The effect of boron nitride on the rheology and processing of polyolefins

The influence of a new processing additive (fine particles of boron nitride) on the rheology and processability of polyolefins is studied. The equipment used includes an Instron capillary rheometer equipped with capillary and special annular dies (Nokia Maillefer wire coating crosshead) and two rheometers, namely a parallel-plate and a sliding-plate rheometer. Several types of boron nitride powders, varying in average particle size and distribution and in morphology are tested at various concentration levels. The additive with the smallest average particle size and free of agglomeration was found to have the greatest influence on the processability (melt fracture performance) of the polyolefins tested. Specifically, it was found that boron nitride not only eliminates surface melt fracture but also postpones the critical shear rate for the onset of gross melt fracture to significantly higher values, depending on the additive concentration, surface energy, and morphology. A flow visualization technique was used to visualize the polymer flow at the entrance of a transparent capillary die in order to determine the mechanism by which boron nitride eliminates gross melt fracture. Received: 18 January 2000 Accepted: 15 June 2000     

Fingerprinting the processing behavior of polyethylenes from transient extensional flow and peel experiments in the melt state

The flow curves of linear (linear-low and high density) and branched polyethylenes are known to differ significantly. At increasing shear rates, the linear polymers exhibit a surface melt fracture or sharkskin region that is followed by an unstable oscillating or stick-slip flow regime when a constant piston speed capillary rheometer is used. At even higher shear rates, gross melt fracture appears. Unlike their linear counterparts, branched polyethylenes rarely exhibit sharkskin melt fracture and although gross melt fracture appears at high shear rates there is no discontinuity in their flow curve. The various flow regimes of these two types of polyethylenes are examined by performing experiments in the melt state using a unique extensional rheometer (the SER by Xpansion Instruments) that is capable of performing accurate extensional flow and peel experiments at very high rates not previously realized. The peel strength curves of these linear and branched polyethylenes exhibit all of the distinct flow regimes exhibited in their respective flow curves, thereby providing a fingerprint of their melt flow behavior. Moreover, these extensional flow and peel results in the melt state provide insight into the origins and mechanisms by which these melt flow phenomena may occur with regard to rapid tensile stress growth, melt rupture, and adhesive failure at the polymer wall interface.     

Comparison of the melt fracture behavior of metallocene and conventional polyethylenes

The influence of sparse long-chain branching and molecular weight distribution on the melt fracture behavior of polyethylene melts was investigated. Four commercial polyethylene resins were employed for this study: a conventional low-density polyethylene, a conventional linear low-density polyethylene, a linear metallocene polyethylene, and a sparsely branched metallocene polyethylene. Rheological measurements were obtained for both shear and extensional deformations, and melt fracture experiments were carried out using a controlled rate capillary rheometer. A single capillary geometry was used to focus on the effects of material properties rather than geometric factors. For the linear polyethylenes, surface melt fracture, slip-stick fracture, and gross melt fracture were all observed. Conversely, the branched PE resins did not exhibit a slip-stick regime and the degree of gross fracture was observed to be much more severe than the linear resins. These variations can be explained by the effects that long-chain branching has on the onset of shear-thinning behavior (slip-stick fracture) and the degree of extensional strain hardening (gross melt fracture). Although there is some indication that the breadth of molecular weight distribution indirectly influences surface melt fracture, the results remain inconclusive.     

In-line measurement of rheological properties of polymer melts

Shear viscosity (), first normal stress difference (N ₁), and extensional viscosity ( _E ) of polymer melts measured under processing conditions are important in process modeling, quality control, and process control. A slit rheometer that could simultaneously measure , N ₁, and the planar extensional viscosity ( _p ) was designed and tested by attaching it in-line to a laboratory model single-screw extruder. A tube (circular cross-section) rheometer to measure and the uniaxial extensional viscosity ( _u ) simultaneously was also designed and tested. Two commercial grades of LDPE (low density polyethylene) with melt index values of 6 and 12 were used as test materials for the study. Exit and hole pressure methods were used to estimate N ₁, and the entrance pressure drop method using the analyses of Cogswell, Binding, and Gibson (the last analysis used with the axisymmetric case only) was used to estimate _E .The hole pressure method was considered better than the exit pressure method to estimate N ₁ (due to the greater susceptibility of the latter to experimental errors). From the hole pressure method N ₁ was obtained from 100 kPa to 500 kPa over a range of shear rates from 40 s^–1 to 700 s^–1. Among the analyses used to estimate the extensional viscosity, Cogswell's is recommended due to its simpler equations without loss of much information compared to the other analyses. The range of extension rates achieved was 1 to 30 s^–1. The combination of the hole pressure and entrance pressure drop methods in a slit rheometer is a feasible design for a process rheometer, allowing the simultaneous measurement of the shear viscosity, first normal stress difference and planar extensional viscosity under processing conditions. Similarly, combining the entrance pressure drop measurements with a tube rheometer is also feasible and convenient.     

Can extensional viscosity be measured with opposed-nozzle devices?

Opposed-nozzle devices are widely used to try to measure the extensional viscosity of low-viscosity liquids. A thorough literature survey shows that there are still several unanswered questions on the relationship between the quantity measured in opposed-nozzle devices and the true extensional viscosity of the liquids. In addition to extensional stresses, opposed nozzle measurements are influenced by dynamic pressure, shear on the nozzles, and liquid inertia. Therefore the ratio of the apparent extensional viscosity that is measured to the shear viscosity that is independently measured is greater than three even for Newtonian liquids. The effect of inertia on the extensional measurements is analyzed by computer-aided solution of the Navier-Stokes system, and by experiments on low-viscosity Newtonian liquids(1 mPa sS 800 mPa s). The effect of nozzle separation-to-diameter ratio on the average residence time of the liquid is analyzed under the assumption of simple extensional flow kinematics. The average residence time of the liquid is independent of this ratio unless the radial inflow section of the extensional flow volume is related to the nozzle separation. Experiments indicate that in some cases widening the gap lowers the apparent extensional viscosity that is measured, whereas in other cases the opposite is true. In the light of these theoretical considerations and experimental observations, the use of systematic corrections to extensional viscosity measurements on non-Newtonian liquids is not recommended. Thus opposed nozzle devices should be considered as useful indexers rather than rheometers. Finally, measurements on a series of semi-dilute solutions of high molecular weight poly(ethylene oxide) in. water are also reported.Dedicated to the memory of Anastasios C. Papanastasiou     

Extensional rheology of a shear-thickening cornstarch and water suspension

A filament-stretching rheometer is used to measure the extensional viscosity of a shear-thickening suspension of cornstarch in water. The experiments are performed at a concentration of 55 wt.%. The shear rheology of these suspensions demonstrates a strong shear-thickening behavior. The extensional rheology of the suspensions demonstrates a Newtonian response at low extension rates. At moderate strain rates, the fluid strain hardens. The speed of the strain hardening and the extensional viscosity achieved increase quickly with increasing extension rate. Above a critical extension rate, the extensional viscosity goes through a maximum and the fluid filaments fail through a brittle fracture at a constant tensile stress. The glassy response of the suspension is likely the result of jamming of particles or clusters of particles at these high extension rates. This same mechanism is responsible for the shear thickening of these suspensions. In capillary breakup extensional rheometry, measurement of these suspensions demonstrates a divergence in the extensional viscosity as the fluid stops draining after a modest strain is accumulated.     

Extensional flow —a mathematical perspective

Extensional flow has been studied extensively for less than half the lifetime of the word rheology, although measurement of viscosity from extensional flow experiments can be traced back to the beginning of this century. In recent years extensional flow has, however, attracted a great deal of attention in conferences, workshops and special issues of journals. This has coincided with interest, both scientific and industrial, in elasticoviscous fluids, notably polymer solutions and molten polymers. The particular success of specialized, carefully targetted or focussed, workshops is highlighted.A personal reflection is offered here on some of the issues in extensional flow from the point of view of an applied mathematician. The state of the art, as far as extensional viscosity is concerned, is briefly surveyed. Both theoretical and practical aspects of the task of obtaining useful extensional flow properties are outlined, drawing heavily on a recent review by James and Walters. Particular attention is paid to spinning experiments, drawing heavily on recent theoretical investigations by the author. The merits of defining a spinning viscosity, in addition to the formally defined tensile viscosity, are advanced. The idea of general approximations for extensional flows is reviewed and some aspects of this are highlighted, particularly in connection with Metzner's idea of extensional primary field (EPF) approximations. Finally qualitative investigations of the behaviour of model fluids (in model flows) are illustrated and a new result on the boundedness of solutions for unsteady uniaxial extension of a FENS-P dumbbell model is presented.Presented as a keynote lecture at the 4the European Rheology Conference, September 4–9, 1994, Seville, Spain     

Viscoelastic behaviour and flow instabilities of biodegradable poly (ε-caprolactone) polyesters

The viscoelastic behaviour of a number of commercial and newly synthesized linear biodegradable polyesters—poly (ε-caprolactone) (PCLs) with different molecular characteristics was investigated using both rotational and extensional rheometry. The variation of the zero-shear viscosity and relaxation spectrum with molecular weight was studied in detail. The damping function of these PCLs was also determined in order to model their viscoelastic behaviour. The classic Wagner constitutive equation was found to represent the rheology of all PCL polymers quite well. Finally, the PCL processing instabilities were studied by capillary extrusion using a number of capillary dies having various diameter and length-to-diameter ratios. Sharkskin and gross melt fracture was observed at different shear rates depending on the molecular characteristics of the resins and the geometrical details of the capillary dies.     

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.     

A model long-discontinuous-fiber filled thermoplastic melt in extensional flow

The shear cell model works for dilute fiber filled systems in extensional flow. This research investigates the suitability of the idea for highly aligned fibers in a concentrated suspension. A model fiber-filled polymer system made from nylon fibers in low-density polyethylene provided a means of controlling the material parameters. Two systems, with fiber aspect ratios of 20 and 100, containing 50% 0.5 mm fibers by volume are investigated. The thickness of the polymer layer, i.e. with fibers this size, allows bulk viscosity data to be compared with the data from the filled fluid. A weaving process created the discontinuous fiber/polyethylene preforms with high alignment of the fibers and with control of the fiber to fiber overlap. Testing the polyethylene in simple shear and extending the nylon/polyethylene provided the data needed to check the micro mechanics. A cone and plate rheometer and a capillary instrument produced the viscosity/strain rate data that characterized the specific polyethylene used in the composite. A furnace inset placed in an Instron hydraulic test machine allowed extension of the filled system at strain rates from 0.002 to 0.4 s⁻¹. The shear experiments show that the low-density polyethylene is a simple shear-thinning melt that provides a good model fluid. The extension of the filled systems shows an increase of the apparent extensional viscosity from that of neat polyethylene. Apparent viscosity rises two to three orders of magnitude for the systems investigated. The micromechanics allowed the conversion of the extensional data from the two filled systems to the shear viscosity of the polymer surrounding the fibers. The calculated polyethylene viscosity compares well with the data from the standard rheometers. The shear cell approach may be applied to highly aligned, high fiber-volume-fraction suspensions when the viscosity of the polymer is known at the scale of the film surrounding each fiber.     

Determination of the elongational viscosity of polymer melts by melt spinning experiments. A comparison with different experimental techniques

In this work, melt spinning experiments were tentatively used for the determination of the elongational viscosity of polymer melts at different levels of tensile strain and strain rate. The materials examined were two high-density polyethylene grades for blow moulding with similar number-average molecular mass but different polydispersity index. The data from melt spinning tests were compared with transient extensional viscosity data obtained by uniform isothermal tensile tests, performed by means of an extensional rheometer, as well as with those produced by converging flow tests (Cogswell model). The results showed that for high strain and strain rate levels, the melt spinning experiments provide elongational viscosity data quite close to the transient extensional viscosity values obtained from the tensile tests.     

Microfluidic extensional rheometry using a hyperbolic contraction geometry

Microfluidic devices are ideally suited for the study of complex fluids undergoing large deformation rates in the absence of inertial complications. In particular, a microfluidic contraction geometry can be utilized to characterize the material response of complex fluids in an extensionally-dominated flow, but the mixed nature of the flow kinematics makes quantitative measurements of material functions such as the true extensional viscosity challenging. In this paper, we introduce the ‘extensional viscometer-rheometer-on-a-chip’ (EVROC), which is a hyperbolically-shaped contraction-expansion geometry fabricated using microfluidic technology for characterizing the importance of viscoelastic effects in an extensionally-dominated flow at large extension rates ( $\lambda \dot \varepsilon _a \gg 1$ , where $\lambda $ is the characteristic relaxation time, or for many industrial processes $\dot \varepsilon _a \gg 1$ s $^{-1}$ ). We combine measurements of the flow kinematics, the mechanical pressure drop across the contraction and spatially-resolved flow-induced birefringence to study a number of model rheological fluids, as well as several representative liquid consumer products, in order to assess the utility of EVROC as an extensional viscosity indexer.     

Wall slip and melt fracture of poly(lactides)

The wall slip and melt fracture behaviour of several commercial polylactides (PLAs) as well as their rheological properties under shear and extensional have been investigated. The PLAs have had weight-average molecular weights in the range of 10⁴–10⁵ g/mol and studied in the temperature range of 160–200°C. The solution properties and linear viscoelastic behaviour of melts indicate linear microstructure behaviour. PLAs with molecular weights greater than a certain value were found to slip, with the slip velocity to increase with decrease of molecular weight. The capillary data were found to agree well with linear viscoelastic envelope once correction for slip effects was applied. The onset of melt fracture for the high molecular weight PLAs was found to occur at about 0.2 to 0.3 MPa, depending on the geometrical characteristics of the dies and independent of temperature. Addition of 0.5 wt.% of a polycaprolactone (PCL) into the PLA that exhibits melt fracture was found to be effective in eliminating and delaying the onset of melt fracture to higher shear rates. This is due to significant interfacial slip that occurs in the presence of PCL.     

Negative wake in the uniform flow past a cylinder

The upstream/downstream streamline shift and the associated negative wake generation (streamwise velocity overshoot in the wake) in a viscoelastic flow past a cylinder are studied in this paper, for the Oldroyd-B, UCM, PTT, and FENE-CR fluids, using the Discrete Elastic Viscous Split Stress Vorticity (DEVSS-ω) scheme (Dou HS, Phan-Thien N (1999). The flow of an Oldroyd-B fluid past a cylinder in a channel: adaptive viscosity vorticity (DAVSS-ω) formulation. J Non-Newtonian Fluid Mech 87:47–73). The numerical algorithm is a parallelized unstructured Finite Volume Method (FVM), running under a distributed computing environment through the Parallel Virtual Machine (PVM) library. It is demonstrated that both the normal stress and its gradient are responsible for the negative wake generation and streamline shifting. Fluid extensional rheology plays an important role in the generation of the negative wake. The negative wake can occur in flows where the fluid extensional viscosity does not increase rapidly with strain rate. The formation of the negative wake does not depend on whether the streamlines undergo an upstream or a downstream shift. Shear-thinning viscosity weakens the velocity overshoot and while shear-thinning first normal stress coefficient enhances the velocity overshoot. Wall proximity is not necessary for the velocity overshoot; however, it enhances the strength of the negative wake. For the Oldroyd-B fluid, the ratio of the solvent viscosity to the zero-shear viscosity plays an important role in the streamline shift. In addition, mesh dependent behaviour of normal stresses along the centreline at high De in most cylinder/sphere simulations is due to the convection of normal stress from the cylinder to the wake, which results in the maximum of the normal stress being located off the centreline by a short distance at high De.     

Effect of processing and particulate fillers on the rheology of a nematic polymer melt

Processing of a nematic HBA/HNA polymer melt increases the capillary diameter dependence of the viscosity and induces structural changes which are evident in oscillatory shear, but cannot be characterized by DSC. The effect of 6-m calcium carbonate particulate fillers is to increase the viscosity uniformly. Low concentrations of sub-micron carbon black particles cause an unexplained viscosity minimum in a large (30-mil) capillary.     

Fibre spinning of a weakly elastic liquid

This paper presents a study of a silicone oil (poly(dimethyl siloxane)) in extensional deformation using an instrument developed recently by the authors. Data from steady shear and low amplitude sinusoidal deformation of this liquid clearly establish that it is weakly elastic. The viscometric data, for shear rates less than 100 s ⁻¹, are best represented by either the Maxwell model or the Jeffrey's model, the latter being marginally superior. The extensional data show that at low deformation rates, this fluid exhibits a Newtonian behavior with an apparent extensional viscosity equal to three times the shear viscosity. Under these conditions the velocity profiles along the spinline are also well represented by the Newtonian model. However, at higher deformation rates better predictions of the velocity profiles are obtained from the Jeffrey's and Maxwell models. At deformation rates above 100 s ⁻¹ none of these simple models is adequate. Under the conditions used in these experiments, the fractional increase in tensile stress along the fiber is shown both theoretically and experimentally to be a unique function of the total strain. Furthermore, the apparent extensional viscosity at any point on the spinline can be calculated from steady state expressions if allowance is made for the variation of stretch rates by defining a time averaged stretch rate.The results obtained here show that elasticity must be considered if these model liquids are used to conduct rheological experiments at high deformation rates. Additionally, it is found that elastic effects in extension can be predicted using simple constitutive equations provided viscometric data can be represented properly in the deformation rate range of interest. Finally, the present research further substantiates the utility of the extensional viscometer developed by the authors.     

Resistance to uniaxial extensional flow of fibre suspensions

The tensile stress due to resistance to uniaxial extensional flow of fibre suspensions in Newtonian and non-Newtonian fluids has been measured using the filament stretching technique. It has been found that addition of fibres to a Newtonian fluid increases the extensional viscosity. The steady state results agree with Bachelors theory and the stress growth behaviour is qualitatively predicted by the theory of Dinh and Armstrong. Experimental results from this work have also shown that the behaviour of a fibre suspension in viscoelastic fluid is qualitatively described by Fans equation. The added fibres increase the extensional stress growth coefficient of the viscoelastic fluid at low strain but have marginal effect on the fluid after the onset of strain-hardening.     

Computational analysis of techniques to determine extensional viscosity from entrance flows

Recent computational analysis of entrance flows (Mitsoulis et al. 1998) suggests that the entrance pressure drop is insensitive to large changes in steady extensional viscosity-a result that directly contradicts a large body of experimental work in this area. A re-examination of entrance flows using numerical simulations is presented in this work which shows that entrance pressure drops do depend on the steady extensional viscosity, provided the extension rate in the entrance flow is large enough. Numerical simulations are presented using both the strain thinning and thickening versions of the Phan-Thien–Tanner (PTT) constitutive model. Several techniques for extracting extensional viscosity from entrance pressure are applied to the results of these simulations. The resulting predictions of extensional viscosity are compared to the steady extensional viscosity curves predicted by the PTT constitutive model used to generate the simulated pressure drop curves. The analytical techniques examined here are shown to provide reasonably accurate estimates of the steady extensional viscosity. This work also clearly demonstrates the advantage of using variable power-law coefficients for the rheological properties, used as inputs to the analyses, to capture the extensional behavior at deformation rates below the power law region more accurately. Received: 23 July 1999/Accepted: 24 November 1999     

Shear fracture of polystyrene melts and solutions

We find that symptoms of polymer melt fracture, such as a time-dependent decrease in apparent sample modulus and apparent slip, can be induced by oscillatory torsional shearing flow of polystyrene melts and solutions, even when the polymer molecular weight is below the entanglement threshold, and thre strain amplidute is as low as 3%. Visualization of samples during and after fracture show crack and bubble formation, as well as delamination of the polymer from the rheometer tools. For polystyrene melts, the critical stress for fracture is ^* 0.1–1.0 MPa, depending on polymer molecular weight and temperature, and for solutions it is as low as 5 × 10³ Pa. Since constitutive instabilities require the viscoelastic properties to be highly nonlinear, our observations of melt fracture in unentangled polymers at shearing strains well within the linear viscoelastic range rule out this mechanism for some of our experiments, and show that melt fracture is not always caused by constitutive instabilities.