When sufficient force is applied to a glassy polymer, it begins to deform through movement of the polymer chains. We used an optical photobleaching technique to quantitatively measure changes in molecular mobility during the active deformation of a polymer glass [poly(methyl methacrylate)]. Segmental mobility increases by up to a factor of 1000 during uniaxial tensile creep. Although the Eyring model can describe the increase in mobility at low stress, it fails to describe mobility after flow onset. In this regime, mobility is strongly accelerated and the distribution of relaxation times narrows substantially, indicating a more homogeneous ensemble of local environments. At even larger stresses, in the strain-hardening regime, mobility decreases with increasing stress. Consistent with the view that stress-induced mobility allows plastic flow in polymer glasses, we observed a strong correlation between strain rate and segmental mobility during creep.
Optical photobleaching experiments and molecular dynamics computer simulations were used to investigate changes in segmental mobility during tensile creep deformation of polymer glasses. Experiments were performed on lightly cross-linked PMMA, and the simulations utilized a coarse-grained model. For both single-step and multistep creep deformations, the experiments and simulations show remarkably similar trends, with changes of mobility during deformation exceeding a factor of 100. Both experiment and simulation show a strong correlation between strain rate and mobility in single-step creep. However, in multistep creep, the correlation between strain rate and mobility is broken in both experiment and simulation; this emphasizes that no simple mechanical variable is likely to exhibit a simple relationship with molecular mobility universally. Both simulations and experiments show many features that are inconsistent with the Eyring model.
An optical photobleaching method has been used to measure the segmental dynamics of a poly(methyl methacrylate) (PMMA) glass during uniaxial creep deformation at temperatures between T g À 9 K and T g À 20 K. Up to 1000-fold increases in mobility are observed during deformation, supporting the view that enhanced segmental mobility allows flow in polymer glasses. Although the Eyring model describes this mobility enhancement well at low stress, it fails to capture the dramatic mobility enhancement after flow onset, where in addition the shape of the relaxation time distribution narrows significantly. Regions of lower mobility accelerate their dynamics more in response to an external stress than do regions of high mobility. Thus, local environments in the sample become more dynamically homogeneous during flow.
The reorientation of dye molecules can be used to monitor the segmental dynamics of a polymer melt. We utilize this technique to measure stress-induced mobility in a lightly cross-linked poly(methyl methacrylate) (PMMA) glass during tensile creep deformation. At 377 K (18 K below the glass transition temperature Tg), the mobility increased by a factor of 100 during deformation with a stress of 20 MPa. Generally, the mobility increased as the stress, strain, and strain rate increased. After removing the stress, we observed that the enhanced mobility slowly disappeared during strain recovery. At 377 K, when the stress is lower than 11 MPa, almost no mobility enhancement was observed. Once the stress crossed this threshold value, the mobility dramatically increased.
Molecular dynamics simulations of the nonlinear creep response of a polymer glass under tension and compression have been performed at the glass transition temperature. The dynamics were measured as the deformation proceeds using the bond autocorrelation function, and the relaxation times measured as the system is compressed or elongated exhibit a universal response. In tension, the volume increases with strain rate and the relaxation times decrease. In compression, however, the volume decreases by approximately the same amount for all of the applied stresses. Thus, decreases in free volume take place alongside a decrease of the relaxation times by over a factor of 100. We find direct evidence that a characteristic length scale exists below which the deformation of the system exhibits distinct anomalies.
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