Effects of crystallization behavior on morphological change in poly(trimethylene terephthalate) spherulites

In poly(trimethylene terephthalate) (PTT) spherulites during isothermal crystallization, the morphological changed from an axialite/or elliptical banded spherulite to banded spherulite and then non-banded spherulite with temperature decreasing were studied by following the lamellar growth behaviors. We report lamellar growth mechanism on varied crystallization temperature, which explicitly probes the link between microscopic structure and macroscopic morphology in the development of patterns. Fibrillation of the edge-on lamellae was observed on the surfaces of axialite and the convex bands of banded spherulite. Terrace-like lamellae were observed on the surface of the non-banded spherulite and the concave bands of banded-spherulite. In thin film crystallization, PTT banded spherulite exhibits a texture of alternate edge-on and flat-on lamellae, wavy-like surface and rhythmic growth. The deceleration of growth rate takes place in convex bands with a growth habit of fibrillation of the edge-on lamellae for emerging ridge surface. On the other hand, the acceleration of growth rate appears in concave bands with a growth habit of terrace-like lamellae for emerging valley surface. The alternating growth mechanism of the lamellae was considered to be related with the formation of spatiotemporal self-organization patterns far from equilibrium. In order to explain the rhythmic growth and periodic growth of the lamellae, we may conjecture that the emergence of PTT banded spherulite in thin film crystallization is associated with an oscillatory dynamics of the spherulite growth front driven by latent heat diffusion. We present some tentative ideas on the possibility of band-to-nonband (BNB) morphological transition, which might be analogous with the second order transition in non-equilibrium phase transition.     

Banded spherulites of HDPE molded by gas-assisted and conventional injection molding

Crystal morphologies of high density polyethylene (HDPE) with low molecular weight obtained by gas-assisted injection molding (GAIM), conventional injection molding (CIM), and spontaneous cooling, respectively, were studied by scanning electronic microscopy (SEM). It is found that banded spherulites are generated in the inner zone of GAIM parts and the outer zone of CIM parts but are absent in quiescent parts. According to the results, the representative morphologies of crystal change with gradual increment of instantaneous flow field in crystallization from non-banded spherulite to banded spherulite and then to oriented lamellae. This morphological evolution indicates that banded spherulites could be induced by flow field with certain intensity, which is confined by both an upper critical value and a lower one.     

Formation of ring-banded spherulites of α and β modifications in Poly(butylene adipate)

The morphology and crystalline structure of banded spherulites of poly(butylene adipate) (PBA) were investigated by polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), atomic force microscopy (AFM) and scanning electronic microscopy (SEM). It was found that after purification and fractionation, the obtained PBA fractions with different molecular weight formed ring-banded spherulites at different temperature ranges. Pure α and β form of PBA can form regular ring-banded spherulites. AFM and SEM observations of the thin film revealed that the alternative ridges and valleys along the radial direction consisted of edge-on and flat-on lamellae, respectively, indicating the ring-bands in PBA spherulites are the consequence of lamellar twisting. In addition, sequential growth of α and β form in one PBA spherulite at the same temperature is reported and interpreted by competition of primary nucleation and radial growth of the two crystalline modifications. At a certain temperature range, the α form PBA has larger primary nucleation rate but lower radial growth rate than the β form PBA, leading to formation of spherulites consisted of α form at center and β form at the outer region. But finally, a layer of α form ringless region appears at the outside of the β form ring-banded region before impingement of the neighboring spherulites. These results suggest that besides crystallization temperature, molecular weight has considerable effect on the formation of crystal modification of PBA and the corresponding banded spherulites.     

Structural analysis of poly(butylene adipate) banded spherulites from their biodegradation behavior

Poly(butylene adipate) (PBA) has been reported to have polymorphic crystal structures and only the mixture of two crystal modifications (α and β crystals) forms banded spherulites. However, how the two crystals coexist in banded spherulites remains to be solved. In this work, the morphological structure of PBA banded spherulites was analyzed from their biodegradation behavior by means of polarized optical microscopy (POM), scanning electron microscopy (SEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). It was found that the banded spherulites were made up of alternate flat-on and edge-on domains in lamellar crystals along the radiating direction. To determine the distribution of two crystal modifications in banded spherulites and the interrelationships between the alternate domains with polymorphic crystal structures, the relative contents of two crystal modifications in banded spherulites were first quantified, and their changes were then correlated to the morphological changes of banded spherulites in the course of biodegradation in terms of the difference in biodegradation kinetics of two crystal modifications. It was found that the flat-on domains show a slower crystal growth rate but a faster biodegradation rate than the edge-on domains. The analysis indicates that the flat-on domains in spherulites are composed of α crystals, while the edge-on domains are composed of β crystals. The primary growth mechanism of PBA banded spherulite was proposed based on the difference in crystallization heat and kinetics of two crystal modifications.     

Microbeam X-ray diffraction of non-banded polymer spherulites of it-polystyrene and it-poly(butene-1)

The orientation of lamellar crystals in non-banded spherulites of it-polystyrene and it-poly(butene-1) was investigated by microbeam X-ray diffraction. The two-dimensional intensity map of diffraction enables us to examine the local orientation of lamellar crystallites in the non-banded spherulites. The obtained results indicated the re-orientation of crystallites in non-banded spherulites and confirmed our previous observation on the anisotropic birefringence of a group of crystal stacks by polarizing optical microscopy.     

Thermal reversibility in crystalline morphology of LLDPE crystallites

We investigated the temperature dependence of the crystalline morphology in linear low density polyethylene by light scattering, small-angle X-ray scattering (SAXS) and oscillating-DSC. Optical anisotropy in the spherulite, defined by model calculation of the Vv scattering pattern, and the order parameter of crystal orientation within spherulite, estimated by sharpness of the Hv scattering profile, increased in the cooling process while they decreased in the heating process. That is, the morphology is thermally reversible. The morphological change with time after the temperature drop or jump was found to be very fast in several seconds. Oscillating-DSC and SAXS results suggest that the disordering in the heating process is caused by melting of thermally unstable thin lamellae existing between the thick lamellae, which are already developed at high crystallization temperature. Thus, the thermal reversibility is ascribed to the thermally unstable thin lamellae; i.e. the thin lamellae are developed fast at wide temperature range in the cooling process and they melt fast in the heating process at the temperature close to the temperature they are developed. Owing to the fast development of the thin lamellae, the crystalline morphology obtained at high temperature cannot be frozen by quenching.     

Study on the crystal morphology and melting behavior of isothermally crystallized composites of short carbon fiber and poly(trimethylene terephthalate)

The spherulites of the short carbon fiber(SCF)/poly (trimethylene terephthalate) (PTT) composites formed in limited space at designed temperatures, and their melting behaviors were studied by the polarized optical microscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM), respectively. The results suggest that SCF content, isothermal crystallization temperatures, and the film thicknesses influence the crystal morphology of the composites. The dimension of the spherulites is decreased with increasing SCF content, but whether banded or nonbanded spherulites will form in the composites is not dependent on SCF content. However, the crystal morphology of the composites depends strongly on the temperature. When the isothermal crystallization temperatures increase from 180°C to 230°C, the crystal morphology of SCF/PTT composites continuously changes in the following order: nonbanded → banded → nonbanded spherulites. Discontinuous circle lines form in the film when the film thickness increases from 30 to 60 μm. Basing on the SEM observation, it is found that these circle lines are cracks formed due to the constriction difference of the different parts of the spherulites. These cracks are formed when the film is cooled from the isothermal crystallization temperature to the room temperature at a slow cooling rate; while they will disappear gradually at different temperatures in the heating process. The crack will appear/disappear first around the center of the spherulite when the film was cooled/heated. The nontwisted or slightly twisted lamellas will reorganize to form highly twisted lamellas inducing apparent banded texture of the spherulites.     

RuO4 staining and lamellar structure of α‐ and β‐PP

Monoclinic (α) and hexagonal (β) polypropylene (α‐ and β‐PP) were stained in the vapor of a ruthenium tetroxide solution prepared in situ. The effect of staining on the fusion behavior was investigated using a DSC. A staining duration between 10 and 24 h was found suitable for obtaining a good electron contrast between the crystalline and amorphous regions for TEM examination without causing severe damage to the crystals. The spherulites of the water‐quenched α‐PP were found to be composed of very fine cross‐hatched lamellae whose long period was about 10 nm. In comparison, the β‐PP spherulites crystallized isothermally at 130°C had a category 2 morphology and the lamellae have a long period of 20 nm. The morphology of the spherulite boundary varied depending on the contact angle between the lamellae of the neighboring spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1529–1538, 1999     

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.     

Confined crystallization morphology of poly(ϵ‐caprolactone) block within poly(ϵ‐caprolactone)–poly(l‐lactide) copolymers

The confined crystallization of poly(?‐caprolactone) (PCL) block in poly(?‐caprolactone)–poly(l ‐lactide) (PCL‐PLLA) copolymers was investigated using differential scanning calorimetry, polarized optical microscopy, scanning electronic microscopy and atomic force microscopy. To study the effect of crystallization and molecular chain motion state of PLLA blocks in PCL‐PLLA copolymers on PCL crystallization morphology, high‐temperature annealing (180 °C) and low‐temperature annealing (80 °C) were applied to treat the samples. It was found that the crystallization morphology of PCL block in PCL‐PLLA copolymers is not only related to the ratio of block components, but also related to the thermal history. After annealing PCL‐PLLA copolymers at 180 °C, the molten PCL blocks are rejected from the front of PLLA crystal growth into the amorphous regions, which will lead to PCL and PLLA blocks exhibiting obvious fractionated crystallization and forming various morphologies depending on the length of PLLA segment. On the contrary, PCL blocks more easily form banded spherulites after PCL‐PLLA copolymers are annealed at 80 °C because the preexisting PLLA crystal template and the dangling amorphous PLLA chains on PCL segments more easily cause unequal stresses at opposite fold surfaces of PCL lamellae during the growth process. Also, it was found that the growth rate of banded spherulites is less than that of classical spherulites and the growth rate of banded spherulites decreases with decreasing band spacing. © 2019 Society of Chemical Industry     

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.     

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     

Evidence for the formation of interpenetrated spherulites in poly(butylene succinate-co-butylene carbonate)/poly(l-lactic acid) blends investigated by atomic force microscopy

The spherulitic morphology in poly(butylene succinate-co-butylene carbonate)/poly(l-lactic acid) (PEC/PLLA) blends was investigated by atomic force microscopy (AFM) to obtain direct evidence for the formation of interpenetrated spherulites (IPS), where the spherulites of PEC penetrate into PLLA spherulites. The observation actually revealed that PEC crystals penetrated into interfibrillar regions of edge-on lamellae in a PLLA spherulite. The penetration process was also investigated by AFM with a temperature controller. An edge-on PLLA lamella or a fibril that ran nearly perpendicular to the growth direction of a PEC spherulite obstructed the growth of PEC spherulite. The PEC crystals filled the blocked space after growing around the PLLA lamella. These results showed that the spherulites of PEC and PLLA grow on the same layer instead of forming a layered structure of two spherulites. All the results supported the formation of IPS.     

Influence of the thin‐film thickness and crystallization temperature on the spherulitic structure of polymer thin films

The spherulitic structure and morphology of poly(3‐hydroxybutyrate) (PHB) thin films crystallized from the melt were observed with a polarizing optical microscope. Depending on the thickness of the PHB thin film and crystallization temperature, banded and nonbanded spherulites could form. Reducing the thin‐film thickness and crystallization temperature was favorable for the formation of the banded structure. The morphology transition from banded spherulites to nonbanded spherulites was related to the ratio of the crystallization rate to the diffusion rate. The formation mechanism of the banded structure was examined with the discontinuity growth theory. A depletion zone was considered to appear periodically at the crystal growth front because of the slow diffusion rate, and this may have resulted in the banded spherulites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A multiscale model for polymer crystallization. II: Solidification of a macroscopic part

In part I of this paper, we presented two efficient front-tracking methods to simulate the growth of a spherulite within an imposed temperature field. In this second part we present a method that predicts the final microstructure in a macroscopic part by coupling these front-tracking techniques with (a) a stochastic model for the nucleation of individual spherulites, (b) a cellular model for spherulite impingement and solid fraction evolution and (c) a Finite Difference Method (FDM) for latent heat release and heat diffusion. The method tracks the physical phenomena on several length scales: a course grid for the heat diffusion, a fine grid for solid fraction evolution and a very fine grid for the shape of the individual spherulites and the lamellae within them. To our knowledge this is the first time that fully coupled multiscale model has been applied to the solidification of polymers which gives realistic microstructure evolution, orientation of the different lamellae within spherulites and maps of the solid fraction and temperature fields during solidification. The model provides us with a quantitative predictive tool that can be used to optimize industrial processes.     

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.     

Crystallization kinetics and morphology of nylon 1212

The isothermal and non-isothermal crystallization processes of nylon 1212 were investigated by polarized optical microscopy. The crystal growth rates of nylon 1212 measured in isothermal conditions at temperatures ranged from 182 to 132 °C are well comparable with those measured by non-isothermal procedures (cooling rates ranged from 0.5 to 11 °C/min). The kinetic data were examined with the Hoffman-Lauritzen nucleation theory on the basis of the obtained values of the thermodynamic parameters of nylon 1212. The classical regime I→II and regime II→ III transitions occur at the temperatures of 179 and 159 °C, respectively. The crystal growth parameters were calculated with (100) plane assumed to be the growth plane. The regime I →II→ III transition is accompanied by a morphological transition from elliptical-shaped structure to banded spherulite and then non-banded spherulite. The development of morphology during isothermal and non-isothermal processes shows a good agreement.     

全同立构聚丙烯拉伸过程中球晶形变机理的研究进展

介绍了近来国内外对单向、双向拉伸过程中全同立构聚丙烯(i-PP)晶体内部球晶形变机理的研究进展。单向拉伸过程中，为响应所施加的应力，i-PP晶体内部的球晶、晶片、分子链等不同层次的结构均会产生相应形变。双向拉伸过程中，受拉伸温度、纵横拉伸比等因素的影响，i-PP晶体内部的晶型转化及球晶形变机理非常复杂。     

Spherulite morphology and crystallization behavior of poly(trimethylene terephthalate)/poly(ether imide) blends

The spherulite morphology and crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(ether imide) (PEI) blends were investigated with optical microscopy (OM), small-angle light scattering (SALS), and small-angle X-ray scattering (SAXS). Thermal analysis showed that PTT and PEI were miscible in the melt over the entire composition range. The addition of PEI depressed the overall crystallization rate of PTT and affected the texture of spherulites but did not alter the mechanism of crystal growth. When a 50/50 blend was melt-crystallized at 180 °C, the highly birefringent spherulite appeared at the early stage of crystallization (t < 20 min). After longer times, the spherulite of a second form was developed, which exhibited lower birefringence. The SALS results suggested that the observed birefringence change along the radial direction of the spherulite was mainly due to an increase in the orientation fluctuation of the growing crystals as the radius of spherulite increased. The lamellar morphological parameters were evaluated by a one-dimensional correlation function analysis. The amorphous layer thickness showed little dependence on the PEI concentration, indicating that the noncrystallizable PEI component resided primarily in the interfibrillar regions of the growing spherulites.     

Microscopic lamellar organization in high-density polyethylene banded spherulites studied by scanning probe microscopy

Surface topography and lamellar aggregation structure of high-density polyethylene (HDPE) banded spherulites were investigated by scanning probe microscopy. HDPE films were prepared by isothermal crystallization at various crystallization temperatures from the melt. Polarizing near-field scanning optical microscopic (NSOM) observations for the HDPE films revealed submicron-scale correlation between surface topography and birefringence of banded spherulites. The height profile of the film surface along the spherulitic radius periodically changed corresponding to the intensity profile of transmitted light along the radius of the extinction ring. This correlation was more clearly observed in the topographic and NSOM images of permanganic etched PE films. Therefore, it was apparently suggested that the crystallographic c-axis of the orthorhombic unit cell was parallel and perpendicular to the film surface at the peak and the valley in the surface corrugation of the banded spherulite, respectively. The band spacing obtained by polarizing NSOM and atomic force microscopy (AFM) was comparable to that determined by polarizing far-field optical microscopic observation under crossed nicols. The band spacing and the peak-to-valley height difference in the corrugation increased with an increase in isothermal crystallization temperature. AFM observations directly indicated local lamellar orientation and stacking manner.