Melting and crystallization behavior of poly(trimethylene 2,6-naphthalate)

The melting and crystallization behavior of poly(trimethylene 2,6-naphthalate) (PTN) are investigated by using the conventional DSC, the temperature-modulated DSC (TMDSC), wide angle X-ray diffraction (WAXD) and polarized light microscopy. It is observed that PTN has two polymorphs (α- and β-form) depending upon the crystallization temperature. The α-form crystals develop at the crystallization temperature below 140 °C while β-form crystals develop above 160 °C. Both α- and β-form crystals coexist in the samples crystallized isothermally at the temperature between 140 and 160 °C. When complex multiple melting peaks of PTN are analyzed using the conventional DSC, TMDSC and WAXD, it is found that those arise from the combined mechanism of the existence of different crystal structures, the dual lamellar population, and melting-recrystallization-remelting. The equilibrium melting temperatures of PTN α- and β-form crystals determined by the Hoffman-Weeks method are 197 and 223 °C, respectively. When the spherulitic growth kinetics is analyzed using the Lauritzen-Hoffmann theory of secondary crystallization, the transition temperature of melt crystallization between regime II and III for the β-form crystals is observed at 178 °C. Another transition is observed at 154 °C, where the crystal transformation from α- to β-form occurs.     

Effects of crystallization temperature on the polymorphic behavior of syndiotactic polystyrene

The influence of crystallization temperature on formation of the α- and β-form crystals of syndiotactic polystyrene (sPS) was investigated by X-ray diffraction and non-isothermal differential scanning calorimetry analysis. For sPS samples without any thermal history, the crystallization temperature must be the intrinsic factor controlling the formation the α and β-form crystals. Being crystallized at different cooling rate from the melt, sPS forms the β-form crystal until the temperature cooled down to about 230 °C, and α-form crystal can only be obtained when the temperature was below about 230 °C.     

Thermal analysis, X-ray and electron diffraction studies on crystalline phase transitions in solvent-treated poly(hexamethylene terephthalate)

The crystal polymorphism, transformation, and morphologies in chloroform solvent-cast poly(hexamethylene terephthalate) (PHT) were examined by using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and temperature in situ transmission electron microscopy (TEM). Solvent-induced crystallization of PHT at room temperature yielded an initial crystal of γ-form, as confirmed by WAXD. Upon DSC scanning, the original γ-form in PHT exhibited three endothermic peaks, whose origins and association were carefully analyzed. The first peak, much smaller than the other two, is in the temperature range of ca. 100-120 °C. It was found that the solvent-induced γ-form was transformed to β-form at 125 °C via a solid-to-solid transformation mechanism. In addition, WAXD showed that γ- and β-forms co-existed in the temperature range of 100-125 °C. These mixed crystal forms were further identified using TEM, and the selected-area electron diffraction (ED) patterns revealed that both γ- and β-form crystals co-existed and were packed within the same spherulite. Solid-solid transformation from the solvent-induced γ-form to β-form in PHT upon heat scanning was presented with evidence and discussed.     

Amorphous phase and crystalline morphology in blend of two polymorphic polyesters: Poly(hexamethylene terephthalate) and poly(heptamethylene terephthalate)

Crystalline/crystalline blends of two polymorphic aryl-polyesters, poly(hexamethylene terephthalate) (PHT) and poly(heptamethylene terephthalate) (PHepT), were prepared and the crystallization kinetics, polymorphism behavior, spherulite morphology, and miscibility in this blend system were probed using polarized-light optical microscopy (POM), differential scanning calorimetry (DSC), temperature-resolved wide-angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS). The PHT/PHepT blends of all compositions were proven to be miscible in the melt state or quenched amorphous glassy phase. Miscibility in PHT/PHepT blend leads to the retardation in the crystallization rate of PHT; however, that of PHepT increases, being attributed to the nucleation effects of PHT crystals which are produced before the growth of PHepT crystals. In the miscible blend of polymorphic PHT with polymorphic PHepT, the polymorphism states of both PHT and PHepT in the blend are influenced by the other component. The fraction of the thermodynamically stable β-crystal of PHT in the blend increases with increasing PHepT content when melt-crystallized at 100 °C. In addition, when blended with PHT, the crystal stability of PHepT is altered and leads to that the originally polymorphic PHepT exhibits only the β-crystal when melt-crystallized at all T_c's. Apart from the noted polymorphism behavior, miscibility in the blend also shows great influence on the spherulite morphology of PHT crystallized at 100 °C, in which the dendritic morphology corresponding to the β-crystal of PHT changes to the ring-banded in the blend with higher than 50 wt% PHepT. In blends of PHT/PHepT one-step crystallized at 60 °C, PHepT is located in both PHT interlamellar and interfibrillar region analyzed using SAXS, which further manifests the miscibility between PHT and PHepT.     

Anomalous molecular orientation of isotactic polypropylene sheet containing N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide

Small amount of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide as a β-form nucleating agent is dissolved beyond 280 °C in a molten isotactic polypropylene (iPP) and appears as needle crystals around at 240 °C during cooling procedure. Further, iPP molecules crystallize on the surface of the needle crystals, in which c-axis of the β-form iPP crystals grows perpendicular to the long axis of the needle crystals. Under flow field at extrusion processing, the needle crystals orient to the flow direction prior to the crystallization of iPP. As a result, c-axis of the β-form iPP crystals orients perpendicular to the applied flow direction with a small amount of α-form iPP. Moreover, the vertical molecular orientation of the extruded sheet sample is responsible for unique mechanical anisotropy; the fracture occurs along the transversal direction.     

Carbon nanocapsules-reinforced syndiotactic polystyrene nanocomposites: Crystallization and morphological features

Syndiotactic polystyrene (sPS) composites filled with well-dispersed carbon nanocapsules (CNC) were prepared through solution blending along with ultrasonication. Several analytic techniques, including DSC, FTIR, PLM, WAXD, TEM, and TGA were performed to reveal the CNC effects on the crystallization, morphology and the thermal degradation of the as-prepared sPS/CNC composites. Addition of CNC was found to favor the crystalline modification of β-form sPS and depress the α-form ones. For the dynamic crystallization, a gradual reduction of cold-crystallization temperature of the α-form sPS was observed by increasing the CNC content although the glass transition temperature remained unchanged (∼96 °C). In contrast, the melt-crystallization temperature of the β-form sPS was elevated from 238 °C for the neat sPS to 251 °C for the 99/5 composite in spite of the fact that the equilibrium melting temperature (∼290 °C) determined from the linear Hoffman-Weeks plot was irrelevant with CNC concentrations. The former was attributable to the formation of an effective heat-conduction path to trigger an earlier overall crystallization. On the other hand, the latter resulted from the enhanced nucleation sites due to the presence of uniformly dispersed CNCs. Results of the isothermal crystallization of the β-form sPS concluded that the presence of 1% CNCs led to a significant increase in the crystallization rate as much as an order of magnitude. Moreover, the Avrami exponent changed to ∼2.0 from a value of 2.8 for the neat sPS, suggesting a different crystallization mechanism involved. At a given crystallization temperature, PLM results showed a negligible variation in the crystal growth rates and a decrease in spherulitic sizes, indicating that nucleation played the key role in enhancing the crystallization rate. For samples isothermally crystallized at 260 °C, the lamellar thickness was constant to be ∼7.2 nm regardless of the CNC content. Due to the enhanced nucleation, however, lamellar stacks were more randomly oriented and its lateral dimensions became shorter with increasing CNC contents. For composites with more than 1 wt% CNC, the crystallizability of sPS chains was reduced and the annealing peak located ca. 4 °C higher than the crystallization temperature became more evident, suggesting the plausible formation of micro-crystals in between the lamellar stacks. The TGA results illustrated that a better thermal stability was reached for the CNC-filled sPS composites.     

Regime II–III transition in isotactic polybutene-1 tetragonal crystal growth

The lateral growth rate and growth shape morphology of isotactic polybutene-1 tetragonal crystals were investigated for crystallization from the melt at temperatures of 68–101 °C. The growth rate of tetragonal crystals shows supercooling dependence derived from the nucleation theory, and a regime II–III transition is observed at temperatures of 77–82.2 °C. The morphology of single crystals is rounded below temperatures of 77–85 °C, while the growth shape has a faceted morphology at a higher crystallization temperature of 100 °C. The kinetic roughening transition occurs between 77 and 85 °C. The regime II growth mode is observed above 82.2 °C and proceeds by multiple nucleation on the faceted growth front, while the regime III growth mode is observed below 77 °C and proceeds by rough surface growth on the kinetically roughened growth front. The observed regime II–III transition can therefore be explained by the morphology transition of crystal growth shape.     

Effects of polyoxyethylene nonylphenol on dynamic mechanical properties and crystallization of polypropylene

Polypropylene (PP) was blended with polyoxyethylene nonylphenol (PN) in a twin-screw extruder and injection moulded. The dynamic mechanical properties of PP/PN blends were characterized by dynamic mechanical analyser (DMA). The glass transition temperature (T_g) of PP showed a slight decrease with incorporation of PN. Differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarized optical microscopy (POM) were employed to investigate the effects of PN on crystallization of PP. In a study of nonisothermal crystallization of PP and PP/PN blends, crystallization parameter analysis showed the addition of PN reduced the peak temperature of crystallization. β-form crystals of PP coexisted with α-form crystals in PP/PN blends, and oriented on the surface layer of injection moulded bar as revealed by WAXD. The degree of orientation was determined using Hermans orientation function. The thermal stability of β-form crystals was evaluated using high temperature WAXD and POM.     

Regulating the β′→β polymorphic transition in food fats

Hydrogenated cottonseed oil (HCSO) is commonly used as a β′-stable fat in margarines and shortenings. In the present study, the crystallization behavior of HCSO is altered via dilution, agitation, tempering regime, and the addition of an emulsifier [polyglycerol polyricinoleate (PgPr)]. Key properties assessed include crystal morphology (with polarized light microscopy), polymorphic behavior (with X-ray diffraction), and crystallization kinetics (with DSC). It is demonstrated that on considerable dilution with canola oil (4% w/w), HCSO can be crystallized in the β′ or β polymorph with associated changes in crystal morphology, depending on tempering regime. Crystallization from the melt to 25°C results in the β′-form, as there is insufficient supercooling to form the β polymorph but enough to form the metastable β′. With cooling from the melt to 5°C, there is adequate supercooling for the δ polymorph to form, with the presence of the canola oil facilitating the transformation toward this stable phase. Static vs. crystallization under agitation does not lead to visible changes in either polymorphic behavior or crystal morphology. However, there is extensive secondary nucleation and growth as a result of crystals breaking off accreting agglomerates. The presence of PgPr, added as a crystal modifier, does not affect the final crystal polymorph or morphology, except under one set of conditions—crystallization from the melt to 5°C with agitation, whereby it considerably alters crystallization behavior.     

Miscibility and crystallization in crystalline/crystalline blends of poly(butylene succinate)/poly(ethylene oxide)

Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-T_m component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-T_m component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.     

Relationships Between the Crystal Structures and the Multiple Melting Behaviors of Poly(ethylene 2,6‐naphthalate)

Summary: Poly(ethylene 2,6‐naphthalate) (PEN) can crystallize either from the glassy state or from the melt state. When crystallized from the glassy state, the sample was quenched from the melt in liquid nitrogen and then annealed at certain crystallization temperatures. When crystallized from the melt state, the sample was cooled to a preset temperature from the melt and then annealed for a certain time. The crystal modifications, morphologies and melting behaviors of PEN were investigated by means of wide‐angle X‐ray diffraction (WAXD), polarized optical microscopy (POM), small‐angle light scattering (SALS) and differential scanning calorimetry (DSC). The results show that an α crystal modification of PEN was obtained when PEN crystallized from the glassy state, whilst a β crystal modification was obtained when PEN crystallized from the melt state at a higher temperature. An hedritic morphology of PEN crystal was obtained with only one melting peak observed in DSC curves when PEN was crystallized at a higher temperature from either the glassy state or the melt state. The α crystal modification could also be obtained when PEN was crystallized at a lower temperature from the melt. Spherulitic or banded spherulitic morphologies of PEN crystals, exhibiting multiple melting peaks in DSC curves, were observed when PEN was crystallized at a lower temperature. The multiple melting behaviors of PEN crystals may be associated with spherulitic structures composed of lamellae of varying thickness.

WAXD patterns of PEN isothermally crystallized from different states.     

Effect of copolymerized ethylene unit on the crystallization behavior of poly(propylene-co-ethylene)s

The crystallization behavior of two kinds of commercial poly(propylene-co-ethylene)s (PPE1, PPE2) with similar average molecular weight and molecular weight distribution, isotacticity and copolymerized ethylene unit content and their fractions was investigated by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and polarized optical microscopy (POM) techniques. The results indicate that the PPE1 isothermally crystallized films possess thicker and less cross-hatched lamellar structure than those of the PPE2. As for the fractionated samples, the thin films of low temperature (≤90 °C) fractions (PPE1-80, PPE2-80) of both PPE1 and PPE2 exhibit similar crystallization behavior, while for the high temperature (≥95 °C) fractions (PPE1-108, PPE2-108), the crystalline morphology has marked differences. Compared with PPE2-108, the PPE1-108 isothermally crystallized thin films possess thicker lamellae and less cross-hatched lamellar structure, while for the fibrous crystal number, the former is less than that of the latter. The main reason to create the crystallization behavior differences between the two PPEs and their fractions is due to the effect of molecular chain structure, i.e. the different distribution of copolymerized ethylene unit in polypropylene chains.     

Crystallization and Morphology of Poly(ethylene 2,6‐naphthalene dicarboxylate) Containing Additives

The influence of nucleating agents (AClyn^®, Surlyn^® and sodium benzoate (SB)) alone and together with nucleating promoter (Ceraflour^® 993 and Ceraflour^® 991 and poly(1,4‐butylene sebacate)) on the crystallization and morphology of poly(ethylene 2,6‐naphthalene dicarboxylate) (PEN) was investigated by means of differential scanning calorimeter, polarized optical microscopy and small angle light scattering. It was revealed that AClyn, Surlyn and SB effectively accelerate nucleation and crystallization of PEN with increasing the ratio of nucleating agent up to 1 wt.‐%. A combination of nucleating agent and nucleating promoter leads to further increase in crystallization rate at low temperature, but only a slight change at high temperature. Hedrites were obtained in pure PEN and the addition of SB and Ceraflour 993 produces small crystals with poor perfection upon crystallization in high temperature region. When crystallization temperature was below 210 °C, spherulites were observed in pure PEN and also in the samples of PEN/Ceraflour 993 and PEN/SB but with smaller size.

Crystal morphology of PEN crystallized at 240 °C for 40 min.     

Structure, morphology and non-isothermal crystallization behavior of polypropylene catalloys

The structure, morphology and non-isothermal crystallization behavior of polypropylene catalloys (PP-cats) as well as pure polypropylene were investigated via differential scanning calorimeter (DSC), wide angle X-ray diffraction (WAXD) and real-time hot-stage optical microscopy (OM). The results reveal that the crystalline structures of PP-cats change with variations of the crystallization conditions and composition. The crystalline phase might consist of α-PP, β-PP and PE crystals. The content of β-PP increases with the increase of EP copolymer content and the cooling rate. At lower cooling rates, the morphologies of all non-isothermal crystallized PP-cats show spherulitic structure, and the decrease of crystal perfection and the increase of nucleation density of PP-cats system could be evidently observed. Considering the compositions of PP-cats, these indicated that the interactions between propylene homopolymer and the ethylene-propylene copolymers (both random and block ones) are in favor of the enhancement of the nucleation ability of α-form as well as β-form. In comparison with pure PP, the overall crystallization rates of the PP-cats increase dramatically, while the growth rates of the spherulites in all PP-cats decrease distinctly under the given cooling conditions. These experimental results were explained on the basis of diluting effect and obstructing effect on the mobility of PP chains in the ethylene-propylene copolymer.     

Isothermal crystallization of isotactic polypropylene blended with low molecular weight atactic polypropylene. Part I. Thermal properties and morphology development

The thermal properties and morphology development of isotactic polypropylene (iPP) homopolymer and blended with low molecules weigh atactic polypropylene (aPP) at different isothermal crystallization temperature were studied with differential scanning calorimeter and wide-angle X-ray scattering. The results of DSC show that aPP is local miscible with iPP in the amorphous region and presented a phase transition temperature at T_c=120 °C. However, below this transition temperature, imperfect α-form crystal were obtained and leading to two endotherms. While, above this transition temperature, more perfect α- and γ-form crystals were formed which only a single endotherm was observed. In addition, the results of WAXD indicate that the contents of the γ-form of iPP remarkably depend both on the aPP content and isothermal crystallization temperature. Pure iPP crystallized was characterized by the appearance of α- and γ-forms coexisting. Moreover, the highest intensity of second peak, i.e. the (0 0 8) of γ-form coexisting with (0 4 0) of α-form, and crystallinity were obtained for blended with 20% of aPP, the γ-form content almost disappeared for iPP/aPP blended with 50% aPP content. Therefore, detailed analysis of the WAXD patterns indicates that at small amount aPP lead to increasing the crystallinity of iPP blend, at larger amount aPP, while decreases crystallinity of iPP blends with increasing aPP content. On the other hand, the normalized crystallinity of iPP molecules increases with increasing aPP content. These results describe that the diluent aPP molecular promotes growth rate of iPP because the diluent aPP molecular increases the mobility of iPP and reduces the entanglement between iPP molecules during crystallization.     

Miscibility, crystallization and morphologies of syndiotactic polystyrene blends with isotactic polystyrene and with atactic polystyrene

Two-component blends of differing polystyrene (PS), one syndiotactic (sPS) and the other isotactic (iPS) or atactic (aPS), were discussed. The phase behavior, crystallization and microstructure of binary polystyrene blends of sPS/iPS and sPS/aPS with a specific composition of 5/5 weight ratio were investigated using optical microscopy (OM), differential scanning calorimetry, wide-angle X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM). Based on the kinetics of enthalpy recovery, complete miscibility was found for the sPS/aPS blends where a single recovery peak was obtained, whereas phase separation was concluded for the sPS/iPS blends due to the presence of an additional recovery shoulder indicating the heterogeneity in the molten state. These findings were consistent with OM and SEM observations; sPS/iPS exhibits the dual interconnectivity of phase-separated phases resulting from spinodal decomposition.Both iPS and aPS have the same influence on the sPS crystal structure, i.e., dominant β-form sPS and mixed α-/β-form sPS obtained for melt-crystallization at high and low temperatures respectively, but imperfect α-form sPS developed when cold-crystallized at 175 °C. Co-crystallization of iPS and sPS into the common lattice was not observed regardless the thermal treatments, either cold or melt crystallization. Due to its slow process, crystallization of iPS was found to commence always after the completion of sPS crystallization in one-step crystallization kinetics. Segregation of rejected iPS component during sPS crystallization was extensively observed from TEM and SEM images which showed iPS pockets located between sPS lamellar stacks within spherulites, leading to the interfibrillar segregation, which was similar with that observed in the sPS/aPS blends. The addition of iPS (or aPS) component will reduce the overall crystallization rate of the sPS component and the retardation of crystal growth rates can be simply accounted by a dilution effect, keeping the surface nucleation intact. The phase-separated structure in the sPS/iPS blend shows a negligible effect on sPS crystallization and the signature of phase separation disappears after sPS crystallization. Depending on the relative dimensions of the segregated domains and iPS lamellar nucleus, subsequent crystallization of iPS can proceed to result in a crystalline/crystalline blend, or be inhibited to give a crystalline/amorphous blend morphology similar with that of sPS/aPS blends.     

Dry Fractionation of Cupuassu (Theobroma grandiflorum) Fat: Physical–Chemical Properties and Polymorphic Behavior

Physical chemical properties of cupuassu fat were modified by dry fractionation. Stearin and olein fractions were obtained at 29, 26, and 24 °C. Polymorphic behavior of unfractionated cupuassu fat (UCF) and its fractions were studied in situ by small-angle (SAXS) and wide-angle (WAXS) X-ray scattering using synchrotron light. Polymorphic transitions were followed in real time tempering samples with a thermal cycle. For UCF, the main polymorphic form crystallized under selected conditions was the β’₂. α and β’₁-forms appeared in trace amounts. β₂-form was obtained after storage at 25 °C for 3 months. Stearins obtained at 26 (S-26) and 24 °C (S-24) showed a similar polymorphic behavior. However, S-26 with improved physical properties might be more suitable for chocolate production or as a trans-fat alternative than UCF. Stearin fraction obtained at 29 °C (S-29) had a complex polymorphic behavior. The α-form was the first polymorphic form detected followed by β’₂-form. There was a polymorphic transition from α to β’₁-form but no transition between β’-forms. They were independent to each other showing fractionation in two different solid solutions. Increased contents of the triacylglycerols (TAG) SOA and SOB together with lower contents of SOO compared to UCF led to co-crystallization because there was no complete compatibility among all TAG present in S-29. β₁-form crystallized after storage forming crystals with a double-layer arrangement and a characteristic morphology. This form could be useful for accelerating crystallization process in melted liquid systems.     

Influence of crystallization temperature on the morphologies of isotactic polypropylene single-polymer composite

The supermolecular structures of iPP fiber/matrix composites as a function of crystallization temperature were studied by means of optical microscopy. The results show that, even though partial melting of the iPP fibers is in favor of initiating the β-iPP crystal growth, the interfacial morphology of iPP single-polymer composites induced by its own fiber depends strongly on the crystallization temperature. It was found that transcrystalline structures of negative radial β_III-iPP or banded β_IV-iPP can be produced within the crystallization temperature range 105-137 °C, while transcrystallization zone of pure negative radial α_II-iPP crystals is observed at higher crystallization temperature, e.g. 141 °C. On the other hand, the surrounding iPP spherulites grown from the bulk are composed of α-iPP in the whole crystallization temperature range. However, the optical character of the spherulites is controlled by the thermal condition.     

Halloysite nanotubes as a novel β-nucleating agent for isotactic polypropylene

The nucleating ability of halloysite nanotubes (HNTs) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), polarized optical microscopy (POM) and scanning electron microscopy (SEM). HNTs are identified to have dual nucleating ability for α-iPP and β-iPP under appropriate kinetics conditions. The formation of β-iPP is dependent on the HNTs loading in the iPP/HNTs composites. The composite with 20 phr of HNTs is found to have the highest content of β-iPP. Under non-isothermal crystallization the content of β-iPP increases with decreasing of the cooling rate. The maximum β-crystal content is obtained at cooling rate of 2.5 °C/min. The supermolecular structure of the β-iPP is identified as β-hedrites with flower-cup-like and axialite-like arrangements of the lamellae. Under isothermal crystallization the β-crystal can be formed in the temperature range of 115-140 °C. Outside the temperature range, no β-iPP can be observed. The content of β-crystal reaches the maximum value at crystallization temperature of 135 °C. The formation of the β-iPP in the composites is correlated to the unique surface characteristics of the HNTs.