Crystallization kinetics of high-density polyethylene/linear low-density polyethylene blend

This article presents crystallization kinetics studies on a cocrystallizing polymer highdensity polyethylene (HDPE)/linear lowd-ensity polyethylene (LLDPE) blend. The nonisothermal crystallization exotherms obtained by differential scanning calorimetry (DSC) were analyzed to investigate the effect of cocrystallization on kinetics parameters, namely the Avrami exponent and activation energy. The regular change of Avrami exponent with blend composition from a value of about 3 corresponding to HDPE to a value of 2 corresponding to LLDPE is observed. A sheaf-like crystalline growth with variation of nucleation depending on blend composition is concluded from these results of DSC exotherm analysis in conjunction with the small-angle light scattering observations. The observed variation of activation energy of crystallization with blend composition suggests the role of interaction of side chains and comonomer units present in the LLDPE. © 1994 John Wiley & Sons, Inc.     

Crystallization behavior of high-density polyethylene/linear low-density polyethylene blend

Binary blend of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE), prepared by melt mixing in an extruder, in the entire range of blending ratio, is studied for crystallization behavior by differential scanning calorimetry (DSC) and X-ray diffraction measurements. Cocrystallization was evident in the entire range of blend composition, from the single-peak character in both DSC crystallization exotherms and meltingendotherms and the X-ray diffraction peaks. A detailed analysis of DSC crystallization exotherms revealed a systematic effect of the addition of LLDPE on nucleation rate and the subsequently developed crystalline morphology, which could be distinguished in the three regions of blending ratio, viz, the “HDPE-rich blend,” “LLDPE-rich blend,” and the “middle range from 30–70% LLDPE content.” Variations in crystallinity, crystallite size, and d spacing are discussed in terms of differences in molecular structure of the components.     

Crystallization kinetics of polyethylene terephthalate. I. Isothermal crystallization from the melt

The crystallization behavior of polyethylene terephthalate (PET) was investigated as a function of molecular weight, temperature of crystallization, and polycondensation catalyst system. A detailed analysis of the crystallization course has been made utilizing the Avrami expression. The crystallization rate constants and the Avrami exponents were calculated. The results show that the rate constant and the mechanism of crystallization are dependent on the molecular weight, temperature, and the polycondensation catalyst system. The catalyst system often exhibits a more significant influence than the molecular weight in controlling the rate of crystallization of PET.     

Elongational flow properties of low-density polyethylene and linear low-density polyethylene from nonisothermal melt spinning experiments

Low-density polyethylene (LDPE) and also linear low-density polyethylene (LLDPE) resins can be characterized by the degree of strain hardening and down-gaging during elongation. A new method for the determination of the apparent elongational flow characteristics is presented. In a small scale apparatus, a molten monofilament is stretched under nonisothermal conditions similar to those found in tubular film extrusion. Measurement of resistance to elongational flow and apparent elongational strain rates permit the comparison of the process-ability of different resins under specified conditions. The effect of melt temperature and extension ratio are examined. The importance of the molecular structure of both LDPE and LLDPE resins on these properties is also outlined.     

A study of melt density of flowing linear polyethylene

Linear polyethylene was extruded from a capillary rheometer with the driving piston operated at fixed speed and at fixed pressure. Apparent viscosity and melt density were measured in both extrusion modes. Apparent density decreased at shear rates approaching the melt fracture region in fixed piston-speed operation. Flow of other polymer melts was essentially incompressible in fixed piston-speed operation, and all polymers exhibited incompressible flow in fixed-pressure extrusion. The oscillating portion of the flow curve of linear polyethylene reflects alternating periods in which the polymer exits faster and slower than the rate at which the advancing piston clears the rheometer reservoir. Linear polyethylene behaves differently from most other polymers in fixed piston-speed extrusion and during melt fracture because of the existence of a more extensive entanglement network in the melt. It is suggested that melt fracture in general results from a tensile failure of the entanglement network, which may occur at the die inlet and in the orifice.     

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.     

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.     

Crystallization of high-density polyethylene–linear low-density polyethylene blend

The crystallization studies revealed that the high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) formed strong cocrystalline mass when they were melt blended in a single screw extruder. The progress of crystallization was observed through a small-angle light scattering instrument, scanning electron microscope, and differential scanning calorimeter. Analysis showed that these constituents followed individual nucleation and combine growth of crystallites in blends. The growth of crystallites all through the blend compositions were two-dimensional. Interestingly, the crystallites resembled each other for a particular blend composition; however, they differ widely as the composition changes. The rate of crystallization depends greatly to the number of crystallites and their interfacial boundary in contact with the amorphous phase pool. The t_1/2 and percentage of crystallinity showed a mutually exclusive trend and were seen to be varied in the following three regions of blend composition: the HDPE-rich, the LLDPE-rich, and the middle region of blend composition. The percentage of crystallinity decreases in both the HDPE-rich and LLDPE-rich blends, and it showed a plateau value in the middle region of blend composition. The t_1/2 showed opposite trend to that of % crystallinity. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2599–2607, 1998     

Evidence for isothermal lamellar thickening at and behind the growth front as polyethylene crystallizes from the melt

The poorly characterized and little understood phenomenon of isothermal lamellar thickening, central to melt crystallization, has been studied morphologically in polyethylene rows, grown around high-melting fibres as linear nuclei revealing that thickening is a function of position within the morphology as well as of elapsed time. In contrast to polyethylene spherulites whose central lamellae are the thickest, in rows the first lamellae to form remain the thinnest because, being close-packed, they have no space into which to thicken. The thickness of lamellae at the growth front increases linearly with the logarithm of elapsed time but, as the thickest lamellae are found at finite radius, thickening must also occur behind the growth front. The data are consistent with a uniform rate of thickening throughout spherulitic polyethylene but melt crystallization must now be envisaged as occurring not at an interface in steady-state condition but at one whose thickness increases asymptotically and where interference will reduce thickening.     

Crystallization and phase separation kinetics in blends of linear low-density polyethylene copolymers

We have systematically studied the crystallization and liquid-liquid phase separation (LLPS) kinetics in statistical copolymer blends of poly(ethylene-co-hexene) (PEH) and poly(ethylene-co-butene) (PEB) using primarily optical microscopy. The PEH/PEB blends exhibit upper critical solution temperature (UCST) in the melt and crystallization temperature below the UCST. The time evolution of the characteristic morphology for both crystallization and LLPS is recorded for blends at various compositions and following a quench from initial homogenous melts at high temperature to various lower temperatures. The crystallization kinetics is measured as the linear growth rate of the super structural crystals, whereas the LLPS kinetics is measured as the linear growth rate of the characteristic length of the late-stage spinodal decomposition. The composition dependence crystallization kinetics, G, shows very different characteristics at low and high isothermal crystallization temperature. Below 116 °C, G decreases with increasing PEB content in the blend, implying primarily the composition effect on materials transport; whereas at above 116 °C, G shows a minimum at about the critical composition for LLPS, implying the influence of the LLPS. On the other hand, LLPS kinetics at 130 °C is relatively invariant at different compositions in the two-phase regime. The length scale at which domains are kinetically pinned, however, depends strongly on the composition. In a blend near critical composition, a kinetics crossover is shown to separate the crystallization dominant and phase separation dominant morphology as isothermal temperature increases.     

Morphology of polyethylene spherulite crystallized from melt

The morphology of melt‐crystallized polyethylene is reported. The samples were crystallized for different times at high temperature to produce early stages of spherulitic growth. Morphology studies using transmission electron microscopy showed that the largest proportion of the early objects was monolayers associated with a giant screw dislocation, and the remaining objects were multilayers. At the basal surfaces of these objects, the traces of the {1 0 0} planes were identified, and the angle between the different planes was found to be 67°30′. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1125–1129, 1999     

Crystallization from a strained melt or solution

The elongation and orientation of randomly coiled macromolecules in a strained melt or solution reduces their entropy and thus increases the crystallization or melting temperature of the ideal lattice. At any given temperature of experiment this enhances nucleation and crystal growth rate. As a rule, linear primary nuclei are formed. They contain more or less extended chains. The existence of row nuclei reduces the local gradient in the liquid to such an extent that further crystallization proceeds by epitaxial overgrowth of folded chain lamellae. Densely packed cylindrites are formed with the ribbon-like lamellae radiating from the central row nucleus. The irregular shish-kebab structure observed in stirred or sonicated solutions seems to be formed by subsequent exial deformation of cylindrites in the flow field. It displaces the lamellae irregularly and thus produces a great many microfibrillar elements parallel to the original row nuclei. The almost completely extended chains in the shish yield a high elastic modulus and tensile strength for exial loading. The shish-kebab morphology in fibers as spun does not affect to a great extent the mechanical properties obtainable by subsequent drawing. The lamellae are transformed into microfibrils in very much the same manner as in spherulitic samples. But the highly regular orientation of lamellae seems to result in a more uniform drawing and hence a stronger fiber. In an extremely high temperature and pressure gradient, the melt extrusion produces hard elastomers where the lamellae of the cylindrites seem to be locally stapled. Upon application of tensile load in the extrusion direction, the intervening sections bend like beams, thus forming thin holes extending in the direction perpendicular to the load. The holes enormously enhance the permeability for gases and liquids. The elastic bending of lamellae yields the high recoverable strain and low tensile modulus.     

Crystallization behaviour of isotactic polypropylene/linear low density polyethylene blends

Crystallization behaviour of isotactic polypropylene/linear low density polyethylene (iPP/LLDPE) blends has been investigated by optical microscopy and DSC. Crystallization of iPP depends upon blend composition and thermal history. When blended with LLDPE, the crystallization temperature of iPP, T_c, decreased slightly. Crystallinity did not change in the range 0-80wt% LLDPE; there were only slight changes in the crystalline structure, but LLDPE seemed to resist forming the β type of spherulites. Below 80 wt% of LLDPE, iPP was a continuous phase. The iPP spherulite growth rate was almost constant; however, overall crystallization decreased due to decreasing primary nuclei density.     

Crystallization behavior of carbon nanofiber/linear low density polyethylene nanocomposites

Crystallization behavior of LLDPE nanocomposites is reported in the presence of three types of carbon nanofibers (CNFs) (MJ, PR‐19, and PR‐24). During nonisothermal crystallization studies, all three crystalline melting peaks for LLDPE matrix were observed in the presence of PR‐19 nanofibers (up to 15 wt % content), but only the high‐ and low‐temperature peaks were observed in the presence MJ nanofibers. The broad melting peak at low‐temperature became bigger, suggesting an increase in the relative content of thinner lamellae in the presence of MJ nanofibers. TEM results of nanocomposites revealed transcrystallinity of LLDPE on the surface of CNFs, and a slightly broader distribution of lamellar thickness. STEM studies revealed a rougher surface morphology of the MJ nanofibers relative to that of PR nanofibers. Also, BET studies confirmed a larger specific surface area of MJ nanofibers relative to that of PR nanofibers, suggesting that the larger and the rougher surface of MJ nanofibers contributes toward the different crystallization behavior of MJ/LLDPE nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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.     

Crystallization kinetics modeling of high density and linear low density polyethylene resins

This paper describes isothermal and nonisothermal crystallization kinetics of a Ziegler‐Natta catalyzed high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) resins. Standard techniques such as differential scanning calorimetry (DSC) and light depolarization microscopy (LDM) techniques were used to measure isothermal kinetics at low supercoolings. DSC was also used to measure nonisothermal crystallization kinetics at low cooling rates. Extrapolation of isothermal crystallization half‐times of Z‐N catalyzed LLDPE resin using the isothermal half‐time analysis led to erroneous predictions, possibly due to Z‐N LLDPE consisting of a mixture of molecules having different amounts of short chain branching (comonomer). However, predicted reciprocal half‐times at high supercoolings, using isothermal half‐time analysis and using nonlinear regression of nonisothermal crystallization kinetics measured at low cooling rates using the differential Nakamura model, of the HDPE were similar to measured reciprocal half times at high supercoolings of a similar HDPE by Patki and Phillips. It is also shown that the differential Nakamura model can be effectively used to model nonisothermal crystallization kinetics of HDPE resins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Crystallization temperature effect on the solid-state rheology of a high-density polyethylene under compression

The plane-strain compression test provides quantitative data on the polymer rheology in homonogeneous large deformation at constant strain-rate, and on the friction shear stress between the film and the dies. Thin HDPE films with a homogeneous morphology were formed by quenching or isothermal crystallization. The structure was modified by varying the crystallization temperature over a wide range: 118°C ? T_c ? 130°C. A mechanical model with a pressure-dependent rheology and two friction laws was tested. The rheological parameters are different in tension and in compression. The occurrence of brittle fracture under compression depends on the crystallization temperature, but the rheological parameters are almost independent of the crystallization conditions.     

Crystal structure changes during isothermal crystallization, cooling and heating of linear polyethylene

The dynamic process of crystal structure change during isothermal crystallization, cooling and heating of linear polyethylene with different molecular weight and polydispersity was followed by wide-angle X-ray diffraction (WARD) measurement. From the WARD data, variations of unit cell parameters a and b and changes in crystallinity were estimated. During isothermal crystallization, both cell parameters were found to decrease with time, suggesting that the crystal structure was becoming more perfect. With an increase in molecular weight or crystallization temperature, the rate of crystal perfection and the attainable crystallinity were found to decrease. This behavior can be explained by the formation of thicker lamellae, which probably have a lower degree of defects and a reduced surface-to-volume ratio in the crystals. Upon cooling and heating, the cell parameters appeared to contract and expand accordingly. The thermal contraction and expansion of parameter a is considerably larger than that of b, which probably results from the weaker intra-chain interactions along the a-axis, which is perpendicular to the spherulite growth direction.