Crystal deformation in aromatic polyesters

A study has been carried out of the changes in the x-ray diffraction patterns which occur when oriented fibers or tapes of poly(trimethylene terephthalate) (3GT) and poly-(tetramethylene terephthalate) (4GT) are subjected to mechanical tensile stress. Although the polymers show very different behavior in detail, in both cases comparatively large reversible lattice strains are observed (～ several %). The diffraction pattern of 3GT changes monotonically with increasing macroscopic strain, suggesting that the lattice responds immediately to the applied stress, and deforms as though it were a coiled spring. In 4GT, on the other hand, there is no detectable change in the x-ray diffraction pattern at low macroscopic strains, i.e., low values of the applied stress. At higher stresses, changes in the pattern occur which suggest a definite change in the crystal structure. Finally at the highest values of applied stress, the lattice deformations cease to increase. A preliminary discussion is presented of the relationship of these x-ray diffraction results to the mechanical stress–strain behavior.     

Deformation behavior of electrospun poly(L‐lactide‐co‐ε‐caprolactone) nonwoven membranes under uniaxial tensile loading

Biodegradable poly(L ‐lactide‐co‐ε‐caprolactone) copolymers with different L ‐lactide (LLA)/ε‐caprolactone (CL) ratios of 75/25 and 50/50 were electrospun into fine fibers. The deformation behavior of the electrospun membranes with randomly oriented structures was evaluated under uniaxial tensile loading. The electrospun membrane with a higher LLA content showed a significantly higher tensile modulus but a similar maximum stress and a lower ultimate strain in comparison with the membrane with a lower LLA content. The beaded fibers that formed in the membranes caused lower tensile properties. X‐ray diffraction and differential scanning calorimetry results suggested that the electrospun fine fibers developed highly oriented structures in CL‐unit sequences during the electrospinning process even though the concentration was only 25 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3205–3212, 2005     

Random-coil configurations of aromatic polyesters: Birefringence of poly(triethylene glycol terephthalate) networks in elongation

Hydroxyl-terminatd poly(triethylene glycol terephthalate) was crosslinked with an aromatic triisocyanate. Birefringence–stress–strain experiments, performed on the networks at 70°C, showed an anomalous increase in the modulus and a downturn in the birefringence–strain isotherms at high elongations. These results suggest that crystallinity is not responsible for the non-Gaussian behavior of the chains at high extension. The same kind of experiments were performed over the range 20–70°C. Values of the optical configuration parameter Δa of the order of 13.3 × 10^?24 cm³ with negligible temperature coefficient were found for these networks. The quantities Δa and d In Δa/dT were calculated by means of the rotational isomeric state model. Better agreement between the theoretical and experimental values of these parameters was found for poly(triethylene glycol terephthalate) than for poly(diethylene glycol terephthalate). Since the polarities of the two chains are similar, intermolecular interactions involving terephthaloyl residues may be responsible for the discrepancies observed between theory and experiment for Δa in aromatic polyesters.     

Correlation between the tensile properties and network draw ratio of CO2‐laser‐heated drawn poly(ethylene terephthalate) fibers

Low‐orientation and amorphous poly(ethylene terephthalate) fibers were drawn continuously with heating by carbon dioxide (CO₂) laser radiation. The tensile properties were examined in terms of the birefringence and network draw ratio, which was estimated from the strain shift of true stress–strain curves. Two drawing forms, neck drawing with a draw efficiency (the ratio of the network draw ratio to the actual draw ratio) of about unity and flow drawing with a draw efficiency of about zero, were found to be stable in the continuous drawing process. Meanwhile, any draw‐efficiency value between zero and unity could be obtained in the batch‐drawing process. The object whose orientation was estimated by the network draw ratio differed from that estimated by birefringence. Two linear relationships were found, between the network draw ratio and tensile strength and between the birefringence and initial modulus. The true stress at breaking increased with the network draw ratio of the CO₂‐laser‐heated drawn fibers, and when the draw ratio exceeded 5.0, it became higher than that for batch‐drawn fibers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2322–2331, 2003     

Change in Young’s modulus of poly(N-isopropylacrylamide) gels by volume phase transition

Mechanical properties of poly(N-isopropylacrylamide) (PNIPA) gels were examined both in swollen and collapsed state. Stress–strain curve of the gel in the swollen state was linear and the collapsed gel also showed almost linear stress–strain behavior. The initial Young’s modulus (E₀) in the collapsed state was much higher than that in the swollen state. The number of cross-links increased largely by the introduction of the physical cross-links due to collapse of the gels.     

Formation of micro-crystals in poly(ethylene terephthalate) fiber by a short heat treatment and their influence on the mechanical properties

The morphological change of poly(ethylene terephthalate) (PET) fibers by a short heat treatment under free-to-relax condition (i.e., without mechanical constraints imposed on the fibers during the treatment) was investigated. Heat treatment on polymeric fibers, in particular free-to-relax condition, has been known to lower the initial elastic modulus due to the relaxation of the amorphous molecules; however a short heat treatment at 190 °C for 1.2 s in the present study increased the initial modulus, whereas the yield strength was decreased significantly. During the short heat treatment, the PET molecules in the PET fibers were relaxed and became crystallized to some extent. The PET chains in the amorphous regions were also relaxed, promoting the formation of micro-crystals. These micro-crystals in the amorphous region can explain the increase in the initial modulus. The mechanism for such unusual behavior was investigated using mechanical tests, thermal stress analysis, wide and small angle X-ray diffraction, and FTIR spectrum analysis. Furthermore, a morphological model for the molecular arrangements in the PET fibers due to the short heat treatment is proposed, offering the possibility of developing PET fibers with shape retention function that can behave similarly to metal fibers.     

Crystallization in oriented poly(ethylene terephthalate) fibers. I. Fundamental aspects

The nature of crystallization- and mobility-induced changes during annealing of melt-spun poly(ethylene terephthalate) precursor fibers of a range of orientations has been examined. The kinetics of crystallization and the accompanying orientational changes have been studied under conditions of constant, low tensile stress, with the accompanying dimensional changes and under a constraint against shrinkage in length, with the stress developed being monitored. The effects of precursor orientation and externally imposed constraints on the course of the fundamental crystallization and orientational relaxation processes are revealed. Oriented crystallization has been shown to have a significant effect on the stress developed and on the dimensions of oriented precursor fibers, with a strong tendency to spontaneously extend as a consequence of the reorientation of crystallizing segments predominantly along the preferred fiber direction. The sequence in which crystallization and major orientational relaxation, if any, occur is found to have a profound effect on the structure and thus the deformability of oriented fibers after annealing above the glass transition temperature.     

Does the strain hardening modulus of glassy polymers scale with the flow stress?

Using a generic coarse‐grained bead‐spring model, Hoy and Robbins reproduced important experimental observations on strain hardening, specifically the generally observed Gaussian strain hardening response and its dependence on network density and temperature. Moreover, their simulation results showed that the strain hardening response at different strain rates collapses to a single curve when scaled to the value of the flow stress, a phenomenon that has not yet been verified experimentally. In the present study, the proposed scaling law is experimentally investigated on a variety of polymer glasses: poly(methyl methacrylate), poly(phenylene ether), polycarbonate, polystyrene, and poly(ethylene terephthalate)‐glycol. For these polymers, true stress–strain curves in uniaxial compression were collected over a range of strain rates and temperatures and scaled to the flow stress. It was found that, generally, the curves do not collapse on a mastercurve. In all cases, the strain hardening modulus is observed to increase linearly, but not proportionally to the flow stress. The experimental data, therefore, unambiguously demonstrate that the proposed scaling law does not apply within the range of temperature and strain rate covered in this study. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2475–2481, 2008     

Drawing behavior and characteristics of laser‐drawn polypropylene fibers

Drawing behavior, flow drawing, and neck drawing, was studied for isotacticpolypropylene fibers in CO₂ laser drawing system, and the fiber structure and the mechanical properties of drawn fibers were analyzed. For a certain laser power, flow drawing of polypropylene (PP) was possible up to draw ratio (DR) 19.5. Though the drawing stress was very low, the flow‐drawn PP fiber exhibited oriented crystal structure and improved mechanical properties. On the other hand, neck‐drawing was accomplished from DR 4 to 12, with significant increase in drawing stress that enhanced the development of fiber structure and mechanical properties. Unlike PET, the drawing stress depends not only on the DR, but on irradiated laser power also. The 10–12 times neck‐drawn fibers were highly fibrillated. The fibers having tensile strength 910 MPa, initial modulus 11 GPa, and dynamic modulus 14 GPa were obtained by single‐step laser drawing system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 398–408, 2006     

Thermal shrinkage of oriented semicrystalline poly(ethylene terephthalate)

The shrinkage of commercial oriented poly(ethylene terephthalate) filaments was studied within the framework of the kinetic theory of rubberlike elasticity. Previous workers had found that the shrinkage and optical behavior of amorphous polymers could be satisfactorily explained in terms of this theory. Such an analysis is now applied to semicrystalline samples of moderate and high draw ratios (from 2× to 6×). It was found in this work that the thermal shrinkage force behavior as well as the optical anisotropy as a function of stretch can be explained in terms of the theory of rubberlike elasticity, if the following reasonable assumption is made: the average number of statistical segments per network chain in the noncrosslinked sample increases as a function of the draw ratio. A possible mechanism for such behavior is the relaxation of some of the chain entaglements due to the strain imposed externally on the fiber.     

Relationship of deformation behavior to thermal transitions of ethylene/styrene and ethylene/octene copolymers

The stress‐strain response of low‐crystallinity ethylene‐octene (EO) and ethylene‐styrene (ES) copolymers with 7–20 mol % comonomer was compared over a temperature range that spanned the glass‐transition and crystal melting regions. Above the onset temperature of the glass transition, the copolymers exhibited elastomeric behavior with low initial modulus, uniform deformation to high strains, and high recovery after the stress was released. In the glass‐transition range, an initial low‐stress elastomeric response was followed by a distinct “bump” in the stress‐strain curve. On the basis of the temperature and rate dependence of the stress‐strain curve, local strain‐rate measurements, local temperature changes, and recovery characteristics, the “bump” was identified as high strain yielding. Hence, the stress‐strain curve sequentially exhibited the features of elastomeric and plastic deformation. Following high strain yielding, strain hardening dramatically increased the fracture strength. This behavior was defined as elastomeric‐plastic. Elastomeric‐plastic behavior in the broad glass‐transition range constituted a gradual transition from elastomeric behavior at higher temperatures to low‐temperature plastic behavior with high modulus and macroscopic necking. Because of the lower glass‐transition temperature of EO, ?40 °C as compared with ?10 °C for ES, the onset of elastomeric‐plastic behavior occurred at a significantly lower temperature. The concept of a network of flexible chains with fringed micellar crystals serving as the multifunctional junctions that provides the structural basis for elastomeric behavior of low‐crystallinity ethylene copolymers was extended to elastomeric‐plastic behavior by considering a network with a fraction of rigid, glassy chains. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 142–152, 2002     

高取向聚对苯二甲酸乙二酯纤维的热收缩应力

为得到具有更高拉伸强度和模量的半晶聚合物纤维,需要使分子链充分结晶和取向,然而这种高度取向样品受热时,随着温度的升高,取向的非晶态分子链熵力增大,解取向可以自发进行.在外加张力较小时,纤维产生热收缩;在定长状态下,表现为外加张力增大,此过程被视为取向材料中＂冻结＂内应力的释放,通常将这种内应力称为热收缩应力。     

Grafting on wool. II. Stress–strain behavior of grafted fiber in water

The stress–strain behavior and hysteresis properties of various grafted wool fibers were studied. Three distinct regions on the stress–strain curve and hysteresis properties characteristic of the native wool fiber remain substantially intact, even though a large amount of a rigid polymer occurs. It was suggested that the microfibril and the matrix nature in the native wool fiber exist in the grafted wool structures. The electron microscopic results were also supported. These results can be explained on the basis of Menefee's model that the longitudinal mechanical behavior is more directly controlled by a high modulus matrix.     

Viscoelasticity of oriented poly(ethylene terephthalate)

Time–temperature superposition can be successfully applied to both the stress relaxation and dynamic mechanical properties of oriented PET fibers. Two curves result; one is the time dependence of the modulus at constant temperature, while the other is the shift, log aT, of this curve along the time scale as a function of temperature. This temperature dependence is less than that for both unoriented PET and typical amorphous polymers above T_g. It is about the same as that for oriented nylon 66 and unoriented glassy poly(methyl methacrylate). The isothermal modulus has the same time dependence as that of the unoriented PET; however, it is a factor of 3.3 larger. The modulus curve is almost identical in both shape and magnitude with that of oriented nylon 66. However, a temperature of 82°C. is required to place the viscoelastic dispersion region of PET at the same time scale as nylon 66 at 25°C. This temperature increase is the major difference in viscoelasticity between these two oriented polymers.     

取向聚对苯二甲酸乙二酯纤维的非等温结晶动力学

取向聚对苯二甲酸乙二酯纤维的非等温结晶动力学张志英，赵家森（天津纺织工学院材料科学系天津３００１６０）关键词取向高聚物，聚对苯二甲酸乙二酯，非等温结晶，结晶动力学研究高聚物结晶动力学常用的等温方法有光透射法、密度法、显微镜法、Ｘ－射线衍射法、差示扫描...     

Extrusion,fiber formation,and characterization of thermotropic copolyesters

The flow behavior and the effect of the spinning conditions on the fiber properties and structure of poly(ethylene terephthalate) modified with 60 mol% p-hydroxybenzoic acid (PET/60PHB) were investigated. PET and its copolyesters with 28 and 80 mol% PHB were used as control samples. The melt of PET/60PHB at temperatures above 265°C exhibited extremely low viscosity and low flow activation energy. High birefringence, indicating the presence of a mesophase, was observed between 265 and 300°C on a hot-stage polarizing light microscope. The maximum tensile strength and initial modulus, 438 MPa and 37 GPa, respectively, were obtained at 275°C for a 0.69 IV polymer. The fiber strength and modulus were significantly lowered when extrusion was conducted at temperatures below 265°C. The fiber properties could also be improved when a high extrusion rate and/or a high draw down ratio was used. Scanning electron microscopy revealed that the fibers spun at temperatures above 265°C had a well-developed, highly oriented fibrillar structure. The fibers spun at lower temperatures, however, were poorly oriented and nonfibrillar in character. The high orientation and superior mechanical performance achieved at high temperatures were attributed to the presence of the nematic mesophase in the polymer melt.     

Microstructure and mechanical properties of hot‐air drawn poly(ethylene terephthalate) fibers

Hot‐air drawing method has been applied to poly(ethylene terephthalate) (PET) fibers in order to investigate the effect of strain rate on their microstructure and mechanical properties and produce high‐performance PET fibers. The hot‐air drawing was carried out by blowing hot air controlled at a constant temperature against an as‐spun PET fiber connected to a weight. As the hot air blew against the fibers weighted variously at a flow rate of about 90 ℓ/min, the fibers elongated instantaneously at a strain rate in the range of 2.3–18.7 s⁻¹. The strain rate in the hot‐air drawing increased with increasing drawing temperature and applied tension. When the hot‐air drawing was carried out at a drawing temperature of 220°C under an applied tension of 27.6 MPa, the strain rate was the highest value of 18.7 s⁻¹. A draw ratio, birefringence, crystallite orientation factor, and mechanical properties increased as the strain rate increased. The fiber drawn at the highest stain rate had a birefringence of 0.231, degree of crystallinity of 44%, tensile modulus of 18 GPa, and dynamic storage modulus of 19 GPa at 25°C. The mechanical properties of fiber obtained had almost the same values as those of the zone‐annealed PET fiber reported previously. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1703–1713, 1999     

Fiber property and structure development of polyester blend fibers reinforced with a thermotropic liquid‐crystal polymer

Ternary blend fibers (TBFs), based on melt blends of poly(ethylene 2,6‐naphthalate), poly(ethylene terephthalate), and a thermotropic liquid‐crystal polymer (TLCP), were prepared by a process of melt blending and spinning to achieve high‐performance fibers. The reinforcement effect of the polymer matrix by the TLCP component, the fibrillar structure with TLCP fibrils of high aspect ratios, and the development of more ordered and perfect crystalline structures by an annealing process resulted in the improvement of the tensile strength and modulus for the TBFs. An increase in the apparent crystallite size with the spinning speed was attributed to the development of larger crystallites and more ordered crystalline structures in the annealed TBFs. The birefringence and density of the TBFs increased with increasing spinning speed, the TBFs becoming more oriented and the crystal packing becoming more enhanced. The molecular orientation was an important factor in determining the tensile strength and modulus of the TBFs. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 395–403, 2004