Growth Front Of Spherulites Research Articles

Using PCL oligomers to study the differences in melting behavior between polymers and small molecules crystals

Polymer crystals usually show a completely different melting behavior than small molecules. Instead of starting from the crystal growth front, the lamellar crystals within polymer spherulites always experience a successive thickening process upon heating before they simultaneously melt. However, a systematic comparative study of the different melting behavior of crystals formed by small and large polymer chains is still scarce. In this work, two PCL oligomers with similar molecular weight are selected to study their crystallization and melting behavior. The defect-free oligomer (PCL2.4) exhibits a similar melting behavior as polymeric crystals (where spherulites melt simultaneously). In contrast, the other oligomer (PCL2.0) with a mid-chain defect shows prominent surface melting starting at the spherulite growth front. SAXS, SSA thermal fractionation, and flash DSC results confirm that an extended chain-like crystal structure could form at relatively high crystallization temperatures. According to the Gibbs-Thomson equation, the melting temperature of PCL2.0 crystals at the spherulite growth front is relatively lower than in the inner part due to different surface free energies. On the other hand, the thermal stability of PCL2.4 is enhanced due to melting and recrystallization during heating, and the spherulites show identical melting points and lamellar thicknesses at their growth front centers.

Investigating the Effect of Temperature History on Crystal Morphology of Thermoplastic Composites Using In Situ Polarized Light Microscopy and Probabilistic Machine Learning.

Processing parameters including temperature history affect the morphology of semicrystalline thermoplastic composites, and in turn their performance. In addition, the competition between spherulite growth in resin-rich areas, and transcrystallinity growth from fiber surfaces, determines the final morphology. In this study, growth of crystals in low volume fraction PEEK-carbon fiber composites was studied in situ, using a polarized microscope equipped with a heating and cooling controlled stage and a probabilistic machine learning approach, Gaussian Process Regression (GPR). GPR showed that for spherulites, growth kinetics follows the established Lauritzen-Hoffman equation, while transcrystallinity growth deviates from the theory. Combined GPR model and Lauritzen-Hoffman equation were used to deconvolute the underlying competition between diffusion and secondary nucleation at growth front of spherulites and transcrystalline regions.

The αβ-iPP growth transformation of commercial-grade iPP during non-isothermal crystallization

In the present study, the crystallization of commercial-grade isotactic polypropylene (iPP) was studied by optical microscopy, scanning electron microscopy (SEM) and wide-angle X-ray diffraction (WAXD). It was found that isothermal crystallization of used iPP at 135 °C leads to the formation of pure α-iPP crystals. During non-isothermal crystallization at a cooling rate of 10 °C min−1, growth transformation of α into β-iPP occurs at the growth front of α-iPP spherulites. This is not common and has only been found during crystallization in a temperature gradient. The observed αβ-iPP growth transformation is confirmed to be a result of the existence of some impurities, which exhibited their ability to nucleate β-iPP. The ability of the impurities to nucleate β-iPP is dependent on concentration and temperature. Therefore, interlamellar rejection of the impurities caused by fast cooling (40 °C min−1) cannot induce the αβ-iPP growth transformation. On the other hand, even though isothermal crystallization of iPP at 135 °C can result in the accumulation of impurities at the spherulite growth front, it still cannot induce the αβ-iPP growth transformation at a low concentration.

β-Crystal in the iPP melt encapsulated by transcrystallinity and spherulites: effect of molecular weight

The crystallization in isotactic polypropylene (iPP) melt inclusions, encapsulated by transcrystallinity and spherulites, was investigated by polarized light microscope. Generally, owing to the proceeding of crystallization in melt inclusions, a negative pressure will be built up. Up to a critical value, the negative pressure is released by the formation of cavitation in melt. Unexpectedly, β-crystals with different morphologies emerge at different locations in the melt inclusions. For low molecular weight iPP, only smaller β-crystals around bubbles are discernable. Turn to higher molecular weight iPP, apart from the smaller β-crystals, fan-shaped ones can be developed under suitable conditions (e.g., lower than 131 °C) at the growth front of spherulites and transcrystallinity. Considering the characteristics of molecular weight and morphology, it is proposed that β-crystals are induced by different mechanisms. That is, smaller β-crystals are resulted from the stress caused by the appearance of bubbles while the fan-shaped ones are derived due to the temperature gradient during the release of negative pressure.

Real time observation of crystallization in polyethylene oxide with video rate atomic force microscopy

Video rate atomic force microscopy (VideoAFM), with a frame rate of 14 frames/s and a tip velocity of up to 15 cms −1, is used to image polyethylene oxide films during crystal growth. The capabilities of VideoAFM when applied to semicrystalline polymer surfaces are explored. Image quality comparable to that found with conventional contact AFM is achieved but with a nearly 1000 times improvement in time resolution. By applying the technique to the real-time observation of crystal growth, different modes of rapid crystallization are followed in real time. Observation of the spherulite growth front allows measurement of growth rates at the lamellar scale, from which a factor of two difference in the rate of radial growth to the rate of tangential growth is observed, confirming that the elongated nature of spherulite lamellae is due to geometric constraints rather than an inherent fibrillar character. Measurements on screw dislocation growth, when large amounts of crystallizable material is trapped at the surface show that the terrace height does not influence the rate of crystal growth, confirming that under these conditions processes at the lamellar growth front control the rate of growth. When only a thin film of molten material is left on the surface of the already crystallized film dendritic growth is observed, implying a diffusion controlled process under these far from equilibrium conditions.

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.

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.

Non-linear spherulite growth and phase change at the spherulite growth front in isotactic polypropylene/partially hydrogenated oligo(styrene-co-indene) blend

In a previous study, an immiscibility loop in the isotactic polypropylene/partially hydrogenated oligo(styrene-co-indene) (HSI) blend was found by the cloud point method. Then morphology development both at one phase region outside the loop and at two phases inside the loop was investigated. At temperatures studied, a non-linear growth of the spherulite was observed and it was ascribed to the rejected HSI at the growth front of the spherulite. At one phase region just outside the loop, crystallization preceded, and it induced liquid-liquid phase separation at the trapped region between spherulites. At two phases inside the loop, spinodal decomposition proceeded, the crystallization from the decomposed state followed, and then the crystallization induced the dissolution of the liquid-liquid phase separation at the growth front of the spherulite. This behaviour, phase change from the one phase to the two phases and from the two phases to the one phase, was interpreted by the rejected impurity (HSI) at the growth front during crystallization.

Phase separation, crystallization, and structure formation in immiscible polymer solutions

AbstractMorphological and calorimetric studies of phase separation have been carried out in solutions of a crystallizable polymer in poor solvents. Hydrogenated polybutadiene with low branch content was investigated in solutions with diphenyl ether and diphenyl methane, in which the equilibrium phase diagram exhibits both liquid–liquid phase separation and crystallization of the polymer. Emphasis is placed on sample preparation protocols using thermal treatments at low concentrations where it is anticipated that both phase separation mechanisms may influence the resulting morphology. Samples prepared using either ramp cooling or isothermal crystallization exhibit porous structures such as those seen in membrane materials, that predominantly reflect liquid phase separation. However, the interplay between the different kinetics of liquid demixing and crystallization provides a mechanism to control, for instance, pore size. DSC studies during ramp cooling showed evidence of two discrete crystallization processes associated with the two liquid phases expected to be present under these circumstances. Finally, high concentration samples showed morphological evidence of liquid phase separation induced at the growth front of spherulites in otherwise single‐phase polymer solutions. © 1995 John Wiley & Sons, Inc.

Syndiotactic polystyrene: crystallization and melting behaviour

The results of an investigation into the isothermal crystallization and thermal behaviour of syndiotactic polystyrene (sPS) are reported. The study was carried out using differential scanning calorimetry, optical microscopy and dilatometry. From the melt, sPS crystallizes according to a spherulite morphology. The spherulite growth rate and overall crystallization rate depend on crystallization temperature and sample preparation. During the crystallization process, segregation of impurities and non-crystallizable molecules at the spherulite growth front was observed. The nucleation rate, probably very fast, hindered the determination of crystallization kinetic parameters for some crystallization temperatures. Comparing the melt crystallization process of sPS with that of isotactic polystyrene (iPS) for the same value of undercooling, sPS crystallizes more rapidly than iPS, indicating the influence of the tacticity of the materials on the crystallization process. The equilibrium melting temperature T° m was determined and found to be 275°C.

Rapid small‐angle and wide‐angle x‐ray studies of crystallization behavior in polymers

AbstractSmall‐angle and wide‐angle x‐ray scattering measurements, using a position‐sensitive detector, were made during melt‐crystallization of linear polyethylenes and PEO–PS–PEO triblock copolymer. The scattering measurements indicated that the triblock copolymer grew by the enlargement of regions in which lamellae are regularly stacked. During primary crystallization at higher temperatures similar behavior is observed in two linear polyethylenes. At lower temperatures, changes in the shape of small‐angle scattering curves during the primary stage of crystallization indicate that amorphous gaps within the lamellar stacking become filled in. During secondary crystallization at higher temperatures new crystallites appear to grow between those formed in the primary stage. Concurrent decrease of the overall scattered intensity leads to the conclusion that secondary crystallization has two components: crystallization of new lamellae behind the spherulite growth front and the thickening of existing lamellae.