Modeling elongational viscosity of blends of linear and long-chain branched polypropylenes

To enhance the melt strength of a conventional linear polypropylene (L-PP), blends with a long-chain branched polypropylene (LCB-PP) were produced by adding 2, 5, 10, 25, 50, and 75 wt% of LCB-PP to L-PP and mixing in a twin screw extruder. It was found that, already, an addition of 10% or less of LCB-PP to L-PP leads to significant strain hardening. Elongational viscosity data of L-PP and LCB-PP and those of their blends were analyzed by the use of the molecular stress function (MSF) theory. While L-PP is characterized by the MSF parameter, β=1 (typical for linear melts), and shows very little chain stretch (), melt elongational behavior of LCB-PP is characterized by the MSF parameters, β=2 (typical of LCB melts), and (which corresponds to a maximum stretch of molecular chains by a factor of 15). By extruding LCB-PP, a refining effect is observed similar to the refining effects seen in low density polyethylene (LDPE), which reduces the steady-state elongational viscosity and reduces to 121. A second-order mixing rule for the fractional relaxation moduli, g _i , was found to show good agreement with the linear-viscoelastic data of the blends. To simulate the elongational viscosities of the L-PP/LCB-PP blends, a similar second-order mixing rule was used for the MSF parameter, β, while a first-order mixing rule was found to be appropriate for . This allows for a quantitative prediction of the time-dependent elongational viscosities of all L-PP/LCB-PP blends on the basis of the linear and nonlinear parameters of the mixing components L-PP and LCB-PP only. Comparison between the steady-state elongational viscosities as obtained from creep experiments shows good agreement with predictions.     

Rheological and foaming behavior of linear and branched polylactides

In this work, a chain extender (CE) was added to polylactide (PLA) to improve its foamability. The steady and transient rheological properties of neat PLA and CE-treated PLA revealed that the introduction of the CE profoundly affected the melt viscosity and elasticity. The linear viscoelastic properties of CE-enriched PLA suggested that a long-chain branching (LCB) structure was formed from the reaction with the CE. LCB-PLA exhibited an increased viscosity, more shear sensitivity, and longer relaxation time in comparison with the linear PLA. The LCB structure was also found to affect the transient shear stress growth and elongational flow behavior. LCB-PLA exhibited a pronounced strain hardening, whereas no strain hardening was observed for the linear PLA. Batch foaming of the linear and LCB-PLAs was also examined at foaming temperatures of 130, 140, and 155 °C. The LCB structure significantly increased the integrity of the cells, cell density, and void fraction.     

Rheological properties of branched polystyrenes: linear viscoelastic behavior

Oscillatory shear measurements on a series of branched graft polystyrenes (PS) synthesized by the macromonomer technique are presented. The graft PS have similar molar masses (M _w between 1.3×10⁵ g/mol and 2.4×10⁵ g/mol) and a polydispersity M _w /M _n around 2. The molar masses of the grafted side chains M _w,br range from 6.8×10³ g/mol to 5.8×10⁴ g/mol, which are well below and above the critical entanglement molar mass M _c of linear polystyrene. The average number of side chains per molecule ranges from 0.6 to 6.7. The oscillatory measurements follow the time–temperature superposition principle. The shift factors do not depend on the number of branches. The zero-shear viscosities of all graft PS are lower than those of linear PS with the same molar mass, which can be attributed to the smaller coil size of the branched molecules. It is shown that the influence of branching on the frequency dependence of the dynamic moduli is weak for all graft PS that were investigated, which can be explained by the low entanglement density.Electronic Supplementary Material Supplementary material is available for this article at This article has already been published online first (DOI: ). Due to an oversight at the publisher's, this version contained several mistakes. The article is herewith republished in its entirety as a "publisher's erratum".     

Rheological characterization of highly branched poly(ethyleneterephthalate)

Linear and highly branched poly(ethyleneterephthalate) samples were synthesized and characterized in terms of intrinsic viscosity, molecular weight and melt viscosity over a wide range of shear rates at several temperatures, in the range from 265° to 295 °C. Linear samples exhibited Newtonian behavior over a wide range of shear rates, while the branched ones became shear thinning at relatively low shear rates. Our experimental data, as well as data previously reported, were found to be described by a proposed correlation between the melt viscosity ratio and a branching index. Moreover, the activation energy for melt flow was found for the highly branched samples to be a little higher than that of the linear samples.     

Rheological characterization and modeling of end-functionalized polybutadienes

The rheological characterization and modeling of a series of polybutadienes obtained by anionic solution polymerization is presented in this work. The polybutadienes are synthesized using two different initiators: R,R′,R′′-silyloxyalkyllithium (F1) and R,R′,R′′-silylalkyllithium (F3). In addition, a polybutadiene obtained with a conventional alkyllithium initiator (n-butyllithium) is used as a reference. The rheological characterization is carried out under small amplitude oscillatory shear in the stress-controlled mode. Microstructure, molecular weight, and molecular weight distribution are determined by FTIR and GPC. The vinyl content of the polybutadienes synthesized using the functionalized initiators is similar to that obtained with n-butyllithium (8–11%). Materials obtained with F1 show a relatively low polydispersity within a narrow molecular weight range (250,000–300,000 g/mol), while samples obtained with F3 cover a wider range of molecular weights (65,000–670,000 g/mol) and display higher values of polydispersity. In all cases, a parallel reaction using propylene oxide in the termination step is done to place a functional group at the chain ends. The effect of this group on the rheological behavior appears to be negligible. Three rheological models are used and their predictions of the experimental data are compared. The models include the Doi and Edwards reptation model, expressions using a discrete spectrum of relaxation times based in the rubber-like liquid constitutive equation and the fractional Maxwell equation in which a given analytical relaxation-spectrum is used. Relevant relations are obtained between the models' parameters and the molecular properties of these systems, which in turn are related to the presence of functional groups at the polymer chain ends.     

Rheological characterization and constitutive modeling of bread dough

Bread dough (a flour–water system) has been rheologically characterized using a parallel-plate, an extensional, and a capillary rheometer at room temperature. Based on the linear and nonlinear viscoelastic and viscoplastic data, two constitutive equations have been applied, namely a viscoplastic Herschel–Bulkley model and a viscoelastoplastic K–BKZ model with a yield stress. For cases where time effects are unimportant, the viscoplastic Herschel–Bulkley model can be used. For cases where transient effects are important, it is more appropriate to use the K-BKZ model with the addition of a yield stress. Finally, the wall slip behavior of dough was studied in capillary flow, and an appropriate slip law was formulated. These models characterize the rheological behavior of bread dough and constitute the basic ingredients for flow simulation of dough processing, such as extrusion, calendering, and rolling.     

Rheological and molecular characterization of long-chain branched poly(ethylene terephthalate)

Reactive extrusion with pyromellitic dianhydride (PMDA) and tetraglycidyl diamino diphenyl methane (TGDDM) was conducted to create long-chain branched poly(ethylene terephthalate) (LCB-PET). The mechanical and molecular properties were analyzed by linear and non-linear viscoelastic rheology in the melt state and by size-exclusion chromatography measurements with triple detection. The two tetra-functional chain extenders lead to strong viscosity increases, increasing strain hardening effects, and increasing LCB with increasing chain extender concentration. Molecular stress function model predictions show good agreement with the elongational data measured and allowed a quantification of the strain hardening. Analysis of SEC triple detection data shows a strong increase of the average molar mass, polydispersity, radius of gyration, and hydrodynamic radius with increasing chain extender concentration. Branching was confirmed by a decreasing Mark-Houwink exponent, and the analysis of the contraction of the molecule revealed either star-like, comb-like, random tree-like or hyperbranched structures depending on concentration and type of chain extender.     

Rheological properties of electron beam-irradiated polypropylenes with different molar masses

Electron beam-irradiated polypropylene undergoes chain scission initiated by the loss of a proton. The resulting macroradicals can lead to branched molecules. However, the understanding of the influence of irradiation on the branching of polypropylene is still scarce. Therefore, this paper investigates structure?Cproperty relationships in such irradiated polymers. In general, irradiation yields long-chain branches, which develop from a star-like into a tree-like branching architecture with increasing dose. These conclusions can be drawn from the relation between the zero shear-rate viscosity ?? ₀ and the weight average molar mass M _w as well as from the elongational behavior.     

Application of melt flow index for rheological characterization of branched and linear polymers

A procedure for evaluating rheological characteristics, such as the master curves log/ ₀ vs. log % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xd9Gqpe0x% c9q8qqaqFn0dXdir-xcvk9pIe9q8qqaq-xir-f0-yqaqVeLsFr0-vr% 0-vr0db8meaabaqaciGacaGaaeqabaWaaeaaeaaakeaaieGaceWFZo% Gbaiaaaaa!3B59!\[\dot \gamma \] ₀ and flow curves, using the melt flow index is described for branched and linear polymers. Experimental data on the melt flow index and branching degree are needed for this purpose, as well as some polymer constants, i.e. coefficients of the ₀ vs. MFI relation and coefficients of fluidity dependence on molecular characteristics. An example is given for bisphenol A polycarbonate.     

Rheological behaviour and molecular structure of long-chain branched semifluorinated thermoplastics

The long-chain branched thermoplastic tetrafluoroethylene–hexafluoropropylene–vinylidenefluoride terpolymers (LCB THV) investigated in this paper are new polymers with a unique combination of properties like a high stability against aging or weathering and a very good chemical resistance. But not much is known about the rheological behaviour of the LCB THV, yet. In this paper, non-linear rheological properties like shear thinning and strain hardening are studied. Two different types of the THV with different contents of comonomers and, therefore, different melting points are examined. The THV with the higher melting point is insoluble. The other with the lower melting temperature is soluble and, therefore, was characterised by size exclusion chromatography coupled with light scattering with respect to its molecular structure. The results of the rheological measurements show a pronounced shear-thinning and strain-hardening behaviour for the long-chain branched materials. Both properties are of great importance for processing operations governed by shear and elongational flows.

Creep recovery behavior of metallocene linear low-density polyethylenes

The rheological behavior of two metallocene linear low-density polyethylenes (mLLDPE) is investigated in shear creep recovery measurements using a magnetic bearing torsional creep apparatus of high accuracy. The two mLLDPE used are homogeneous with respect to the comonomer distribution. The most interesting feature of the two mLLDPE is that their molecular mass distributions are alike. Therefore, as one of the mLLDPE contains long-chain branches, the influence of long-chain branching on the elastic properties of polyethylene melts could be investigated. It was found that long-chain branches increase the elasticity of the melt characterized by the steady-state recoverable compliance. The long-chain branched mLLDPE has a flow activation energy of 45 kJ/mol which is distinctly higher than that of the other mLLDPE. The shear thinning behavior is much more pronounced for the long-chain branched mLLDPE. A discrepancy between the weight average molecular mass M _w calculated from size exclusion chromatography measurements by the universal calibration method and the zero shear viscosities of the two mLLDPE was observed. These observations are discussed with reference to the molecular architecture of the long-chain branched mLLDPE. The rheological properties of the long-chain branched mLLDPE are compared with those of a classical long-chain branched LDPE. It is surprisingly found that the rheological behavior is very much the same for these two products although their molecular mass distributions and presumedly the branching structures differ largely. Received: 15 February 1999 Accepted: 10 June 1999     

Rheological properties of branched polystyrenes: nonlinear shear and extensional behavior

Nonlinear shear and uniaxial extensional measurements on a series of graft-polystyrenes with varying average numbers and molar masses of grafted side chains are presented. Step-strain measurements are performed to evaluate the damping functions of the melts in shear. The damping functions show a decreasing dependence on strain with an increase in mass fraction of grafted side chains. Extensional viscosities of the melts of graft-polystyrenes exhibit a growing strain hardening with increasing average number of grafted side chains as long as the side branches have a sufficient molar mass to be entangled. Graft-polystyrenes with side arms below the critical molar mass M _c for entanglements of linear polystyrene but above the entanglement molar mass M _e of linear polystyrene (M _e < M _w,br < M _c) still show a distinct strain hardening. With decreasing molar mass of the grafted side chains (M _w,br < M _e) the nonlinear-viscoelastic properties of the graft-polystyrene melts approach the behavior for a linear polystyrene with comparable polydispersity.Electronic Supplementary Material Supplementary material is available for this article at     

Rheological and molecular characterization of linear backbone flexible polymers with the Cole-Cole model relaxation spectrum

The empirical Cole-Cole distribution is an analytical three parameter model of the relaxation spectra that provides accurate fits to experimental dynamic viscosity data for many systems of commercial linear backbone flexible polymers. We demonstrate that for disparate systems of polyethylenes, the three Cole-Cole model parameters have simple power law relationships to moments of the molecular weight distribution enabling direct molecular interpretation of the mechanical relaxation spectrum. A simple relationship between the Cole-Cole distribution and the Cross model for the non-linear flow curve can be deduced utilizing the empirical Cox-Merz rule. Accurately representing the linear viscoelastic material functions with empirical analytical relaxation spectra containing relatively few fitting parameters that can be readily interpreted is a major advance in polymer characterization. The three Cole-Cole parameters effectively replace single point material characterizations such as melt flow index. Development of higher resolution polymer characterization methods is imperative with the advent of metallocene catalyst technology, which enables the molecular weight and backbone architecture to be carefully controlled. Received: 3 March 1998 Accepted: 30 September 1998     

Classification of thermorheological complexity for linear and branched polyolefins

Thermorheological complexity in polyolefins has been reported many times but so far it has not been systematically investigated. Here, a classification of the different types of thermorheologically complex behavior is proposed, which categorize the available data in five different types and describe key characteristics. These definitions are based on polyethylene, but other polymers show similar patterns for materials with comparable branching structure. Linear materials are thermorheologically simple as long as many very long short-chain branches do not introduce phase separation. Sparsely branched materials show the most significant thermorheological complexity, with significant shape changes of rheological functions with temperature, while higher amounts of branching (such as trees or combs) reduce thermorheological complexity and increase E_a at the same time. Low-density polyethylene shows a significant modulus shift at different temperatures probably due to excessive low molecular components.     

Rheological properties of reactive polymer melts.

A new method for describing the rheological properties of reactive polymer melts, which was presented in an earlier paper, is developed in more detail. In particular, a detailed derivation of the equation of a first-order rheometrical flow surface is given and a procedure for determining parameters and functions occurring in this equation is proposed. The experimental verification of the presented approach was carried out using our data for polyamide-6.Notation E Dimensionless reduced viscosity, eq. (34) - E ₀ Newtonian asymptote of the function (36) - E power-law asymptote of the function (36) - E _{= 1} the value ofE at = 1 - k degradation reaction rate constant, s^–1 - k ₁ rate constant of function (t), eq. (26), s^–1 - k ₂ rate constant of function (t), eq. (29), s^–1 - K(t) residence-time-dependent consistency factor, eq. (22) - M _w weight-average molecular weight - M _x x-th moment of the molecular weight distribution - R gas constant - S _x M _x /M _w - t residence time in molten state, s - t _j thej-th value oft, s - T temperature, K - % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xd9vqpe0x% c9q8qqaqFn0dXdir-xcvk9pIe9q8qqaq-xir-f0-yqaqVeLsFr0-vr% 0-vr0db8meaabaqaciGacaGaaeqabaWaaeaaeaaakeaaieGaceWFZo% Gbaiaaaaa!3B4E!\[\dot \gamma \] shear rate, s^–1 - _i thei-th value of , s^–1 - _r =1 the value of at = 1, s^–1 - ^* reduced shear rate, eq. (44), s^–1 - dimensionless reduced shear rate, eq. (35) - viscosity, Pa · s - shear-rate and residence-time dependent viscosity, Pa · s - zero-shear-rate degradation curve - degradation curve at - _{t0 (t)} zero-residence-time flow curve - Newtonian asymptote of the RFS - instantaneous flow curve - power-law asymptote of the RFS - _0,0 zero-shear-rate and zero-residence-time viscosity, Pa · s - _E=1 value of viscosity atE=1, Pa · s - ^* reduced viscosity, eq. (43), Pa · s - zero-residence-time rheological time constant, s - density, kg/m³ - (t),(t) residence time functions     

Melt viscosity of linear and branched poly(butyleneisophthalate)

Linear and branched poly(butyleneisophthalate) samples were synthesized and characterized in terms of the intrinsic viscosity, the molecular weight and the melt viscosity over a wide range of shear rates at 200 °C. An exponent of about 4.6 in the equation relating ₀ to was found for linear samples; this high value is probably due to the high content of cyclic oligomers in low molecular weight samples. Both linear and branched samples exhibited Newtonian behaviour over a rather wide range of shear rates, but for any given melt-viscosity, the branched samples became shear thinning at lower shear rates than the linear ones. Our experimental data were found to fit a previously proposed correlation between the melt viscosity ratio ( _{0, b} / _{0, 1} ) and a branching index quite well.