Rheological behaviour and shear thickening exhibited by aqueous CTAB micellar solutions

In this experimental work we carefully investigate the rheological behaviour and in particular the shear thickening exhibited by aqueous micellar solutions of CTAB with NaSal as added counterion. We are particularly interested in the evolution of the critical shear rate (at which shear thickening occurs) versus C _D , the surfactant concentration. We show that , at fixed salt concentration C _S , increases with C _D following a power law evolution with a positive exponent of + 5.8. On the other hand we show that if the ratio C _D / C _S is fixed, decreases with C _D with a negative exponent of -2.0. Nevertheless investigations of the zero shear viscosity indicate that in all situations (implying variation of the surfactant concentration C _D , or the salt concentration C _S or the temperature) is a decreasing function of the length of the micelles. All these evolutions are compatible with a gelation mechanism which could possibly be associated with entanglement effects of large interacting flowing structures. Received: 3 March 1998 / Revised: 16 June 1998 / Accepted: 3 July 1998     

A thermodynamic framework to model thixotropic materials

Thixotropic materials are widely used in a variety of industrial applications. The constitutive relations to describe these materials are based on one-dimensional experiments in which the material is subjected to a shear motion and there is no unique methodology to obtain proper three-dimensional models. The path towards generalization to a three-dimensional framework is invariably carried out in a ad hoc manner. Here we propose a three-dimensional model that stems from a general thermodynamic framework that has proved to be quite robust in the development of constitutive relations, namely the application of the second law of thermodynamics together with the maximization of the entropy production. This leads to a constitutive equation that has the same form of a generalized Upper Convected Maxwell equation, if we require that changes of microstructure due to the deformation of each Maxwell element that comprises the model are reversible. Changes in microstructure are governed by a potential that is a measure of the difference between the current structure and the equilibrium structure associated with it. The equilibrium structure associated with the current structure is determined by the current value of stress, considered the main break up agent. We assume that the state of equilibrium would be achieved in a Motion With Constant Stress History, starting from the current stress state, until a steady state where the kinematics is not changing.     

Synthesis of cation-exchanged laponite suspensions by laser ablation of microsized-metal particles in liquid

Laser ablation in the liquid technique has been used to synthesize cation-exchanged laponite suspensions. In summary, laser ablation of the microsize-metal powder (Co, Al, and Cu) dispersed in an aqueous solution containing deionized water laponite crystals was carried out using laser beam generated by a single-mode, Q-switched Nd-Yag laser operating at 532 nm with a pulse duration of 5.5 ns and 10 Hz repetition rate. Laser fluence was 0.265 J/cm² for all tests. For all samples, the mass fraction of laponite was 1%. General observations of the prepared samples indicated that an aqueous suspension of 1 wt% laponite retained its free flowing liquid phase characteristics even after aging for several weeks. When bivalent cationic metals (Cu, Co, Al) were ablated in it for about 1 h, even with a small amount of the metal (0.025% and 0.050%) were generated, the suspension became highly viscous and behaved as a shear-thinning and thixotropic material. That is, the suspension gelled strongly when it was allowed to rest. The gels, however, could easily be reverted to a low viscosity liquid with simple shaking. Information from TEM and XRD analysis indicated that such a sol-gel transformation might be due to the charge exchange between the cationic species produced during the laser ablation and the sodium ions in the interlayers of the clay sheets.     

A structural model for the time-dependent recovery of mineral suspensions

A thixotropic recovery model has been developed that is based on consideration of the microstructural interactions that occur between particles within a suspension particle network. The model is based on Smoluchowski coagulation rate theory, utilizing second order kinetics to describe the thixotropic recovery behavior. The model is applied to Na-montmorillonite-based coal tailings suspensions and is also shown to be applicable to brown coal and bauxite residue suspensions. The model describes all the recovery data well, especially at intermediate to large recovery times. The recovery of the montmorillonite suspensions at short times was faster than predicted, indicating the existence of additional factors in early-time structure development. The discrepancy may have also been due to the highly anisotropic nature of the clay platelets. The recovery rate constant, K _r , increases with increasing solids concentration (for constant surface chemical conditions) as would be expected from the basis of the model. Received: 22 September 2000 Accepted: 16 March 2001     

Rheological characterization of a solder paste for surface mount applications

Solder pastes used in surface mount soldering techniques (SMT) are very complex suspensions containing high volumes of metallic powder in a carrier fluid. The rheological complexity results largely from the carrier fluid itself, which is a suspension of colloidal particles. In this work, we have characterized the rheological properties of a typical carrier fluid and its solder paste containing 64 vol.% metallic powder. A six-blade vane geometry was used to avoid wall slip and sample fracture. All measurements were carried out following pre-shearing and rest time in order to obtain reproducible results. Steady shear experiments showed that the solder paste was highly shear-thinning and thixotropic. In oscillatory shear, the linear viscoelastic domain was found to be very narrow for both the suspending fluid and the paste. Frequency sweep tests in the linear domain revealed a gel-like structure with a nearly constant G′ for the suspending fluid and a slightly increasing G′ for the solder paste. From creep experiments, a yield stress of about 40 Pa was determined for the suspending fluid at temperatures between 25 and 40°C, and of 100 Pa at 4°C. A much larger yield stress, 480 Pa, was determined for the solder paste at 25°C.     

A new microstructure-based constitutive model for human blood

A new constitutive equation for whole human blood is derived using ideas drawn from temporary polymer network theory to model the aggregation and disaggregation of erythrocytes in normal human blood at different shear rates. Each erythrocyte is represented by a dumbbell. The use of a linear spring law in the dumbbells leads to a multi-mode generalized Maxwell equation for the elastic stress and both the relaxation times and viscosities are functions of a time-dependent structure variable. An approximate constitutive equation is derived by choosing a single mode corresponding to the cell aggregate size where the largest number of cells are to be found. This size is identified in the case of steady flows. The model exhibits shear-thinning, viscoelasticity and thixotropy and these are clearly related to the microstructural properties of the fluid. Agreement with the experimental data of Bureau et al. [M. Bureau, J.C. Healy, D. Bourgoin, M. Joly, Rheological hysteresis of blood at low shear rate, Biorheology 17 (1980) 191–203] in the case of a simple triangular step shear rate flow is convincing.     

Simulations of thixotropic liquids

In thixotropic liquids the rheological properties depend on the liquid’s deformation history. Clay suspensions (as encountered in oil sands mining) are a prominent example. Activated clay particles form a network. As a consequence of (ionic) transport limitations, the network is not an instantaneous feature; it takes time to build up, and also to break down, the latter as a result of deformation in the liquid. In this paper a procedure for detailed simulations of flow of viscous thixotropic liquids is outlined. The local viscosity of the liquid relates to the level of integrity of the network. The time-dependence of the liquid’s rheology is due to the finite rate with which the network in the liquid builds up or breaks down. This concept has been incorporated in a lattice-Boltzmann discretization of the flow equations. With this methodology the way thixotropic liquids are mobilized in mixing tanks and the drag force experienced by dense assemblies of coarse particles (e.g. sand) in thixotropic liquids have been studied.     

Application of the Casson model to thixotropic waxy crude oil

The rheological behavior of a waxy crude oil was investigated using a coaxial cylinder viscometer. Experimental flow curves were fitted with the Casson equation. The Casson model was modified to interpret the hysteresis between upward and downward curves obtained in a series of consecutive runs. At the same shear rate, the mean axial ratio of the flow unit related to a down-curve (↓) is smaller than that related to an equilibrium up-curve (↑). This results in a decrease of the Casson yield stress τ_c↓ with respect to τ_c↑. A certain ξ coefficient describing departure from the equilibrium mean axial ratio was introduced into the model. Values of ξ calculated from the Casson yield stresses agreed satisfactorily with the theoretically predicted ones. Deviations from the Casson model at low shear rates were also explained. Received: 28 July 1998 Accepted: 18 February 1999     

水性乳液/聚氨酯模型缔合增稠剂的触变性机理

以异佛尔酮二异氰酸酯(IPDI)与聚乙二醇(PEG,分子量为4000,6000和8000)为原料,以直链醇(C12,C14,C16和C18)为封端剂,合成了疏水改性乙氧基化氨基甲酸酯(HEUR),并将其应用于乳液增稠.采用核磁共振波谱(¹H NMR)、傅里叶变换红外光谱(FTIR)及凝胶渗透色谱(GPC)表征了HEUR的结构、分子量及其分布,研究了其在水性乳液中的流变行为.研究结果表明,当HEUR封端基团为C14,C16和C18,且质量分数增加到1. 0%以上时,增稠的乳液(Latex/HEUR)的流变曲线出现触变环,为触变性流体.当HEUR亲疏水比值(R_h)减小时,疏水性增强,触变环向低剪切速率(γ˙)方向移动,黏度下降率(Δη)增大;当HEUR用量增加时,触变环面积(S_loop)也增大.这些触变性特点归因于HEUR在乳液中的缔合作用、氢键作用及链缠结.利用扫描电子显微镜(SEM)和原子力显微镜(AFM)对Latex/HEUR的聚集态和表面形貌进行了表征.结果表明,随着HEUR封端基团链长增加,Latex/HEUR颗粒...