Rheology of lyotropic and thermotropic lamellar phases

We investigate the steady-state rheological behaviour of the lamellar phase of a lyotropic system (CpCl, hexanol, brine) and of a thermotropic system (8CB). Power laws characterize the behaviour of the imposed stress as a function of the measured shear rate and similarities are observed for both systems; the same regime γ˙∼σ ^m with m≈1.7 is obtained at low shear stresses corresponding to a texture of oily streaks oriented in the direction of the flow, as shown by microscopic observations. The “onion state” only exists in the case of dilute samples of the lyotropic lamellar phase; the stress then varies as γ˙∼σ ^m with m≈4.8, as already observed by other groups with different systems. Rheological measurements at different temperatures allow determination of different activation energies relating to the still badly understood processes involved in the different rheological regimes. We propose a model which reproduces the experimental power laws and which is based on an analogy with the theory of high-temperature creep in metals and alloys. Received: 19 October 1999/Accepted: 1 November 1999     

Orientation behavior of AB and ABC block copolymers under large amplitude oscillatory shear flow

Flow alignment in a large amplitude oscillatory shear field (LAOS) of a lamellar AB and a lamellar ABC block copolymer (A,B are lamellae, C forms cylinders in B-lamellae) has been studied. 2D-small angle X-ray scattering (2D-SAXS) and scanning electron microscopy were used for morphological characterization, and flow birefringence and Fourier-Transform rheology were used to monitor the orientation. The diblock copolymer shows the known frequency-dependent orientation behavior, i.e., a perpendicular or a parallel orientation of the lamellae, while under all conditions for the ABC block copolymer only a perpendicular orientation after a long induction period was found. Due to the introduced third block C the AB lamellar structure with a high viscosity contrast between the A and B domains cannot adapt a parallel orientation of sliding phases. Dynamic mechanical analysis indicates shear induced improvement of the microphase separation of the short C block.     

Linear and nonlinear rheology of micellar solutions in the isotropic,cubic and hexagonal phase probed by rheo-small-angle light scattering

Aqueous solutions of a branched nonionic surfactant were studied in the isotropic, cubic and hexagonal phase by means of rheological and small-angle light scattering (SALS) experiments. The isotropic phase behaved like a Newtonian liquid. An increase of activation energy of viscous flow was found near the overlap concentration of spherical micelles, but no shear thinning was observed. The viscosity of low concentrated samples increased slightly when the lower critical solution temperature was approached. This increase of viscosity was much smaller compared to common nonionic surfactants. The cubic phases behaved as elastic solids with a high plateau modulus, and shear melting occurred at high shear stresses. The hexagonal phase showed complex behavior. Shear orientation could be achieved by large amplitude oscillatory shear and was proved by rheo-small-angle light scattering. Two orientations were observed, at first perpendicular to the flow direction, i.e., log-rolling state and, secondly, an in-shear-plane orientation parallel to the flow direction. The linear viscoelastic region of the hexagonal phase was extremely small and was detected by simultaneous rheo-small angle light scattering. Shear alignment lead to a decrease of the moduli.     

Shear orientation of a lamellar lyotropic liquid crystal

Shear orientation of a lyotropic lamellar liquid crystalline phase of tetra ethyleneglycol mono dodecylether, C₁₂A₄ in water was studied by combined rheo-small-angle light scattering. Shear thinning was observed with a sample of 500 m thickness. The scattering patterns showed that domains were aligned and stretched in flow direction. Shear thinning was also observed with a thinner sample, but caused a strong change in light-scattering pattern. A maximum of scattering intensity was observed at finite scattering vector and shifted to a higher scattering vector with increasing shear stress. This observation can be explained by a fragmentation of domains at high shear stress and is supported by a mosaic texture observed in optical microscopy.     

Polydomain model predictions of liquid crystalline polymer orientation in mixed shear/extensional channel flows

 The Larson-Doi (LD) polydomain model is used to simulate orientation development along the centerline of slit-expansion and slit-contraction flows of liquid crystalline polymers (LCPs). Orientation is computed using the LD structural evolution equations, subject to an imposed velocity field that accounts for the spatial variation of both shear and extension rates characteristic of this class of flows. Computed axial distributions of orientation averaged through the sample thickness are qualitatively similar to birefringence and X-ray scattering measurements of molecular orientation in similar flows of lyotropic and thermotropic LCPs. In slit-expansion flows, the simulations predict a 90^∘ flip in orientation direction near the midplane due to transverse stretching in the expansion region. Far away from the midplane where shear gradients dominate, orientation remains primarily along the flow direction. Within the LD model, tumbling and flow aligning materials respond in a qualitatively similar manner to mixed shear and extension, although tumbling materials are systematically more susceptible to the effects of extension. Received: 22 October 1999/Accepted: 13 January 2000     

Multilamellar vesicles (“onions”) under shear quench: pathway of discontinuous size growth

The size growth of multilamellar vesicles (MLV; “onions”) of a non-ionic surfactant system composed of 40 wt.% C₁₀E₃ in D₂O was investigated by shear quench experiments, i.e. by reducing the shear rate. Structural changes were monitored by means of viscosity, rheo-small angle neutron scattering, rheo-small angle light scattering and optical microscopy. Discontinuous growth of vesicle size was observed in addition to the continuous process reported previously. In the discontinuous size growth, first lamellar domains are formed, which afterwards transform into larger MLVs. The lamellar domains coexist with the original small vesicles leading to a bimodal size distribution. The transition of the lamellar domains into new MLVs follows the same pathway as was observed for the MLV formation from aligned lamellar phases.     

Structure and dynamics of a polymer solution subject to flow-induced phase separation

Experiments combining mechanical rheometry with polarimetry (birefringence and scattering dichroism) have been conducted on a 6% solution of polystyrene (1.86x10⁶ molecular weight) in dioctyl phthalate. Birefringence is used to measure the extent of segmental orientation, whereas the dichroism is sensitive to orientation and deformation of concentration fluctuations associated with the process of flow-induced phase separation. The results indicate that these fluctuations grow predominately along the neutral (or vorticity axis) of a simple shear flow. At higher rates of shear, orientation in the flow direction is favored. The transition in orientation direction is accompanied by time-dependent behavior in the optical properties of the solution during shear and the onset of shear thickening of the viscosity and the first normal stress difference coefficient.     

Rheology and birefringence of Fomblin YR at very high shear rates

The rheological and structural properties of perfluoropolyether (PFPE) lubricant films including viscosity, shear stress, and birefringence were measured at relatively low to extremely high shear rates using a rotational optical rheometer. The viscosity of various films with different thicknesses exhibit Newtonian behavior up to a shear rate 1 × 10⁴ s⁻¹, with a transition to shear-thinning behavior obvious at higher shear rates. Birefringence of these films was also measured for the first time, and these results indicate chain alignment with shear in the shear-thinning regime. The shear rate at which alignment occurs is similar to that of the onset of shear thinning. This correlation between chain alignment and shear thinning provides direct evidence that the ability of PFPEs to lubricate hard drives at high shear rates is a direct consequence of the ability of the applied shear field to align the molecules on a molecular level.     

Conoscopic observations of shear-induced rotations in nematic liquid crystals

Orientational changes in monodomains of flow-aligning liquid crystals, 4-n-pentyl-4′-cyanobiphenyl and N-(4-methoxybenzylidene)-4-butylaniline, were studied during shear and recovery in a linear shearing device fitted to an optical microscope. Planar alignment (director in the shear plane) allows the study of twist effects and was generated by strong planar anchoring at the walls with orientations in a range of 0–90° with the shear direction. While being held back by the anchoring walls, shear caused the bulk director to rotate towards a steady-state alignment angle in the shear direction (Leslie angle θ_L). The transient director rotation was observed with conoscopy. It was found that increasing the initial alignment towards the vorticity direction increased the measured θ_L. Upon stopping the flow, the bulk director returned to its initial state. With initial alignment orientation changing from parallel to perpendicular to the flow direction, the rate of the twist-driven recovery process increases. This rate increase is not seen in the splay-driven recovery which is constant and consistently faster than twist-driven recovery at all orientations studied. Received: 10 December 1998/Accepted: 7 June 1999     

超声纯横波法测试45#钢的内部应力

声各向同性的金属材料在应力作用下,材料表现出声各向异性,这是用声弹性法分析材料内部应力的基础。本文用垂直于应力方向传播的超声纯横波对45#钢进行测试,测试时横波的偏振化方向分别平行和垂直于应力方向。实验结果表明:材料在拉、压应力作用下,相互正交的两超声纯横波的声速都发生了变化,且声各向异性因子与应力成线性关系。利用此关系可测试材料内部应力,提供了一种无损测试材料内部应力的方法,另外本实验方法也可以对材料内部残余应力进行评估。实验中利用回振法测量声速,可测量声速的微小变化,精度高。     

Non-linear rheology and flow-induced transition of a lamellar-to-vesicle phase in ternary systems of alkyldimethyl oxide/alcohol/water

 The time-dependent transformation of an ionically charged lamellar phase (L _α-phase) into a vesicle phase under the influence of shear is investigated using rheological and conductivity measurements. The L _α-phase consists of the zwitterionic surfactant tetradecyldimethylaminoxide (C₁₄DMAO), hexanol, oxalic acid and water. The experiments were carried out on the L _α-phase in a well defined state. It was prepared by a special route from the neighbouring L ₃-phase that consists of 100 mM C₁₄DMAO, 250 mM hexanol and 5 mM oxalicdiethylester (OEE). The OEE hydrolyses in the L ₃ -phase to oxalic acid and ethanol. The result is a virgin L _α-phase which consists of stacked bilayers and which has not been exposed to shear. When this low-viscous phase is subjected to shear it is transformed into a highly viscous vesicle phase. The transformation of the L _α-phase into vesicles under constant shear was monitored by recording the viscosity and conductivity with time. It is observed that at least three different time constants can be distinguished in the transformation process. The conductivity passes through a minimum (τ₁) in the direction of shear. The viscosity first passes through a minimum (τ₂) and then over a maximum (τ₃). It is concluded that τ₁ belongs to the complete alignment of the bilayer parallel to the wall, τ₂ to the beginning of the break-up of the bilayers to the vesicles and τ₃ to the complete transformation of the L _α- to the vesicle phase. When the shear rate was varied, it was noted that the product of the time constants and shear is constant. Received: 30 June 1999/Accepted: 30 August 1999     

Divergent channel flow of a liquid crystalline polymer solution

 The flow of a `model' lyotropic liquid crystal polymer, (hydroxypropyl)cellulose in water, through a rectangular channel with a divergence in the channel width, is studied by in situ light microscopy. Microscopic texture observations are related to measurements of the flow velocity field, in order to characterize the shear and elongational aspects of the flow and to examine the effects of the divergence from a narrow channel to a wide channel. A strong dependence of flow-induced texture on position in the channel is observed and is related to the interplay of shear and elongational strain. The divergence generates both a perpendicular elongational strain due to the widening of the channel, and subsequently an elongational strain along the flow direction due to the change in flow pattern from quasi-radial to unidirectional down the wide channel. Additionally side wall structure is observed to be more complex than a simple strong alignment, displaying a fine birefringent texture. Finally there is a marked dependence of the macroscopic structure on the strain history of the fluid prior to entry into the channel, indicating that very different structures of, for instance, moulded parts, can result from differences in geometry and fluid treatment prior to entry into the mould itself. Received: 12 October 1999/Accepted: 29 October 1999     

Exponential shear flow of branched polymer melts

  The behavior of a low-density polyethylene melt in exponential shear strain histories is examined and compared to its behavior in constant rate planar elongation. A new set of shear stress and first normal stress difference data in exponential shear are presented and used in several different material functions that have been previously proposed. Viscosities composed of principal stress differences for the two flows showed no correspondence suggesting that, contrary to previous assertions, exponential shear and constant rate planar elongation flows are fundamentally different. It is further suggested that the presence of vorticity makes exponential shear a weak, rather than strong, flow. Received: 5 March 1999/Accepted: 1 September 1999     

Rheology and flow-birefringence from viscoelastic polymer-clay solutions

 The shear orientation of viscoelastic clay-polymer solutions was investigated by means of rheology and flow birefringence (Δn). The polymer chains are in dynamic adsorption/desorption equilibrium with the clay particles to form a “network”. The elastic behavior of the network was characterized by constant stress, oscillatory shear, and stress relaxation experiments. Constant stress experiments indicated a yield stress upon which shear flow started and no strain recovery could be observed. Oscillatory shear experiments showed a broad elastic region followed by flow when a critical strain was reached. Stress relaxation experiments showed several relaxation times when the same critical strain was reached. Experiments under steady flow characterized the transient behavior of the network. With increasing steady shear rate a pronounced minimum in birefringence was observed at a critical shear rate. The shear rate dependent viscosity showed near power law behavior and no corresponding critical feature. While birefringence detects orientational effects on a microscopic length scale, rheology averages over macroscopic changes in the sample. The same degree of orientation could be achieved under constant shear rate or constant stress conditions. Received: 25 January 2001 Accepted: 22 May 2001     

Excluded volume effects on the birefringence and stress of dilute polymer solutions in extensional flow

An algorithm is derived for calculating flow-induced birefringence using a bead-spring model with and without excluded volume effects. The simulation results for the bead-spring model compare well with experimental results for stress and birefringence in extensional flows of dilute solutions of polystyrene molecular weight 2 million in a filament-stretching device in both “theta” and “good” solvents (Orr and Sridhar 1999; Sridhar et al. 2000). In a “good” solvent, both stress and birefringence rise much more rapidly with strain than in a “theta” solvent, making extensional rheology a very sensitive indicator of solvent quality. Received: 7 December 1999 Accepted: 23 May 2000     

Structural rearrangements in hairy-rod polymer solutions undergoing shear

 We report on a rheooptical investigation of hairy-rod poly(p-phenylene) solutions at different concentrations and temperatures. These polymers have a reasonably high persistence length (about 28 nm) and behave as worm-like chains in dilute solutions, whereas they form nearly spherical fractal aggregates with internal anisotropy at higher concentrations. By exposing these systems to time-dependent simple shear and following the evolution of birefringence in start-up and its subsequent relaxation upon the cessation of shear, we find a substantial broadening of the cluster size distribution, resulting from flow-induced cluster deformation and break-up. In contrast to the very dilute solutions, where polymers align in the flow direction, the deformed clusters main axes are aligned in the vorticity direction, presumably due to their strong steric local pretransitional type of ordering, with the constituent polymers following the velocity vector. At the highest concentration, which corresponds to a weak gel, shear is shown to break-up the gel and the steady-state response of a broad-size aggregate suspension is eventually recovered. Received: 18 February 1999/Accepted: 6 July 1999     

Stress effects on the performance of optical waveguides

Stresses can cause anisotropic and inhomogeneous distribution of the refractive index. Their effects on the performance of optical waveguides have been observed in photoelectric devices. In this paper, the photo-elastic relation and wave equations for inhomogeneous and anisotropic waveguides are reviewed. The effective refractive indexes and mode shapes of planar waveguides under different stress states are obtained analytically. It is found that stress can affect the optical performance; different stress states play different roles: high stress value can change the cutoff thickness, which may induce multimode; in-plane stress causes birefringence, which may induce polarization shift and polarization dependent loss; stress concentration can change the mode shape, which may induced large transition loss; and pure shear stress has little effects on the effective refractive index.     

Thinning and thickening effects induced by shearing in lecithin solutions of polymer-like micelles

 The effects of shear flow on the lecithin organogels consisting of reverse polymer-like micelles have been investigated by dynamic rheology. It was established that the shear effects depended on the molar ratio of water to lecithin that determined the micellar type in the system. For an organogel with linear flexible polymer-like micelles, thinning was observed. The main features of the rheological behavior bore a resemblance to previously investigated aqueous systems made up of similar but direct polymer-like surfactant micelles. The thinning effects are explicable on the basis of alignment of micellar aggregates along the flow direction and their disentanglement. An organogel with branched micelles did not demonstrate any notable response to the shearing. Unusual behavior was noticed in the case of a jelly-like phase that included the highest amounts of water. The applied steady shear flow induced a thickening effect. This was followed by restructuring of the micellar system at the level of polymer-like micelles and their network. The shearing effects were characterized by slow kinetics. In addition, the system did not revert to the original state after the cessation of steady shear flow even within 8 h. Measurements performed in an oscillation regime on this system showed that shearing should promote a substantial growth of the polymer-like micelles and affect their alignment. Received: 18 May 1999 Accepted: 27 March 2000     

Investigation of the band texture occurring in hydroxypropylcellulose solutions using rheo-optical, rheological and small angle light scattering techniques

The band texture occurs in lyotropic and thermotropic main-chain polymers after cessation of flow. This paper begins with a review of work concerned with band texture formation following shear and is followed by the presentation of original results obtained during a recent investigation. The evolution of band texture formation in a Klucel EF, 50% hydroxypropylcellulose (HPC) water solution, has been observed using polarized optical microscopy. The relationship determined between the primary shear rate and the rate of evolution of the band texture is complex and three different behaviours have been observed corresponding to three shear rate regions. Both steady flow and dynamic rheological investigations have been conducted on the HPC solution, the results of which have been related to the optical behaviour of the band texture. Data from steady flow investigations suggest that the viscosity of the solution when the band texture is present, decreases following increasing primary shear rates, is shear thinning and increases linearly with the time following its formation. Dynamic investigations suggest a definite link between the band texture evolution and the evolution of both G′ and G′′. In addition, the perfection of the band texture versus the primary shear rate has been quantified by studying the evolution of tan(δ) following the cessation of the primary shear. Dynamic experiments show that the structure of the band texture remains longer than suggested by the optical aspect of the texture. Small angle light scattering patterns have been correlated with the development of the band texture and confirm the continuing presence of the band texture structure following its optical disappearance. Received: 2 March 1999/Accepted: 26 July 1999     

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.