Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001     

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     

Solid‐state polymerization and bulk crystallization behavior of poly(ethylene terephthalate) (PET)

The main variables involved in solid‐state polymerization of PET homopolymers, originally with molecular weight within the commercial range, were sequentially studied to determine their influence in polymerized products. These variables were precursor crystallinity, catalyst, and time and reaction temperature. An increasing molecular weight sequence was then used to study the bulk crystallization behavior with Avrami analyses. It was determined that thermal conditions at dissolution affect the prereaction morphology. This was important in the polymerization process because it was found that high crystallinity levels in precursors result in higher molecular weights. In agreement with other reports, typical catalysts used in melt polymerizations enhance postpolycondensation processes in the solid state. High reaction times and temperatures were also required to obtain high molecular weights. As the molecular weight increased, there was a decrease in nucleation density and Avrami analyses, applied to the isothermal bulk crystallization, indicating that the nucleation process changed from instantaneous to spontaneous with the increase in molecular weight. The consequences and relative importance of the observed results is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 78–86, 2000     

Nonisothermal crystallization kinetics and morphology of poly(ethylene terephthalate) modified with poly(lactic acid)

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) copolymers modified with poly(lactic acid) (PLA) were investigated with differential scanning calorimetry, and a crystal morphology of the samples was observed with scanning electron microscopy. 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) or 50/50 (P50) in the modified samples. The nonisothermal melt‐crystallization kinetics of the modified samples were compared with those of P100. The segmented block copolymer structure (PET‐b‐PLA‐b‐PET) 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 nucleation mechanism and overall crystallization rate. On the basis of the results of the crystallization kinetics determined by several models (Ozawa, Avrami, Jeziorny, and Liu–Mo) and morphological observations, the crystallization rate of the samples decreased in the order of P50 > P90 > P100, depending on the amount of PLA in the copolymer structure. However, the apparent crystallization activation energies of the samples decreased in the order of P90 > P100 > P50. It was concluded that the nucleation rate and mechanism were affected significantly by the incorporation of PLA into the copolymer structure and that these also had an effect on the overall crystallization energy barrier. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of styrene-co-acrylonitrile on cold crystallization and mechanical properties of poly(ethylene terephthalate)

Blends of poly(ethylene terephthalate) (PET) with small amounts of styrene-co-acrylonitrile (SAN) were prepared by melt blending, and cold crystallization of these mixtures was investigated by means of differential scanning calorimetry. The results suggest that SAN interacts with the amorphous phase of PET, as observed by variations in the glass transition temperature and in the morphology of the blends, analyzed by scanning electron microscopy. The addition of 1% SAN promoted a significant reduction in the crystallization rate of PET, in a manner similar to that of an antinucleating agent. However, the crystallinity of the PET/SAN blends was comparable with that of neat PET; hence, mechanical properties were only slightly affected. Kinetic parameters were determined using Avrami theory; Avrami plots presented a nonlinear behavior at the end of crystallization, indicating that cold crystallization proceeds in two stages. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Preparation,crystallization, and spinnability of poly(ethylene terephthalate)/silica nanocomposites

Poly(ethylene terephthalate) (PET)/silica nanocomposites were successfully prepared by in situ polymerization. Silica nanoparticles were uniformly dispersed in the process of polymerization. By means of hot‐stage polarization microscope and DSC, the influence of nanosilica on the crystallization of PET/silica nanocomposites has been clarified. The results show that nanosilica does not behave as a nucleating agent in PET but postpones the appearance of crystallite. This phenomenon is very favor to improve spinnability. The investigation on melt spinning of PET/silica nanocomposites also shows that it is advantageous to spinning with descending the spinning temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2564–2568, 2007     

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     

The complicated influence of branching on crystallization behavior of poly(ethylene terephthalate)

The randomly branched poly(ethylene terephthalate) (BPET) was prepared by bulk polycondensation from dimethyl terephthalate (DMT) and ethylene glycol (EG), with 0.4–5.0 mol % (with respect to DMT) of glycerol (GL) as a branching agent. The glass transition and crystallization behavior was studied by differential scanning calorimetry (DSC). It was found that the glass transition temperature of BPET reduced with the increasing content of GL until 1.2 mol %, and then increases a little at high degrees of branching. When compared with a linear PET, the crystallization temperature of BPET from the melt shifted to higher temperature as GL content was smaller than 1.2 mol %, and then became lower while GL load was added. Nonisothermal crystallization kinetics was studied through the modified Avrami analysis. It was revealed that the overall crystallization rate parameter of BPET became larger when the GL content was less than 1.2 mol %, then turned to lower at higher branching degree. This indicated that low degree of branching could enhance the overall crystallization of poly(ethylene terephthalate) (PET), whereas high degree of branching in the range of 3.5–5.0 mol % would block the development of crystallization. On the basis of Hoffman's secondary crystallization theory, the product σσ_e of the free energy of formation per unit area of the lateral and folding surface was calculated. According to the change of the product σσ_e with the degree of branching, a possible explanation was presented to illuminate this diverse effect of different degrees of branching on crystallization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)等温结晶行为研究

以对苯二甲酸(PTA)、乙二醇(EG)、异山梨醇(ISB)为原料,通过直接熔融缩聚法合成聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)(PEIT)共聚酯。利用差示扫描量热法(DSC)研究了共聚酯的结晶行为,采用Avrami方程分析了共聚酯的等温结晶动力学。结果表明,PEIT共聚酯结晶行为受共聚组成和结晶温度影响。随着ISB用量的增加或结晶温度的降低,共聚酯半结晶周期t1/2增加、结晶速率变慢;ISB摩尔分数超过20%,共聚酯无法结晶。     

Thermal and crystallization characteristics of poly(ethylene terephthalate) with poly(oxybenzoate‐p‐trimethylene terephthalate) copolymer

Poly(ethylene terephthalate) (PET) was blended with two different poly(oxybenzoate‐p‐trimethylene terephthalate) copolymers, designated T28 and T64, with the level of copolymer varying from 1 to 15 wt %. All samples were prepared by solution blending in a 60/40 (by weight) phenol/tetrachloroethane solvent at 50°C. The crystallization behavior of the samples was studied by DSC. The results indicate that both T28 and T64 accelerated the crystallization rate of PET in a manner similar to that of a nucleating agent. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with a maximum level at 5 wt % of T64. The melting temperatures for the blends are comparable to that of pure PET. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1599–1606, 2002     

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     

DSC analysis of crystallization and melting behavior of polypropylene in model composites with glass and poly(ethylene terephthalate) fibers

Isothermal and nonisothermal crystallization of maleic anhydride grafted polypropylene (PP), which is used for the production of split warp knit composite preforms,¹ are analyzed in model composites to determine the influence of reinforcement glass fibers (GF) and poly(ethylene terephthalate) (PET) binding yarns on the crystallization kinetics. Basic energetic parameters of crystallization are determined, and the melting behavior of PP in model composites is analyzed. The crystallization of PP carried out in nonisothermal and isothermal regimes is facilitated in the presence of GF, and the additional effects of PET fibers are also shown. Better conditions for nucleation, resulting in lower energy for formation of a stable nucleus and lower critical dimensions, are proposed as a reason for this. The crystal structure of PP in model composites exhibits lower lamellae thickness and is less disposed to recrystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 239–246, 1999     

Finite strain behavior of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate)-glycol (PETG)

Uniaxial and plane strain compression experiments are conducted on amorphous poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate)-glycol (PETG) over a wide range of temperatures (25-110 °C) and strain rates (.005-1.0 s⁻¹). The stress-strain behavior of each material is presented and the results for the two materials are found to be remarkably similar over the investigated range of rates, temperatures, and strain levels. Below the glass transition temperature (θ_g=80 °C), the materials exhibit a distinct yield stress, followed by strain softening then moderate strain hardening at moderate strain levels and dramatic strain hardening at large strains. Above the glass transition temperature, the stress-strain curves exhibit the classic trends of a rubbery material during loading, albeit with a strong temperature and time dependence. Instead of a distinct yield stress, the curve transitions gradually, or rolls over, to flow. As in the sub-θ_g range, this is followed by moderate strain hardening and stiffening, and subsequent dramatic hardening. The exhibition of dramatic hardening in PETG, a copolymer of PET which does not undergo strain-induced crystallization, indicates that crystallization may not be the source of the dramatic hardening and stiffening in PET and, instead molecular orientation is the primary hardening and stiffening mechanism in both PET and PETG. Indeed, it is only in cases of deformation which result in highly uniaxial network orientation that the stress-strain behavior of PET differs significantly from that of PETG, suggesting the influence of a meso-ordered structure or crystallization in these instances. During unloading, PETG exhibits extensive elastic recovery, whereas PET exhibits relatively little recovery, suggesting that crystallization occurs (or continues to develop) after active loading ceases and unloading has commenced, locking in much of the deformation in PET.     

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

The morphology development and crystallization behavior of an extruded poly(ethylene terephthalate)/polycarbonate blend were studied with optical microscopy, light scattering, and differential scanning calorimetry (DSC). During annealing at 280°C, liquid–liquid phase separation via spinodal decomposition proceeded in a melt‐extruded specimen. After the formation of the domain structure, the blend slowly underwent phase homogenization by transesterification between the two polymers. The specimen, annealed for various times (t_s's) at 280°C, was subjected to a temperature drop to 180°C for the isothermal crystallization, and then the effects of liquid‐phase changes on crystallization were investigated. The crystal growth rate decreased with t_s. The slow crystallization with a large t_s value was associated with the composition change of the separated phases and the change of the sequence distribution in the polymer chains during annealing. The influence of t_s on the endothermic behavior of the samples was examined. As t_s increased, the recrystallization rate was retarded during the DSC scan, displaying multiendothermic behavior. The DSC data also suggested that the increased level of transesterification would give rise to a higher number of species being rejected from the primary crystals, leading to enhanced secondary crystallization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Crystallization behavior of poly(ethylene terephthalate)/multiwalled carbon nanotubes composites

Crystallization behavior of poly(ethylene terephthalate)/multiwalled carbon nanotubes (PET/MWNTs) composites have been investigated under isothermal conditions and in comparison with the conventional nucleating agents, sodium benzoate, and micrometric carbon/glass fibers. In the PET/MWNTs composites, MWNTs promote the crystallization of PET as a heterogeneous nucleating agent, and the nucleation efficiency is greatly enhanced when MWNTs was homogeneously dispersed in PET matrix. In comparison with pure PET, spherulites size of PET/MWNTs composites is significantly reduced, and the shape becomes quite irregular. TEM images indicate that MWNTs bundles locate in the center of spherulites of PET and act as nuclei. Fold surface free energy during nucleation process for MWNTs nucleated PET is just half of pure PET, suggesting that MWNTs are efficient nucleating agents for PET. The sequence of nucleating ability of is given as follows: sodium benzoate>MWNTs>talc>carbon fibers≈glass fibers. The nucleation in the presence of sodium benzoate is a chemical nucleation process that may cause severe degradation of PET, but MWNTs nucleate PET through “particle effect,” which does not affect the molecular weight of PET. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

PET/PTT共混聚酯的等温结晶行为

使用差示扫描量热仪(DSC)研究不同比例的PET/P1T共混聚酯在205℃的等温结晶行为,并使用Avrami方程对其等温结晶过程进行研究.结晶半周期t1/2,总结晶速率常数k和Avrami指数n的变化表明:在共混体系中,对于PET和PTT而言,另一组分的加入都会对结晶产生阻碍作用,PET与P1T相互影响成核与晶体生长机理.     

Crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were investigated by DSC as functions of crystallization temperature, blend composition, and PET and PEN source. Isothermal crystallization kinetics were evaluated in terms of the Avrami equation. The Avrami exponent (n) is different for PET, PEN, and the blends, indicating different crystallization mechanisms occurring in blends than those in pure PET and PEN. Activation energies of crystallization were calculated from the rate constants, using an Arrhenius‐type expression. Regime theory was used to elucidate the crystallization course of PET/PEN blends as well as that of unblended PET and PEN. The transition from regime II to regime III was clearly observed for each blend sample as the crystallization temperature was decreased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 23–37, 2001     

Crystalline and thermal behavior of poly(ethylene terephthalate)/polyphenoxy blends

Poly(ethylene terephthalate) (PET)/polyphenoxy blends were prepared by melt blending. Crystalline and thermal behaviors of PET/polyphenoxy blends were verified by use of DSC. The experiment results show that the initial temperature, peak temperature, and ending temperature of cold crystallization increase with increasing phenoxy content. On the contrary, the onset melting temperature, finishing melting temperature, and peak temperature in the first heating and the secondary heating processes decrease with increasing phenoxy content. The crystallization enthalpy and melting enthalpy, as well as the crystallization rate, decrease with increasing phenoxy content. Avrami exponents of the blends are slightly higher than that of pure PET and almost independent of phenoxy content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 878–885, 2005