This research effort examined the application of Nafion polymers in alcohol solvents as an anti-ice surface coating, as a mixture with hydrophilic polymers and freezing point depressant salt systems. Co-soluble systems of Nafion, polymer and salt were applied using dip coating methods to create smooth films for frost observation over a Peltier plate thermal system in ambient laboratory conditions. Cryo-DSC was applied to examine freezing events of the Nafion-surfactant mixtures, but the sensitivity of the measurement was insufficient to determine frost behavior. Collaborations with the Fog Chamber at Sandia-Albuquerque, and in environmental SAXS measurements with CINT-LANL were requested but were not able to be performed under the research duration. Since experimental characterization of these factors is difficult to achieve directly, computational modeling was used to guide the scientific basis for property improvement. Computational modeling was performed to improve understanding of the dynamic association between ionomer side groups and added molecules and deicing salts. The polyacrylic acid in water system was identified at the start of the project as a relevant system for exploring the effect of varying counterions on the properties of fully deprotonated polyacrylic acid (PAA) in the presence of water. Simulations were modeled with four different counterions, two monovalent counterions (K+ and Na+) and two divalent counterions (Ca2+ and Mg2+). The wt% of PAA in these systems was varied from ~10 to 80 wt% PAA for temperatures from 250K to 400K. In the second set of simulations, the interpenetration of water into a dry PAA film was studied for Na+ or Ca2+ counterions for temperatures between 300K and 400K. The result of this project is a sprayable Nafion film composite which resists ice nucleation at -20 °C for periods of greater than three hours. It is composed of Nafion polymer, hydrophilic polyethylene oxide polymer and CaCl2 anti-ice crosslinker. Durability and field performance properties remain to be determined.
Tang, Yanfei T.; McLaugahan, John E.; Grest, Gary S.; cheng, shengfeng c.
A method of simulating the drying process of a soft matter solution with an implicit solvent model by moving the liquid-vapor interface is applied to various solution films and droplets. For a solution of a polymer and nanoparticles, we observe “polymer-on-top” stratification, similar to that found previously with an explicit solvent model. Furthermore, “polymer-on-top” is found even when the nanoparticle size is smaller than the radius of gyration of the polymer chains. For a suspension droplet of a bidisperse mixture of nanoparticles, we show that core-shell clusters of nanoparticles can be obtained via the “small-on-outside” stratification mechanism at fast evaporation rates. “Large-on-outside” stratification and uniform particle distribution are also observed when the evaporation rate is reduced. Polymeric particles with various morphologies, including Janus spheres, core-shell particles, and patchy particles, are produced from drying droplets of polymer solutions by combining fast evaporation with a controlled interaction between the polymers and the liquid-vapor interface. Our results validate the applicability of the moving interface method to a wide range of drying systems. The limitations of the method are pointed out and cautions are provided to potential practitioners on cases where the method might fail.
Due to significant computational expense, discrete element method simulations of jammed packings of size-dispersed spheres with size ratios greater than 1:10 have remained elusive, limiting the correspondence between simulations and real-world granular materials with large size dispersity. Here, invoking a recently developed neighbor binning algorithm, we generate mechanically stable jammed packings of frictionless spheres with power-law size distributions containing up to nearly 4 000 000 particles with size ratios up to 1:100. By systematically varying the width and exponent of the underlying power laws, we analyze the role of particle size distributions on the structure of jammed packings. The densest packings are obtained for size distributions that balance the relative abundance of large-large and small-small particle contacts. Although the proportion of rattler particles and mean coordination number strongly depend on the size distribution, the mean coordination of nonrattler particles attains the frictionless isostatic value of six in all cases. The size distribution of nonrattler particles that participate in the load-bearing network exhibits no dependence on the width of the total particle size distribution beyond a critical particle size for low-magnitude exponent power laws. This signifies that only particles with sizes greater than the critical particle size contribute to the mechanical stability. However, for high-magnitude exponent power laws, all particle sizes participate in the mechanical stability of the packing.
Mohottalalage, Supun S.; Senanayake, Manjula S.; Clemmer, Joel T.; Perahia, Dvora P.; Grest, Gary S.; O'Connor, Thomas O.
Response to elongational flow is fundamental to soft matter and directly impacts new developments in a broad range of technologies form polymer processing and microfluidics to controlled flow in biosystems. Of particular significance are the effects of elongational flow on self-assembled systems where the interactions between the fundamental building blocks control their adaptation. Here we probe the effects of associating groups on the structure and dynamics of linear polymer melts in uniaxial elongation using molecular dynamics simulations. We study model polymers with randomly incorporated backbone associations with interaction strengths varying from 1kBT to 10kBT. These associating groups drive the formation of clusters in equilibrium with an average size that increases with interaction strength. Flow drives these clusters to continuously break and reform as chains stretch. These flow-driven cluster dynamics drive a qualitative transition in polymer elongation dynamics from homogeneous to nanoscale localized yield and cavitation as the association strength increases.
For strongly charged polyelectrolytes in salt-free solutions, we use molecular dynamics simulations of a coarse-grained bead-spring model to calculate overlap concentrations c∗ and chain structure for polymers containing N = 10 to 1600 monomers. Over much of this range, we find that the end-to-end distance R∗ at c∗ increases faster than linearly with increasing N, as chains at the overlap concentration approach strongly extended conformations. This trend results in the overlap concentration c∗ decreasing as a stronger function of N than the classical prediction c∗ ∼N-2. This stronger dependence can be fit either by a logarithmic correction to scaling or by an apparent scaling c∗ ∼N-m, with m > 2.
This report summarizes molecular and continuum simulation studies focused on developing physics - based predictive models for the evolution of polymer molecular order during the nonlinear processing flows of additive manufacturing. Our molecular simulations of polymer elongation flows identified novel mechanisms of fluid dissipation for various polymer architectures that might be harnessed to enhance material processability. In order to predict the complex thermal and flow history of polymer realistic additive manufacturing processes, we have developed and deployed a high - performance mesh - free hydrodynamics module in Sandia's LAMMPS software. This module called RHEO – short for Reproducing Hydrodynamics and Elastic Objects – hybridizes an updated - Lagrange reproducing - kernel method for complex fluids with a bonded particle method (BPM) to capture solidification and solid objects in multiphase flows. In combination, our two methods allow rapid, multiscale characterization of the hydrodynamics and molecular evolution of polymers in realistic processing geometries.
By generalizing a geometric argument for frictionless spheres, a model is proposed for the jamming density φJ of mechanically stable packings of bidisperse, frictional spheres. The monodisperse, μs-dependent jamming density φJmono(μs) is the only input required in the model, where μs is the coefficient of friction. The predictions of the model are validated by robust estimates of φJ obtained from computer simulations of up to 107 particles for a wide range of μs, and size ratios up to 40:1. Although φJ varies nonmonotonically with the volume fraction of small spheres fs for all μs, its maximum value φJ,max at an optimal fmaxs are both μs dependent. The optimal fmaxs is characterized by a sharp transition in the fraction of small rattler particles.
Senanayake, Manjula; Aryal, Dipak; Grest, Gary S.; Perahia, Dvora
Ionizable block copolymers with distinctive block characteristics display the diversity crucial for the design of macromolecules for targeted applications. In contrast to van der Waals copolymers, their interfaces, which are critical to their function, consist of nanodomains, each of a different nature and thus unique interfacial behavior. Here, the interfacial response of a symmetric block copolymer with a sulfonated polystyrene polyelectrolyte center, tethered to polyethylene-r-propylene and terminated by poly(t-butyl styrene) is probed as polymer films are exposed to three polar solvents, water, propanol, and tetrahydrofuran (THF), using molecular dynamics simulations. Each of the solvents captures a distinctive interaction with the individual blocks. We find that at the film boundary, the interfacial response is initially dominated by that of the hydrophobic blocks to all solvents. At later times, the solvent distribution among the blocks, where water molecules associate predominantly with the sulfonated groups and propanol and THF reside at multiple different sites, determines the chemical composition and the polymer conformation at the interface. Overall, these simulations provide the first direct molecular insight into the interfacial response of ionizable copolymers.
Parisi, Daniele; Costanzo, Salvatore; Jeong, Youncheol; Ahn, Junyoung; Chang, Taihyun; Vlassopoulos, Dimitris; Halverson, Jonathan D.; Kremer, Kurt; Ge, Ting; Rubinstein, Michael; Grest, Gary S.; Srinin, Watee; Grosberg, Alexander Y.
Steady-state shear viscosity (γ˙) of unconcatenated ring polymer melts as a function of the shear rate γ˙ is studied by a combination of experiments, simulations, and theory. Experiments using polystyrenes with Z ≈ 5 and Z ≈ 11 entanglements indicate weaker shear thinning for rings compared to linear polymers exhibiting power law scaling of shear viscosity ∼γ˙-0.56 ± 0.02, independent of chain length, for Weissenberg numbers up to about 102. Nonequilibrium molecular dynamics simulations using the bead-spring model reveal a similar behavior with ∼γ˙-0.57 ± 0.08 for 4 ≤ Z ≤ 57. Viscosity decreases with chain length for high γ˙. In our experiments, we see the onset of this regime, and in simulations, which we extended to Wi ∼104, the nonuniversality is fully developed. In addition to a naive scaling theory yielding for the universal regime ∼γ˙-0.57, we developed a novel shear slit model explaining many details of observed conformations and dynamics as well as the chain length-dependent behavior of viscosity at large γ˙. The signature feature of the model is the presence of two distinct length scales: the size of tension blobs and much larger thickness of a shear slit in which rings are self-consistently confined in the velocity gradient direction and which is dictated by the size of a chain section with relaxation time 1/γ˙. These two length scales control the two normal stress differences. In this model, the chain length-dependent onset of nonuniversal behavior is set by tension blobs becoming as small as about one Kuhn segment. This model explains the approximate applicability of the Cox-Merz rule for ring polymers.
A small number of associating groups incorporated onto a polymer backbone have dramatic effects on the mobility and viscoelastic response of the macromolecules in melts. These associating groups assemble, driving the formation of clusters, whose lifetime affects the properties of the polymers. Here, we probe the effects of the interaction strength on the structure and dynamics of two topologies, linear and star polymer melts, and further investigate blends of associative and non-associating polymers using molecular dynamics simulations. Polymer chains of approximately one entanglement length are described by a bead-spring model, and the associating groups are incorporated in the form of interacting beads with an interaction strength between them that is varied from 1 to 20 kBT. We find that, for all melts and blends, interaction of a few kBT between the associating groups drives cluster formation, where the size of the clusters increases with increasing interaction strength. These clusters act as physical crosslinkers, which slow the chain mobility. Blends of chains with and without associating groups macroscopically phase separate for interaction strength between the associating groups of a few kBT and above. For weakly interacting associating groups, the static structure function S(q) is well fit by functional form predicted by the random phase approximation where a clear deviation occurs as phase segregation takes place, providing a quantitative assessment of phase segregation.
We describe recent efforts to improve our predictive modeling of rate-dependent behavior at, or near, a phase transition using molecular dynamics simulations. Cadmium sulfide (CdS) is a well-studied material that undergoes a solid-solid phase transition from wurtzite to rock salt structures between 3 and 9 GPa. Atomistic simulations are used to investigate the dominant transition mechanisms as a function of orientation, size and rate. We found that the final rock salt orientations were determined relative to the initial wurtzite orientation, and that these orientations were different for the two orientations and two pressure regimes studied. The CdS solid-solid phase transition is studied, for both a bulk single crystal and for polymer-encapsulated spherical nanoparticles of various sizes.
Adding small amounts of ring polymers to a matrix of their linear counterparts is known to increase the zero-shear-rate viscosity because of linear-ring threading. Uniaxial extensional rheology measurements show that, unlike its pure linear and ring constituents, the blend exhibits an overshoot in the stress growth coefficient. By combining these measurements with ex-situ small-angle neutron scattering and nonequilibrium molecular dynamics simulations, this overshoot is shown to be driven by a transient threading-unthreading transition of rings embedded within the linear entanglement network. Prior to unthreading, embedded rings deform affinely with the linear entanglement network and produce a measurably stronger elongation of the linear chains in the blend compared to the pure linear melt. Thus, rings uniquely alter the mechanisms of transient elongation in linear polymers.
Peters, Brandon L.; Salerno, K.M.; Ge, Ting; Perahia, Dvora; Grest, Gary S.
Polymer synthesis routes result in macromolecules with molecular weight dispersity M that depends on the polymerization mechanism. The lowest dispersity polymers are those made by anionic and atom-transfer radical polymerization, which exhibit narrow distributions M = Mw/Mn ∼1.02-1.04. Even for small dispersity, the chain length can vary by a factor of two from the average. The impact of chain length dispersity on the viscoelastic response remains an open question. Here, the effects of dispersity on stress relaxation and shear viscosity of entangled polyethylene melts are studied using molecular dynamics simulations. Melts with chain length dispersity, which follow a Schulz-Zimm (SZ) distribution with M = 1.0-1.16, are studied for times up to 800 μs, longer than the terminal time. These systems are compared to those with binary and ternary distributions. The stress relaxation functions are extracted from the Green-Kubo relation and from stress relaxation following a uniaxial extension. At short and intermediate time scales, both the mean squared displacement and the stress relaxation function G(t) are independent of M. At longer times, the terminal relaxation time decreases with increasing M. In this time range, the faster motion of the shorter chains results in constraint release for the longer chains.
Intuition tells us that a rolling or spinning sphere will eventually stop due to the presence of friction and other dissipative interactions. The resistance to rolling and spinning or twisting torque that stops a sphere also changes the microstructure of a granular packing of frictional spheres by increasing the number of constraints on the degrees of freedom of motion. We perform discrete element modeling simulations to construct sphere packings implementing a range of frictional constraints under a pressure-controlled protocol. Mechanically stable packings are achievable at volume fractions and average coordination numbers as low as 0.53 and 2.5, respectively, when the particles experience high resistance to sliding, rolling, and twisting. Only when the particle model includes rolling and twisting friction were experimental volume fractions reproduced.
Polymer-tethered nanoparticles (NPs) are commonly added to a polymer matrix to improve the material properties. Critical to the fabrication and processing of such composites is the mobility of the tethered NPs. Here, we study the motion of tethered NPs in unentangled polymer melts using molecular dynamics simulations, which offer a precise control of the grafted chain length Ng and the number z of grafted chains per particle. As Ng increases, there is a crossover from particle-dominated to tethered-chain-dominated terminal diffusion of NPs with the same z. The mean squared displacement of loosely tethered NPs in the case of tethered-chain-dominated terminal diffusion exhibits two subdiffusive regimes at intermediate time scales for small z. The first one at shorter time scales arises from the dynamical coupling of the particle and matrix chains, while the one at longer time scales is due to the participation of the particle in the dynamics of the tethered chains. The friction of loosely grafted chains in unentangled melts scales linearly with the total number of monomers in the chains, as the friction of individual monomers is additive in the absence of hydrodynamic coupling. As more chains are grafted to a particle, hydrodynamic interactions between grafted chains emerge. As a result, there is a nondraining layer of hydrodynamically coupled chain segments surrounding the bare particle. Outside the nondraining layer is a free-draining layer of grafted chain segments with no hydrodynamic coupling. The boundary of the two layers is the stick surface where the shear stress due to the relative melt flow is balanced by the friction between the grafted and melt chains in the interpenetration layer. The stick surface is located further away from the bare surface of the particle with higher grafting density.
Molecular dynamics simulations confirm recent extensional flow experiments showing ring polymer melts exhibit strong extension-rate thickening of the viscosity at Weissenberg numbers Wi « 1. Thickening coincides with the extreme elongation of a minority population of rings that grows with Wi. The large susceptibility of some rings to extend is due to a flow-driven formation of topological links that connect multiple rings into supramolecular chains. Links form spontaneously with a longer delay at lower Wi and are pulled tight and stabilized by the flow. Once linked, these composite objects experience larger drag forces than individual rings, driving their strong elongation. The fraction of linked rings depends non-monotonically on Wi, increasing to a maximum when Wi 1 before rapidly decreasing when the strain rate approaches 1/Te.
Using random walk analyses we explore diffusive transport on networks obtained from contacts between isotropically compressed, monodisperse, frictionless sphere packings generated over a range of pressures in the vicinity of the jamming transition p→0. For conductive particles in an insulating medium, conduction is determined by the particle contact network with nodes representing particle centers and edges contacts between particles. The transition rate is not homogeneous, but is distributed inhomogeneously due to the randomness of packing and concomitant disorder of the contact network, e.g., the distribution of the coordination number. A narrow escape time scale is used to write a Markov process for random walks on the particle contact network. This stochastic process is analyzed in terms of spectral density of the random, sparse, Euclidean and real, symmetric, positive, semidefinite transition rate matrix. Results show network structures derived from jammed particles have properties similar to ordered, euclidean lattices but also some unique properties that distinguish them from other structures that are in some sense more homogeneous. In particular, the distribution of eigenvalues of the transition rate matrix follow a power law with spectral dimension 3. However, quantitative details of the statistics of the eigenvectors show subtle differences with homogeneous lattices and allow us to distinguish between topological and geometric sources of disorder in the network.
Pressure-driven assembly of ligand-grafted gold nanoparticle superlattices is a promising approach for fabricating gold nanostructures, such as nanowires and nanosheets. Optimizing this fabrication method will require extending our understanding of superlattice mechanics to regimes of high pressures. We use molecular dynamics simulations to characterize the response of alkanethiol-grafted gold nanoparticle superlattices to applied hydrostatic pressures up to 15 GPa. At low applied pressures, intrinsic voids govern the mechanics of compaction. As applied pressures increase, the void collapse and ligand compression depend significantly on the ligand length. These microstructural observations correlate directly with trends in bulk modulus and elastic constants. For short ligands, core-core contact between gold nanoparticles is observed at high pressures, which augurs irreversible response and eventual sintering. This presintering behavior was unexpected under hydrostatic loading and is observed only for the shortest ligands.
Large scale molecular dynamics simulations are used to study drying suspensions of a binary mixture of large and small particles in explicit and implicit solvents. The solvent is first modeled explicitly and then mapped to a uniform viscous medium by matching the diffusion coefficients and the pair correlation functions of the particles. "Small-on-top" stratification of the particles, with an enrichment of the smaller ones at the receding liquid-vapor interface during drying, is observed in both models under the same drying conditions. With the implicit solvent model, we are able to model much thicker films and study the effect of the initial film thickness on the final distribution of particles in the dry film. Our results show that the degree of stratification is controlled by the Péclet number defined using the initial film thickness as the characteristic length scale. When the Péclet numbers of large and small particles are much larger than 1, the degree of "small-on-top" stratification is first enhanced and then weakens as the Péclet numbers are increased.
Pressure-driven assembly of ligand-grafted gold nanoparticle superlattices is a promising approach for fabricating gold nanostructures, such as nanowires and nanosheets. However, optimizing this fabrication method requires an understanding of the mechanics of their complex hierarchical assemblies at high pressures. We use molecular dynamics simulations to characterize the response of alkanethiol-grafted gold nanoparticle superlattices to applied hydrostatic pressures up to 15 GPa, and demonstrate that the internal mechanics significantly depend on ligand length. At low pressures, intrinsic voids govern the mechanics of pressure-induced compaction, and the dynamics of collapse of these voids under pressure depend significantly on ligand length. These microstructural observations correlate well with the observed trends in bulk modulus and elastic constants. For the shortest ligands at high pressures, coating failure leads to gold core-core contact, an augur of irreversible response and eventual sintering. This behavior was unexpected under hydrostatic loading, and was only observed for the shortest ligands.
The temperature response of luminescent ionizable polymers confined into far from equilibrium nanoparticles without chemical links was studied using molecular dynamics simulations. These nanoparticles, often referred to as polydots, are emerging as a promising tool for nanomedicine. Incorporating ionizable groups into these polymers enables biofunctionality; however, they also affect the delicate balance of interactions that hold these nanoparticles together. Here polydots formed by a model polymer dialkyl p-phenylene ethynylene with varying number of carboxylate groups along the polymer backbone were probed. We find that increasing temperature affects neutral and charged polydots differently, where neutral polydots exhibit a transition above which their structure becomes dynamic and they unravel. The dependence of the transition temperature on the surface to volume ratio of these polydots is much stronger than what has previously been observed in polymeric thin films. Charged polydots become dynamic enabling migration of the ionizable groups toward the particle interface, while retaining the overall particle shape.
While nearly all theoretical and computational studies of entangled polymer melts have focused on uniform samples, polymer synthesis routes always result in some dispersity, albeit narrow, of distribution of molecular weights (Crossed D signM=Mw/Mn∼1.02-1.04). Here, the effects of dispersity on chain mobility are studied for entangled, disperse melts using a coarse-grained model for polyethylene. Polymer melts with chain lengths set to follow a Schulz-Zimm distribution for the same average Mw=36 kg/mol with Crossed D signM=1.0 to 1.16, were studied for times of 600-800 μs using molecular dynamics simulations. This time frame is longer than the time required to reach the diffusive regime. We find that dispersity in this range does not affect the entanglement time or tube diameter. However, while there is negligible difference in the average mobility of chains for the uniform distribution Crossed D signM=1.0 and Crossed D signM=1.02, the shortest chains move significantly faster than the longest ones offering a constraint release pathway for the melts for larger Crossed D signM.
Large scale molecular dynamics simulations for bidisperse nanoparticle suspensions with an explicit solvent are used to investigate the effects of evaporation rates and volume fractions on the nanoparticle distribution during drying. Our results show that "small-on-top" stratification can occur when Pesøs ≳ c with c ∼ 1, where Pes is the Péclet number and øs is the volume fraction of the smaller particles. This threshold of Pesøs for "small-on-top" is larger by a factor of ∼α2 than the prediction of the model treating solvent as an implicit viscous background, where α is the size ratio between the large and small particles. Our simulations further show that when the evaporation rate of the solvent is reduced, the "small-on-top" stratification can be enhanced, which is not predicted by existing theories. This unexpected behavior is explained with thermophoresis associated with a positive gradient of solvent density caused by evaporative cooling at the liquid/vapor interface. For ultrafast evaporation the gradient is large and drives the nanoparticles toward the liquid/vapor interface. This phoretic effect is stronger for larger nanoparticles, and consequently the "small-on-top" stratification becomes more distinct when the evaporation rate is slower (but not too slow such that a uniform distribution of nanoparticles in the drying film is produced), as thermophoresis that favors larger particles on the top is mitigated. A similar effect can lead to "large-on-top" stratification for Pesøs above the threshold when Pes is large but øs is small. Our results reveal the importance of including the solvent explicitly when modeling evaporation-induced particle separation and organization and point to the important role of density gradients brought about by ultrafast evaporation.