The third-normal stress difference in entangled melts: Quantitative stress-optical measurements in oscillatory shear

Stress-optical measurements are used to quantitatively determine the third-normal stress difference (N ₃ = N ₁ + N ₂) in three entangled polymer melts during small amplitude (<15%) oscillatory shear over a wide dynamic range. The results are presented in terms of the three material functions that describe N ₃ in oscillatory shear: the real and imaginary parts of its complex amplitude ₃ ^* = ₃ - i ₃ , and its displacement ₃ ^d . The results confirm that these functions are related to the dynamic modulus by ² ₃ ^* ()=(1-)[G ^*())– G ^*(2)] and ² ₃ ^d ()=(1- )G() as predicted by many constitutive equations, where = –N ₂/N ₁. The value of (1-) is found to be 0.69±0.07 for poly(ethylene-propylene) and 0.76±0.07 for polyisoprene. This corresponds to –N ₂/N ₁ = 0.31 and 0.24±0.07, close to the prediction of the reptation model when the independent alignment approximation is used, i.e., –N ₂/N ₁ = 2/7 – 0.28.     

A shear rheometer for measuring shear stress and both normal stress differences in polymer melts simultaneously: the MTR 25

The MTR 25 is a multitask rheometer (for shear and squeeze flow) with 25 kg of normal force and a partitioned plate. Torque and normal force are measured at both, the inner disk and the outer ring of the plate. The first and second normal stress differences can be determined from a single test. The axial stiffness is high (10⁷ N/m) by using rigid springs and strain gauges for the load cell. Monodisperse polystyrene (M _w = 206 kg/mol, 180°C) has been sheared in the range from 0.05 to 47 s^− 1. The viscosity and first normal stress difference are highly reproducible. The second normal stress difference scatters and mirrors the instability at the rim. A critical comparison is made between the MTR 25 method and the single transducer evaluation method (RMS 800 method, Schweizer, Rheol Acta 41:337–344, 2002): Both yield excellent and coinciding viscosity and first normal stress difference data. The RMS 800 method gives more stable second normal stress difference data, since the normal force from the outer ring, which is influenced by edge fracture, is not used. Data for the RMS 800 method can be acquired on the MTR 25. The high normal force capacity permits larger samples and higher shear rates than on the RMS 800.

The determination of the first normal stress coefficient of an exopolysaccharide solution by rheo-optical measurements

This paper illustrates how rheo-optical techniques may be utilized to determine the first normal stress coefficient for an exopolysaccharide (EPS) produced by the Lactobacillus delbrueckii ssp. bulgaricus LY03, which is widely used in yoghurt production. In this technique both shear stress, optical birefringence and extinction angle are measured simultaneously as a function of shear rate. From the stress optical rule the first normal stress difference can be determined directly without relying on any specific rheological model. Of special interest is the point where the first normal stress difference become comparable in magnitude to the shear stress. Here we expect to find a notable influence of the first normal stress difference on mouthfeel.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

The normal stress behaviour of suspensions with viscoelastic matrix fluids

 We investigate the variations in the shear stress and the first and second normal stress differences of suspensions formulated with viscoelastic fluids as the suspending medium. The test materials comprise two different silicone oils for the matrix fluids and glass spheres of two different mean diameters spanning a range of volume fractions between 5 and 25%. In agreement with previous investigations, the shear stress–shear rate functions of the viscoelastic suspensions were found to be of the same form as the viscometric functions of their matrix fluids, but progressively shifted along the shear rate axis to lower shear rates with increasing solid fraction. The normal stress differences in all of the suspensions examined can be conveniently represented as functions of the shear stress in the fluid. When plotted in this form, the first normal stress difference, as measured with a cone and plate rheometer, is positive in magnitude but strongly decreases with increasing solid fraction. The contributions of the first and the second normal stress differences are separated by using normal force measurements with parallel plate fixtures in conjunction with the cone-and-plate observations. In this way it is possible for the first time to quantify successfully the variations in the second normal stress difference of viscoelastic suspensions for solid fractions of up to 25 vol.%. In contrast to measurements of the first normal stress difference, the second normal stress difference is negative with a magnitude that increases with increasing solid content. The changes in the first and second normal stress differences are also strongly correlated to each other: The relative increase in the second normal stress difference is equal to the relative decrease of the first normal stress difference at the same solid fraction. The variations of the first as well as of the second normal stress difference are represented by power law functions of the shear stress with an unique power law exponent that is independent of the solid fraction. The well known edge effects that arise in cone-and-plate as well as parallel-plate rheometry and limit the accessible measuring range in highly viscoelastic materials to low shear rates could be partially suppressed by utilizing a custom- designed guard-ring arrangement. A procedure to correct the guard-ring influence on torque and normal force measurements is also presented. Received: 20 December 2000 Accepted: 7 May 2001     

Use of a sliding plate rheometer to measure the first normal stress difference at high shear rates

The use of a sliding plate rheometer (SPR) to determine the first normal stress difference of molten polymers and elastomers at high shear rates is demonstrated. The simple shear flow in this instrument is not subject to the flow instabilities that limit the use of rotational rheometers to shear rates often below 1 s⁻¹. However, issues of secondary flow and wall slip must be addressed to obtain reliable data using an SPR. A highly entangled, monodisperse polybutadiene and a commercial polystyrene were the polymers studied. The inclusion of the polystyrene made it possible to compare data with those obtained by Lodge using a stressmeter, which is an instrument based on the measurement of the hole pressure. The data from the two instruments are in good agreement and are also close to the predictions of an empirical equation of Laun based on the storage and loss moduli.     

Time dependent flow in equimolar micellar solutions: transient behaviour of the shear stress and first normal stress difference in shear induced structures coupled with flow instabilities

Recently we studied time dependent structural changes that are coupled with flow instabilities (Fischer 1998; Wheeler 1998; Fischer 2000). Within a stability analysis, a classification scheme for the feedback circuit of coupled shear-induced structure and flow instabilities was derived by Schmitt et al. (1995) and applied to our samples. Here, inhomogeneous flow layers of different concentration and viscosity are generated by shear-induced diffusion (spinodal demixing) and, as consequence, one no longer observes a homogeneous solution but a type of shear banding that is seen here for the first time. In this paper we present the behaviour of the first normal stress difference observed in the critical shear-rate regime where transient shear-induced structure is coupled with flow instability. Similar to the oscillations of the shear stresses (strain-controlled rheometer) one observes oscillations in the first normal stress difference. This behaviour indicates that elastic structures are built up and destroyed while the shear-induced structures occur and that the induced phase is more elastic than the initial one. Oscillations of shear stress and first normal stress difference are in phase and indicate that both phenomena are caused by the same mechanism. Received: 30 June 1999/Accepted: 14 December 1999     

Shear and normal stress relaxation in polymer blends: stress predictions from interface velocity and Laplace pressure terms

We derived for the first time the relationships among shear stress and normal stress differences for ellipsoidal interfaces under large step shear strains considering interface velocity term and Laplace pressure term in the expression of the stress tensor for mixtures of two Newtonian fluids. In the derivation, orientation angle of the interface is assumed to be given by the affine deformation assumption and is independent of time based on experimental results for blends with 0.048 ≤ K ≤ 0.54 where K is the ratio of droplet viscosity to matrix viscosity. For ellipsoidal droplets, the shear stress is only proportional to the first normal stress difference. On the other hand, for spheroidal droplets, proportionality among the shear stress, the first and the second normal stress differences was derived, and the ratio of the second normal stress difference to the first normal stress difference was given as a function of step strain. The shear stress and the first normal stress difference obtained experimentally satisfy the derived relationship, indicating applicability of the stress expression for polymer blends.     

正装结构非线性应力应变累加规律研究

基于有限位移理论的正装结构非线性分析理论对解决超大跨度、柔性结构的非线性计算有重大意义.文中探讨了正装结构非线性的分析特点,研究了其应变场与应力场的Kirchhoff应力张量与Lagrange应变张量的适用性,提出了正装结构非线性分析中应力场与应交场的累加规律,导出了拖动坐标法的虚功增量方程,以此对杆系结构非线性分析常用的CR法和UL列式进行了精度比较分析.文中研究成果可为正装结构的非线性分析提供理论指导.     

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对于连续截面直梁平面横力弯曲情形, 分析了剪切变形引起横截面翘曲的影响. 基于位移模式假定, 用材料力学方法得到相应的正应力与切应力表达式, 并以均布力作用的矩形截面简支梁为例说明截面翘曲对于应力的影响. 该分析方法及其结果适用于材料力学教学.     

求解结构动应力的振型函数差分法

本文利用常规有限元方法的计算结果，结合数值计算方法对振型函数进行［Ｌ］算子的微分计算，从而可方便迅速获得到复杂结构动应力响应，并对梁和板进行了计算，计算结果表明该方法具有较高的精度，较一般的动态有限元具有通用性强，计算简单等特点。     

Rheo-optical measurements of the first and third normal stresses of homopolymer poly(vinyl methyl ether) melt

Normal stresses play a key role in polymer processing, yet accurate measurements are still challenging. Simultaneous rheo-optical measurements are conducted on a poly(vinyl methyl ether) homopolymer melt over a wide range of temperatures and oscillatory shear frequencies, in an effort to measure the normal stresses, by using quantitative flow birefringence measurements. The stress optical rule holds well for this polymer as expected, with the value of the stress optic coefficient of (6.38±0.19)×10⁻¹¹ cm²/dyn at 30°C. The first and third normal stress difference coefficients, calculated using a single memory constitutive equation applied to the stress and birefringence data, are in excellent agreement. The ratio of the measured third and first normal stress difference coefficients, (1−β)=0.71±0.05, agrees well with the result of the Doi–Edwards model with independent alignment approximation (β=0.28). The measurement of normal stress difference coefficients with such small deviations proves the robust nature of the improved rheo-optical instrument and its ability to measure complete stress tensor.     

平面应力下薄壁管材连续矫直压弯量力学模型与数值解法

薄壁管材在连续矫直过程中,各矫直辊组的压弯量作为核心工艺参数直接决定了薄壁管材的矫直精度。而目前现场仍沿用经验图表结合人工经验和反复试矫对其进行估定,亟待建立针对性的压弯量数学模型以指导生产。为此从薄壁管材的结构特点和矫直辊系组成出发,构建了针对压弯量计算的简化悬臂结构模型,基于相关假设和弹塑性相关理论,分别确定了平面应力状态下弹性区和弹塑性区管材横截面的弯矩模型,运用虚功原理建立了矫直辊压弯量力学模型,并给出了数值计算方法,完成了程序开发。经有限元动态仿真试验证明了模型的正确性和适用性,通过对典型管材数据的计算绘制了一系列工艺参数曲线,得到管材轴线弯曲半径和压弯量随管材直径、壁厚和屈服极限的变化关系,为现场压弯量的调整提供理论依据。     

Flow birefringence study of sharkskin and stress relaxation in polybutadiene melts

In this paper we report rheo-optical and rheological observations made through a transparent slit die attached to a capillary rheometer. We find that the flow birefringence signal oscillates periodically near the die exit when sharkskin-like extrudate distortion is present. In contrast, steady behavior is observed in the die inland region. Specifically, the flow birefringence varies at the die exit with a period identical to that measured directly from the sharkskin extrudate. We also show that the exit flow instability leading to sharkskin can be observed directly through cross-polarizers in terms of the temporal change of the retardation order. We demonstrate that the same kind of interfacial flow instability can occur at a boundary discontinuity within the die land where the upper portion of a clean die wall meets the lower portion of a polysiloxane-coated die wall. Finally, stress relaxation upon the cessation of the slit die flow of two polybutadiene melts is studied through time-dependent flow birefringence measurements. The stress relaxation is then correlated with sharkskin time scales to describe the role of relaxation in sharkskin ridge formation. Received: 8 February 1999 Accepted: 28 July 1999     

Stress optical measurement of the third normal stress difference in polymer melts under oscillatory shear

Results are reported for the dynamic moduli,G andG, measured mechanically, and the dynamic third normal stress difference, measured optically, of a series bidisperse linear polymer melts under oscillatory shear. Nearly monodisperse hydrogenated polyisoprenes of molecular weights 53000 and 370000 were used to prepare blends with a volume fraction of long polymer, _L, of 0.10, 0.20, 0.30, 0.50, and 0.75. The results demonstrate the applicability of birefringence measurements to solve the longstanding problem of measuring the third normal stress difference in oscillatory flow. The relationship between the third normal stress difference and the shear stress observed for these entangled polymer melts is in agreement with a widely predicted constitutive relationship: the relationship between the first normal stress difference and the shear stress is that of a simple fluid, and the second normal stress difference is proportional to the first. These results demonstrate the potential use of 1,3-birefringence to measure the third normal stress difference in oscillatory flow. Further, the general constitutive equation supported by the present results may be used to determine the dynamic moduli from the measured third normal stress difference in small amplitude oscillatory shear. Directions for future research, including the use of birefringence measurements to determineN ₂/N ₁ in oscillatory shear, are described.     

Secondary flows in pipes of square cross-section and the measurement of the second normal stress difference

In this paper, we are concerned with the possibility of determining the second normal stress difference v₂ for elastic liquids from a study of the direction and strength of the secondary flows in pipes of non-circular cross-section.Experimental results show that the direction of the secondary flows in pipes of square cross-section is the same for six different elastico-viscous systems, although there is some evidence to suggest that the sign of v₂ may not be the same for all the test liquids. The situation is clarified by a theoretical analysis which involves the numerical solution of coupled partial differential equations. From the analysis, it is concluded unequivocally that the direction of the streamlines is no indication of the sign of v₂.     

Thickness dependence of viscoelastic stress relaxation of laminated microbeams due to mismatch strain

Time-dependent behaviors due to various mismatch strains are very important to the reliability of micro-/nano-devices. This paper aims at presenting an analytical model to study the viscoelastic stress relaxation of the laminated microbeam caused by mismatch strain. Firstly, Zhang’s two-variable method is used to establish a mechanical model for predicting the quasi-static stress relaxation of the laminated microbeam. Secondly, the related analytical solutions are obtained by combining the diffe...     

On the measurement of normal stress differences in steady shear flow

Summary Compared to the similar pressure-distribution cone-and-plate apparatus of Adams and Lodge (4), the new apparatus' improvements include: temperature control of the cone (as well as the plate); increased stiffening of the frame; four (not three) pressuremeasuring holes in the cone/plate region; inclusion of a pressure-measuring hole on the axis under the cone truncation; exclusive use of a vertical free liquid boundary at the cone rim (without a sea of liquid). Temperature control of the rotating cone and of the fixed plate leads to acceptable temperature uniformity in the test liquid for working temperatures within 10°C or 20°C of ambient; the corresponding interval is about 1°C if the cone temperature control is abandoned. Pressure gradients measured using a Newtonian liquid agree with those calculated using Walters' eq. (3). For a viscoelastic liquid, after subtracting inertial contributions, pressure distributions measured at a given shear rate in the cone/plate region do not change when the gap angle is changed from 2° to 3°, showing that the effects of secondary flow are negligible. Values ofN ₃ =N ₁ + 2N ₂ obtained from the gradients of these distributions are believed to be in error by not more than ±1 Pa, in favorable cases. The present most useful ranges are: 10 to 5000 Pa forN ₃; 0.1 to 200 sec^–1 for shear rate; up to 5 Pa s for viscosity; and 5 to 40°C for temperature. As an application, it is shown that adding 0.1% of a high molecular weight polyisobutylene to a 2% polyisobutylene solution doublesN ₃ and has no detectable effect on the viscosity measured at low shear rates with a Ferranti-Shirley viscometer.

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Zusammenfassung Im Vergleich zu dem ähnlichen Kegel-Platte-Gerät von Adams und Lodge (4) zur Messung der Druckverteilung wurden an dem neuen Gerät die folgenden Verbesserungen vorgenommen: Temperaturregelung an Kegel und Platte, Versteifung des Rahmens, vier (anstatt drei) Druckmeßlöcher im Kegel-Platte-Bereich, ein zusätzliches Druckmeßloch auf der Achse unter der Kegelstumpf-Deckfläche, ausschließliche Verwendung einer vertikalen freien Grenzfläche der Flüssigkeit am Kegelrand (ohne umgebenden Flüssigkeitssee). Die Temperaturregelung des rotierenden Kegels und der festen Platte führt zu einer ausreichenden Temperaturgleichförmigkeit in der Testflüssigkeit für Betriebstemperaturen, die höchstens um 10–20°C von der Umgebungstemperatur abweichen. Dieses Intervall beträgt dagegen nur etwa 1°C, wenn auf die Temperaturregelung am Kegel verzichtet wird. Für newtonsche Flüssigkeiten entsprechen die gemessenen Druckgradienten den mittels der Gleichung von Walters (3) berechneten. Für viskoelastische Flüssigkeiten zeigen sich bei der Änderung des Spaltwinkels von 2° auf 3° nach Abzug der Trägheitsbeiträge keine Änderungen der bei einer bestimmten Schergeschwindigkeit gemessenen Druckverteilung. Dies zeigt, daß Sekundärströmungseffekte vernachlässigbar sind. Es darf angenommen werden, daß die Werte vonN ₃ =N ₁ + 2N ₂, die man aus den Gradienten dieser Verteilungen erhält, unter günstigen Umständen mit einem Fehler von nicht mehr als ±1 Pa behaftet sind. Gegenwärtig liegen die günstigsten Bereiche bei 10 bis 5000 Pa fürN ₃, 0,1 bis 200 s^–1 für die Schergeschwindigkeit, unterhalb von 5 Pa s für die Viskosität und 5 bis 40°C für die Temperatur. Als Anwendung wird gezeigt, daß ein Zusatz von 0,1% hochmolekularen Polyisobutylens zu einer 2%igen Polyisobutylenlösung den Wert vonN ₃ verdoppelt, aber keinen erkennbaren Einfluß auf die (bei geringen Schergeschwindigkeiten mit einem Ferranti-Shirley-Viskosimeter gemessen) Viskosität hat.

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udsf unidirectional shear flow - TCP truncated-cone and plate - N ₁,N ₂ 1st and 2nd normal stress differences in udsf - N ₃ N ₁ + 2N ₂ - : = A is defined by the equationA := B - P ^* hole pressurePw – Pm; Pw, Pm = pressures measured by flush transducer and by hole-mounted transducer - t time - , strain rate, shear rate - (P,t) covariant body metric tensor at particleP and timet - ⁱ , _i covariant and contravariant udsf body base vectors (i = 1, 2, 3) - ^–1 inverse of - R, plate radius, cone/plate gap angle - r ₀,h ₀ radius and height of cone truncation - r,, spherical polar coordinates; cone axis = 0; plate surface = /2 - physical components of stress; for a tensile component - cone angular velocity - p on the plate = /2 - ,T, density, absolute temperature, viscosity - P 0.15 ²(r ² –R ²) (inertial contribution) [2.7] - P _ve contribution [2.8] from flow perturbations of viscoelastic origin - r _i i = 1,2,3,4; values ofr at centers of holes in cone/plate region - P _i () pressure change recorded by transducerTi when cone angular velocity goes from zero to - 1/2 {P _i ()+ P _i (–)} (average for 2 senses of rotation) - rim pressure, from least-squares line through four points - Re Reynolds' number:R ²/ - (P,t)/t With 11 figures and 2 tables     

Computation of backward-facing step flows by a second-order Reynolds stress closure model

This paper scrutinizes the predictive ability of the differential stress equation model in complex shear flows. Two backward-facing step flows with different expansion ratios are solved by the LRR turbulence model with an anisotropic dissipation model and the near-wall regions of the separated side resolved by a near-wall model. The computer code developed for solving the transport equations is based on the finite-volume-finite-difference method. In the numerical solution of the time-averaged momenum equations the Reynolds stresses are treated partially as a diffusion term and partially as a source term to avoid numerical instability. Computational results are compared with experimental data. It is found that the near-wall region of the separated side resolved by the near-wall model, the LRR model with a simple modification of an anisotropic dissipation model can predict backward step flows well.     

Edge fracture in cone-plate and parallel plate flows

Edge fracture is an instability of cone-plate and parallel plate flows of viscoelastic liquids and suspensions, characterised by the formation of a `crack' or indentation at a critical shear rate on the free surface of the liquid. A study is undertaken of the theoretical, experimental and computational aspects of edge fracture. The Tanner-Keentok theory of edge fracture in second-order liquids is re-examined and is approximately extended to cover the Criminale-Ericksen-Filbey (CEF) model. The second-order theory shows that the stress distribution on the semi-circular crack is not constant, requiring an average to be taken of the stress; this affects the proportionality constant, K in the edge fracture equation −N _2c = KΓ/a, where N _2c is the critical second normal stress difference, Γ is the surface tension coefficient and a is the fracture diameter. When the minimum stress is used, K = 2/3 as found by Tanner and Keentok (1983). Consideration is given to the sources of experimental error, including secondary flow and slip (wall effect). The effect of inertia on edge fracture is derived. A video camera was used to record the inception and development of edge fracture in four viscoelastic liquids and two suspensions. The recorded image was then measured to obtain the fracture diameter. The edge fracture phenomenon was examined to find its dependence on the physical dimensions of the flow (i.e. parallel plate gap or cone angle), on the surface tension coefficient, on the critical shear rate and on the critical second normal stress difference. The critical second normal stress difference was found to depend on the surface tension coefficient and the fracture diameter, as shown by the theory of Tanner and Keentok (1983); however, the experimental data were best fitted by the equation −N _2c = 1.095Γ/a. It was found that edge fracture in viscoelastic liquids depends on the Reynolds number, which is in good agreement with the inertial theory of edge fracture. Edge fracture in lubricating grease and toothpaste is broadly consistent with the CEF model of edge fracture. A finite volume method program was used to simulate the flow of a viscoelastic liquid, obeying the modified Phan-Thien-Tanner model, to obtain the velocity and stress distribution in parallel plate flow in three dimensions. Stress concentrations of the second normal stress difference (N ₂) were found in the plane of the crack; the velocity distribution shows a secondary flow tending to aid crack formation if N ₂ is negative, and a secondary flow tending to suppress crack formation if N ₂ is positive. Received: 4 January 1999 Accepted: 19 May 1999