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.     

Miniaturized Compression Test at Very High Strain Rates by Direct Impact

A modified miniaturized version of the Direct Impact Compression Test (DICT) technique is described in this paper. The method permits determination of the rate-sensitive plastic properties of materials up to strain rate ∼10⁵ s⁻¹. Miniaturization of the experimental setup with specimen dimensions: diameter d _S = 2.0 mm and thickness l _S = 1.0 mm, Hopkinson bar diameter 5.2 mm, with application of a novel optical arrangement in measurement of specimen strain, makes possible compression tests at strain rates from ∼10³ s⁻¹ to ∼10⁵ s⁻¹. In order to estimate the rate sensitivity of a low-alloy construction steel, quasi-static, Split Hopkinson Pressure Bar (SHPB) and DICT tests have been performed at room temperature within the rate spectrum ranging from 5*10⁻⁴ s⁻¹ to 5*10⁴ s⁻¹. Adiabatic heating and friction effects are analyzed and the final true stress versus true strain curves at different strain rates are corrected to a constant temperature and zero friction. The results have been analyzed in the form of true stress versus the logarithm of strain rate and they show two regions of a constant rate sensitivity : relatively low up to the strain rate threshold ∼50 s⁻¹, and relatively high above the threshold, up to strain rate ∼4.5*10⁴ s⁻¹.     

An experimental study of dynamic tensile properties of glass fiber at low-temperatures

Tensile impact experiments of EC8.0−24×7 glass fiber bundles at different low temperaturesT(14°C, −40°C and −10°C) and strain rates ɛ were carried out, and complete stress-strain curves were obtained. Within the range of the experiment temperatures and strain rates, it is found that the initial modulusE, the ultimate strength σ_max and the unstable strain ɛ _b of the glass fiber bundles all increase with ɛ at an identicalT. At an identical ɛ, with the decrease ofT, E and σ_max increase; but ɛ _b increases when 10°C>T>−40°C and decreases when −40°C>T>−100°C. The strain-rate- and temperature-dependent bimodal Weibull statistical constitutive theory was adopted for the statistical analysis of the experimental results, and the Weibull parameters of single fiber were obtained. The results show that the bimodal Weibull distribution function is suitable to represent the strength distribution of the glass fiber at low temperature and different strain rates. The differences in the mechanical properties between EC8.0−24×7 and EC5.5−12 ×14 glass fiber bundles were also discussed. Project supported by the National Natural Science Foundation of China (No. 19772058).     

Supersonic leeside flow topology on delta wings revisited

The leeside vortex structures on delta wings with sharp leading edges were studied for supersonic flow at the Institute of Theoretical and Applied Mechanics of the Russian Academy of Sciences in Novosibirsk. The experiments were carried out with three wings with sweep angles of χ=68°, 73°, and 78° and parabolic profiles in the 0.6 × 0.6 m² test section of the blow-down wind tunnel T-313 of the institute. The test conditions were varied from Mach numbers M=2 to 4, unit Reynolds numbers from Re _l=26 × 10⁶ to 56 × 10⁶ m⁻¹, and angles of attack from α=0° to 22°. The results of the investigations revealed that for certain flow conditions shocks are formed above, below, and between the primary vortices. The experimental data were accurate enough to detect the onset of secondary and tertiary separation as well as other boundaries. The various flow regimes discussed in the literature were extended in several cases. The major findings are reported. Received: 6 September 1999/Accepted: 24 January 2000     

Unsaturated Transport with Linear Kinetic Sorption Under Unsteady Vertical Flow

We consider transport of a solute obeying linear kinetic sorption under unsteady flow conditions. The study relies on the vertical unsaturated flow model developed by Indelman et al. [J. Contam. Hydrol. 32 (1998), 77–97] to account for a cycle of infiltration and redistribution. One of the main features of this type of transport, as compared with the case of a continuous water infiltration, is the finite depth of solute penetration. In the infiltration stage an analytical solution that generalizes the previous results of Lassey [Water Resour. Res. 24 (1988), 343–350] and Severino and Indelman [J. Contam. Hydrol. 70 (2004), 89–115] is derived. This solution accounts for quite general initial solute distributions in both the mobile and immobile concentration. When the redistribution is also considered, two timescales become relevant, namely: (i) the desorption rate k⁻¹, and (ii) the water application time t_ap. In particular, we have assumed that the quantity ε =(k t_ap)⁻¹ can be regarded as a small parameter so that a perturbation analytical solution is obtained. At field-scale the concentration is calculated by means of the column model of Dagan and Bresler [Soil Sci. Soc. Am. J. 43 (1979), 461–467], i.e. as ensemble average over an infinite series of randomly distributed and uncorrelated soil columns. It is shown that the heterogeneity of hydraulic properties produces an additional spreading of the plume. An unusual phenomenon of plume contraction is observed at long times of solute propagation during the drying period. The mean solute penetration depth is studied with special emphasis on the impact of the variability of the saturated conductivity upon attaining the maximum solute penetration depth.     

Precursor vacuum-ultraviolet radiation ahead of strong shock waves in a shock tube

The profile and excitation mechanism of vacuum-ultraviolet radiation emitted from shock wave is investigated in a shock tube. For shock wave in argon, the rdiation is due to resonant transition excited by argon-argon collision in the shock front with excitation cross section coefficientS ^*=1.0×10⁻¹⁷ cm²·ev⁻¹ and activation energyE ^*=11.4 ev. For shock wave in air the radition is emitted from a very thin shock layer in which the mechanism ofX ¹∑→b ¹∑ of N₂ is excited with excitation cross sectionQ=2×10⁻¹⁶cm² and activation energyE ^*=12.1 ev. Institute of Mechanics, Academia Sinica     

Characterization of the flow properties of sodium carboxymethylcellulose via mechanical and optical techniques

Sodium carboxymethylcellulose (NaCMC) in solution represents a complex rheological system, since it forms aggregates and associations and hence higher-level structures and, depending on the synthesis, is only found in a molecularly dispersed form in exceptional cases. Rheo-mechanical investigations of the viscoelasticity showed that the Cox-Merz rule is not fulfilled. The aim was therefore to examine whether rheo-optics could be employed to provide more detailed conclusions about the parameters that influence the flow behavior of NaCMC than has hitherto been available with mechanical methods. The flow birefringence, Δn ^′, rises as the degree of polymerization increases, and exhibits the same dependence on molar mass as does the viscosity: Δn ^′∝M _w ^3.4. As the degree of polymerization increases while the shear rate remains constant, the polymer segments become more distinctly aligned in the direction of shear. Hence increasing the degree of polymerization also affects the solution structure, i.e. the interaction of the molecules with one another. The stress-optical rule only applies to a limited extent for this system. The stress-optical coefficient, C, is almost independent of the shear rate, but is strongly influenced by the concentration and attains a limiting value of 3 × 10⁻⁸ Pa⁻¹. C was determined for a polymer in dilute solution and the curve obtained also enabled transitions in the solution structure to be recognized. Received: 1 May 1998 Accepted: 5 October 1998     

Rheology of SiO2/(acrylic polymer/epoxy) suspensions. I. Linear viscoelasticity

Linear viscoelastic properties of SiO₂/(AP/EP) suspension with various SiO₂ volume fractions (ϕ) in a blend of acrylic polymer (AP) and epoxy (EP) were investigated at various temperatures (T). The AP/EP contained 70 vol.% of EP. The SiO₂ particles were treated with epoxy silane coupling agent. The effects of the SiO₂ particles are more pronounced in the terminal zone: a transition from viscoelastic liquid (ϕ ≤ 30 vol.%) to viscoelastic solid (ϕ ≥ 40 vol.%) was observed which can be interpreted as a critical gelation occurring at a critical particle content and critical gel temperature. The SiO₂/(AP/EP) systems exhibited a critical gel behavior at ϕ ≅ 35 vol.% and T ≅ 100°C characterized with a power–law relationship between the storage and loss moduli (G ^′ and G ^″) and frequency (ω); G ^′ = G ^″/tan(nπ/2) ∝ ω ⁿ . The critical gel exponent (n) was estimated to be about 0.45. The gelation occurred with increasing T.     

Squeeze flow between plane and spherical surfaces

Experiments are described in which a constant force F squeezed a fluid, either between two parallel circular plates, or between a plate and convex spherical lens. Newtonian fluids obeyed the relation of Stefan (1874) for plates, and the relation of Adams et al. (1994) for plate and lens. The non-Newtonian yield stress fluids Brylcreem, Laponite and Sephadex were squeezed between plates of various diameter D to attain a stationary separation h. Only for separations greater than h ^* (which depended on the fluid) did Brylcreem and Laponite obey the relation F/D ³ ∝ h ⁻¹ of Scott (1931) and give a yield stress in agreement with the vane method. For Sephadex the dependence of F/D ³ on h disagreed with Scott's relation, but varied as h ^−5/2 for h > 0.6 mm and h ^−3/2 for h < 0.6 mm. On rotating one plate in its plane the yield stress fluids at a fixed F suffered a marked decrease of h. This, and the existence of h ^*, are discussed in terms of the soft glassy material model of Sollich et al. (1997) and Sollich (1998). Brylcreem and Laponite were squeezed between a plate and lenses of various curvature and their yield stress obtained using the relation of Adams et al. (1994) was compared with measurements by plate-plate squeeze-flow and vane methods. Received: 12 April 2000 Accepted: 26 October 2000     

Linear viscoelastic behavior of perfluorooctyl sulfonate micelles: effects of counter-ions

Linear viscoelastic behavior was investigated for aqueous solutions of perfluorooctyl sulfonate (C₈F₁₇SO⁻ ₃; abbreviated as FOS) micelles having a mixture of tetraethylammonium (N⁺(C₂H₅)₄; TEA) and lithium (Li⁺) ions as the counter-ions. The solutions had the same FOS concentration (0.1 mol l⁻¹) and various Li⁺ fractions in the counter-ions, φ_Li = 0−0.6, and the FOS micelles in these solutions formed threads which further organized into dendritic networks. At T ≤ 15 °C, the terminal relaxation time τ and the viscosity η, governed by thermal scission of the networks, increased with increasing φ_Li up to 0.55. A further increase of φ_Li resulted in decreases of τ and η and in broadening of the relaxation mode distribution. These rheological changes are discussed in relation to the role of TEA ions in thermal scission: Previous NMR studies revealed that only a fraction of TEA ions were tightly bound to the FOS micellar surfaces and these bound ions stabilized the thread/network structures. The concentration of non-bound TEA ions, C_TEA ^*, decreased and finally vanished on increasing φ_Li up to φ_Li ^* ≅ 0.6, and the concentration of the bound TEA ions significantly decreased on a further increase of φ_Li. The non-bound TEA ions appeared to catalyze the thermal scission of the FOS threads, and the observed increases of τ and η for φ_Li < 0.55 were attributed to the decrease of C_TEA ^*. On the other hand, the decreases of τ and η as well as the broadening of the mode distribution, found for φ_Li > 0.55 (where C_TEA ^* ≅ 0), were related to destabilization of the FOS threads/networks due to a shortage of the bound TEA ions and to the existence of concentrated Li⁺ ions. Viscoelastic data of pure FOSTEA and FOSTEA/FOSLi/TEACl solutions lent support to these arguments for the role of TEA ions in the relaxation of FOSTEA/FOSLi solutions. Received: 12 October 1999/Accepted: 1 November 1999     

Experiments on the lift of a spinning sphere in a range of intermediate Reynolds numbers

 The lift force experienced by a spinning sphere moving in a viscous fluid, with constant linear and angular velocities, is measured by means of a trajectographic technique. Measurements are performed in the range of dimensionless angular velocities γ=aω/V lying between 1 and 6, and in the range of Reynolds numbers Re=2aV/ν lying between 10 and 140 (a sphere radius, ω angular velocity, V relative velocity of the sphere centre, ν fluid kinematic viscosity). A notable departure from the theoretical relationship at low Reynolds number, C _L =2γ, is obtained, the ratio C _L /γ being found to significantly decrease with increasing γ and increasing Re. The following correlation is finally proposed to estimate the lift coefficient in the range 10<Re<140: C _L ≅0.45+(2γ−0.45) exp (−0.075γ^0.4 Re ^0.7) Received: 20 May 1996/Accepted: 9 November 1997     

Bentonite slurries—zeta potential,yield stress,adsorbed additive and time-dependent behaviour

Bentonite clay is a vital ingredient of drilling mud. The time-dependent and high shear thinning yield stress behaviour of drilling mud is essential for maintaining wellbore stability and to remove cuttings, cool and clean the drill bit of debris. As-prepared 3, 5 and 7 wt.% bentonite clay slurries displayed time-dependent behaviour where the yield stress (measured after quick stirring) decreased with time of rest. An equilibrium value is reached after 24 h. Despite the low solids concentration, the yield stress is already relatively high and is displayed at all pH level. The yield stress is maximum at pH 2 and minimum at pH ∼ 7. This yield stress is due to the formation of gel structure by the swelling clay particles. However the addition of phosphate additives such as (PO₃)^19 −, (P₃O₁₀)^5 − and (P₂O₇)^4 − completely dispersed the clay slurries at pH above 6. At pH below 6, yield stress is still present but is 3-folds smaller than that of the pure bentonite slurry. With phosphate additives, the magnitude of the critical zeta potential at the complete dispersion pH is ca 48 mV. However for the pure bentonite, the slurry remained flocculated at zeta potential of >50 mV in magnitude. Interestingly, (P₂O₇)^4 − anions is more effective than the other two phosphate additives in reducing the yield stress at low pH, ∼ 2.0.     

Laminarisation and re-transition of a turbulent boundary layer subjected to favourable pressure gradient

 Experimental results are reported for the response of an initially turbulent boundary layer (Re _θ≈1700) to a favourable pressure gradient with a peak value of K≡(−υ/ρU ³ _E ) dp/dx equal to 4.4×10^-6. In the near-wall region of the boundary layer (y/δ<0.1) the turbulence intensity u′ scales roughly with the free-stream velocity U _E until close to the location where K is a maximum whereas in the outer region u′ remains essentially frozen. Once the pressure gradient is relaxed, the turbulence level increases throughout the boundary layer until K falls to zero when the near wall u′ levels show a significant decrease. The intermittency γ is the clearest indicator of a fundamental change in the turbulence structure: once K exceeds 3×10^-6, the value of γ in the immediate vicinity of the wall γ _s falls rapidly from unity, reaches zero at the location where K again falls below 3×10^-6 and then rises back to unity. Although γ is practically zero throughout the boundary layer in the vicinity of γ _s =0, the turbulence level remains high. The explanation for what appears to be a contradiction is that the turbulent frequencies are too low to induce turbulent mixing. The mean velocity profile changes shape abruptly where K exceeds 3×10^-6. Values for the skin friction coefficient, based upon hot-film measurements, peak at the same location as K and fall to a minimum close to the location where K drops back to zero. Received: 28 January 1998/Accepted: 8 April 1998     

Squeezing flow of semi liquid foods between parallel Teflon coated plates

Samples of commercial tomato paste, low fat mayonnaise and mustard about 6–8 mm thick were squeezed to 0.8 mm at various speeds between 5 mm min⁻¹ and 25 mm min⁻¹ between Teflon-coated parallel plates 127 mm in diameter using an Instron UTM Model 5542. All the log force vs log height relationships had a clearly identified linear region. This indicated that a dominant squeezing flow regime was achieved at about 3 mm height, and that the machine has the proper stiffness to perform the tests. The stress level at a pre-selected height in this region is a measure of consistency, sensitive enough to distinguish between products of different brands. The residual stress after relaxation for about 2 min was on order of 10–50% of the initial stress, an indication that all three foods have a considerable structural integrity. In all three products there was a considerable discrepancy between the observed rate effects and predictions based on a pseudoplastic (power law) model. It could be described by the empirical relation (F_v1 − F_R)/(F_v2 − F_R)=(V₁/V₂)^m where F_v1 and F_v2 are the forces at the given displacement reached at speeds v₁ and v₂ respectively, F_R is the residual force after relaxation (found to be practically rate independent), and m is a constant of the order of 0.15–0.33, independent of the compression velocities ratio but characteristic of the food and brand. The calculated elongational viscosity was not a unique function of biaxial strain rate. To a certain extent, this was probably due to imperfect lubrication. But it was also a manifestation of these products considerable structural integrity which cannot be accounted for by models developed for ideal liquids. Received: 1 November 1999 Accepted: 2 May 2000     

Laminar-turbulent transition in the boundary layer on cones in a hypersonic flow at high Reynolds numbers per meter

The laminar-turbulent transition is experimentally studied in boundary-layer flows on cones with a rectangular axisymmetric step in the base part of the cone and without the step. The experiments are performed in an A-1 two-step piston-driven gas-dynamic facility with adiabatic compression of the working gas with Mach numbers at the nozzle exit M _∞ = 12–14 and pressures in the settling chamber P₀ = 60–600 MPa. These values of parameters allow obtaining Reynolds numbers per meter near the cone surface equal to Re _1e = (53–200) · 10⁶ m ⁻¹. The transition occurs at Reynolds numbers Re _tr = (2.3–5.7) · 10⁶. __________ Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 48, No. 3, pp. 76–83, May–June, 2007.     

A comparison of extensional viscosity measurements from various RME rheometers

The transient uniaxial extensional viscosity η _e of linear low density polyethylene (LLDPE) has been measured using the commercial Rheometric Scientific RME and the Münstedt Tensile Rheometer in an effort to compare the performance of available extensional rheometers. The RME indicated a significant strain hardening of the LLDPE, especially at a strain rate of 1 s⁻¹. In contrast, the Münstedt rheometer showed the LLDPE to be only slightly strain hardening. This artificial strain hardening effect in the RME resulted from the strain rate applied to the sample, determined from the sample deformation, being up to 20% less than the set strain rate. These results initiated a round-robin experiment in which the same LLDPE was tested on several RMEs in various locations around the world. All but one of the RMEs indicated a deviation between set and applied strain rates of at least 10%, especially at strain rates above 0.1 s⁻¹. The strain rate deviation was found to depend strongly on the value of the basis length L ₀ , and may result from the upper pair of belts not properly gripping the sample during extension. Thus visual inspection of the sample deformation is necessary to determine the applied strain rate. The most accurate measurements of η _e with respect to the strain rate deviation were obtained when the correct L ₀ value and belt arrangement were used. A list of recommendations for running an RME test is provided. Future work focusing on the fluid mechanics during the test may identify fully the cause of the strain rate deviation, but from a practical point of view the problem can be corrected for in the determination of η _e . Received: 27 September 2000/Accepted: 5 February 2001     

Single bubble deformation and breakup in simple shear flow

Experiments in a parallel band apparatus and a transparent concentric cylinder device allow the observation of bubble deformation (shape and orientation) and breakup as a function of the viscosity ratio λ and the Capillary number Ca. For viscosity ratios between 3.1 × 10⁻⁷ and 6.7 × 10⁻⁸, critical Capillary numbers Ca _c for bubble breakup between 29 and 45 are found. It is furthermore shown that in the given parameter space no clear distinction between tip breakup and fracture can be made for bubbles. An erratum to this article can be found at     

Radial filtration during constant-force squeeze flow of soft solids

Various soft solid suspensions were squeezed at constant force between polished and roughened circular glass plates and the time-dependence of the interplate separation was measured. The filterability of suspensions was quantified by their desorptivity S obtained from measurements of capillary suction time. The squeeze flow (SF) of suspensions for which S < 2 μm s^−1/2 was largely consistent with rheological theory, which neglected radial filtration: the relative motion between the liquid and solid phases of the suspension in the radial pressure gradient. Suspensions having S > 2 μm s^−1/2 showed SF behavior that was consistent with the presence of radial filtration.     

Strain energy function of an uncross-linked butadiene rubber estimated from planar extension

The derivatives of the strain energy function u with respect to the invariants of the strain tensor (I₁ and I₂) are estimated for uncross-linked butadiene rubber by using the BKZ constitutive equation. The derivatives at small deformations show anomalous behavior; namely, an upturn for ∂u/∂I₁ and a downturn for ∂u/∂I₂ take place, as is the case of cross-linked rubbers. At large deformations, u is well described by u = A₁(I₁ −3) + A₂(I₂ −3) with numerical constants A₁ and A₂. This behavior is also quite similar to that for cross-linked rubbers. The non-zero positive constant A₂ for the melt suggests that the non-zero value is due to neither the inhomogeneity in network structure nor high extension of constituent polymer chains.     

Three-dimensional Turbulent Boundary Layer in a Shrouded Rotating System

A thre-dimensional direct numerical simulation is combined with a laboratory study to describe the turbulent flow in an enclosed annular rotor-stator cavity characterized by a large aspect ratio G = (b − a)/h = 18.32 and a small radius ratio a/b = 0.152, where a and b are the inner and outer radii of the rotating disk and h is the interdisk spacing. The rotation rate Ω considered is equivalent to the rotational Reynolds number Re = Ωb ²/ν= 9 .5 × 10⁴ (ν the kinematic viscosity of water). This corresponds to a value at which experiment has revealed that the stator boundary layer is turbulent, whereas the rotor boundary layer is still laminar. Comparisons of the computed solution with velocity measurements have given good agreement for the mean and turbulent fields. The results enhance evidence of weak turbulence by comparing the turbulence properties with available data in the literature (Lygren and Andersson, J Fluid Mech 426:297–326, 2001). An approximately self-similar boundary layer behavior is observed along the stator. The wall-normal variations of the structural parameter and of characteristic angles confirm that this boundary layer is three-dimensional. A quadrant analysis (Kang et al., Phys Fluids 10:2315–2322, 1998) of conditionally averaged velocities shows that the asymmetries obtained are dominated by Reynolds stress-producing events in the stator boundary layer. Moreover, Case 1 vortices (with a positive wall induced velocity) are found to be the major source of generation of special strong events, in agreement with the conclusions of Lygren and Andersson (J Fluid Mech 426:297–326, 2001).