Preparation of poly(lactic acid) fiber by dry–jet–wet spinning. II. Effect of process parameters on fiber properties

The dry–jet–wet spinning process was employed to spin poly(lactic acid)(PLA) fiber by the phase inversion technique using chloroform and methanol as solvent and nonsolvent, respectively, for PLA. The as spun fiber was subjected to two‐stage hot drawing to study the effect of various process parameters, such as take‐up speed, drawing temperature, and heat‐setting temperature on the fiber structural properties. The take‐up speed had a pronounced influence on the maximum draw ratio of the fiber. The optimum drawing temperature was observed to be 90°C to get a fiber with the tenacity of 0.6 GPa for the draw ratio of 8. The heat‐setting temperature had a pronounced effect on fiber properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3774–3780, 2006     

Effect of zone drawing on the structure and properties of melt‐spun poly(trimethylene terephthalate) fiber

Melt‐spun poly(trimethylene terephthalate) (PTT) fibers were zone‐drawn and the structures and properties of the fibers were investigated in consideration of the spinning and zone‐drawing conditions. The draw ratio increased up to 4 with increasing drawing temperature to 180°C, at a maximum drawing stress of 220 MPa. Higher take‐up velocity gave lower drawability of the fiber. The PTT fiber taken up at 4000 rpm was hardly drawn, in spite of using maximum drawing stress, because a high degree of orientation had been achieved in the spinning procedure. However, an additional enhancement of birefringence was observed, indicating a further orientation of PTT molecules by zone drawing. The exotherm peak at 60°C disappeared and was shifted to a lower temperature with an increase in the take‐up velocity, which means that the orientation and crystallinity of the fiber increased. The d‐spacing of (002) plane increased with increasing take‐up velocity and draw ratio, whereas those of (010) and (001) planes decreased. In all cases, the crystal size increased with take‐up velocity and draw ratio. The cold‐drawn PTT fiber revealed a kink band structure, which disappeared as the drawing temperature was raised. The physical properties of zone‐drawn PTT fibers were improved as the draw ratio and take‐up velocity increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3471–3480, 2001     

High temperature zone‐drawing of nylon 66 microfiber prepared by CO2 laser‐thinning

A high temperature zone‐drawing method was applied to a nylon 66 microfiber, obtained by using CO₂ laser‐thinning, to develop its mechanical properties. The microfiber used for the high temperature zone‐drawing was prepared by winding at 150 m min^?1 the microfiber obtained by irradiating the laser at 4.0 W cm^?2 to an original fiber with a diameter of 50 μm, and had a diameter of 9.6 μm and a birefringence of 0.019. The high temperature zone‐drawing was carried out in two steps; the first drawing was carried out at a temperature of 230°C at supplying and winding speeds of 0.266 and 0.797 m min^?1, the second at 250°C at supplying and winding speeds of 0.266 and 0.425 m min^?1, respectively. The diameter of the microfiber decreased, and its birefringence increased stepwise with the processing. The high temperature zone‐drawn microfiber finally obtained had a diameter of 4.2 μm, a birefringence of 0.079, total draw ratio of 4.8, tensile modulus of 12 GPa, and tensile strength of 1.0 GPa. The wide‐angle X‐ray diffraction photograph of the drawn microfiber showed the existence of highly oriented crystallites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 42–47, 2006     

Structure evolution of melt‐spun poly(vinyl alcohol) fibers during hot‐drawing

The drawability of melt‐spun poly(vinyl alcohol) (PVA) fibers and its structure evolution during hot‐drawing process were studied by differential scanning calorimetry (DSC), two dimensional X‐ray diffraction (2‐D WAXD) and dynamic mechanical analysis (DMA). The results showed that the water content of PVA fibers should be controlled before hot‐drawing and the proper drying condition was drying at 200°C for 3 min. PVA fibers with excellent mechanical properties could be obtained by drawing at 200°C and 100 mm/min. The melt point and crystallinity of PVA fibers increased with the draw ratio increasing. The 2‐D WAXD patterns of PVA fibers changed from circular scattering pattern to sharp diffraction point, confirming the change of PVA fibers from random orientation to high degree orientation. Accordingly, the tensile strength of PVA fibers enhanced by hot‐drawing, reaching 1.85 GPa when the draw ratio was 16. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt spinning of high‐strength fiber from low‐molecular‐weight polypropylene

Polypropylene (PP) with high melt flow index (MFI) or low molecular weight, although desired in melt spinning for enhanced productivity, is difficult to be spun into high‐strength fiber using the standard process where extensive jet stretching is applied. In this work, a processing route involving minimal jet stretch has been explored. A two‐stage hot drawing procedure in the solid state was found to be suitable for producing high‐strength fiber from low‐molecular‐weight PP with an ultrahigh MFI of 115 g/10 min. Fibers produced achieve a maximum tensile strength and Young's modulus of approximately 600 MPa and 12 GPa, respectively. The melt temperature of the fiber reached 170.8°C, approximately 5°C higher than that of the original resin. Wide‐angle X‐ray diffraction (WAXD) study shows that the stable α‐monoclinic crystalline structure is developed during the drawing process. A well‐oriented crystalline structure along the fiber axis is generated, having a crystalline orientation factor as high as 0.84. POLYM. ENG. SCI., 56:233–239, 2016. © 2015 Society of Plastics Engineers     

Melt spinning of poly(L‐lactic acid) and its biodegradability

The melt spinning and melt drawing of poly(L ‐lactic acid) (PLLA) were carried out with a melt‐spinning machine, and the mechanical properties, structure, and biodegradability of PLLA fiber were investigated. PLLA fiber with a tensile strength of 0.81 GPa was successfully obtained through two steps of drawing at a draw ratio of 18 in hot water. This fiber had enough tensile strength for common engineering use. The fiber could be degraded under controlled composting conditions at 70°C for 1 week. In scanning electron microscopy observations of the fiber, a regular pattern of cracks running along the vertical direction to the fiber axis was clearly observed. This suggested that the PLLA fiber built up a highly ordered structure arranged along the direction of the fiber axis. After the fiber was left to lie in the ground for 1 year, however, the surface of the fiber was still smooth, and the tensile strength did not decrease much. This PLLA fiber could not be hydrolyzed after 1 month of steeping in a buffer solution at 37°C, but it was rapidly hydrolyzed at more than 60°C. It was suggested that the degradation (hydrolysis) rate of PLLA depended on the glass‐transition temperature. Upon hydrolysis at 80°C for 48 h, a regular crack along the vertical direction to the fiber axis was found that was very similar to that observed in degradation under composting conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2118–2124, 2005     

Effects of water on drawability,structure, and mechanical properties of poly(vinyl alcohol) melt‐spun fibers

Poly(vinyl alcohol) (PVA) melt‐spun fibers with circular cross‐section and uniform structure, which could support high stretching, were prepared by using water as plasticizer. The effects of water content on drawability, crystallization structure, and mechanical properties of the fibers were studied. The results showed that the maximum draw ratio of PVA fibers decreased with the increase of water content due to the intensive evaporation of excessive water in PVA fibers at high drawing temperature. Hot drying could remove partially the water content in PVA as‐spun fibers, thus reducing the defects caused by the rapid evaporation of water and enhancing the drawability of PVA fibers at high drawing temperature. The decreased water content also improved the orientation and crystallization structure of PVA, thus producing a corresponding enhancement in the mechanical properties of the fibers. When PVA as‐spun fibers with 5 wt % water were drawn at 180 °C, the maximum draw ratio of 11 was obtained and the corresponding tensile strength and modulus reached ～0.9 GPa and 24 GPa, respectively. Further drawing these fibers at 215 °C and thermal treating them at 220 °C for 1.5 min, drawing ratio of 16 times, tensile strength of 1.9 GPa, and modulus of 39.5 GPa were achieved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45436.     

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     

Improvement of Flexural Strengths of Poly(L‐lactic acid) by Solid‐State Extrusion, 2. Extrusion Through Rectangular Die

Solid‐state extrusion of poly (L ‐lactic acid) (PLLA) through rectangular die was performed to produce high flexural strength plates that can be used as internal fixation devices. A single‐angle wedge‐shaped rectangular die was utilized having the die exit dimension of 4 mm × 1 mm. Billets were machined out from vacuum compression molded PLLA having different crystallinities to have various thicknesses and thus various imposed draw ratios. Solid‐state extrusion of billets was performed at various drawing rates at 130 °C, above glass transition and below melting temperature. Extruded plates had the width and thickness smaller than the die due to the further drawing outside the die. The decrease in width was larger than the decrease in thickness, and this became more prominent with increasing draw ratio and drawing rate, resulting in a significantly smaller aspect ratio. Contributions of die drawing and further drawing outside the die were estimated from the extruded plate dimensions, by which the drawing rate effect was attributed to the further drawing outside the die. As actual draw ratio increased, crystallinity, melting temperature, crystalline orientation factor, and birefringence increased. Throughout the whole process the decrease in molecular weight was largely suppressed to be about 10%. As billet crystallinity, draw ratio, and drawing rate increased, both flexural strength and flexural modulus increased up to the maxima of 202 MPa and 9.7 GPa, respectively. This enhancement in mechanical properties was correlated with structural developments.

Changes in flexural strength of solid‐state extruded PLLA plates as a function of draw ratio (the effect of drawing rate is co‐plotted by hollow symbols at corresponding draw ratio.).     

Enhancement of the dimensional stability of poly(ethylene‐2,6‐naphthalene dicarboxylate) filament by multistep zone annealing spinning

Both good tensile properties and good resistance to thermal shrinkage are prerequisites for tire cord applications. For these purposes, poly(ethylene‐2,6‐naphthalene dicarboxylate) (PEN) filaments were prepared by multistep zone annealing (MSZA) spinning with a specially devised system. The melting temperature of the PEN filaments so obtained was slightly increased with an increasing total draw ratio. All the filaments exhibited a sharp melting peak around 270°C, but glass‐transition behavior was barely visible via differential scanning calorimetry. Rheovibron experiments showed α relaxation in the vicinity of 175°C. Increasing the draw ratio above 4 did not increase the birefringence value much, but it did lead to increases in the tensile properties. The PEN filaments consisted exclusively of α‐form crystals. The PEN filaments showed excellent resistance to thermal shrinkage, which was less than 1% even with heating to 140°C. In the MSZA spinning process, increasing the degree of hot drawing proved more effective than increasing the degree of cold drawing for obtaining PEN filaments with better dimensional stability at elevated temperatures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 916–922, 2002     

Fabrication of highly isotactic polypropylene fibers to substitute asbestos in reinforced cement composites and analysis of the fiber formation mechanism

Highly isotactic polypropylene (PP) is currently studied as a cement‐reinforcement fiber that could potentially be substituted for asbestos because of its resistance to prolonged high‐temperature curing. The higher the isotacticity of the PP fiber is, the higher the tensile modulus and breaking strength of the cured fiber are. The PP fiber that exhibits a isotacticity of 99.6% (XI) and draw ratio of 6.0 retains a tensile modulus of 4.23 GPa, even after high‐temperature curing at 175°C for 5 h. PP fiber is cut into 6‐mm lengths and dispersed throughout a cement mixture to prepare a reinforced cement composite. The mixture is cured in an autoclave at 175°C for 5 h. The Charpy impact strength and flexural strength of the obtained cement composite tends to increase with increasing PP isotacticity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 981‐988, 2013     

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     

Development of a gel spinning process for high‐strength poly(ethylene oxide) fibers

This article describes a new gel‐spinning process for making high‐strength poly(ethylene oxide) (PEO) fibers. The PEO gel‐spinning process was enabled through an oligomer/polymer blend in place of conventional organic solvents, and the gelation and solvent‐like properties were investigated. A 92/8 wt% poly(ethylene glycol)/PEO gel exhibited a melting temperature around 45°C and was highly stretchable at room temperature. Some salient features of a gel‐spun PEO fiber with a draw ratio of 60 are tensile strength at break = 0.66 ± 0.04 GPa, Young's modulus = 4.3 ± 0.1 GPa, and a toughness corresponding to 117 MJ/m³. These numbers are significantly higher than those previously reported. Wide‐angle x‐ray diffraction of the high‐strength fibers showed good molecular orientation along the fiber direction. The results also demonstrate the potential of further improvement of mechanical properties. POLYM. ENG. SCI., 54:2839–2847, 2014. © 2014 Society of Plastics Engineers     

Melt spinning and drawing process of PET side‐by‐side bicomponent fibers

The change of crimp contraction and shrinkage in the melt spinning and drawing process of polyethylene terephthalate (PET) side‐by‐side bicomponent fibers was studied. Regular PET and modified PET were selected to make a latent crimp yarn. The modified PET was synthesized to increase thermal shrinkage. The crimp contraction is mainly dependent on drawing conditions such as draw ratio, heat‐set temperature, and drawing temperature. Difference in shrinkage between the PET and the modified PET causes the self‐crimping of bicomponent fibers. Although changing the heat‐set temperature and the drawing temperature can not affect dimensional change, the crimp contraction varies with those variables. As the heat‐set temperature and the drawing temperature decrease, the crimp contraction increases. Difference in elongation also affects the crimp contraction in the effect of draw ratio. When the modified PET with neopentyl group was used for highly shrinkable part, the crimp contraction is greater in comparison with modified PET with dimethyl isophthalate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1362–1367, 2006     

Mechanical properties and superstructure of isotactic polypropylene fibers prepared by continuous vibrating zone‐drawing

A continuous vibrating zone‐drawing (CVZD) was applied to study the effect of vibration on the mechanical properties and superstructure of isotactic polypropylene fibers. The CVZD treatment was a new drawing method by which the fiber was continuously drawn at a rate of 0.5 m/min under vibration using the specially designed apparatus. The CVZD treatment was carried out in five steps at a drawing temperature of 150°C and a frequency of 100 Hz, and applied tensions increased step by step with processing in the range of 14.8 to 207 MPa. The obtained fiber had a birefringence of 0.0373, crystallinity of 62.4%, tensile modulus of 17.6 GPa, and tensile strength of 1.11 GPa. These values are higher than those of the continuous zone‐drawn isotactic polypropylene fiber previous reported. The vibration added to the fibers during the zone‐drawing was effective in developing amorphous orientation and improving the mechanical properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 600–608, 2001     

Effect of annealing on the structure and properties of polyvinylidene fluoride hollow fiber by melt‐spinning

Polyvinylidene fluoride hollow fibers were prepared by melt‐spinning technique under three spinning temperatures. The effects of annealing treatment on the structure and properties of hollow fiber were studied by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), tensile test, and scanning electron microscopy (SEM) measurements. DSC and WAXD results indicated that the annealing not only produced secondary crystallization but also perfected primary crystallization, and spinning and annealing temperature influenced the crystallinity of hollow fiber: the crystallinity decreased with the increase of spinning temperature; 140°C annealing increased the crystallinity, and hardly influenced the orientation of hollow fiber; above 150°C annealing increased the crystallinity as well, and furthermore had a comparative effect on the orientation. The tensile tests showed that the annealed samples, which did not present the obvious yield point, exhibited characteristics of hard elasticity, and all the hollow fiber had no neck phenomenon. Compared with the annealed sample, the precursor presented a clear yield point. In addition, the annealed samples had a higher break strength and initial modulus by contrast with the precursor, and the 140°C annealed sample showed the smallest break elongation. SEM demonstrated the micro‐fiber structure appeared in surface of drawn sample. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 935–941, 2007     

Improvement in mechanical properties of poly(p‐phenylene sulfide) fibers by high‐tension multiannealing method

High‐tension multiannealing (HTMA) was applied to improve the tensile properties of poly(p‐phenylene sulfide) fibers, which was furthermore applied to the fibers produced and improved with the zone‐drawing and zone‐annealing treatments. The HTMA treatment was repeatedly applied to the fibers under the conditions of a 250°C temperature and an applied tension of between 201.0 and 188.0 MPa. As a result, at the 13th treatment the degree of crystallinity increased to 40%. On the other hand, the orientation factor of crystallites increased dramatically to 0.982 during the zone‐drawing treatment, but increased only slightly during the subsequent treatments of zone annealing and HTMA. The finally obtained fiber had a tensile modulus of 10.4 GPa and a tensile strength of 0.73 GPa. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1569–1576, 2000     

Orientation of HDPE inclusions within solid‐state drawn rubber‐modified isotactic polypropylene: DSC insight

Effect of drawing temperature on the melting behavior of oriented isotactic polypropylene (PP) modified with ethylene‐propylene‐diene monomer rubber with a small amount of high‐density polyethylene (HDPE) is explored in this study. Injection‐molded specimens both neat and 8 vol % modified PP were solid‐state drawn to natural drawing ratio and characterized by X‐ray diffraction, dynamic mechanical analysis (DMA), Charpy impact test and differential scanning calorimetry (DSC). A synergy of orientation and embedding rubber particles caused a significant increase of low‐temperature notched impact strength of oriented blends. It was shown, that the DSC method can be used successfully for the indirect but very sensitive characterization of orientation on a nanometre scale. At the drawing temperature of 120°C, the DSC data indicated an incomplete transition of the PP crystalline structure: This is reflected by splitting and shifting of the melting peak of PP. An increase of the melting temperature of the HDPE inclusions by 3.5°C reflects the high orientation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical and physical properties of ultraoriented polyoxymethylene produced by microwave heating drawing

The properties of ultra-oriented polyoxymethylene tubes produced by drawing under microwave heating have been assessed by mechanical testing, optical microscopy, scanning electron microscopy, X-ray analysis, birefringence and differential scanning calorimetry. The highest Young's modulus of 58 GPa was obtained at room temperature (77 GPa at ?150°C) at a draw ratio of 33. The maximum tensile strength was 1.7 GPa at a draw ratio of 26. The nonuniformity of Young's modulus in a radial direction has been compared with the nonuniformity of the birefringence and heat of fusion.     

Dry‐jet‐wet spun polyurethane fibers. I. Optimization of the spinning parameters

This study examined the spinning of polyurethane‐based elastomeric fibers with the dry‐jet‐wet spinning method. The three important spinning variables that were chosen were the coagulation bath ratio (dimethylformamide/water), the bath temperature, and the stretch ratio. A three‐variable factorial design method, proposed by Box and Behnken, was used to optimize these process parameters. The spinning process was further fine‐tuned by the variation of the stretch ratio and the dope solid content. The effect of the dry‐jet length on the fiber properties was also studied. The tenacity and elastic recovery properties of the fibers were found to be optimum at a bath ratio (dimethylformamide/water) of 60 : 40, a bath temperature of 15°C, and a stretch ratio of 2.5. The density and sonic modulus were measured to determine the effect of varying the process variables on structural parameters such as the density and orientation. The surface morphological features, as revealed by scanning electron microscopy, were correlated to the fiber properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010