Effect of fine structure on fatigue resistance property of poly(ethylene terephthalate) tire cord fibers

Seven experimental poly(ethylene terephthalate) (PET) fibers were spun and then drawn under different processing conditions (i.e., spinning speed and draw ratio) in such a way that the fibers possessed different long periods but retained the same crystal structure. Wide angle X‐ray diffraction, small angle X‐ray scattering, loss modulus, initial modulus, and taut tie molecules measurements were used to characterize the fine structure and the physical property of the fibers. The influence of the fine structure on the extensional fatigue behavior of the PET fibers was studied by subjecting them to 120–180 rpm at a repeated extension at 10⁴–10⁶ cycles. In order to detect the molecular motion of PET with the extensional fatigue, we carried out differential scanning calorimetry, X‐ray diffraction, density, and thermoluminescence (TL) experiments. The high temperature TL (above room temperature) intensity decreased with a 10⁴ cycle extension but increased with a 10⁵ cycle extension. The extent of change in the TL intensity was found to be a function of the long period and loss modulus. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 90–100, 2000     

Influence of diethylene glycol content on behavior of poly(ethylene terephthalate) fibers

Relationship between structural parameters of poly(ethylene terephthalate) (PET) fibers, their mechanical properties, and nonisothermal sorption of disperse dyes are investigated. Influence of diethylene glycol (DEG) addition and small changes in draw ratio are studied. Mechanical properties are characterized by stress–strain curves at constant deformation rate. The stress–strain relationships are described by means of derivative analysis. For treatment of nonisothermal experiments a simple kinetic model is suggested enabling to determine activation parameters of sorption. Further, the influence of a blank dye bath on the structure and properties of PET fibers is studied.     

Aspects of the yield behavior in poly(ethylene terephthalate) fibers

The yield behavior during cold drawing of commercially spun poly(ethylene terephthalate) (PET) filament yarn was investigated. Microscopic examination revealed the presence of inherent flaws within the spun filaments; these act as points for localized stress concentration. These inhomogeneities appear to be either internal cracks or crazes developed during the fiber melt spinning process. During elongation, stress magnification at these flaws results in shear band formation, indicating the onset of inhomogeneous yielding. At the yield bend in the load-elongation curve a circumferential crack propagates within these shear band regions. This yield crack develops into the classical neck geometry which further localizes additional plastic deformation within the sample at the neck.     

Influence of branching on the properties of poly(ethylene terephthalate) fibers

A series of branched poly(ethylene terephthalate) samples was prepared by employing 0.07–0.42 mol % trimethylolpropane (TMP) for melt polycondensation. These polymers were characterized with respect to molar mass, intrinsic viscosity, and melt viscosity. Spinning into fibers took place at spinning speeds ranging from 2500 to 4500 m/min. The molecular orientation of the fibers as measured by birefringence and polarized fluorescence decreases with growing amounts of TMP, as does crystallinity. Thus with slightly branched polymers, higher spinning speeds than with a linear polymer can be used to achieve a certain property profile. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 728–734, 1999     

Lamellar structure and properties in poly(ethylene terephthalate) fibers

The fibrillar and the lamellar structures in a range of poly(ethylene terephthalate) fibers were studied by small-angle X-ray scattering. The intensity maxima in the lamellar peaks lie on a curve that can be described as an ellipse. Therefore, the two-dimensional images were analyzed in elliptical coordinates. The dimensions of the coherently diffracting lamellar stack, the dimensions of the fibrils, the interfibrillar spacing, and the orientation of the lamellar surfaces were measured in addition to the lamellar spacing. The orientation of the lamellar planes and the size of the lamellar stacks had a better correlation with mechanical properties of the fibers than did the lamellar spacing. In particular, longer and wider lamellar stacks reduced fiber shrinkage, as did the closer alignment of the lamellar normal to the fiber axis. These structural features were also associated with lower tenacity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2527–2538, 1998     

The use of aqueous alkaline hydrolysis to reveal the fine structure of poly(ethylene terephthalate) fibers

The fine structure and physical properties of bright and semidull poly(ethylene terephthalate) (PET) fibers were investigated as successive layers of the polymer were removed by hydrolysis using aqueous solutions of sodium hydroxide up to weight losses of 90 and 68%, respectively. For both types large changes in molecular weight distribution did not occur, although as weight loss increased, the density of the remaining fiber increased. Alterations in fine structure with weight loss were also observed by thermal analysis. Greater strength loss with decreasing weight occurred for the semidull fiber than for the bright sample. Larger pits formed on the surface of the hydrolyzed semidull fibers than on the surface of the bright products. This observation is attributed to the titanium oxide present in the semidull fibers. It was also noted that as the density of the bright PET samples was increased by heatsetting, the rate of hydrolysis decreased.     

Crystallization behavior of poly(ethylene terephthalate)

The crystallization behavior of poly(ethylene terephthalate) (PET) was studied by the methods of small angle light scattering, depolarized light intensity and density measurements. Spherulite growth rates and the overall rates of crystallization were determined at various temperatures. A detailed analysis of the crystallization course has been made with special emphasis on the early stages of crystallization. The results indicate that a significant amount of crystallization takes place in the extraspherulitie material during isothermal crystallization.     

Carrier effect on structure and properties of heat-treated poly(ethylene terephthalate) fibers. II. Dyeing behavior

The changes in the morphology of heat-setted poly (ethylene terephthalate) (PET) fibers (as spun and 2.8×) submitted to benzoic acid action at different concentrations and times were analyzed by wide-angle x-ray scattering and dynamic and mechanical thermal analysis. Also, dyeings in the presence of two different Disperse dyes were performed. Therefore, the calculated diffusivities as well as the dye absorption percentage at equilibrium were related to the morphological changes of the fibers, due to the benzoic acid action. The plasticization effect of the benzoic acid over the as-spun fiber occurs in the first 30 min of exposition and in 24 h for the drawn one. This plasticizing action of the benzoic acid seems to be the commanding factor over the dyeing behavior of the fibers, as demonstrated by an increase of the diffusion coefficient with the increase of benzoic acid concentration. However, the morphological changes due to exposition for long periods of time at increased benzoic acid concentrations are one of the major responsible factors by the observed maxima in the figures of percentage of dye on the fibers at equilibrium versus benzoic acid concentration. Also, changes in the angular coefficient (B) calculated from the free volume theory equation are indicative that factors such as the size of the dye molecules as well as their solubilities in water in addition to the morphological changes may be playing a role in the dyeing behavior. © 1996 John Wiley & Sons, Inc.     

Poly(ethylene terephthalate)/polyarylate blends: Influence of interchange reactions on the melting behavior of poly(ethylene terephthalate)

The influence of the interchange reactions of poly(ethylene terephthalate) (PET)/polyarylate (PAr) blends on the melting behavior of isothermally crystallized PET has been studied. PET shows three melting endotherms in the pure state and also when mixed with PAr. These endotherms are explained in terms of primary and secondary crystallization processes as well as recrystallization during the calorimetric scan. It is also shown that interchange reactions hinder the crystallization processes of PET.     

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.     

Characterization of the physical and molecular structure of thermally elongating poly(ethylene terephthalate) fibers

The mechanism of thermally induced elongation in poly(ethylene terephthalate) fiber spun at 3500 m min⁻¹ has been examined. This partially oriented fiber has a crystalline content of about 25% and a high degree of orientation. The effect of time and tension during heat treatment was examined, and it was found that yarns that were allowed to relax during an initial brief heat treatment at 130°C subsequently elongated by up to 5% during a long heat treatment at the same temperature. Yarns that were not allowed to relax during the brief heat treatment did not elongate on subsequent heating. The morphological and mechanical changes associated with these processes have been studied using differential scanning calorimetry, X-ray diffraction (XRD), birefringence measurement, microscopy, and tensile testing. A large increase in crystallinity was observed during the brief heat treatment, but a much smaller increase took place during the long heat treatment. XRD indicated that substantial crystal reorganization occurred during both heat treatments, but c-axis growth was most significant in those materials that elongated during long heat treatment. It is proposed that it is this c-axis growth, in conjunction with conversion of disordered amorphous material into oriented crystalline material, that is responsible for the observed elongation. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 989–995, 1997     

Improved mechanical properties of poly(ethylene terephthalate) nanocomposite fibers

Improvements in Young's modulus and strength (tenacity) of poly(ethylene terephthalate) (PET) fibers were obtained by drawing unoriented nanocomposite filaments containing low concentrations (<3 wt%) of various organically modified montmorillonites (MMTs) in a second step at temperatures above the glass transition. Prior to melt spinning, solid‐state polymerization was used to rebuild lost molecular weight, due to MMT‐induced degradation, to a level suitable for producing high strength fibers. Greater improvements in mechanical properties occurred when the MMT stacks were intercalated with PET. A nominal 1 wt% loading of dimethyl‐dehydrogenated tallow quaternary ammonium surface modified MMT in drawn PET fiber showed a 28% and 63% increase in Young's modulus and strength, respectively. Relative to an unfilled PET fiber, these results surpassed the upper bound of the rule of mixtures estimate and suggested that both the type of surface modification and concentration of MMT affect the degree of PET orientation and crystallinity. Furthermore, drawability above T_g and elongation at break increased upon the addition of organically modified MMT to unoriented PET fibers, which was a key distinction of this work from others examining similar systems. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Composition depth profiles of plasma-fluorinated poly(ethylene terephthalate) fibers

Composition depth profiles of the outer 50 Å of plasma-fluorinated poly(ethylene terephthalate) fibers were obtained by angle-dependent X-ray photoelectron spectroscopy (XPS). The effect of sample geometry on XPS sampling depth and the depth distribution function (DDF) was determined theoretically for cylindrical and hemispherical surfaces. The theoretical DDFs are nonexponential. For cylindrical surfaces, the effect is small, a 22% increase in surface sensitivity. The average XPS sampling depth for smooth, properly oriented fibers is shown to vary, as it does for a planar surface, as the sine of the nominal takeoff angle. The DDF appropriate for cylindrical surfaces was incorporated into a computer program for inversion of angle-dependent XPS data to obtain composition depth profiles of the fibers. Plasma-fluorinated PET fibers were used to demonstrate the use of angle-dependent XPS on fibers. XPS results indicate that most fluorination occurs within the top few “monolayers,” attack is preferentially at the phenyl ring, both ? CHF? and ? CF₂ ? moieties are formed, and fluorination causes partial loss of aromaticity. © 1994 John Wiley & Sons, Inc.     

PEN/PET共混物结晶行为研究

用差示扫描量热法(DSC)研究了不同共混比例PEN/PET共混物的熔体结晶行为,并进行了等温结晶动力学测定。结果表明:随着两种组分向中间比例(50/50)靠近,共混物的熔融温度越低,结晶速率也越慢。     

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。     

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     

Micromechanical behavior of impact modified poly(ethylene terephthalate)

The micromechanical behavior of poly(ethylene terephthalate), PET, modified with a metallocene polyolefin copolymer (mPE) was investigated. Uniaxial deformation tests were performed using a tensile stage in a scanning electron microscope. This technique allowed the identification of the main deformation mechanisms that are associated with energy dissipation and toughness improvement. The poly(ethylene terephthalate) was blended with 5 wt% mPE by single‐screw extrusion. Films with thicknesses ranging from 200 to 500 μm were produced. Observation of the surfaces of the films during uniaxial deformation revealed the sequence of events leading to the full yielding of the matrix. In the early stages of deformation, the particles deform together with the matrix. As the deformation is increased, cavitation inside the particles occurs and fibrillation at the particle/matrix interface is observed, as well as the onset of shear banding. In order to study the effect of interfacial adhesion of the deformation mechanisms, the PET/mPE blends were compatibilized by grafting with glycidyl methacrylate (GMA). The reduction of the particle size was significant, which is indicative of the efficiency of GMA grafting in this type of blend. In this case, the particles were difficult to detect on the surface. Cavitation and shear banding occurred simultaneously. A similar behavior was observed in the case of oriented blends.     

Cold-drawing behavior of naturally aged poly(ethylene terephthalate)

The cold-drawing behavior of naturally aged poly(ethylene terephthalate) (PET) is investigated and an attempt is made to compare the mechanical behavior of unaged commercial PET and material which has been naturally aged for 11 years. Mechanical, viscometric, DSC and IR measurements are applied. The previously observed unusual ability of fresh PET bristles to be cold drawn up to 15:1 is not achieved for the naturally aged material. This fact is related to chemical cross-linking occurring on the surface of bristles after drawing and thermal treatment. The cross-linked skin is unsoluble, infusible, and uncrystallizable. The natural aging defeats the ability of PET to respond to external treatments which would otherwise change the internal structure. Such a “stabilization” of material properties is a result of the transformation, during natural aging, of the original physical network into a chemical network consisting of covalent bonds.     

Influence of compatibilizer precursor structure on the phase distribution of low density poly(ethylene) in a poly(ethylene terephthalate) matrix

In attempt to enhance the compatibility of PET/LDPE blends by using a proper functionalized polymer as third component, diethyl maleate (DEM)‐functionalized ultralow density poly(ethylene) (ULDPE‐g‐DEM) and styrene‐b‐(ethylene‐co‐1‐butene)‐b‐styrene triblock copolymer (SEBS‐g‐DEM) were prepared by radical functionalization in the melt. Immiscible PET/LDPE blends having compositions of 70/30 and 80/20 by weight were then extruded in the presence of 1–10% by weight of ULDPE‐g‐DEM and SEBS‐g‐DEM as compatibilizer precursors and ZnO (0.3% by weight) as transesterification catalyst. In both cases, evidences about the occurring of compatibilization between the two immiscible phases, thanks to the studied reactive processes, were obtained. Moreover, the phase distribution and particle size of blends were deeply investigated. Completely different kinds of phase morphology were achieved, as ULDPE‐g‐DEM stabilized a dispersed phase morphology, whereas SEBS‐g‐DEM favored the development of a cocontinuous phase morphology. The observed differences are tentatively explained onthe basis of reactivity and physical features of polymers. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.