Influence of molecular parameters on the stress dependence of viscous and elastic properties of polypropylene melts in shear

The stress dependencies of the steady-state viscosity η and, particularly, that of the steady-state elastic compliance J _e of various linear isotactic polypropylenes (PP) and one long-chain branched PP are investigated using creep-recovery tests. The creep stresses applied range from 2 to 10,000 Pa. In order to discuss the stress-dependent viscosity η and elastic compliance J _e with respect to the influence of the weight average molar mass M _w and the polydispersity factor M _w/M _n the PP are characterized by SEC–MALLS. For the linear PP, linear steady-state elastic compliances J_e⁰J_{\rm e}^0 in the range of 10^− 5–10^− 3 Pa^− 1 are obtained depending on the molar mass distribution. J_e⁰J_{\rm e}^0 of the LCB-PP is distinctly higher and comes to lie at around 10^− 2 Pa^− 1. J_e⁰J_{\rm e}^0 is found to be independent of M _w but strongly dependent on polydispersity. η and J _e decrease with increasing stress. For the linear PP, J _e as a function of the stress τ is temperature independent. The higher M _w/M _n the stronger is the shear thinning of η and the more pronounced is the stress dependence of J _e. For the LCB-PP, the strongest stress dependence of η and J _e is observed. Furthermore, for all PP J _e reacts more sensitively to an increasing stress than η. A qualitative explanation for the stronger stress dependence of J _e compared to η is given by analyzing the contribution of long relaxation times to the viscosity and elasticity.     

The peculiar rheo-optical behavior of bisphenol A-polycarbonate and polymethylmethacrylate

The rheological and stress-optical behavior of the melts of several grades ob bisphenol-A-polycarbonate (PC) and polymethylmethacrylate (PMMA) is investigated. Pertinent flow birefringence measurements are carried out in a remodelled cone-plate apparatus [1]. The shear stress in the polymer melt is calculated from the dynamic moduli, which are determined separately. It is shown that the linear stress optical rule is obeyed. In this way, the stress-optical coefficient C of the melt can be determined. The low-Mw polycarbonates all behave as Maxwellian fluids. The main stress direction does not deviate significantly from 45°. In the temperature range from 160° to 260°C the stress-optical coefficients of the different grades lie between 3 and 4×10^–9 Pa^–1 and show a weak temperature dependence. The stress-optical coefficient of PMMA is about a factor of 100 lower and shows a peculiar temperature-dependence, changing its sign at 144°C. The results are discussed in terms of the anisotropy of the polarizability of the polymer chain.     

A note on the coefficient of viscosity of pure molten 2,4,6-trinitrotoluene (TNT)

The viscosity of pure molten TNT has been investigated over the temperature range 82.0°–95.4°C. The temperature dependence of viscosity was found to be best represented by a relation of the type = A e ^B/T whereA = 0.000541,B = 3570, is the viscosity in mPa s andT is the temperature in Kelvin. Earlier work, which suggests an inverse temperature dependence of the flow activation energy, is shown to include an error in the published equation for the temperature dependence of the viscosity of molten TNT.     

An automated dynamic viscometer with air bearing and inductive transducers for angular displacement detection

A dynamic viscometer is described, with which the dynamic moduli in the frequency range from 2 × 10^–3 to 10 Hz can be determined for liquids with 10^–3 Pa< |G ^* | <10² Pa. Due to the application of an air bearing and inductive transducers for the detection of the angular displacement of both the drive and the measuring cylinder a sensitive apparatus has been made. Very small strains (₀ 10^–3) can be applied and only a small amount of sample (4 ml) is needed. The operation of the apparatus is fully computer-controlled, thus, long runs at various frequencies and temperatures are possible without operator intervention. The theoretical background, calibration procedure, and operation window are described. A presentation of some measurements on two polyisoprene/polystyrene triblock copolymer solutions concludes the work.     

Effect of solids concentration in dense suspensions of silica-iron(III) oxide and water

The rheological properties of dense suspensions, of silica, iron (III) oxide and water, were studied over a range of solids concentrations using a viscometer, which was modified so as to prevent settling of the solid components. Over the conditions studied, the material behaved according to power—law flow relationships. As the concentrations of silica and iron(III) oxide were increased, an entropy term in the flow equation was identified which had a silica dependent and an iron (III) oxide dependent component. This was attributed to a tendency to order into some form of structural regularity. A, A, B, C pre-exponential functions (K Pa^–n s^–1) - C _ox volume fraction iron (III) oxide - Q activation energy (kJ mol^–1) - R gas constant (kJ mol^–1 K^–1) - R _v silica/water volume ratio - T temperature (K) - n power-law index - H enthalpy (kJ mol^–1) - S entropy change (kJ mol^–1 K^–1) - shear strain rate (s^–1) - shear stress (Pa)     

Measuring device for precise evaluation of torsional creep and recovery data

An apparatus has been designed and built up to determine the shear creep compliance and viscosity with high accuracy in a wide range of temperature and time. The characteristic feature of this apparatus is the possibility to measure directly the recoverable compliance and to determine the steady state recoverable complianceJ _e . Disturbing instrumental forces are minimized by use of a magnetic bearing. The torque is applied inductively by a modified three phase asynchronous motor. The torsional angle is measured with a laser beam reflected from a mirror to an electro-optical measuring device. Sample thermostating is performed by radiation in a heating chamber, which allows observation of the specimen during measurement.First results of creep and creep recovery measurements are reported, which were carried out on a technical polystyrene above the glass rubbery transition.Dedicated to Prof. Dr. H. Janeschitz-Kriegl on the occasion of his 60th birthday.     

New laboratory tests to measure rheological properties of paper coatings in transient and steady-state flows

The paper describes pertinent laboratory tests to characterize the rheological properties of paper coatings with regard to blade coating over a very wide range of shear rates in both transient and steady-state shear flows. Shear rates as high as 10⁶ s^–1 can be reached by means of a gas-driven capillary rheometer. Examples for the evaluation of end effects, wall effects, and coating thixotropy are given. A stiff and fast Couette rheometer is used to determine flow curves and the shear stress overshoot in step shear rate tests. The primary normal stress difference can be measured up to 10⁴ s^–1 by means of a high shear cone-plate rheometer with piezo transducer. A correct evaluation of the measurements has to take into account inertia contributions to the normal force. First results using a sinusoidal modulation of the shear rate are presented.Paper presented at: International Symposium on Pigment Coating Structure and Rheology, Helsinki, Febr. 8–9, 1989     

Viscosity of some clay-based coating colors at high shear rates

The shear viscosity of clay-based coating colors containing latex and carboxymethyl cellulose (CMC) has been measured over a relatively large shearrate region. In the shear-rate range of 50–1500 s^–1 the measurements were performed using a rotational viscometer and, at higher shear rates extending into the region 10⁵ – 10⁶ s^–1, a high pressure capillary viscometer was employed. The viscosity of the clay colors increased with increasing CMC-concentration, but the influence of the CMC-content was less pronounced at higher shear rates. The apparent shear-thinning behavior of the investigated colors could, in part, be attributed to the shear-thinning of the corresponding polymer (CMC) solution constituting the liquid phase of the color, but the influence of another factor was also indicated. At low shear rates, the interaction between the color components can produce relatively high viscosity levels, but in the high shear rate region these interactions appear to be less important for the viscosity level. It is also of interest to note that the viscosity dependence on the solids content in the high shear-rate region could be described with reasonable accuracy using an empirical equation neglecting interactions between the color components.     

Rheological properties of skim milk gels at various temperatures; interrelation between the dynamic moduli and the relaxation modulus

The rheological properties of rennet-induced skim milk gels were determined by two methods, i.e., via stress relaxation and dynamic tests. The stress relaxation modulusG _c (t) was calculated from the dynamic moduliG andG by using a simple approximation formula and by means of a more complex procedure, via calculation of the relaxation spectrum. Either calculation method gave the same results forG _c (t). The magnitude of the relaxation modulus obtained from the stress relaxation experiments was 10% to 20% lower than that calculated from the dynamic tests.Rennet-induced skim milk gels did not show an equilibrium modulus. An increase in temperature in the range from 20° to 35 °C resulted in lower moduli at a given time scale and faster relaxation. Dynamic measurements were also performed on acid-induced skim milk gels at various temperatures andG _c (t) was calculated. The moduli of the acid-induced gels were higher than those of the rennet-induced gels and a kind of permanent network seemed to exist, also at higher temperatures. G storage shear modulus,N·m^–2; - G loss shear modulus,N·m^–2; - G _c calculated storage shear modulus,N·m^–2; - G _c calculated loss shear modulus,N·m^–2; - G _e equilibrium shear modulus,N·m^–2; - G _ec calculated equilibrium shear modulus,N·m^–2; - G(t) relaxation shear modulus,N·m^–2; - G _c (t) calculated relaxation shear modulus,N·m^–2; - G ^*(t) pseudo relaxation shear modulus,N·m^–2; - H relaxation spectrum,N·m^–2; - t time,s; - relaxation time,s; - angular frequency, rad·s^–1. Partly presented at the Conference on Rheology of Food, Pharmaceutical and Biological Materials, Warwick, UK, September 13–15, 1989 [33].     

Driven torsion pendulum for measuring the complex shear modulus in a steady shear flow

To investigate the viscoelastic behavior of fluid dispersions under steady shear flow conditions, an apparatus for parallel superimposed oscillations has been constructed which consists of a rotating cup containing the liquid under investigation in which a torsional pendulum is immersed. By measuring the resonance frequency and bandwidth of the resonator in both liquid and in air, the frequency and steady-shear-rate-dependent complex shear modulus can be obtained. By exchange of the resonator lumps it is possible to use the instrument at four different frequencies: 85, 284, 740, and 2440 Hz while the steady shear rate can be varied from 1 to 55 s^–1. After treatment of the theoretical background, design, and measuring procedure, the calibration with a number of Newtonian liquids is described and the accuracy of the instrument is discussed.Notation a radius of the lump - A geometrical constant - b inner radius of the sample holder - c constant - C ₁, C ₂ apparatus constants - D damping of the pendulum - e _x , e _y , e _z Cartesian basis - e _r , e , e _z orthonormal cylindrical basis - E geometrical constant - E _t , ⁰ E _t , _t relative strain tensor - f function of shear rate - F _t relative deformation tensor - G (t) memory function - G ^* complex shear modulus - G Re(G ^* ) - G Im(G ^* ) - h distance between plates - H ^* transfer function - , functional - i imaginary unit: i ²= – 1 - I moment of inertia - J _exc excitation current - J ₀ amplitude of J _exc - k ^* = k – ik complex wave number - K torsional constant - K fourth order tensor - l length of the lump - L mutual inductance - M _dr driving torque - M _liq torque exerted by the liquid - ⁰ M _liq, _liq steady state and dynamic part of Mliq - n power of the shear rate - p isotropic pressure - Q quality factor - r radial position - R,R ₀, R _c Re(Z ^*, Z ₀ ^* , Z _c ^* ) - s time - t, t time - T temperature - T, ⁰ T, stress tensor - u velocity - U lock-in output - ₀ velocity - V _det detector output voltage - V _sig, V _cr signal and cross-talk part of V _det - x Cartesian coordinate - X , X ₀, X _c Im(Z ^*, Z ₀ ^* , Z _c ^* ) - y Cartesian coordinate - z Cartesian coordinate, axial position     

Flow behaviour of molten 2,4,6-trinitrotoluene (TNT) between concentric cylinders

The flow behaviour of pure and commercial molten TNT when subjected to very high rates of shear in a rotational viscometer over the temperature range 82.0 to 95.4°C is presented. All data obtained suggest that the behaviour of molten TNT is Newtonian, contrary to the conclusions of some published work, and the temperature dependence of the viscosity of pure TNT is adequately described by an Arrhenius-type relationship of the form = A e ^B/T whereA = 0.000 541,B = 3 570 andT is the Kelvin temperature. A similar relationship is obtained for commercial TNT. Under some instrumental conditions discontinuities are seen in the shear stress—shear rate flow curves. An analysis of these discontinuities shows them to be caused by the transition from laminar to turbulent flow. Possible implications for processibility and initiation of explosives are discussed.     

The rheology of a smectic main-chain polymer

The rheology of a smectic main-chain polymer shows that the activation energy is high (275 kJ mol^–1) and that the viscosity is more than two orders of magnitude higher than in the isotropic phase. The recoverable strain in the smectic phase is largely due to the reformation of the smectic layers after cessation of shear.     

Direct measurement of static yield properties of cohesive suspensions

A technique of yield stress investigation based upon the combined use of two devices (an applied stress rheometer and an instrument for measuring the propagation velocity of small amplitude, torsional shear waves) is described. Investigations into the low shear rate rheological properties of illitic suspensions are reported for shear rates, typically, in the range 10^–4— 10^–1 s^–1 under applied stresses in the range 0.01 — 10 Nm^–2 and involving shear strains between 10^–1 and 10^–4. Results are presented which demonstrate that the technique does not invoke the excessive structural disruption of material associated with applied shear rate based methods (direct and otherwise) and the widely encountered problem of wall slip at the surface of rotational measuring devices is avoided using miniature vane geometries. Results are compared with those obtained using smooth-walled cyclindrical measuring devices in both applied stress and applied shear rate instruments.Yield measurements are considered in relation to the structural properties of the undisturbed material state and shear moduli obtained by studying the propagation of small amplitude (10^–5 rad), high frequency (~ 300 Hz) torsional shear waves through the test materials are reported. Experimental techniques and instrument modifications to permit these measurements are described.     

Comportement rhéologique de sols d'acide polysilicique.

Résumé Le comportement rhéologique de sols d'acide silicique a été examiné au cours du temps à des pH compris entre 6 et 8 à la concentration de 10 g 1^–1 de silice, et à pH = 8 à des concentrations variant entre 0,5 et 10 g 1^–1. Les courbes d'écoulement révélent un comportement rhéologique complexe. L'analyse des rhéogrammes en fonction du temps, du pH et de la concentration contribue à la connaissance de l'état structural du polymère au cours de la formation du gel. Il ressort que le comportement initialement rhéoépaississant aux faibles concentrations correspondant à l'état d'une solution colloïdale, laisse place à un écoulement rhéofluidifiant dans les conditions favorables á la polymérisation de l'acide silicique. La transition sol-gel est marquée par un breakpoint; en prolongeant les mesures on observe un comportement plastique dû à l'apparition d'agrégats sous l'effet du cisaillement. Tous les processus rhéologiques se trouvent exacerbées à pH = 8.

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The rheological behaviour of silicic acid in aqueous solutions was studied over a period of time for pH values between 6 and 8 at the concentration 10 g 1^–1, and at pH = 8 for different concentrations varying from 0.5 to 10 g 1^–1. The shear stress-shear rate curves indicate a very complex character of rheological behaviour. Its analysis with respect to the influence of time, pH and concentration contributes to the knowledge of the structure of the polymer during the process of gel formation. It is shown that the inital shear-thickening behaviour of the colloïdal sol at low concentrations is followed by a shear-thinning behaviour under conditions of polymerization of the silicic acid. The sol-gel transition is marked by a breakpoint. When measurements pass beyond this point, plastic flow behaviour is observed because of the shear induced formation of amorphous silicic aggregates. All rheological processes of silicic acid sols are intensified at pH = 8.

     

Rheological properties of service weathered road bitumens

A study was carried out of the rheological properties of service weathered bitumens and their properties were compared with road performance. Bitumen from 39 test sites was recovered from the uppermost layer of stone particles covering the road surfacing and tested under dynamic and transient loading. Dynamic testing was carried out under forced sinusoidal loading. Testing under transient loading was mainly with a viscosity test conducted at 45°C, but some creep testing in compression was conducted at 0°C. From the results of dynamic testing, master curves of modulus and loss angle were constructed, spanning over ten decades in loading frequency. The hyperbolic expressions of Dickinson and Witt successfully described the frequency dependence of bitumen modulus and loss angle. The Williams, Landel and Ferry (WLF) equation, with newly derived coefficients, described the temperature dependence of the shift factor (or Newtonian viscosity) for the temperature range –10 to 60°C. Attempts were made to compare the measured transient response with that calculated from dynamic results. The result of the viscosity test conducted at 45°C as an indicator of modulus at low temperatures was assessed. Surfacing distress increased as the bitumen viscosity or modulus increased, however service performance of the bitumens was best correlated with the modulus calculated at conditions representative of traffic stressing and lowest site temperature. The changes in the rheological properties of bitumens induced by weathering is discussed.     

Drilling fluid shear stress overshoot behavior

Shear stress overshoot behavior was studied in four drilling fluid systems and ten bentonite dispersions. These overshoot properties, also described by the American Petroleum Institute as gel strengths, were measured after gelation times of 10 s to 24 h at temperatures of 20–80 °C. Two different rheometers were used to measure overshoot behavior. Gel strength development with time followed a first-order model. Gel development rates at 20 °C varied from 0.005 to 0.01 min^–1 for drilling fluid systems and from 0.0004 to 0.02 min^–1 for bentonite dispersions. Increasing the gelation temperature for each drilling fluid system caused an increase in the gelling rate constant. Comparison of gel strengths in bentonite dispersions were made using a Fann 35 A viscometer and a Weissenberg Rheogoniometer. Higher gel strength values observed using the Rheogoniometer were believed to be due to differences in instrument spring stiffness and fixture inertia.     

Slit die viscometry at shear rates up to 5 × 106s−1: An analytical correction for small viscous heating errors

If the viscosity can be expressed in the form = (T)f(), the walls are at a constant temperatureT ₀, and the extra stress, velocity and temperature fields are fully developed, then the wall shear rate can be calculated by applying the Weissenberg-Rabinowitsch operator toF _c Q instead of to the flow rateQ, whereF _c is a correction factor which differs from 1 when the temperature field is non-uniform; the isothermal equation relating the wall shear stress and pressure gradient is still valid. For the case in whcih = ₀|| ⁿ /(1 +(T–T ₀)), wheren, ₀, and are independent of shear stress and temperatureT, an exact analytical expression forF _c in terms of the Nahme-Griffith numberNa andn is obtained. Use of this expression gives agreement with data obtained for degassed decalin ( = 2.5 mPa s) from a new miniature slit-die viscometer at shear rates up to 5 × 10⁶s^–1; here, the correction is only 7%,Na is 1.3, andGz, the Graetz number at the die exit, is 119. For a Cannon standard liquidS6 ( = 9 mPa s), agreement extends up to 5 × 10⁵s^–1; at 2×10⁶s^–1 (whereNa = 7.2 andGz = 231), the corrections are 11% (measured) and 36% (calculated).Notation x, y Cartesian coordinates - v _x ,v velocity inx-direction, dimensionless velocity - p _xx ,p _yy normal stress onx- andy-planes - N ₁ first normal stress difference - shear stress ony-planes acting inx-direction - _w value of shear stress at the wall - shear rate, shear rate at the wall - Q, Q flow rate (Eqs. (2.13), (2.15)) - T, T ₀ temperature, temperature at the wall - ø, dimensionless temperature (Eqs. (2.24), (2.25)) - h, w half of die height, width of die - R diameter of a tube - , ₀ viscosity, viscosity atT = T ₀ - viscosity-temperature coefficient - k thermal conductivity - c _p specific heat at constant pressure - n, m dimensionless parameters characterizing shear stress dependence of viscosity - Na Nahme Griffith number (Eq. (2.21)) - Gz Graetz number (Eq. (5.1)) - F _c viscous heating correction factor (Eq. (2.18)) - ( ) a function characterizing temperature dependence of viscosity (Eq. (2.8)) - J _k ( ) Bessel function of the first kind This paper is dedicated to Professor Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

Comportement rheologique de sols d'acide polysilicique. II. Etude de la gélification

Résumé L'analyse du comportement rhéologique de sols d'acide polysilicique en solution aqueuse de concentration supérieure à 7 g 1^–1 de silice en fonction du pH entre 6 et 11 et de la température entre 25 et 45 °C a permis de situer la gélification dans un domaine de pH compris entre 8 et 10. Ce processus prend une intensité maximale à 30°C. Le comportement rhéofluidifiant à bas gradients de cisaillement et antithixotrope donne naissance sur les rhéogrammes à un point d'inversion à pH = 9. L'ionisation des groupes silanols à la surface des particules colloïdales permet la réorganisation du milieu après cisaillement. Un état d'ionisation trop élevé est responsable d'un effet electro-répulsif à pH = 10. L'influence de la concentration et de la température sur ces processus est discutée.

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The rheological behavior of polysilicic acid in aqueous solutions at higher concentrations than 7 g 1^–1 of silice is studied for pH between 6 and 11 with temperature varying from 25° to 45°C. This study indicates that gelification takes place between pH 8 and 10. The process of gel formation attains the highest intensity at 30°C. The shear-thinning behavior at low shear rate gives rise to an inversion point at pH = 9 in shear stress—shear rate curves. The state of ionization at the surface of colloïdal silice particles after shear involve shear thickening observed at pH = 9. A high ionization degree causes an electrostatic repulsion at pH = 10. The concentration and temperature effects upon the organization of network are discussed.

     

Measurement of the first normal-stress difference at high shear rates for a polyisobutylene/decalin solution “D2”

Reasonable agreement is found between values of the first normal-stress differenceN ₁ for samples of D2, a polyisobutylene/decalin solution, measured in steady shear flow using three different instruments: a Weissenberg Rheogoniometer (a cone-plate rotational rheometer), a Torsional Balance (plate-plate rotational) Rheometer, and a Stressmeter (a transverse-slot slit-die rheometer). Viscosity values are also in reasonable agreement. Ranges of variables common to at least two rheometers include values of shear stress up to 3,700 Pa and shear rate up to 20,700 s^–1 near 25 °C. The agreement supports the approximate validity of the semi-empirical HPBL equation used to calculateN ₁ from Stressmeter data over a range of shear rates up to 20,700 s^–1 near 25 °C. Time-temperature superposition behavior exhibited by Stressmeter data at temperatures in the range 21 °C to 111 °C suggest that the range of validity of the Stressmeter method for determiningN ₁ approximately may extend up to shear rates of 290,000 s^–1 at 111 °C.     

On some nearly viscometric flows of viscoelastic liquids

Superposition of oscillatory shear imposed from the boundary and through pressure gradient oscillations and simple shear is investigated. The integral fluid with fading memory shows flow enhancement effects due to the nonlinear structure. Closed-form expressions for the change in the mass transport rate are given at the lowest significant order in the perturbation algorithm. The elasticity of the liquid plays as important a role in determining the enhancement as does the shear dependent viscosity. Coupling of shear thinning and elasticity may produce sharp increases in the flow rate. The interaction of oscillatory shear components may generate a steady flow, either longitudinal or orthogonal, resulting in increases in flow rates akin to resonance, and due to frequency cancellation, even in the absence of a mean gradient. An algorithm to determine the constitutive functions of the integral fluid of order three is outlined.Nomenclature A _n Rivlin-Ericksen tensor of order . - A _k Non-oscillatory component of the first order linear viscoelastic oscillatory velocity field induced by the kth wave in the pressure gradient - d Half the gap between the plates - e _x, e _z Unit vectors in the longitudinal and orthogonal directions, respectively - G(s) Relaxation modulus - G History of the deformation - Stress response functional - I() Enhancement defined as the ratio of the frequency dependent part of the discharge to the frequencyindependent part of it at the third order - I ^*() Enhancement defined as the ratio of the increase in discharge due to oscillations to the total discharge without the oscillations - k Power index in the relaxation modulus G(s) - k _i ^–1 Relaxation times in the Maxwell representation of the quadratic shear relaxation modulus (s ₁, s ₂) - m _i ^–1, n _i ^–1 Relaxation times in the Maxwell representations of the constitutive functions ₁(s ₁,s ₂,s ₃) and ₄ (s ₁, s ₂,s ₃), respectively - P Constant longitudinal pressure gradient - p Pressure field - _mx ,⁽³⁾ _nz ,⁽³⁾ Mean volume transport rates at the third order in the longitudinal and orthogonal directions, respectively - ₀,⁽³⁾, ₁,⁽³⁾ Frequency independent and dependent volume transport rates, respectively, at the third order - s = t- Difference between present and past times t and