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.     

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.     

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.     

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     

Crystal morphology,melting behaviors and isothermal crystallization kinetics of SCF/PTT composites

Isothermal crystallization kinetics, subsequent melting behavior, and the crystal morphology of short carbon fiber and poly(trimethylene terephthalate) composites (SCF/PTT) were investigated by using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The crystal morphology of the composites isothermally crystallized at T_c = 205°C is predominantly banded spherulites observed under polarizing micrographs, while the pattern of banded spherulites changed from ring to serration as the SCF content added into the PTT. Moreover, nonbanded spherulites formed at T_c = 180°C. The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponents n are evaluated to be 1.6–2.0 for the neat PTT and 2.7–3.0 for SCF/PTT composites, and the SCF acting as nucleation agents in composites accelerates the crystallization rate with decreasing the half‐time of crystallization and the sample with SCF component of 2% has the fastest crystallization rate. The crystallization activation energy calculated from the Arrhenius formula suggests that the adding SCF component improved the crystallization ability of the PTT matrix greatly, and the sample with of 2% SCF component has the most crystallization ability. Subsequent melting scans of the isothermally crystallized composites all exhibited triple melting endotherms, in which the more the component of SCF, the lower temperature of the melting peak, indicating the less perfect crystallites formed in those composites. Furthermore, the melting peaks of the same sample are shifted to higher temperature with increasing T_c, suggesting the more perfect crystallites formed at higher T_c. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Crystallization of poly(3‐hydroxybutyrate) by exfoliated graphite nanoplatelets

Poly(3‐hydroxybutyrate) (PHB) has been shown to be efficiently nucleated by exfoliated graphite nanoplatelets (xGnP). The nucleating effect of xGnP was investigated using differential scanning calorimetry, optical microscopy and atomic force microscopy. Nonisothermal crystallization of PHB from the melt required lower activation energies for PHB containing 1 wt % and 3 wt % xGnP (?214 and ?102 kJ/mol respectively) than for pure PHB (?60 kJ/mol). A kinetic study of the PHB/xGnP crystallization employing a modified form of the Avrami equation revealed that the presence of xGnP increased the PHB crystallization temperature, as well as the crystallization rates, and generated smaller and more numerous spherulites. Optical microscopy and atomic force microscopy confirmed the incorporation of xGnP into the lamellar structure of the PHB spherulites and provided insight into the influence of xGnP on spherulite size and lamellae thickness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Investigation of the effect of nano-clay type on the non-isothermal crystallization kinetics and morphology of poly(3(R)-hydroxybutyrate) PHB/clay nanocomposites

PHB is a thermoplastic biopolymer produced by fermentation of renewable resources. Secondary crystallization during storage leading to an increased degree of crystallinity is a principal reason of PHB brittleness. In addition, pure PHB has no residues of catalysts, meaning low nucleation density and slow crystallization rates, leading to the formation of large spherulites with cracks and brittleness. To overcome the brittleness of PHB, polymer composites based on PHB, plasticizers, and nano-clays A and B were prepared by solvent casting. The addition of plasticizer decreases T _g from 5 to ?13 °C in all composites. Furthermore, the addition of nano-clays acts as a nucleating agent to PHB. The effect of nano-clays A and B on spherulites morphology, thermal behavior, and crystal structure of PHB composites were tested by several techniques. Differential scanning calorimetry analysis shows that the addition of nano-clay A does not change the crystallization temperature and the crystallization half-time (t _1/2) of the PHB matrix but that nano-clay B accelerates the crystallization process. Thermogravimetric analysis revealed an increase in thermal stability of composites containing nano-clay B. Polarized optical microscopy showed that nano-clays serve as nucleating agents in PHB matrix. Therefore, the spherulites become smaller and the nuclei density increases at the selected crystallization temperature, compared to pure PHB.     

Configurational effects on the crystalline morphology and amorphous phase behavior in poly(3‐hydroxybutyrate) blends with tactic poly(methyl methacrylate)

Poly(3‐hydroxybutyrate) (PHB) blends with two tactic poly(methyl methacrylate)s [PMMAs; isotactic poly(methyl methacrylate) (iPMMA) and syndiotactic poly(methyl methacrylate) (sPMMA)], being chiral/tactic polymer pairs, were investigated with regard to their crystalline spherulite patterns, optical birefringence, and amorphous phase behavior with polarized optical microscopy and differential scanning calorimetry. The PHB/sPMMA and PHB/iPMMA blends exhibited upper critical solution temperatures of about 225 and 240°C, respectively, on the basis of the results of thermal analysis and phase morphology. The interactions of two constituents in the blends (PHB/iPMMA or PHB/sPMMA) were measured to be insignificantly different for the PHB/sPMMA and PHB/iPMMA blends. However, syndiotacticity in PMMA exerted a prominent effect on the alteration of the PHB spherulite morphology, whereas, by contrast, isotacticity in PMMA had almost no effect at all. At high sPMMA contents (e.g., 30 wt %) in the PHB/sPMMA blend, the spherulites were all negatively birefringent and ringless when they were crystallized at any crystallization temperature between 50 and 90°C. That is, not only was the original ring‐banded pattern in the neat PHB spherulites completely disrupted, but the optical sign was also reverted completely from positively to negatively birefringent in the sPMMA/PHB blend; this was not observed in the iPMMA/PHB one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Disclosing the crystallization behavior and morphology of poly(ϵ‐caprolactone) within poly(ϵ‐caprolactone)/poly(l‐lactide) blends

In this work, the effect of poly(l ‐lactide) (PLLA) components on the crystallization behavior and morphology of poly(?‐caprolactone) (PCL) within PCL/PLLA blends was investigated by polarized optical microscopy, DSC, SEM and AFM. Morphological results reveal that PCL forms banded spherulites in PCL/PLLA blends because the interaction between the two polymer components facilitates twisting of the PCL lamellae. Additionally, the average band spacing of PCL spherulites monotonically decreases with increasing PLLA content. With regard to the crystallization behaviors of PCL, the crystallization ability of PCL is depressed with increase of the PLLA content. However, it is interesting to observe that the growth rate of PCL spherulites is almost independent of the PLLA content while the overall isothermal crystallization rate of PCL within PCL/PLLA blends decreases first and then increases at a given crystallization temperature, indicating that the addition of PLLA components shows a weak effect on the growth rate of the PCL but mainly on the generation of nuclei. © 2018 Society of Chemical Industry     

Synthesis and characterization of maleated poly(3‐hydroxybutyrate)

Graft copolymerization of maleic anhydride (MA) onto poly(3‐hydroxybutyrate) (PHB) was carried out by use of benzoyl peroxide as initiator. The effects of various polymerization conditions on graft degree were investigated, including solvents, monomer and initiator concentrations, reaction temperature, and time. The monomer and initiator concentrations played an important role in graft copolymerization, and graft degree could be controlled in the range from 0.2 to 0.85% by changing the reaction conditions. The crystallization behavior and the thermal stability of PHB and maleated PHB were studied by DSC, WAXD, optical microscopy, and TGA. The results showed that, after grafting MA, the crystallization behavior of PHB was obviously changed. The cold crystallization temperature from the glass state increased, the crystallization temperature from the melted state decreased, and the growth rate of spherulite decreased. With the increase in graft degree, the banding texture of spherulites became more distinct and orderly. Moreover, the thermal stability of maleated PHB was obviously improved, compared with that of pure PHB. Its thermal decomposition temperature was enhanced by about 20°C. In addition, the introduction of the MA group promoted the biodegradability of PHB. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 659–668, 2003     

Ring‐banded spherulites in poly(ϵ‐caprolactone) blended with hydroxyethyl cellulose acetate as an indication for partial miscibility

The morphologies of poly(?‐caprolactone) (PCL) blends with hydroxyethyl cellulose acetate (HECA), a thermotropic liquid crystalline polymer (TLCP), were investigated by optical microscopy. It is demonstrated that when the pure PCL is crystallized from the melt, a spherulitic morphology arises with distinct Maltese crosses. With the addition of the HECA, the spherulites of the PCL/HECA blends show not only the Maltese crosses but also distinct extinction rings (i.e., a ring‐banded spherulitic morphology). The average periodic distance of the extinction rings decreases drastically with the increase of the HECA content from 0.5 to 5 wt % in the mixture, whereas it decreases only slightly with the further increase of HECA. The periodicity of extinction rings is also influenced by the crystallization temperature. The formation of the ring‐banded spherulites of PCL in PCL/HECA blends is explained in terms of stress‐induced twisted lamellar crystallization and used as an indication of the molecular solubility of the HECA in the PCL. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1681–1686, 2001     

Crystallization and morphology of poly(ethylene succinate) and poly(β-hydroxybutyrate) blends

Summary The melting and crystallization behavior of poly(β-hydroxybutyrate) (PHB) and poly(ethylene succinate) blends has been studied by differential scanning calorimetry and optical microscopy. The results indicate that PHB and PES are miscible in the melt. Consequently the blend exhibits a depression of the melting temperature of both PHB and PES. In addition, a depression of the equilibrium melting temperature of PHB is observed. The Flory-Huggins interaction parameter (χ₁₂ ), obtained from melting point depression data, is composition dependent, and its value is always negative. Isothermal crystallization in the miscible blend system PES/PHB is examined by polarized optical microscope. The presence of the PES component gives a wide variety of morphologies. The spherulites exhibit a banded structure and the band spacing decreases with increase PES content. Received: 29 June 1998/Revised version: 31 August 1998/Accepted: 10 September 1998     

Effect of nylon 6 inclusions on the crystalline morphology of polypropylene–nylon 6 blends

Crystallization behavior and crystalline morphology of plain polypropylene (PP) and its blend with 0 to 30 wt % nylon 6 were studied by the hot‐stage polarized light microscopy method. Radial growth rate and the size and number of PP spherulites were measured as a function of both the isothermal crystallization temperature and the nylon 6 content of the blend. The study revealed that a reduction in the isothermal crystallization temperature from 135 to 120°C, for both the plain PP and its blend with nylon 6, leads to the formation of a large number of fast‐growing, small spherulites. Moreover, the size and growth rate of PP spherulites decreased on increasing the nylon 6 content of the blend; whereas the number of PP spherulites decreased sharply on initial addition of 10% nylon 6 and, thereafter, increased slightly by further addition of nylon 6. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1769–1775, 2000     

Crystallization, and morphology of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) segmented block copolymers

A new type of poly(ether-ester) based on poly(trimethylene terephthalate) as rigid segments and poly(ethylene oxide terephthalate) as soft segments was synthesized and its crystallization behavior and morphology were investigated. Differential Scanning Calorimetry revealed that the copolymer containing 57 wt% soft segments presented a low glass transition temperature (−46.4 °C) and a high melting temperature (201.8 °C), suggesting that it had the typical characteristic of thermoplastic elastomer. With increasing soft segment content from 35 to 57 wt%, the crystallization morphology transformed from banded spherulites to compact seaweed morphology at a certain film thickness, which was due to the change of surface tension and diffusivity caused by increasing the soft segment content. Moreover, with the decrease of film thickness from 15 to 2 μm, the crystallization morphology of the copolymer (57 wt% soft segment) changed from wheatear-like, compact seaweed to dendritic. Scanning Electron Microscopy revealed that some flower-like crystals presenting in the bulk, which had been surprisingly found in the poly(ether-ester) segmented block copolymers for the first time. Possible mechanism was discussed in the text.     

Spherulitic formation and characterization of partially fluorinated copolymers and their nanohybrids with functional fillers

Poly[vinylidenefluoride‐co‐(tetrafluoroethylene)] (P(VDF‐TeFE)) exhibited clear spherulitic texture with negative birefringence. The number and growth rates of the spherulites decreased at high crystallization temperature than at low crystallization temperature. Nonetheless, overall larger spherulites were found at high crystallization temperature and the brightness of the spherulites increased very fast at low crystallization temperature, thereafter it seemed as diminution of birefringence. AFM was used to investigate the impact of organo modified nanodiamond(ND) on spherulitic textures, lamellar thickness, and thickness distribution of P(VDF‐TeFE) copolymer. Poly[ethylene‐co‐(tetrafluoroethylene)] (ETFE) also confirmed spherulites structure and the boundaries could be clearly observed. By incorporation of the organo modified nanodiamond (ND) and organo‐modified montmorillonite (MMT) in fluropolymer matrix, it was found that spherulitic texture was seriously disordered and their nanohybrids was found only to have poorly developed spherulite structure. Both of the nanohybrids samples show better crystallization temperature as compared to their neat copolymer samples. Furthermore, the incorporation of nanoparticles decreased the size of the spherulites. POLYM. ENG. SCI., 57:161–171, 2017. © 2016 Society of Plastics Engineers     

Crystallization temperature dependence of interference color and morphology in poly(trimethylene terephthalate) spherulite

The relationship between retardation and morphology in highly birefringent poly(trimethylene terephthalate) spherulites was studied from the viewpoint of crystallization temperature dependence. Both the retardation and the morphology relate with the degree of orientation of the molecular chains. Therefore, the degree of orientation of the crystal lamellae was estimated by image processing of transmission electron microscope (TEM) images of the spherulite. It was found that the degree of orientation changed remarkably between the non-banded and the banded morphology and the temperature dependence of the degree of orientation correlated with that of the retardation. Based on the image-processed TEM images, it was recognized that the crystal lamellae formed bundles in the banded spherulite, while few bundled lamellae were observed in the non-banded ones. It is suggested that the formation of bundled lamellae played the significant role for both the magnitude of retardation and determination of the morphology; i.e. whether to form banded spherulites or non-banded ones.     

Miscibility,melting, and crystallization behavior of poly(hydroxybutyrate) and poly(D,L‐lactic acid) blends

Melting behavior and crystal morphology of poly(3‐hydroxybutyrate)‐poly(D ,L ‐lactic acid) (PHB‐RPLA) blends with various compositions have been investigated by modulated temperature differential scanning calorimetry (mt‐DSC), polarized optical thermomicroscopy (POTM), modulated force thermomechanometry (mf‐TM), and small angle X‐ray scattering (SAXS). Thermal properties were investigated after fast cooling crystallization treatment. Multiple melting peak behavior was observed for all polymers. mt‐DSC data revealed that PHB‐RPLA blends undergo melting‐recrystallization‐remelting during heating, as evidenced by exothermic peaks in the nonreversing heat capacity. A decrease in degree of crystallinity due to significant melt‐recrystallization was observed for blends. PHB‐RPLA showed different crystal morphologies for various compositions. POTM results showed that the crystallization rates and sizes of spherulites were significantly reduced as RPLA content increased. mf‐TM results confirmed miscibility of these two polymers. SAXS data provided evidence of lamella thickness of blends, which increased with increasing RPLA content. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Morphology and crystallization behavior of PCL/SAN blends containing nanosilica with different surface properties

Morphology and crystallization behavior of poly(?‐caprolactone) (PCL) in its 80/20 blends with poly(styrene‐co‐acrylonitrile) (SAN) containing hydrophobic or hydrophilic nanosilica was investigated. It was found that hydrophilic nanosilica displayed a more significant refinement effect on co‐continuous morphology of PCL/SAN blends than hydrophobic nanosilica for its selective distribution within the PCL matrix but closer to the two‐phase interface. Ring‐banded spherulites were observed in both kinds of nanosilica‐filled blends, the periodic distance of which decreased with increasing nanosilica content. Hydrophilic nanosilica reduced the dependence of the periodic distance of ring‐banded spherulites on the crystallization temperature more efficiently than hydrophobic nanosilica. Furthermore, crystallization process of PCL/SAN blends filled with hydrophobic nanosilica was suppressed as the restriction effect of nanosilica on the crystal growth always outweighed their heterogeneous nucleation effect. In contrast, low content of hydrophilic nanosilica (≤1 wt %) were more likely to exhibit growth restriction effect rather than nucleation effect, whereas heterogeneous nucleation effect of higher content of hydrophilic nanosilica (>1 wt %) dominated over growth restriction effect on facilitating the crystallization behavior. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44157.     

Crystallization studies of isotactic polystyrene

The kinetics of lamellar crystallization in thin films of isotactic polystyrene have been determined using transmission electron microscopy. The morphological changes accompanying crystallization have also been investigated as a function of solvent, supercooling and strain prior to crystallization. Crystallization temperatures have been attained by both cooling from the melt and warming from the glass. Similar growth rates were obtained in both cases. The nucleation density of spherulites is difficult to control when warming from the glass but does depend on the solvent used in preparing the thin film. The rate of lamellar growth follows a ‘bell’ shaped curve versus crystallization temperature and the kinetics were analysed using the secondary nucleation theory of Hoffman and Lauritzen. The end surface free energy, δ_e, of the lamellar crystals was determined using the variation of lamellar thickness with supercooling.     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997