New insight into the crystallization behavior of poly(ethylene terephthalate)/clay nanocomposites

Crystallization behavior of poly(ethylene terephthalate) (PET)/clay nanocomposites has been investigated in terms of differential scanning calorimeter (DSC) analysis, polarizing optical microscopy (POM), and scanning electron microscopy (SEM) observation. The nanocomposites for investigation were prepared via in situ polycondensation. Crystalline morphologies were observed through POM and SEM. The nonisothermal and isothermal crystallization rates of different samples were determined for comparison based on DSC data. Secondary nucleation analysis was also performed based on bulk crystallization data derived from DSC analysis. The results revealed that nucleating abilities of montmorillonites (MMT) depended on the dispersion state of clay in matrix, the surface modification status, and the metallic derivatives released from MMT during in situ synthesis. The quantities of metallic elements released were measured by inductively coupled plasma (ICP) analysis. The results showed that the release of these metallic derivatives was also affected by surfactant molecules anchored on the surface of MMT. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2380–2394, 2008     

Isothermal crystallization kinetics and melting behavior of poly(ethylene terephthalate)/barite nanocomposites

Poly(ethylene terephthalate) (PET)/Barite nanocomposites were prepared by direct melt compounding. The effects of PET‐Barite interfacial interaction on the dynamic mechanical properties and crystallization were investigated by DMA and DSC. The results showed that Barite can act as a nucleating agent and the nucleation activity can be increased when the Barite was surface‐modified (SABarite). SABarite nanoparticles induced preferential lamellae orientation because of the strong interfacial interaction between PET chains and SABarite nanoparticles, which was not the case in Barite filled PET as determined by WAXD. For PET/Barite nanocomposites, the Avrami exponent n increased with increasing crystallization temperature. Although at the same crystallization temperature, the n value will decrease with increasing SABarite content, indicating of the enhancement of the nucleation activity. Avrami analyses suggest that the nucleation mechanism is different. The activation energy determined from Arrhenius equation reduced dramatically for PET/SABarite nanocomposite, confirming the strong interfacial interaction between PET chains and SABarite nanoparticles can reduce the crystallization free energy barrier for nucleus formation. In the DSC scan after isothermal crystallization process, double melting behavior was found. And the double endotherms could be attributed to the melting of recrystallized less perfect crystallites or the secondary lamellae produced during different crystallization processes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 655–668, 2009     

Crystallization and melting behavior of liquid crystalline copolyesters based on poly(ethylene terephthalate)

A series of copolyesters were prepared by the incorporation of p‐hydroxybenzoic acid (HBA), hydroquinone (HQ), and terephthalic acid (TA) into poly(ethylene terephthalate) (PET). On the basis of viscosity measurements, high molar mass copolyesters were obtained in the syntheses, and ¹H‐NMR analyses indicated the total insertion of comonomers. They exhibit nematic phase above melting temperature, as observed by polarized light microscope (PLM). Their crystallization and melting behaviors were also studied by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). It was found that these copolyesters are more crystalline than copolyesters prepared from PET and HBA. Introduction of HQ/TA disrupts longer rigid‐rod sequences formed by HBA, and thus enhances molecular motion and increases crystallization rate and crystallinity. Isothermal crystallization at solid phase polymerization conditions (up to 24 h at 200°C) resulted in increased copolymer randomness (by NMR) and higher melting point, the latter attributed to structural annealing. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 369–377, 1999     

Heterogeneous nucleation on the crystallization poly(ethylene terephthalate)

The crystallization behavior of poly(ethylene terephthalate) (PET) with disodium terephthalate (DST) as nucleating agent was investigated. A detailed analysis of the crystallization course from the melt was made with the Avrami expression. The results demonstrated that DST additive can promote the PET crystallization rate in its entire crystallizable temperature range, and the acceleration degree of DST decreases with increasing temperature after a temperature higher than 180 °C. The values of the Avrami exponent indicated that the crystallization mode in Avrami theory is not suitable for the crystallization of these polymers, and the mechanism of the heterogeneous nucleation on PET crystallization is discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2135–2144, 2003     

Random copolymers of poly(butylene terephthalate): Effect of thiodiethylene terephthalate units on melting behaviour and crystallization kinetics

The melting behavior and the crystallization kinetics of poly(butylene terephthalate/thiodiethylene terephthalate) copolymers were investigated by DSC technique. The multiple endotherms were influenced both by T _c and composition. By applying the Hoffman—Weeks' method, T _m ⁰ the of the copolymers was derived. The isothermal crystallization kinetics was analyzed according to the Avrami's treatment. Values of the exponent n close to 3 were obtained, independently of T _c and composition. The introduction of thiodiethylene terephthalate units decreased the PBT crystallization rate. H _m was correlated to c _p for samples with different degree of crystallinity and the results were interpreted on the basis of the existence of an interphase.This revised version was published online in November 2005 with corrections to the Cover Date.     

Morphology development and crystallization behavior of poly(ethylene terephthalate)/phenoxy blend

The morphological development and crystallization behavior of a poly(ethylene terephthalate)/poly(hydroxyl ether of bisphenol A) (phenoxy) blend were studied with time‐resolved light scattering, optical microscopy, differential scanning calorimetry, and small‐angle X‐ray scattering (SAXS). During annealing at 280 °C, liquid–liquid phase separation via spinodal decomposition proceeded in the melt‐extruded specimen. After the formation of a domain structure, the blend slowly underwent phase homogenization by the interchange reactions between the two polymers. Specimens annealed for various times (t_s) at 280 °C were subjected to a temperature drop and the effects of liquid‐phase changes on crystallization were then investigated. The shifts in the position of the cold‐crystallization peaks indicated that the crystallization rate is associated with the composition change of the separated phases as well as the change of the sequence distribution in polymer chains during annealing. The morphological parameters at the lamellar level were determined by a correlation function analysis on the SAXS data. The crystal thickness (l_c) increased with t_s, whereas the amorphous layer thickness (l_a) showed little dependence on t_s. Observation of a constant l_a value revealed that a large number of noncrystallizable species formed by the interchange reactions between the two polymers were excluded from the lamellar stacks and resided in the interfibrillar regions, interspherulitic regions, or both. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 223–232, 2008     

Fast crystallization of poly(ethylene terephthalate)

The crystallization of poly(ethylene terephthalate) (PET) was studied in the presence of nucleating agents and promoters. The effect of both by themselves and in concert was investigated using differential scanning calorimetry. The aim of this work is to find conditions of fast crystallization of PET. Sodium benzoate(SB) and Surlyn® (S) substantially increase the crystallization rate of PET at higher temperature owing to a reduction in the energy barrier towards primary nucleation, but they accelerate crystallization even more at lower temperature with an additional improvement of the molecular mobility of PET chains. Chain scission of PET caused by the reaction with the nucleating agents was proven by determination of molecular weight. The addition of S alone led to a lower reduction in molecular weight. A series of N-alkyl-p-toluenesulfonamides (ATSAs) were shown to effectively promote molecular motion of the PET chains, leading to an increase in crsytallization rate at lower temperature. A remarkable acceleration of crystallization of PET was attained at lower temperature when S and ATSA were added together. When the content of ATSA is low, S has the dominant influence due to its dual effect of decreasing energy barrier towards nucleation and promoting molecular motion of PET chains. A further increase of crystallization rate of PET was found only after an addition of ATSA of above 5 wt.%.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThis work was supported by State Science and Technology Commission, and partially by National Science Foundation.     

Synthesis and characterization of poly(ethylene glycol) methyl ether endcapped poly(ethylene terephthalate)

Linear and branched poly(ethylene terephthalate) (PET) copolymers with polyethylene glycol) (PEG) methyl ether (700 or 2000 g/mol) end groups were synthesized using conventional melt polymerization. DSC analysis demonstrated that low levels of PEG end groups accelerated PET crystallization. The incorporated PEG end groups also decreased the crystallization temperature of PET dramatically, and copolymers with a high content of PEG (>17.6 wt%) were able to crystallize at room temperature. Rheological analysis demonstrated that the presence of PEG end groups effectively decreased the melt viscosities and facilitated melt processing. XPS and ATR-FTIR revealed that the PEG end groups tended to aggregate on the surface, and the surface of compression molded films containing 34.0 wt% PEG were PEG rich (85 wt% PEG). PEG end-capped PET (34.0 wt% PEG) and PET films were immersed into a fibrinogen solution (0.7 mg/mL BSA) for 72 h to investigate the propensity for protein adhesion. XPS demonstrated that the concentration of nitrogen (1.05%) on the surface of PEG endcapped PET film was statistically lower than PET (7.67%). SEM analysis was consistent with XPS results, and revealed the presence of adsorbed protein on the surface of PET films.     

Thermal,crystallization, mechanical,and rheological characteristics of poly(trimethylene terephthalate)/poly(ethylene terephthalate) blends

Blends of poly(trimethylene terephthalate) (PTT) and poly(ethylene terephthalate) in the amorphous state were miscible in all of the blend compositions studied, as evidenced by a single, composition‐dependent glass‐transition temperature observed for each blend composition. The variation in the glass‐transition temperature with the blend composition was well predicted by the Gordon–Taylor equation, with the fitting parameter being 0.91. The cold‐crystallization (peak) temperature decreased with an increasing PTT content, whereas the melt‐crystallization (peak) temperature decreased with an increasing amount of the minor component. The subsequent melting behavior after both cold and melt crystallizations exhibited melting point depression behavior in which the observed melting temperatures decreased with an increasing amount of the minor component of the blends. During crystallization, the pure components crystallized simultaneously just to form their own crystals. The blend having 50 wt % of PTT showed the lowest apparent degree of crystallinity and the lowest tensile‐strength values. The steady shear viscosity values for the pure components and the blends decreased slightly with an increasing shear rate (within the shear rate range of 0.25–25 s^?1); those of the blends were lower than those of the pure components. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 676–686, 2004     

Phase separation in semicrystalline blends of poly(phenylene sulfide) and poly(ethylene terephthalate). II. Effect of poly(phenylene sulfide) homopolymer solubilization of PPS‐graft‐PET copolymer on morphology and crystallization behavior

The morphology and crystallization behavior of poly(phenylene sulfide) (PPS) and poly(ethylene terephthalate) (PET) blends compatibilized with graft copolymers were investigated. PPS‐blend‐PET compositions were prepared in which the viscosity of the PPS phase was varied to assess the morphological implications. The dispersed‐phase particle size was influenced by the combined effects of the ratio of dispersed‐phase viscosity to continuous‐phase viscosity and reduced interfacial tension due to the addition of PPS‐graft‐PET copolymers to the blends. In the absence of graft copolymer, the finest dispersion of PET in a continuous phase of PPS was achieved when the viscosity ratio between blend components was nearly equal. As expected, PET particle sizes increased as the viscosity ratio diverged from unity. When graft copolymers were added to the blends, fine dispersions of PET were achieved despite large differences in the viscosities of PPS and PET homopolymers. The interfacial activity of the PPS‐graft‐PET copolymer appeared to be related to the molecular weight ratio of the PPS homopolymer to the PPS segment of the graft copolymer (M_H/M_A). With increasing solubilization of the PPS graft copolymer segment by the PPS homopolymer, the particle size of the PET dispersed phase decreased. In crystallization studies, the presence of the PPS phase increased the crystallization temperature of PET. The magnitude of the increase in the PET crystallization temperature coincided with the viscosity ratio and extent of the PPS homopolymer solubilization in the graft copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 599–610, 2000     

Isothermal and nonisothermal crystallization kinetics of poly(propylene terephthalate)

The kinetics of crystallization of poly(propylene terephthalate) (PPT) samples of different molecular weights were studied under both isothermal and nonisothermal conditions. The Avrami and Lauritzen–Hoffmann treatments were applied to evaluate kinetic parameters of PPT isothermal crystallization. It was found that crystallization is faster for low‐molecular‐weight samples. The modified Avrami equation, and the combined Avrami–Ozawa method were found to successfully describe the nonisothermal crystallization process. Also, the analysis of Lauritzen–Hoffmmann was tested and it resulted in values close to those obtained with isothermal crystallization data. The nonisothermal kinetic data were corrected for the effect of the temperature lag and shifted alone with the isothermal kinetic data to obtain a single master curve, according to the method of Chan and Isayev, testifying to the consistency between the isothermal and corrected nonisothermal data. A new method for ranking of polymers, referring to the crystallization rates, was also introduced. This involved a new index that combines the maximum crystallization rate observed during cooling with the average crystallization rates over the temperature range of the crystallization peak. Furthermore, the effective energy barrier of the dynamic process was evaluated with the isoconversional methods of Flynn and Friedmann. It was found that the energy barrier is lower for the low‐molecular‐weight PPT. The effect of the catalyst remnants on the crystallization kinetics was also investigated and it was found that this is significant only for low‐molecular‐weight samples. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3775–3796, 2004     

A differential scanning calorimetry study on poly(ethylene terephthalate) isothermally crystallized at stepwise temperatures: multiple melting behavior re-investigated

The multiple melting behavior of poly(ethylene terephthalate) (PET) was investigated with differential scanning calorimetry (DSC) by examining PET samples having been subjected to special schemes of crystallization and annealing treatment at multiple descending temperatures. Upon such step-wise annealing in decreasing temperatures, the existence of doublet melting peaks in addition to a series of multiple minor peaks in the PET has been demonstrated using carefully designed thermal schemes. Using the Hoffman theory, multiple lamellae populations, might be suggested to be simultaneously present in the PET subjected to such thermal treatments. However, direct experimental evidence has yet to be provided. The low-temperature minor crystals simply melt during normal scanning without having time enough to reorganize into higher-melt crystals. Nevertheless, the effect of scanning on non-isothermal crystallization does exist but is primarily confined to the temperature range much below the main melting region where the crystallization of polymer chains can progress at a reasonable rate. At higher temperatures near the main melting region, annealing for extended times is required in order to result in relative changes of the melting endotherms of the upper and lower peaks in the main melting doublet. In all we have shown that interpretations of the multiple melting phenomenon in semicrystalline polymers can be better refined.     

Synthesis and non‐isothermal crystallization kinetics of poly(ethylene terephthalate)‐co‐poly(propylene glycol) copolymers

Poly(ethylene terephthalate)‐co‐poly(propylene glycol) (PET‐co‐PPG) copolymers with PPG ratio ranging from 0 to 0.90 mol% were synthesized by the melt copolycondensation. The intrinsic viscosity, structure, non‐isothermal crystallization behavior, nucleation and spherulitic growth of the copolymers were investigated by Ubbelohde viscometer, Proton Nuclear Magnetic Resonance (¹H‐NMR), differential scanning calorimetry, and polarized optical microscopy, respectively. The non‐isothermal crystallization process of the copolymers was analyzed by Avrami, Ozawa, Mo's, Kissinger, and Dobreva methods, respectively. The results showed that the crystallizability of PET was apparently enhanced with incorporating a small amount of PPG, which first rose and then reduced with increasing amount of PPG in the copolymers at a given cooling rate. The crystallization mechanism was a three‐dimensional growth with both instantaneous and sporadic nucleation. Particularly, PET‐co‐PPG containing 0.60 mol% PPG exhibited the highest crystallizability among all the copolymers. Copyright © 2015 John Wiley & Sons, Ltd.     

High‐pressure DTA of poly(butylene terephthalate), poly(hexamethylene terephthalate), and poly(ethylene terephthalate)

Pressure effect on the melting behavior of poly(butylene terephthalate) (PBT) and poly(hexamethylene terephthalate) (PHT) was studied by high‐pressure DTA (HP‐DTA) up to 320 and 530 MPa, respectively. Cooling rate dependence on the DSC melting curves of the samples cooled from the melt was shown at atmospheric pressure. Stable and metastable samples were prepared by cooling from the melt at low and normal cooling rates, respectively. DTA melting curves for the stable samples showed a single peak, and the peak profile did not change up to high pressure. Phase diagrams for PBT and PHT were newly determined. Fitting curves of melting temperature (T_m) versus pressure expressed by quadratic equation were obtained. Pressure coefficients of T_m at atmospheric pressure, dT_m/dp, of PBT and PHT were 37 and 33 K/100 MPa, respectively. HP‐DTA curves of the metastable PBT showed double melting peaks up to about 70 MPa. In contrast, PHT showed them over the whole pressure region. HP‐DTA of stable poly(ethylene terephthalate) (PET) was also carried out up to 200 MPa, and the phase diagram for PET was determined. dT_m/dp for PET was 49 K/100 MPa. dT_m/dp increased linearly with reciprocal number of ethylene unit. The decrease of dT_m/dp for poly(alkylene terephthalate) with increasing a segmental fraction of an alkyl group in a whole molecule is explained by the increase of entropy of fusion. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 262–272, 2000     

The effect of annealing on the crystallization of poly(ethylene terephthalate)/polycarbonate blends

The effect of annealing on the morphology and subsequent crystallization kinetics of poly (ethylene terephthalate)/polycarbonate blends have been investigated using differential scanning calorimetry (DSC), polarized light microscopy, and scanning electron microscopy (SEM). During annealing transesterification and phase coarsening occurred, and the final properties were compromizes between these two competing effects. Initially, the effect of phase separation dominated and the rate of cold crystallization of PET increased. Transesterification, however, became increasingly important and the rate of crystallization decreased progressively until finally the blend completely lost the ability to crystallize. At this stage in the reaction a single glass transition was observed and uniform glassy material observed in the SEM. The maximum crystallinity of the blend achieved on heating showed the same trend in first increasing and then decreasing with annealing time. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2129–2136, 2004     

Non-isothermal crystallization kinetics of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) blends

The glass-transition temperature and non-isothermal crystallization of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) (PTT/PEN) blends were investigated by using differential scanning calorimeter (DSC). The results suggested that the binary blends showed different crystallization and melting behaviors due to their different component of PTT and PEN. All of the samples exhibited a single glass-transition temperature, indicating that the component PTT and PEN were miscible in amorphous phase. The value of T_g predicted well by Gordon-Taylor equation decreased gradually with increasing of PTT content. The commonly used Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of non-isothermal crystallization. The kinetic parameters suggested that the PTT content improved the crystallization of PEN in the binary blend. The crystallization growth dimension, crystallization rate and the degree of crystallinity of the blends were increased with the increasing content of PTT. The effective activation energy calculated by the advanced iso-conversional method developed by Vyazovkin also concluded that the value of E_a depended not only on the system but also on temperature, that is, the binary blend with more PTT component had higher crystallization ability and the crystallization ability is increased with increasing temperature. The kinetic parameters U^* and K_g were also determined, respectively, by the Hoffman-Lauritzen theory.     

Multiple melting endotherms in isothermally melt-crystallized poly(butylene terephthalate)

The melting behavior of poly(butylene terephthalate) crystallized isothermally for various times was examined using differential scanning calorimetry. After short crystallization times, the DSC analysis gave two melting peaks, but after longer times, the analysis gave three peaks. The latter triplet of DSC peaks can be denoted as low, middle, and high, starting with the lowest temperature endotherm. The DSC peaks were simulated using a measured recrystallization rate and behavior for PBT and an assumed initial melting point distribution. The low and middle peaks represent the original melting peaks arising from isothermal crystallization. The high melting peak arises from recrystallization during the DSC heating scan. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1757–1767, 1998     

Structural features of crystallized poly(ethylene terephthalate) polymers

Polyethylene terephthalate (PET) is a widely used polymeric material. In this work, the microstructural features before and after the solid‐state polymerization (SSP) of several DuPont PET products were investigated by low‐voltage scanning electron microscopy (LV‐SEM) and atomic force microscopy (AFM). The microstructural features on the cross section of various PET samples included crystallites, voids, boundaries, defects, and amorphous phases. The SEM images revealed layered and stepped structural features at the micron and 10‐micron scales that are highly crystallized at the near‐edge region of the cross section for both linear and branched PET samples after the SSP process. The AFM images demonstrate that the degree of crystallization for the linear and branched PET samples increases gradually from the central area to the edge on the cross section. The linear crystallized PET has a higher degree of orientation than the branched crystallized PET in the 10‐micron to micron scales, but their crystalline structures have no significant differences in the submicron to nanometer scales. The PET crystallization process occurs when the molecular chains in the amorphous phase are aligned and folded to form straight molecular chains at the nanometer scale, and small crystallites are formed. The crystallites aggregate and align together into a polygon rod‐like‐shaped crystallites at the submicron scale. Finally, large crystallites at the micron size are formed that appear on the edge area of the cross section. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 245–254, 2002     

Isothermal crystallization kinetics of poly(trimethylene terephthalate) under the influence of self-seeding nucleation

The effect of self-seeding nucleation on the crystallization behavior of poly(trimethylene terephthalate) (PTT) was studied. Differential scanning calorimetry (DSC) indicated that the crystallization temperature of PTT notably increased after self-seeding nucleation. Avrami equation was applied in the analysis of the isothermal crystallization process of PTT. The resulting average value of the Avrami exponent at n = 3.34 suggests that primary crystallization may correspond to a three-dimensional spherulitic growth. Self-seeding nucleation, leading to a decrease in active energy for crystallization and chain folding work, promotes the overall crystallization process of PTT. Translated from Acta Polymerica Sinica, 2006, (3): 414–417 (in Chinese)     

Miscibility of poly(ethylene terephthalate)/poly(ethylene 2,6-naphthalate) blends by transesterification

The effects of transesterification on the miscibility of poly(ethylene terephthalate)/poly(ethylene 2,6-naphthalate) were studied. Blends were obtained by solution precipitation at room temperature to avoid transesterification during blend preparation. The physical blends and transesterified products were analyzed by wide-angle x-ray scattering, differential scanning calorimetry, and nuclear magnetic resonance spectroscopy. It was found that the physical blends are immiscible and when the extent of transesterification reaches 50% of the completely randomized state, independent of blend composition, the blends are not crystallizable and show a single glass transition temperature between those of starting polymers. The interchange reactions were significantly influenced by annealing temperature and time but negligibly by blend composition. © 1996 John Wiley & Sons, Inc.