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     

Thermal properties and non‐isothermal crystallization behavior of poly(trimethylene terephthalate)/poly(lactic acid) blends

Thermal properties and non‐isothermal melt‐crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(lactic acid) (PLA) blends were investigated using differential scanning calorimetry and thermogravimetric analysis. The blends exhibit single and composition‐dependent glass transition temperature, cold crystallization temperature (T_cc) and melt crystallization peak temperature (T_mc) over the entire composition range, implying miscibility between the PLA and PTT components. The T_cc values of PTT/PLA blends increase, while the T_mc values decrease with increasing PLA content, suggesting that the cold crystallization and melt crystallization of PTT are retarded by the addition of PLA. The modified Avrami model is satisfactory in describing the non‐isothermal melt crystallization of the blends, whereas the Ozawa method is not applicable to the blends. The estimated Avrami exponent of the PTT/PLA blends ranges from 3.25 to 4.11, implying that the non‐isothermal crystallization follows a spherulitic‐like crystal growth combined with a complicated growth form. The PTT/PLA blends generally exhibit inferior crystallization rate and superior activation energy compared to pure PTT at the same cooling rate. The greater the PLA content in the PTT/PLA blends, the lower the crystallization rate and the higher the activation energy. Moreover, the introduction of PTT into PLA leads to an increase in the thermal stability behavior of the resulting PTT/PLA blends. Copyright © 2011 Society of Chemical Industry     

Miscibility and crystallization kinetics of poly(trimethylene terephthalate)/amorphous poly(ethylene terephthalate) blends

The miscibility and crystallization kinetics of the blends of poly(trimethylene terephthalate) (PTT) and amorphous poly(ethylene terephthalate) (aPET) have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that PTT/aPET blends were miscible in the melt. Thus, the single glass transition temperature (T_g) of the blends within the whole composition range and the retardation of crystallization kinetics of PTT in blends suggested that PTT and aPET were totally miscible. The nucleation density of PTT spherulites, the spherulitic growth, and overall crystallization rates were depressed upon blending with aPET. The depression in nucleation density of PTT spherulites could be attributed to the equilibrium melting point depression, while the depression in the spherulitic growth and overall crystallization rates could be mainly attributed to the reduction of PTT chain mobility and dilution of PTT upon mixing with aPET. The underlying nucleation mechanism and growth geometry of PTT crystals were not affected by blending, from the results of Avrami analysis. POLYM. ENG. SCI., 47:2005–2011, 2007. © 2007 Society of Plastics Engineers     

Polymorphic and miscibility behavior in crystalline/crystalline blends of poly(pentamethylene terephthalate) with poly(heptamethylene terephthalate)

BACKGROUND: The phase behavior of blends of semicrystalline aryl polyesters with long methylene segments (? (CH₂)_n? with n = 5 or 7) in the repeat units has not been much studied. Thus, crystalline/crystalline blends comprising monomorphic poly(pentamethylene terephthalate) (PPT) and polymorphic poly(heptamethylene terephthalate) (PHepT) were prepared and the crystal growth kinetics, polymorphism behavior and miscibility in this blend system were probed using polarized‐light optical microscopy, differential scanning calorimetry and wide‐angle X‐ray diffraction. RESULTS: The PPT/PHepT blends of all compositions were first proven to be miscible in the melt state or quenched amorphous phase, whose interaction strength was determined (χ₁₂ = ? 0.35), showing favorable interactions and phase homogeneity. Although the spherulites of neat PPT and PHepT could exhibit ring bands at different crystallization temperature (T_c) ranges (100–110 and 50–65 °C, respectively), the spherulites of PPT/PHepT (50/50) blend became ringless in the range 50–110 °C. Growth analysis and polymorphic behavior in the crystalline phases of the blends provided extra evidence for the miscibility between these two crystalline polymers. Spherulitic growth rates of PPT in the PPT/PHepT blends were significantly reduced in comparison with those of neat PPT. In addition, miscible blending of a small fraction of monomorphic PPT (20 wt%) with polymorphic PHepT altered the crystal stability and led to the originally polymorphic PHepT exhibiting only the β‐crystal form when melt‐crystallized at all values of T_c. CONCLUSION: The highly intimate mixing in polymer chains of crystalline PPT and PHepT causes significant disruption in ring‐band patterns and reduction in crystallization rates of PPT as well as alteration in the polymorphic behavior of PHepT. Copyright © 2009 Society of Chemical Industry     

Miscibility of poly(ether imide)/poly(ethylene terephthalate) blends

Summary Miscibility of blends of poly(ether imide) (PEI) and poly(ethylene terephthalate) (PET) were studied by differential scanning calorimetry (DSC). Single and composition-dependent T_g's are observed over the entire composition range, indicating that the blends are miscible in the amorphous region. The overall crystallization rate of PET in the blends decreased with increasing the PEI content. The interaction energy density B, which was calculated from the melting point depression of the blends using Nishi-Wang equation, was-5.5 cal/cm³.     

Effects of molecular weight on phase structure of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The phase structure of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends was studied in relation to the molecular weight. The samples were prepared by both solution blends, which showed two glass‐transition temperatures (T_g), and melt blends (MQ), which showed a single T_g, depending on the composition of the blends. The T_g of the MQ series was independent of the molecular weight of the homopolymer, although the degree of transesterification in the blends was affected by the molecular weight. The MQ series showed two exotherms during the heating process of a differential scanning calorimetry scan. The peak temperature and the heat flow of the exotherms were affected by the molecular weight of the homopolymers. The strain‐induced crystallization of the MQ series suggested the independent crystallization of PET and PEN. Based on the results, a microdomain structure of each homopolymer was suggested. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2428–2438, 2005     

Crystallization of poly(butylene terephthalate)/poly(ethylene octene) blends: Isothermal crystallization

Poly(ethylene‐octene) (POE), maleic anhydride grafted poly(ethylene‐octene) (mPOE), and a mixture of POE and mPOE were added to poly(butylene terephthalate) (PBT) to prepare PBT/POE, PBT/mPOE, and PBT/mPOE/POE blends by a twin‐screw extruder. Observation by scanning electron microscopy revealed improved compatibility between PBT and POE in the presence of maleic anhydride groups. The melting behavior and isothermal crystallization kinetics of the blends were studied by wide‐angle X‐ray diffraction and differential scanning calorimeter; the kinetics data was delineated by kinetic models. The addition of POE or mPOE did not affect the melting behavior of PBT in samples quenched in water after blending in an extrude. Subsequent DSC scans of isothermally crystallized PBT and PBT blends exhibited two melting endotherms (T_mI and T_mII). T_mI was the fusion of the crystals grown by normal primary crystallization and T_mII was the melting peak of the most perfect crystals after reorganization. The dispersed second phase hindered the crystallization; on the other hand, the well dispersed phases with smaller size enhanced crystallization because of higher nucleation density. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization kinetics of poly(trimethylene terephthalate)/poly(ether imide) blends

The crystallization kinetics of a melt‐miscible blend, consisting of poly(trimethylene terephthalate) (PTT) and poly(ether imide) (PEI) prepared by solution precipitation, has been investigated by means of optical polarized microscopy and differential scanning calorimeter. It was found that both the PTT spherulitic growth rate (G) and overall crystallization rate constant (k_n) were depressed, with increasing PEI composition or crystallization temperature (T_c). The kinetic retardation was attributed to the decrease in PTT molecular mobility, and the dilution of PTT concentration due to the addition of PEI, which has a higher glass transition temperature (T_g). According to the Lauritzen–Hoffman theory of secondary nucleation, the crystallization of PTT in blends was similar to that of neat PTT as regime III, n = 4 and regime II, n = 2 growth processes, while the transition point of regime III to II has been shifted from 194°C for neat PTT to 190°C for blends. POLYM. ENG. SCI. 46:89–96, 2006. © 2005 Society of Plastics Engineers     

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.     

Polycarbonate/polyalkylene terephthalate blends: Interphase interactions and impact strength

Blends of polycarbonate (PC) and poly(alkylene terephthalate) (PAT) such as poly(butylene terephthalate) (PBT) and poly(ethylene terephthalate) (PET) were investigated. It was learned that processes of phase separation in blends consisting of PC and PAT can cause variations in properties of both the amorphous and crystalline phases. In PC/PBT blends the DSC technique did not detect crystalline portion of PBT with its concentrations up to 20 wt %. For PBT = 40 wt %, it forms a continuous phase, and blend's crystallinity is close to the additive values. The glass transition temperature (T_g) shifts to the lower temperature region. The relaxation spectrometry revealed strong adhesion between phases in the blends over the temperature range from the completion of β‐transition to T_gPAT. This interaction becomes weaker between T_gPAT and T_gPC. Temperature‐dependent variations in the molecular mobility and interphases interactions in the blends affect their impact strength. Over the temperature range where interphases interactions occur and the two components are in the glassy state, the blend is not impact resistant. Over the temperature range between T_gPAT and T_gPC the blends become impact‐resistant materials. This is because energy of crack propagation in the PAT amorphous phase—being in a high‐elastic state—dissipates. It is postulated that the effect of improving the impact strength of PC/PAT blends, which was found for temperatures between the glass transition temperatures of the mixed components, is also valid for other binary blends. © 2002 Wiley Perioodicals, Inc. J Appl Polym Sci 84: 1277–1285, 2002; DOI 10.1002/app.10472     

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.     

Crystallization, hydrolytic degradation, and mechanical properties of poly (trimethylene terephthalate)/poly(lactic acid) blends

Crystallization, melting, hydrolytic degradation, and mechanical properties of poly(trimentylene terephthalate)/poly(lactic acid) (PTT/PLA) blends have been investigated. The blends show a single and composition-dependent glass-transition temperature (T _g) over the entire composition range, implying that these blends are fully miscible in the amorphous state. The observed T _g is found to increase with increasing PLA content and fitted well with the Gordon–Taylor equation, with the fitting parameter k being 0.91. The cold-crystallization peak temperature increases, while the melt-crystallization peak decreases with increasing the PLA content. Both the pure PTT and PTT/PLA blends cannot accomplish the crystallization during the cooling procedure and the recrystallization occurs again on the second heating. Therefore, on the thermogram recorded, there is exothermal peak followed by endothermal peak with a shoulder. However, to pure PLA, no crystallization takes place during cooling from the melt, therefore, no melting endothermic peak is found on the second heating curve. WAXD analysis indicates PLA and PTT components do not co-crystallize and the crystalline phase of the blends is that of their enriched pure component. With increasing PLA content, the hydrolytic degradation of the blend films increases, while both the tensile strength and the elongation at break of the blend films decrease. That is to say, the hydrolytic degradation of the PTT/PLA blends increases with the introduction of PLA at the cost of the decrease of the flexibility of PTT.     

Glass transition and cold crystallization in carbon dioxide treated poly(ethylene terephthalate)

An amorphous poly(ethylene terephthalate) (aPET) and a semicrystalline poly(ethylene terephthalate) obtained through the annealing of aPET at 110°C for 40 min (aPET‐110‐40) were treated in carbon dioxide (CO₂) at 1500 psi and 35°C for 1 h followed by treatment in a vacuum for various times to make samples containing various amount of CO₂ residues in these two CO₂‐treated samples. Glass transition and cold crystallization as a function of the amount of CO₂ residues in these two CO₂‐treated samples were investigated by temperature‐modulated differential scanning calorimetry (TMDSC) and dynamic mechanical analysis (DMA). The CO₂ residues were found to not only depress the glass‐transition temperature (T_g) but also facilitate cold crystallization in both samples. The depressed T_g in both CO₂‐treated poly(ethylene terephthalate) samples was roughly inversely proportional to amount of CO₂ residues and was independent of the crystallinity of the poly(ethylene terephthalate) sample. The nonreversing curves of TMDSC data clearly indicated that both samples exhibited a big overshoot peak around the glass transition. This overshoot peak occurred at lower temperatures and was smaller in magnitude for samples containing more CO₂ residues. The TMDSC nonreversing curves also indicated that aPET exhibited a clear cold‐crystallization exotherm at 120.0°C, but aPET‐110‐40 exhibited two cold‐crystallization exotherms at 109.2 and 127.4°C. The two cold crystallizations in the CO₂‐treated aPET‐110‐40 became one after vacuum treatment. The DMA data exhibited multiple tan δ peaks in both CO₂‐treated poly(ethylene terephthalate) samples. These multiple tan δ peaks, attributed to multiple amorphous phases, tended to shift to higher temperatures for longer vacuum times. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. I. Effect of orientation

The present study examined poly(ethylene terephthalate) (PET) and a series of statistical and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate by copolymerization and melt blending, respectively. Some level of transesterification during processing of melt blends resulted in blocky copolymers, as confirmed by NMR. Random and blocky copolymers exhibited similar properties in the glassy state, including a single glass transition, due to miscibility of the blocks. However, random copolymerization effectively retarded cold‐crystallization from the glass whereas blocky copolymers readily cold‐crystallized to a crystallinity level close to that of PET. The polymers were oriented at four temperatures in the vicinity of the T_g and characterized by oxygen transport, wide‐angle X‐ray diffraction, positron annihilation lifetime spectroscopy, and infrared spectroscopy. Orientation of all the copolymers resulted in property changes consistent with strain‐induced crystallization. However, blocky copolymers oriented more easily than random copolymers of the same composition and after orientation exhibited slightly lower oxygen permeability, higher density, and higher fraction trans conformers. Analysis of oxygen solubility based on free volume concepts led to a two‐phase model from which the amount of crystallinity and the amorphous phase density were extracted. Dedensification of the amorphous phase correlated with the draw temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1615–1628, 2005     

Crystallization of poly(butylene terephthalate)/poly(ethylene octene) blends: Nonisothermal crystallization

Poly(ethylene octene) (POE), maleic anhydride grafted poly(ethylene octene) (mPOE), and a mixture of POE and mPOE were added to poly(butylene terephthalate) (PBT) to prepare PBT/POE (20 wt % POE), PBT/mPOE (20 wt % mPOE), and PBT/mPOE/POE (10 wt % mPOE and 10 wt % POE) blends with an extruder. The melting behavior of neat PBT and its blends nonisothermally crystallized from the melt was investigated with differential scanning calorimetry (DSC). Subsequent DSC scans exhibited two melting endotherms (T_mI and T_mII). T_mI was attributed to the melting of the crystals grown by normal primary crystallization, and T_mII was due to the melting of the more perfect crystals after reorganization during the DSC heating scan. The better dispersed second phases and higher cooling rate made the crystals that grew in normal primary crystallization less perfect and relatively prone to be organized during the DSC scan. The effects of POE and mPOE on the nonisothermal crystallization process were delineated by kinetic models. The dispersed phase hindered the crystallization; however, the well‐ dispersed phases of an even smaller size enhanced crystallization because of the higher nucleation density. The nucleation parameter, estimated from the modified Lauritzen–Hoffman equation, showed the same results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of poly(ethylene glycol) on the solid‐state polymerization of poly(ethylene terephthalate)

Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol^?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in T_g and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb₂O₃ as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry     

Thermal studies of blends of poly(phenylene sulfide) (PPS) with poly(phenylene sulfide sulfone) (PPSS) and with poly(phenylene sulfide ether) (PPSE)

The miscibilities of poly(phenylene) sulfide/poly(phenylene sulfide sulfone) (PPS/PPSS) and poly(phenylene) sulfide/poly(phenylene sulfide ether) (PPS/PPSE) blends were invesigated in terms of shifts of glass transition temperatures T_g of pure PPS, PPSS, a dn PPSE. The crystallization kinetics of PPS/PPSS blends was also studied as a function of molar composition. The PPS/PPSS and PPS/PPSE blends are respectively partially and fully miscible. PPSE shows a plasticizing effect on PPS as does PPS on PPSS, which necessarily improves te processibility in the respective systems. We can control T_g and melting temperature T_m of PPS by varying amounts of PPSE in blends. The melt crystallization temperature T_mc of PPS/PPSE blends was higher than that of the PPSE homopolymer. Therefore, these blends require shorter cycle times in processing than pure PPSE. The overall rate of crystallization for PPS/PPSS blends follows the Avrami equation with an exponent ?2. The maximal rate of crystallization for PPS/PPSS blends occurs at a temperatre higher by 10°C than that for PPS, while the crystallization half time t_1/2 is 4 times shorter. In the cold crystallization range, crystal growth rates increase and Avrami exponents decrease significantly as the temperature increases.     

Crystallization behavior and morphology of double crystalline poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers

Double crystalline poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers (PTT/PEOT), with PTT content ranging from 16.5 to 65.5 wt%, were synthesized by melt copolycondensation. The morphological transformation of samples from microphase separation to macrophase separation was investigated by gel permeation chromatography and transmission electron microscopy. Differential scanning calorimetry and in situ wide‐angle X‐ray diffraction suggested that all copolycondensation samples displayed double crystalline behavior. The melt‐crystallization peak temperatures (T_{m, c} values) of PTT chains monotonously increased with increasing PTT content and were higher than that of homo‐PTT when the content of PTT was above 30.6 wt%. Interestingly, T_{m, c} values of PEOT chains were also increased with increasing PTT content. Polarized optical microscopy revealed that all copolycondensation samples studied could form ring‐banded spherulites and band spacing increased with increasing T_c values. In addition, band spacing decreased with increasing PTT content at a given T_c. Strangely, although PEOT was the main component in all copolycondensation samples, spherulitic morphology formed by the advance crystallization of PTT did not change after PEOT crystallization. Only a subtle change of quadrant tones was detected. © 2012 Society of Chemical Industry     

Effect of CO2 on crystallization kinetics of poly(ethylene terephthalate)

The effect of CO₂ on the isothermal crystallization kinetics of poly(ethylene terephthalate), PET, was investigated using a high‐pressure differential scanning calorimeter (DSC), which performed calorimetric measurements while keeping the polymer in contact with presurized CO₂. It was found that the crystallization rate followed the Avrami equation with values of the crystallization kinetic constant dependent on the crystallization temperature and concentration of CO₂ in PET. The presence of CO₂ in the PET increased its overall crystallization rate. CO₂ also decreased the glass transition temperature, T_g, and the melting temperature, T_m. As a result, the observed changes in crystallization rate caused by CO₂ can be qualitatively predicted from the magnitude of T_g depression and that of the equilibrium melting temperature, T_m⁰.