The effect of pre-shear flow on the subsequent crystallization process of polymeric melt was investigated and a flow-induced crystallization(FIC) model based on the conformation tensor incorporating the pre-shear effect was proposed. The model is capable of predicting the overshoot phenomena of the stress and the flow-induced free energy change of the polymeric system at high pre-shear rates.Under the condition of flow,the increase in the activated nuclei number was contributed by the flow-induced free energy change,which showed an overwhelming effect on the nuclei formation during the pre-shear process at high shear rates.The half crystallization time(f_(1/2)) of polypropylene(PP) as functions of pre-shear rate and pre-shear time at different crystallization temperatures was predicted and compared with the experiment data.Both numerical and experimental results showed that t_(1/2) of PP decreased dramatically when the flow started but leveled off at long times.It was found that two transformation stages in t_(1/2) existed within a wide range of shear rates.For the first stage where the melting polymer experienced a relatively weak shear flow,the acceleration of crystallization kinetics was mainly contributed by the steady value of free energy change while in the second stage for high shear rates,strong overshoot in flow-induced free energy change occurred and the crystallization kinetics was thus significantly enhanced.The overshoots in stress and flow-induced free energy change reflected an important role of flow on the primary nucleation especially when the flow was strong enough.
Finite element method is used to simulate the high-speed melt spinning process,based on the equation system proposed by Doufas et al.Calculation predicts a neck-like deformation,as well as the related profiles of velocity,diameter, temperature,chain orientation,and crystallinity in the fiber spinning process.Considering combined effects on the process such as flow-induced crystallization,viscoelasticity,filament cooling,air drag,inertia,surface tension and gravity,the simulated material flow behaviors are consistent with those observed for semi-crystalline polymers under various spinning conditions.The structure change of polymer coils in the necking region described by the evolution of conformation tensor is also investigated.Based on the relaxation mechanism of macromolecules in flow field different types of morphology change of polymer chains before and in the neck are proposed,giving a complete prospect of structure evolution and crystallization of semi-crystalline polymer in the high speed fiber spinning process.
Experimental miscibility studies were performed on different compositions of i'PP/sPP blends, where sPP has a low syndiotacticity ([rrrr] = 81%). Combining optical microscopy, rheology, and solid state NMR spectroscopy, the miscibility of the blends was investigated at different scales in the traditionally thought to be 'immiscible' iPP/sPP blends. For the composition of iPP/sPP (90/10) blend, it shows to be miscible in the melt, and furthermore, the existence of intermolecular chain interactions between sPP and ;'PP components was detected in the solid state.
