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 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 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.

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.     

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 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 behavior of composites made from linear medium-density polyethylene and hemp fibers treated by surface-initiated catalytic polymerization

This work presents different rheological methods to determine the effect of fiber surface treatment on their interaction with a polymer matrix. In particular, surface-initiated catalytic polymerization was investigated on hemp fibers to improve their adhesion with linear medium-density polyethylene (LMDPE). The selected rheological tests (creep-recovery (solid state), small and large amplitude oscillation shear, and transient rheology (melt state)) were used to compare the treated and untreated fiber composites with the neat matrix. The results showed a significant improvement of the treated hemp composite (LPHC) creep modulus with respect to its untreated counterpart (LNHC) leading to a reduction of the creep strain, especially as temperature increases. The transient viscosity was modeled using a modified Kohlrausch-Williams-Watt (KWW) equation showing an increase in the transient viscosity (\( {\eta}_0^{+} \)) and relaxation time (τ) with fiber addition and surface treatment. These results were confirmed by large amplitude oscillatory shear (LAOS) through the reduction of the relative third harmonic (I_3/1), intrinsic nonlinearity parameter (Q₀), and nonlinear viscoelastic ratio (NRL). The results clearly show that catalytic polymerization is a good surface modification technique to increase the compatibility between natural fibers and polymer matrices as to improve all their final properties.

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Rheological behavior of water-creosote and creosote-water emulsions

The effect of temperature on the steady-shear viscosity of two base emulsions (water-in-creosote (w/o) and creosote-in-water (o/w)) and a pigment emulsified creosote (PEC) was investigated. The PEC is a water-in-creosote emulsion which contains also a solid, micronised pigment, and is used industrially as a wood preservative. All three emulsions exhibited shear thinning characteristics at different temperatures. The viscosity-shear rate relationships follow a modified Quemada model. A temperature-superposition method using the reduced variables / and t _c was applied to yield a master plot for each of these emulsions at different temperatures. The effect of creosote concentration on the viscosity of four other o/w emulsions at different temperatures was also studied. The same reduced variables were able to produce a temperature-concentration superposition plot for all of the o/w emulsion results.The effective (average) radius of the globules (dispersed phase) was found to increase with increasing temperature for the base w/o and the PEC emulsion. The collision theory could be used to explain the increase in the droplet size. However, while little overall variation in globule size was observed for the o/w emulsions, microscopic observation indicated an increase in the proportion of large diameter droplets with temperature at the highest creosote concentration (60%). A creaming effect (phase concentration) was observed with these emulsions at higher temperatures, precluding an accurate estimate of droplet size based on collision theory.Seconded from Koppers Coal Tar Products, Newcastle, N.S.W., Australia.     

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.     

Predicting the rheology of linear with branched polyethylene blends

A series of melt blended commercial linear and branched polyethylenes are used to explore the generality of blending laws. The measured relaxation modulus G(t), and zero shear viscosity ₀ for each blend and blend fraction, have been compared with prediction for miscible blends, particularly using equations derived by Tsenoglou (1987). Plus or minus deviation between theory and measurement is dependent on the relative molecular weights of the blend components. We have found empirically that a generalised form of the blending law for G(t) and for ₀, with a floating index C, provides an improved prediction of the blend fraction data. In particular the function defining C is non-symmetrical, from which we infer the significance of branching as well as molecular weight. The optimum value of the index differs for each of our blends, in the range 1.25 to 4, the variability being accounted for by the different degrees to which branched and linear polymers relax co-operatively in the melt. Blends of two near linear polymers do not fit the floating index prediction and conform more closely, though not precisely, to the original Tsenoglou rule.     

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 behavior of sewage sludge and strain-induced dewatering

In order to study the strain-induced water release in sewage sludge and its connection with rheological behavior, two types of rheological tests have been carried out. The rheology of sewage sludge samples stemming from a urban sewer was first characterized using a Couette cell system. In particular, the yielding behavior and the elastic modulus of the sludge has been considered under shear flow conditions. In these pure shear tests the reproducibility of the measurements was rather poor, limiting this study to low strains. Consequently, a second type of rheological tests, namely the squeeze test, which is more appropriate for these paste-like materials, has been considered. The rheological behavior along with the dewatering efficiency have been studied under the squeeze flow conditions. Surprisingly, it was found that, under certain conditions, the strain-induced water release mechanism became more effective when decreasing the squeeze speed. This was interpreted in terms of a competition between the paste flow and the water filtration through the porous media made up by the flocs.     

From linear viscoelasticity to the architecture of highly branched polyethylene

In this work, the linear viscoelastic behavior of some low-density polyethylene in the melt is used to obtain their architecture. In this way, the number of branches per molecule and long chain branching (LCB) content is determined. For this purpose, a method based on the molecular dynamics of simple star-shaped molecules is presented. It allows one to infer the topology of an average molecule through a set of 2N _c parameters {C ⁿ _i , the number concentration of a level i} and {M _bi , the mass of a segment of level i} representing an irregular Cayley tree with N _c levels. The inverse problem uses the complex shear modulus as a function of the frequency data along with a minimization algorithm. Results from the present method are compared with NMR and SEC measurements of the level of branching. It appears that SEC and rheology leads to similar results on the determination of LCB while NMR overestimate the number of branch points per molecule. Moreover, rheology allows one to go further than the basic evaluation of LCB content and shows a picture of the structure of the molecules that is in agreement with the kinetics of free radical polymerization of polyethylene.     

Shear flow properties of concentrated solutions of linear and star branched polystyrenes

Summary The linear viscoelastic and viscometric functions have been determined for solutions of wellcharacterized monodisperse linear and star-branched polystyrenes and for commercial, polydisperse polystyrene. The value of the product c for these solutions was large and was obtained by using both high and low The effect of structure on the rheological properties was determined by examining how parameters in a modified Carreau viscosity equation (used to fit the data) varied with c, , and branching. No enhancement effects on the rheological properties were observed because of branching.The Cox-Merz rule was observed to describe the similarities between the viscosity and complex viscosity for most of the monodisperse samples studied. The broad molecular weight distribution polystyrene solutions did not follow this empiricism.With 17 figures and 4 tables     

Flow instability for binary blends of linear polyethylene and long-chain branched polyethylene

The rheological properties and flow instability are studied for binary blends composed of a long-chain branched polyethylene and a linear polyethylene. It is found that the blends containing a linear-polyethylene with high shear viscosity exhibit higher oscillatory moduli, drawdown force, and strain-hardening behavior. The blends showing the anomalous rheological phenomena show sharkskin failure in low shear rate region as compared with a pure linear polyethylene. Moreover, the blends exhibit severe gross melt fracture at low output rate. Enhanced strain-hardening in elongational viscosity and large entrance angle at a die entry will be responsible for the severe gross melt fracture for the blends.     

Rheological behavior of needle-like hydroxyapatite nano-particle suspensions

We describe here the preparation and rheological behavior of stable suspensions of needle-like hydroxyapatite nanoparticles dispersed in organic media, including methylethylketone (MEK), polycaprolactone (PCL) solutions in MEK, and PCL melt. These suspensions are the main ingredients in preparing certain biodegradable orthopedic materials that have some advantages over traditional implants. Rheological properties were experimentally determined at shear rates approaching those used in the processing methods such as roll coating, extrusion, and pultrusion. Analysis of the flow behavior suggests possible shear alignment at high Pe number (Pe ≈ 6,000). The linear viscoelastic properties and the paste-like behavior suggest the formation of a network as the particle content increases. These results are critical in designing a process for making composite materials containing highly oriented anisotropic particles.     

Calculation of the dynamic behavior of branched cable systems

A technique for the study of the dynamic behavior of three-dimensional elastic branched cable structures is proposed. Parametric local spline functions of spatial variables is used to reduce the boundary-value problem to a Cauchy problem. A graph of a three-dimensional cable structure is used to construct the solution algorithm. A study of the dynamic behavior of a hydrophysical anchored buoy system affected by the action of sea waves is performed, taking into account relaxation effects in individual elements. S. P. Timoshenko Institute of Mechanics, National Academy of Sciences of Ukraine, Kiev. Translated from Prikladnaya Mekhanika, Vol. 35, No. 9, pp. 106–110, September, 1999.     

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.