Melt spinning of metallocene catalyzed polypropylenes. II. As‐spun filament structure and properties

The melt spinning of metallocene catalyzed isotactic polypropylene (miPP) resins was investigated. The as‐spun filament properties from six miPP resins were studied with melt flow rates (MFR) between 10 and 100, and a Ziegler–Natta catalyzed isotactic polypropylene (zniPP) resin with a MFR of 35 was studied for a comparison. Generally, as the molecular weight increased the filament density increased, the birefringence decreased, the tensile strength decreased, and the elongation to break increased. As the spinning speed increased, the density, birefringence, tensile strength, and crystalline and noncrystalline orientation functions generally increased. However, the low MFR miPP and the zniPP resin had decreases in the birefringence and tensile strength with an increase of the spinning speed. The miPP resins were found to have breaking tensile strengths up to 50% higher than the zniPP resin at similar spinning speeds. The observed fiber properties were explained based on the nature and orientation of noncrystalline portions of the fibers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3237–3247, 2001     

Melt spinning and drawing of 2‐methyl‐1,3‐propanediol‐substituted poly(ethylene terephthalate)

The structure and properties of fibers prepared from copolymers of poly(ethylene terephthalate) (PET) in which 2‐methyl‐1,3‐propanediol (MPDiol® Glycol is a registered trademark of Lyondell Chemical Company) at 4, 7, 10, and 25 mol% was substituted for ethylene glycol were studied and compared with those of PET homopolymer. Filaments were melt spun over a range of spinning conditions, and some filaments that were spun at relatively low spinning speeds were subjected to hot drawing. The filaments were characterized by measurements of birefringence, differential scanning calorimetry (DSC) crystallinity, melting point, glass transition temperature, wide‐angle X‐ray diffraction patterns, boiling water shrinkage, tenacity, and elongation to break. Filaments containing 25 mol% MPDiol did not crystallize in the spinline at any spinning speed investigated, whereas the other resins did crystallize in the spinline at high spinning speeds. However, compared with PET homopolymer, increasing substitution of MPDiol reduced the rate at which the crystallinity of the melt spun filaments increased with spinning speed and reduced the ultimate crystallinity that could be achieved by high‐speed spinning. The rate of development of molecular orientation, as measured by birefringence, also decreased somewhat with increasing MPDiol content. Shrinkage in boiling water decreased at high spinning speeds as the amount of crystallinity increased; however, the shrinkage decreased more slowly with increase in spinning speed as MPDiol content increased. Tenacity also decreased slightly at any given spinning speed as MPDiol content increased, but there was no significant effect on elongation to break. The addition of MPDiol in amounts up to 7 mol% increased the maximum take‐up velocity that could be achieved at a given mass throughput. This result indicates that the use of higher spinning speeds could potentially increase the productivity of melt spun yarns. Copolymer filaments spun at low speeds were readily drawn to produce highly oriented fibers with slightly less birefringence, crystallinity, and tenacity than similarly processed PET homopolymer. Preliminary dyeing experiments showed that the incorporation of MPDiol improved the dyeability of the filaments. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2598–2606, 2003     

Processing,structure, and properties of gel spun PAN and PAN/CNT fibers and gel spun PAN based carbon fibers

Polyacrylonitrile (PAN) and PAN/carbon nanotube (PAN/CNT) fibers were manufactured through dry‐jet wet spinning and gel spinning. Fiber coagulation occurred in a solvent‐free or solvent/nonsolvent coagulation bath mixture with temperatures ranging from ?50 to 25°C. The effect of fiber processing conditions was studied to understand their effect on the as‐spun fiber cross‐sectional shape, as well as the as‐spun fiber morphology. Increased coagulation bath temperature and a higher concentration of solvent in the coagulation bath medium resulted in more circular fibers and smoother fiber surface. as‐spun fibers were then drawn to investigate the relationship between as‐spun fiber processing conditions and the drawn precursor fiber structure and mechanical properties. PAN precursor fiber tows were then stabilized and carbonized in a continuous process for the manufacture of PAN based carbon fibers. Carbon fibers with tensile strengths as high as 5.8 GPa and tensile modulus as high as 375 GPa were produced. The highest strength PAN based carbon fibers were manufactured from as‐spun fibers with an irregular cross‐sectional shape produced using a ?50°C methanol coagulation bath, and exhibited a 61% increase in carbon fiber tensile strength as compared to the carbon fibers manufactured with a circular cross‐section. POLYM. ENG. SCI., 55:2603–2614, 2015. © 2015 Society of Plastics Engineers     

Comparison of tensile,thermal, and thermo‐mechanical properties of polyester filaments having different cross‐sectional shape

One of the most important morphological features of fibers is their cross‐sectional shape. Nowadays, the circular fiber cross‐section is the most common shape of melt‐spun man‐made fibers. Other shapes are beginning to emerge for a variety of reasons such as performance, comfort, pilling propensity, bulkiness, tactility, processing etc. The filaments' cross‐section can be easily varied by changing the spinneret hole shape. Synthetic fibers that are predominantly spun by the melt spinning method with spinnerets having the noncircular hole geometry are called profiled or noncircular fibers. Modifications of the fiber cross‐section allow designing surface properties in yarn and fabric. However, the effect of profiled fibers on yarn properties has not been well documented yet. In this article, the influence of different filament cross‐section geometry on fiber properties was studied. PET (polyethylene terephthalate) filament yarns having two different cross‐sectional shaped filaments, circular and cruciform, were manufactured by melt spinning. Differences in tensile properties of filament yarn and as well as of individual filament depending on the cross‐sectional type were studied and revealed. More over, thermal and thermomechanical properties of filament yarn of both the cross‐sections were studied and revealed by DSC and TMA method, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure and properties of thermotropic liquid crystal polymer and poly(ethylene 2,6‐naphthalate) blend fibers

BACKGROUND: The melt blending of thermotropic liquid crystal polymers (TLCPs) using conventional thermoplastics has attracted much attention due to the improved strength and tensile modulus of the resulting polymer composites. Moreover, because of their low melt viscosity, the addition of small amounts of TLCPs can reduce the melt viscosity of polymer blends, thereby enhancing the processability. RESULTS: In this study, TLCP/poly(ethylene 2,6‐naphthalate) (PEN) blend fibers were prepared by melt blending and melt spinning to improve fiber performance and processability. The relation between the structure and the mechanical properties of TLCP/PEN blend fibers and the effect of annealing on these properties were also investigated. The mechanical properties of the blend fibers were improved by increasing the spinning speed and by adding TLCP. These properties of the blend fibers were also improved by annealing. The tensile strength of TLCP5/PEN spun at a spinning speed of 2.0 km h^?1 and annealed at 235 °C for 2 h was about three times higher than that of TLCP5/PEN spun at a spinning speed of 0.5 km h^?1. The double melting behavior observed in the annealed fibers depended on the annealing temperature and time. CONCLUSION: The improvement of the mechanical properties of the blend fibers with spinning speed, by adding TLCP and by annealing was attributed to an increase in crystallite size, an increase in the degree of crystallinity and an improvement in crystal perfection. The double melting behavior was influenced by the distribution in lamella thickness that occurred because of a melt‐reorganization process during differential scanning calorimetry scans. Copyright © 2007 Society of Chemical Industry     

Investigations of the preparation technology for polyglycolic acid fiber with perfect mechanical performance

Polyglycolic acid (PGA) fibers were prepared by melt‐spinning process in this report. The effects of spinning parameters, such as windup rates and drawn ratio, on the mechanical properties of the fibers were discussed by analyzing the internal stress of as‐spun fibers, axial sound velocity, fiber tenacity, etc. The results showed that windup rate had a slight effect on the macromolecular orientation degree of the as‐spun fibers, which was quite unusual for melt spinning, whereas, the subsequent drawing process effectively increased the macromolecular orientation degree of the PGA fibers and consequently increased the tensile strength of the fibers. Low internal stress of as‐spun fibers obtained at lower windup rate led to higher drawing ratio, and the drawn fibers possessed relatively excellent mechanical properties. As a contrast, higher windup rate resulted in the strong internal stress of the as‐spun fibers, which had a negative influence on the drawing process, and so the tensile strength of the drawn fibers was relatively poor. Therefore, PGA fiber with perfect mechanical performance could be prepared at the technical parameters of lower windup rate and higher drawing multiples as well as slow drawing rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Structure and properties of melt‐spun PET/MWCNT nanocomposite fibers

Polyethylene terephthalate (PET) melt‐spun fibers were modified with multiwall carbon nanotubes (MWCNT) to obtain conductive microfibers smaller than 90 μm in diameter. Physical properties such as crystallinity and orientation of as‐spun fibers were studied by X‐ray diffraction, Raman spectroscopy, and microscopy techniques at different draw ratios (DR) and MWCNT concentrations. Morphological and orientation analysis of MWCNT after melt‐spinning process showed agglomerates formation and highly oriented CNTs. The study of the orientation of PET crystalline phase in drawn fibers proved that the addition of nanoparticles decreases the orientation of crystalline units inside the fibers. The orientation of MWCNT as well as that of PET chains was studied using Raman spectroscopy at different DR and a high degree of CNT orientation was observed under high DR conditions. Mechanical and electrical properties of as‐spun fibers were also investigated. Our results showed that it was possible to achieve conductive fibers at a MWCNT concentration of 2% w/w, and more conductive fibers using higher DR were also obtained without increasing the MWCNT concentration. Mechanical properties results showed interestingly high value of maximum tensile strain at break (ε_max) of nanocomposite fibers, up to three times more than pure PET fibers. POLYM. ENG. SCI., 50:1956–1968, 2010. © 2010 Society of Plastics Engineers     

Resorbable materials of poly(L-lactide). II. Fibers spun from solutions of poly(L-lactide) in good solvents

Fibers of poly(L -lactide) (PLLA) with a tensile strength up to 1.2 GPa and Young's modulus in the range of 12–15 GPA were obtained by a hot drawing of fibers spun from solution of PLLA in good solvents such as dichloromethane and trichloromethane. The tensile strength of fibers was strongly dependent on the molecular weight of PLLA and on polymer concentrations in the spinning solution. Changing of the polymer concentration in the spinning solution gives rise to formation of fibers with different shape and porosity. Fibers spun from 10–20% solutions at room temperature exhibit a regular structurization, due to the melt fracture. These fibers had knot strengths up to 0.6 GPa, whereas fibers with a smooth surface spun from more dilute solutions had weaker square knots up to 0.3 GPa.     

Effect of copolymer mixing on elongation property of as‐spun PET fibers

The change of elongation property in the melt spinning process of polyethylene terephthalate (PET) fibers, mixed with small amount of additive copolymer less than 5% by weight, was studied. The additive polymer was synthesized to improve the extensibility of matrix PET in the spinning process. The amount, molecular weight of additive polymer, and spinning conditions were changed to investigate the extensibility of as‐spun fibers. Experimental results show that the blend of copolymer improves the extensibility of as‐spun PET fibers. The elongation at break of as‐spun fibers increases with molecular weight and amount of additive polymer. The additive polymer prevents the fiber orientation and this causes the increase of extensibility of as‐spun fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1426–1431, 2006     

聚丙烯腈熔融纺丝技术进展

叙述了聚丙烯腈的结构特征，丙烯腈聚合物的增塑，增塑和非增塑聚丙烯腈熔融纺丝工艺和纤维性质。熔纺制得的聚丙烯腈纤维，适用于纺织、地毯以及用作碳纤维原丝。增塑熔融纺丝技术已达到相当高的水平，熔纺纤维的形态与普通聚丙烯腈纤维类似，但存在皮芯结构，芯部有微孔。制得的聚丙烯腈基碳纤维原丝，拉伸强度达５．５～６．６ｃＮ／ｄｔｅｘ，用这种原丝生产的碳纤维的拉伸强度约为３．６×１０３ＭＰａ，模量约为２．３３×１０５ＭＰａ，伸长率约为１．５％，可制得性能优良的航空航天用复合材料。非增塑熔融纺丝，采用特定的丙烯腈聚合物和纺丝条件，不添加任何增塑剂，用普通熔融纺丝机在１０００ｍ／ｍｉｎ或２０００ｍ／ｍｉｎ以上的速度纺丝，经拉伸可得强度２．２～１１ｃＮ／ｄｔｅｘ、伸长率５％～３０％和模量５５～２２２ｃＮ／ｄｔｅｘ的纤维。     

Study on the melt‐spinnability of poly(L‐lactic acid)

In this work, three kinds of different poly(L ‐lactic acid) (PLLA) materials for melt‐spinning were investigated with respect to the molecular weight (MW) and molecular weight distribution (MWD), racemization, optical purity, thermal properties, and melt‐spinnability. It was found that the high MW was not the only factor to affect the melt spinnability of PLLA, the racemization and the amount of residual monomer would also affect the thermal properties and melt‐spinnability of PLLA. The results showed that it could be melt‐spun and hot‐drawn by using the general melt‐spinning device for PLLA pellet with good stereoregularity and comparatively high MW. For PLLA pellet with high MW and moderate stereoregularity, it must be treated at an appropriate temperature to increase the crystallinity before dry and extrusion, which could make the pellet be spun without agglomeration, whereas the draw ability of such as‐spun fiber was still poor. However, if the stereoregularity of PLLA pellet was poor, it could not be spun even it had very high MW. Only when MW, racemization, and the amount of residual monomer of the PLLA pellets all meet the requirements, PLLA fibers could be prepared by melt‐spinning. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

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.     

New functional bicomponent fibers with core/sheath‐configuration using poly(phenylene sulfide) and poly(ethylene terephthalate)

Bicomponent fibers using the high‐performance polymer poly(phenylene sulfide) (PPS) together with poly(ethylene terephthalate) (PET) were melt‐spun. Both possibilities of using PPS, either as core or as sheath material, were realized to provide special functionalities like improved thermobonding capability, flame retardancy, or chemical resistance. Parameters that guarantee stable processing of PPS and PET during coaxial extrusion with different core/sheath volume ratios were explored. Microscopic studies of the cross‐sections showed holes and cavities, which were formed at the interface between PPS and PET. Possible mechanisms for cavity formation were evaluated. Results of thermal and mechanical characterization by means of TGA, DSC, and tensile testing revealed a strong influence of the processing parameters, namely draw ratio and core/sheath volume ratio, on the crystallization and the tensile strength of the drawn fibers. By changing the core/sheath volume ratio from 2 to 0.5 in the PPS/PET fiber, the crystallinity of the PET‐component was switched from 10 to 50%, whereas the crystallinity of the PPS dropped from 68 to 7%. It was determined that bicomponent fibers can exceed the strength of monocomponent fibers up to 28%. The flammability and chemical resistance of the new developed fibers were characterized. In contrary to what was expected, the encasing of PET with PPS reduced the flame retardancy, though PPS has a higher flame resistance than PET. The chemical resistance of the PET core against hydrolysis was imparted by coextruding a PPS sheath. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Spinning fibers from poly(ethylene terephthalate) bottle‐grade waste

Poly(ethylene terephthalate) bottle‐grade (BG) waste was converted into spinnable chips and spun on a laboratory‐scale melt‐spinning apparatus into filaments. Virgin fiber‐grade (FG) polyester chips were blended with BG waste during melt spinning so that the influence of blending on the fiber properties could be studied. Subsequently, the scaling‐up of the process was carried out in a polyester recycling plant so that staple fibers could be obtained. In this part of the study, the spinning of blends of BG waste and FG waste was carried out. The BG waste was found to be superior feed stock for melt processing. Fibers with unique properties were obtained from the BG waste. Staple fibers obtained by the blending of FG and BG waste showed properties different from those of fibers spun from BG waste alone. This study also showed that using blends of BG and FG waste could improve the melt processing and staple‐fiber properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3536–3545, 2003     

Characterization of poly(L‐lactic acid) fibers produced by melt spinning

Biodegradable poly(L ‐lactic acid) (PLLA) fibers were processed by a two‐step melt‐spinning method (melt extrusion and hot draw) from PLLA with three different viscosity‐average molecular weights (494,600, 304,700, and 262,800). Before spinning, the polymer flakes were first milled into powders and dried under vacuum. Viscosity‐average molecular weight of PLLA following the fabrication process was monitored. Tensile properties of as‐spun and hot‐drawn fibers were investigated. Morphology of the PLLA fibers was viewed under a scanning electron microscope. Crystallinity of these fibers was assessed by thermogram analysis of differential scanning calorimetry. Results showed that the extent of decrease in the viscosity‐average molecular weight of PLLA dropped sharply by 13.1–19.5% during pulverization and by 39.0–69.0% during melt‐extrusion. The hot‐draw process in this study had a little effect on the viscosity‐average molecular weight of PLLA. Smoother fibers could be obtained for the die temperature at least 230°C for raw materials with higher crystallinity (more than 75%) and at least 220°C for raw materials with lower crystallinity (about 60%). The as‐spun fibers showed crystallinity of 16.5–22.8% and the value increased to 50.3–63.7% after hot draw. Tensile moduli of the as‐spun fibers were in the range of 1.2–2.4 GPa, which were raised to 3.6–5.4 GPa after hot draw. The final PLLA fibers with 110–160 μm diameters showed tensile strengths of 300–600 MPa. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 251–260, 2001     

The influence of resin characteristics on the high speed melt spinning of isotactic polypropylene. I. Effect of molecular weight and its distribution on structure and mechanical properties of as-spun filaments

The fine structures and tensile mechanical properties were characterized for high speed melt spun filaments prepared from three polypropylenes with melt flow indices in the range 12–300. It was found that spinnability and the resulting structure and properties are affected by both the weight average molecular weight and the polydispersity of the polymer. Higher tenacities, with consequent lower percent elongation to break, could be achieved by spinning the narrow molecular weight distribution polymers at high spinning speeds. This effect was associated with the development of higher birefringence in these samples. Modulus did not correlate with birefringence in the present study, but it was found to be controlled by the nature and level of crystalline order developed in the filaments.     

Influence of the spinning conditions on the structure and properties of polyamide 12/carbon nanotube composite fibers

The inclusion of nanoparticles in polymer fibers is potentially useful for improving or bringing new properties such as mechanical strength, electrical conductivity, piezoresistivity, and flame retardancy. In this study, composite fibers made of polyamide 12 and multiwall carbon nanotubes were investigated. The fibers were spun via a melt‐spinning process and stretched at different draw ratios. The influence of several spinning factors, including spinning speed, extrusion rate, and draw ratio were investigated and correlated to the structure and properties of the fibers. X‐ray diffraction analyses and mechanical tests indicated that the spinning speed barely affected the structure and mechanical properties of the fibers under tension. The spinning speed, however, is critical for future industrial applications because it determines the possible production rates. By contrast, drawing during spinning or after spinning strongly affected the polymer chain alignment and fiber mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure and properties of partially cyclized polyacrylonitrile‐based carbon fiber—precursor fiber prepared by melt‐spun with ionic liquid as the medium of processing

Carbon fiber has many excellent properties. Currently, the precursor fiber of polyacrylonitrile (PAN)‐based carbon fiber is made from solution by wet or dry spinning process that requires expensive solvents and costly solvent recovery. To solve this problem, we developed a melt‐spun process with ionic liquid as the medium of processing. The melt‐spun precursor fiber exhibited partially cyclized structure. The structure and properties of the melt‐spun PAN precursor fiber were analyzed by combination of scanning electron microscope, Fourier transform infrared spectroscopy, differential scanning calorimetry, X‐ray diffraction, thermogravimetry, ultraviolet spectroscopy, flotation technique, sound velocity orientation test, linear density, and tensile strength tests. The results showed that the tensile strength of melt‐spun PAN precursor fiber was fairly high reached up to 7.0 cN/dtex. The reason was the low imperfect morphology and a cyclized structure formed by in situ chemical reaction during melt‐spun process. Due to the existence of partially cyclized structure in the melt‐spun PAN precursor fiber, exothermic process was mitigated and the heat evolved decreased during thermal stabilization stage in comparison with commercial precursor fibers produced by solution‐spun, which could shorten the residence time of thermal stabilization and reduce the cost of final carbon fiber. POLYM. ENG. SCI., 55:2722–2728, 2015. © 2015 Society of Plastics Engineers     

Melt spun thermoresponsive shape memory fibers based on polyurethanes: Effect of drawing and heat‐setting on fiber morphology and properties

Thermoresponsive shape memory (SMP) fibers were prepared by melt spinning from a polyester polyol‐based polyurethane shape memory polymer (SMP) and were subjected to different postspinning operations to modify their structure. The effect of drawing and heat‐setting operations on the shape memory behavior, mechanical properties, and structure of the fibers was studied. In contrast to the as‐spun fibers, which were found to show low stress built up on straining to temporary shape and incomplete recovery to the permanent shape, the drawn and heat‐set fibers showed significantly higher stresses and complete recovery. The fibers drawn at a DR of 3.0 and heat‐set at 100°C gave stress values that were about 10 times higher than the as‐spun fibers at the same strain and showed complete recovery on repeated cycling. This improvement was likely due to the transformation brought about in the morphology of the permanent shape of the SMP fibers from randomly oriented weakly linked regions of hard and soft segments to the well‐segregated, oriented and strongly H‐bonded regions of hard‐segments. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2172–2182, 2007     

Morphology and tensile properties of polypropylene‐multiwalled carbon nanotubes composite fibers

In this work, we analyzed tensile properties of polypropylene‐multiwalled carbon nonotubes composite fibers. The multiwalled carbon nanotubes (MWCNTS) were used in different contents of 0, 1, 2, 3, 4, and 5 wt %. Dispersing agents were used to disperse MWCNTs in polypropylene matrix. After the dispersing agent was removed, the mixture was melt mixed. The fibers were spun by a home‐made melt spinning equipment and stretching was done at a draw ratio of 7.5. By using 1–5 wt % of MWCNTs, the modulus of composite fibers increased by 69–84% and tensile strength increased about 39% when compared with the virgin polypropylene fibers. In addition, the MWCNTs dispersion in the matrix was monitored by scanning electron microscopy and transmission electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011