistically defined rather than visually inferred, obtaining an estimate for Tg without any human intervention. The method is also capable of finding multiple linear regimes across density vs temperature curves. We compare the predictions of our proposed method across multiple IL and semiconductor molecular dynamics simulation results from the literature and compare other proposed methods for automatically detecting Tg from density–temperature data. We believe that our proposed method would allow for more consistent predictions of Tg. We make this methodology available and open source through GitHub.

Chemistry↗