a b s t r a c tIsothermal melt and cold crystallizations of a poly(etherketoneketone) (PEKK) copolymer prepared from diphenyl ether (DPE), terephthalic acid (T) and isophthalic acid (I) with a T/I ratio of 60/40 have been investigated by differential scanning calorimetry, wide-angle X-ray scattering and polarized optical microscopy. For the first time, the two-stage overall crystallization kinetics of PEKK taking into account effects of nucleation and crystal growth has been identified by using a modified Hillier type model. The primary crystallization stage is found to be an instantaneous two dimensional nucleation growth with an Avrami exponent of 2 whereas the secondary stage is found to be an instantaneous one dimensional nucleation growth with an Avrami exponent of 1. The evolution of the crystallization kinetic constants for two-stage crystallizations has been modeled according to the Hoffman and Lauritzen growth theory. Due to low crystallization kinetics, a crystallization induction time has been added to obtain a good fit with experimental data. Based on this modeling, Time-Temperature-Transformation (TTT) diagrams of the relative volume crystallinity have been established for the overall crystallization mechanism and also for the separated primary and secondary crystallization mechanisms providing an original crystallization mapping of the material.

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A slit viscometer to measure the viscosity of polymer melts under processing conditions is described. Along the slit a pressure drop is generated by applying a pressure at both the entrance and the exit. In this way the pressure in the center can be controlled independently of the shear rate. The pressure gradient in the slit is measured by means of three pressure transducers which are mounted in the region of fully developed flow. Results of pressure‐dependent viscosity measurements on polystyrene, polyacrylonitrile‐butadiene‐styrene, and polypropylene are presented in a shear rate range of five decades. The flow curves obtained at different pressures and temperatures can be shifted onto a master curve. The shear thinning behavior of the three materials is adequately described with the generalized Cross‐Carreau equation, while the zero shear viscosity is modeled with a generalized Arrhenius‐W.L.F. relationship, incorporating a pressure dependency. Alternatively, it is possible to describe the zero shear viscosity in terms of the free volume fraction and the temperature.

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