Coalescence Of Free Volume Research Articles

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The cover image is based on the Research Article Effect of hexyl‐branched backbone size on the size distribution and coalescence of free volume around an amphiphilic molecule by Sajjad Kavyani et al., https://doi.org/10.1002/pen.26705. image

Effect of hexyl‐branched backbone size on the size distribution and coalescence of free volume around an amphiphilic molecule

AbstractWe used molecular dynamics simulation to study the size distribution and coalescence of free volume around an amphiphilic molecule (nonyl ethoxylate (NE)) at a concentration of 0.5 wt% in blends of linear and branched polyethylene that contained a small four‐arm alkane (7,12 hexyl octadecane). The branched polyethylene chains had 10 and 82 hexyl branches/1000 backbone carbons. The coalescence dynamics (fluctuation of free volume in time) was quantified by the number of Fourier frequencies and the corresponding power (amplitude). In our previous work, we hypothesized that cavitation, the first step of environmental stress cracking observed experimentally, starts from the free volume coalescence at the interface between NE and polyethylene molecules and showed that hexyl branches in the branched polyethylene molecules suppress such coalescence, suggesting that cavitation, a much longer time scale process, could also be slowed down. The current work showed that the behavior of hexyl branches in branched polyethylene in a blend with linear polyethylene was similar to that in pure branched polyethylene, but that the hexyl branches in the 7,12 hexyl octadecane exhibited the opposite behavior. In particular, they intensified free volume coalescence, especially around the hydrophilic ethylene oxide segments of NE. The addition of 7,12 hexyl octadecane to branched polyethylene alone or blended with linear polyethylene does not seem to slow down free volume coalescence (cavitation), leading us to conclude that the effect of hexyl branches on the free volume coalescence around NE depends on the size of the backbone to which the branches are attached.Highlights Hexyl branches reduce free volume coalescence activities. The longer the backbone is, the stronger the hexyl branch effect. More coalescence activities occur on the hydrophilic segment of NE.

Cavitation instability in bulk metallic glasses

Recent experiments have shown that fracture surfaces of bulk metallic glasses (BMGs) usually exhibit an intriguing nanoscale corrugation like fractographic feature mediated by nanoscale void formation. We attribute the onset of this nanoscale corrugation to TTZs (tension transformation zones) mediated cavitation. In our recent study, the spall experiments of Zr-based BMG using a single-stage light gas gun were performed. To uncover the mechanisms of the spallation damage nucleation and evolution, the samples were designed to be subjected to dynamic tensile loadings of identical amplitude but with different durations by making use of the multi-stress pulse and the double-flyer techniques. It is clearly revealed that the macroscopic spall fracture in BMGs originates from the nucleation, growth and coalescence of micro-voids. Then, a microvoid nucleation model of BMGs based on free volume theory is proposed, which indicates that the nucleation of microvoids at the early stage of spallation in BMGs is resulted from diffusion and coalescence of free volume. Furthermore, a theoretical model of void growth in BMGs undergoing remote dynamic hydrostatic tension is developed. The critical condition of cavitation instability is obtained. It is found that dynamic void growth in BMGs can be well controlled by a dimensionless inertial number characterizing the competition between intrinsic and extrinsic time scales. To unveil the atomic-level mechanism of cavitation, a systematic molecular dynamics (MD) simulation of spallation behaviour of a binary metallic glass with different impact velocities was performed. It is found that micro-void nucleation is determined TTZs while the growth is controlled by shear transformation zones (STZs) at atomic scale.

How does spallation microdamage nucleate in bulk amorphous alloys under shock loading?

Specially designed plate-impact experiments have been conducted on a Zr-based amorphous alloy using a single-stage light gas gun. To understand the microdamage nucleation process in the material, the samples are subjected to dynamic tensile loadings of identical amplitude (∼ 3.18 GPa) but with different durations (83–201 ns). A cellular pattern with an equiaxed shape is observed on the spallation surface, which shows that spallation in the tested amorphous alloy is a typical ductile fracture and that microvoids have been nucleated during the process. Based on the observed fracture morphologies of the spallation surface and free-volume theory, we propose a microvoid nucleation model of bulk amorphous alloys. It is found that nucleation of microvoids at the early stage of spallation in amorphous alloys results from diffusion and coalescence of free volume, and that high mean tensile stress plays a dominant role in microvoid nucleation.

Free-volume evolution of glassy Zr65Al7.5Ni10Cu17.5 during inhomogeneous deformation

Free-volume evolutions of the as-cast and pre-annealed Zr65Al7.5Ni10Cu17.5 metallic glasses during cold-rolling were investigated using differential scanning calorimetry. As deformation degree increases, free volume in the glasses always increases first and then saturates above a critical strain, while the structure remains completely amorphous. The glass with less initial free volume possesses a higher increase rate of free-volume content during deformation, and as a result the free-volume contents of all the glasses approach each other at higher strains. Coalescence of free volume in shear bands into nanovoids is proposed to be responsible for the saturation of free-volume content at high strains.

Free volume coalescence and void formation in shear bands in metallic glass

We have investigated the possibility of void nucleation from the coalescence of excess free volume generated in shear bands during deformation of the Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 bulk metallic glass. Excess free volume in a shear band results in excess free energy relative to a relaxed glass with less free volume. To calculate the free energy of the material in a shear band with excess free volume, we model it as having the same structure as a glass solidified at an elevated glass transition temperature, which we call the fictive temperature. This excess free energy can be correlated with a free volume chemical potential that provides a driving force for void nucleation. The results of this modeling indicate that any free volume generated in the shear band during deformation is unstable, with the consequence that voids are predicted to form spontaneously from the coalescence of free volume. These voids are then expected to coarsen. Under tension, void growth and linkage would be facilitated by a tensile stress state, perhaps leading to premature fracture, whereas a compressive stress state would hinder void growth. This may explain the common observation that failure under uniaxial tension occurs as the result of the propagation of a single shear band, whereas multiple shear bands can form under uniaxial compression without causing failure.