The micromechanics and microstructure of CO2 crazes in polystyrene

Although CO₂ at 1 atmosphere pressure is not a crazing and/or cracking agent for polystyrene (PS), we have established that it becomes one at higher pressure. Crazes grown from cracks in PS thin films in high pressure CO₂ are investigated using transmission electron microscopy (TEM). The fact that broken craze fibrils retract strongly upon exposure to high pressure CO₂ gas suggests that the primary effect of the CO₂ is plasticization, not surface energy reduction. Quantitative analyses of TEM micrographs of crazes grown at CO₂ pressures in the range 5 to 100 MPa at 34°C and 45°C have been carried out to find the craze fibril volume fractions v_f(x) and the surface displacements w(x) along each craze. From the fibril volume fraction profile along the craze, the dominant craze thickening mechanism of CO₂ crazes is shown to be the same as that for air crazes, i.e. the surface drawing mechanism, and not the fibril creep mechanism. The craze surface stress profile is computed from the craze surface displacements using a distributed dislocation analysis. These profiles all show a stress concentration at the craze tip which falls to a roughly constant value σ_b, over the rest of the craze. The fracture toughness G_Ic (and critical stress intensity factor K_Ic) for propagation of a crack in PS at these CO₂ pressures can also be computed. All these quantities (V_f, σ_b, G_Ic and K_Ic) show pronounced minima as a function of CO₂ pressure at 20 MPa, the same CO₂ pressure at which T_g of the polymer also reaches a minimum. These minima are more pronounced at 45°C than at 34°C. The G_Ic's and K_Ic's are depressed by orders of magnitude at the minimum, which corresponds to the qualitative observation that CO₂ becomes a severe cracking agent at these pressures. These observations provide additional confirmation that the major mechanism for the environmental crazing and cracking of PS by CO₂ is plasticization of the craze fibrils and surfaces.