Thermodynamics description of startup flow of soft particles glasses.

Particle dynamics simulations are used to study the startup flow of jammed soft particle suspensions in shear flow from a thermodynamic perspective. This thermodynamic framework is established using the concept of the two-body excess entropy extracted from the transient pair distribution function and elastic energy of the suspension as a function of strain at different shear rates and suspension volume fractions. Although the evolution of the elastic energy in these soft particle glasses closely mimics the stress-strain behavior at different shear rates and volume fractions, there are several differences corresponding to their overshoots in terms of the broadness and location of the peaks. The transient excess entropy shows an anisotropic behavior due to the anisotropic distribution of contacts at high shear rates. The excess entropy at high shear rates increases as a function of the strain and attains a steady state. On the other hand, it is nearly constant and isotropic in the quasi-static regime, where the stress response is close to the dynamic yield stress. Using the transient elastic energy and excess entropy, a transient temperature is defined to establish a relationship between thermodynamics and the static yield stress data. This transient temperature increases with the strain and then diverges at strains close to the static yield point at high shear rates.

Effect of dynamic bond concentration on the mechanical properties of vitrimers.

The presence of dynamic covalent bonds allows vitrimers to undergo topology alterations and display self-healing properties. Herein, we study the influence of varying the concentration of dynamic bonds on the macroscopic properties of hybrid vitrimer networks by subjecting them to triaxial stretching tests using molecular simulations. Results show that the presence of dynamic bonds allows for continuous stress relaxation in the hybrid networks leading to delayed craze development and higher stretching as compared to permanently crosslinked networks. The work highlights the ability of glassy vitrimer networks to relax tensile stress during deformation successfully.

A Molecular Rheology Dynamics Study on 3D Printing of Liquid Crystal Elastomers.

This work presents a rheological study of a biocompatible and biodegradable liquid crystal elastomer (LCE) ink for three dimensional (3D) printing. These materials have shown that their structural variations have an effect on morphology, mechanical properties, alignment, and their impact on cell response. Within the last decade LCEs are extensively studied as potential printing materials for soft robotics applications, due to the actuation properties that are produced when liquid crystal (LC) moieties are induced through external stimuli. This report utilizes experiments and coarse-grained molecular dynamics to study the macroscopic rheology of LCEs in nonlinear shear flow. Results from the shear flow simulations are in line with the outcomes of these experimental investigations. This work believes the insights from these results can be used to design and print new material with desirable properties necessary for targeted applications.

Influence of solute association on the phase behavior of 12-hydroxystearic acid/n-alkane solutions.

The phase behavior of 12-hydroxystearic acid (12-HSA) in even-numbered alkanes ranging from octane (C8) to hexatriacontane (C36) was measured by visual observation of liquid + solid to liquid and liquid-liquid to liquid cloud points and liquid + solid to liquid + liquid transitions. In general solid phases were stabilized to low concentration and higher temperature with increasing alkane length. Liquid-liquid immiscibility was observed in larger alkanes starting with octadecane. The liquidus lines of shorter alkanes (octane to hexadecane) showing only liquid to liquid + solid transitions were fit with an attenuated associated solution model based on the Flory-Huggins lattice model assuming that 12-HSA forms a carboxylic acid dimer over all concentrations investigated. The fit results show that 12-HSA forms associated structures with degrees of association ranging from 3.7-4.5 dimers in the neat 12-HSA. At low concentrations, the 12-HSA is dissociated into dimers, however the free energy cost of dissociation stabilizes the solid phase giving a sharp knee at low concentrations. The role of 12-HSA association in its phase behavior and gelation behavior are discussed. More broadly, the importance of solute association in small molecule organogelators and its potential as a molecular design parameter similar to other component thermodynamic parameters, such as melting temperature and heat of fusion, is discussed.

Osmotic Contribution of Synthesized Betaine by Choline Dehydrogenase Using In Vivo and In Vitro Models of Post-traumatic Syringomyelia.

Introduction: Syringomyelia (SM) is a debilitating spinal cord disorder in which a cyst, or syrinx, forms in the spinal cord parenchyma due to congenital and acquired causes. Over time syrinxes expand and elongate, which leads to compressing the neural tissues and a mild to severe range of symptoms. In prior omics studies, significant upregulation of betaine and its synthesis enzyme choline dehydrogenase (CHDH) were reported during syrinx formation/expansion in SM injured spinal cords, but the role of betaine regulation in SM etiology remains unclear. Considering betaine's known osmoprotectant role in biological systems, along with antioxidant and methyl donor activities, this study aimed to better understand osmotic contributions of synthesized betaine by CHDH in response to SM injuries in the spinal cord. Methods: A post-traumatic SM (PTSM) rat model and in vitro cellular models using rat astrocytes and HepG2 liver cells were utilized to investigate the role of betaine synthesis by CHDH. Additionally, the osmotic contributions of betaine were evaluated using a combination of experimental as well as simulation approaches. Results: In the PTSM injured spinal cord CHDH expression was observed in cells surrounding syrinxes. We next found that rat astrocytes and HepG2 cells were capable of synthesizing betaine via CHDH under osmotic stress in vitro to maintain osmoregulation. Finally, our experimental and simulation approaches showed that betaine was capable of directly increasing meaningful osmotic pressure. Conclusions: The findings from this study demonstrate new evidence that CHDH activity in the spinal cord provides locally synthesized betaine for osmoregulation in SM pathophysiology. Supplementary Information: The online version of this article contains supplementary material available 10.1007/s12195-022-00749-5.

Creep and Recovery Behavior of Vitrimers with Fast Bond Exchange Rate.

Vitrimers encompass the desirable mechanical properties of thermosets with the recyclability of thermoplastics. This ability arises from the rearrangement of the vitrimer covalent network upon heating via a bond shuffling mechanism while its cross-link density remains preserved. This unique feature makes vitrimers interesting candidates for the design of materials that combine dimensional stability at high temperatures and solvent resistance with the ability to be reshaped and processed. Despite these advantages, vitrimer exhibits significant creep at operating conditions where thermosets show little or no creep. As the mechanical properties of vitrimers not only depend on their chemical composition but also on the dynamics of the polymer chains, molecular dynamics (MD) simulations can provide detailed molecular mechanisms of the system of interest under macroscopic stress-induced deformations. In this regard, the recently developed MD/Monte Carlo simulation methodology capable of capturing the bond exchange mechanics in vitrimers is used to study the creep and recovery response of a coarse-grained model thermoset and vitrimer with a fast bond exchange rate. The time-stress superposition principle is then successfully applied to the creep response. The resulting universal curves enable us to predict the long-time creep behavior of both systems extending the timescale from 4 to over 10 orders of magnitude.

Extending the timescale of molecular simulations by using time-temperature superposition: rheology of ionic liquids.

Molecular dynamics simulations are used to determine the temperature dependence of the dynamic and rheological properties of a model imidazolium-based ionic liquid (IL). The simulation results for the volumetric properties of the IL are in good agreement with the experimental results. The temperature dependence of the diffusion coefficient of anions and cations follows the Vogel-Fulcher-Tammann equation over the range of the temperatures studied. The shear viscosity of the IL shows a Newtonian plateau at low shear rates and shear-thinning behavior at high shear rates. The dynamic modulus values indicate that the IL behaves like a viscous liquid at high temperatures and low frequencies, while its viscoelastic response becomes similar to that of an elastic solid at low temperatures and high frequencies. Using the time-temperature superposition (TTS) principle, the dynamic moduli, shear viscosity, and mean squared displacement of cations and anions in the diffusive regime can be collapsed onto master curves by applying a single set of shift factors. Due to the large mismatch in the timescale investigated by the atomistically detailed simulations and experiments, the glass transition temperature predicted in simulations shifts to higher values. When this timescale mismatch is accounted for by using appropriate shift factors, the master curves of the dynamic moduli obtained in simulations closely match those obtained in experiments. This result demonstrates the exciting ability of TTS to overcome the large timescale disparity between simulations and experiments which will enable the use of molecular simulations for quantitatively predicting the rheological property values at frequencies of practical interest.

Thermodynamics and Rheology of Imidazolium-Based Ionic Liquid-Oil Mixtures: A Molecular Simulation Study.

Conventional lubricants decrease the wear and friction between rolling and sliding surfaces while raising environmental concerns. The thermodynamics and flow behavior of lubricants that contain environmentally friendly additives such as ionic liquids (ILs) are of interest to industries that require lubricants with superior tribological properties. Noncorrosive ILs are promising additives for conventional oil that not only further decrease friction but also create a less hazardous alternative to existing lubricants. In this study, thermodynamics, dynamics, and rheology of IL-oil mixtures are studied by using atomistically detailed molecular dynamics (MD) simulations. A combination of different imidazolium-based cations with linear ([CnC1Im]+[NTf2]-, n = 3, 7) and branched chains ([(n - 2)mCn-1C1Im]+, n = 3, 7) and bis[(trifluoroethane)sulfonyl]imide ([NTf2]-) anion are selected as the model IL which is suspended in bulk hexadecane. The effects of IL content, architecture, size of cation, and temperature are examined on the thermorheological and dynamics of the IL-hexadecane mixture. At equilibrium, ILs self-assemble and create clusters with different shapes and sizes and affect the dynamics and rheology of the mixtures. Mixtures show a significant deviation from ideal solutions behavior. Shear and extensional rheology simulations show that mixtures mostly show Newtonian behaviors at low and moderate rates which is followed by a weak thinning behavior at high rates. It is shown that a small addition of ILs (x=2% mole fraction) to oil significantly increases both the shear and extensional viscosity of the mixture by a factor of 3.

Molecular Dynamics Simulations of Aqueous Nonionic Surfactants on a Carbonate Surface.

The interactions and structure of secondary alcohol ethoxylates with 15 and 40 ethoxylate units in water near a calcite surface are studied. It is found that water binds preferentially to the calcite surface. Prediction of the free-energy landscape for surfactant molecules shows that single-surfactant molecules do not adsorb because they cannot get close enough to the surface because of the water layer for attractive ethoxylate-calcite or dispersion interactions to be significant. Micelles can adsorb onto the surface even with the intervening water layer because of the integrative effect of the attractive interactions of all the surfactant molecules. Adsorption is found to increase because of the closer proximity of the micelles to the surface due to a weakened water layer at higher temperatures. The free-energy well and barrier values are used to estimate surface to bulk partition coefficients for different surfactants and temperatures, and qualitative agreement is found with experimental observations. The combined effect of surfactant-water and surfactant-solid interactions is found to be responsible for an increased adsorption for nonionic surfactants as the system approaches the cloud point.