Effect of cooling rate on melt-crystallization of random propylene-ethylene and propylene-1-butene copolymers

Summary  The effect of variation of the rate of cooling on melt-crystallization of random copolymers of isotactic polypropylene with low amount of either ethylene or 1-butene is evaluated using X-ray techniques, atomic force microscopy, and calorimetry. Slow non-isothermal melt-crystallization mainly results in formation of monoclinic α-crystals of lamellar geometry. The presence of comonomers leads to a decrease of the degree of crystallinity, and of the thickness of lamellae. These changes are proportional to the concentration of co-units, and are more distinct in propylene-ethylene copolymers. Rapid cooling of propylene-1-butene copolymers leads to formation of non-lamellar mesomorphic domains, independent of the concentration of co-units within the investigated range of concentrations. In quenched propylene-ethylene copolymers, in contrast, the formation of mesomorphic structure partially is replaced by formation of monoclinic α-crystals of still non-lamellar geometry.     

Deformation behavior of isotactic polypropylene crystallized via a mesophase

The mechanical behavior of semicrystalline isotactic polypropylene (iPP) of different crystallinity, crystal morphology and superstructure was investigated by standard tensile stress–strain analysis, dynamic-mechanical analysis, and in situ observation of the deformation by atomic force microscopy (AFM). Emphasis is put on the comparison of the mechanical characteristics of specimens containing either non-isometric lamellae, being arranged in spherulites, or nodular isometric domains, which are not organized in a superstructure. The formation of lamellae/spherulites and of nodules was controlled by the conditions of crystallization. The replacement of cross-hatched monoclinic lamellae and a spherulitic superstructure by randomly arranged isometric nodules leads to a distinct increase of the ductility and toughness, even if the crystallinity is identical. The modulus of elasticity and the yield stress increase as expected with increasing crystallinity. Slightly lower values of Young’s modulus and yield strength are detected if samples contained non-lamellar crystals in a non-spherulitic superstructure, proving an effect of the crystal shape on the deformation behavior. For the first time, tensile deformation of semicrystalline iPP which contains nodular ordered domains instead of lamellae has been followed by in situ AFM.     

Effect of the structure at the micrometer and nanometer scales on the light transmission of isotactic polypropylene

The spherulitic superstructure, crystallinity, and structure and morphology of crystals of isotactic polypropylene were controlled by the conditions of melt crystallization and related to the transmittance of visible light. Spherulitic samples, which contained monoclinic lamellae, were prepared by slow cooling of the quiescent melt at rates lower than 10 K/s and by isothermal melt crystallization at temperatures between 373 and 413 K. Nonspherulitic specimens, which contained nonlamellar mesomorphic domains, in contrast, were obtained by rapid cooling of the melt with rates faster than 100 K/s. The crystallinity and the size of crystals were furthermore fine‐tuned by subsequent annealing at elevated temperatures. Analysis of such films of different structure by ultraviolet–visible spectroscopy revealed that the light transmission was independent of (1) the fraction, (2) the internal structure, and (3) the size of the crystals. In contrast, the light transmission increased with decreasing size of spherulites and finally exceeded 90% in films of 100 μm thickness when spherulites were completely absent. The crystallinity and the structure and size of the crystals of the films of isotactic polypropylene could be adjusted within wide limits without affecting the light transmission. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Atomic force microscopy study of the lamellar growth of isotactic polypropylene

The growth behaviors of cross-hatched and lath-like lamellae of α-form spherulites and flat-on lamellae of β-form pherulites of isotactic polypropylene were studied with a high-temperature atomic force microscopy in situ and in real time. The growth rates of crystal lamellae in types I, II and mixed α-form spherulites and in β-form spherulites, as well as the spatial frequency of tangential branching, were measured. The frequency of tangential branching increases with decreasing crystallization temperature, while the growth rates of leading radial and tangential lamellae are approximately the same at a given temperature. Observations of as-crystallized materials demonstrated that the spacing and length of transverse lamellae is sufficient to differentiate among spherulite types. Height measurements in the melt near the growth surface indicate roles of molecular transport in the crystallization process.     

Formation of lamellar structure by competition in crystallization of both components for crystalline-crystalline block copolymers

Crystallization and structure formation of poly(ethylene oxide)-poly(?-caprolactone) block copolymers (PEG-PCL) in which the melting temperatures of the components are close to each other were elucidated using differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. The diblock copolymers with 33, 46 and 59 wt% of PEG composition formed ordinary single spherulites similar to those of PCL homopolymers, while concentric double-circled spherulites appeared for the PCL-PEG-PCL triblock copolymer with 66 wt% PEG composition as observed previously. For the diblock copolymers, despite of the ordinary appearance of the single spherulites, the DSC thermograms and the WAXD patterns indicated the crystallization of PEG as well as PCL. The time-resolved SAXS profiles for the diblock copolymers showed that long spacings of the crystal lamellae decreased stepwise in the crystallization process. Synthesizing these results for the single spherulites, it was concluded that PCL crystallized first followed by the crystallization of PEG with preservation of the PCL crystal lamellar structure. This means that PEG must crystallize within confined space between the formerly formed PCL crystal lamellae. Such confined crystallization of PEG caused the suppressed melting temperature, crystallinity and crystallization rate especially in the smaller PEG compositions. In the melting process of the diblock copolymers, it was observed that the PEG component first melted with a stepwise increase in the long spacing.     

On the lamellar morphology of isotactic polypropylene spherulites

The lamellar structures within melt-grown spherulites of the monoclinic form of isotactic polypropylene have been studied by transmission electron microscopy following permanganic etching. Spherulites grown at 160°C are composed solely of α laths which develop in the classical radiating branching manner from axialitic precursors. The branching units are not, however, fibres but individual dominant lamellae as previously found for polyethylene and isotactic polystyrene. The theory of instability of planar interfaces of Keith and Padden is not applicable to this textural situation, although local diffusion fields may add an additional structural dimension to spherulites which form quickly at, say, 130°C. Instead, one may possibly look to pressure from compressed cilia as the cause of splaying between adjacent lamellae. Cross-hatching is present in spherulites grown at 155°C and below in the early stages, and thereafter is concentrated in specific locations and subsidiary lamellae. The cross-hatching members are less stable, probably because they are composed of shorter and/or less tactic molecules.     

On the lamellar morphology of melt-crystallized isotactic polystyrene

The lamellar morphology of melt-crystallized isotactic polystyrene has been investigated by extending the technique of permanganic etching for electron microscopy. This paper reports on objects grown at 220°C which are comparatively uncomplicated, being aggregates of hexagonal lamellae, with smooth facets and distinguishable internal sectors, organized into axialites. To a first approximation only, hexagonal lamellae splay apart about a common diagonal presenting three characteristic projections in orthogonal directions. These are hexagonal, sheaflike and an array of approximately parallel lamellae. In reality the term axialite is an oversimplification. Splaying is not restricted to a single axis but occurs in three dimensions making these objects incipient spherulites. Polystyrene spherulites grown as low as 180°C the temperature of maximum growth rate are also constructed on the same principles as are spherulites of polyethylene and isotactic polypropylene. These are that a framework is established by individual dominant lamellae which branch and splay apart leaving interstices to be filled by later-crystallizing subsidiary lamellae. There is evidence that subsidiary lamellae contain shorter molecules on average than do dominant lamellae. The dominant/subsidiary construction is not what had been assumed in the Keith and Padden theory of spherulitic growth nor is there evidence of cellulation or local diffusion influencing development even though crystal sizes exceed the Keith and Padden parameter · by two orders of magnitude. We conclude that polymer spherulites can form independently of the mechanism proposed by Keith and Padden¹⁴. It is suggested that the cause of lamellae splaying apart is a mutual repulsion due to uncrystallized portions of molecules between dominant lamellae.     

Mechanical behavior and optical transparency of polyamide 6 of different morphology formed by variation of the pathway of crystallization

The phase composition and supermolecular structure of polyamide 6 (PA 6) melt-crystallized on cooling at different rates or cold-crystallized at different temperatures were characterized and related to the optical transparency, stiffness and the stress–strain behavior. Cold-crystallization results in non-spherulitic formation of γ-mesophase or α-crystals, depending on the maximum annealing temperature. Both mesophase and crystals are of nodular shape. Melt-crystallization at low supercooling leads to formation of lamellar α-crystals and spherulites, while at high supercooling the nodular mesophase is forming. The absence of spherulites in cold-crystallized PA 6 films leads to high see-through clarity which is in contrast to the slowly melt-crystallized samples with opaque appearance. While Young’s modulus and the glass transition temperature increase with increasing crystallinity, for samples of identical crystallinity stiffness is considerably higher if the crystals are of lamellar rather than of nodular shape. The higher glass transition temperature of cold-crystallized PA 6 is related to a higher rigid amorphous fraction than in melt-crystallized samples pointing to a stronger coupling of the amorphous phase to ordered domains.     

Spherulite nucleation in blends of isotactic polypropylene with isotactic poly(butene-1)

The phase morphology and the influence of composition on the primary nucleation of isotactic polypropylene in isotactic polypropylene/isotactic poly(butene-1) (iPP/iPB) blends were investigated by electron and light microscopy and small-angle light scattering. It was found that iPP and iPB are miscible but the thermal treatment induces partial phase separation of components and the formation of iPP-rich and iPB-rich phases. The complete phase separation needs high temperatures and/or a long time of melt annealing. In samples crystallized isothermally at low undercooling the heterogeneous primary nucleation in blends is depressed as compared to plain iPP. In blends the less active heterogeneities lose their activity because of an increase of the energy barrier for critical size nucleus formation due to phase separation of blend components during crystallization. For the same reason the rate of homogeneous nucleation in blends decreases, as observed in samples crystallized at very high undercooling. At very high undercooling iPP and iPB are able to crystallize with similar rates, which results in the formation of a fraction of iPB spherulites in addition to iPP spherulites. Consequently the number of spherulites in the blend is larger than that in plain iPP, in spite of the decrease in the homogeneous nucleation rate of iPP in the blend. © 1994 John Wiley & Sons, Inc.     

Highly active thermally stable β‐nucleating agents for isotactic polypropylene

Calcium salts of suberic (Ca‐Sub) and pimelic (Ca‐Pim) acids were synthesized and implemented as in different grades of isotactic polypropylene (iPP). Propylene homopolymer, as well as random and block copolymers containing these additives, crystallized iPP into pure or nearly pure β modification in the isothermal and nonisothermal crystallization experiments. Recently, Ca‐Sub proved to be the most effective β‐nucleating agent of iPP. The Ca‐Sub nucleating agent widens the upper crystallization temperature range of pure β‐iPP formation up to 140°C. In this study the effect of the these additives on the crystallization, melting characteristics, and structure of the PP were studied. The degree of crystallinity of β‐iPP was markedly higher than that of α‐iPP. A widening in the melting peak of the samples crystallized in a high temperature range was first observed and discussed in regard to literature results of the same phenomenon for α‐iPP. The morphology of the β‐iPP samples was revealed by scanning electron microscopy. Independent of the type of polymer or nucleating agent, hedritic structures were found in the early stages of growth of the β‐spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2357–2368, 1999     

Isotactic polypropylene crystallized from the melt. I. Morphological study

The spherulitic structure of isotactic polypropylene (iPP) from the melt was studied by polarized light and scanning electron microscopy. From the crystallization morphology, it can be observed that crystallization of iPP from the melt below 132°C forms two types of spherulites, termed α- and β-spherulites. The structure of iPP isothermally crystallized above 132°C shows α-type only. The α-spherulites have a complex crosshatched array of radial and tangential lamellar structures, while β-spherulites have, to some extent, simpler lamellar morphology with lower crosshatching content compared with α-type. However, in α-spherulites the radial lamellar thickness is greater than that of tangential lamellae, but in β-spherulites the radial and tangential lamellae have approximately the same thickness. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1259–1265, 1998     

Growth process of homogeneously and heterogeneously nucleated spherulites as observed by atomic force microscopy

A poly(bisphenol A octane ether) (BA-C8) was synthesized. The isothermal spherulitic growth process was studied in situ using atomic force microscopy (AFM) at room temperature. For spherulites formed by homogeneous nucleation, the growth process includes the birth of a primary nucleus, the development of a founding lamella and the growth of the founding lamella into a spherulite. An embryo below a critical size is unstable. A stable embryo grows into a founding lamella. There is only one founding lamella in each spherulite. All other lamellae originate from this founding lamella. Two eyes can be seen at the center of a spherulite. For spherulites formed through heterogeneous nucleation, many lamellae grow at the nucleus surface and propagate outward radially. The spherulites acquire spherical symmetry at the early stage of crystallization. No eyes are found for this kind of spherulites.     

α‐ and β‐crystalline forms of isotactic polypropylene investigated by nanoindentation

Under special crystallization conditions from the melt, both α‐ and β‐forms of isotactic polypropylene were produced simultaneously. The α‐ and β‐spherulites of polypropylene were differentiated under optical microscope, allowing the nanoindentation of individual spherulites of each crystallographic form. Elastic modulus and hardness of β‐spherulites were found to be 10 and 15% respectively lower than in α‐spherulites. The higher stiffness of α may be related to the particular interlocked structure with cross‐hatched lamellae, and to a lower molecular mobility in the crystallites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 195–200, 1999     

Effect of polycyclopentene on crystallization of isotactic polypropylene

The application of some polymers as nucleating agents for polypropylene has been examined. Among various polymeric nucleating agents, polycyclopentene was found to be a superior nucleating agent to typical organic nucleating agents. When polycyclopentene was added to polypropylene, the crystallization temperature and the degree of crystallinity of polypropylene increased. In addition, the crystallization rate and the number of spherulites increased whereas the size of spherulites decreased remarkably. As a result of polycyclopentene addition, the transparency of polypropylene film could be improved considerably. © 1994 John Wiley & Sons, Inc.     

Effects of EPDM and wollastonite on structure of isotactic polypropylene blends and composites

Polypropylene blends and composites with 5, 10, and 15 vol % of EPDM and 2, 4, and 6 vol % of untreated and treated wollastonite filler were examined by applying different techniques. Elastomeric ethylene/propylene/diene terpolymer (EPDM) component and wollastonite influenced the crystallization process of isotactic polypropylene (iPP) matrix in different ways. The nucleation of hexagonal β‐iPP, the increase of overall degree of crystallinity, and crystallite size of iPP were more strongly affected by wollastonite than the addition of EPDM was. Both ingredients also differently influenced the orientation of α‐form crystals in iPP matrix. Wollastonite increased the number of a*‐axis‐oriented α‐iPP lamellae plan parallel to the sample surface, whereas the addition of EPDM reoriented the lamellae. The orientation parameters of ternary composites exhibited intermediate values between those for binary systems because of the effects of both components. EPDM elastomer considerably affected well‐developed spherulitization of iPP, increasing the spherulite size. Contrary to EPDM, because of nucleating ability or crystal habit, wollastonite caused significantly smaller iPP spherulites. Small spherulites in ternary iPP/EPDM/wollastonite composites indicated that the wollastonite filler (even in smallest amounts) exclusively determined the morphology of ternary composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4072–4081, 2004     

Optical properties of thermally crystallized poly(ethylene terephthalate)

The optical properties of thermally crystallized polyethylene terephthalate (PET) were investigated using the methods of small-angle light scattering, density, and haze measurements. The results indicate that the haze in crystallized PET results from scattering due to crystalline aggregates called spherulites. The formation of spherulites can lead to high levels of haze even at very low levels of crystallinity. A detailed analysis of polarized light-scattering patterns was employed in order to define the various structural parameters responsible for haze. The relationships between haze, crystallinity, spherulite size, and volume fraction of spherulites were developed for PET.     

Highly transparent thermoplastic elastomer from isotactic polypropylene and styrene/ethylene‐butylene/styrene triblock copolymer: Structure‐property correlations

Polypropylene (PP) is one of the most useful general purpose plastics. However, the poor transparency and brittleness of PP restricts its applications in the field of medical and personal care where silicone and polyvinyl chloride (PVC) are presently used. This work concentrates on developing highly transparent elastomeric PP blends and also thermoplastic elastomer by blending isotactic polypropylene (I‐PP) with styrene/ethylene‐butylene/styrene (SEBS) triblock copolymer. PP/SEBS blend derived from high melt flow index (MFI) PP and high MFI SEBS exhibit remarkable transparency (haze value as low as 6%) along with good percentage of elongation and processability. The reduction in difference of refractive index (RI) between PP and SEBS has been observed by blending SEBS with PP. The wide angle X‐ray diffraction studies show that there is significant reduction in the percentage crystallinity of PP by the addition of SEBS block copolymer. Temperature‐dependent polarized light microscopy studies reveal the reduction in spherulites size by the addition of SEBS block copolymer. Transmission electron micrographs show that the SEBS polymer forms a fine lamellar structure throughout the PP matrix with phase inversion at higher SEBS concentration. Development of phase morphology, crystalline morphology, and crystallinity in different blends has been analyzed and microstructure‐haze correlations have been developed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Comparison of propylene/ethylene copolymers prepared with different catalysts

This study compared a series of experimental propylene/ethylene copolymers synthesized by a transition metal‐based, postmetallocene catalyst (xP/E) with homogeneous propylene/ethylene copolymers synthesized by conventional metallocene catalysts (mP/E). The properties varied from thermoplastic to elastomeric over the broad composition range examined. Copolymers with up to 30 mol % ethylene were characterized by thermal analysis, density, atomic force microscopy, and stress–strain behavior. The xP/Es exhibited noticeably lower crystallinity than mP/Es for the same comonomer content. Correspondingly, an xP/E exhibited a lower melting point, lower glass transition temperature, lower modulus, and lower yield stress than an mP/E of the same comonomer content. The difference was magnified as the comonomer content increased. Homogeneous mP/Es exhibited space‐filling spherulites with sharp boundaries and uniform lamellar texture. Increasing comonomer content served to decrease spherulite size until spherulitic entities were no longer discernable. In contrast, axialites, rather than spherulites, described the irregular morphological entities observed in xP/Es. The lamellar texture was heterogeneous in terms of lamellar density and organization. At higher comonomer content, embryonic axialites were dispersed among individual randomly arrayed lamellae. These features were characteristic of a copolymer with heterogeneous chain composition. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1651–1658, 2006     

Temperature-resolved SAXS studies of morphological changes in melt-crystallized poly(hexamethylene terephthalate) and its melting upon heating

Temperature-resolved small-angle X-ray scattering (SAXS) on poly(hexamethylene terephthalate) (PHT) samples crystallized from the melt yields direct information about the morphological changes in lamellar crystals and interlamellar amorphous layers upon melt-crystallization and subsequent heating to melting. Absolute intensities of these SAXS patterns were further analyzed via one-dimensional correlation and interface distribution functions. These analyses indicate that melt-crystallization at low temperature produces lamellar crystals having diverse thicknesses whereas crystallization at high temperature tends to favor growth of thick lamellar crystals with a nearly uniform distribution of thickness. When heating the PHT samples in the melting temperature region, the melting of the lamellar crystals was found to correlate well with the sequential-melting features. When these crystals are heated to higher temperatures, structural alterations from stacked lamellae to isolated lamellar crystals evolve with increasing extent of sequential melting, but, upon re-crystallization during extended annealing, the isolated lamellar crystals can pass through a reversible transition back to stacked lamellae.     

Dynamic X-ray diffraction studies of spherulitic poly-alpha-olefins in relation to the assignments of alpha and beta mechanical dispersions

The dynamic tensile deformation mechanism of spherulitic poly-alpha-olefins, high-density polyethylene, isotactic polypropylene, and isotactic polybutene-1, was investigated by dynamic X-ray diffraction at various temperatures and frequencies in order to assign the α and β mechanical dispersions explicitly. The uniaxial orientation distribution function q_j(ζ_j, 0) of the j-th crystal plane and its dynamic response Δq_j′(ζ_j, 0) in-phase with dynamic strain were observed for several crystal planes, and then the orientation distribution function ω(§, 0, η) of crystallites (crystal grains) and its dynamic response Δω′(§, 0, η), also in-phase with the dynamic strain, were determined by a mathematical transformation procedure proposed by Roe and Krigbaum on the basis of the Legendre addition theorem. The temperature and frequency dependences of Δω′(§, 0, η) were analyzed in terms of a spherulite deformation model combining affine orientation of crystal lamellae with several types of preferential reorientation of the crystal grains within the orienting lamellae. The following assignments are made: (1) the a mechanical dispersion must be assigned to the dynamic orientation dispersions of crystal grains within lamellae involving two types of preferential rotations of the grains associated with lamellar detwisting mostly in the equatorial zone of uniaxially deformed spherulites and with lamellar tilting mostly in the polar zone of the spherulites. Both processes are intralamellar grain-boundary phenomena, and the former process of lamellar detwisting is hardly activated for polypropylene and polybutene-1 spherulites in contrast to polyethylene spherulites. (2) The β mechanical dispersion must be assigned to the dynamic orientation dispersion of the crystal lamellae behaving as rigid bodies unaccompanied by reorientation of crystal grains within the orienting lamellae. This process is an interlamellar grain-boundary phenomenon.