Rheology of Ziegler–Natta and metallocene high-density polyethylenes: broad molecular weight distribution effects

The linear viscoelastic properties of two series of Ziegler–Natta and metallocene HDPEs (ZN-HDPEs and m-HDPEs, respectively) of broad molecular weight distribution (MWD) have been studied. Correlations between zero-shear viscosity and molecular weight and molecular weight distribution show that the breadth of the MWD for m-HDPEs plays a role. Other interesting correlations between the crossover modulus and steady-state compliance with MWD of both these classes of polymers have also been derived. Finally, the steady-shear viscosities from capillary rheometry are compared with LVE data to check the applicability of the empirical Cox–Merz rule. It is shown that the original Cox–Merz rule is applicable for the ZN-HDPEs, while it apparently fails for the m-HDPEs. However, once the capillary data for m-HDPEs are corrected for slip effects, the applicability of the Cox–Merz rule is validated for their case as well.     

Correlation between thermal and rheological studies to characterize the behavior of bitumen

The objective of this work is a comprehensive thermo-rheological study of pure bitumen. The bitumen is a complex material consisting of asphaltenes dispersed in a maltene matrix. As a consequence, its flow behavior is characterized by the presence of a yield stress, which depends on temperature below 50°C. Applying the Cox–Merz rule, a master curve of viscosity can be obtained over a wide range of shear rates for temperatures above 50°C. It can be accurately modeled by a Carreau–Yasuda law with a yield stress. This specific rheological behavior can be explained by the changes induced by the temperature on the microstructure, evidenced by modulated differential scanning calorimetry measurements.     

The use of the capillary rheometer for the rheological evaluation of extrudable cement-based materials

In this paper, the rheological properties of an extrudable cement-based paste are investigated by means of an original ram extrusion apparatus (capillary rheometer). The experimental results indicate that a careful measurement of the die pressure is necessary to obtain a realistic viscosity vs shear rate curve, as required in extrusion technology. In particular, it is shown that the optimal test configuration is when the pressure measurement is made directly inside the rheometer die. By applying this rheological methodology in steady-state conditions, it has been observed that the extrudable cement-based material here evaluated obeys to a simple power–law equation, in the range of shear rates investigated, which are suitable for an industrial extrusion process. This paper was presented at the third Annual European Rheology Conference (AERC) held in Hersonissos, Crete, Greece, April 24–27, 2006.     

Viscoelastic properties of ultra-high viscosity alginates

Ultra-high viscosity alginates were extracted from the brown seaweeds Lessonia nigrescens (UHV_N, containing 61% mannuronate (M) and 2% guluronate (G)) and Lessonia trabeculata (UHV_T, containing 22% M and 78% G). The viscoelastic behavior of the aqueous solutions of these alginates was determined in shear flow in terms of the shear stress σ ₂₁, the first normal stress difference N ₁, and the shear viscosity η in isotonic NaCl solutions (0.154 mol/L) at T = 298 K in dependence of the shear rate [(g)\dot]\dot{\gamma} for solutions of varying concentrations and molar masses (3–10 × 10⁵ g/mol, homologous series was prepared by ultrasonic degradation). Data obtained in small-amplitude oscillatory shear (SAOS) experiments obey the Cox–Merz rule. For comparison, a commercial alginate with intermediate chemical composition was additionally characterized. Particulate substances which are omnipresent in most alginates influenced the determination of the material functions at low shear rates. We have calculated structure–property relationships for the prediction of the viscosity yield, e.g., η–M _w–c–[(g)\dot]\dot{\gamma} for the Newtonian and non-Newtonian region. For the highest molar masses and concentrations, the elasticity yield in terms of N ₁ could be determined. In addition, the extensional flow behavior of the alginates was measured using capillary breakup extensional rheometry. The results demonstrate that even samples with the same average molar mass but different molar mass distributions can be differentiated in contrast to shear flow or SAOS experiments.     

Rheo-optics of cationic surfactant micellar solutions with mixed aromatic counterions

The effects of different ratios of mixed aromatic counterions of sodium salicylate (NaSal) and sodium 4-ethylbenzenesulfonate (NaEBS) at a total counterion concentration of 0.125 M on the rheo-optical behaviors of 0.05 M cetyltrimethylammonium chloride (CTAC) cationic surfactant solutions were studied. The introduction of NaEBS into CTAC–NaSal solution led to a significant deviation from the Cox–Merz rule. Mixing of the two aromatic counterions lowered the CTAC solutions’ zero shear viscosities, increased their plateau shear modulus, and decreased their relaxation time. In addition, the persistence lengths of the threadlike micelles and the mesh size of the micellar network were also significantly reduced. These effects are believed to be due to increased degree of branching and denser meshes of the micellar networks in the mixed counterion systems.     

Linear viscoelastic model for elongational viscosity by control theory

Flows involving different types of chain branches have been modelled as functions of the uniaxial elongation using the recently generated constitutive model and molecular dynamics for linear viscoelasticity of polymers. Previously control theory was applied to model the relationship between the relaxation modulus, dynamic and shear viscosity, transient flow effects, power law and Cox–Merz rule related to the molecular weight distribution (MWD) by melt calibration. Temperature dependences and dimensions of statistical chain tubes were also modelled. The present study investigated the elongational viscosity. We introduced earlier the rheologically effective distribution (RED), which relates very accurately and linearly to the viscoelastic properties. The newly introduced effective strain-hardening distribution (RED_H) is related to long-chain branching. This RED_H is converted to real long-chain branching distribution by melt calibration and a simple relation formula. The presented procedure is very effective at characterizing long-chain branches, and also provides information on their structure and distribution. Accurate simulations of the elongational viscosities of low-density polyethylene, linear low-density polyethylene and polypropylene, and new types of MWDs are presented. Models are presented for strain-hardening that includes the monotonic increase and overshoot effects. Since the correct behaviour at large Hencky strains is still unclear, these theoretical models may aid further research and measurements.     

Three views of viscoelasticity for Cox–Merz materials

A slight rearrangement of the classical Cox and Merz rule suggests that the shear stress value of steady shear flow, , and complex modulus value of small amplitude oscillatory shear, G^∗(ω) = (G^′2 + G^″2)^1/2, are equivalent in many respects. Small changes of material structure, which express themselves most sensitively in the steady shear stress, τ, show equally pronounced in linear viscoelastic data when plotting these with G^∗ as one of the variables. An example is given to demonstrate this phenomenon: viscosity data that cover about three decades in frequency get stretched out over about nine decades in G^∗ while maintaining steep gradients in a transition region. This suggests a more effective way of exploiting the Cox–Merz rule when it is valid and exploring reasons for lack of validity when it is not. The τ −G^∗ equivalence could also further the understanding of the steady shear normal stress function as proposed by Laun.     

Pressure-dependent viscosity and free volume of atactic and syndiotactic polystyrene

The effect of pressure on viscosity is an important but often overlooked aspect of the flow properties of polymeric materials. In this work, two polymers (an atactic and a syndiotactic Polystyrene) were characterized to determine the effect of pressure on viscosity. In particular, a device was adopted to increase the exit pressure of a standard capillary rheometer, thus obtaining data of viscosity under high pressure and high shear rates. The Simha-Somcynsky equation of state was applied to the pressure–volume–temperature experimental data of both materials to obtain the dependence of free volume on temperature and pressure. The Doolittle equation was eventually employed to verify the dependence of viscosity on free volume. It was found that, for both materials, a linear relationship holds between the logarithm of zero-shear-rate viscosity (at several temperatures and pressures) and the inverse of free volume.     

Instability of entangled polymers in cone and plate rheometry

Flow instability in three entangled polymer systems including a 10 wt% 1,4-polybutadiene (PBD) solution, an 11.4 wt% polyisobutylene (PIB) solution, and a long chain branched polyethylene melt (LD 146) was investigated in both stress-controlled and rate-controlled experiments in the cone–plate geometry. It was found that flow instability occurred for experiments in both rate- and stress-controlled modes. The effects of cone angle or rim gap and shearing time on flow instability were studied. The smaller cone angle and shorter shearing time delay (in terms of stress or shear rate) the occurrence of severe instability and mass loss of the PBD solution but not for the PIB. Our data are consistent with the dramatic shear rate jump for the flow curve constructed from the stress-controlled experiments being associated with mass loss after the severe instabilities. We also find that the Cox–Merz representation gives a powerful tool for investigation of flow instability. Finally, another interesting result in this work is that it seems that the stress overshoot can be related to the onset of flow instability in the present system.     

The rheological characterisation of bread dough using capillary rheometry

An Australian hard wheat flour–water dough has been characterised using parallel plate and capillary rheometers over an extensive range of apparent shear rates (10^− 3–10³ s^− 1) relevant to process conditions. Torsional measurements showed that the shear viscosity of the dough increased with strain to a maximum value and then decreased, suggesting a breakdown of the dough structure. Both torsional and capillary experiments revealed the shear-thinning behaviour of the dough. The wall slip phenomenon in capillary rheometry was investigated and found to be diameter dependent and occurred at a critical shear stress of approximately 5–10 kPa. A two-regime power law behaviour was observed, with the power law index approximately 0.3 in the low shear rate range increasing to 0.67 in the high shear rate range. Pressure fluctuation was observed in the capillary data and increased with shear rate, in particular, at shear rates approaching 10⁴ s^− 1. The results demonstrate that capillary rheometry is a viable means of rheologically testing dough at high shear rates provided pressure fluctuation is carefully monitored and capillary rheometry corrections, including wall slip, are accounted for.     

Evaluation and comparison of routes to obtain pressure coefficients from high-pressure capillary rheometry data

A capillary rheometer equipped with a pressure chamber is used to measure the pressure-dependent viscosity of polymethylmethacrylate (PMMA), poly-α-methylstyrene-co-acrylonitrile (PαMSAN), and low-density polyethylene (LDPE). Data analysis schemes are discussed to obtain pressure coefficients at constant shear rate and at constant shear stress. It is shown that the constant shear stress pressure coefficients have the advantage of being shear stress independent for the three polymers. The constant shear rate pressure coefficients, on the other hand, turn out to depend on shear rate, which makes them less suitable for use, e.g., in process simulations. In addition to the commonly used superposition method, a direct calculation method for the pressure coefficients is tested. Values obtained from both methods are equivalent. However, the latter requires less experimental and calculational efforts. From the obtained pressure coefficients, it is clear that PMMA and PαMSAN have a very similar pressure dependence, while LDPE is less sensitive to pressure.     

An intriguing empirical rule for computing the first normal stress difference from steady shear viscosity data for concentrated polymer solutions and melts

The Cox–Merz rule and Laun’s rule are two empirical relations that allow the estimation of steady shear viscosity and first normal stress difference, respectively, using small amplitude oscillatory shear measurements. The validity of the Cox–Merz rule and Laun’s rule imply an agreement between the linear viscoelastic response measured in small amplitude oscillatory shear and the nonlinear response measured in steady shear flow measurements. We show that by using a lesser-known relationship also proposed by Cox and Merz, in conjunction with Laun’s rule, a relationship between the rate-dependent steady shear viscosity and the first normal stress difference can be deduced. The new empirical relation enables a priori estimation of the first normal stress difference using only the steady flow curve (i.e., viscosity vs shear rate data). Comparison of the estimated first normal stress difference with the measured values for six different polymer solutions and melts show that the empirical rule provides values that are in reasonable agreement with measurements over a wide range of shear rates, thus deepening the intriguing connection between linear and nonlinear viscoelastic response of entangled polymeric materials.     

Measurement of pressure coefficient of melt viscosity: drag flow versus capillary flow

The pressure coefficient of viscosity of poly(α-methylstyrene-co-acrylonitrile) was measured using a high-pressure sliding plate rheometer (HPSPR) and two types of capillary rheometer: a piston-driven device with a throttle at the exit [piston capillary rheometer with throttle (PCRWT)] operated at a fixed flow rate, and a counter-pressure nitrogen capillary rheometer (CPNCR) operated at a fixed pressure drop. In the HPSPR, the pressure, shear rate, density, and viscosity are all uniform throughout the sample, while the analysis of capillary data is complicated by the axial pressure gradient and the radial shear rate gradient. The polymer was found to be piezorheologically simple, and the HPSPR data indicated that the pressure coefficient of viscosity β ≡ dln(a _P)/dP decreased slightly with increasing pressure at high pressure. While β from PCRWT data from different laboratories and instruments agreed fairly well, the β values were on average about 2/3 of that from the HPSPR. The CPNCR yields β about 18% lower than that of the HPSPR.     

Experimental analysis of pressure distribution in a twin screw compressor for multiphase duties

This paper presents the results of an experimental investigation of pressure distribution inside working chamber of a twin screw compressor for multiphase duties. A mathematical model for describing the pressure distribution inside working chamber is proposed. By means of a small pressure transducer embedded into the groove at the root of the rotor, the pressure distributions of a multiphase compressor under various running conditions have been recorded successfully to verify the model. It is found that the pressure curve during the discharge process has a higher level under the conditions of the lower gas void fraction, higher discharge pressure, higher rotational speed and higher inlet pressure. The pressure distribution calculated by model in this paper shows good agreement with the data recorded by a small pressure sensor in a prototype multiphase compressor at the high gas void fractions under different operating conditions.     

Molecular orientation in sheared molten thermotropic random copolyester

The macromolecular alignment and texture orientation in sheared thermotropic copolyester were investigated using in situ wide-angle X-ray scattering (WAXS) and polarizing optical microscopy (POM). The molecular behavior was correlated with viscoelastic properties. The polymer is a random copolyester based on 60 mol% 1,4-hydroxybenzoic acid (B) and 40 mol% ethylene terephthalate (ET) units. X-ray scattering showed that the molecular chains were aligned along the flow direction. The degree of molecular orientation, , is an increasing function of the applied shear rate. However, rheo-optics showed that shear flow could not orient the polydomain texture, i.e., neither defect stretching nor elimination of defects was observed. Instead, shear compressed the microdomains and gave rise to long-range orientation correlations. Rheology showed that the nematic melt is viscoelastic, the loss modulus G″ dominates the elastic modulus G′, and the dynamic viscosity η* is shear thinning. Moreover, the steady shear viscosity, η, also behaved shear thinning, while the first normal stress difference N ₁ remained positive. The empirical Cox–Merz rule did not hold, , within the shear rate range studied. The microscopic and rheological properties suggest that B–ET is a flow-aligning nematic polymer.     

Permeability identification of a weakly permeable partially saturated porous rock

The present paper deals with the determination of permeability in partially saturated conditions for weakly permeable porous continua such as argillites or deep clayey formations. The permeability can be deduced from measurements of transient weight loss of a sample submitted to a laboratory drying test: a decrease of relative humidity is imposed by saline solution in an hermetic chamber. Assumptions of constant gas pressure equal to atmospheric pressure and of negligible Fickean diffusive transport of vapour are adopted. The only transport phenomenon taken into account inside the sample is the Darcean advective transport of the water liquid. The forward problem is solved by following two modelling approaches: a linear one and a nonlinear one. The parameter identification procedure is based upon the solution of corresponding inverse problems. In the two cases, the Levenberg–Marquardt algorithm has been used for the minimization problem. In the linear approach, the solution of the forward problem is explicit. In the non linear approach, finite volume method for the spatial discretization combined with a Newton–Raphson algorithm has been used to solve the non linear forward problem. The identification method enables variations of permeability and capillary capacity to be estimated. Comparisons between linear and non linear approaches show that the first one is useful to give mean values and order of magnitude of permeability and capacity. A more complete information is deduced from the non linear approach as variations of equivalent capacity and permeability during a test are significant in most cases. The analysis of the obtained results shows that the basic modelling assumption of constant gas pressure inside the sample would not be relevant for lower range of relative humidities and liquid permeability than those investigated.     

A procedure to determine the viscosity function from experimental data of capillary flow

The accurate calculation of the viscosity η as function of the shear rate &γdot; from capillary viscometry is still a matter of debate in the literature. In fact, this problem involves the inversion of an integral equation, which leads to multiple solutions due to the unavoidable noise present in the experimental data. The purpose of this work is to develop an efficient procedure to determine the viscosity function from experimental data of capillary flow without presenting the difficulties inherent in other methods discussed previously in the literature. The system identification procedure is used here to estimate the parameters of a viscosity model, which is appropriately selected for the fluid under study through preliminary calculations involving the apparent shear rate – shear stress data. Once the model is chosen by satisfying criteria for the fit goodness and its parameters are evaluated, a smooth and continuous function η(γdot;) is obtained in the range of experimental shear rates. The procedure proposed is also applicable to fluids in shear flow that present two Newtonian plateaus, as it is typically found in macromolecular dilute solutions. The mean value theorem of continuous functions is used to reduce significantly the computational time. Received: 15 November 1999 Accepted: 7 November 2000     

Dynamics of worm-like micelles: the Cox–Merz rule

The viscoelastic behaviour of worm-like micelles in small-amplitude oscillatory, steady simple shear and uniaxial extensional flows are analyzed with a model that couples the Oldroyd-B constitutive equation with a kinetic equation that accounts for the structural changes induced by the flow. In some cases, the constitutive equation predicts a viscoelastic behaviour that is consistent with the Cox–Merz rule. Departures from this rule are also predicted. Experimental data obtained for two worm-like micellar systems indicate that in these solutions, the Cox–Merz rule is not usually followed, in agreement with the predictions of our model. In uniaxial extensional flow, the model predicts a strain hardening in the extensional viscosity at low extensional rates and a strain-thinning at high extensional rates.     

Exponential shear flow of branched polyethylenes in rotational parallel-plate geometry

Exponential shear flow, as a strong flow with the potential to generate a high degree of molecular stretching, has attracted considerable interest in recent years. So far, exponential shear flow has been realized by either sliding-plate or cone-and-plate (CP) geometry. Both geometries guarantee homogeneous shear flow. Here, we present experimental data on exponential shear flow of several long-chain branched polyethylene melts with different degrees of strain hardening obtained by using parallel-plate (PP) geometry in a rotational rheometer. This type of geometry, which is standard in linear-viscoelastic characterization of polymer materials, produces inhomogeneous shear flow. A comparison of exponential shear flow data obtained by PP and CP geometry is made. Additionally, the experimental data are compared to predictions of the rubber-like liquid (RLL) and the molecular stress function (MSF) theories. For this purpose, the relaxation spectra of the polymer melts considered were obtained by standard linear-viscoelastic characterization. In addition, two irrotational parameters and one rotational parameter are required by the MSF theory. While the irrotational parameters were obtained from fitting to elongational viscosity data, the value of the rotational parameter was used as given in the literature. It can be concluded that viable experimental data in exponential shear flow can be obtained by PP geometry. For finite linear-viscoelasticity (RLL theory), predictions of reduced shear stress for CP and PP geometry coincide, but nonlinear material behavior (as modeled by the MSF theory) leads to small differences between both geometries. Furthermore, it is shown that the MSF predictions are in excellent agreement with the experimental data in exponential shear flow and that this type of flow leads to much less chain stretching than elongational flow.Dedicated to the memory of Prof. Arthur S. Lodge (1922–2005).