High-performance PET fibers via liquid isothermal bath high-speed spinning: Fiber properties and structure resulting from threadline modification and posttreatment

Poly(ethylene terephthalate) fibers with improved mechanical properties and dimensional stability were spun via controlled threadline dynamics by a liquid isothermal bath (LIB) spinning process, followed by postdrawing and annealing. Control fibers were made by unperturbed spinning and posttreatment similar to a traditional spin—draw process. The two sets of as-spun fibers were spun at take-up speed in the range of 2000–5000 m/min. Fiber properties of the as-spun fibers and posttreated fibers of each process were compared. Two commercial tire cords, i.e., conventional tire cord and low shrinkage tire cord, were also included. Unlike unperturbed spinning, the LIB as-spun fibers show unique structural properties of high amorphous orientation, low crystallinity, high strength, and high initial modulus. Moreover, noncrystalline chains are further extended during posttreatment. The posttreated LIB fibers exhibit mechanical properties with tenacity higher than approximately 9 g/d, initial modulus higher than 120 g/d, and ultimate elongation less than approximately 10%. They also demonstrate superior dimensional stability with thermal shrinkage less than 6% and LASE-5 higher than 5 g/d. The overall properties are not obtainable by either the traditional spin—draw process or any modified process that produces low shrinkage tire cord. Unlike the case for unperturbed fibers, the mechanical properties of the posttreated LIB fibers demonstrate a strong/dependency on the birefringence of their respective as-spun fibers. There are at least three significant pieces of evidence that strongly indicate the existence of a third phase, referred to as the taut—tie noncrystalline phase (TTNC), in addition to the traditional two-phase model, i.e., crystalline and random amorphous phases. A unique feature involving a high fraction of taut—tie noncrystalline phase (TTNC %) in the LIB as-spun and the posttreated fibers is also found and which is, in fact, achieved neither by the traditional spin—draw nor the commercial tire cord processes. Further, different from the posttreated unperturbed fibers, the posttreated LIB fibers have an enhanced fraction of taut—tie noncrystalline chains with shorter length, which is believed to be one of the important factors leading to the superior mechanical properties and excellent dimensional stability achieved. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2441–2455, 1997     

Theoretical and experimental studies of anisotropic shrinkage in injection moldings of various polyesters

A novel approach to predict anisotropic shrinkage of slow crystallizing polymers in injection moldings was proposed, using the flow‐induced crystallization, frozen‐in molecular orientation, elastic recovery, and PVT equation of state. In the present study, three different polyesters, polyethylene terephthalate, polybutylene terephthalate, and polyethylene‐2,6‐naphthalate (PEN), are used. The anisotropic thermal expansion and compressibility affected by the frozen‐in orientation function and the elastic recovery that was not frozen during moldings were introduced to obtain the in‐plane anisotropic shrinkages. The frozen‐in orientation function was calculated from the amorphous contribution based on the frozen‐in and intrinsic amorphous birefringence and crystalline contribution based on the crystalline orientation function determined from the elastic recovery and intrinsic crystalline birefringence. To model the elastic recovery and frozen‐in stresses related to birefringence during molding process, a nonlinear viscoelastic constitutive equation was used with the temperature‐dependent viscosity and relaxation time. Occurrence of the flow‐induced crystallization was introduced through the elevation of melting temperature affected by entropy production during flow of the viscoelastic melt. Kinetics of the crystallization was modeled using Nakamura and Hoffman‐Lauritzen equations with the rate constant affected by the elevated melting temperature. Numerous injection molding runs were carried out by varying the packing time, packing pressure, flow rate, melt and mold temperature, and anisotropic shrinkage of moldings were measured. The experimental results were compared with the simulated data and found in a fair agreement. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3526–3544, 2006     

Theoretical and experimental studies of anisotropic shrinkage in injection moldings of semicrystalline polymers

A novel approach to predict anisotropic shrinkage of semicrystalline polymers in injection moldings was proposed using flow‐induced crystallization, frozen‐in molecular orientation, elastic recovery, and PVT equation of state. The anisotropic thermal expansion and compressibility affected by the frozen‐in orientation function and the elastic recovery that was not frozen during moldings were introduced to obtain the in‐plane anisotropic shrinkages. The frozen‐in orientation function was calculated from amorphous and crystalline contributions. The amorphous contribution was based on the frozen‐in and intrinsic amorphous birefringence, whereas the crystalline contribution was based on the crystalline orientation function, which was determined from the elastic recovery and intrinsic crystalline birefringence. To model the elastic recovery and frozen‐in stresses related to birefringence during molding process, a nonlinear viscoelastic constitutive equation was used with temperature‐ and crystallinity‐dependent viscosity and relaxation time. Occurrence of the flow‐induced crystallization was introduced through the elevation of melting temperature affected by entropy production during flow of the viscoelastic melt. Kinetics of the crystallization was modeled using Nakamura and Hoffman‐Lauritzen equations with the rate constant affected by the elevated melting temperature. Numerous injection molding runs on polypropylene of various molecular weights were carried out by varying the packing time, flow rate, melt temperature, and mold temperature. The anisotropic shrinkage of the moldings was measured. Comparison of the experimental and simulated results indicated a good predictive capability of the proposed approach. POLYM. ENG. SCI., 46:712–728, 2006. © 2006 Society of Plastics Engineers     

Molecular Orientation and Mechanical Properties of Poly(Vinyl Alcohol) Fibers

Abstract

A number of poly(vinyl alcohol) fibers with different draw ratios was characterized by measuring the birefringence, crystalline orientational order, crystallinity, tensile strength, and modulus. The birefringence, tensile strength and modulus increased with increasing draw ratio whereas the crystallinity and crystalline order parameters remained constant within narrow limits. The increase in birefringence has to be attributed solely to an increase in chain orientation in the amorphous phase of the semicrystalline fiber. The tensile strength and modulus are therefore directly related to the chain orientation in the amorphous phase. With the aid of a simple two-phase model it was found that the modulus of the amorphous phase in its disordered conformation was 4.8 GPa. The intrinsic birefringence of the amorphous phase was found to be 79 × 10^?3, i.e. much higher than the value obtained for the crystalline phase (52 × 10^?3). When this value was used in calculations, it was found that the order parameter of the amorphous phase increased from around 0.1 for a draw ratio of 1 to approximately 0.6 for a draw ratio of 5, whereas the order parameter of the crystalline phase was close to 1 for all draw ratios.     

Characterisation and properties of oriented PVC fibres

Drawn PVC fibres were investigated using birefringence, DSC and TMA techniques, and their tenacity was measured. An increase in fibre draw ratio (DR) for heat set samples produced an increase in tenacity, birefringence and X-ray intensity. The linearity of a tenacity/birefringence plot suggested that tenacity was a good indicator of molecular orientation. An ‘undrawn’ filament was substantially amorphous. Drawing without heat setting produced little three dimensional order, and samples relaxed readily on heating. X-ray results for heat set fibres suggested both an increase in the amount of crystallinity, and in crystallite alignment. After heat setting, a minor DSC endotherm was produced; the onset of this endotherm corresponded to the heat setting temperature, as did the onset of shrinkage measured by TMA. For samples with a DR>1.5, maximum shrinkage measured by TMA corresponded to complete elastic recovery.     

An optical investigation of high‐tenacity polyester (H‐T PET) fibers annealed at different temperatures

A two‐beam “Interphako” interference microscope was used to study the effect of annealing on the physical properties of high‐tenacity poly(ethylene terephthalate) H‐T PET fibers. The PET fibers were annealed with free ends for 1 h at temperatures ranging from 100 to 200°C. The shrinkage, refractive indices, and orientation angle of the PET fibers were determined for different annealing temperatures. The measured birefringence and orientation function were found to have decreased with increasing temperature, whereas the degree of crystallinity and the onset temperature (DSC) increased. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of coupling agent on structure and properties of micro–nano composite fibers based on PET

Poly(ethylene terephthalate) (PET)/carbon black (CB) micro–nano composite fibers were manufactured by melt spinning method. To achieve good dispersion, nano‐CB particles were modified by coupling agent (CA). The effect of CA on structure and properties of the fibers were investigated via scanning electron microscopy (SEM), tensile testing, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), sonic orientation, and birefringence, respectively. At 2 wt % CA dosage, CB particles present the optimal dispersion in the fibers, shown in SEM images. Besides, the fibers possess the maximum breaking strength, the lowest crystallization temperature, and the highest crystallinity. After CA modification, the superior interfacial structure between PET and CB is beneficial to improve mechanical properties of the fibers. The well dispersed CB particles provide more heterogeneous nucleation points, resulting in the highest crystallinity. Furthermore, the fibers with 2 wt % CA dosage possess the maximum orientation and shrinkage ratio. According to Viogt–Kelvin model, the thermal shrinkage curves of the fibers can be well fitted using single exponential function. The three‐phase structure model of crystal phase–amorphous phase–CB phase was established to interpret the relationship among shrinkage, orientation, and dispersion of CB particles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43846.     

Structure development in high-speed spinning of polyethylene naphthalate (PEN) fibers

The structural evolution in fibers produced by high-speed fiber spinning of Polyethylene 2,6 naphthalene dicarboxylate (polyethylene naphthalate) was investigated. The fibers were found to remain amorphous at speeds up to 2500 m/min, and subsequent increases in speed resulted in highly oriented crystalline domains containing primarily α crystalline modification. The fibers processed at and above 3500 m/min were found to contain the β modification together with the α modification. At the highest speed investigated, 4000 m/min, the crystalline regions became disordered, and this was attributed to low deformation temperatures that accompany neck-like deformation. Constrained annealing of the fibers results in relatively unoriented crystalline structure at 500 m/min. Although the WAXS patterns of fibers spun in the 1000–2500 m/min range do not show any crystalline peaks, these fibers develop crystalline regions with significant orientation upon constrained annealing. In addition, these regions were found to have both α and β crystalline phases, indicating that not only the α but also the β phase can be grown from the oriented amorphous precursors upon constrained annealing. From our experimental results we extrapolated a value of 0.791 100% crystalline PEN. The estimated intrinsic birefringence value for the amorphous PEN is 0.75. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 729–747, 1997     

Effect of winding speed on the structure and properties of as‐spun poly(trimethylene 2,6‐naphthalenedicarboxylate) fibers as compared to poly(ethylene terephthalate) fibers

We present a comparative study of melt spinning of poly(trimethylene 2,6‐naphthalenedicarboxylate) (PTN) and poly(ethylene terephthalate) (PET) fibers with respect to the effect of winding speed (2000–6000 m/min): Structural changes were followed by X‐ray analysis, calorimetry, and measurements of density, boiling water shrinkage, and birefringence. As‐spun PTN fibers exhibited a low degree of crystallinity at relatively low speeds (< 2000 m/min). An increase in winding speed up to 6000 m/min only resulted in a minor enhancement of crystallinity and orientation. The small change of structural parameters accounted for the fact that tenacity and modulus did not rise significantly with increasing winding speed, contrary to the PET fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2489–2497, 2002     

Creep deformation and its correspondence to the microstructure of different polyester industrial yarns at room temperature

The room temperature creep behaviors and related microstructural changes of a high‐tenacity (HT) poly(ethylene terephthalate) (PET) industrial yarn and a super‐low‐shrinkage (SLS) PET industrial yarn were investigated and compared by using wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS), birefringence measurements and Fourier transform infrared spectroscopy (FTIR) in order to identify their respective underlying creep mechanisms. The crystal structure including crystalline orientation and crystallinity of fibers did not show obvious changes after the creep process, while the amorphous structures varied with creep stress. The HT yarn creep deformation was mainly elastic, and its creep recovery ratio was high. The amorphous orientation, amorphous layer thickness and degree of conformation change from gauche to trans conformers showed a slight increase. The mechanism of this slight change is that the coiled molecular chains are oriented under tensile loading and most of the extended chains are disoriented under offloading in the small amorphous region. By contrast, the SLS yarn underwent plastic creep deformation with a low recovery ratio. After the creep test, the amorphous orientation and lamellar thickness both increased but the crystallinity remained unchanged. The creep mechanism for the SLS yarn is that the molecular chains in the large amorphous domain are easily extended and oriented subjected to tensile loading, while conformation transition from gauche to trans conformers and the formation of irreversible mesophase take place. © 2018 Society of Chemical Industry     

The effect of a liquid isothermal bath in the threadline on the structure and properties of poly(ethylene terephthalate) fibers

The process of melt-spinning poly(ethylene terephthalate) (PET) filament at high speeds was modified through the inclusion of a liquid isothermal bath (LIB) in the spinline. A wide range of positions, temperatures, and depths associated with the operation of the LIB were utilized in this study. The structural characteristics and mechanical properties of the as-spun fibers were characterized by birefringence, wide-angle X-ray diffraction (WAXD), infrared spectroscopy, and tensile testing. Experimental results showed that the structure and mechanical properties of the as-spun fibers were significantly influenced by the LIB operating conditions. The as-spun fibers prepared under optimum LIB conditions exhibit high birefringence and excellent mechanical properties. Results suggest the development of a critical value of threadline stress that is determined primarily by LIB depth and take-up velocity. Below this critical value, raising of LIB temperature, LIB depth, and take-up velocity resulted in increases of the apparent crystallite size, sample crystallinity, and both the crystalline and amorphous orientation. As would be expected, the mechanical properties of the fiber samples were improved in a corresponding manner. Above this critical stress value, molecular chains in the amorphous phase are stretched tautly, but the crystal growth process is restricted, resulting in a decrease in crystallite size and crystallinity, as well as a continued increase in mechanical properties. The fiber properties were also found to be very responsive to the relative location of the LIB. A unique structure, believed never before obtained in a one-step high-speed PET melt-spinning process, has been achieved that combines high amorphous orientation, low crystallinity, and high tenacity. © 1995 John Wiley & Sons, Inc.     

Toward a viscoelastic modeling of anisotropic shrinkage in injection molding of amorphous polymers

A novel approach to predict anisotropic shrinkage of amorphous polymers in injection moldings was proposed using the PVT equation of state, frozen‐in molecular orientation, and elastic recovery that was not frozen during the process. The anisotropic thermal expansion and compressibility affected by frozen‐in molecular orientation were introduced to determine the anisotropy of the length and width shrinkages. Molecular orientation calculations were based on the frozen‐in birefringence determined from frozen‐in stresses by using the stress‐optical rule. To model frozen‐in stresses during the molding process, a nonlinear viscoelastic constitutive equation was used with the temperature‐ and pressure‐dependent relaxation time and viscosity. Contribution of elastic recovery that was not frozen during the molding process and calculated from the constitutive equation was used to determine anisotropic shrinkage. Anisotropic shrinkages in moldings were measured at various packing pressures, packing times, melt temperatures, and injection speeds. The experimental results of frozen‐in birefringence and anisotropic shrinkage were compared with the simulated data. Experimental and calculated results indicate that shrinkage is highest in the thickness direction, lowest in the width direction, and intermediate in the flow direction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2300–2313, 2005     

Properties of PET fibers with high modulus and low shrinkage (HMLS). I. Yarn properties and morphology

Classical morphological analysis has been performed on novel PET fibers of high modulus and low shrinkage (HMLS). As expected, amorphous orientation controls the degree of shrinkage and tenacity. The uniqueness of these materials is derived from a high “effective” crosslink density which results in a high retractive force during elevated temperature shrinkage and significant stress-amplification during room temperature extension. Although the morphological origin of the high effective crosslink density is unknown, it is speculated that the interfibrillar regions contribute to the observed behavior by suppressing yielding.     

Intrinsic Birefringence of γ‐Form Crystal of Nylon 6: Application to Orientation Development in High‐Speed Spun Fibers of Nylon 6

The intrinsic birefringences of the α‐ and the γ‐form crystals of nylon 6 were calculated from the atomic coordinates and the bond polarizabilities using the Lorentz‐Lorenz equation. The intrinsic birefringence of the γ‐form crystal was found to be significantly smaller than that of the α‐form crystal. Those values were applied to the evaluation of the orientation function of the amorphous phase of the nylon 6 fibers produced by the high‐speed spinning process. The molecular orientation in the amorphous phase increased to the maximum point and then decreased with the spinning speed. These results suggested that an inhomogeneous structure in the fiber was formed for the higher take‐up speed.     

The influence of processing parameters on the structural and mechanical properties of drawn polypropylene fibres: A factorial design approach

This article reports a study of multi‐stage polypropylene fiber drawing (stretching) as a continuous, but independent stage of the overall fiber‐forming process. The fibers were drawn according to a factorial experimental design, once appropriate spinning conditions had been devised. The structures of the drawn fibers were studied using wide‐angle X‐ray diffraction and birefringence measurements. In addition, the fibers were characterized with respect to filament tenacity, elongation to break, specific secant modulus, and extent of shrinkage at 130°C. All these properties were quantitatively assessed as responses to nine specially selected process control parameters in the drawing equipment. For every property analyzed, the temperatures of the hot plates in the draw frame were found to exert no significant influence, whereas the temperatures of the initial rollers were in most cases significant. Furthermore, the speed of the final roller also played an influential role, and a number of interactions between process parameters were identified as significant. Explanations are advanced for the parts played by significant process parameters on the properties of the drawn fibers. The article also demonstrates the advantages of factorial experimental design in determining correct settings for process parameters to give drawn fibers with the properties desired. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of initial take-up speed on properties and structure of as-spun and drawn/heat-set poly(ethylene terephthalate) filaments

The effect of initial take-up speed on the properties and structure of both as-spun and drawn/heat-set poly(ethylene terephthalate) filaments was characterized through measurements of birefringence, percent crystallinity, tensile properties, high temperature shrinkage, loss tangent temperature dependence, DSC melting behavior, and wide-angle (WAXS) and small-angle X-ray scattering (SAXS). While a steady trend toward improved as-spun filament orientation and tensile properties occurred with increasing initial take-up speed, the reduced drawability of these more structured precursor filaments resulted in corresponding drawn/heat-set filaments that were of relatively lower overall orientation and tensile strength. The observed trends in tenacity, initial modulus, and high temperature shrinkage of the drawn/heat-set filaments appeared to be well correlated with the extent and distribution of amorphous phase rigidity as perceived through inferences made from the loss tangent temperature dependence. The WAXS patterns of the drawn/heat-set samples indicated that these filaments all possess a well-developed and highly oriented crystalline structure. Application of a simple two phase model allowed the determination of an amorphous orientation factor, which for the drawn/heat-set filaments was generally found to decrease as the draw ratio imposed in order to achieve comparable levels of elongation to break decreased. The SAXS patterns of the drawn/heat-set filaments indicated that comparable long period spacings exist in all cases and that a transition from a four-point pattern to a two-point bar-shaped pattern occurred when the precursor filament possessed some significant amount of as-spun crystallinity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2115–2131, 1998     

不同软硬段含量的聚醚酯纤维结构与性能的关系

为了说明聚醚酯纤维的形态结构与性能的对应关系,选择不同软硬段含量的聚醚酯切片进行熔融纺丝试验。结果发现:随着硬段含量的增加,纤维的断裂强度增大,但回弹性降低;当硬段质量分数为65%时,纤维的断裂强度为1.12 cN/dtex,而回弹性降至50%左右。通过广角X射线散射、小角X射线散射以及双折射、声速取向等试验进一步分析了不同软硬段含量的聚醚酯纤维的形态结构变化,发现在硬段含量高的聚醚酯纤维内部有利于形成较高的取向结构,有助于纤维强度的提升;然而,此时纤维内形成较小尺寸的结晶结构分散于无定形区内,相分离程度低,致使其回弹性降低。     

Study of Optical and Structure Properties of Polyester (PET) and Copolyester (PETG) Fibers by Interferometry

In this article results on the influence of drawing on the optical and structure properties of polyester (polyethylene terephthalate) and copolyester (glycol-modified polyethylene terephthalate) (4 wt% of ethylene glycol) fibers are reported. Refractive indices, intrinsic birefringence, mean polarizability per unit volume, optical orientation function, density, volume fraction of crystalline material, weight fraction crystallinity, and volume fraction of amorphous and work per chain of these fibers have been evaluated at different draw ratios. A comparison of optical and structure parameters for copolyester fiber and referenced monopolyester fiber has been done. This study has been carried out by means of computerized double-refracting Pluta interference microscope combined with opto-mechanical devices. Microinterferograms and relationships between the parameters obtained are given for illustration.     

Intrinsic birefringence of amorphous poly(bisphenol-A carbonate)

The birefringence of uniaxially oriented poly(bisphenol-A carbonate) (PC) samples stretched over a wide range of temperatures has been measured accurately with a combination of the compensator and the wedge methods. The Hermans' orientation function of anisotropic PC was calculated from the measured dichroic ratio of the infrared absorption band at 1364 cm^-1. Measurements using differential scanning calorimetry, X-ray diffraction, or infrared spectroscopy indicated no stress-induced crystallinity in stretched amorphous PC. At each state having a defined molecular orientation, samples stretched below the glass transition temperature (T_g) always exhibited excess birefringence and slightly higher density. This phenomenon is attributed to bond distortion during stretching, a result of the suppression of large-scale segmental motions of polymer chains below the T_g. The birefringence of samples stretched above the T_g arises exclusively from the orientation effect as a result of greater chain mobility. These measured birefringence values are proportional to Hermans' orientation functions, yielding a linear relationship which allows precise determination of the intrinsic birefringence of amorphous PC as 0.192 ± 0.006.     

Elastic response of copolyether-ester fiber on its phase morphology under different heat-treatment condition

In order to verify the elastic response of copolyether-ester (PEE) fibers on their phase morphology and structure, the PEE fibers based on poly(butylene terephthalate) (PBT) as hard segments and poly(terramethylene glycol) (PTMG) as soft segments were prepared by melt spinning, the as-spun fibers were then heat-drawn and heat-set at different conditions. From the analysis of the mechanical properties, it is shown that the tenacity as well as elastic recovery of the fibers increased with the increasing heat-draw ratios, the elongation at break decreased. The morphological and structural were evaluated by small angle X-ray scattering (SAXS), wide angle X-ray scattering (WAXS) and birefringence. When the melt-spun PEE fibers were heat-drawn, higher crystallinity and orientation, larger size of lamellae structure was formed within the fibers, it is also much easier to form higher phase separation. This structure will contribute to better elastic performances of PEE fibers.