homopolymer was presented.
Thermal analysisrevealed the presence of two populations of lamel-lae with different melting temperatures, and atechnique of partial melting identiﬁed the realspace location of the two sets of lamellae, with theupper melting peak corresponding to the contin-uous radial dominant lamellae revealed in micro-graphs of etched specimens. In addition, thecrosshatched centers of the spherulites alsomelted at a temperature lower than the dominantradiating lamellae. The progressive developmentin the thermal properties with growth from thecenter was shown by comparison with a similarspecimen with added nucleant. In this, the spaceavailable for the development of each spherulitewas severely restricted, and during the middlestages of growth, which characterized the bulk of this specimen, the difference in the melting pointwas not so great, so it could be deduced that thedifferentiation of the two melting populationsshould occur progressively, from the center of thespherulite outward.The earlier investigation also shed light on thequestion of whether the development of doublemelting peaks was associated with molecularfractionation. In PE, sizeable fractions of lowermolecular weights
or greater short-chainbranching stay molten during the main crystalli-zation
and give a lower melting lamellar pop-ulation on cooling. However, the question wasstill open with respect to PP. Previously availablePP materials generally contained material of lower tacticity in lower molecular weight frac-tions.
However, the availability for the afore-mentioned work of a very highly tactic materialknown as high-crystallinity polypropylene (HCPP)showed that the behavior was intrinsic to PP, re-gardless of molecular defects.The previous work
only compared one nucle-ated specimen with its unnucleated counterpart. At the high crystallization temperature chosen(145 °C), the density of nuclei given by addedforeign nucleating agents is limited. In this work,the self-nucleation technique
allows the in- vestigation to be extended to much higher nucle-ation densities, particularly those at which theentire specimen is ﬁlled with a material charac-teristic of the very earliest stages of growth.Moreover, the conclusions drawn indirectly in theprevious work, that the radial morphological de- velopments are largely independent of molecularfractionation, are conﬁrmed by their observationin a series of fractions of various narrowly distrib-utedmolecularweights.Thechangesinthemeltingpoint stem instead from morphologically relateddifferences in isothermal lamellar thickening.
The PPs used were a modern HCPP homopolymerfrom Borealis (HCPP1) studied in the previouswork,
along with fractions prepared from it, anda very similar polymer (HCPP2) that was nucle-ated with Borstar nucleation technology. Thefractionation was carried out according to the mo-lecular weight with ethylene glycol monobutylether/diethylene glycol monobutyl ether as a sol- vent/nonsolvent pair (see ref. 16 for details). Forcomparison, a somewhat older type of Ziegler–Natta polypropylene (ZNPP) was also used insome experiments. The characteristics of all thesematerials are given in Table 1.
All the specimens were prepared in a PerkinElmerDSC-2C. Some of these, of HCPP1 and HCPP2,
Properties of the PP Homopolymers and Their FractionsHCPP1 KN6 KN8 KN10 KN11 KN12 HCPP2 ZNPPMelt Flow Rate (2.16 kg g/10 min) 6.5 8.6 19 Xylene-soluble (wt %) 1.4 1.1 3.1mmmm 97.8 97.38 99.42 99.1 99.32 99.61 98.2 93.0Melting Temperature,
(°C) 165.8 163.8 165.3 166.3 166.6 167.6 167.2 164.3Crystallinity (%) 53.7 58.2 57.1 57.2 55.6 54.2 55.4 42.8Crystallization Temperature,
(°C) 121.9 118.5 119.5 119.6 120.8 122.2 129.4 109.4
(Da) 64,700 56,600 77,800 104,200 192,900 215,300 62,300 75,100
(Da) 305,000 120,000 170,000 219,000 416,000 478,000 293,000 208,000
4.7 2.1 2.2 2.1 2.2 2.2 4.7 2.8
ISOTACTIC POLYPROPYLENE SPHERULITES