Experimental investigation of the influence of molecular weight distribution on the rheological properties of polypropylene melts

An experimental study of steady shear and elongational flow Theological properties of a series of polypropylene melts of varying molecular weight and distribution is reported. Broadening the molecular weight distribution increases the non-Newtonian character of the shear viscosity function and increases the principal normal stress differences at fixed shear stress. The behavior is compared to earlier rheological property-molecular weight studies. Correlations are developed for these properties in terms of molecular structure. Elongational flow studies indicate that for commercial and broader molecular weight distribution samples, ready failure by neck development occurs and the elongational viscosity appears to decrease with increasing elongation rate. For narrower molecular weight distribution samples, the elongational viscosity is an increasing function of elongation rate, The implication of these experimental results to viscoelastic fluid constitutive equations and polymer melt processing is developed.     

Pressure dependent viscosity of Surlyn/montmorillonite nanocomposite

Abstract

Nanocomposites of extrusion-type Surlyn ionomer and intercalated sodium-type montmorillonite were compounded on a KO-kneader and measured on a modified capillary rheometer for strain rate versus pressure dependencies of shear and elongational viscosities for various clay concentrations. The modified White–Metzner model was employed to simultaneously fit the viscosity data and determine pressure coefficients; these have been found to decrease with the loading level of the nanocomposites. Increasing relaxation times with rising filler content indicate earlier onset of non-Newtonian behaviour under shearing, and hardening at strain.     

Melt rheology of organoclay and fumed silica nanocomposites

The objective of the present work is to investigate, from the open literature, the recent developments in the rheology of silica and organoclay nanocomposites. In particular, this paper focuses on general trends of the linear viscoelastic behaviour of such nanocomposites. Hence, the variations of the equilibrium shear modulus and critical strain (limit of linearity), which depend on power laws of the volume fraction of particles, are discussed as filler fractal structure. In the third section, the strong nonlinearity behaviour (Payne effect) of filled polymers has been discussed in terms of filler nature. Typically two mechanisms arise to depict the linear solid-like behaviour and the Payne effect: particle–particle interactions is the dominant mechanism in fumed silica nanocomposites whereas particle–polymer interaction is the dominant one in colloidal silica nanocomposites at identical filler concentrations. However, these interactions are balanced in each nanocomposite systems by the silica surface treatments (chain grafting, silane modification) and the molecular weight of the matrix. Finally, we aim to unify the main findings of the literature on this subject, at least from a qualitative point of view.We finally report on the thixotropy and modulus recovery after a large deformation in steady and dynamic shear conditions. Following this, the nonlinear rheological properties of nanocomposite materials have been discussed. The discussion is particularly focused on the effect of flow history (transient shear experiments) on the orientation–disorientation of clay platelets. Actually, the linear and nonlinear rheological properties are consistent with a network structure of a weakly agglomerated tactoids. As far as exfoliated clay nanocomposites are concerned, the inter-particle interaction is the dominant effect in the nonlinearity effect.     

The role of flow‐induced microstructure in rheological behavior and nonisothermal crystallization kinetics of polyethylene/organoclay nanocomposites

The evolution of polyethylene/organoclay nanocomposite microstructure via shear and extentional flow fields was studied by tracing rheological behavior and nonisothermal crystallization kinetics. Although studying microstructure formed through flow fields, two phenomena were noticed: the breaking of three‐dimensional (3D) network containing filler–filler, filler–matrix, and matrix–matrix interactions, and organoclay platelets orientation. Utilizing nonlinear viscoelastic measurements and thermal analyses, it was proven that clay alignment was present only in large enough shear flows and all elongational flows. It was observed that regardless of the type of flow field and its magnitude, due to the breaking of 3D network, the extent of crystallization can be increased. The half‐lives of the crystallization of film samples and those samples subjected to large enough shear rates for clay platelets to be aligned decreased, proving the effect of clay orientation on crystallization rate increment. Based on endotherms observed through melting behavior studies of samples, it was proven that in elongation and large amplitude shear flows, clay orientation had resulted in forming thicker crystalline lamellae, likely because of forcing the adjacent polymer chains to align with the clay platelets. POLYM. ENG. SCI., 54:1839–1847, 2014. © 2013 Society of Plastics Engineers     

Shear flow effect on the crystalline forms in polyamide 6/montmorillonite nanocomposites

The influence of shear flow on the crystallization of polyamide 6/MMT nanocomposites prepared by melt intercalation process was investigated in detail by differential scanning calorimetry. The melted nanocomposites were controlled sheared in the steady and oscillatory shear flow, using a rotational rheometer, and cooled in an inert atmosphere. The effects of shear rate or frequency, clay concentration, and crystallization conditions on PA 6 crystalline phase development were studied. As expected, an opposite impact of shearing on γ‐phase formation in the nanocomposites and neat matrix was found. Surprisingly, a critical shear frequency for the onset of γ‐form crystallinity formation in the nanocomposites, increasing with the filler content as a consequence of polymer chains confinement within oriented clay platelets was found. At higher shear frequencies, the proportion of γ‐form in the nanocomposites increased dramatically with the clay concentration and reached 30–40%. The shear flow effects were influenced by cooling conditions, and more significant effect for rapidly cooled samples was observed. The isothermal crystallization at the solidification temperature 205°C reduced the γ‐form content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Structure and melt rheology of long‐chain branching polypropylene/clay nanocomposites

Long‐chain branching polypropylene (LCB‐PP)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder. The microstructure and melt rheology of these nanocomposites were investigated using x‐ray diffraction, transmission electron microscopy, oscillatory shear rheology, and melt elongation testing. The results show that, the clay layers are intercalated by polymer molecular chains and exfoliate well in LCB‐PP matrix in the presence of maleic anhydride grafted PP. Rheological characteristics, such as higher storage modulus at low‐frequency and solid‐like plateau in tan‐ω curve, indicate that a compact and stable filler network structure is formed when clay is loaded at 4 phr (parts per hundred parts of) or higher. The response of the nanocomposite under melt extension reveals an initial decrease in the melt strength and elongational viscosity with increasing clay concentration up to 6 phr. Later, the melt strength and elongational viscosity show slight increases with further increasing clay concentration. These results might be caused by a reduction in the molecular weight of the LCB‐PP matrix and by the intercalation of LCB‐PP molecular chains into the clay layers. Increases in the melt strength and elongational viscosity for the nanocomposites with decreasing extrusion temperature are also observed, which is due to flow‐induced crystallization under lower extrusion temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of nano clay on the constrained polymer volume of chlorobutyl rubber nanocomposites

The dynamic mechanical properties of chlorobutyl rubber nanocomposites containing different varieties of clay have been investigated. The clay moieties have been chosen so that they vary in their organic modification, modifier concentration, and d spacing. The viscoelastic properties such as storage modulus, damping behavior, and loss modulus of polymer composites depends on matrix filler interaction, crystallinity, and extent of crosslinking. The prepared composites were characterized by X Ray Diffraction, and the extend of exfoliation/intercalation was studied. It has been observed that the storage modulus of the composites increased with the addition of filler due to the enhancement in stiffness of the material. The damping behavior was found to decrease with the addition of filler and this was attributed to the restricted movement of the polymer segments. The higher surface area to volume ratio of the layered silicate resulted in the better interaction between the polymer matrix and filler. The variation of loss as well as storage modulus of the nanocomposites were evaluated as a function of filler loading, and a comparison of the properties of the rubber nanocomposites containing different organic clay was also carried out. Finally, a calculation of constrained volume of polymer chains was done in the nanocomposites. POLYM. COMPOS., 36:2135–2139, 2015. © 2014 Society of Plastics Engineer     

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.     

Linear and nonlinear melt rheology and extrudate swell of acrylonitrile‐butadiene‐styrene and organoclay‐filled acrylonitrile‐butadiene‐styrene nanocomposite

Melt viscoelastic behavior and the die swell of Acrylonitrile‐Butadiene‐Styrene (ABS) and ABS/clay nanocomposites varying in organoclay loading were studied. A pronounced low‐frequency nonterminal behavior exhibited in linear viscoelastic experiments along with an apparent yield stress in transient startup flow tests suggested the existence of a network type, because of interconnection of rubber particles in ABS matrix. From the results of linear and nonlinear viscoelastic measurements, it was found that the incorporation of organoclay can lead to the formation of an additional network formed between organoclay tactoids that caused reduced temperature dependency of linear viscoelastic properties of the nanocomposite samples compared with ABS matrix. The swelling behavior of samples was interpreted using the results of stress relaxation experiments after cessation of steady shear flow. The great reduction in the die swell of nanocomposite samples could be explained in terms of great surface area and anisometric nature of organoclay tactoids and/or platelets, which promote energy consumption and less energy to be stored in chains. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

A rheological study of aqueous separan solutions

The concentration dependence of the rheological response of aqueous Separan solutions was measured. The shear and primary normal stress response in steady shearing flow, and the relaxation of shear stress following cessation of steady shear flow, were measured with four different polymer solution concentrations. Two different nonlinear constitutive equations, Bird-Carreau and Meister, were used to analyse the data. The Bird-Carreau model fit the steady shear data very well and the parameters obtained from steady shear data allow reasonable estimates of the stress relaxation of these systems. The Meister model provided a fit of the transient stress relaxation data and could be used to estimate the steady shear response. No quantitative molecular theory was developed in this work. However, the nature of the concentration dependence of the Bird-Carreau parameters suggests that as the polymer concentration of aqueous Separan solutions decreases from 2.0 to 0.05 weight percent the solutions should be modeled less by an entangled network theory and more as slightly overlapping hydrodynamic units. The concentration where this behavior seems to be changing appears to be about 0.25 percent by weight of polymer.     

Rheological characterization of controlled-rheology polypropylenes using integral constitutive equations

Controlled-rheology polypropylene melts were prepared via molecular modification of a commercial polypropylene resin. A peroxide-initiated degradation was performed, resulting in materials with different molecular weight distributions. These resins were subjected to rheological characterization, and an integral constitutive equation of the K-BKZ type was used to study the effect of molecular weight characteristics on their rheological properties. Data for the linear viscoelastic spectrum and shear viscosities was used to obtain the model constants. The same constitutive equation has been used to predict the stress and Trouton ratios for simple shear and simple elongational flows, thus giving a quantitative assessment of the viscoelastic character of the melts. The results show the effect of the molecular modification on the rheological behavior of the melts. Polymers produced at higher peroxide concentrations exhibit reduced viscoelasticity manifested in less shear-and strain-thinning behavior. The present work clearly shows the potential of integral constitutive equations in fitting and interpreting experimental data and, thus, giving a much better understanding of the rheological behavior of commercial polymers. © 1996 John Wiley & Sons, Inc.     

聚乳酸／蒙脱土纳米复合材料的流变行为

采用熔融插层法制备了插层型的聚乳酸／蒙脱土纳米复合材料，利用旋转流变仪对其流变行为进行了研究。稳态预剪切和大振幅振荡剪切实验结果表明，蒙脱土晶粒逾渗网络结构具有剪切敏感性，但稳态预剪切更容易破坏蒙脱土晶粒的逾渗结构；反向流和起始流实验结果表明，剪切破坏的逾渗网络在静态退火过程中可以重建，而应力过冲现象的出现则是网络重建的标志；不同剪切速率下应力过冲的最大值都出现在2％应变处，这种应力与应变之间的标度关系表明蒙脱土晶粒类液晶态的形成可能是网络重建的驱动力。     

Systematic coarse graining flowing polymer melts: thermodynamically guided simulations and resulting constitutive model

Complex fluids, such as polymers, colloids, liquid-crystals etc., show intriguing viscoelastic properties, due to the complicated interplay between flow-induced structure formation and dynamical behavior. Starting from microscopic models of complex fluids, a systematic coarse-graining method is presented that allows us to derive closed-form and thermodynamically consistent constitutive equations for such fluids. Essential ingredients of the proposed approach are thermodynamically guided simulations within a consistent coarse-graining scheme. In addition to this new type of multiscale simulations, we reconstruct the building blocks that constitute the thermodynamically consistent coarse-grained model. We illustrate the method for low-molecular polymer melts, which are subject to different imposed flow fields like planar shear and different elongational flows. The constitutive equation for general flow conditions we obtain shows rheological behavior including shear thinning, normal stress differences, and elongational viscosities in good agreement with reference results.     

On the mechanisms for drag reduction: A viscoelastic evaluation based on a bead-spring model

Two possible drag reduction mechanisms were examined by studying the viscoelastic effects of polymer solutions for the separate cases of oscillatory shear flow and elongational flow. The constitutive equation used was based on a modified dumbbell molecular model which predicts non-Newtonian viscosity and both the primary and the secondary normal stress differences. It can be shown that when this constitutive equation is arranged in the form of the Oldroyd model, the latter becomes a special case of this more general equation. The present results show that viscoelastic effects on the mean local rate of energy dissipation of a fluid element in an oscillatory motion are negligibly small. However, such effects introduce very large increases in the elongational viscosity as the stretching rate exceeds a certain limiting value and the flow time exceeds the terminal relaxation time of the fluid. The relative merits of these findings as possible explanations of turbulent drag reduction are briefly discussed.     

Elongational rheology of biodegradable poly(lactic acid)/poly[(butylene succinate)‐co‐adipate] binary blends and poly(lactic acid)/poly[(butylene succinate)‐co‐adipate]/clay ternary nanocomposites

A series of blends based on poly(lactic acid) (PLA) and poly[(butylene succinate)‐co‐adipate] (PBSA) as well as their nanocomposites with nanoclay (PLA/PBSA/Clay ternary nanocomposites) were prepared using the twin‐screw extruder. The blends were prepared for PBSA contents ranging from 25 to 75 wt % and their corresponding nanocomposites were prepared at a single‐clay concentration. The morphology and structure of the blends and the nanocomposites were examined using field emission scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. Rheological properties (dynamic oscillatory shear measurements and elongational viscosities) of the blends, nanocomposites, and pure components were studied in detail. The strain hardening intensity of different blends and nanocomposites was compared with the behavior of the pure components. Strong strain hardening behavior was observed for blends composed of 50 wt % and higher PBSA content. However, the effect of PBSA content on the elongational viscosity was less pronounced in PLA/PBSA/Clay ternary nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Rheological properties of high concentrations of carboxymethyl cellulose solutions

The study was concerned with measurements of steady‐state parameters, the transient shear stress response, and the yield stress of carboxymethyl cellulose (CMC) solutions at high concentrations. Tests also included thixotropic and viscoelastic behavior and dynamic responses. The concentrations ranged by weight from 5 to 8% of CMC. The steady‐state shear flow showed that at higher shear rates the viscosities of CMC solutions tend to be less dependent on the concentration. The solutions showed rheopectic behavior for very small shear rates. No yield stress was detected. Measurements recorded the thixotropic behavior. At higher stress values, nonlinear viscoelastic effects were detected. Dynamic viscosities measured in a dynamic test were higher than were the shear viscosities at the same concentrations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1787–1801, 2001     

Modified bead-spring theory of polymer solutions. IV. Extension to polymer melts

A constitutive equation which has proven quite successful in describing the nonlinear viscoelastic behavior of dilute polymer solutions is extended to the case of molten polymers. The techniques utilized and similar to those discussed by Ferry in a similar adaptation of the Rouse–Zimm Theory. The resulting model is found to quantitatively portray the shear rate dependence of the non-Newtonian viscosity and primary normal stress functions and the frequency dependence of the storage and loss moduli. Extensional flow data reported by Spearot and Metzner for two polyethylenes are well described, using parameters calculated from steady shearing measurements. Of major significance is the ability of the model to account for influences of molecular weight, molecular weight distribution, and temperature.     

Time‐dependent response of polypropylene/clay nanocomposites under tension and retraction

Observations are reported in relaxation tests under tension and retraction on polypropylene/clay nanocomposites with various contents of filler. A two‐phase constitutive model is developed in cyclic viscoelasticity and viscoplasticity of nanocomposites. Adjustable parameters in the stress–strain relations are found by fitting the observations. Ability of the constitutive equations to describe characteristic features of the time‐dependent behavior of nanocomposites under cyclic deformation is confirmed by numerical simulation. POLYM. ENG. SCI., 2013 © 2012 Society of Plastics Engineers     

Morphology and melt rheology of nylon 11/clay nanocomposites

Nylon 11 (PA11)/clay nanocomposites have been prepared by melt‐blending, followed by melt‐extrusion through a capillary. Transmission electron microscopy shows that the exfoliated clay morphology is dominant for low nanofiller content, while the intercalated one is prevailing for high filler loading. Melt rheological properties of PA11 nanocomposites have been studied in both linear and nonlinear viscoelastic response regions. In the linear regime, the nanocomposites exhibit much higher storage modulus (G′) and loss modulus (G″) values than neat PA11. The values of G′ and G″ increase steadily with clay loading at low concentrations, while the G′ and G″ for the sample with 5 wt % clay show an inverse dependence and lie between the modulus values of the samples with 1 and 2 wt % of clay. This is attributed to the alignment/orientation of nanoclay platelets in the intercalated nanocomposite induced by capillary extrusion. In the nonlinear regime, the nanocomposites show increased shear viscosities when compared with the neat resin. The dependence of the shear viscosity on clay loading has analogous trend to that of G′ and G″. Finally, a comparison has been made between the complex and steady viscosities to verify the applicability of the empirical Cox‐Merz rule. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 542–549, 2006     

Synthesis and characterization of nylon 6/clay nanocomposites prepared by ultrasonication and in situ polymerization

Nylon 6 nanocomposites were prepared by the in situ polymerization of ε‐caprolactam with ultrasonically dispersed organically modified montmorillonite clay (Cloisite 30B®). Dispersions of the clay platelets with concentrations in the range 1–5 wt % in the monomer were characterized using rheological measurements. All mixtures exhibited shear‐thinning, signifying that the clay particles were dispersed as platelets and forming a “house of cards” structure. Samples with Cloisite concentrations above 2 wt % showed a drop in viscosity between the initial shearing and repeated shearing, indicative of shearing breaking down the initial “house of cards” structures formed on sonication. DMTA measurements of the samples showed an increase in the β‐relaxation temperature with increasing clay concentration. The bending modulus, at temperatures below T_g, showed an increase with increasing clay concentration up to 4 wt %. X‐ray diffraction measurements showed that all nylon 6/Cloisite 30B samples were exfoliated apart from the 5 wt %, which showed that some intercalated material was present. The nylon crystallized into the α‐crystalline phase, which is the most thermodynamically stable form. Preference for this form may be a consequence of the long time associated with the postcondensation step in the synthesis or the influence of the platelets on the nucleation step of the crystal growth. DSC measurements showed a retardation of the crystallization rate of nanocomposite samples when compared with that of pure nylon 6, due to the exfoliated clay platelets hindering chain movement. This behavior is different from that observed for the melt‐mixed nylon 6/clay nanocomposites, which show an enhancement in the crystallization rate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008