Structure and property development of aromatic copolysulfonamide fibers during wet spinning process

The structure and performance changes of aromatic copolysulfonamide (co‐PSA) fibers that occurred during wet spinning process have been studied. While using different length scale characterization, including scan electron microscopy (SEM), wide‐angle X‐ray scattering (WAXS), and small‐angle X‐ray scattering (SAXS), it was found that the molecular chains of co‐PSA formed an isotropic network during coagulation which further lead to extension and orientation of these chains during the subsequent stretching. As a result, only after heat stretching and heat setting the molecular chains tended to pack into crystal lattice in the fibrils. This gave rise to a much denser structure along the spinning line and the glass transition temperature of co‐PSA fibers increased a little after heat setting. Before heat stretching, the co‐PSA fibers were in amorphous state, and only the amorphous orientation was observed within the fibers. After heat stretching at the temperature higher than T_g, the fraction of amorphous region decreased, and the crystal structure formed in the fibers, which became more perfect during heat setting. The structure development during spinning process contributed toward the improvement of thermo‐mechanical stability, tenacity and modulus of the co‐PSA fibers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42343.     

pH‐responsive fibers based on acrylonitrile acrylic acid block copolymers: Effect of spinning conditions and postspinning operations on response and mechanical properties

pH sensitive poly(acrylonitrile‐co‐acrylic acid) having ～50 mol % acrylic acid with block type structure (AA50B) was synthesized by controlled dosing method of free radical polymerization. The polymer was converted into fibers by wet solution spinning technique in DMF‐water system. The resulting block type copolymer could generate a domain type morphology with segregated domains of acrylonitrile and acrylic acid on heat‐setting. The drawing ratio and heat‐setting temperature had a significant effect on the formation of these domains and their stability. The domain formation was more pronounced when the fibers could be drawn to higher draw ratios during coagulation or heat‐set at higher temperature. The stability of the fibers, which is influenced by domain formation, was lowest (at few cycles of transitions) when the fibers were heat‐set at 100°C, while it is improved significantly to more than 50 cycles as the heat‐setting temperature was increased to 150°C. The coagulation conditions, drawing and the heat‐setting also greatly influenced the mechanical properties, transition behavior, and retractive stresses of the responsive fibers. The tenacity improved by 6.6 times in swollen state and 1.4 times in deswollen state, while the retractive stresses during deswelling were significantly increased to about 4.7 times. However, the increased heat‐setting temperature was also found to have a negative effect on the equilibrium swelling values as well as the response rate. The effect of heat‐setting on chemical structure of the copolymer was also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

High modulus polypropylene fibers. II. Influence of fiber preparation upon structure and morphology

The influence of drawing on the limiting draw ratio upon formation of the morphological structure of fibers spun from binary polypropylene (PP) blends was studied. Fibers were spun from a fiber‐grade CR‐polymer and from the blends of a fiber‐grade CR‐polymer with a molding‐grade polymer in the composition range of 10–50 wt % added. As‐spun fibers were immediately moderately and additionally highly drawn at the temperature of 145°C. The structure and morphology of these fibers were investigated by small‐angle X‐ray scattering, wide‐angle X‐ray scattering, differential scanning calorimetry, scanning electron microscopy, density, birefringence, and sound velocity measurements. It was shown that continuously moderately drawn fibers are suitable precursors for the production of high tenacity PP fibers of very high modulus, because of so called oriented “smectic” structure present in these fibers. With drawing at elevated temperature, the initial metastable structure of low crystallinity was disrupted and a c‐axis orientation of monoclinic crystalline modification was developed. Hot drawing increased the size of crystallites and crystallinity degree, the orientation of crystalline domains, and average orientation of the macromolecular chains and resulted in extensive fibrillation and void formation. It was found that the blend composition has some influence on the structure of discontinuously highly drawn fibers. With increasing the content of the molding‐grade polymer in the blend, the size of crystalline and amorphous domains, density and crystallinity, as well as amorphous orientation decreased. Relationship has been established between the mechanical properties, crystallinity, and orientation of PP fibers. It was confirmed that by blending the fiber‐grade CR‐polymer by a small percentage of the molding‐grade polymer, maximization of elastic modulus is achieved, mainly because of higher orientation of amorphous domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1067–1082, 2006     

Poly(butylene succinate) ionomers and their use as compatibilizers in nanocomposites

A series of low‐molecular‐weight poly(butylene succinate‐co‐glutarate‐co−2‐trimethylammonium chloride glutarate) terpolyester ionomers containing 35% mol of total glutarate units but varying in the content of charged units were synthesized by polycondensation at mild temperatures using a scandium catalyst. The terpolyester ionomers started to decompose at the temperatures of >175°C and all of them were semicrystalline and have glass transition temperature similar to poly(butylene succinate) (PBS). These terpolyesters were used to compatibilize the nanocomposites made of PBS‐cloisite (CL) prepared by melt extrusion. X‐ray diffraction revealed that an intercalated structure was present in these nanocomposites. The thermal properties of the three‐component mixtures did not differ substantially from those of PBS–CL but the mechanical properties were significantly improved by the addition of the ionomer, in particular tenacity. The beneficial effect afforded by the terpolyester ionomer was attributed to its ability for strengthening the binding between the PBS and the nanoclay. POLYM. COMPOS., 37:2603–2610, 2016. © 2015 Society of Plastics Engineers     

Evaluation of the microstructure and melting behavior of drawn polypropylene fibers with a microthermal analyzer

The strong correlation of melting behavior with the microstructure of original and zone‐drawn isotactic polypropylene fibers was evaluated by microthermal analysis (micro‐TA) combined with wide‐angle X‐ray diffraction analysis. The crystal structure of both the original and zone‐drawn fibers was a monoclinic α‐form with a ～ 0.64 nm, b ～ 2.03 nm, and c ～ 0.65 nm. In contrast to the absence of any oriented polymer molecules in the original fiber, the polymer molecules in the zone‐drawn fiber were extended and highly oriented in at least two different states; one arranged along the drawn axis and the other at 40° to the drawn axis. The micro‐TA‐derived melting points corresponded to these microstructural changes caused by the zone‐drawing process and differed from the melting points obtained by differential scanning calorimetery. The micro‐TA melting point of 140°C corresponded to the z‐e‐p melting point of the original fiber, being much lower than the conventional differential scanning calorimetery melting point of 163°C. As for the zone‐drawn fiber, an increase of 19°C in the melting temperature revealed its high orientation level, and the appearance of three elevated melting peaks (161, 167, and 178°C) at the highest heating rate (1500°C/min) coincided with its several oriented states. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1306–1311, 2006     

High tensile strength fiber of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] processed by two‐step drawing with intermediate annealing

High tensile strength fibers of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] [P(3HB‐co‐3HH)], a type of microbial polyesters, were processed by one‐step and two‐step cold‐drawn method with intermediate annealing. Thermal degradation behaviors were characterized by differential scanning calorimeter and gel permeation chromatography measurements. Thermal analyses were revealed that molecular weights decreased drastically within melting time at a few minute. One‐step cold‐drawn fiber with drawing ratio of 10 showed tensile strength of 281 MPa, while tensile strength of as‐spun fiber was 78 MPa. When two‐step drawing was applied for P(3HB‐co‐3HH) fibers, the tensile strength was led to 420 MPa. Furthermore, the optimization of intermediate annealing condition leads to enhance the tensile strength at 552 MPa of P(3HB‐co‐3HH) fiber. Wide‐angel X‐ray diffraction measurements of these fibers suggest that the fibers with high tensile strength include much amount of the planer‐zigzag conformation (β‐form) as molecular conformation together with 2₁ helix conformation (α‐form). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41258.     

Structural evaluation and mechanical property of boron nitride fibers during melt‐drawn fabrication process

Boron nitride (BN) fibers were fabricated on a large scale through the melt‐drawn technique from low‐cost boric acid, NH₃, and N₂. Evolution of structure and properties of BN fibers during the fabrication process was studied by Fourier transform infrared (FT‐IR), X‐ray diffraction (XRD), scanning electron microscope (SEM), and X‐ray photoelectron spectroscopy (XPS). The mechanical properties of BN fibers were tested and analyzed. The results shown that both the mechanical properties and the crystallinity of BN fibers slightly increased with the temperature from 450 to 850°C, due to the combination of the fused‐B₃N₃. For BN fibers heat‐treated at 850 or 1000°C, the tensile strength (σ^R) and elastic modulus (E) were strongly increased because of the increase in crystallization of the BN phase. The meso‐hexagonal BN fibers with a diameter of 5.0 μm were fabricated at 1750°C, of which the tensile strength (σ^R) and elastic modulus (E) are 1200 MPa and 85 GPa, respectively. BN fibers with excellent mechanical properties and proper diameters were obtained by nitriding of green fibers during their conversion into ceramic.     

Structure and properties of aromatic poly(benzimidazole‐imide) copolymer fibers

A series of co‐polyimide fibers were prepared by thermal imidization of copolyamic acids derived from 3,3′,4,4′‐biphenyltertracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) in various molar ratios with 2‐(4‐aminophenyl)?5‐aminobenzimidazole (BIA). The dynamic mechanical behaviors of these polyimide (PI) fibers revealed that the glass transition temperature (T_g) was significantly improved upon increasing PMDA content. Heat‐drawing process led to dramatic change on the glass transition behavior of BPDA/BIA system, but had a small impact on BPDA/PMDA/BIA co‐polyimide fibers. This difference for PI fibers is attributed to the different degree of ordered structure of the fibers affected by heat‐drawing. The incorporation of PMDA obviously improved the dimensional stability against high temperature, due to the restricted movement of polymer chains. In addition, the obtained fibers show excellent mechanical and thermal properties because of the strong hydrogen bonding due to the incorporation of benzimidazole moieties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41474.     

Performance and structure changes of the aromatic co‐polysulfonamide fibers during thermal‐oxidative aging process

The changes in performance during thermal‐oxidative aging process of the aromatic co‐polysulfonamide (co‐PSA) fibers over a broad temperature range from 250 °C to 320 °C have been investigated. In addition, the mechanism of thermal‐oxidative aging process has been studied by using structural information obtained from the fibers at varying length scales. The results showed that a significant reduction in tensile strength was observed compared with that of initial modulus during aging process. Macroscopically, thermal‐oxidative aging mainly causes color changes of fibers and thermally induced macro defects begin to appear only at 320 °C for 100 h. On a micro level, the crystal structure of fibers remained stable and did not show significant changes expect that aging at 320 °C. In addition, thermo‐degradation as well as crosslinking has been observed primarily in amorphous region. With the increase of temperature and time duration, the crosslinking became more dominant and crosslinking density increases. Correspondingly, the fibril length decreases due to degradation and then increases due to the formation of crosslinked structures within the fibers. The results suggest that molecular degradation is the main cause of strength loss and the formation of crosslinking structure within the fibers contributes to the retention of modulus and improvement of creep resistance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44078.     

PBT/PET conjugated fibers: Melt spinning,fiber properties,and thermal bonding

This work examines the PBT/PET sheath/core conjugated fiber, with reference to melt spinning, fiber properties and thermal bonding. Regarding the rheological behaviors in the conjugated spinning, PET and PBT show the smallest difference between their melt‐viscosity at temperatures of 290°C and 260°C respectively, which has been thought to represent optimal spinning conditions. The effect of processing parameters on the crystallinity of core material‐PET was observed and listed. In order of importance, these factors are the draw ratio, the heat‐set temperature, and the drawing temperature. The crystallinity of sheath material‐PBT, however, can be considered to be constant, independent of any processing parameters. The bulk orientation, rather than the crystallinity of PET core, dominates the tenacity of PBT/PET sheath/core fiber. Moreover, heat‐set treatment after drawing is recommended to yield a highly oriented conjugated fiber. With respect to thermal bonding, PBT/PET conjugated fibers processed via high draw ratio but low‐temperature heat setting can form optimal thermal bonds at a constant bonding temperature of 10°C above the T_m of PBT.     

Strain‐induced crystallization in uniaxially drawn PETG plates

The copolyester poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) (PETG) is used industrially as an uncrystallizable polymer, whereas PET is an inherently crystallizable polymer. Nevertheless, a crystalline phase could appear in the material. To create a strain‐induced crystalline phase in an initially amorphous PETG material, plates were placed in the heating chamber of a tensile machine at 100°C and uniaxially drawn to obtain different samples with various draw ratios. During DSC analysis of highly drawn samples, perturbations of the baseline appear above the glass‐transition temperature, consisting of weak exothermic and endothermic phenomena. Comparison of DSC and X‐ray diffraction analysis of drawn PETG and PET shows that a strain‐induced crystalline phase appears in this copolyester. A spherulitic superstructure could also appear after lengthy annealing. Analysis of this semicrystalline material allowed estimation of the degree of crystallinity, about 3% after a drawing at high draw ratio and about 11% for undrawn annealed material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3405–3412, 2001     

Properties of high modulus PEEK yarns for aerospace applications

A study has been carried out on the influence of extrusion and drawing related process parameters with an object of obtaining high modulus poly ether ether ketone yarns that can be tailor made to meet critical requirements of aerospace applications. The influence of the interaction between rheological properties, spinning process variables, and drawing conditions has been given special attention to engineer a yarn that exhibit excellent structure property relationships. The wide angle X‐ray diffraction results suggest that drawing carried out above glass transition temperature (T_g) influences the structure that include unit cell parameters, density, and mechanical properties. The degree of orientation characterized in terms of sonic velocity measured as high as 3 km/s with sonic modulus of 105 gpd. With progressive increase in draw temperature, crystallinity was found to increase, and useful properties were observed at an optimum draw temperature of 200°C (may be region of maximum crystallization rate) primarily attributed to the maximum crystallization temperature and the heat setting effect. Thermal studies (TGA) indicate that these materials can be used in high temperature applications (up to 250°C) for long time exposure and 500°C for short term exposure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Superstructure and mechanical properties of poly(ethylene terephthalate) fibers zone‐drawn under critical necking tension

The superstructure and mechanical properties of poly(ethylene terephthalate) fibers zone‐drawn under a critical necking tension (σ_c) were studied. σ_c was defined as the minimum tension needed to generate a neck at a given drawing temperature (T_d) and was measured over a temperature range of 70–120°C. The σ_c value increased rapidly with decreasing T_d in the temperature range below 85°C, but the temperature dependence of σ_c was small above 85°C. The neck profile relied on T_d, becoming more shapely with decreasing T_d. A neck with a gradual decrease in diameter was observed in the fibers drawn at 100°C and above. The draw ratio increased significantly with increasing T_d above 90°C, but birefringence decreased. Density decreased gradually with increasing T_d, and fiber drawn at 120°C had a density of 1.347 g/cc. Wide‐angle X‐ray diffraction photographs of the fibers drawn at 100°C and below showed reflections due to crystallites, but a photograph of the fiber obtained at 120°C showed a ring‐like amorphous halo. The storage modulus (E′) at 25°C increased progressively with decreasing T_d, and the fiber drawn at 70°C had the maximum E′ value among the fibers drawn at a series of T_d's. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 179–185, 2002     

Application of CO2 laser heating zone drawing and zone annealing to nylon 6 fibers

Nlon 6 fibers were zone drawn and zone annealed by using a continuous wave carbon dioxide laser to develop their mechanical properties. A laser‐heating zone drawing was carried out under a applied tension of 35.4 MPa at a power density of 9.65 W · cm^?2, and then the zone‐drawn fiber was annealed. A laser‐heating zone annealing was carried out in two steps at a power density of 9.65 W · cm^?2; the first step was carried out under 423 MPa and the second under 517 MPa. The treating temperature of the fiber heated by the CO₂ laser was measured by using an infrared thermographic camera equipped with a magnifying lens. The treating temperature at the zone drawing is 138°C, and those at the first and the second zone annealing are 121 and 125°C, respectively. The second laser‐heated zone‐annealed fiber has a birefringence of 65.2 × 10^?3, a degree of crystallinity of 54%, and a storage modulus of 21 GPa at 25°C. Wide‐angle X‐ray diffraction patterns for the laser‐heated zone‐drawn and the zone‐annealed fibers show (200) reflection and (002/202) doublet due to only an α form on the equator. The laser‐heated zone‐drawn fiber has a melting endotherm peaking at 216°C and a trace of shoulder on the higher temperature side of its peak, and the laser‐heated zone‐annealed fibers have a single melting endotherm peaking at 216°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1711–1716, 2002     

Enhancing mechanical properties of aromatic polyamide fibers containing benzimidazole units via temporarily suppressing hydrogen bonding and crystallization

The copolymerization modified poly(p‐phenylene terephthalamide) containing 2‐(4‐aminophenyl)?5‐aminobenzimidazole (PABZ) units in the main chain was synthesized and the corresponding poly‐p‐phenylene‐benzimidazole‐terephthalamide (PBIA) fibers were prepared by wet spinning. The HCl, the by‐product released during polymerization, can complex with PABZ units to prevent the formation of hydrogen bonding between PABZ units, resulting in amorphous PBIA fibers and a lower glass transition temperature (T_g). Therefore, for the purpose of gaining strong hydrogen bonding and high orientation degree at the same time in PBIA fibers, two‐step drawing–annealing processing was adopted. The as‐spun PBIA/HCl complex fibers were drawn first at 280°C, higher than the T_g of the PBIA/HCl complex fibers and lower than the decomplexed temperature of HCl, which temporarily suppresses the formation of hydrogen bonding and crystallization. Subsequently, the fibers were annealed to reform hydrogen bonding between PABZ units and crystallization via decomplexation of HCl at 400°C. However, when the drawing is above the decomplexed temperature of HCl, the decomplexation of HCl begins to occur which leads to the reform of hydrogen bonding and crystallization, and the tensile strength of the drawn‐annealed PBIA/HCl complex fibers decreases with a decrease in the HCl content of fibers. The tensile strength of two‐step drawn‐annealed fibers increased by approximately 15% compared to that of one‐step drawn PBIA/HCl complex fibers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42482.     

Effects of zone drawing on the structure of metallocene polyethylene

The influence of zone drawing on bulk properties and structure of metallocene polyethylene (m‐PE) is reported. Two different m‐PE materials were subjected to tensile stresses above the yield point by zone drawing in the temperature range from 50 to 100°C. Drawn materials were characterized by using small‐ and wide‐angle X‐ray scattering (SAXS, WAXS), molecular retraction, and small‐angle light scattering (SALS). Structural changes were studied as a function of drawing temperature, engineering stress, and draw ratio. WAXS showed strong crystalline orientation in drawn samples, and only the orthorhombic crystal modification was observed. SAXS showed lamellar orientation in drawn samples. At low drawing temperatures of 50 or 60°C, draw ratio increased as a step function of stress. There is a stress barrier, which must be exceeded before high‐draw ratios can be achieved at these temperatures. At drawing temperatures of 70°C or above, the barrier stress is low enough that draw ratio increases nearly linearly as a function of stress. Below the stress barrier, spherulitic structure is observed by small‐angle light scattering (SALS). Elongation occurs via deformation of the interspherulitic amorphous phase. Molecular retraction was low for these samples, indicating mostly plastic deformation of the amorphous material. Above the stress barrier, SALS showed that spherulites are destroyed. Elongation occurs via deformation of the intraspherulitic amorphous phase. Molecular retraction for these samples was high, indicating elastic deformation of the amorphous material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3492–3504, 2001     

Determining the Crystal Volume Fraction of BS2 Glass by Differential Scanning Calorimetry and Optical Microscopy

In this work, the crystal volume fraction, α(t), of a barium disilicate (BS₂) glass‐ceramic was carefully investigated by optical microscopy (OM) and differential scanning calorimetry (DSC). X‐ray diffraction experiment revealed that the reflected peaks of the glass‐ceramic, which was prepared by heat treatment at 1000°C for 12 h, were indexed as the low‐temperature orthorhombic sanbornite mineral phase. This result was confirmed by the refinement of the crystal structure parameters. Bulk samples were then heat‐treated in the range of 760°C to 830°C. In each case, the α(t) values obtained by DSC were higher than those determined by OM due to surface crystallization and the formation of new nuclei during the heating/cooling steps in the DSC experiments. OM and DSC techniques were also used to estimate the number of preexisting nuclei, N_q, in a set of samples heat‐treated at 790°C directly in the DSC furnace. At this temperature, it was found that the N_q obtained directly by OM measurements were in reasonable agreement with those calculated from the combination of overall crystallization with crystal growth kinetics.     

Effect of processing parameters of the continuous wet spinning system on the crystal phase of PVDF fibers

Poly(vinylidene difluoride) (PVDF) has been widely used in piezoelectric applications as films and nanofiber mats, but there are limited publications on piezoelectric wet‐spun fibers. In this work, PVDF fibers were prepared using the wet spinning method, and the processing parameters, including the drawing ratio and heat setting temperature, were controlled in the continuous wet spinning system to increase the β‐phase crystallinity of the fibers. In addition, the wet‐spun PVDF fibers were compressed by a rolling press to eliminate voids in the fibers. Then, the compressed PVDF fibers were poled to align the molecular dipoles. The crystal structures of the PVDF fibers were investigated using X‐ray diffraction and Fourier‐transform infrared spectroscopy. Single filament tensile tests were performed to measure the tensile strength of the fibers. The morphologies of the PVDF fibers with respect to the processing parameters were observed by scanning electron microscope (SEM) and polarization optical microscopy. The piezoelectric constant of the prepared PVDF fibers was then measured using a d₃₃ meter. The wet‐spun PVDF fibers showed the highest β‐phase and piezoelectric constants when the drawing ratio and heat setting temperature were 6 and 150 °C, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45712.     

Isotactic polypropylene microfiber prepared by carbon dioxide laser‐heating

An isotactic polypropylene (i‐PP) microfiber was obtained by irradiating a carbon dioxide laser to previously drawn fibers. To prepare the thinner i‐PP microfiber, it is necessary to previously draw original i‐PP fibers under an applied tension of 7.8 MPa at a drawing temperature of 140°C. The drawn fiber was heated under an applied tension of 0.3 MPa using the laser operated at a power density of 39.6 W cm^?2. The thinnest i‐PP microfiber obtained under optimum conditions had a diameter of 1.8 μm and a birefringence of 30 × 10^?3. Its draw ratio estimated from the diameter reached 51,630. It is so far impossible to achieve such a high draw ratio by any drawing. The wide‐angle X‐ray diffraction photograph of the microfiber shows the existence of the oriented crystallites. Laser‐heating allows easier fabrication of microfibers compared with the conventional technology such as the conjugate spinning. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1534–1539, 2004     

Structure–property relationship of polyimide fibers containing ether groups

The copolyimide (co‐PI) fibers with outstanding mechanical properties were prepared by a two‐step wet‐spinning method, derived from the design of combining 4,4′‐oxydianiline (ODA) with the rigid 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA)/p‐phenylenediamine (p‐PDA) backbone. The mechanical properties of PI fibers were drastically improved with the optimum tensile strength of 2.53 GPa at a p‐PDA/ODA molar ratio of 5/5, which was approximately 3.7 times the tensile strength of BPDA/p‐PDA PI fibers. Two‐dimensional wide‐angle X‐ray diffraction indicated that the highly oriented structures were formed in the fibers. Two‐dimensional small‐angle X‐ray scattering revealed the existence of the needle‐shaped microvoids aligned parallel to the fiber axis, and the introduction of ODA led to the reduction in the size of the microvoids. As a result, the significantly improved mechanical properties of PI fibers were mainly attributed to the gradually formed homogeneous structures. The co‐PI fibers also exhibited excellent thermal stabilities of up to 563°C in nitrogen and 536°C in air for a 5% weight loss and glass transition temperatures above 279°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42474.