Thermal oxidative degradation kinetics and thermal properties of poly(ethylene terephthalate) modified with poly(lactic acid)

The thermal oxidative degradation kinetics of poly(ethylene terephthalate) (PET) copolymers modified with poly(lactic acid) (PLA) were investigated with thermogravimetric analyzer (TGA). The thermal properties of the modified products were also determined by differential scanning calorimeter (DSC) technique. Waste PET (P100) obtained from postconsumer water bottles was modified with a low‐molecular‐weight PLA. The PET/PLA weight ratio was 90/10 (P90) and 50/50 (P50) in the modified samples. The thermal oxidative degradation kinetics of the modified samples was compared with those of PET (P100). The segmented block and/or random copolymer structure of the modified samples formed by a transesterification reaction between the PLA and PET units in solution and the length of the aliphatic and aromatic blocks were found to have a great effect on the degradation behavior. On the basis of the results of the degradation kinetics determined by Kissinger method, the degradation rate of the samples decreased in the order of P50 > P90 > P100, depending on the amount of PLA in the copolymer structure. However, the degradation activation energies (E_A) of the samples decreased in the order of P100 > P90 > P50. It was concluded that the degradation rate and mechanism were affected significantly by the incorporation of PLA into the copolymer structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nonisothermal crystallization of reprocessed poly(ethylene terephthalate)

Poly(ethylene terephthalate) was submitted to five reprocessing cycles by extrusion. The materials were analyzed with oligomer and after oligomer extraction. The nonisothermal crystallization of the five samples was investigated by differential scanning calorimetry. Samples with oligomer content and carboxylic end group concentrations between 44 and 98 eqw × 10⁶ g presented a nonlinear correlation with the crystallization temperature. After the oligomer extraction of the polymer, this correlation is linear. The nonisothermal crystallization results were analyzed using the Ozawa model. The polymers containing oligomers obey the Ozawa model for the first reprocessing cycle. After oligomer extraction, the polymers obey the Ozawa model from the first to the third reprocessing cycle. In both cases, the exponential n values are close to 2.0. For the other cycles, deviations from this model occur. The activation energy was calculated using the Kissinger and Varma models. The values obtained for the five reprocessed samples were inversely proportional to the molar mass when analyzed by both models. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 525–531, 2004     

Nonisothermal crystallization kinetics of nucleated poly(ethylene terephthalate)

Studies of the nonisothermal crystallization kinetics of poly(ethylene terephthalate) nucleated with anhydrous sodium acetate were carried out. The chemical nucleating effect was investigated and confirmed with Fourier transform infrared and intrinsic viscosity measurements. The Avrami, Ozawa, and Liu models were used to describe the crystallization process. The rates of crystallization, which initially increased, decreased at higher loadings of the additive. The activation energy, calculated with Kissinger's method, was lower for nucleated samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization kinetics and morphology of poly(ethylene suberate)

The crystallization kinetics and morphology of poly(ethylene suberate) (PESub) were studied in detail with differential scanning calorimetry, polarized optical microscopy, and wide‐angle X‐ray diffraction. The Avrami equation could describe the overall isothermal melt crystallization kinetics of PESub at different crystallization temperatures; moreover, the overall crystallization rate of PESub decreased with increasing crystallization temperature. The equilibrium melting point of PESub was determined to be 70.8°C. Ring‐banded spherulites and a crystallization regime II to III transition were found for PESub. The Tobin equation could describe the nonisothermal melt crystallization kinetics of PESub at different cooling rates, while the Ozawa equation failed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43086.     

Isothermal crystallization kinetics of poly(lactic acid)/synthetic mica nanocomposites

The isothermal crystallization kinetics of PLA/fluoromica nanocomposites was studied. Three types of synthetic mica at three concentrations (2.5, 5.0, and 7.5 wt % mica) were used and the effect of these micas on the crystallization and thermal properties of PLA was investigated by differential scanning calorimetry (DSC). The Avrami and Hoffman‐Weeks equations were used to describe the isothermal crystallization kinetics and melting behavior. Addition of these micas to the PLA matrix increased the crystallization rate, and this effect depended on the mica type and concentration. While the nonmodified Somasif ME‐100 exerted the smallest effect, the effect observed for the organically modified Somasif MPE was the most pronounced. The lower half‐time of crystallization t_1/2 was around 3 min for the PLA/Somasif MPE nanocomposites containing 7.5 wt % of filler at 90°C, which is about 16 min below that found for neat PLA. The equilibrium melting temperature ( ) of PLA were estimated for these systems, showing an increase in the composites and an increase with increasing loading, except for PLA/Somasif MPE, in which the increase of the mica content decreased about 5°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40322.     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) and poly(methyl methacrylate) blends

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA) blends were studied. Four compositions of the blends [PET 25/PMMA 75, PET 50/PMMA 50, PET 75/PMMA 25, and PET 90/PMMA 10 (w/w)] were melt‐blended for 1 h in a batch reactor at 275°C. Crystallization peaks of virgin PET and the four blends were obtained at cooling rates of 1°C, 2.5°C, 5°C, 10°C, 20°C, and 30°C/min, using a differential scanning calorimeter (DSC). A modified Avrami equation was used to analyze the nonisothermal data obtained. The Avrami parameters n, which denotes the nature of the crystal growth, and Z_t, which represents the rate of crystallization, were evaluated for the four blends. The crystallization half‐life (t_½) and maximum crystallization (t_max) times also were evaluated. The four blends and virgin polymers were characterized using a thermogravimetric analyzer (TGA), a wide‐angle X‐ray diffraction unit (WAXD), and a scanning electron microscope (SEM). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3565–3571, 2006     

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     

Crystallization kinetics and crystalline morphology of poly(ethylene naphthalate) and poly(ethylene terephthalate‐co‐bibenzoate)

Copolymers of ethylene glycol with 4,4′‐bibenzoic acid and terephthalic acid are known to crystallize rapidly to surprisingly high levels of crystallinity. To understand this unusual behavior, the isothermal crystallization of poly(ethylene bibenzoate‐co‐terephthalate) in the molar ratio 55:45 (PETBB55) was studied. Poly(ethylene naphthalate) (PEN) was included in the study for comparison. The kinetics of isothermal crystallization from the melt and from the amorphous glass was determined using differential thermal analysis. The results were correlated with the crystalline morphology as observed with atomic force microscopy (AFM). Crystallization of PEN exhibited similar kinetics and spherulitic morphology regardless of whether it was cooled from the melt or heated from the glass to the crystallization temperature. The Avrami coefficient was close to 3 for heterogeneous nucleation with 3‐dimensional crystal growth. The copolymer PETBB55 crystallized much faster than did PEN and demonstrated different crystallization habits from the melt and from the glass. From the melt, PETBB55 crystallized in the “normal” way with spherulitic growth and an Avrami coefficient of 3. However, crystallization from the glass produced a granular crystalline morphology with an Avrami coefficient of 2. A quasi‐ordered melt state, close to liquid crystalline but lacking the order of a recognizable mesophase, was proposed to explain the unusual crystallization characteristics of PETBB55. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 98–115, 2002     

Nonisothermal crystallization kinetics of poly(butylene terephthalate)/multiwalled carbon nanotubes nanocomposites prepared by in situ polymerization

Poly(butylene terephthalate)/multiwalled carbon nanotubes (PBT/MWNT) nanocomposites were prepared by in situ ring‐opening polymerization of cyclic butylene terephthalate oligomers (CBT). The nonisothermal crystallization behavior of the neat PBT and the PBT/MWNT nanocomposites was analyzed quantitatively. The results reveal that the combined Avrami/Ozawa equation exhibits great advantages in describing the nonisothermal crystallization of PBT and its nanocomposites. The presence of MWNTs has the nucleation effect promoting crystallization rate for the nanocomposites, and the maximum one is observed in the nanocomposite having 0.75 wt % MWNT content. On the other hand, the addition of MWNTs has the impeding effect reducing the chain mobility and retarding crystallization, which is confirmed by the crystallization activation energies. However, the nucleation effect of MWNTs plays the dominant role in the crystallization of PBT/MWNT nanocomposites, in other words, the incorporation of MWNTs is increasing the crystallization rate of the nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40849.     

Isothermal crystallization kinetics of anhydrous sodium acetate nucleated poly(ethylene terephthalate)

Studies on the isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nucleated with anhydrous sodium acetate were carried out. The nucleated agent had succeeded in promoting greater rates of crystallization in PET. A study of the melting behavior of the samples revealed that the nucleating agents promoted formation of thinner lamellae. The equilibrium melting temperature (T) of samples was determined using linear and nonlinear Hoffman Weeks procedure. The nonlinear Hoffman Week's procedure was found to be inapplicable in the current study. The Lauritzen‐Hoffman secondary nucleation theory was applied to determine the nucleation parameter (K_g), fold surface energy (σ_e), and work of chain folding (q). σ_e and q decreased on addition of nucleating agent. The approximate and exact form of the Lauritzen Z‐test was used to determine the operating regime. The operating regime was found to be primarily regime II for the range of temperatures studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Banded spherulites in poly(L‐lactic acid): Effects of the crystallization temperature and molecular weight

The spherulitic morphology of pure poly(L ‐lactide) (PLLA) was investigated with polarized optical microscopy as a function of the crystallization temperature and molecular weight. After being melted at 210°C for 3 min, samples were cooled quickly to designated temperatures for isothermal crystallization. It was shown for the first time that a clear banding‐to‐nonbanding morphological transition took place at a critical temperature for PLLA with a number‐average molecular weight of 86,000. With the increasing molecular weight of the material, the spherulite growth rates decreased notably, and the band spacing decreased significantly. On the basis of the main‐chain chirality in PLLA and the observation of a nonbanded spherulitic morphology in a certain temperature region, it was suggested that the crystallization temperature might have an effect on the relationship between the sense of lamellar twisting and the main‐chain chiral structure in PLLA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Nonisothermal crystallization kinetics of biodegradable poly(butylene succinate)/poly(vinyl phenol) blend

Nonisothermal melt crystallization kinetics of biodegradable PBSU/PVPh blend was investigated with differential scanning calorimetry (DSC) from the viewpoint of practical application. PBSU/PVPh blends were cooled from the melt at various cooling rates ranging from 2.5 to 40°C/min. The crystallization peak temperature decreased with increasing the cooling rate for both neat and blended PBSU. Furthermore, the crystallization peak temperature of PBSU in the blend was lower than that of neat PBSU at a given cooling rate. Two methods, namely the Avrami equation and the Tobin method, were used to describe the nonisothermal crystallization of PBSU/PVPh blend. It was found that the Avrami equation was more suitable to predict the nonisothermal crystallization of PBSU/PVPh blend than the Tobin method. The effects of cooling rate and blend composition on the crystallization behavior of PBSU were studied in detail. It was found that the crystallization rate decreased with decreasing the cooling rate for both neat and blended PBSU. However, the crystallization of PBSU blended with PVPh was retarded compared with that of neat PBSU at the same cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 972–978, 2007     

Stereocomplexation and morphology of enantiomeric poly(lactic acid)s with moderate‐molecular‐weight

The thermal behavior and spherulitic morphologies of poly(L ‐lactic acid) (PLLA)/poly(D ‐lactic acid) (PDLA) 1/1 blend with weight‐molecular‐weight of 10⁵ order, together with those of pure PLLA and PDLA, were investigated using differential scanning calorimetry and polarized optical microscopy. It was found that in the blend, stereocomplex crystallites could be formed exclusively or coexisted with homocrystallites depending on thermal history. Banded to nonbanded spherulitic morphological transition occurred for melt‐crystallized PLLA and PDLA, while the blend presented exclusively nonbanded spherulitic morphologies in the temperature range investigated. The spherulite growth of the blend occurred within a wider temperature range (≤180°C) compared with that of homopolymers (≤150°C), while the spherulite growth rates were comparable for both the blend and homopolymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Isothermal crystallization kinetics and melting behaviors of nanocomposites of poly(trimethylene terephthalate) filled with nano‐CaCO3

The isothermal crystallization and subsequent melting behavior of poly(trimethylene terephthalate) (PTT) composites filled with nano‐CaCO₃ were investigated at designated temperatures with differential scanning calorimetry. The Avrami equation was used to fit the isothermal crystallization. The Avrami exponents were determined to be 2–3 for the neat PTT and PTT/CaCO₃ composites. The particles of nano‐CaCO₃, acting as nucleating agents in the composites, accelerated the crystallization rate, with the half‐time of crystallization decreasing or the growth rate constant (involving both nucleation and growth rate parameters) increasing. The crystallization activation energy calculated from the Arrhenius formula was reduced as the nano‐CaCO₃ content increased from 0 to 2%, and this suggested that nano‐CaCO₃ made the molecular chains of PTT easier to crystallize during the isothermal crystallization process. Subsequent melting scans of the isothermally crystallized composites exhibited triple or double melting endotherms: the greater the content was of nano‐CaCO₃, the lower the temperature was of the melting peak. The degree of crystallization deduced from the melt enthalpy of composites with the proper concentration of nano‐CaCO₃ was higher than that of pure PTT, but it was lower when the nano‐CaCO₃ concentration was more than 2%. The transmission electron microscopy pictures suggested that the dispersion state of nano‐CaCO₃ particles in the polymer matrix was even when its concentration was no more than 2%, whereas some agglomeration occurred when its concentration was 4%. Polarized microscopy pictures showed that much smaller or less perfect crystals formed in the composites because of the interaction between the molecular chains and nano‐CaCO₃ particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

聚乙二醇增塑聚乳酸的非等温结晶动力学研究

采用DSC方法对聚乙二醇(PEG)增塑聚乳酸的非等温结晶动力学进行了研究。结果表明,PEG的加入明显提高了聚乳酸的结晶速度。对所得数据分别用Ozawa方程和莫志深方法进行了处理,发现在给定温度范围里非等温结晶时,PLA/PEG主要是以均相成核的三维生长方式结晶;PLA的结晶速度随着PEG分子质量的增加而升高。     

Ultrasonic characterization of the crystallization behavior of poly(ethylene terephthalate)

On the basis of the previous observations that the ultrasonic signals are sensitive to the crystallization of polymers (Tatibouet and Piché, Polymer 1991, 32, 3147), we have expanded our efforts to study the detail relationship between the ultrasonic signals and crystallization process in this work. The nonisothermal and isothermal crystallization of virgin poly(ethylene terephthalate) (PET) and PET samples after degradation were studied by using a specially designed pressure‐volume‐temperature (PVT) device, with which an ultrasonic detector was combined. The results showed that the evolution of the ultrasonic signals not only can be used to probe the crystallization process but also can qualitatively characterize the crystallization rate, crystallinity, crystallite size, and amorphous. DSC measurement was used to verify such results. Ultrasonic signals could be as a complementary tool to polymer chain movement and well be applied to characterize the crystallization behavior. Furthermore, the ultrasonic measurement has the potential use to characterize crystallization of products in‐line during processing (i.e., injection molding, micromoulding). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of plasticizer on the crystallization behavior of poly(lactic acid)

In this article, the spherulitic morphology and growth rate of the neat and plasticized poly(lactic acid) (PLA) with triphenyl phosphate (TPP) were compared and analyzed by polarizing optical microscopy with hot stage at a temperature range of 100?142°C. The spherulitic morphology of the neat PLA underwent a series of changes such as the typical Maltese Cross at less than 132°C, the disappearance of the Maltese Cross at 133°C, the irregular and distorted spherulites at higher than 134 and 142°C, respectively. For plasticized PLA, the spherulitic morphology exhibited the same changes as neat PLA, but these changes were shifted to lower temperature when compared with neat PLA. In the case of the spherulitic growth, neat PLA had the maximum value of 0.28 μm/s at 132°C, and plasticized PLA had higher values than that of neat PLA. Further analysis based on the Lauritzen–Hoffman theory was presented and results showed that the values of nucleation parameter K_g increased with TPP content. The crystallization behavior of PLA was analyzed by differential scanning calorimetry and wide‐angle X‐ray diffraction. The results showed that the degree of crystallinity of plasticized PLA markedly increased when compared with neat PLA sharply with the incorporation of plasticizer. The crystallization kinetics for the neat and plasticized PLA under isothermal crystallization at 114°C was described by the Avrami equation and the Avrami exponent is close to 2, implying that the crystallization mechanism did not change. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Biodegradable poly(ethylene succinate) blends and copolymers containing minor amounts of poly(butylene succinate)

Poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), and PES‐rich copolyesters were synthesized using an effective catalyst, titanium tetraisopropoxide. PES was blended with minor amounts of PBS for the comparison. The compositions of the copolyesters and the blends were determined from NMR spectra. Their thermal properties were studied using a differential scanning calorimeter (DSC), a temperature modulated DSC (TMDSC), and a thermogravimetric analyzer. No significant difference exists among the thermal stabilities of these polyesters and blends. For the blends, the reversible curves of TMDSC showed a distinct glass‐rubber transition temperature (T_g), however, the variation of the T_g values with the blend compositions was small. Isothermal crystallization kinetics and the melting behavior after crystallization were examined using DSC. Wide‐angle X‐ray diffractograms (WAXD) were obtained for the isothermally crystallized specimens. The results of DSC and WAXD indicate that the blends have a higher degree of crystallinity and a higher melting temperature than those of the corresponding copolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010