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     

Computer simulation of melt spinning of polypropylene fibers using a steady-state model

A mathematical model that includes crystallization in the spinline and the effect of crystallization on the extensional viscosity and the various physical properties of polypropylene has been developed and used to help in identifying the various factors that can affect the spun yarn characteristics. The model is used to simulate effects of spinning parameters on fiber physical properties, temperature, and stresses. The experimental observation of a minimum in density of the spun yarn at high throughput rates, when density is plotted as a function of take up velocity, has been investigated in some detail. It has been found that all conditions which can substantially affect the rate of cooling and the orientation of the polymer in the spinline, viz, throughput rate, spinning temperature, and spinning speed have an important bearing on the temperature range in which crystallization can take place in the spinline and thus affect the density. It is suggested that in addition to these factors, the formation of different crystal modifications at different spinning speeds could also contribute to the reduction in density of these samples. The model cannot reflect the observation of density changes occurring due to the formation of different crystal modifications. Nevertheless, it can be of use in understanding the effects of various process conditions on the cooling rate and the orientation of the polymer in the spinline. © 1995 John Wiley & Sons, Inc.     

Dynamics and structure development during high-speed melt spinning of nylon 6. II. Mathematical modeling

A mathematical model of the melt spinning process that includes crystallization has been used to compute the velocity, diameter, temperature, and birefringence as a function of distance from the spinneret. An improved inversion procedure is described and is shown to give better results for the computed apparent elongational viscosity and heat-transfer coefficient data. The computed profiles have been compared directly to the experimental profiles determined earlier and reported in Part I of this paper. The results show that the model describes the major features of the melt spinning process. The reasons for the observed differences between experimental profiles and those computed from the model are discussed.     

Model of steady-state melt spinning at intermediate take-up speeds

A model of melt spinning has been developed for speeds above which the effects of gravity, inertia, and aerodynamic drag become significant. The model has as an upper bound the speed at which stress crystallization begins to occur on the spin line. For poly(ethylene terephthalate), these velocities are approximately 750 and 3500 meters/minute. The calculated temperature and velocity profiles are shown to agree with measured values. The stress at the freeze point is calculated and found to correlate well with the spun yarn birefringence which, in turn, is shown to predict uniquely the spun yarn physical properties on a “simple” spin line. The stress-optical coefficient derived from the calculated stress at the freeze point and measured birefringence agrees well with the literature.     

Preparation and properties of conductive polyaniline/poly‐ω‐aminoundecanoyle fibers

Historically, polyaniline (PANI) had been considered an intractable material, but it can be dissolved in some solvents. Therefore, it could be processed into films or fibers. A process of preparing a blend of conductive fibers of PANI/poly‐ω‐aminoundecanoyle (PA11) is described in this paper. PANI in the emeraldine base was blended with PA11 in concentrated sulfuric acid (c‐H₂SO₄) to form a spinning dope solution. This solution was used to spin conductive PANI / PA11 fibers by wet‐spinning technology. As‐spun fibers were obtained by spinning the dopes into coagulation bath water or diluted acid and drawn fibers were obtained by drawing the as‐spun fibers in warm drawing bath water. A scanning electron microscope was employed to study the effect of the acid concentration in the coagulation bath on the microstructure of as‐spun fibers. The results showed that the coagulating rate of as‐spun fibers was reduced and the size of pore shrank with an increase in the acid concentration in the coagulation bath. The weight fraction of PANI in the dope solution also had an influence on the microstructure of as‐spun fibers. The microstructure of as‐spun fibers had an influence on the drawing process and on the mechanical properties of the drawn fibers. Meanwhile, the electrically conductive property of the drawn fibers with different percentage of PANI was measured. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1458–1464, 2002     

Factorial optimization of the effects of melt‐spinning conditions on biodegradable as‐spun aliphatic–aromatic copolyester fibers. III. Diameter,tensile properties,and thermal shrinkage

To model the melt‐spinning process of biodegradable as‐spun linear aliphatic–aromatic copolyester fibers, a fraction factorial experimental design and appropriate statistical analysis for the 32 screening trials involving five control parameters were used. Because of their central role in the production processes and end use textiles, it is important to simulate the mechanical and thermal shrinkage properties of AAC fibers. Concise statistical models of fiber behavior are based on factorial experimental design data. Process's data are collected, analyzed, and mathematical models created to predict the diameter, tenacity, elongation at break, modulus, and thermal shrinkage of the spun fiber in terms of random variables and their associated probability distributions. The theoretical regression models obtained form the main source code in the enhanced forecasting program, which presents the melt‐spinning process of aromatic–aliphatic copolyester fibers. Factorial statistical approaches, based on over indicated region levels of melt‐spinning process parameters, are given in terms of assumptions and theory to produce biodegradable, environmentally friendly fibers for different applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Manufacture and Characterization of Porous Polypropylene Fibers

Phase separation spinning, a method originally reported by Zwick [1], has been used to produce porous polypropylene fibers by spinning a solution of polypropylene in naphthalene and subsequently extracting the naphthalene with diethyl ether. In phase separation spinning, a hot solution is spun into cool air where the temperature drops below the solubility limit so that the polymer precipitates during spinning. If a relatively nonvolatile solvent in the proper concentration range is used, two continuous phases are formed. Extraction of the nonvolatile solvent produces continuous voids to form a porous fiber.     

Thermotropic polyester carbonates. II. Polyester carbonates as high performance fibers

The fiber spinning and heat treatments of spun fibers from thermotropic polyester carbonates are described. Thermotropic polyester carbonates derived from t-butylhydroquinone, methylhy-droquinone, diphenyl terephthalate, and diphenyl carbonate in the molar ratios of 50 : 50 : 55 : 45; 50 : 50 : 57.5 : 42.5; can be spun successfully, and after proper heat treatment, yield fibers with tenacity as high as 20 g/denier. Normally the best spinning temperature is 10–20°C above melting.     

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.     

Continuous polymerization of caprolactam in a modular intermeshing corotating twin screw extruder integrated with continuous melt spinning of polyamide 6 fiber: Influence of screw design and process conditions

The continuous anionic polymerization of caprolactam to polyamide-6 in a modular, intermeshing, corotating twin screw extruder was investigated. Caprolactam was polymerized by anionic polymerization techniques under a range of processing conditions, including different screw configurations, temperature profiles, screw speeds, and throughputs. Studies were also made of melt spinning polyamide 6 into oriented filaments. The polyamide-6 melt spun filaments were characterized using birefringence and wide angle X-ray diffraction. Uniaxial stress measurements of the fibers were obtained and are reported. The results for the melt spun filaments compare favorably with the previous literature. © 1994 John Wiley & Sons, Inc.     

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     

Spinning and drawing properties of ultrahigh‐molecular‐weight polyethylene fibers prepared at varying concentrations and temperatures

The concentrations and temperatures of ultrahigh‐molecular‐weight polyethylene (UHMWPE) gel solutions exhibited a significant influence on their rheological and spinning properties. The shear viscosities of UHMWPE solutions increased consistently with increasing concentrations at a constant temperature above 80°C. Tremendously high shear viscosities of UHMWPE gel solutions were found as the temperatures reached 120–140°C, at which their shear viscosity values approached the maximum. The spinnable solutions are those gel solutions with optimum shear viscosities and relatively good homogeneity in nature. Moreover, the gel solution concentrations and spinning temperatures exhibited a significant influence on the drawability and microstructure of the as‐spun fibers. At each spinning temperature, the achievable draw ratios obtained for as‐spun fibers prepared near the optimum concentration are significantly higher than those of as‐spun fibers prepared at other concentrations. The critical draw ratio of the as‐spun fiber prepared at the optimum concentration approached a maximum value, as the spinning temperature reached the optimum value of 150°C. Further investigations indicated that the best orientation of the precursors of shish‐kebab‐like entities, birefringence, crystallinity, thermal and tensile properties were always accompanied with the as‐spun fiber prepared at the optimum concentration and temperature. Similar to those found for the as‐spun fibers, the birefringence and tensile properties of the draw fibers prepared at the optimum condition were always higher than those of drawn fibers prepared at other conditions but stretched to the same draw ratio. Possible mechanisms accounting for these interesting phenomena are proposed.     

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.     

Crystallization in polymer melt spinning

The crystallization behavior of poly(ethylene) terephthalate (PET) melt spun into fiber monofilaments was examined using a laboratory set-up. The wind-up speeds ranged from free fall under gravity to 1500 m/min. The major additional variables that were manipulated included the mass flow rate and the filament temperature profile. The structure of the as-spun fibers was probed using tensile tests, differential scanning calorimetry, optical birefringence, and x-ray diffraction. It was found that while the filaments that had been spun nonisothermally were essentially amorphous, those that had been made under isothermal conditions at temperatures ranging from 180°C to 240°C were oriented and crystalline. In addition, the rate of oriented crystallization was much greater than that under quiescent conditions at the same temperature. This is perhaps the first published study which shows that highly crystalline (up to 40% crystallinity) PET fibers can be obtained at low spinning speeds merely by altering the fiber temperature profile while the material is still above the polymer glass transition temperature.     

Measured orientation and internal stress distributions in melt-spun fibers

In this investigation, experimentally measured radial birefringence profiles are compared to internal stress distributions as predicted by a mathematical model. A direct indicator of the degree of molecular orientation, fiber birefringence, is found to correlate well with the stress distributions as calculated from radial temperature variations. In an initial study of glass fibers, no radial birefringence profiles are found, indicating that any residual stresses present are small. In polystyrene fibers, however, large radial variations in birefringence are observed and are shown to be directly related to the calculated internal stresses.     

Melt spinning of nylon 6: Structure development and mechanical properties of as-spun filaments

The structure of melt-spun nylon 6 filaments was studied using on-line x-ray diffraction and birefringence measurements. Measurements were also made on as-spun and treated filaments. On-line wide-angle x-ray scattering measurements indicated that crystallization did not occur on the nylon 6 spinline at spinning rates up to 1000 m/min when spinning was done into either ambient air of 60% relative humidity or into wet saturated air. The filaments did crystalline gradually on the bobbin to a paracrystalline pseudohexagonal (γ) form. The rate of crystallization was dependent on the molecular orientation developed in the spun filaments. Crystalline orientation factors based on hexagonal symmetry were computed as a function of take-up velocity for fibers which were conditioned 24 hr in air at 65% relative humidity. Annealing in air or treatment in water or 20% formic acid solution causes a transformation from the pseudohexagonal form to the α monoclinic form. The tangent modulus of elasticity and tensile strength of spun and conditioned filaments increase with increasing take-up velocity and spinline stress, while elongation to break decreases with these variables.     

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     

聚乙交酯纤维纺丝工艺研究

采用改变纺丝速度、拉伸工艺以及测试纤维内应力、声速值、强度值等方法对聚乙交酯(PGA)的纺丝加工工艺及纤维的力学性能进行了分析研究。结果表明:纺丝速度对PGA初生纤维的取向度几乎没有影响,后拉伸能有效提高纤维的取向度及强度。低速纺丝得到的初生纤维内应力较小,可以进行高倍后拉伸,而高速纺丝得到的初生纤维内应力较大,只能进行低倍后拉伸。适当的加温以及低速拉伸有利于得到较高强度的PGA纤维。总体来说,要得到具有较好力学性能的PGA纤维,必须采用低速纺丝、高倍后拉伸、低速拉伸相加的工艺路线。     

Studies on preparation of immersion‐type polypropylene fragrant fiber. I. Formation of matrix fiber in the melt‐spinning process and its technique of immersion essential oil

Polypropylene/ethylene vinyl acetate (PP/EVA) blends were prepared in a plastic extruder with a static mixer. The thermodynamic compatibility, morphology, crystal form, and rheological behavior of PP/EVA blends were investigated by SEM, DSC, and rheology instruments. The results showed that PP and EVA were thermodynamically incompatible, the viscosity of the PP/EVA blends decreased with increase of shear rate in a range of temperature, the PP/EVA blends had a sea‐islands structure, and the crystalline zones remained in their original state and could not form mixed crystals in the PP/EVA blends. The PP/EVA blends were melt spun to prepare matrix fibers and the spinning conditions such as EVA content, the matching factor between pump delivery and winding velocity, and the melt‐spinning temperature were also determined. The sorption process of a matrix fiber for essential oils, adsorbed under various sorption conditions such as sorption time, sorption temperature, and EVA content, was also studied. The results revealed that the composite isotherm of the adsorption of matrix fiber for essential oil was characteristic of a U model. Through adsorbing essential oil, the immersion‐type PP fragrant fibers could be prepared with the matrix fiber. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1970–1979, 2003     

Studies of converging flows of viscoelastic polymeric melts. III. Stress and velocity distributions in the entrance region of a tapered slit die

An experimental and theoretical study has been carried out, as a continuation of our previous investigation, to better understand the problems associated with converging flows of viscoelastic polymeric melts. In the present study, measurements were taken of both stresses and velocities in the converging velocity field of polymeric melts flowing into a tapered slit die, stresses by means of the flow birefringence technique and velocities by means of streak photography. The material used was polystyrene. A theoretical analysis was also made of converging flow, using a modified second-order fluid model which assumes that all three material functions depend on the second invariant of the rate of deformation. Numerical solutions were obtained of the equations of motion, which give predicted velocity profiles in reasonable agreement with the measured velocity profiles. A comparison was also made of the experimentally determined stress distributions with the theoretically predicted ones.