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.

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.

Influence of morphology of colloidal nanoparticle gels on ion transport and rheology.

We develop a simple model to probe the ion transport and mechanical properties of low volume fraction colloidal nanoparticle gels. Specifically, we study the influence of the morphology of gels on ion diffusion and the corresponding roles of affinity to and enhanced ion transport along nanoparticle surfaces. We employ kinetic Monte Carlo simulations to simulate ion transport in the colloidal gels, and we perform nonequilibrium molecular dynamics to study their viscoelastic behavior. Our results indicate that in the presence of enhanced diffusion pathways for ions along the particle surface, morphology has a significant influence on the diffusivity of ions. We demonstrate that some gel morphologies can exhibit simultaneously enhanced ion transport and mechanical properties, thus illustrating a strategy to decouple ion transport and mechanical strength in electrolytes.

Structure and phase behavior of polymer-linked colloidal gels.

Low-density "equilibrium" gels that consist of a percolated, kinetically arrested network of colloidal particles and are resilient to aging can be fabricated by restricting the number of effective bonds that form between the colloids. Valence-restricted patchy particles have long served as one archetypal example of such materials, but equilibrium gels can also be realized through a synthetically simpler and scalable strategy that introduces a secondary linker, such as a small ditopic molecule, to mediate the bonds between the colloids. Here, we consider the case where the ditopic linker molecules are low-molecular-weight polymers and demonstrate using a model colloid-polymer mixture how macroscopic properties such as the phase behavior as well as the microstructure of the gel can be designed through the polymer molecular weight and concentration. The low-density window for equilibrium gel formation is favorably expanded using longer linkers while necessarily increasing the spacing between all colloids. However, we show that blends of linkers with different sizes enable wider variation in microstructure for a given target phase behavior. Our computational study suggests a robust and tunable strategy for the experimental realization of equilibrium colloidal gels.

On the universality of the flow properties of soft-particle glasses.

We identify the minimal interparticle interactions necessary for a particle dynamics simulation to predict the structure and flow behaviour of soft particle glasses (SPGs). Generally, two kinds of forces between the particles must be accounted for in simulations of SPGs: viscous or frictional drag forces and elastic contact forces. Far field drag forces are required to dissipate energy in the simulations and capture the effect of the rheology of the suspending fluid. Elastic forces are found to be dominant compared to near-field drag or other forms of friction forces and are the most important component to compute the rheology. The shear stress, the first and second normal stress differences for different interparticle force laws collapse onto universal master curves of the Herschel-Bulkley form by non-dimensionalizing the stress with the yield stress and the shear rate with the viscosity of the suspending fluid divided by the low-frequency shear modulus. The Herschel-Bulkley exponents are close to 0.5 with a slight dependence on the repulsive pairwise elastic forces.

Cosolvents as Liquid Surfactants for Boron Nitride Nanosheet (BNNS) Dispersions.

Despite a range of promising applications, liquid-phase exfoliation of boron nitride nanosheets (BNNSs) is limited, both by low yield in common solvents as well as the disadvantages of using dissolved surfactants. One recently reported approach is the use of cosolvent systems to increase the as-obtained concentration of BNNS; the role of these solvents in aiding exfoliation and/or aiding colloidal stability of BNNSs is difficult to distinguish. In this paper, we have investigated the use of a t-butanol/water cosolvent to disperse BNNSs. We utilize solvent-exchange experiments to demonstrate that the t-butanol is in fact essential to colloidal stability; we then utilized molecular dynamics simulations to explore the mechanism of t-butanol/BNNS interactions. Taken together, the experimental and simulation results show that the key to the success of t-butanol (as compared to the other alcohols of higher or lower molecular weight) lies in its ability to act as a "liquid dispersant" which allows it to favorably interact with both water and BNNSs. Additionally, we show that the stable dispersions of BNNS in water/t-butanol systems may be freeze-dried to yield nonaggregated, redispersible BNNS powders, which would be useful in an array of industrial processes.

Liquid phase exfoliation and crumpling of inorganic nanosheets.

Here we demonstrate through experiment and simulation the polymer-assisted dispersion of inorganic 2D layered nanomaterials such as boron nitride nanosheets (BNNSs), molybdenum disulfide nanosheets (MoS2), and tungsten disulfide nanosheets (WS2), and we show that spray drying can be used to alter such nanosheets into a crumpled morphology. Our data indicate that polyvinylpyrrolidone (PVP) can act as a dispersant for the inorganic 2D layered nanomaterials in water and a range of organic solvents; the effectiveness of our dispersion process was characterized by UV-vis spectroscopy, microscopy and dynamic light scattering. Molecular dynamics simulations confirm that PVP readily physisorbs to BNNS surfaces. Collectively, these results indicate that PVP acts as a general dispersant for nanosheets. Finally, a rapid spray drying technique was utilized to convert these 2D dispersed nanosheets into 3D crumpled nanosheets; this is the first report of 3D crumpled inorganic nanosheets of any kind. Electron microscopy images confirm that the crumpled nanosheets (1-2 µm in diameter) show a distinctive morphology with dimples on the surface as opposed to a wrinkled, compressed surface, which matches earlier simulation results. These results demonstrate the possibility of scalable production of inorganic nanosheets with tailored morphology.

Effect of chain architecture on the size, shape, and intrinsic viscosity of chains in polymer solutions: a molecular simulation study.

Effect of chain architecture on the chain size, shape, and intrinsic viscosity was investigated by performing molecular dynamics simulations of polymer solutions in a good solvent. Four types of chains­linear, comb shaped, H-shaped, and star­were studied for this purpose using a model in which the solvent particles were considered explicitly. Results indicated that the chain length (N) dependence of the mean squared radius of gyration of the chains followed a power-law behavior ⟨R(g)(2)⟩(1/2)∼N(υ) with scaling exponents of υ = 0.605, 0.642, 0.602, and 0.608, for the linear, comb shaped, H-shaped, and star shaped chains, respectively. The simulation results for the geometrical shrinking factor were higher than the prior theoretical predictions for comb shaped chains. Analysis of chain shape demonstrated that the star chains were significantly smaller and more spherical than the others, while the comb and H-shaped polymer chains showed a more cylindrical shape. It is shown that the intrinsic viscosity of the chains can be calculated by plotting the specific viscosity determined from simulations against the solution concentration. The intrinsic viscosity exhibited linear behavior with the reciprocal of the overlap concentration for all chain architectures studied. The molecular weight dependence of the intrinsic viscosity followed the Mark-Houwink relation, [η] = KM(a), for all chain architectures. When comparing the calculated values of exponent a with the literature experimental values, agreement was found only for the H and star chains, and a disagreement for the linear and comb chains. The viscosity shrinking factor of the branched chains was compared with the available experimental data and the theoretical predictions and a general agreement was found.

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.

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.

Temperature Dependence of Volumetric and Dynamic Properties of Imidazolium-Based Ionic Liquids.

Atomistically detailed molecular dynamics simulations were used to investigate the temperature dependence of the specific volume, dynamic properties, and viscosity of linear alkyl chain ([CnC1Im][NTf2], n = 3-7) and branched alkyl chain ([(n - 2)mCn-1C1Im][NTf2]) ionic liquids (ILs). The trend of the glass transition temperature (Tg) values obtained in the simulations as a function of the alkyl chain length of cations was similar to the trend seen in experiments. In addition, the system relaxation behavior as determined from the temperature dependence of the diffusion coefficient, rotational relaxation time, and viscosity close to Tg was observed to follow the Vogel-Fulcher-Tammann expression. Furthermore, the reciprocal of the diffusion coefficient of the anion and cation in both linear and branched IL systems showed a linear correlation with viscosity, thus confirming the validity of the Stokes-Einstein relationship for these systems. Similarly, the average rotational relaxation time of the ions was also found to correlate linearly with the viscosity of the ILs over a wide range of temperatures, thereby validating the Debye-Stokes-Einstein relationship for the ILs. These simulation findings suggest that the temperature dependence of the relaxation time of ILs is very similar to that of other glass-forming liquids.

Swelling of Random Copolymer Networks in Pure and Mixed Solvents: Multi-Component Flory-Rehner Theory.

A generalized extension of Flory-Rehner (FR) theory is derived to describe equilibrium swelling of polymer networks, including copolymers with two or more chemically distinct repeat units, in either pure or mixed solvents. The model is derived by equating the chemical potential of each solvent in the liquid and gel phases at equilibrium, while assuming the deformation of the network chains is affine. Simplifications of the model are derived for specific cases involving homopolymer networks, copolymer networks, pure solvents, and binary solvent mixtures. With reasonable assumptions, the number of polymer-solvent interaction parameters that must be determined by experiments can be reduced to two effective parameters (θ1 and θ2), which describe the net interactions between water/copolymer (θ1) and ethanol/copolymer (θ2), respectively. Experimental measurements of the swelling of random copolymer networks of n-butyl acrylate and 2-hydroxyethyl acrylate in water, ethanol, and a 100 g/L ethanol/water mixture are utilized to validate the model. For a random copolymer network, θ1 and θ2 can be obtained by fitting the three-component FR model to equilibrium swelling data obtained in the pure solvents. Predicted solvent volume fractions for swelling in water-ethanol mixtures obtained by inserting fitted values of θ1 and θ2 into the four-component FR model are in reasonable agreement with experimental measurements.

Glass Transition and Molecular Mobility in Styrene-Butadiene Rubber Modified Asphalt.

Asphalt, a soft matter consisting of more than a thousand chemical species, is of vital importance for the transportation infrastructure, yet it poses significant challenges for microscopic theory and modeling approaches due to its multicomponent nature. Polymeric additives can potentially enhance the thermo-mechanical properties of asphalt, thus helping reduce the road repair costs; rational design of such systems requires knowledge of the molecular structure and dynamics of these systems. We have used molecular dynamics (MD) simulations to investigate the volumetric, structural, and dynamic properties of the neat asphalt as well as styrene-butadiene rubber (SBR) modified asphalt systems. The volume-temperature behavior of the asphalt systems exhibited a glass transition phenomenon, akin to that observed in experiments. The glass transition temperature, room temperature density, and coefficient of volume thermal expansion of the neat asphalt systems so evaluated were in agreement with experimental data when the effect of the high cooling rate used in simulations was accounted for. While the volumetric properties of SBR modified asphalt were found to be insensitive to the presence of the SBR additive, the addition of SBR led to an increase in the aggregation of asphaltene molecules. Furthermore, addition of SBR caused a reduction in the mobility of the constituent molecules of asphalt, with the reduction being more significant for the larger constituent molecules. Similar to other glass forming liquids, the reciprocal of the diffusion coefficient of the selected molecules was observed to follow the Vogel-Fulcher-Tammann (VFT) behavior as a function of temperature. These results suggest the potential for using polymeric additives for enhancing the dynamic mechanical properties of asphalt without affecting its volumetric properties.

Structure and Hydrogen Bonding of Water in Polyacrylate Gels: Effects of Polymer Hydrophilicity and Water Concentration.

The ability to tune the hydrophilicity of polyacrylate copolymers by altering their composition makes these materials attractive candidates for membranes used to separate alcohol-water mixtures. The separation behavior of these polyacrylate membranes is governed by a complex interplay of factors such as water and alcohol concentrations, water structure in the membrane, polymer hydrophilicity, and temperature. We use molecular dynamics simulations to investigate the effect of polymer hydrophilicity and water concentration on the structure and dynamics of water molecules in the polymer matrix. Samples of poly(n-butyl acrylate) (PBA), poly(2-hydroxyethyl acrylate) (PHEA), and a 50/50 copolymer of BA and HEA were synthesized in laboratory, and their properties were measured. Model structures of these systems were validated by comparing the simulated values of their volumetric properties with the experimental values. Molecular simulations of polyacrylate gels swollen in water and ethanol mixtures showed that water exhibits very different affinities toward the different (carbonyl, alkoxy, and hydroxyl) functional groups of the polymers. Water molecules are well dispersed in the system at low concentrations and predominantly form hydrogen bonds with the polymer. However, water forms large clusters at high concentrations along with the predominant formation of water-water hydrogen bonds and the acceleration of hydrogen bond dynamics.

Molecular Topology and Local Dynamics Govern the Viscosity of Imidazolium-Based Ionic Liquids.

A series of branched ionic liquids (ILs) based on the 1-(iso-alkyl)-3-methylimidazolium cation from 1-(1-methylethyl)-3-methylimidazolium bistriflimide to 1-(5-methylhexyl)-3-methylimidazolium bistriflimide and linear ILs based on the 1-(n-alkyl)-3-methylimidazolium cation from 1-propyl-3-methylimidazolium bistriflimide to 1-heptyl-3-methylimidazolum bistriflimide were recently synthesized and their physicochemical properties characterized. For the ILs with the same number of carbons in the alkyl chain, the branched IL was found to have the same density but higher viscosity than the linear one. In addition, the branched IL 1-(2-methylpropyl)-3-methylimidazolium bistriflimide ([2mC3C1Im][NTf2]) was found to have an abnormally high viscosity. Motivated by these experimental observations, the same ILs were studied using molecular dynamics (MD) simulations in the current work. The viscosities of each IL were calculated using the equilibrium MD method at 400 K and the nonequilibrium MD method at 298 K. The results agree with the experimental trend. The ion pair (IP) lifetime, spatial distribution function, and associated potential of mean force, cation size and shape, and interaction energy components were calculated from MD simulations. A quantitative correlation between the liquid structure and the viscosity was observed. Analysis shows that the higher viscosities in the branched ILs are due to the relatively more stable packing between the cations and anions indicated by the lower minima in the potential of mean force (PMF) surface. The abnormal viscosity of [2mC3C1Im][NTf2] was found to be the result of the specific side chain length and molecular structure.

Effect of carbon nanotube functionalization on mechanical and thermal properties of cross-linked epoxy-carbon nanotube nanocomposites: role of strengthening the interfacial interactions.

We have used amido-amine functionalized carbon nanotubes (CNTs) that form covalent bonds with cross-linked epoxy matrices to elucidate the role of the matrix-filler interphase in the enhancement of mechanical and thermal properties in these nanocomposites. For the base case of nanocomposites of cross-linked epoxy and pristine single-walled CNTs, our previous work (Khare, K. S.; Khare, R. J. Phys. Chem. B 2013, 117, 7444-7454) has shown that weak matrix-filler interactions cause the interphase region in the nanocomposite to be more compressible. Furthermore, because of the weak matrix-filler interactions, the nanocomposite containing dispersed pristine CNTs has a glass transition temperature (Tg) that is ∼66 K lower than the neat polymer. In this work, we demonstrate that in spite of the presence of stiff CNTs in the nanocomposite, the Young's modulus of the nanocomposite containing dispersed pristine CNTs is virtually unchanged compared to the neat cross-linked epoxy. This observation suggests that the compressibility of the matrix-filler interphase interferes with the ability of the CNTs to reinforce the matrix. Furthermore, when the compressibility of the interphase is reduced by the use of amido-amine functionalized CNTs, the mechanical reinforcement due to the filler is more effective, resulting in a ∼50% increase in the Young's modulus compared to the neat cross-linked epoxy. Correspondingly, the functionalization of the CNTs also led to a recovery in the Tg making it effectively the same as the neat polymer and also resulted in a ∼12% increase in the thermal conductivity of the nanocomposite containing functionalized CNTs compared to that containing pristine CNTs. These results demonstrate that the functionalization of the CNTs facilitates the transfer of both mechanical load and thermal energy across the matrix-filler interface.