Modeling Brittle Fractures in Epoxy Nanocomposites Using Extended Finite Element and Cohesive Zone Surface Methods.

Linear elastic fracture modeling coupled with empirical material tensile data result in good quantitative agreement with the experimental determination of mode I fracture for both brittle and toughened epoxy nanocomposites. The nanocomposites are comprised of diglycidyl ether of bisphenol A cured with Jeffamine D-230 and some were filled with core-shell rubber nanoparticles of varying concentrations. The quasi-static single-edge notched bending (SENB) test is modeled using both the surface-based cohesive zone (CZS) and extended finite element methods (XFEM) implemented in the Abaqus software. For each material considered, the critical load predicted by the simulated SENB test is used to calculate the mode I fracture toughness. Damage initiates in these models when nodes at the simulated crack tip attain the experimentally measured yield stress. Prediction of fracture processes using a generalized truncated linear traction-separation law (TSL) was significantly improved by considering the case of a linear softening function. There are no adjustable parameters in the XFEM model. The CZS model requires only optimization of the element displacement at the fracture parameter. Thus, these continuum methods describe these materials in mode I fracture with a minimum number of independent parameters.

Influence of Interfacial Bonding on the Mechanical and Impact Properties Ring-Opening Metathesis Polymer (ROMP) Silica Composites.

Polymers formed by ring-opening metathesis polymerization (ROMP) such as poly(dicyclopentadiene) (pDCPD) exhibit a technologically desirable combination of high toughness, high glass transition temperature, and outstanding low-temperature performance. However, because of their nonpolar molecular structure, they tend to suffer from relatively low elastic moduli and poor adhesion to common fillers, fibers, and substrates, limiting their utility as adhesives and composite binders without specialized bonding agents. Here, we investigate the mechanical properties of a pDCPD-based copolymer filled with well-defined spherical microparticles having four distinct surface chemistries capable of strong, moderate, or weak bonding to the matrix with surfaces ranging from polar to nonpolar. Measurements in uniaxial tension, quasi-static fracture, and high-velocity impact are complemented by digital image correlation (DIC), scanning electron microscopy (SEM) fractography, and X-ray computed tomography (X-µCT) of subcritically loaded crack tips, yielding insight into the complex roles played by interfacial bonding in strength, stiffness, and toughening mechanisms of an already tough polymer. Analysis using quantitative fracture and impact mechanism models provided valuable guidelines for designing heterogeneous systems that combine structural and tough performance.

AMB2018-04: Benchmark Physical Property Measurements for Powder Bed Fusion Additive Manufacturing of Polyamide 12.

Laser sintering (LS) of polyamide 12 (PA12) is increasingly being adopted for industrial production of end-use parts, yet the complexity of this process coupled with the lack of organized, rigorous, publicly available process-structure-physical property datasets exposes manufacturers and customers to risks of unacceptably poor part quality and high costs. Although an extensive scientific literature has been developed to address some of these concerns, results are distributed among numerous reports based on different machines, materials, process parameters, and users. In this study, a single commercially important LS PA12 feedstock has been processed along four build dimensions of a modern production LS machine, characterized by a wide range of physical techniques, and compared to the same material formed by conventional melt processing. Results are discussed in the context of the literature, offering novel insights including distributions of particle size and shape, localization of semicrystalline phase changes due to LS processing, effect of chemical aging on melt viscosity, porosity orientation relative to LS build axes, and microstructural effects on tensile properties and failure mechanisms. The resulting datasets will be made publicly available to modelers and practitioners for the purpose of improving certifiability and repeatability of end-use parts manufactured by LS.

Mechanics and nanovoid nucleation dynamics: effects of polar functionality in glassy polymer networks.

We use molecular simulations and experiments to rationalize the properties of a class of networks based on dicyclopentadiene (DCPD), a polymer with excellent fracture toughness and a high glass transition temperature (Tg), copolymerized with 5-norbornene-2-methanol (NBOH). DCPD is a highly non-polar hydrocarbon, while NBOH contains a hydroxy group, introducing polar functionality and hydrogen bonds (H-bonds). NBOH thus represents a possible route to improve the chemical compatibility of DCPD-based networks with less-hydrophobic materials. We systematically vary the NBOH content (polar chemistry) in DCPD networks, while keeping other network parameters nearly constant, including the molecular weight between cross-links, chain rigidity, and Tg. Using molecular dynamics (MD) simulations, we quantify the thermovolumetric and mechanical properties, including Tg, cohesive energy density, stiffness, and yield strength. We compare these results with experiments on networks of similar composition, finding good agreement. The relation between these properties and polar chemistry are studied by examining a secondary network of physical cross-links, formed by hydrogen bonds between NBOH units. Further, we examine nanovoid formation, an energy dissipation mechanism hypothesized to contribute to the toughness of pDCPD. Using metadynamics to accelerate sampling, we quantify the nanovoid nucleation rate under hydrostatic tension, similar to the stress state in the plastic zone preceding a crack tip. Small additions of NBOH have minimal effect, but the rate drops steeply with larger amounts. Several properties are mapped at nanometer scales, including stiffness and mobility, and associated with void nucleation. Estimates of the length- and time-scale of the plastic zone near a crack tip are used in discussing nanovoid formation as a plausible toughening mechanism in these materials. Overall, the results suggest that pDCPD tolerates the addition of some polar chemistry without degrading its excellent mechanical properties.

Influence of molecular weight between crosslinks on the mechanical properties of polymers formed via ring-opening metathesis.

The apparent molecular weight between crosslinks (Mc,a) in a polymer network plays a fundamental role in the network mechanical response. We systematically varied Mc,a independent of strong noncovalent bonding by using ring-opening metathesis polymerization (ROMP) to co-polymerize dicyclopentadiene (DCPD) with a chain extender that increases Mc,a or a di-functional crosslinker that decreases Mc,a. We compared the ROMP series quasi-static modulus (E), tensile yield stress (σy), and fracture toughness (KIC and GIC) in the glassy regime with literature data for more polar thermosets. ROMP resins showed high KIC (>1.5 MPa m0.5), high GIC (>1000 J m-2), and 4-5 times higher high rate impact resistance than typical polar thermosets with similar Tg values (100 °C to 178 °C). The overall E values were lower for ROMP systems. The σy dependence on Mc,a and T-Tg for ROMP resins was qualitatively similar to more polar thermosets, but the overall σy values were lower. In contrast to more polar thermosets, the KIC and GIC values of the ROMP resins showed strong Mc,a and T-Tg dependence. High rate impact (∼104-105 s-1) trends were similar to the KIC and GIC behavior, but were also correlated to σy. Overall, a ductile failure mode was observed for quasi-static and high rate results for a linear ROMP polymer (Mc,a = 1506 g mol-1 due to chain entanglement), and this gradually transitioned to a fully brittle failure mode for highly crosslinked ROMP polymers (Mc,a ≤ 270 g mol-1). Molecular dynamics (MD) simulations showed that low Mc,a ROMP resins were more likely to form molecular scale nanovoids. The higher chain stiffness in low Mc,a ROMP resins inhibited stress relaxation in the vicinity of these nanovoids, which correlated with brittle mechanical responses. Overall, these differences in mechanical properties were attributed to the weak non-covalent interactions in ROMP resins.

Mechanical properties of silicone based composites as a temperature insensitive ballistic backing material for quantifying back face deformation.

This paper describes a new witness material for quantifying the back face deformation (BFD) resulting from high rate impact of ballistic protective equipment. Accurate BFD quantification is critical for the assessment and certification of personal protective equipment, such as body armor and helmets, and ballistic evaluation. A common witness material is ballistic clay, specifically, Roma Plastilina No. 1 (RP1). RP1 must be heated to nearly 38°C to pass calibration, and used within a limited time frame to remain in calibration. RP1 also exhibits lot-to-lot variability and is sensitive to time, temperature, and handling procedures, which limits the BFD accuracy and reproducibility. A new silicone composite backing material (SCBM) was developed and tested side-by-side with heated RP1 using quasi-static indentation and compression, low velocity impact, spherical projectile penetration, and both soft and hard armor ballistic BFD measurements to compare their response over a broad range of strain rates and temperatures. The results demonstrate that SCBM mimics the heated RP1 response at room temperature and exhibits minimal temperature sensitivity. With additional optimization of the composition and processing, SCBM could be a drop-in replacement for RP1 that is used at room temperature during BFD quantification with minimal changes to the current RP1 handling protocols and infrastructure. It is anticipated that removing the heating requirement, and temperature-dependence, associated with RP1 will reduce test variability, simplify testing logistics, and enhance test range productivity.

Carbon nanofiber-filled conductive silicone elastomers as soft, dry bioelectronic interfaces.

Soft and pliable conductive polymer composites hold promise for application as bioelectronic interfaces such as for electroencephalography (EEG). In clinical, laboratory, and real-world EEG there is a desire for dry, soft, and comfortable interfaces to the scalp that are capable of relaying the µV-level scalp potentials to signal processing electronics. A key challenge is that most material approaches are sensitive to deformation-induced shifts in electrical impedance associated with decreased signal-to-noise ratio. This is a particular concern in real-world environments where human motion is present. The entire set of brain information outside of tightly controlled laboratory or clinical settings are currently unobtainable due to this challenge. Here we explore the performance of an elastomeric material solution purposefully designed for dry, soft, comfortable scalp contact electrodes for EEG that is specifically targeted to have flat electrical impedance response to deformation to enable utilization in real world environments. A conductive carbon nanofiber filled polydimethylsiloxane (CNF-PDMS) elastomer was evaluated at three fill ratios (3, 4 and 7 volume percent). Electromechanical testing data is presented showing the influence of large compressive deformations on electrical impedance as well as the impact of filler loading on the elastomer stiffness. To evaluate usability for EEG, pre-recorded human EEG signals were replayed through the contact electrodes subjected to quasi-static compressive strains between zero and 35%. These tests show that conductive filler ratios well above the electrical percolation threshold are desirable in order to maximize signal-to-noise ratio and signal correlation with an ideal baseline. Increasing fill ratios yield increasingly flat electrical impedance response to large applied compressive deformations with a trade in increased material stiffness, and with nominal electrical impedance tunable over greater than 4 orders of magnitude. EEG performance was independent of filler loading above 4 vol % CNF (< 103 ohms).