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     

Thermal conductivity of ramie fiber drawn in water in low temperature

To understand the effect of extension of molecular chain in amorphous region in polymer fibers to thermal conductivity, the thermal conductivity, tensile modulus and crystal orientation angle of ramie fibers and those drawn by the stress of 17.4 kg/mm² (water treatment) in the water were investigated. The tensile modulus of ramie fiber in fiber direction increased from 61 to 130 GPa by drawing in the water. The crystal orientation angles of ramie fiber with and without water treatment were measured by X‐ray diffraction. The orientation degrees of ramie fibers without and with water treatment were estimated as 92.9 and 93.6%, respectively. Therefore, the tensile modulus increases two times as that of blank ramie by water treatment although crystal orientation angle does not change distinctly. The increasing of tensile modulus of ramie fiber by water treatment was explained by extension of the molecular chains in the amorphous region. Thermal conductivities of ramie fibers with and without water treatment were measured in the fiber direction in the temperature range from 10 to 150 K. Thermal conductivity of ramie fiber in the fiber direction increased by water treatment. The increasing ratio of thermal conductivity by water treatment agreed to that of sound velocity induced by increasing tensile modulus. Those results suggest that thermal conductivity of polymer fiber increase by the extension of molecular chains in the amorphous region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2196–2202, 2006     

Flexural fatigue behavior of injection-molded composites based on poly(phenylene ether ketone)

Flexural fatigue tests were conducted on injection-molded short fiber composites, carbon fiber/poly(phenylene ether ketone) (PEK-C) and glass fiber/PEK-C (with addition of polyphenylene sulfide for improving adhesion between matrix and fibers), using four-point bending at stress ratio of 0.1. The fatigue behavior of these materials was presented. By comparing the S-N curves and analyzing the fracture surfaces of the two materials, the similarity and difference of the failure mechanisms in the two materials were discussed. It is shown that the flexural fatigue failure of the studied materials is governed by their respective tensile properties. The matrix yielding is main failure mechanism at high stress, while at lower stress the fatigue properties appear fiber and interface dominated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1857–1864, 1997     

Tensile deformation of nylon 6 fibers

Nylon 6 fibers which had been relaxed to different extents by annealing were examined at fixed strains by small angle and wide angle X-ray techniques. It was found that the strain of the long period of the semicrystalline microfibrils is identical to the macroscopic fiber strain. Approximately 1/3 of the tensile deformation results from molecular shear of imperfectly oriented crystalline chains. Virtually no evidence for intercrystalline slip is found; the orientation of the intercrystalline amorphous regions results in a low compliance for the shear of crystals past one another. The majority of the microfibril deformation occurs by stretching these intercrystalline amorphous regions, accompanied by the flow of extrafibrillar amorphous material to maintain constant volume. In highly annealed fibers this “filling” mechanism is less efficient, as the amount of extrafibrillar material has been reduced during shrinkage. This effect leads to a decrease in Poisson's ratio after increasingly severe annealing. A related result of annealing is the dehomogenization of the microstructure, leading to the presence of more stress-induced “microcracks” during the stretching of annealed fibers.     

Fatigue behavior and relation between fatigue resistance and tensile properties of poly(para-phenylene-co-3,4'-oxydiphenylene terephthalamide) fiber

The poly(para-phenylene-co-3,4′-oxydiphenylene terephthalamide) (PPODTA) fiber is one of the high strength organic fibers, and it has been reported that the PPODTA fiber has superior fatigue resistance. The high strength fibers are used in the applications to utilize their high mechanical properties in general. Therefore, the long-term durability of these fibers is also required. In this study, the fatigue tests were conducted for the PPODTA fibers. As a result, it was found that the PPODTA fibers were able to be fractured by the cyclic tensile stress, and the fatigue behavior was influenced by the stress conditions. In addition, the single fiber tensile tests were also conducted for the PPODTA fibers, and the relation between the tensile properties and the fatigue resistance of the PPODTA fiber was investigated. The fatigue resistance of the PPODTA fiber was increased with the decrease of the fiber diameter and the increase of the tensile modulus.     

Fundamental influences on quasistatic and cyclic material behavior of short glass fiber reinforced polyamide illustrated on microscopic scale

In this work, the influences of fiber orientation and weld lines on the morphological structures and the mechanical behavior of polyamide 6.6 (PA6.6‐GF35) are investigated. In quasistatic and fatigue tests tensile and 3‐point‐bending loads are applied. Test temperatures vary between RT and 150°C. Two different specimen types are produced by using injection moulding process to create different fiber orientations as well as weld lines. Fiber orientations are determined using computer tomography. Scanning electron microscopy is used to investigate fracture surfaces of tested specimens. Results show that mechanical properties and morphological structures depend highly on fiber orientation and temperature. Transversely oriented fibers in weld lines result in brittle failure mechanisms and decreased mechanical properties. Different stress distributions in the specimens under tensile and flexural loads have influence on the material behavior as well. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40842.     

Control of molecular orientation

I. Amorphous polymers . The mechanical performance of a glassy amorphous polymer is strongly dependent upon molecular orientation. The pattern of molecular orientation is governed by the kinematics (and temperature) of mechanical forming operations. Three types of controllable orientation are: (a) uniaxial, (b) biaxial, and (c) “crossed.” The optimum pattern of orientation in a part is one which is appropriate for the mechanical stresses encountered in service. For a fiber subjected to tensile and bending loads, uniaxial orientation is appropriate. A shell structure, subjected to multiaxial stresses, requires either biaxial or crossed orientation for maximum performance. As a rule, the maximum achievable multidirectional strength in such a structure is less than the maximum strength of a uniaxially oriented fiber. II. Crystalline polymers . Oriented crystalline polymer structures can be created in two distinct ways. An isotropic polycrystalline polymer can be deformed below the melting point, with extensive reorganization of the crystal morphology, or an oriented amorphous melt can undergo crystallization to yield oriented crystalline polymer. Performance of an oriented semicrystalline polymer depends upon orientation of the amorphous portion as well as orientation of the crystallites. As with amorphous polymers, orientation can be uniaxial, biaxial, or crossed. “Orientation” usually denotes c-axis orientation only, but drawing followed by rolling can result in double orientation—orientation of a-axis, b-axis, and c-axis.     

Nonuniform cooling in multifilament melt spinning of polypropylene fibers: Cooling air speed limits and fiber-to-fiber variations

The cooling of the spinning stage in a commercial compact-spinning line has been studied. A rectangular fiber bundle is extruded from the spinneret and cooled by air entering from one side. The speed of the cooling air is considerably reduced through the fiber bundle. There are practical lower and upper limits for the cooling air entrance speed, corresponding to filament breakage at the leeward and windward sides, respectively. These limits are functions of the material and processing parameters. Due to the nonuniform cooling, fibers sampled at the windward side generally have higher molecular orientation, lower amorphous fraction, higher density, and higher tensile modulus and strength. For most combinations of spinning and material parameters, the structure is either bimodally oriented α-crystalline or uniaxially oriented mesomorphic at all spinneret positions. Fibers with different structure types show opposite windward/leeward side trends with regard to local order and melting behavior. The structure may be mesomorphic at the leeward side and α-crystalline at the windward side, if the average spin-line stress is close to a critical value for orientation-induced crystallization, and the air speed difference across the spinneret is large. The cooling air speed affects the spin-line stress. Hence, the fiber-to-fiber variations due to nonuniform cooling are discussed in terms of the molecular orientation in the melt and the effective time available for arranging molecules into ordered structures. © 1995 John Wiley & Sons, Inc.     

Fabrication of Surlyn ionomer fibers using a novel coextrusion approach and mechanical property characterization

We report the fabrication of poly (ethylene-co-methacrylic acid) sodium-neutralized ionomer (Surlyn 8940) fibers via a forced-assembly coextrusion and layer multiplication process with polystyrene (PS) as the matrix material. The PS separating materials were removed by toluene extraction to yield independent Surlyn fibers. The tensile properties of Surlyn fiber strands were studied under different strain rates. Surlyn fibers were oriented to 300% strain at different temperatures to study the effect of orientation on the tensile properties. The oriented Surlyn fibers were annealed after orientation to further enhance the mechanical properties. Further drawing of these oriented fiber mats to a draw ratio of 4 at 60 °C followed by annealing at 60 °C can afford moduli in excess of 350 MPa and tensile strengths in excess of 70 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48046.     

Study of the microstructure formation mechanisms of poly(ether-ether-ketone) monofilaments via melt spinning

The microstructure formation mechanism of melt-spun Poly(ether-ether-ketone) monofilaments during poststretching was investigated using in-situ wide-angle X-ray diffraction in combination with polarizing microscopy, differential scanning calorimetry and universal testing machine. As PEEK monofilaments were stretched at 210°C, the crystallinity and microcrystal size first increased during the insulation state (Is-S), then decreased during the poststretching state (Ps-S), and further increased during the postcooling state (Pc-S), at last were observed to selective orientation. At 210°C, the anisotropically aligned molecular chains reach a meritocratic orientation in the stress direction under 4.0 times drawing conditions, resulting in the highest tensile strength and modulus. As the stretching ratio increases, the crystallinity and microcrystal size first increase during Pc-S and then decrease due to the effect of the stretched molecular chains on crystal growth and the degree of tearing in the crystalline region. The molecular chains of PEEK monofilaments stretched by uniaxial stress are aligned more flatly and uniformly along the fiber axis. We hope that this work will provide advice and guidance for the industrial production of high-performance fibers.     

Preparation of high-strength and high-modulus poly(vinyl alcohol) fibers by crosslinking wet spinning/multistep drawing method

This study is mainly focused on the preparation of high-strength and high-modulus poly(vinyl alcohol) (PVA) fibers by crosslinking wet spinning and multistep drawing. High strength as well as high modulus can be achieved by introduction of the crosslinks into the oriented chains to reduce entanglement degree and slippage between chains. The relationships between mechanical properties and fine structure of the drawn fibers were examined based on results of measurements of tensile property, thermal property, dynamic viscoelasticity, crystallinity, and orientation. The strength and Young's modulus of the drawn fibers are approximated to 1.82 and 51.76 GPa, respectively. The fiber has a sharp melting peak temperature that appeared at 236.7°C in the differential scanning calorimeter (DSC) curve. Our results indicate the multistep drawing procedure is superior to the conventional one-step drawing procedure. These excellent mechanical properties can be directly attributed to their high orientation of the amorphous chains. © 1994 John Wiley & Sons, Inc.     

聚醋酸乙烯醇解纺丝纤维聚集态结构的研究

用ＷＡＸＤ,ＳＡＸＳ研究了聚醋酸乙烯（ＰＶＡｃ）醇解纺丝过程中不同部位和不同干热拉伸倍数的聚乙烯醇（ＰＶＡ）纤维的聚集态结构。证明该法所得到的初生纤维为凝胶态,随干热拉伸倍数增加,取向度和结晶度随之增大。经高倍拉伸后,晶粒变得细长,且沿纤维轴取向,晶区和非晶区电子密度差减少,长周期增大、纤维中分子链趋近于伸直链结晶结构。     

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.     

Structure and deformation of an elastomeric propylene–ethylene copolymer

The elastic behavior of a propylene–ethylene copolymer was investigated. An initial “conditioning” tensile extension up to 800% strain resulted in an elastomer with low initial modulus, strong strain hardening, and complete recovery over many cycles. Structural changes that occurred in the low crystallinity propylene–ethylene copolymer during conditioning, and that subsequently imparted elastomeric properties to the conditioned material, were investigated. Thermal analysis, wide and small angle X‐ray diffraction, and atomic force microscopy measurements were performed at various strains during the conditioning process. Conditioning transformed crystalline lamellae into shish‐kebab fibers by melting and recrystallization. The fibers, accounting for only 5% of the bulk, were interconnected by a matrix of entangled, amorphous chains that constituted the remaining 95%. It was proposed that the shish‐kebab fibers acted as a scaffold to anchor the amorphous rubbery network. Entanglements of the amorphous chain segments acted as network junctions and provided the elastic response. The stress–strain response of materials conditioned to 400% strain or more was described by the classical rubber theory with strain hardening. The extracted value of M_c, the molecular weight between network junctions, was intermediate between the entanglement molecular weights of polypropylene and polyethylene. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 489–499, 2007     

Effect of intercrystallite straight-chain segments on Young's modulus of gel-spun polyethylene fibers

The tensile stress and Young's modulus of a series of gel-spun polyethylene fibers were measured in parallel to measurements of transverse and longitudinal sizes of crystallites, molecular orientation and straight-chain-segment (SCS) length distribution in order to find the correlation of the mechanical and microstructural characteristics during drawing. The low-frequency-Raman data evidence the predominance of the chain-straining process on the ends of crystallites. As a result, there appears a rigid intermediate substance (rigid amorphous phase (RAP)) between crystal cores and true amorphous phase. The RAP is composed of various-lengths SCS oriented in the fiber axis direction and arranged without longitudinal ordering. The RAP transforms gradually to uniform-length taut-tie molecules (TTM). The Young's modulus correlates to the increase of the RAP in length, but there were no detectable response of the mechanical parameters to the formation of the TTM.     

Stretching-induced deformation of polyacrylonitrile chains both in quasicrystals and in amorphous regions during the in situ thermal modification of fibers prior to oxidative stabilization

In situ thermal stretching to modify the conformation of polyacrylonitrile (PAN) chains in quasicrystals and amorphous regions is carried out on PAN copolymer fibers prior to oxidative stabilization. Meanwhile, a model to evaluate the deformation of PAN quasicrystals and amorphous regions is proposed, in which deformation behavior (orientation or extension) and type (elastic or plastic) in the two regions are analyzed. PAN chains exhibit various deformations as a consequence of combined thermal treatment and mechanical stretching. The orientation of PAN chains occurs prior to their extension when the stretching ratio is under 1.06, however, no significant orientation but extension is observed when the deformation ratio ranges from 1.08 to 1.16. As the stretching ratio increases, elastic-dominated orientation of PAN chains is stronger in quasicrystals before 1.03 and is prominent in amorphous regions between 1.04 and 1.08. The mechanical properties of the resulting carbon fibers strongly depend on the orientation degree of PAN chains in amorphous regions.     

Polyimide fibers prepared by a dry‐spinning process: Enhanced mechanical properties of fibers containing biphenyl units

Polyimide (PI) fibers with enhanced mechanical properties and high thermal and dimensional stability were prepared via a two‐step dry‐spinning process through the introduction of 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride (BPDA) containing biphenyl units into rigid homopolyimide of pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline. The attenuated total reflectance–Fourier transform infrared spectra results imply that the incorporated BPDA moieties accelerate the imidization process and increase the imidization degree (ID) of the precursor fibers; this was attributed to the increased molecular mobility of the polymer chains. Two‐dimensional wide‐angle X‐ray diffraction spectra indicated that the prepared PI fibers possessed a well‐defined crystal structure and polymer chains in the crystalline region were highly oriented along the fiber axis. The PI fiber, with the molar ratio of PMDA/BPDA being 7/3, showed optimum tensile strength and modulus values of 8.55 and 73.21 cN/dtex, respectively; these were attributed to the high IDs and molecular weights. Meanwhile, the PI fibers showed better dimensional stability than the commercial P84 fiber, and this is beneficial for its security applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43727.     

Change of molecular aggregation state in amorphous region with uniaxial extension of preoriented polypropylene

Preoriented isotactic polypropylene was uniaxially drawn at various testing directions and testing temperatures. Change of the molecular aggregation state in amorphous region with extension was elucidated by measurements of melting temperature, enthalpy of fusion, and birefringence at each stage of extension. Melting temperature depends on both crystallite thickness and orientation function of amorphous chains. It is assumed that the enthalpy change of amorphous region takes place when oriented amorphous chains are transformed into random state by heating. The ratio of the enthalpy change of amorphous region in the sample after extension to that in the sample before extension monotonously increased with increasing orientation function of amorphous chains, f_a, independent of testing direction and testing temperature. Increase of true stress with drawing led to increase of f_a. Increase of f_a with extension depended on the testing angle θ between the testing direction and the direction of the crystal c-axis of the preoriented sample, and f_a most remarkably increased in extension at θ = 45°.     

Mechanical properties,stress‐relaxation,and orientation of double bubble biaxially oriented polyethylene films

Biaxially oriented linear low density polyethylene (LLDPE) films were produced using the double bubble process with different machine direction (MD) orientation levels and the same transverse direction (TD) blow‐up ratio. Their mechanical behavior was characterized in terms of the tensile strength and tear resistance. The viscoelastic behavior of oriented films was studied using dynamic‐mechanical thermal analysis (DMTA). The microstructure and orientation were characterized using microscopy, X‐ray diffraction pole figures, and birefringence. The results indicate that MD ultimate tensile strength increases and the TD one decreases with MD stretching ratio. Tear propagation resistance, in general, remained mainly constant in TD and decreased in MD, as the draw ratio was increased. The morphology analyses exhibit a typical biaxial lamellar structure for all samples with different lamellar dimensions. Orientation of c‐axis in crystalline phase, molecular chain in amorphous phase along MD increased with draw ratio. In most crystals, a‐axis was located in the normal direction (ND) and the b‐axis in the ND–TD plane. A good correlation was observed between c‐axis orientation factor and MD mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3545–3553, 2006