Structure and properties of an oriented fluorosulfonated/PTFE copolymer

This polymer is a precursor of Nafion, an ionomer developed for ion‐selective membranes. In this work various stretching procedures were carried out on the precursor, in order to explore the possibilities of enhanced performance. First, the crystallization behavior and properties of the unoriented precursor were investigated. It was found that the precursor copolymer contains crystallinity, which melts over a very wide temperature range. The amount of crystallinity is modified both by thermal history and applied shear. Thermal analysis can be used to determine processing/annealing temperatures for samples with unknown thermal history. It was found that the precursor possessed a maximum elongation at break at 70°C. Stretching was carried out at 70°C using a laboratory‐based tentering process, to produce both uniaxial and biaxial films. Films were characterized to monitor their shrinkage behavior, and orientation was measured by birefringence. Their tensile properties were measured with respect to stretching direction. Using tentering, which is carried out at relatively low temperatures, large amounts of orientation were produced, resulting in a significant increase in tensile strength, and decrease in elongation at break.     

The effects of thermal history on the structure/property relationship in polyphenylenesulfide/carbon fiber composites

The purpose of this investigation was to examine the effects of thermal history during cooling from the melt on the degree of crystallinity, morphology, and mechanical properties of polyphenylenesulfide (PPS)/carbon fiber composites. Three thermal treatments were employed in this tudy: isothermal crystallization from the melt at 140, 160, 180, 200, and 22O°C; quenching from 315°C and then annealing at 160 and 200°C; and nonisothermal crystallization from the melt at rates varying from 0.4°C/min to 38°C/s. The effect of varying the thermal history of the sample on the degree of crystallinity developed in the matrix polymer was determined using differential scanning calorimetry (DSC). The effect of thermal history on and the resulting matrix morphology was examined by scanning electron microscopy (SEM). The subsequent effects of the degree of crystallinity and the morphology on the mechanical behavior of the samples were monitored by transverse tensile tests and flexural tests. In all cases, the transverse tensile and flexural moduli increased as the amount of crystallinity in the samples increased. However, samples with greater amounts of crystallinity did not always yield higher transverse tensile or flexural strengths. Upon examination of the composite samples by electron miscroscopy, it was observed that large increases in the values of the transverse tensile and flexural strengths could be correlated with structural changes in the matrix.     

The influence of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers

An investigation was carried out on the effects of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers annealed in an air heated environment at temperatures ranging from 60 to 140°C. Analysis of the equatorial X‐ray diffraction traces showed the presence of a three phase system of amorphous‐smectic‐monoclinic forms and revealed the transformation of the metastable smectic form to the highly stable monoclinic form as the annealing temperature is increased, resulting in an enhanced degree of crystallinity and the crystallite size. The improvements in the degree of crystallinity and the crystallite size became more remarkable above 120°C. Evaluation of the crystallinity was carried out using an analysis of density, infrared spectroscopy, and X‐ray diffraction methods whereas the state of the molecular orientation was evaluated using polarized infrared spectroscopy measurements only. Polarized infra‐red spectroscopy measurements after the curve fitting procedure showed a slight increase of the molecular orientation of the helical chain segments present in the crystalline phase represented by the IR bands at 841 and 998 cm^?1 whereas the amorphous structure represented by the IR band at 974 cm^?1 showed no significant change with increasing annealing temperature. The improvement in the molecular orientation of the crystalline phase became more remarkable above 120°C. Tensile strength of the annealed fibers increased with increasing annealing temperature but the elongation at break and the initial modulus were not affected as much as the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Mechanical properties and microstructure of poly(ethylene terephthalate) microfiber prepared by carbon dioxide laser heating

We determined that a poly(ethylene terephthalate) microfiber was easily obtained by irradiating a carbon dioxide laser to an annealed fiber. The annealed fiber was prepared by zone drawing and zone annealing. First, an original fiber was zone drawn at a drawing temperature of 90°C under an applied tension of 4.9 MPa, and the zone‐drawn fiber was subsequently zone annealed at 150°C under 50.9 MPa. The zone‐annealed fiber had a degree of crystallinity of 48%, a birefringence of 218.9 × 10^?3, tensile modulus of 18.8 GPa, and tensile strength of 0.88 GPa. The microfiber prepared by laser heating the zone‐annealed fiber had a diameter of 1.5 μm, birefringence of 172.8 × 10^?3, tensile modulus of 17.6 GPa, and tensile strength of 1.01 GPa. The draw ratio estimated from the diameter was 9165 times; such a high draw ratio has thus far not been achievable by any conventional drawing method. Microfibers may be made more easily by laser heating than by conventional technologies such as conjugate spinning. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1955–1958, 2003     

Enhanced compatibilization and orientation of polyvinyl alcohol/gelatin composite fibers using carbon nanotubes

Polyvinyl alcohol (PVA)/gelatin composite fibers containing carbon nanotubes (CNTs) had been prepared by wet‐spinning method. A remarkable increase of tensile strength of the PVA/gelatin fibers was achieved by adding small amount of CNT. The mechanism of reinforcement has been studied using a combination of differential scanning calorimetry (DSC), 2D wide‐angle X‐ray diffraction (2D‐WAXD) and scanning electron microscopy (SEM). SEM showed a decreased gelatin domain size by adding CNTs, suggesting a possible compatibilization effect between PVA and gelatin. On the other hand, an increased crystallinity and degree of orientation of PVA/gelatin fibers has been observed by adding CNTs. Thus, the increased compatibilization, crystallinity and degree of orientation in PVA/gelatin/CNTs composite fibers should be the reasons for the observed increase of mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

PGLA纤维成形过程中的结品性能

采用熔融纺丝法纺制聚乙丙交酯（PGLA）纤维,运用X-射线衍射、DSC等方法对PGLA纤维拉伸和定形过程中结晶性能的变化进行测试和研究。实验表明,拉伸比、拉伸温度和定形温度是常用的3个工艺参数,它们对纤维结晶度有着最直接的影响。制备的PGLA纤维具有良好的力学性能,在60℃下拉伸5．5倍,强度达5．2cN／dtex,断裂伸长为24％,可以满足医用缝合线的力学性胄皂要求。     

Crystalline structure and morphology of poly(L‐lactide) formed under high pressure

The poly(l ‐lactide) (PLLA) samples were prepared by the annealing under 100 MPa at 75–145^°C and 200 MPa at 105–145^°C for 6 h, respectively. The crystalline structures, thermal properties and morphology were investigated using differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and scanning electron microscopy (SEM). On the basis of the DSC and WAXD results, it can be seen that the α′ form was formed by the annealing under 100 MPa at 85–95°C but not found under 200 MPa at 105–145°C. A phase diagram of PLLA crystal form under high pressure was constructed under the given experimental conditions, which displayed the α′ form was formed at limited temperature and pressure range. Besides, SEM suggested that the PLLA samples annealed under 100 MPa crystallize to form lamellar‐like crystals due to the low growth rate and the confined crystallization behavior under high pressure. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40637.     

Facile fabrication of PVA composite fibers with high fraction of multiwalled carbon nanotubes by gel spinning

Poly(vinyl alcohol) (PVA) composite fibers with high fraction of multiwalled carbon nanotubes (MWCNTs) were prepared by gel spinning process. Here, a modified process was introduced to prepare concentrated PVA/MWCNTs/DMSO spinning dope, and to attain good dispersion of MWCNTs in the fibers. The final composite fibers were studied by thermogravimetric analyzer (TGA), Fourier transform infrared spectrometer (FTIR), Raman spectroscopy, differential scanning calorimetry (DSC), and WAXD analysis. The total content of MWCNTs in PVA composite fibers, from 5 to 30 wt%, was confirmed by TGA analysis. FTIR and Raman measurements demonstrated the existence of strong hydrogen interaction between MWCNTs and PVA matrix. SEM images of composite fibers showed smooth surface, regular cross‐section shape and good dispersion of MWCNTs in the fibers. DSC analysis showed that the crystallinity first increased and then decreased with the increase of MWCNTs contents. It can be concluded that low concentration of MWNCTs can act as nucleation sites for crystallization of PVA component, and large amount of MWCNTs may impede the crystallization of PVA component. The WAXD analysis results indicated that the crystal orientation of the PVA component in PVA composite fibers is almost identical at the same drawn ratio. Polarized Raman analysis indicated a small increase in MWCNTs orientation for the composite fibers. The mechanical properties tests showed that the composite fibers exhibit significant improvement in tensile strength and modulus as compared to the neat PVA fibers. The composite fibers also showed sustained growth in electrical conductivity. POLYM. ENG. SCI., 58:37–45, 2018. © 2017 Society of Plastics Engineers     

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

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

Preparation of high-modulus and high-strength poly(ethylene terephthalate) fiber by zone annealing

To prepare high-modulus and high-strength PET fiber, a new method using zone drawing and zone annealing has been studied. The apparatus used for this method is the usual tensile tester equipped with a band heater 2 mm wide and a sample holder which can apply a high tension to the fiber. The experimental procedure consists of two stages: zone drawing and zone annealing. The zone drawing was done on the original as-spun fiber in order to produce a fiber with as high an orientation and as low a crystallinity as possible. The zone-drawn fiber was subsequently zone annealed under high tension by moving the band heater from one end to the other of the fiber at a temperature above the crystallization temperature at a considerably low moving speed. In spite of the simple apparatus and procedure, Young's modulus of the fiber obtained was 19.4 × 10¹⁰ dyn/cm², which is comparable to the maximum value of the high-tenacity PET filament commercially available. In order to elucidate the change in the superstructure with zone drawing or zone annealing, optical, x-ray, IR, DSC, and dynamic mechanical measurements were performed. It is suggested that the zone-annealed fiber consists of almost perfectly oriented crystallites and fully extended amorphous chains.     

Process–structure–property relationship of melt spun poly(lactic acid) fibers produced in the spunbond process

We report on the process–structure–property relationships for Poly(lactic acid) (PLA) filaments produced through the spunbond process. The influence of spinning speed, polymer throughput, and draw ratio on crystallinity and birefringence of fibers were evaluated. We established that increasing spinning speed increases crystallinity and birefringence of fibers. We also investigate the role of fiber structures on fiber tensile properties—breaking tensile strength, strain at break, initial modulus, and natural draw ratio. An increase in spinning speed leads to a higher breaking tensile strength, higher initial modulus and lower strain at break. We have shown an almost linear relationship between breaking tensile strength of PLA fibers and birefringence. This indicates that improved tensile properties at high spinning speeds can be attributed to enhanced molecular orientation. The dependency of fiber breaking tensile strength and strain at break on spun orientation were explained with natural draw ratio, as a measure of spun orientation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44225.     

The influence of processing parameters on the properties of melt‐spun polypropylene hollow fibers

Isotactic polypropylene hollow fibers were produced by melt spinning. Spinning speeds up to 1880 m/min were used, and sample hollowness (percentage void in cross section) ranged from 0 to 69%. The fiber samples were characterized using dynamic mechanical analysis, birefringence, tensile testing, and differential scanning calorimetry. The hollow fibers were found to have higher crystallinity, orientation, and strength than the analogous solid fibers. In general, the polymer orientation in a hollow fiber was larger than the orientation in a solid fiber, even when the spinning speed for the latter was much larger. For a fixed outer diameter, increasing the hollowness improved fiber properties. However, as hollowness was further increased, fiber properties declined slightly. At a given percentage hollowness, increased spinning speed increased modulus and tenacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1759–1772, 2002     

Investigation on the melt spinning fibers of PP/organoclay nanocomposites prepared by in‐situ polymerization

Fibers prepared by melt spinning process from the PP (polypropylene)/organoclay nanocomposite were characterized in details with the aid of SEM, FTIR, XRD, DSC, and mechanical measurements. The results suggested that the lower content of organoclay (0.1%) added to the PP matrix increased the crystallinity and mechanical property (tensile strength) of the PP/organoclay nanocomposite fiber. With increasing the content of organoclay (≥ 0.3%), the crystallinity and the tensile strength both a little decreased, and the fiber containing organoclay exhibited multi‐peaks at the same draw ratio during the heating process. Furthermore, the degree of orientation of the fiber increased a little with lower content of organoclay (0.1%) introduction to PP during the infrared dichroism measurement. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of high‐performance poly(ether ether ketone) fibers with improved spinnability based on thermotropic liquid crystalline poly(aryl ether ketone) copolymer

High‐performance poly(ether ether ketone) (PEEK) fibers were prepared by melt‐spinning in the presence of thermotropic liquid crystalline poly(aryl ether ketone) copolymer (FPAEKLCP). The rheological and mechanical properties, birefringence, orientation, and crystallization of the resulting PEEK/FPAEKLCP fibers were characterized by using a melt flow indexer, capillary rheometer, single fiber electronic tensile strength tester, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD), respectively. The results indicate that the melt viscosity of PEEK significantly reduced by introducing FPAEKLCP, followed by the improvements in the spinnability and the quality of as‐spun fibers. The tensile properties of PEEK/FPAEKLCP fibers mainly depend on the content of FPAEKLCP, drawing temperature, drawing ratio, and annealing processes. Moreover, the tensile strength and modulus of PEEK/FPAEKLCP fibers are obviously higher than those of neat PEEK fibers under the same processing conditions. This should be attributed to an enhancement in the orientation and crystallization of PEEK compounded with FPAEKLCP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1406‐1414, 2013     

冷却温度对聚丙烯薄膜结晶、形态和拉伸性能的影响

采用示差扫描量热法(DSC)、广角X射线衍射(WAXD)和扫描电镜(SEM)对聚丙烯(PP)薄膜的结晶、形态进行了研究,并测试了薄膜的拉伸性能.结果表明:冷却水温度变化对生产PP薄膜的结晶、形态和拉伸性能有很大影响.在冬季,PP薄膜的结晶度更小,晶体尺寸更均一;但在夏季,PP薄膜的拉伸强度、杨氏模量和断裂伸长率分别提高45%、85%和94%.最后,通过数值模拟,得到了给定条件下相关冷却参数的合理数值.     

Effect of crystallinity on enthalpy recovery peaks and cold‐crystallization peaks in PET via TMDSC and DMA studies

Poly(ethylene terephthalate) (PET) sheets of different crystallinity were obtained by annealing the amorphous PET (aPET) sheets at 110°C for various times. The peaks of enthalpy recovery and double cold‐crystallization in the annealed aPET samples with different crystallinity were investigated by a temperature‐modulated differential scanning calorimeter (TMDSC) and a dynamic mechanical analyzer (DMA). The enthalpy recovery peak around the glass transition temperature was pronounced in TMDSC nonreversing heat flow curves and was found to shift to higher temperatures with higher degrees of crystallinity. The magnitudes of the enthalpy recovery peaks were found to increase with annealing times for samples annealed ≤30 min but to decrease with annealing times for samples annealed ≥40 min. The nonreversing curves also found that the samples annealed short times (≤40 min) having low crystallinity exhibited double cold‐crystallization peaks (or a major peak with a shoulder) in the region of 108–130°C. For samples annealed long times (≥50 min), the cold‐crystallization peaks were reduced to one small peak or disappeared because of high crystallinity in these samples. The double cold‐crystallization exotherms in samples of low crystallinity could be attributed to the superposition of the melting of crystals, formed by the annealing pretreatments, and the cold‐crystallizations occurring during TMDSC heating. The ongoing crystallization after the cold crystallization was clearly seen in the TMDSC nonreversing heat flow curves. DMA data agreed with TMDSC data on the origin of the double cold‐crystallization peaks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Drawing and annealing of polypropylene fibers: Structural changes and mechanical properties

A study has been carried out on the influence of cold drawing (25°C), hot drawing (140°C), and annealing (140°C) on the structure and mechanical properties of a series of four different well-characterized melt spun polypropylene filaments. The influence of the interaction between melt spinning and drawing variables was given special attention. Cold drawing increased the orientation in the samples, disrupts the initial monoclinic crystal structure and the morphology of the filaments, and it results in extensive fibrillation. Annealing restored the monoclinic structure but eliminated only a small part of the fibrillation. Hot drawing produced changes which were qualitatively similar to the combined effects of cold drawing and annealing. The orientation and morphology of the asspun filaments were found to have major effects on drawing behavior and the mechanical properties of the drawn fibers for a given draw ratio. It was found, however, that the mechanical properties (tensile strength, tangent elastic modulus, and elongation to break) of the melt spun, hot drawn and cold drawn, and annealed fibers could all be correlated with birefringence measurements.     

Effects of annealing on the hierarchical crystalline structures and mechanical properties of injection‐molded bars of high‐density polyethylene

The effect of annealing on the microstructural evolution and mechanical properties of high‐density polyethylene parts molded via gas‐assisted injection molding was investigated using scanning electron microscopy, differential scanning calorimetry, two‐dimensional wide‐angle X‐ray diffraction and tensile testing. The results indicated that a variety of annealing temperatures could induce considerable variations in the hierarchical structures, crystallinity, lamellar thickness and yield stress of the molded bars. According to these results, the annealing temperatures could be divided into three regions. In the low‐temperature region of annealing at 80 °C, the spatial variation of the superstructure developed along the thickness direction and mechanical properties of the annealed sample were mainly unchanged and similar to those of the original specimen. At 100 and 120 °C, the intermediate temperature region of annealing, the thickness of the crystals, degree of orientation and yield stress of annealed samples were greatly improved. Finally, at 127 °C, the degree of orientation decreased and yield stress slightly improved, an indication of the high‐temperature annealing region being characterized by increasing melting/recrystallization and causing relaxation of oriented molecular chains. A model is proposed to interpret the mechanism of the annealing treatment of the samples at various temperatures. © 2013 Society of Chemical Industry     

Tailoring the thermal and mechanical properties of injection-molded poly (lactic acid) parts through annealing

The effect of cold-crystallization on poly (lactic acid) (PLA) injection-molded parts was systemically investigated at different annealing temperatures (80/100/120°C) and annealing times (0.5/1/1.5/2 hr). The relative crystallinity (X_c) and crystal form (α' and α) of samples was investigated by differential scanning calorimetry (DSC) and wide X-ray angle diffraction (WAXD). The dependence of the thermal and mechanical performance on relative crystallinity and crystal form/morphology was discussed in detail. A linear relationship between the increment of heat distortion temperature (HDT) and that of X_c was found. The tensile strength, tensile modulus and storage modulus all increased with annealing time and annealing temperature, while the tensile toughness presented a different behavior. The elongation at break for specimens reached a maximum value of 16.9% after annealing at 80°C for 2 hr, which is a threefold improvement compared to PLA samples prepared without annealing. This work suggests that annealing is an effective method for tailoring the physical properties of PLA products.     

拉伸条件对涤纶四孔中空纤维结构性能的影响

应用ＷＡＸＤ、声速法等研究了涤纶四孔中空纤维在不同拉伸条件下结晶、取向变化,讨论了拉伸工艺变化对涤纶四孔中空纤维结构与性能的影响。结果表明,由于拉伸方式和拉伸温度的不同,纤维结晶和取向程度有明显的区别,导致了中空纤维成品质量的差异。