Structure development during melt spinning of linear polyethylene fibers

Apparatus has been developed for studying the development of crystallinity and orientation during the melt spinning of synthetic fibers. Tension in the fiber and temperature, diameter, and x-ray diffraction patterns are measured as a function of distance from the spinneret for a running monofilament. Measurements are presented for linear polyethylene over a range of spinning variables together with other investigations carried out on the final as-spun fibers. These data indicate that the development of crystallinity in polyethylene is controlled by a balance between increased crystallization kinetics caused by the stress in the fiber and a tendency for increased supercooling with change in any spinning variable that increases cooling rates in the fiber. The type of crystalline orientation observed, its development during the spinning process, and the changes observed with changes in spinning conditions suggest a model for the as-spun fiber structure in which varying amounts of row nucleation and twisting of lamellar, folded-chain crystal overgrowths occur depending on the spinning conditions. As-spun fiber birefringence was shown to depend primarily on the crystalline orientation. Mechanical properties correlated well with c-axis crystalline orientation function and spinline stress.     

Melt strength,local velocity,and elongational viscosity profiles of low‐density polyethylene filaments affected by the die design and process conditions

An experimental arrangement to simultaneously measure the melt strength, velocity profiles, and elongational viscosity profiles across the cross section of a molten filament that emerged from either a circular or slit die for low‐density polyethylene (LDPE) under nonisothermal and isothermal conditions is proposed. The proposed experimental rig was based on a parallel coextrusion technique of colored LDPE melt layers into an uncolored melt flowing from the barrel into and out of a die to form a continuous filament before they were pulled down by mechanical rollers until the filament failed. The experimental rig was also equipped with a high‐speed data‐logging system and a personal computer for real‐time measurements. The results suggest that the draw‐down forces changed continuously with changing roller speed, and the velocity profiles of the melt were not uniform across the LDPE filament during the stretching of the melt. Greater draw‐down forces and local melt velocities were obtained in the slit die or under the nonisothermal condition. The draw‐down forces and velocity profiles in both dies were affected by the volumetric flow rates from the extruder and the roller speeds used, with the effect being more pronounced for the circular die. The elongational viscosity profiles of the LDPE filament were not uniform across the filament cross section and corresponded well to the obtained velocity profiles. The elongational viscosities of the LDPE filament were relatively higher when the filament was extruded and stretched in the circular die and under the nonisothermal condition. The changes in the elongational viscosity profiles were more sensitive to changes in the volumetric flow rate and roller speed in the circular die. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Elongational viscosity in the isothermal melt spinning of polypropylene

The elongational viscosity of polypropylene has been investigated by isothermal melt spinning, carried out over a range of experimental conditions. The filament diameter and the elongational force were measured for running filaments and the relationship between elongational viscosity and elongational strain rate reported. The elongational viscosity was observed to decrease in the vicinity of the spinneret and then remained constant before increasing along the thread line. An increase in elongational viscosity did not occur within the isothermal zone until the elongational flow was fully developed. The onset of an increase in elongational viscosity was determined from the constant total elongational strain. The degree of molecular orientation was also studied by birefringence measurements and was investigated as a function of elongational stress. At a high elongational stress, the relation between birefringence and elongational stress departed from linearity and exhibited a rapid increase which can be related to the increase in elongational viscosity.     

Simulation of non‐isothermal melt densification of polyethylene in rotational molding

Rotational molding involves powder mixing, heating and melting of powder particles to form a homogeneous polymer melt, as well as cooling and solidification. The densification of a loose powder compact into a homogeneous melt occurs over a wide range of conditions as the material passes from a solid state into a melt state. The numerical simulation of the non‐isothermal melt densification in the rotational molding process is presented in this work. The simulation combines heat transfer, polymer sintering and bubble dissolution models, and is based on an idealized packing arrangement of powder particles. The predictions are in general agreement with experimental observations presented in the literature for the rotational molding of polyethylenes. The simulation allows for systematic and quantitative studies on the effect of molding conditions and material properties on the molding cycle and molded part density. Results indicate that the densification process is primarily affected by the powder characteristics, which are accounted for in terms of the particle size and the particle packing arrangement. The material rheological properties become increasingly important as the powder characteristics lessen in quality. The simulation demonstrated that while certain combinations of processing conditions help reduce the molding cycle, they have a detrimental effect on the densification process.     

On-line density and crystallinity of polyethylene terephthalate during melt spinning

The density and crystallinity of polyester fiber were measured on the moving threadline during the melt spinning process. The density was calculated by applying the continuity equation at points along the length of the threadline. Experimental inputs to the equation included paralle, on-line measurements of fiber diameter, fiber velocity, polymer mass flowrate, fiber temperature, and fiber birefringence. When spinning speeds exceeded 4500 m/min, a distinct rise in density occurred along the threadline. This rise corresponded with the rise in birefringence.     

Instabilities and failure in elongational flow and melt spinning of fibers

A theoretical and experimental study of instability and failure behavior during melt spinning is presented. From an analysis of system dynamics, draw resonance is shown to be a continuous processing analogue of ductile failure. Using viscoelastic fluid mechanics and the White-Metzner constitutive model, it is shown that melts which exhibit ductile failure in elongational flow tend to show draw resonance in melt spinning. Deformation hardening melts exhibit cohesive fracture in elongational flow and melt-spinning processes.     

Non‐isothermal crystallization kinetics and segmental dynamics of high density polyethylene/butyl rubber blends

Non‐isothermal crystallization kinetics and dynamics of polymer blends are important to both theory and applications. In this work, we studied the morphology, crystal structure, non‐isothermal crystallization kinetics and dynamics of high density polyethylene/butyl rubber (HDPE/IIR) blends. The non‐isothermal crystallization kinetics is analyzed by Mo's model and the dynamics behavior is analyzed by a linear method. The results of morphology, non‐isothermal crystallization kinetics and dynamics show that the condensed structure of HDPE/IIR blends has a marked influence on their non‐isothermal crystallization kinetics and segmental dynamics. © 2015 Society of Chemical Industry     

Studies on melt spinning process of hollow polyethylene terephthalate fibers

Dimensional change and profile development in the melt spinning process of polyethylene terephthalate hollow fibers were studied through the numerical simulations and experimental results. The simulation predicts the final dimensions and profiles development of the hollow fibers at various positions from the die. Experimental results show that the melt extruded from the spinneret coalesces initially to form a hollow inner core and the cross‐sectional shape holds for over the whole spinline with only variation in the hollow portion. Analysis of the effect of spinning parameters on hollow portion shows that the spinning temperature, mass throughput rate, and take‐up speed are the most critical variables in controlling the hollow portion followed by quench air velocity. The quench air temperature has relatively less effect than the other variables. As the mass throughput rate and quench air velocity increase and the take‐up speed and spinning temperature decrease, the hollow portion increases. To investigate the effect of die geometry, die having a different ratio of inner to outer diameter was used. The effect of change of process variables decreases as the die gap becomes narrow. POLYM. ENG. SCI. 46:609–616, 2006. © 2006 Society of Plastics Engineers     

Effect of blending high‐pressure low‐density polyethylene on the crystallization kinetics of linear low‐density polyethylene

It is well known that the addition of a small amount of high‐pressure low‐density polyethylene (HP‐LDPE) to linear low‐density polyethylene (LLDPE) can improve the optical properties of LLDPE, and LLDPE/HP‐LDPE blend is widely applied to various uses in the field of film. The optical haziness of polyethylene blown films, as a result of surface irregularities, is thought to be as a consequence of the different crystallization mechanisms. However, not much effort has been directed toward understanding the effect of HP‐LDPE blending on the overall crystallization kinetics (k) of LLDPE including nucleation rate (n) and crystal lateral growth rate (v). In this study, we investigated the effect of blending 20% HP‐LDPE on the crystallization kinetics of LLDPE polymerized by Ziegler‐Natta catalyst with comonomer of 1‐butene. Furthermore, by combining depolarized light intensity measurement (DLIM) and small‐angle laser light scattering (SALLS), we have established a methodology to estimate the lateral growth rate at lower crystallization temperatures, in which direct measurement of lateral growth by polarized optical microscopy (POM) is impossible due to the formation of extremely small spherulites. This investigation revealed that HP‐LDPE blending leads to enhanced nucleation rate, reduced crystal lateral growth rate, and a slight increase in the overall crystallization kinetics of pure LLDPE. From the estimated crystal lateral growth rate, it was found that the suppression in v from HP‐LDPE blending is larger at lower temperatures than at higher temperatures. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

High‐performance filaments by melt spinning low viscosity nylon 6 using horizontal isothermal bath process

Several techniques and treatments have been developed for the production of high‐performance nylon‐6 fibers. The inherent problems of low productivity, high production cost, and high energy consumption, complexity of chemical reaction, mass transfer, and waste recovery systems make most of them inappropriate for industrial application. Horizontal isothermal bath (hIB) is an alternative ecofriendly simple treatment that can be used during melt spinning process for production of technical textile fibers. The efficacy of hIB in improving the mechanical properties of multifilament nylon‐6 yarn is studied in this research. The results showed that such treatment can increase the molecular orientation of the amorphous and crystalline functions up to 0.54 and 0.983, respectively, and raised both the amorphous isotropy and fiber birefringence by 67 and 45%, respectively. Hot drawing of the yarn at a very low draw ratio of 1.38, increased the tenacity and modulus up to 10 and 43.9 g/den, respectively, and decreased the elongation to 27%. POLYM. ENG. SCI., 55:2457–2464, 2015. © 2015 Society of Plastics Engineers     

Studies on the kinetics of orientation and crystallization of nylon‐66 during high‐speed melt spinning

A new way of applying on‐line experimental data and basic theory to study the mechanism of orientation of a high‐speed melt spinning process is described. The relationship of birefringence and stress for Nylon‐66 was developed to understand the phenomena in the spinning line. The value of birefringence along the spinning line was calculated by various models to predict the orientation change. By comparison of the model prediction and on‐line experimental birefringence, a suitable mechanical model to simulate the change of the profiles along the spinning line was chosen, and the structural development mechanism is discussed. The results show that the orientation mechanism of high‐speed melt spinning of Nylon‐66 is determined by deformation and deformation rate along the spinning line. For Nylon‐66, molecular and crystal orientations develop independently and are controlled by the rotation of crystals and chain segments in the deformation field. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3157–3163, 2001     

Effect of the high‐density polyethylene melt index on the microcellular foaming of high‐density polyethylene/polypropylene blends

The effect of high‐density polyethylene (HDPE)/polypropylene (PP) blending on the crystallinity as a function of the HDPE melt index was studied. The melting temperature and total amount of crystallinity in the HDPE/PP blends were lower than those of the pure polymers, regardless of the blend composition and melt index. The effects of the melt index, blending, and foaming conditions (foaming temperature and foaming time) on the void fractions of HDPEs of various melt indices and HDPE/PP blends were also investigated. The void fraction was strongly dependent on the foaming time, foaming temperature, and blend composition as well as the melt index of HDPE. The void fraction of the foamed 30:70 HDPE/PP blend was always higher than that of the foamed 50:50 HDPE/PP blend, regardless of the melt index. The microcellular structure could be greatly improved with a suitable ratio of HDPE to PP and with foaming above the melting temperature for long enough; however, using high‐melt‐index HDPE in the HDPE/PP blends had a deleterious effect on both the void fraction and cell morphology of the blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 364–371, 2004     

Isothermal and non‐isothermal crystallization behavior of PET nanocomposites

Polyethylene terephthalate (PET)/clay nanocomposites (PCNs) containing 1 wt% Cloisite 30B (C30B) were prepared via melt compounding. Modulated differential scanning calorimetry (MDSC) for isothermally crystallized samples revealed that the third endotherm at the highest temperature may be attributed to the recrystalization and melting of crystals, reorganized during heating. The first and second endotherms may be associated with melting of the secondary and primary crystals, respectively. The overall isothermal crystallization rate in PCNs was faster than in the neat resin. Growth kinetics revealed that the work required for chain folding and the equilibrium melting temperature in PCNs were somewhat higher than for neat PET. During isothermal crystallization, the steric hurdles introduced by clay layers lead to a reduction in the transport of the PET chains into crystallites. The effective non‐isothermal activation energy for the PCNs was higher than for PET, possibly leading to less perfect crystals in the PCNs. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Structure development during polymer processing: Studies of the melt spinning of polyethylene and polypropylene fibers

Experimental studies of structure development in melt spinning of polyethylene and polypropylene fibers are described. Emphasis is given to the influence of applied stresses on the rates of crystallization and on the development of crystalline morphology. The relationship of fiber morphology to mechanical properties, especially “hard elastic fibers” is considered. The relevance of such studies to other polymer processing operations such as film extrusion is discussed.     

An investigation of heat transfer effects in isothermal crystallization studies of low‐density polyethylene

Isothermal crystallization kinetics of low‐density polyethylene (LDPE) were measured from 96°C‐103°C using a power‐compensating differential scanning calorimetry (DSC). Crystallization kinetics were measured using different sample thicknesses and on samples compounded with nickel, a filler with high thermal conductivity. For the unfilled material, sample thickness and temperature had a significant effect on the rate of crystallization as measured by the Avrami rate constant K, but had no effect on the nucleation mechanism and dimensionality of growth, as measured by the Avrami constant n. The crystallization growth rate as expressed by K^1/n scaled approximately with the thickness of the sample. For the filled material, K was much higher and independent of nickel content, suggesting a limiting growth rate for polyethylene at a given temperature in this equipment. The dependence of crystallization rale on sample thickness indicates that barriers to heat transfer can be important. This work shows that for most crystallization rates, thermal conductivity, rather than interfacial resistance between sample and pan, limits heat transfer. Even though thermal conductivity typically dominates heat‐transfer resistance, sample‐pan thermal contact is still important, and some guidelines are given to determine whether good contact is being made.     

Radial temperature differences during the melt spinning of fibers

In this investigation, a numerical model was developed to predict the temperature distribution in a fiber during melt spinning. This model uses the implicit Crank–Nicolson method to solve the governing differential equation for the problem. The model was applied to a series of numerical experiments on a liquid crystalline fiber which is melt-spun. These simulations used typical sets of operating conditions to determine the effect of various operating parameters on the predicted radius profile, spinline tension, and temperature distribution. The effects of spinneret capillary diameter, mass flow rate, ambient air temperature, spinning temperature, and elongational viscosity were investigated. The results of the various runs showed that ambient air temperature and mass flow rate had a significant effect on the predicted radius profile, spinline tension, and temperature distribution. The spinning temperature was an important parameter, but its only significant effect was on the spinline tension. Spinneret capillary diameter and elongational viscosity had little effect on the predicted results.     

Fine‐structure and physical properties of polyethylene fibers in high‐speed spinning. I. Effect of melt‐flow rate in the high‐density polyethylene

High‐density polyethylene (HDPE) fibers, obtained from a melt‐flow rate (g/10 min) of 11 and 28, was produced by a high‐speed melt‐spinning method in the range of take‐up velocity from 1 to 8 km/min and from 1 to 6 km/min, respectively. The change of fiber structure and physical properties with increasing take‐up velocity was investigated through birefringence, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), a Rheovibron, and a Fafegraph‐M. With an increase in take‐up velocity, the birefringence showed a sigmoidal increase, which has distinct changes in the range of 1–5 km/min. Throughout the whole take‐up velocities, the birefringence of HDPE(11) was higher than that of HDPE(28). With increasing take‐up velocity, the crystalline orientation was transformed from a‐axis orientation to c‐axis orientation. These crystalline relaxations are confirmed by the tan δ peak of high‐speed spun HDPE fibers. The intensity of the crystalline relaxation peak decreases with increasing take‐up velocity in both HDPE(11) and HDPE(28). As above, the crystalline relaxation peaks shift to lower temperature with increasing take‐up velocity. With increasing take‐up velocity, the ultimate strain decreases while both specific stress and the initial modulus increase. The mechanical behavior may be closely related to, as investigated by birefringence, orientation of the amorphous region, etc., the take‐up velocity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1182–1195, 2000     

Effect of bark flour on melt rheological behavior of high density polyethylene

The melt rheological behavior of neem bark flour (BF) filled high density polyethylene (HDPE) has been studied at varying volume fraction (?_f) from 0 to 0.26 at 180, 190, and 200°C in the shear rate range from 100 to 5000 s^?1 using extruded pellets of the composites. The melt viscosity of HDPE increases with ?_f because the BF particles obstruct the flow of HDPE. With the incorporation of the coupling agent HDPE‐g‐MAH, the viscosity decreased compared to the corresponding compositions in the HDPE/BF systems due to a plasticizing/lubricating effect by HDPE‐g‐MAH. The composites obeyed power law behavior in the melt flow. The power law index decreases with increase in the filler content and increases with temperature for the corresponding systems while the consistency index showed the opposite trend. The activation energy for viscous flow exhibited inappreciable change with either ?_f or inclusion of the coupling agent, however, the pre‐exponential factor increased with filler concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure evolution of ultra high molecular weight polyethylene/montmorillonite nanocomposite fibers prepared by melt spinning

Nanocomposite fibers of ultra high molecular weight polyethylene (UHMWPE) and organic montmorillonite (OMMT) were successfully prepared by a melt‐spinning process. The evolution of the microstructures of the nanocomposite fibers in the drawing process was preliminarily studied by X‐ray diffraction (XRD), differential scanning calorimetry, and small‐angle X‐ray scatters. With the increase of draw ratio values, the crystallinity of the nanocomposite fibers increased, the grain size decreased, and the folded chain crystals gradually transformed into extended chain crystals. The results suggested the evolution of the nanocomposite fibers was similar with that of the fibers made by gel‐spun drawing process. The addition of OMMT in UHMWPE improved the fluidity of the composites yet without affecting the crystal structure of UHMWPE in the drawing process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3930–3936, 2013     

Effect of PMR‐POI on the melt behavior and isothermal crystallization of poly(phenylene sulfide)

The crystallization behavior of neat PPS and PPS in blends with PMR‐POI prepared by melt mixing were investigated by differential scanning calorimetry (DSC). It was found that POI was an effective nucleation agent of the crystallization for PPS. The enthalpy of crystallization of PPS in the blends increased compared with that of neat PPS. During isothermal crystallization from melt, the dependence of relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of POI causes an increase in the overall crystallization rate of PPS; it also changed the mechanism of nucleation of the PHB crystals from homogeneous nucleation to heterogeneous nucleation. The equilibrium melting temperature of PPS and PPS/POI blends were determined. The analysis of kinetic data according to nucleation theories shows that the increase in crystallization rate of PPS in the composite is due to the decrease in surface energy of the extremity surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 436–442, 2002