Poly(ethylene terephthalate)/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate)/clay nanocomposites: Effects of biaxial stretching

In this study, we fabricated poly(ethylene terephthalate) (PET)/clay, PET/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate) (PETG), and PET/PETG/clay nanocomposite plates and biaxially stretched them into films by using a biaxial film stretching machine. The tensile properties, cold crystallization behavior, optical properties, and gas and water vapor barrier properties of the resulting films were estimated. The biaxial stretching process improved the dispersion of clay platelets in both the PETG and PET/PETG matrices, increased the aspect ratio of the platelets, and made the platelets more oriented. Thus, the tensile, optical, and gas‐barrier properties of the composite films were greatly enhanced. Moreover, strain‐induced crystallization occurred in the PET/PETG blend and in the amorphous PETG matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42207.     

Liquid-liquid phase separation and crystallization behavior of poly(ethylene terephthalate)/poly(ether imide) blend

The liquid-liquid (L-L) phase separation and crystallization behavior of poly(ethylene terephthalate) (PET)/poly(ether imide) (PEI) blend were investigated with optical microscopy, light scattering, and small angle X-ray scattering (SAXS). The thermal analysis showed that the concentration fluctuation between separated phases was controllable by changing the time spent for demixing before crystallization. The L-L phase-separated specimens at 130 °C for various time periods were subjected to a temperature-jump of 180 °C for the isothermal crystallization and then effects of L-L phase separation on crystallization were investigated. The crystal growth rate decreased with increasing L-L phase-separated time (t_s). The slow crystallization for a long t_s implied that the growth path of crystals was highly distorted by the rearrangement of the spinodal domains associated with coarsening. The characteristic morphological parameters at the lamellar level were determined by the correlation function analysis on the SAXS data. The blend had a larger amorphous layer thickness than the pure PET, indicating that PEI molecules in the PET-rich phase were incorporated into the interlamellar regions during crystallization.     

Crystallization of poly(ethylene terephthalate) under tensile strain: crystalline development versus mechanical behaviour

The crystallization of poly(ethylene terephthalate) (PET) under tensile strain was investigated using wide angle X-ray diffraction. Real-time investigation of the crystallization state, including the crystalline ratio and the crystallite orientation, of the material could be undertaken due to the high brilliance of the synchrotron X-ray source used in our study. Initially amorphous PET specimens were stretched at different strain rates and draw ratios at the same temperature (above and close to T_g). Our experimental set-up was designed to undertake simultaneous recording of the X-ray diffraction patterns and the mechanical parameters. Up to the draw ratio of 500% and draw rate of 0.75 s⁻¹, the crystalline development dynamics corresponded to three different regimes. (i) For small enough extension rates, there was no measurable crystallinity during the drawing process. The crystallization developed after cessation of deformation. (ii) For intermediate extension rates, the whole crystallization process took place during the deformation. (iii) For the highest extension rate involved in our experiments, the crystallization started during the drawing process and continued after cessation of deformation. The mechanical behaviour of the polymer was simultaneously recorded and correlated with the induced crystalline microstructure. In particular, we were able to discriminate the influence of crystallite orientation and crystallization growth on the mechanical behaviour of the material.     

Crystallization in blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Blends composed of poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) were melt-mixed in a Brabender cam mixer at different mixing speeds. The glass transition (T_g) and the crystallization behavior of the blends from glassy state were studied using DSC. It was found that although the blends had the same composition and exhibited the similar T_g, their properties of crystallization could be different; some exhibited a single crystallization peak and some exhibited multiple crystallization peaks depending upon experimental conditions. Results indicated that the behavior of crystallization from glassy state were influenced by entanglement and transesterification of chains. The crystallization time values were obtained over a wide range of crystallization temperature. From curve fitting, the crystallization time values and the temperature, at which the crystallization rate reaches the maximum, were found.     

Carbon nanotubes induced crystallization of poly(ethylene terephthalate)

We have investigated the crystallization characteristics of melt compounded nanocomposites of poly(ethylene terephthalate) (PET) and single walled carbon nanotubes (SWNTs). Differential scanning calorimetry studies showed that SWNTs at weight fractions as low as 0.03 wt% enhance the rate of crystallization in PET, as the cooling nanocomposite melt crystallizes at a temperature 10 °C higher as compared to neat PET. Isothermal crystallization studies also revealed that SWNTs significantly accelerate the crystallization process. WAXD showed oriented crystallization of PET induced by oriented SWNTs in a randomized PET melt, indicating the role of SWNTs as nucleating sites.     

Poly(ethylene terephthalate)/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate)/clay nanocomposites: Mechanical properties,optical transparency,and barrier properties

Poly(ethylene terephthalate) (PET)/clay, PET/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate) (PETG), and PET/PETG/clay nanocomposites were fabricated using the twin‐screw extrusion technique. The spherulitic morphologies, thermomechanical, mechanical, and gas‐barrier properties, as well as the effect of clay on the transparency of the resulting nanocomposites were identified. The clay induced the heterogeneous nucleation of the nanocomposites during the cold crystallization process, thereby increasing the crystallinities and melting temperatures of the resulting nanocomposites. The incorporation of clay increased the storage moduli, Young's moduli, impact strengths, and barrier properties of the PET, PETG, and PET/PETG blend. Regarding the optical transparency, the inclusion of clay can make the crystallizable PET matrix crystalline opaque. However, the amorphous PETG maintained its transparency. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39869.     

Oxygen solubility and specific volume of rigid amorphous fraction in semicrystalline poly(ethylene terephthalate)

The existence of rigid amorphous fraction (RAF) in semicrystalline poly(ethylene terephthalate) (PET) is associated with the lamellar stack crystalline morphology of this polymer, the regions where several crystalline lamellas are separated by very thin (20-40 Å) amorphous layers. In contrast, regular or mobile amorphous fraction is associated with much thicker interstack regions. The oxygen transport properties of PET isothermally crystallized from the melt (melt-crystallization) or quenched to the glassy state and then isothermally crystallized by heating above T_g (cold-crystallization) were examined at 25 °C. Explanation of unexpectedly high solubility of crystalline PET was attributed to the formation of RAF, which in comparison with mobile amorphous phase is constrained and vitrifies at much higher than T_g temperature thus developing an additional excess-hole free volume upon cooling. Measurements of crystallinity and jump in the heat capacity at T_g were used to determine the amount of mobile and rigid amorphous fractions. Overall oxygen solubility was associated with the solubility of mobile and rigid amorphous fractions. The oxygen solubility of the RAF was determined and related to the specific volume of this fraction. The specific volume of the RAF showed a direct correlation with the crystallization temperature. It was shown that upon crystallization from either melt or glassy state, the constrained between crystalline lamellas PET chains consisting of the RAF, vitrify at the crystallization temperature and resemble the glassy behavior despite high temperature. When cooled to room temperature, the RAF preserves a memory about the melt state of polymer, which is uniquely defined by the crystallization temperature.     

Melt crystallization of poly(ethylene terephthalate): Comparing addition of graphene vs. carbon nanotubes

Poly(ethylene terephthalate) (PET)-based nanocomposites with graphene or multi-wall carbon nanotubes (MWCNT) were prepared by melt mixing. Aspect ratio, A_f, and interparticle distance, λ, of graphene in the nanocomposites were obtained from melt rheology and transmission electron microscopy respectively. λ of PET/graphene nanocomposites was much smaller than λ in PET/MWCNT. For PET/graphene with highest A_f, λ became <1 μm at more than 0.5 wt% graphene. Non-isothermal crystallization behavior from the melt was investigated by differential scanning calorimetry. The crystallization temperatures suggest that the nucleation effect of graphene was stronger than that of MWCNT. The half crystallization time of PET/graphene became longer than PET/MWCNT with increasing graphene loading, suggesting that confinement by graphene suppressed the crystal growth rate. XRD analysis indicated that smaller crystals formed in PET/graphene than in PET/MWCNT. From Raman spectroscopy, the π–π interaction between PET and graphene was stronger than that between PET and MWCNT. This stronger interaction in PET/graphene appears to result in formation of crystals with higher perfection.     

Novel impacts of glycol-modified poly(ethylene terephthalate)(PETG) to crystallization behavior of polyethylene naphthalate (PEN) within stretched miscible blends

For studied blends of amorphous glycol-modified poly(ethylene terephthalate) (PETG) and semicrystalline polyethylene naphthalate (PEN), melt miscibility is understood from the linear variation of a single glass transition temperature (T_g) over the entire composition range. The diluent effect of PETG component severely retarded the crystallization of PEN component within blends. Nevertheless, after being through isothermal stretching at 120 °C, crystallization was able to progress efficiently during heating in a continuous manner. Instead of being thermally relaxed back to amorphous state, parallel sliding motions of stretched PEN segments toward crystallization appear rather dominant. Within stretched blends, the PETG content emerged as a critical factor to the crystallinity increase of PEN fraction and the absence of lattice defect, instead of behaving as a diluent component. Furthermore, as being indicated by in-situ small-angle X-ray experiments, regular lamellar stacking gradually developed within stretched blends through heating, which indicates the involvement of thermally activated self-association of randomly distributed crystalline lamellae. With including a higher fraction of PETG component, these secondary ordering processes including lamellar thickening can be activated at lower temperature. Hence, the accompanied thermal relaxation of flexible PETG segment is inferred able to lubricate the sliding of stretched PEN segments in amorphous regions via lowering encountered frictional hindrance, and thus enhance both primary and secondary ordering processes within stretched blends.     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.     

Confined crystallization of nanolayered poly(ethylene terephthalate) using X-ray diffraction methods

The development of crystalline lamellae in ultra-thin layers of poly(ethylene terephthalate) PET confined between polycarbonate (PC) layers in an alternating assembly is investigated as a function of layer thickness by means of X-ray diffraction methods. Isothermal crystallization from the glassy state is in-situ followed by means of small-angle X-ray diffraction. It is found that the reduced size of the PET layers influences the lamellar nanostructure and induces a preferential lamellar orientation. Two lamellar populations, flat-on and edge-on, are found to coexist in a wide range of crystallization temperatures (T_c = 117–150 °C) and within layer thicknesses down to 35 nm. Flat-on lamellae appear at a reduced crystallization rate with respect to bulk PET giving rise to crystals of similar dimensions separated by larger amorphous regions. In addition, a narrower distribution of lamellar orientations develops when the layer thickness is reduced or the crystallization temperature is raised. In case of edge-on lamellae, crystallization conditions also influence the development of lamellar orientation; however, the latter is little affected by the reduced size of the layers. Results suggest that flat-on lamellae arise as a consequence of spatial confinement and edge-on lamellae could be generated due to the interactions with the PC interface.     

Miscibility and melting behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting behavior of binary crystalline blends of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) have been investigated with differential scanning calorimetry and scanning electron microscope. The blends exhibit a single composition‐dependent glass transition temperature (T_g) and the measured T_g fit well with the predicted T_g value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (T_cc) value can be observed and it decreases nearly linearly with the low T_g component, PTT, which can also be taken as a valid supportive evidence for miscibility. The SEM graphs showed complete homogeneity in the fractured surfaces of the quenched PET/PTT blends, which provided morphology evidence of a total miscibility of PET/PTT blend in amorphous state at all compositions. The polymer–polymer interaction parameter, χ₁₂, calculated from equilibrium melting temperature depression of the PET component was ?0.1634, revealing miscibility of PET/PTT blends in the melting state. The melting crystallization temperature (T_mc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest T_mc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization characteristics of weakly branched poly(ethylene terephthalate)

A series of branched poly(ethylene terephthalate) (BPET) samples were prepared from melt polycondensation by incorporation of various amount (0.4-1.2 mol%) of glycerol as a branching agent. These polymers were characterized by means of H¹ NMR, intrinsic viscosity. The general crystalline and melting behavior was investigated via DSC. It was found that the crystalline temperature T_cc from the melt shifted to high temperature and the T_hc from the glass got low for BPETs while the melting temperatures of BPETs kept almost unchanged. The kinetics of isothermal crystallization was studied by means of DSC and POM. It was found that the present branching accelerated the entire process of crystallization of BPETs, although prolonged the induced time. In addition, branching reduced nucleation sites; hence the number of nucleates for BPET got smaller. Therefore, more perfect geometric growth of crystallization and greater radius of spherulites could develop in BPET due to less truncation of spherulites.     

Crystallization of poly(ethylene terephthalate) and poly (butylene terephthalate) modified by diamides

Poly(ethylene terephthalate) (PET) and poly (butylene terephthalate) have been modified by diamide units (0.1–1 mol%) in an extrusion process and the crystallization behavior studied. The diamides used were: for PET, T2T‐dimethyl (N, N′‐bis(p‐carbomethoxybenzoyl)ethanediamine) and for PBT, T4T‐dimethyl (N, N′‐bis(p‐carbomethoxybenzoyl)butanediamine). The above materials were compared to talc (0.5 wt%), this being a standard heterogeneous nucleator, and to diamide modified copolymers obtained by a reactor process. Two PET materials were used: a slowly crystallizing recycled grade obtained from soft drink bottles and a rapidly crystallizing injection molding grade. The crystallization was studied by differential scanning calometry (DSC) and under injection molding conditions using wedge shaped specimens; the thermal properties were studied by dynamic mechanical analysis. T2T‐dimethyl is effective in increasing the crystallization of PET in both of the extrusion compounds as well as in the reactor materials. It was also found that the crystallization temperature of poly(butylene terephthalate) could be slightly increased by the addition of nucleators.     

Properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends

Blends composed of poly(ethylene terephthalate) (PET) as the majority component and poly(ethylene naphthalate)(PEN) as the minority component were melt-mixed in a single screw extruder at various PET/PEN compound ratios. Tensile and flexural test results reveal a good PET/PEN composition dependence, indicating that the compatibility of the blends is effective in a macrodomain. In thermal tests, single transitions for T_g, T_m and T_c (crystallization temperature), respectively, are observed from DSC as well as single T_g from DMA except for 50/50 blends. These results suggests that the compatibility is sufficient down to the submicron level. Moreover, isothermal DSC tests along with Avrami analysis indicate that PET's crystallization is significantly retarded when blended with PEN. Results in this study demonstrate that PEN is a highly promising additive to improve PET's spinnability at high speeds.     

Liquid phase behavior and its effect on crystalline morphology in the extruded poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blend

Morphology in an extruded poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) was investigated using time-resolved light scattering, optical microscope and small-angle X-ray scattering. During annealing at 280 °C, the domain structure via spinodal decomposition preceded, the transesterification followed, and then the transesterification between the two polyesters induced the dissolution of the liquid-liquid (L-L) phase separation, i.e. the homogenization. The annealed specimen for various time periods (t_s) at 280 °C was subjected to a temperature-drop to 120 °C for the isothermal crystallization and then the effects of liquid phase morphology on crystallization was investigated. With t_s, the H_ν (cross-polarization) light scattering patterns exhibited the dramatic change from a four-leaf clover pattern with maximum intensity at azimuthal angle 45° (×-type scattering pattern) to a diffuse pattern of circular symmetry and then a four-leaf clover pattern with maximum intensity at azimuthal angles 0 and 90° (+-type scattering pattern). This suggests that the crystalline structure depends on the level of the block and/or random copolymer produced by the transesterification during annealing. The H_ν scattering patterns reflected differences in the principle polarizability of the crystalline lamellae with respect to the spherulitic radius. On the other hand, the long period L_B, an average distance between two adjacent crystalline lamellae, increased with t_s at 280 °C. The dependence of L_B on t_s was explained by the change in the crystallization rate G.     

Nonisothermal crystallization of poly(ethylene terephthalate) and its blends in the injection-molding process

We investigated the nonisothermal crystallization during the cooling process of injection molding of poly(ethylene terephthalate) (PET), PET/talc, and PET/Surlyn blends. We applied the isothermal crystallization parameters obtained by the Hoffman–Lauritzen theory to the kinetics of nonisothermal crystallization and then calculated the relative crystallinity χ/χ_c as a function of the mold temperature. χ/χ_c were nicely interpreted by calculation without effect of the pressure history on crystallization in PET and PET/talc (1 wt %) blends. In contrast, in the PET/Surlyn (3 wt %) blend, crystallization occurred at a lower mold temperature than predicted by our calculation. The transmission electron micrograph near the surface of the injection-molded PET/Surlyn blend showed deformation and stretching of dispersed Surlyn particles, suggesting that orientation of the PET matrix proceeds with the flow in processing. The orientation of the PET matrix resulted in acceleration of the crystallization in the injection molding. © 1995 John Wiley & Sons, Inc.     

Nonisothermal crystallization kinetics of poly(butylene terephthalate)/poly(ethylene terephthalate)/glass fiber composites

The influences of the glass fiber (GF) content and the cooling rate for nonisothermal crystallization process of poly(butylene terephthalate)/poly(ethylene terephthalate) (PBT/PET) blends were investigated. The nonisothermal crystallization kinetics of samples were detected by differential scanning calorimetry (DSC) at cooling rates of 5°C/min, 10°C/min, 15°C/min, 20°C/min, 25°C/min, respectively. The Jeziony and Mozhishen methods were used to analyze the DSC data. The crystalline morphology of samples was observed with polarized light microscope. Results showed that the Jeziony and Mozhishen methods were available for the analysis of the nonisothermal crystallization process. The peaks of crystallization temperature (T_p) move to low temperature with the cooling rate increasing, crystallization half‐time (t_1/2) decrease accordingly. The crystallization rate of PBT/PET blends increase with the lower GF contents while it is baffled by higher GF contents. POLYM. COMPOS. 36:510–516, 2015. © 2014 Society of Plastics Engineers