Isothermal crystallization measurements on poly(ethylene terephthalate) by differential enthalpic analysis

The process of solid-phase crystallization in poly(ethylene terephthalate) has been followed by means of differential enthalpic analysis. Kinetic data for the process has been obtained for isothermal annealing from 100 to 115°C., showing induction times and first-order rate dependence. For the material studied, undrawn polyester filaments, an activation energy of 44 kcal./mole was determined. The technique used provides more direct monitoring of the crystallization phenomenon than that achieved with other methods.     

Liquid-induced crystallization of poly(ethylene terephthalate)

Amorphous unoriented poly(ethylene terephthalate) was crystallized at 25°C by various organic liquids. The crystalliznity induced in the amorphous polymer was measured by differential scanning calorimetry and infrared spectroscopy. The ability of liquids to interact with and induced crystallinity in the amorphous polymer was classified on the basis of their solubility parameters. Measurements of the density of liquid-crystallized 0.8-mil films of poly(ethylene terephthalate) indicated the presence of extensive internal voids in the semicrystalline polymer matrix. Comparison of differential scanning calorimetric thermograms and infared spectra of heat-crystalized and liquid-crystallized polymer indicated significant differences in the polymer morphologies induced by the two crystallization processes.     

Antinucleating action of polystyrene on the isothermal cold crystallization of poly(ethylene terephthalate)

The effect of polystyrene (PS) on the kinetics of the cold crystallization of poly(ethylene terephthalate) (PET) was thoroughly investigated. The PET/PS blends were essentially immiscible, as observed by dynamic mechanical thermal analysis, which showed two distinct glass‐transition temperatures, and by scanning electron microscopy. The neat PET and its blends were isothermally cold‐crystallized at various temperatures, and the kinetic parameters were determined with the Avrami approach. PET and its blends presented values of the Avrami exponent close to 2, and the kinetic constant increased with the crystallization temperature increasing. For all the crystallization temperatures studied, the presence of only 1 wt % PS significantly reduced the rate of cold crystallization of PET. A further increase in the PS concentration did not show any significant influence. The blends presented higher values of the activation energy for cold crystallization, which was estimated from Arrhenius plots. The equilibrium melting temperature of neat PET was determined on the basis of the linear Hoffman–Weeks extrapolative method to be ～ 255°C. This value decreased in the presence of PS, and this suggested limited solubility between PET and PS. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter was obtained, and it was shown to be higher for the neat PET than for the blends. Moreover, a transition of regimes (I → II) was observed in both PET and its blends. From the investigations conducted here, it is clear that PS in small amounts causes a reduction in the rate of PET crystallization, acting as an antinucleating agent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Strain-induced crystallization of poly(ethylene terephthalate)

The fabrication of poly(ethylene terephthalate), PET, into fibers, films, and containers usually involves molecular orientation caused by molecular strain, which may lead to stress- or strain-induced crystallization (SIC). The SIC of PET was studied by the methods of birefringence, density, thermal analysis, light scattering, and wide-angle X-ray. The development of crystallinity is discussed in relation to the rate of crystallization, the residual degree of orientation, and stress relaxation. The experimental procedure involves stretching samples at temperatures above the glass transition temperature, Tg, to a given extension ratio and at a specific strain rate of an Instron machine. At the end of stretching, the sample is annealed in the stretched state and at the stretching temperature for various periods of time, after which the sample is quickly quenched to room temperature for subsequent measurements. During stretching, the stress strain and the stress relaxation curves are recorded. The results indicate that the SIC of annealed, stretched PET can proceed in three different paths depending on the residual degree of orientation. At a low degree of residual orientation, as indicated by the birefringence value, annealing of stretched PET leads only to molecular relaxation, resulting in a decrease of birefringence. At intermediate orientation levels, annealing causes an initial decrease in birefringence followed by a gradual increase and finally a leveling off of birefringence after a fairly long period of time. At higher orientation levels, annealing causes a rapid increase in birefringence before leveling off. The interpretation of the above results is made using the measurements of light scattering, differential scanning calorimetry, and wide-angle X-ray. The rate of the SIC of PET is also discussed in terms of specific data analysis.     

聚酯固相缩聚等温结晶特性的研究

聚酯(PET)固相缩聚(SSP)中切片的结晶性能及其演变影响固相缩聚反应,采用差示扫描量热仪(DSC)和热台偏光显微镜研究了固相缩聚反应前后PET切片的等温结晶特性。结果表明:PET切片在DSC中的等温结晶符合Avrami 方程,等温结晶温度升高,结晶速率常数K值减小,即结晶速率降低;热台偏光显微镜中不同等温结晶温度下形成了不同的球晶形态:黑十字消光图以及环形消光图;随着PET特性粘数(平均分子质量)增大,结晶速率常数K值减小,球晶生长速率减小,Avrami指数n值增大,形成更加复杂的消光图。对于固相缩聚前PET基础切片,球晶最大结晶速率在190℃左右。     

High temperature crystallization of poly(ethylene terephthalate)

Annealing poly(ethylene terephthalate) (PET) at high temperature results in a crystalline phase stable to 10°C higher than the temperature previously regarded as the equilibrium melting point. Melting temperatures as high as 289°C can be attained, which is equivalent to the equilibrium melting point determined herein for PET. The high melting point and tendency to superheat suggest that the crystals possess a substantial extended chain structure, notwithstanding the magnitude of the infrared fold band.     

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     

Morphology and crystallization of poly(ethylene terephthalate)

The melting behaviour and the morphology of poly(ethylene terephthalate) crystallized from the melt are reported. In general, dual or triple melting endotherms are seen, and single endotherms are seen when the samples are crystallized above 215°C for long times. The location of the uppermost endotherm was found to be constant below T_c = 230°C, and above that temperature the location depends on T_c. Therefore, we have shown that samples of PET which are crystallized above T_c = 230°C contain perfect crystals only; below T_c = 230°C, they contain perfect and imperfect crystals. Scanning electron microscopy showed that the perfect crystals are the dominant lamellae in the spherulitic structure, while the imperfect crystals are the subsidiary lamellae in the spherulitic structure, The amorphous regions are located between individual lamellae.     

The crystallization of oriented poly(ethylene terephthalate)

The rate of crystallization of oriented poly(ethylene terephthalate) has been measured at 100°, 120° and 150°C using carefully prepared amorphous fibre samples. The samples were held to length during crystallization so that shrinkage did not occur, and the course of crystallization was followed by measuring the changes in density and boiling water shrinkage of the samples. The results show that the rate of crystallization is strongly dependent on the degree of orientation. Nucleation and initial growth of crystallites occur in times of the order of milliseconds at 120°C in samples of birefringence 0.08 compared with times of several minutes in isotropic material. It was found that crystallization in oriented material cannot be described by the Avrami equation.     

Crystalline morphology and isothermal crystallization kinetics of poly(ethylene terephthalate)/clay nanocomposites

A poly(ethylene terephthalate) (PET)/montmorillonite clay nanocomposite was synthesized via in situ polymerization. Microscopic studies revealed that in an isothermal crystallization process, some crystallites in the nanocomposite initially were rod‐shaped and later exhibited three‐dimensional growth. The crystallites in the nanocomposite were irregularly shaped, rather than spherulitic, being interlocked together without clear boundaries, and they were much smaller than those of neat PET. With Avrami analysis, the isothermal crystallization kinetic parameters (the Avrami exponent and constant) were obtained. The rate constants for the nanocomposite demonstrated that clay could greatly increase the crystallization rate of PET. The results for the Avrami exponent were consistent with the observation of the rodlike crystallites in the PET/clay nanocomposite during the initial stage. Wide‐angle X‐ray scattering and Fourier transform infrared studies showed that, in comparison with neat PET, the crystal lattice parameters and crystallinity of the nanocomposite did not change significantly, whereas more defects may have been present in the crystalline regions of the nanocomposite because of the presence of the clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1381–1388, 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     

Solidification of poly(ethylene terephthalate) with incomplete crystallization

Cooling is a critical step in any crystalline polymer molding or extrusion process. A simulation is proposed which will predict the transient temperature and crystallinity profiles developed when a finite polymeric slab comes in contact with a cooling fluid. A generalized, phenomenological model of the crystallization kinetics of polymers is incorporated to account for the effect of the latent heat of crystallization on the thermal history as well as on the crystalline structure at any point in the slab. The model assumes heterogeneous nucleation and temperature-dependent radial growth of spherulites. DSC cooling thermograms for the polymer are used to verify the kinetic model for comparing experimental measurements against simulated results. Observed spherulite sizes should also be matched by the simulation. Kinetic data have been obtained for two grades of poly(ethylene terephthalate) which have the same growth rate expression but different nucleation characteristics. Crystallinity of these two polymers decreases rapidly as either quench temperatures or nucleation densities are decreased independently. Calculations have been carried out for 1/16 in. thick sheets of polymer exposed to a cooling medium with a heat transfer coefficient of 100 Btu/hr/ft²/°F. Temperature gradients are also presented. The simulation can be used for optimizing quench conditions in polyester film extrusion.     

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.     

The crystallization kinetics of filled poly(ethylene terephthalate)

The crystallization kinetics of poly(ethylene terephthalate) was measured under isothermal conditions by DSC in the presence of various fillers and with varying filler concentrations. The fillers used were carbon, titanium dioxide, glass fiber, and calcium carbonate. The kinetics was calculated using the slope of the crystallization vs. time plot, the times for 10% and 50% reduced crystallization, and the Avrami equation. Activation energies were determined from measurements under different isothermal temperatures. The fillers caused athermal nucleation to be inhibited as shown by the increased values of the Avrami exponent, n. Interactions between the polyester and filler were interpreted to reduce the mobility of the polymer in the melt. This decreased the rate of crystallization and increased its activation energy. The order of the filler effect in reducing crystallization was the following: no filler < carbon < titanium dioxide < glass fiber < calcium carbonate. The concentrations of filler were above those typically used for nucleation and more in the range expected for reinforcement or dilution of the polymer. © 1993 John Wiley & Sons, Inc.     

Comparative study of orientation in hot-drawn poly(ethylene terephthalate) by means of refractive index and microhardness measurements

Refractive index and microhardness of drawn samples of poly(ethylene terephthalate) were measured by means of an Abbé refractometer and a microindentation hardness equipment. The optical and mechanical anisotropies determined from these measurements were compared with the birefringences obtained by using compensators and fitted to the affine deformation scheme, showing that microhardness anisotropy is a suitable technique for studying the overall orientation in polymers.     

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     

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 sulfur mustard on microhardness of poly(ethylene terephthalate) films

The effect of sulfur mustard (SM), a well-known chemical warfare agent on the microhardness of two poly(ethylene terephthalate) (PET) films was investigated at different loads. SM induces hardness in PET films, perhaps due to an antiplasticizing effect. Heat treatment of the films enhanced their microhardness. The heat-set films show a further increase in their microhardness after exposure to SM. These results were supported by physicochemical techniques like plasma and amine etching, which revealed complex etching phenomena giving rise to a structure-specific pattern. The film having a higher weight loss due to plasma and amine etching showed lower microhardness. © 1996 John Wiley & Sons, Inc.     

Melting behaviors and isothermal crystallization kinetics of poly(ethylene terephthalate)/mesoporous molecular sieve composite

Isothermal crystallization and subsequent melting behavior of mesoporous molecular sieve (MMS) filled poly(ethylene terephthalate) (PET) composites have been investigated at the designated temperature by using differential scanning calorimeter (DSC). The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponents n were evaluated to be 2<n<3 for the neat PET and composites. MMS particles acting as nucleating agent in composite accelerated the crystallization rate with decreasing the half-time of crystallization. The crystallization activation energy calculated from the Arrhenius' formula was reduced as MMS content increased. It is shown that the MMS particles made the molecular chains of PET easier to crystallize during the isothermal crystallization process. Subsequent differential scanning calorimeter scans of the isothermally crystallized samples exhibited different melting endotherms. It is found that much smaller or less perfect crystals formed in composites due to the interaction between molecular chains and the MMS particles. The crystallinity of composites was enhanced by increasing MMS content.     

The rate of crystallization of poly(ethylene terephthalate) by differential scanning calorimetry

The value of t_max in differential scanning calorimetry is correlated with the crystallization kinetics of poly(ethylene terephthalate) (PET). The Avrami exponent, n, obtained varies as a result of a change in slope of the curve at the point t_n, a secondary crystallization transition. The plot of t_n vs. t_max shows a linear relationship. The rate of crystallization depends upon both molecular weight and crystallization temperature. Under a nucleation controlling step, the plot of log t_max vs. \documentclass{article}\pagestyle{empty}\begin{document}$ t_{\max } vs.\frac{1}{{T^2 \Delta T}} $\end{document}gives a linear relationship. Theoretical concepts of the treatment are discussed.