The shock Hugoniot for full-density and porous CeO2 was investigated in the liquid regime using ab initio molecular dynamics (AIMD) simulations with Erpenbeck's approach based on the Rankine-Hugoniot jump conditions. The phase space was sampled by carrying out NVT simulations for isotherms between 6000 and 100 000 K and densities ranging from ρ=2.5 to 20g/cm3. The impact of on-site Coulomb interaction corrections +U on the equation of state (EOS) obtained from AIMD simulations was assessed by direct comparison with results from standard density functional theory simulations. Classical molecular dynamics (CMD) simulations were also performed to model atomic-scale shock compression of larger porous CeO2 models. Results from AIMD and CMD compression simulations compare favorably with Z-machine shock data to 525 GPa and gas-gun data to 109 GPa for porous CeO2 samples. Using results from AIMD simulations, an accurate liquid-regime Mie-Grüneisen EOS was built for CeO2. In addition, a revised multiphase SESAME-Type EOS was constrained using AIMD results and experimental data generated in this work. This study demonstrates the necessity of acquiring data in the porous regime to increase the reliability of existing analytical EOS models.
Gold nanostructured materials exhibit important size- and shape-dependent properties that enable a wide variety of applications in photocatalysis, nanoelectronics and phototherapy. Here we show the use of superfast dynamic compression to synthesize extended gold nanostructures, such as nanorods, nanowires and nanosheets, with nanosecond coalescence times. Using a pulsed power generator, we ramp compress spherical gold nanoparticle arrays to pressures of tens of GPa, demonstrating pressure-driven assembly beyond the quasi-static regime of the diamond anvil cell. Our dynamic magnetic ramp compression approach produces smooth, shockless (that is, isentropic) one-dimensional loading with low-temperature states suitable for nanostructure synthesis. Transmission electron microscopy clearly establishes that various gold architectures are formed through compressive mesoscale coalescences of spherical gold nanoparticles, which is further confirmed by in-situ synchrotron X-ray studies and large-scale simulation. This nanofabrication approach applies magnetically driven uniaxial ramp compression to mimic established embossing and imprinting processes, but at ultra-short (nanosecond) timescales.
The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. The methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for the UDMA system, with parameters calibrated based on fully atomistic simulations of the UDMA monomer in the liquid state. Detailed metrics based on network graph theoretical approaches were implemented to quantify the bond network topology resulting from simulations. For a broad range of polymerization parameters, no discernible differences were seen between TRP and CRP UDMA simulations at equal conversions, although clear differences exist as a function of conversion. Both findings are consistent with experiments. Despite a number of shortcomings, these models have demonstrated the potential of molecular simulations for studying network topology in these systems.
We have conducted molecular dynamics (MD) simulations of quasi-isentropic ramp-wave compression to very high pressures over a range of strain rates from 1011 down to 108 1/s. Using scaling methods, we collapse wave profiles from various strain rates to a master profile curve, which shows deviations when material response is strain-rate dependent. Thus, we can show with precision where, and how, strain-rate dependence affects the ramp wave. We find that strain rate affects the stress-strain material response most dramatically at strains below 20%, and that above 30% strain the material response is largely independent of strain rate. We show good overall agreement with experimental stress-strain curves up to approximately 30% strain, above which simulated response is somewhat too stiff. We postulate that this could be due to our interatomic potential or to differences in grain structure and/or size between simulation and experiment. Strength is directly measured from per-atom stress tensor and shows significantly enhanced elastic response at the highest strain rates. This enhanced elastic response is less pronounced at higher pressures and at lower strain rates.
Nanoparticles (NPs) grafted with organic layers form hybrids able to retain their unique properties through integration into the mesoscopic scale. The organic layer structure and response often determine the functionality of the hybrids on the mesoscopic length scale. Using molecular dynamics (MD) simulations, we probe the conformation of luminescent rigid polymers, dialkyl poly(p-phenylene ethynylene)s (PPE), end-grafted onto a silica nanoparticle in different solvents as the molecular weights and polymer coverages are varied. We find that, in contrast to NP-grafted flexible polymers, the chains are fully extended independent of the solvent. In toluene and decane, which are good solvents, the grafted PPEs chains assume a similar conformation to that observed in dilute solutions. In water, which is a poor solvent for the PPEs, the polymer chains form one large cluster but remain extended. The radial distribution of the chains around the core of the nanoparticle is homogeneous in good solvents, whereas in poor solvents clusters are formed independent of molecular weights and coverages. The clustering is distinctively different from the response of grafted flexible and semiflexible polymers.
