Primary and Secondary Crystallization in a Homogeneous Ethylene-1-Octene Copolymer: Crystallinity Heterogeneity Studied by SAXS B. Goderis,* ,† H. Reynaers, † and M. H. J. Koch ‡ Laboratorium voor Macromoleculaire Structuurchemie, Departement Scheikunde, Katholieke Universiteit Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Belgium; and European Molecular Biology Laboratory, EMBL c/o DESY, Notkestrasse 85, D-22603 Hamburg, Germany Received October 8, 2001; Revised Manuscript Received April 23, 2002 ABSTRACT: The structural changes occurring in a 5.2 mol % 1-octene homogeneous ethylene-1-octene copolymer sample during a cooling and heating cycle at 10 °C/min are described in detail using DSC, AFM, SALLS, and synchrotron WAXD and SAXS. The DSC cooling curve exhibits two exothermic maxima where the high-temperature maximum marks out the temperature window associated with primary crystallization (spherulite nucleation and growth). The morphology after spherulite impingement is characterized by local differences in crystallinity. Secondary crystallization by lamellar insertion is fastest in the largest amorphous areas and results in a spatial homogenization of the crystallinity at a given temperature between the two DSC maxima. The small low-temperature DSC peak is associated with the nucleation of small or imperfect crystals in the confined spaces between existing crystals. During heating, regions with different degrees of crystallinity develop again. An evaluation method for SAXS linear correlation functions is introduced to handle crystallinity heterogeneity. The underlying, basic model is a pseudo-two-phase structure with part of the crystalline-amorphous interphase contributing to the WAXD and DSC crystallinity. 1. Introduction In the 1990s homogeneous copolymers of ethylene and R-olefins became available on a large scale due to the industrial implementation of metallocene catalysts. Hexyl branches are appended to the linear polyethylene (PE) chain if 1-octene is used as a comonomer. Such fairly bulky aliphatic branches cannot be incorporated in an orthorhombic PE crystal, 1-4 and consequently, crystallinity decreases with increasing amount of 1-octene. In the thermodynamic model of Flory, the degree of crystallinity at a given temperature is fully determined by the crystallizable ethylene sequence length distribu- tion (ESLD). 5 Sequences that do not have the minimum length required for crystallization at a given tempera- ture, do not crystallize although they can do so at a lower temperature. All sequences of the same length are supposed to merge into extended-sequence crystallites of a related thickness with infinite lateral dimension. Such a thorough selection and segregation of ethylene sequences is, however, never reached and crystallinity is always considerably lower than predicted because of a number of restrictions. First, nucleation, which is a statistical process, takes time and consequently reduces the crystallinity evalu- ated after finite times. This effect is particularly notice- able at the highest temperatures where nucleation of extended sequence crystals is extremely slow. Upon cooling at a given rate, not-yet-crystallized very long ethylene sequences readily fold and crystallize into lamellar crystals at lower temperatures. At these lower temperatures, shorter ethylene sequences cocrystallize with the folded longer ones provided they have the required minimum length. Second, besides a minimum length for crystallization at a given temperature a minimum amount of refolding chains is needed for growth into a lamellar habit. At least 60% of the stems reaching the surface of a PE crystal have to bend back into the crystal of origin to avoid the creation of an amorphous phase with too high a density. 6 This problem is known as “overcrowding” and in the present case is acute because chain parts with hexyl branches are expelled from the crystal. For this reason, a fraction of the ethylene sequences, which have the critical length for nucleation at a given temperature, do not nucleate and the expected crystallinity is not reached. In principle, such sequences may cocrystallize with shorter ones at lower temperatures, but when the remaining melt is considerably enriched with shorter ethylene sequences, segregation is no longer efficient. Overcrowding is then prevented by the genesis of lamellar crystals with corrugated surfaces or crystals with limited lateral dimensions, including blocklike entities and fringed micelles. Third, the mobility of free ethylene sequences in the amorphous phasesneeded for selection and segregations is reduced as soon as other sequences that are connected to the same chain are incorporated into crystals. This “pinning” gains importance as crystallinity increases. Alizadeh et al. 7 put forward the idea that classical laterally extended lamellar crystals can only be formed when such constraints are minimum as e.g. during primary crystallization. Beyond a given crystallinity, only local segmental motions are possible giving rise to fringed micelle or chaincluster crystals. Blocks can be formed at an intermediate degree of pinning. 7 The restrictions above give rise to kinetically deter- mined morphologies that depart considerably from Flory’s ideal picture. Lamellae are formed at the highest * To whom correspondence should be addressed. † Katholieke Universiteit Leuven. ‡ European Molecular Biology Laboratory, 5840 Macromolecules 2002, 35, 5840-5853 10.1021/ma011749c CCC: $22.00 © 2002 American Chemical Society Published on Web 06/11/2002