Effect of molecular and processing parameters on the flow-induced crystallization of poly-1-butene. Part 1: Kinetics and morphology

In this work the effect of molecular parameters (molecular weight (M_W), molecular weight distribution (MWD)) and processing conditions (crystallization temperature, flow conditions) on the isothermal crystallization behavior of three isotactic poly-1-butene (iPB) samples is investigated by means of rheo-optical techniques. The emphasis in this paper will be on the kinetics and the resulting morphology.Turbidity measurements show a strong effect of M_W and the degree of undercooling on the flow-induced crystallization (FIC), whereas the effect of MWD is not quite clear. Scaling relations, proposed in literature, that are based on polymer chain relaxation were found to predict correctly the dependence of FIC, at least when samples of similar MWD are considered. A mastercurve is presented combining effects of M_W, shear strain, shear rate and temperature.Optical microscopy observations provide information on the quiescent growth rate and the morphology of the crystallites. The effect of the different parameters on the observed transition from an isotropic morphology at low shear rates to a rod-like crystalline structure at high shear rates, could again be explained in terms of polymer chain relaxation.     

Modeling of flow‐induced crystallization in blends of isotactic polypropylene and poly(ethylene‐co‐octene)

Poly(ethylene‐co‐octene) (PEOc) has been shown to provide a high toughening contribution to isotactic polypropylene (iPP). The theoretical modeling of flow‐induced crystallization (FIC) of blends of iPP and PEOc is not much reported in the literature. The aim of the present work is to clarify the FIC of iPP upon addition of PEOc in terms of theoretical modeling. The crystallization of iPP and PEOc blends in flow is simulated by a modified FIC model based on the conformation tensor theory. Two kinds of flow fields, shear flow and elongational flow, are considered in the prediction to analyze the influence of flow field on the crystallization kinetics of the polymer. The simulation results show that the elongation flow is much more effective than shear flow in reducing the dimensionless induction time of polymer crystallization. In addition, the induction time of crystallization in the blends is sensitive to the change of shear rate. In comparison with experimental data, the modified model shows its validity for the prediction of the induction time of crystallization of iPP in the blends. Moreover, the simulated relaxation time for the blends becomes longer with increasing percentage of PEOc in the blends. Copyright © 2012 Society of Chemical Industry     

Transient flow-induced crystallization of a polyethylene melt

Extensional, flow-induced crystallization (FIC) of a high-density polyethylene (HDPE) melt has been studied using a four-roll mill flow cell. Simultaneous measurement of the birefringence and scattering dichroism are used to quantify the crystallization process during and following transient flow deformation in planar extensional flow. Suspension of the HDPE phase as a droplet in a linear low-density polyethylene carrier phase prevents die blockage on crystallization and allows measurement of the flow kinematics. Initial crystallization rates following a transient flow deformation show a stress-strain dependence. Crystallization induction times during flow correlate with the extension rate during the transient flow deformation. Measurement of the HDPE melt steady and oscillatory flow rheological properties, along with measurements of time constants following step-shear and extensional strains, allow determination of the viscoelastic properties which enhance FIC. Parameters obtained from these experiments are used in a phenomenological model for FIC which allows qualitative and semiquantitative analysis of the data trends, particularly the relaxation behavior of the birefringence during flow cessation/crystallization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2165–2176, 1997     

Rheological study of crystallization behavior of polylactide and its flax fiber composites

In this work, the isothermal crystallization of compounded polylactide (PLA) and PLA-flax fiber composites was investigated by means of rheometry using small amplitude oscillatory shear (SAOS). The rheological measurements were carried out in parallel plate flow geometry at a crystallization temperature (T _c ) ranging from 110 to 140 °C. In addition, the effect of shear on polylactide crystallization was studied at 140 °C. Rheological behavior in the molten state was employed to predict the initial viscosity in the T _c interval by applying time-temperature superposition, and results were found to be in agreement with experimental values at low crystallization rates. A simple empirical model was also used to determine the crystallization induction time in a wide range of supercooling conditions. The evolution of the complex viscosity under quiescent conditions of the PLA-based flax-fiber composite indicated an enhancement of the rate of crystallization due to the presence of cellulosic fibers, while shear flow effectively accelerated the crystallization of neat PLA. This work shows that rheometry is an accurate technique for analyzing the crystallization behavior of polymers in a temperature range which presents low to very low crystallization rates, which is the case for PLA at T ≥ 130 °C.     

Modeling/simulating the injection molding of isotactic polypropylene

A unified formulation is presented for modeling the injection molding of isotactic polypropylene (i‐PP). The crystallization kinetics are based upon the differential Nakamura equation in which the characteristic time is dependent upon temperature, pressure and flow‐induced shear stress, without any explicit need for an induction time. A Cross/WLF model is used to represent the shear viscosity in which η_O is dependent upon temperature, pressure and crystallinity. Use is made of a recent correlation for the PVT behavior of i‐PP with an explicit dependence upon crystallinity. A finite‐difference implementation of the modeling is applied to two independent molding experiments available from the literature, with notable results concerning the late‐time cavity pressure traces and time‐dependent gapwise shrinkage prior to ejection.     

Shear-induced conformational fluctuations of polystyrene probed by 2D infrared microspectroscopy

In-situ shear-induced conformational fluctuations of isotactic and syndiotactic polystyrene (iPS and sPS) were studied by 2D infrared microspectroscopy measurements. For iPS at temperatures above the nominal melting temperature (T_m), it was found that the area of long helices induced by shear flow mainly corresponded to macro ‘row-nucleated’ or ‘shish-like’ precursors while only short helices in amorphous domain. The long helices became to disappear during the heating process which was consistent with the melting of micron-scale precursors. From an intra-molecular view, long helices in precursors could be related to shear-induced coil–helix transition. To our knowledge, this is the first in-situ FT-IR evidence for flow-induced macro-precursors. For sPS after applying a pulse shear flow, compared with the monophonic morphology in absence of flow, a dual crystalline morphology including α and β form was observed at 250 °C which could be attributed to the accelerated crystal growth of both crystalline phases by shear flow.     

Effects of high molecular weight species on shear-induced orientation and crystallization of isotactic polypropylene

In situ rheo-SAXS (small-angle X-ray scattering) and—rheo-WAXD (wide-angle X-ray diffraction) techniques were used to investigate the role of high molecular weight species on the evolution of oriented microstructure in isotactic polypropylene (iPP) melt under shear flow. The two iPP samples, designated as PP-A and PP-B, respectively, had the same number-average (M_n) but different weight-average (M_w) and Z-average (M_z) molecular weights. Molecular weight distribution (MWD) of PP-A and PP-B was such that for MW<10⁵ the MWD curves overlapped; whereas in the high MW tail region, the amount of high molecular weight species was higher in PP-B than PP-A. Both samples were subjected to an identical shear condition (rate=60 s⁻¹, duration=5 s, T=155 °C). In situ 2D SAXS and WAXD images allowed the tracking of shear-induced oriented structures in the melt. It was found that the shish structures evolved much earlier, and the degree of crystal orientation and oriented crystal fractions were higher in PP-B than PP-A. Moreover, PP-B exhibited faster crystallization kinetics than PP-A. These results, along with the predictions of double reptation models of chain motion and experimental studies of chain conformation dynamics in dilute solutions under flow, suggest the following: When a polymer melt that consists of entangled chains of different lengths is deformed, the chain segments aligned with the flow eigenvector can undergo the abrupt coil-stretch-like transition, while other segments would remain in the coiled state. Since, flow-induced orientation decays much more slowly for long chains than for short chains, oriented high molecular weight species play a prominent role in formation of the stretched sections, where shish originates. Our experimental results are strong evidence of the hypothesis that even a small increase in the concentration of high molecular weight species causes a significant increase in the the formation, stability and concentration of the flow-induced oriented microstructure.     

Flow-induced crystallization of linear polyethylene above its normal melting point

The phenomenon of flow-induced crystallization was investigated using a linear polyethylene above its normal melting point flowing continuously in a Biconical Rheometer. It was found that the resin crystallized in the superheated state at rates which increased with increasing shear rate and decreasing temperature. A method of analysis of the temperature dependence of the various stages of flow induced crystallization is proposed. It deals with and attempts to explain the experimental fact that a higher viscosity enhances the rate of flow-induced crystallization in contrast to the effect of viscosity on the rate of quiescent crystallization. Some of the flow-induced crystallization samples were transparent and exhibited a high DSC thermogram “tail”.     

Influence of a particulate nucleating agent on the quiescent and flow-induced crystallization of isotactic polypropylene

Flow induced crystallization of commercial isotactic polypropylene (iPP) and its blends with sodium 2,2′-methylene bis-(4,6-di-tert-butylphenyl) phosphate (also known as NA11) is studied by means of in-situ time resolved small-angle X-ray scattering (SAXS). The isothermal crystallization at 145 °C (i.e. well below melting temperature of polymer) is performed after the application of steady shear to probe the anisotropic structure formation. In order to separate the influence of shear rate and shear time on polymer crystallization, four different shear conditions (60 s⁻¹ for 1 s, 30 s⁻¹ for 2 s, 15 s⁻¹ for 4 s and 6 s⁻¹ for 10 s) are applied while maintaining the same imposed strain in the polymer melt. Further the effect of different concentration of nucleating agent on the crystallization kinetics of iPP is examined both under quiescent and shear flow conditions. For instance, under quiescent condition, the crystallization half-time (τ_1/2) decreases with the increasing concentration of nucleating agent in the polymer. Under shear flow conditions, our observations are as follows: In the case of neat iPP, τ_1/2 decreases significantly at higher shear rates (≥30 s⁻¹). Compared to the neat iPP, for the same concentration of NA11 in the NA11/iPP blends differences in τ_1/2 with the increase in applied shear rates are significantly smaller. In other words, the crystallization kinetics is dominated by the amount of nucleating agent in the NA11/iPP blends as opposed to shear rates in the neat iPP. The present study shows that the critical value of shear rate required for chain orientation in the molten polymer is lower in the presence of the nucleating agent compared to neat iPP. The self-nucleation process investigated with the aid of differential scanning calorimetry (DSC), indicates that the nucleating efficiency of NA11 on iPP is around 60%.     

Effects of liquid–liquid phase separation on crystallization of poly(ethylene glycol) in blends with isotactic poly(methyl methacrylate)

To analyze the interplay between crystallization and liquid–liquid phase separation (LLPS), isothermal crystallization behavior of poly(ethylene glycol) (PEG) in blends with isotactic poly(methyl methacrylate) (i-PMMA) was investigated by differential scanning calorimetry (DSC). The blend system had an upper critical solution temperature (UCST) type phase diagram. When the crystallization occurred simultaneously with LLPS, the overall crystallization rate was enhanced at high crystallization temperatures T_c, relatively compared with that of neat PEG. This behavior was interpreted by the combination of the effects of spinodal quench depth ?T_s and usual supercooling degree ?T_c, according to the theory of Mitra and Muthukumar, namely, the crystallization rate is enhanced by the concentration fluctuation-assisted nucleation at high T_c. In the crystallization after LLPS proceeded, on the other hand, the overall crystallization rate was slow and less dependent on the blend composition. In addition, it was revealed by small-angle X-ray scattering measurements that amorphous i-PMMA was excluded from the interlamellar region of PEG crystals in SQ as well as WQ.     

Precursor of shish-kebab in isotactic polystyrene under shear flow

We performed polarized optical microscope (POM), depolarized light scattering (DPLS) and small- and wide-angle X-ray scattering measurements on the structure formation process or the crystallization process of isotactic polystyrene (iPS) under shear flow below and above the nominal melting temperature T_m. It was found that an anisotropic oriented structure termed here as a string-like object was formed in μm scale even above the nominal melting temperature and stable for more than 24 h, but melted at around 270 °C far above the nominal melting temperature. The string-like object acts as a nucleation agent for the folded chain lamella crystal (or the kebab), and was assigned to a precursor of the shish-kebab. We also examined the shear rate dependence of the structure formation to find a critical shear rate for the formation of the string-like object, suggesting the relaxation of the chains plays an important role in the formation of the structure. Based on the results we have discussed the inner structure of the string-like object.     

Shear‐Induced Skin‐Core Structure of Molten Isotactic Polypropylene and the Formation of β‐Crystal

The study of crystallization behavior and crystalline morphology of polymer melt under shear flow is of great interest due to the strong effect of flow field on the final properties of polymer products in the practical processing. In this respect, the shearing hot stage provides a unique tool which monitors sensitively the changes in crystalline structure induced by precise experimental conditions. Herein, the impacts of both melting temperature and shear rate on the crystallization behavior of isotactic polypropylene (iPP) melt are investigated. Under static conditions, there are only random spherulite structures. Once shear is involved, the cylindrite‐layers appear near both surfaces of the sample, which is consistent with the skin‐core structure in the injection molded parts. Meanwhile, the β‐crystals can be developed and are related to the molecular orientation, depending on the applied melting temperatures and shear rates. More interestingly, the crystallinity of β‐crystal in the pure iPP can reach 15%. The above results indicate that the melting temperature and shear rate are important factors in determining the β‐form crystal development of iPP matrix.     

Modeling of melt electrospinning for semi-crystalline polymers

A comprehensive model for the stable jet region in electrospinning of crystallizing polymer melts has been presented. First, the conventional flow-induced crystallization (FIC) model by Ziabicki was coupled with the non-isothermal melt electrospinning model. The modeled initial jet profiles were compared to digitized experimental images of the stable Nylon-6 melt jet near the spinneret. The final jet diameters were also compared to the average thickness of collected fibers. The results were in good agreement with the flow visualization experiments for various melt temperatures and flow rates. The modeled crystallinity predictions were also in agreement with experimental data from collected fiber mats. Then, a new FIC model that can provide microstructure information, such as crystallite number density and average size, has been proposed and validated under isothermal and non-isothermal conditions in the bulk as well as in the confined geometry of the polymer melt jet in electrospinning. Nylon-6,6 was used as the model polymer in this crystallization study, and the results are in good agreement with the widely-used Ziabicki FIC model.     

Phase behavior of semicrystalline polymer blends

The phase behavior of the semicrystalline polymer blend composed of isotactic polypropylene (iPP) and linear low density polyethylene (PE) was studied using small angle X-ray scattering (SAXS) and optical microscopy (OM). Based on the random phase approximation, the iPP/PE interaction parameter, χ, was obtained, and used to construct the iPP/PE phase diagram. The χ values reported in this study are lower than the χ values for deuterium-labeled moieties, measured by small angle neutron scattering (SANS). The predicted phase diagram has upper critical solution temperature (UCST) behavior with a critical temperature of 143 °C for the molecular weights used in this study. OM was used to locate cloud points and the results are consistent with the predicted phase diagram. Since iPP melts above the critical point, care was taken to distinguish phase separation from iPP crystallization by studying the kinetics of iPP crystallization, and the iPP crystallization was discerned from dewetting. In PE-rich blends, the iPP crystallization was suppressed and no dewetting was observed.     

A novel effective way of comprising a β-nucleating agent in isotactic polypropylene (i-PP): Polymerized dispersion and polymer characterization

A kind of β-nucleating agent, namely a stearic acid and stearate lanthanum complex (NAβ), was introduced into isotactic polypropylene (i-PP) via an in situ polymerization method for the first time. A dynamic adhesion model was constructed for interpreting the β-nucleating agent dispersion process. The effects of a polymerized dispersion of the β-nucleating agent on the content of β-crystal and crystallization behavior of i-PP were investigated. The results show that the crystallization peak temperature of thus β-nucleated i-PP was greatly increased while the spherulite size dramatically decreased compared with those of net i-PP. The content of β-phase (k_β value) can reach as high as 88.7% with only 0.135 wt% of NAβ addition, which holds constant with a further increase of NAβ concentration up to 3.41 wt%. The non-isothermal crystallization kinetics of thus β-nucleated i-PP was studied with Mo equation and crystallization activation energy estimated by Kissinger method, giving unique results pertaining to the unprecedented NAβ polymerized dispersion.     

The effect of shear on the crystallization of cocoa butter

This paper examines the effect of shear on the crystallization of cocoa butter using a combination of three different experimental techniques and a single crystallization temperature of 20°C. Rheological measurements were carried out to study the effect of a shear step on the crystallization kinetics of the fat. Without a shear step, little rheological change was observed at 20°C; however, with the application of a shear step the onset of significant rheological change occurred and was strongly influenced by the magnitude of the shear step. Detailed crystallographic measurements could be made with in situ X-ray experiments during flow-induced crystallization. The imposition of continuous shear changed both crystal polymorphic structure and crystallization kinetics in a systematic way. Finally, optical measurements were used to follow changes in crystal morphology as a consequence of continuous shear. These results revealed the form and kinetics of crystal growth. In general the results complemented each other, and an overall picture of the way shear influenced cocoa butter growth could be formed. The observations could be the basis for a future mathematical model of growth kinetics and provide insight into the way shear influences crystallization kinetics, morphology, and polymorphic structure.     

Mechanisms of polymer crystallization from flowing solutions

The recent experimental results on flow-induced crystallization by Pennings and coworkers show that extremely rigid polyethylene fibers can be obtained in a shear flow. On the other hand, the mechanism by which these flow-induced crystals are produced is still open to investigation. In this work a few aspects of fibrous crystal growth are theoretically investigated. The molecular dynamics of chains partly attached to the crystal and partly immersed in the solution is considered. The influence of temperature and of geometrical factors is also discussed.     

Effect of lanthanum-modified magnesium silicate on isotactic polypropylene crystallization in composite materials during shear flow

The activity of isotactic polypropylene (iPP) nucleating additives during shear flow of composite materials is still not entirely explained. In current work the sol-gel method was employed to synthesize MgO·SiO₂ filler, surface-modified with trivalent lanthanum. The crystallization of commercial iPP in the presence of 0.5% by weight La³⁺ modified or unmodified silicates was analyzed. The wide angle X-ray scattering analysis proved that the presence of even small amount of filler influences significantly on supermolecular structure of iPP. The results of microscope observations confirmed that the lanthanum-modified filler shows the nucleating ability for iPP. In that case a significant reduction of crystallization induction time was noticed. The investigation of iPP crystallization in composites after shear treatment confirmed that the increase of shear rate reduces the nucleating ability of additives. Moreover, the flow of filler particles during shearing may impede the shear-induced crystallization phenomenon.     

Wall slip of molten polymers

There is considerable experimental evidence that the classical no-slip boundary condition of fluid mechanics is not always a valid assumption for the flow of high molecular weight molten polymers. In fact, molten polymers slip macroscopically at solid surfaces when the wall shear stress exceeds a critical value. Moreover, for linear polymers there exists a second critical wall shear stress value at which a transition from a weak to a strong slip occurs. These two modes of slip (weak and strong) are due to flow-induced chain detachment/desorption at the polymer/wall interface and to chain disentanglement of the polymer chains in the bulk from a monolayer of polymer chains adsorbed at the interface. In this review, the two physical mechanisms of slip are discussed and validated on the basis of published experimental data. The slip velocity of molten polymers is a complex function and has been reported to depend on wall shear and normal stresses, temperature, and molecular characteristics of polymers (molecular weight and its distribution). Proposed slip models, static and dynamic, are also reviewed and their significance on the rheology and flow simulations of molten polymers is discussed.     

注射成型中聚合物剪切诱导结晶行为的三维模拟

在考虑剪切导致分子链取向并升高其平衡熔点的基础上,建立了基于Nakamura方程的剪切诱导结晶动力学模型。在WLF-Cross黏度模型中引入结晶对黏度系数的影响,构建了考虑结晶的注射成型过程模型。采用改进的有限体积法对聚合物剪切诱导结晶行为进行了三维数值模拟,模拟中耦合了流动场、熔体压力、温度、诱导时间与结晶度。结果表明,本方法可清晰模拟出注射成型过程中聚合物的三维“喷泉”流动行为以及3层“皮-芯”结晶结构,同时,诱导结晶时间指数与相对结晶度的模拟结果与理论及实验结果吻合。