Micromechanics, macromechanics and constitutive modeling of the elasto-viscoplastic deformation of rubber-toughened glassy polymers

Under certain conditions, such as sufficiently low temperatures, high loading rates and/or highly triaxial stress states, glassy polymers display an unfavorable characteristic—brittleness. A technique used for reducing the brittleness (increasing the fracture toughness) of these materials is rubber toughening. While there is significant qualitative understanding of the mechanical behavior of rubber-toughened polymers, quantitative modeling tools for the large-strain deformation of rubber-toughened glassy polymers are largely lacking.In this paper, we develop a suite of numerical tools to investigate the mechanical behavior of rubber-toughened glassy polymers, with emphasis on rubber-toughened polycarbonate. The rubber particles are modeled as voids in view of their deformation-induced cavitation early during deformation. A three-dimensional micromechanical model of the heterogeneous microstructure is developed to study the effects of initial rubber particle (void) volume fraction on the underlying elasto-viscoplastic deformation mechanisms in the material, and how these mechanisms influence the macroscopic response of the material. A continuum-level constitutive model is developed for the large-strain elasto-viscoplastic deformation of porous glassy polymers, and it is calibrated against micromechanical modeling results for porous polycarbonate. The constitutive model can be used to study various boundary value problems involving rubber-toughened (porous) glassy polymers. As an example, the case of an axisymmetric notched bar is simulated for the case of polycarbonate with varying levels of initial porosity. The quality of the constitutive model calibration is assessed using a multi-scale modeling approach.     

Plastic flow in oriented glassy polymers

A manufactured product often possesses residual texture which was either incidentally or deliberately acquired during its processing history. This is particularly true for the case of polymers, where the ability to easily preferentially preorient the material in specific directions is exploited in order to obtain a higher strength product. Specific examples include synthetic fibers, and biaxially-oriented films and containers. The response of the preoriented/textured product to normal service life loading conditions will differ considerably from that of a product composed of isotropic material. This paper addresses the issue of the effects of texture on the deformation behavior of glassy polymers. Here, the physically-based constitutive model of Boyce, Parks, and Argon describing the rate, temperature, and pressure dependent inelastic deformation of initially isotropic glassy polymers is used to model the effects of preorientation (i.e., initial texture), via the use of appropriate initial conditions on internal state variables. The model is then utilized in an analysis of the effects of texture on the yield of glassy polymers and the shear localization which normally follows yielding in oriented polymers. These results are compared with trends found in experiments as reported in the literature. The effectiveness of the proposed model for the present application is also compared with earlier models of yielding of anisotropic materials such as Hill's criterion.     

Tomographic reconstruction of shock layer flows

The tomographic reconstruction of supersonic flows faces two challenges. Firstly, techniques used in the past, such as the direct Fourier method (DFM) (Gottlieb and Gustafsson in On the direct Fourier method for computer tomography, 1998; Morton in Tomographic imaging of supersonic flows, 1995) or various backprojection (Kak and Slaney in Principles of computerized tomographic imaging, vol. 33 in Classics in Applied Mathematics, 2001) techniques, have only been able to reconstruct areas of the flow which are upstream of any opaque objects, such as a model. Secondly, shock waves create sharp discontinuities in flow properties, which can be difficult to reconstruct both in position and in magnitude with limited data. This paper will present a reconstruction method, matrix inversion using ray-tracing and least squares conjugate gradient (MI-RLS), which uses geometric ray-tracing and a sparse matrix iterative solver (Paige and Saunders in ACM Trans. Math. Softw. 8(1):43–71, 1982) to overcome both of these challenges. It will be shown, through testing with a phantom object described in tomographic literature, that the results compare favourably to those produced by the DFM technique. Finally, the method will be used to reconstruct three-dimensional density fields from interferometric shock layer images, with good resolution (Faletič in Tomographic reconstruction of shock layer flows, 2005). This paper was based on work that was presented at the 3rd International Symposium on Interdisciplinary Shock Wave Research, Canberra, Australia, March 1–3, 2006.     

Mechanics of nanoindentation on a monolayer of colloidal hollow nanoparticles

We explore the collective mechanical behavior of monolayer assemblies composed of close-packed arrays of hollow silica nanoparticles using a spherical nanoindentor. Seven types of well-defined hollow nanoparticles are studied with their radii ranging from 100 to 300 nm and shell thickness ranging from 14 to 44 nm. Micromechanical models reveal the underlying deformation mechanisms during indentation, where the consecutive contacting of the indentor with an increasing number of nanoparticles results in a nonlinear increase in the indentation force with penetration depth. Each contacted hollow nanoparticle successively locally bends, flattens, and then locally buckles. The effective indentation modulus of the monolayer film, which is obtained by a Hertzian fit to the experimental data, is found to be proportional to the elastic modulus of the nanoparticle shell material and scales exponentially with the ratio of particle shell thickness t to radius R to the power of 2.3. Furthermore, we find that for a constant film density with the same (t)/(R) of the constituent nanoparticles, smaller particles with a thinner shell can provide a higher effective indentation modulus, compared to their larger diameter and thicker shell counterparts. This study provides useful insights and guidance for constructing high-performance lightweight nanoparticle films and coatings with potential applications in tailoring stiffness and mechanical energy absorption.     

Analysis of Pathogenic Bacterial and Yeast Biofilms Using the Combination of Synchrotron ATR-FTIR Microspectroscopy and Chemometric Approaches

Biofilms are assemblages of microbial cells, extracellular polymeric substances (EPS), and other components extracted from the environment in which they develop. Within biofilms, the spatial distribution of these components can vary. Here we present a fundamental characterization study to show differences between biofilms formed by Gram-positive methicillin-resistant Staphylococcus aureus (MRSA), Gram-negative Pseudomonas aeruginosa, and the yeast-type Candida albicans using synchrotron macro attenuated total reflectance-Fourier transform infrared (ATR-FTIR) microspectroscopy. We were able to characterise the pathogenic biofilms’ heterogeneous distribution, which is challenging to do using traditional techniques. Multivariate analyses revealed that the polysaccharides area (1200–950 cm⁻¹) accounted for the most significant variance between biofilm samples, and other spectral regions corresponding to amides, lipids, and polysaccharides all contributed to sample variation. In general, this study will advance our understanding of microbial biofilms and serve as a model for future research on how to use synchrotron source ATR-FTIR microspectroscopy to analyse their variations and spatial arrangements.     

Does the local structure play a role in high temperature superconductivity?

Many highT_csystems exhibit structural distortions or anomalies, some of which correlate withT_c. We present our results for three such systems and discuss them in the context of providing any evidence for coupling of the lattice to the superconducting pairs. We then propose a modulation type of experiment that should provide unambiguous results if a significant lattice-pair coupling does exist.     

EXAFS study of the local Gd environment in the magnetic superconductor (La1−xGdx)Os2

The near-neighbor environment of Gd in the pseudobinary compound La_1?xGd_xOs₂ has been investigated by studying the EXAFS on the Gd LIII, La LII, and Os LIII edges. For Gd concentrations of x = 0.07 and x = 0.14, we find that the Gd predominantly substitutes on the La sites in the LaOs₂ lattice rather than forming local Gd metal or GdOs₂ clusters. These results are discussed in view of the fact that La_1?xGd_xOs₂ shows spin-glass-like properties (x ≤ 0.15) in the superconducting phase.     

Photolytic closure of 4,5-diphenyl-oxazol-2-ones to phenanthro[9,10-d]oxazol-2-ones and an improved synthesis of benzoins

The synthesis of phenathrenes substituted by nitrogen and oxygen atoms in position 9 and 10 by photolysis of 4,5-diphenyl-oxazol-2-ones (cf. Scheme 4) is described. Moreover an improved general procedure for the synthesis of benzoins in aprotic solvent (tetra-t-butylammonium cyanide in DMF/DMSO) is developed.     

Breakdown of absolute rate theory and prefactor anomalies in superionic conductors

We suggest that the anomalously low prefactors observed for the ionic hopping rate in defect-structure superionic conductors are due to a breakdown of absolute rate theory. A treatment that takes dissipative processes into account is introduced and a new expression for the prefactor is obtained. We present NMR data on the superionic conductor Li₂Ti₃O₇ that supports these ideas and extract the value of the elemental energy transfer per collision.