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     

Morphology and Structure of Constituent Fibres in Thermally Bonded Nonwovens

Summary: A new process has been developed to produce three‐dimensional nonwovens directly from staple fibres. In order to establish suitable windows of the process parameters to achieve high‐quality nonwoven products, the effects of thermal bonding temperature, dwell time and mould material on the morphology and structure of the fibre have been investigated using PP/PET bi‐component fibres. It was evident from both scanning electron microscope images and Raman spectra that thermal‐induced shrinkage of the PP sheath fibre occurred in the thermal bonding process, leading to deformation and cracking of the PP sheath and exposure of the PET core. X‐ray diffraction results revealed crystal imperfection and/or less ordered polymer chains, more γ‐form and thermal contraction of the crystal lattice for the PP sheath fibre, while birefringence measurements indicated that both the birefringence and the orientation factor for the PP fibre decreased after the thermal bonding process. The degrees of the thermal‐induced shrinkage increased, and the crystallinity, birefringence and orientation factor of the PP sheath fibre decreased with increasing thermal bonding temperature, dwell time and thermal conductivity of the mould material. All these can be attributed to the different levels of modification of chemical composition caused by thermal oxidative degradation and thermal‐induced relaxation of the orientation during the thermal bonding process.

Changes of morphology and crystalline features of PP/PET fibre after thermal bonding process.     

A study of tensile modulus and molecular orientation in drawn and shrunk poly(ethylene terephthalate) combining refractive index,polarized fluorescence,and X-ray diffraction measurements

Earlier studies of the orientation of the crystalline and amorphous regions in drawn and shrunk PET tapes by refractive index, X-ray, and polarized fluorescence measurements have been extended to include a study of young's modulus of such samples. The results show that for samples of low crystallinity, whether drawn or drawn and shrunk, the modulus correlates well with the overall orientation, as indicated by the birefringence. For such samples the overall orientation and modulus fall with increasing shrinkage. For samples which crystallize substantially, either on drawing or subsequent shrinkage, the behavior is more complicated. In particular, for samples originally drawn at 80°C to λ = 3.44 there is a range of shrinkage temperatures for which greater shrinkage can be accompanied by a smaller loss of overall orientation and modulus because of an increase in crystallinity for the same degree of crystalline and amorphous orientation. The modulus results are discussed in the light of current understanding of the structure of oriented PET. In the case of the samples which crystallize substantially on shrinkage it is shown that changes in modulus primarily related to changes in crystallinity.     

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     

Effect of morphology on barrier properties of poly(ethylene terephthalate)

The effects of morphology on the barrier properties of poly(ethylene terephthalate) (PET) have been investigated. Various levels of crystallinity can be developed in PET as a result of thermal exposure, orientation, and heat setting. The morphologies of the crystalline phase are affected by the conditions of their formation. As a result of morphological differences, samples with equivalent levels of crystallinity have been found to exhibit different oxygen barrier properties. These differences are most apparent at low and intermediate levels of crystallinity. For thermally crystallized systems, at the same crystalline content, increasing superstructure size in the crystalline phase leads to greater tortuosity for the permeant molecules, resulting in lower permeability. For stretched and heat set PET, transport properties can be correlated with birefringence as well as overall orientation, measured in terms of fraction of molecules in the trans or extended chain conformation. At high levels of crystallinity, where the spherulites become volume filling, permeation takes place primarily through the interlamellar regions of the crystalline phase and is controlled by level of crystallinity, independent of the mode of crystallization. The barrier properties of PET, before spherulitic impingement occurs, are governed by the size and number of spherulites as well as by the amorphous orientation present in non‐crystalline regions. POLYM. ENG. SCI., 45:400–409, 2005. © 2005 Society of Plastics Engineers     

An infra-red study of the structure of oriented poly(ethylene terephthalate) fibres

Procedures have been developed for quantitative infra-red spectroscopic measurements on poly(ethylene terephthalate) fibres in conventional yarns. Following computer reconstruction methods already established for films, measurements of molecular orientation and trans/gauche conformer content have been carried out for a wide range of fibres produced by different processing routes. The trans bands can be separated into load-bearing and non-load-bearing conformations, where the former govern the modulus. It is also shown that a quantitative measure of amorphous orientation can be obtained from the infra-red measurements. While there are similarities between the development of overall molecular orientation and changes in molecular conformation for high wind-up speed yarns and drawn yarns produced from a low wind-up speed yarn, there are also major differences, which confirms previous work showing that these two classes of fibres are basically different in structure. These differences are shown by the relationships between the load-bearing trans conformations and the amorphous orientation with the overall orientation.     

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.     

Determination of intrinsic birefringence values of polycaprolactone filaments

Intrinsic birefringences of polycaprolactone filaments are determined using the approach suggested by Samuels. First, intrinsic lateral moduli are determined from the values of crystallinity and sonic moduli of unoriented filaments. These values are found to be 3.473 GPa and 0.071 GPa, respectively, for crystalline and amorphous regions. The crystallinity, sonic moduli and crystalline orientation function of drawn and heat set filaments are used to evaluate amorphous orientation functions. Finally, Stein and Norris's equation along with birefringence data is used to obtain intrinsic birefringence values of crystalline and amorphous regions and these values are found to be 0.079 ± 0.002 for crystalline regions and 0.066 ± 0.008 for amorphous regions. Copyright © 2012 Society of Chemical Industry     

The role of nanoclay in the generation of poly(ethylene terephthalate) fibers with improved modulus and tenacity

The effect of nanoclay concentration on the molecular orientation and drawability of poly(ethylene terephthalate) PET was examined using thermal and vibrational spectroscopic analysis. Although drawability at 83 °C in hot air increased by the addition of nanoclay, the maximum draw ratio was independent of nanoclay concentration. The average molecular orientation of the PET chain was found to mimic the trend in mechanical property improvements. Both Young's modulus and tenacity (i.e. strength) showed the maximum improvement at a 1 wt% loading of clay, which was shown to coincide with the maximum amount of molecular orientation. Nanoclay was shown to intercalate with PET and enhanced amorphous orientation that led to modulus and strength improvements. However, at higher concentrations of nanoclay the presence of large agglomerates prevented efficient orientation to the fiber axis and acted as stress concentrators to aid in cavitation and failure during testing. Raman spectroscopy showed that the as-spun unfilled PET fibers possessed significantly more trans rotamer content of the ethylene glycol moiety than the nanocomposite fibers.     

Uniaxial Orientation and Crystallization Behavior of Amorphous Poly(ethylene terephthalate) Fibers

The effects of drawing conditions on the orientation and crystallinity of poly(ethylene terephthalate) (PET) fibers were investigated by using optical birefringence, sonic velocity, and wide-angle X-ray diffraction measurements, respectively. The preferred condition for preparation of uniaxially oriented amorphous PET fibers was suggested. The crystallization behavior of oriented PET fibers under relaxed and fixed length conditions was investigated by using differential scanning calorimetry (DSC). The multi-overlapping peaks were observed in the non-isothermal DSC curves of oriented PET fibers under relaxed condition. The kinetics of non-isothermal crystallization of oriented PET fibers under relaxed condition was analyzed by using an equation which takes the multi-crystallization processes into account. The kinetic parameters of every process were obtained and the crystallization mechanism was discussed. The crystallization behavior under fixed length condition differs from that under relaxed condition.     

Inversion of infra-red dichroism in linear crystallizable polyurethanes

Infar-red spectroscopic and calorimetric data for a number of linear crystallizable polyurethanes based on n-tetramethylene glycol oligomers (n = 1,2,3,4) and hexamethylene diisocyanate are given. A degree of similarity has been found in the orientation behaviour of stretching vibration bands of NH groups (inversion of dichroism with elongation) and of CH₂ groups (no inversion) in the spectra of polyurethanes studied and in the spectra of segmented polyurethanes. It is concluded that in polyurethanes with a glycol ether component of relatively small length a somewhat independent behaviour of segments of different nature localized in separate micro-regions may take place. A supposition is made that the polyurethanes examined, except for the first member of a series (n = 1), can be considered as segregated systems with an ether glycol unit enriched amorphous phase in which crystallites formed mainly by urethane chain fragments are distributed.     

Chain confinement in electrospun nanofibers of PET with carbon nanotubes

Composite nanofibers of poly(ethylene terephthalate), PET, with multiwalled carbon nanotubes (PET/MWCNT) were prepared by the electrospinning method. Confinement, chain conformation, and crystallization of PET electrospun (ES) fibers were analyzed as a function of the weight fraction of MWCNTs. For the first time, we have characterized the rigid amorphous fraction (RAF) in polymer electrospun fibers, with and without MWCNTs. The addition of MWCNTs causes polymer chains in the ES fibers to become more extended, impeding cold crystallization of the fibers, resulting in more confinement of PET chains and an increase in the RAF. The fraction of rigid amorphous chains greatly increased with a small amount of MWCNT loading: with addition of 2% MWCNTs, RAF increased to 0.64, compared to 0.23 in homopolymer PET ES fibers. Spatial constraints also inhibit the folding of polymer chains, resulting in a decrease in crystallinity of PET. For fully amorphous PET/MWCNT composites, MWCNTs do not affect the chain conformation of PET in the ES fibers. For cold crystallized PET/MWCNT composite nanofibers, more trans conformers were formed with the addition of MWCNTs. The increase of RAF (chain confinement) is associated with an increase of the concentration of the trans conformers in the amorphous region as the MWCNT concentration increases in the semicrystalline nanofibers.     

Studies of post drawing relaxation phenomena in poly(ethylene terephthalate) by infrared spectroscopy

In this paper, we study the relaxation behavior of initially amorphous poly(ethylene terephthalate) (PET) films drawn, at 80°C using a draw rate of 2 cm/min, to a draw ratio (λ) from 1 to 5 and then quenched to room temperature. These films were then heated at different temperatures from 68 to 80°C for different times and their orientation determined. The orientation measurements were performed by transmission infrared spectroscopy and the bands used for the determination of orientation were those at 1340 and 970 cm^?1 for the trans conformers, normalized using the 1410 cm^?1 benzene ring vibration. The crystallinity was determined by thermal analysis. It is shown that when PET is drawn to λ values up to 2–2.5 (before stress-induced crystallization), the orientation relaxes rapidly at temperatures close to the glass transition temperature of PET. For λ values of 3 or higher, the orientational relaxation of the amorphous regions is hindered. This effect is ascribed to the development of strain-induced crystallites, which are believed to act as pseudo-crosslinks.     

Structure–property relationship in heat-set poly(ethylene terephthalate) fibers. I. Structure and morphology

Poly(ethylene terephthalate) (PET) fibers having a range of structure and morphology were prepared by heat-setting commercial PET yarn at temperatures of 100–250°C for 5 min under two conditions, while the yarn was free to relax and when it was held taut at constant length. The crystallinity, crystallinity orientation, and crystallite size were determined by X-ray diffraction while birefringence was measured with the help of optical microscopy. The amorphous orientation factor was computed from the structural parameters. The coupling between the crystalline and amorphous regions was determined using the Takayanagi model. While crystallinity and crystallite orientation values for the corresponding samples of the free-annealed and taut-annealed series did not show very large differences, the free-annealed samples had much lower amorphous orientation, especially when heat-set at higher temperatures. Also while the free-annealed samples showed a predominantly series type of coupling between the crystalline and amorphous regions, the taut-annealed samples showed a significant degree of parallel coupling. It is shown that samples in which there is distinct phase separation between the crystalline and amorphous regions have a predominantly series type coupling.     

Disclosing the fatigue deformation mechanisms of different types of poly (ethylene terephthalate) industrial fibers on the base of the multiscale structural evolutions

The fatigue behavior of poly (ethylene terephthalate) industrial fibers is a key issue in their long-term service for engineering applications. To have a comprehensive understanding of the fatigue behavior, the high-tenacity (HT) and low-shrinkage (LS) PET fibers were selected to analyze the room temperature dynamic fatigue properties with different stress. Various techniques such as WAXD/SAXS and FTIR were employed to study the multiscale structure changes to disclose the fatigue mechanisms. Although the crystalline structure including orientation and crystallinity did not change, the amorphous structures varied with fatigue stress. The HT fiber exhibited a higher fatigue recovery ratio. The slight increase in amorphous orientation, and amorphous thickness was attributed to the oriented coiled molecular chains during tensile fatigue stress. In contrast, the LS fiber experienced plastic fatigue deformation with a lower recovery ratio. The molecular chains in the large amorphous domain are easily extended and oriented under tensile loading, increasing amorphous orientation and lamellar thickness. The fatigue mechanism for the LS fiber involved the conformation transition from gauche to trans conformers and a higher proportion of irreversible amorphous regions were formed. It is indicated that developing industrial filaments with small amorphous orientation and content is crucial to improving their fatigue resistance.     

Swollen-state polymerization of poly(ethylene terephthalate) in fibre form

The swollen-state polymerization of poly(ethylene terephthalate) in fibre form was performed in hydrogenated terphenyl as the swelling solvent. Ultra-high-molecular-weight poly(ethylene terephthalate) (CHMW-PET) fibre with an intrinsic viscosity of 3–4dl g⁻¹ (M_n = 2–3 × 10⁵) was obtained. The polymerization rate of as-spun PET fibres in the swollen state was greater than that of PET granules in the swollen state. It was clarified that the polymerization rate was related to the chain mobility of the starting materials. The chain mobility was influenced by various conditions, such as changing rigidity of the segments during copolymerization, the chain orientation of the starting fibre before swollen-state polymerization and the temperature of pretreatment with the solvent. Pretreatment with solvent before polymerization was effective in increasing the chain mobility. The relation between chain mobility and polymerization rate was examined by wide-angle X-ray diffraction, density, differential scanning calorimetry, solvent content and viscoelastic measurements. Undrawn UHMW-PET fibres could be drawn 10 times or more by the zone drawing technique in spite of their high crystallinity, and the drawn fibre showed high tensile strength (12 g d⁻¹) and high modulus (240 g d⁻¹).     

An analysis of the correlation between structural anisotropy and dimensional stability for drawn poly(lactic acid) films

The anisotropic structures found in drawn poly(lactic acid) films are strongly correlated to their overall dimensional stability. Several aspects of this relationship can be efficiently characterized by Raman spectroscopy. We determined the degree of orientation in these drawn films by measuring the relative intensity of the polarized and depolarized components and the shift in the relative band positions. The bandwidth and specific band frequency also correlated well with the degree of sample crystallinity. These aspects make the Raman method amenable for the online monitoring of orientation and crystallinity in commercial processes. A molecular understanding of heat setting to reduce film shrinkage is also proposed. Raman data from films that were heat-set while physically constrained suggest that amorphous-phase relaxation does not occur during heat setting. Rather, the level of crystallinity increases substantially, indicating that the cause of low shrinkage in the films was due to crystalline network formation rather than amorphous-phase relaxation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2497–2505, 2001     

Molecular structure and orientation of gel‐spun polyethylene fibers

Characterization of molecular structure and orientation of six commercially available gel‐spun polyethylene fibers have been carried out using infra‐red and Raman spectroscopy, thermal and X‐ray diffraction analysis, together with optical microscopy techniques. Thermal and X‐ray diffraction analysis revealed the existence of highly oriented orthorhombic and monoclinic crystallites together with a highly oriented intermediate phase known as pseudohexagonal mesophase structure. The results suggest the existence of a three‐phase structure consisting, at room temperature, of orthorhombic and monoclinic polymorphic crystallites, oriented noncrystalline and un‐oriented noncrystalline (amorphous) phases, respectively. The crystallinity measurements have been carried out using density, thermal and X‐ray diffraction analysis together with infra‐red and Raman spectroscopy techniques whereas the molecular orientation measurements have been carried out using birefringence and polarized IR spectroscopy, respectively. The results obtained from density, thermal analysis, and Raman spectroscopy based on a simple two‐phase modeling approach lead to the overestimated amorphous fractions and appears to ignore the presence of an intermediate phase known as oriented noncrystalline structure. X‐ray analysis has also been used for the measurement of the apparent crystallite sizes. The birefringence values have been used to determine the overall orientation parameters whereas the dichroic measurements of IR bands have been used to determine the crystalline and oriented noncrystalline orientation parameters. The results show that the orthorhombic and monoclinic phases are more highly oriented than the oriented pseudohexagonally packed noncrystalline chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1317–1333, 2006     

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.     

Structure and dynamic mechanical properties of poly(ethylene terephthalate-co-4,4′-bibenzoate) fibers

Poly(ethylene terephthalate-co-4,4′-bibenzoate) (PETBB) fibers containing 5, 15, 35, 45, 55, and 65 mol% bibenzoate (BB) were melt spun. Fiber structure has been determined using wide angle X-ray diffraction, birefringence, and FTIR spectroscopy. When drawn to their respective maximum draw ratios, the structures and properties of high BB containing fibers (PETBB45, 55 and 65) are significantly different than those of PET and low BB containing fibers (PETBB5, 15, and 35). For example, 90% of the ethylene glycol units in high BB containing fibers are in the trans conformation, while only 80% of these units are in trans conformation in PET and low BB containing fibers. Overall orientation of the high BB containing fibers is higher (orientation factor f > 0.85) than those of PET and low BB containing fibers (f < 0.6). Orientation of the crystalline regions is quite high (f_cr ∼ 0.95) for both groups of fibers, while orientation of the amorphous regions (f_am) of high BB containing fibers is higher (∼0.8) than those of the PET and low BB containing fibers (∼0.4). High BB containing fibers exhibit much higher storage modulus and modulus retention with temperature than low BB containing fibers. Glass transition temperature determined from the dynamic loss tangent peak decreased with increasing BB content, while this transition completely disappeared in the high BB containing fibers. The magnitude of the secondary transition, observed at about −50 °C, decreased with increasing BB content. Another secondary transition, not observed in PET, was observed at about 70 °C in high BB containing fibers. These dynamic mechanical results have been rationalized in terms of the observed structural parameters.