Analysis of rheology and wall depletion of microfibrillated cellulose suspension using optical coherence tomography

A rheometric method based on velocity profiling by optical coherence tomography (OCT) was used in the analysis of rheological and boundary layer flow properties of a 0.5% microfibrillated cellulose (MFC) suspension. The suspension showed typical shear thinning behaviour of MFC in the interior part of the tube, but the measured shear viscosities followed interestingly two successive power laws with an identical flow index (exponent) and a different consistency index. This kind of viscous behaviour, which has not been reported earlier for MFC, is likely related to a sudden structural change of the suspension. The near-wall flow showed existence of a slip layer of 2–12 μm thickness depending on the flow rate. Both the velocity profile measurement and the amplitude data obtained with OCT indicated that the slip layer was related to a concentration gradient appearing near the tube wall. Close to the wall the fluid appeared nearly Newtonian with high shear rates, and the viscosity approached almost that of pure water with decreasing distance from the wall. The flow rates given by a simple model that included the measured yield stress, viscous behavior, and slip behavior, was found to give the measured flow rates with a good accuracy.     

Flocculated flow of microfibrillated cellulose water suspensions: an imaging approach for characterisation of rheological behaviour

Our aim was to characterise the suspension rheology of microfibrillated cellulose (MFC) in relation to flocculation of the cellulose fibrils. Measurements were carried out using a rotational rheometer and a transparent cylindrical measuring system that allows combining visual information to rheological parameters. The photographs were analyzed for their floc size distribution. Conclusions were drawn by comparing the photographs and data obtained from measurements. Variables selected for examination of MFC suspensions were degree of disintegration of fibres into microfibrils, the gap between the cylinders, sodium chloride concentration, and the effects of changing shear rate during the measurement. We studied changes in floc size under different conditions and during network structure decomposition. At rest, the suspension consisted of flocs sintered together into a network. With shearing, the network separated first into chain-like floc formations and, upon further shear rate increase, into individual spherical flocs. The size of these spherical flocs was inversely proportional to the shear rate. Investigations also confirmed that floc size depends on the geometry gap, and it affects the measured shear stress. Furthermore, suspension photographs revealed an increasing tendency to aggregation and wall depletion with sodium chloride concentration of 10⁻³ M and higher.     

Effect of polyvinylpyrrolidone and sodium lauroyl isethionate on kaolinite suspension in an aqueous phase

Suspension of concentrated kaolinite (20 g/30 ml-medium) in the presence of polyvinylpyrrolidone (PVP) and sodium lauroyl isethionate (SLI) was allowed to evaluate its degree of dispersion based on their rheological studies. Flow curves at low shear rate, measured by means of cone-plate method, showed a non-Newtonian flow. Plastic viscosity and Bingham yield value were derived from the flow curves. Relative viscosity, effective volume fraction and void fraction of secondary particle were also obtained. Results of dispersity and fluidity of the suspension were explained. PVP acted as a flocculant at a concentration lower than 0.1% but as a dispersant at a higher concentration. The presence of SLI could decrease both the Bingham yield value and suspension viscosity. Cooperative and competitive effects of PVP and SLI were found. Results indicated that SLI enhanced the degree of dispersion of kaolinite when PVP was less than 0.1%. The suspension, however, showed a maximum flocculation (i.e., aggregation) at 4 mM SLI when the concentration of PVP was higher than 0.1%.     

Influence of poly(ethylene oxide) brushes on the rheological properties of MgO colloidal suspensions in water

A combined experimental and multiscale simulation study of the influence of polymer brush modification on interactions of colloidal particles and rheological properties of dense colloidal suspensions has been conducted. Our colloidal suspension is comprised of polydisperse MgO colloidal particles modified with poly(ethylene oxide) (PEO) brushes in water. The shear stress as a function of shear rate was determined experimentally and from multiscale simulations for a suspension of 0.48 volume fraction colloids at room temperature for both bare and PEO-modified MgO colloids. Bare MgO particles exhibited strong shear thinning behavior and a yield stress on the order of several Pascals in both experiments and simulations. In contrast, simulations of PEO-modified colloids revealed no significant yielding or shear thinning and viscosity only a few times larger than solvent viscosity. This behavior is inconsistent with results obtained from experiments where modification of colloids with PEO brushes formed by adsorption of PEO-based comb-branched chains resulted in relatively little change in suspension rheology compared to bare colloids over the range of concentration of comb-branch additives investigated. We attribute this discrepancy in rheological properties between simulation and experiment for PEO-modified colloidal suspensions to heterogeneous adsorption of the comb-branch polymers.     

Solution properties of thermothickening copolymers bearing hydrocarbon end‐capped oxyethylene units

Novel thermothickening copolymers composed of acrylamide and a macromer bearing hydrocarbon end‐capped oxyethylene units were synthesized. Influences of polymer concentration, salt content, shear rate, and temperature on the solution behavior were investigated. The polymer solution exhibited shear‐thickening behavior at low‐to‐moderate shear rates (<50 s^?1), and the shear‐thickening behavior was dependent on polymer concentration, NaCl content, and temperature. With the increase of salinity, apparent viscosity of polymer solution increased dramatically (especially at low shear rates). At higher NaCl content (>20 wt %), polymer solutions became physical gel, and the apparent viscosity increased by several orders of magnitude. The polymer solutions exhibited excellent thermothickening behavior, even at the low concentration of 0.15 wt %. The results of rheological measurements showed that the storage and loss modulus were successfully fitted to a single Maxwell element at low temperature (<60 °C). © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1799–1808, 2010     

Time dependent viscosity of concentrated alumina suspensions

Viscometric investigations of concentrated aqueous alumina suspensions with particles smaller than 5 μm have been performed. Experimental flow curves indicate thixotropy in the shear rate interval between =20 and 640 s⁻¹. In the range smaller than =200 s⁻¹ we found pseudoplastic flow behavior, in the higher range the material shows dilatancy. The non-Newtonian behavior results from a small content of sodium aluminum oxide in the alumina suspension. This gives rise to interparticle forces that can drive the suspension into a gel-like state. The time scale of this process is some days. On the short-time scale of some hours the material ages slowly increasing moderately the apparent viscosity. Studying the relaxation process after a shear rate jump, the shear stress time dependency at constant shear rate follows an exponential law. There is a single particular relaxation time for each shear rate. The relaxation towards a steady state occurs asymptotically over some 10³ s. Flow curves calculated from steady state data after relaxation processes are below the experimental flow curves which were measured during some 100 s. The flow curves follow the Herschel–Bulkley formula. The shape of the viscosity curves indicates changes of suspension structure at ca. =200 and 400 s⁻¹. At constant shear rates in the interval between =400 and 450 s⁻¹ the apparent viscosity of the alumina suspension fluctuates periodically in time in the same manner found for other suspensions. This effect is interpreted as periodic organization of agglomeration and deglomeration processes. Supposing, that the stabilisation energy of agglomerates is of the order of the energy introduced by the mechanical shear field, the observation of oscillations at =400 s⁻¹ is in agreement with the drastic slope change in the viscosity curves.     

Rheological Modeling of Dispersion System of Nano/Microsized Polymer Particles Considering Swelling Behavior

Rheological behavior of dispersion system containing nano/microsized cross-linked polymer particle was studied considering particle hydration and swelling. Viscosity of the dispersion system depends on swelling kinetics of polymer particles. Under shear flow, dispersion of swollen polymer particles is shear thinning. According to experimental results, kinetics of particle swelling and hydration was described well by second-order kinetic equation. Relational expression between equilibrium particle size and influencing factors of swelling such as salt concentration and temperature was presented. Assume that swollen polymer particles are uniform and have a simple core-shell structure, interacting through a repulsive steric potential. The rheological modeling of such dispersion system at low shear rate was presented using the concept of effective volume fraction, which depends on swelling kinetics and interparticle potential. Cross model was introduced to describe shear-thinning behavior. The viscosity equation allows correlation of experimental data of relative viscosity versus shear rate or hydration time; accounting for effect of temperature and salt concentration on viscosity. Predictions of the model have a good agreement with experimental results.     

Experimental study on the rheological behavior of nanolubricant-containing MCM-41 nanoparticles with viscosity measurement

In this study, the rheological behavior and viscosity of a stable nanofluid, which is prepared with the suspension of MCM-41 nanoparticles in SAE40 engine oil as base fluid, would be presented. Two-step method has been used to stabilize the nanoparticles in engine oil. To obtain structural and morphological properties of the synthesized nanoparticles, small-angle X-ray scattering, N₂ adsorption/desorption analysis and scanning electron microscopy have been done. Then, viscosity of nanofluids has been measured in temperature range of 25–55 °C, shear rates up to 13,000 s^?1 and different concentrations (0 mass%, 0.5 mass%, 1 mass%, 3 mass% and 5 mass% of MCM-41 nanoparticles). For all the samples, the shear stress versus shear rate diagrams showed that SAE40 oil has Newtonian behavior, in which adding mesoporous silica nanoparticles causes non-Newtonian or pseudoplastic behavior. The results declared that viscosity decreases with increasing temperature and increases with an enhancement in concentration. Furthermore, based on experimental results, an accurate correlation has been proposed to predict the viscosity of SAE40/MCM-41 nanolubricants.

     

Role of Electrostatic Repulsion on the Viscosity of Bidisperse Silica Suspensions

The flow behavior of bidisperse aqueous silica suspensions has been studied at different electrolyte concentrations as a function of shear rate, total volume fraction of the particles, and volume ratio of small to large particles. It is shown that the range of the electrostatic repulsion plays an important role in determining the viscosity of the suspension. Binary mixtures of particles of longer range repulsive forces showed higher viscosities than the suspensions of shorter range electrostatic interactions. Bimodal suspensions of long-range interactions showed non-Newtonian behavior over wider ranges of shear due to the deformation of the ionic cloud around the particles, which is larger in these systems. The viscosity of bimodal suspensions used in this study was scaled with respect to the viscosity of the related monosized systems and the viscosity of one bimodal suspension at a fixed total volume fraction of the particles, employing our earlier scaling method. The model normalizes the effect of colloidal forces by introducing a scaling factor that collapses the data into a single curve for bimodal suspensions of a particular size ratio, and it is shown that the model is valid for systems with both short-range and long-range repulsive forces. Copyright 1999 Academic Press.     

Disintegration of periodate–chlorite oxidized hardwood pulp fibres to cellulose microfibrils: kinetics and charge threshold

Periodate–chlorite oxidized bleached hardwood kraft pulp fibre samples with six levels of charge densities ranging from 0.5 to 1.8 mmol/g were gradually disintegrated to microfibrils using a high-shear homogenizer. The disintegration kinetics and mechanisms were studied by a flow fractionation method, and the properties of the resulting particles were determined using low shear viscosity and transmittance measurements. The particles formed during the disintegration were visualized with a charge-coupled device camera and by field-emission scanning electron microscopy. The result showed that cellulose fibres with a low charge density disintegrated at a low rate and produced ragged fibres and bunches of microfibrils via bursting of the fibre walls, whereas those with a higher charge density broke down at a high rate and microfibrils were formed through swelling and the creation of balloon structures. A carboxyl content of 1.2 mmol/g was found to be the threshold value for the efficient formation of high aspect ratio microfibrils and also for the change in the disintegration mechanism in the high-shear homogenizer.     

Rheological behavior and particle suspension capability of guar gum: sodium tetraborate decahydrate gels containing cellulose nanofibrils

Guar gum (GG) fracturing fluids were studied by incorporating cellulose nanofibrils (CNFs) in anhydrous borax crosslinked guar gum gels. To fully understand the impact of CNF on the proppant suspension capability of developed fracturing fluids, their shear rate-dependent viscosity and viscoelasticity were investigated. The shear rate dependencies of fluids was fitted to the Carreau model. The zero shear rate viscosity and elasticity of fracturing fluids increased significantly by incorporating CNF in guar gum gels. On the other hand, the viscosity at high shear rates (>100 s^?1) decreased as desired. The proppant settling velocities through fracturing fluids were evaluated by modeling the terminal falling velocity of proppants moving through a Carreau model fluid. The experimental results of the rheological behavior and the modeling results of the proppant settling rate indicated that the fracturing fluids containing CNF had better suspension capabilities. In addition, the lower viscosities of CNF formulated GG gels at higher shear rates will make them more pumpable.     

铝/镁混合金属氢氧化物正电胶体粒子体系的触变性

采用恒定低剪切速率方法和动态实验方法研究了铝/镁混合金属氢氧化物(MMH)悬浮体的流变性,着重考察了剪切历史和恢复时间等因素对悬浮体触变性的影响,发现MMH粒子深度的增加使得悬浮体从粘性流体变为“类固体”;恒定低剪切速率方法和动态实验方法研究悬浮体的结构恢复过程给出了不同的结果,唯象地解释了MMH悬浮体触变性产生的原因,认为触变性结构是由于粒子间的静电排斥作用而形成的,与粘土悬浮体相比,两者的流变性具有诸多相似之处,只是所带电荷符号相反。     

Influence of cellulose nanofibers on the rheological behavior of silica-based shear-thickening fluid

In this work, the influence of cellulose nanofibers (CNFs) on the rheological behavior of silica-based shear-thickening fluid (STF) is investigated. CNFs of 150–200 nm in diameter were extracted from cotton fibers using a supermasscolloider. CNF-reinforced STF of different concentrations (0.1–0.3 wt.%) was prepared via an ultrasonication technique. The presence of CNFs and their interaction with the silica nanoparticles in the STF were analyzed using SEM and FTIR. The addition of a minute quantity of CNF to the STF (0.3% CNF-reinforced STF) caused a marked increase in the peak viscosity, from 36.8 (unmodified STF) to 139.0 Pa s (0.2% CNF-reinforced STF), and a concomitant decrease in the critical shear rate from 33.45 to 14.8 s^?1 . The presence of a large number of hydroxyl groups on the CNFs enhanced their interaction with the nanoparticles via hydrogen bonding, which induced shear thickening. The mechanism of the interaction between silica nanoparticles and CNF was also demonstrated. Oscillatory dynamic rheological analysis showed that the addition of even a small amount of CNF led to higher elastic behavior in the system at lower shear rates. In contrast, a more viscous nature was demonstrated at higher angular frequencies. As the concentration of  nanofibers in the STFs increased, the crossover point between storage and loss modulus shifted to higher angular frequencies, implying stronger interaction between the constituents of the STF. The dynamic viscosity profile of all samples also exhibited shear-thickening behavior.     

Viscometric behavior of mesomorphic ethyl cellulose solution in chloroform

A simple modification of the viscometer used to determine the viscosity of concentrated solutions is described which permits the ready measurement of viscosity versus shear rate behavior above room temperature. Basic experimental viscometry was performed on the ethyl cellulose–chloroform system using a B-type (Brookfield-like) rotating-cylinder viscometer. Data are compared with theoretical predictions. The flow curves exhibit yield stress at low shear rate. The yield stress is dependent on concentration and temperature. The viscosity versus concentration curves show typical mesomorphic behavior. The concentration dependences of viscosity and yield stress are similar. The critical concentration increases with temperature. In the single-phase region (isotropic or anisotropic state) the viscosity decreases with temperature and the apparent activation energy (E_a) for flow is positive, but in the biphasic range the viscosity increases with temperature and E_a is negative. The experimental results for the critical concentration appear to agree with Flory's theory of rodlike molecules when the ratio of persistence length to diameter of the chain is taken as the aspect ratio.     

Modified graessley theory for non-newtonian viscosities of polydimethylsiloxanes and their solutions

A deviation from Graessley's theory of entanglement viscosity appears at very high shear rates when the flow of polydimethylsiloxanes of various molecular weights and their solutions with various concentrations is measured by the capillary method. In order to explain this deviation, a modified Graessley theory is proposed according to the previously reported suggestion that frictional viscosity appears not to be negligible at high shear rates. A reducing procedure taking a frictional viscosity parameter into account was performed. All of the reduced data are combined to give a master curve in spite of a wide range of molecular weight, concentration, and shear rate (from the lower Newtonian to very highest non-Newtonian flow region). The findings from the reducing procedure completely explain the mechanism of non-Newtonian flow for the bulk polymers with various molecular weights, including those below the critical molecular weight for entanglement, and for polymer solutions at any concentration. The viscosity of the linear polymer system consists of the shear-dependent entanglement term η_ent proposed by Graessley and the shear-independent frictional term η_fric. The non-Newtonian behavior depends on the ratio of η_ent/η_fric at the shear rate of measurement. The ratio of zero-shear entanglement viscosity η_ent,0 to η_fric and the critical shear rate for onset of the non-Newtonian flow may be used as a measure of the non-Newtonian behavior of the system and a measure of capability for its rising, respectively. The Graessley theory is to be included in the present modified theory and is applicable to the case of η_entη_fric ? 1.     

Viscosity modification of lubricating oil based on high-concentration silica nanoparticle colloidal system

In this study, colloidal systems with SiO₂ nanoparticle as viscosity modifier additive were synthesized in the lubricating oil via an in situ Stober sol-gel method. The fluid characters of lubricating oil and viscosity variation were carefully investigated via rheological methods. The results showed that the lubricating oil transformed from Newtonian fluid to non-Newtonian fluid with increasing the concentration of nanoparticles, and smaller particles displayed better thickening effect toward lubricating oil. For the system with highly concentrated nanoparticle (20?wt%), the rheological behavior mainly depends on the size of nano-SiO₂. The lubricating oil with smaller nano-SiO₂ particles displayed higher structural strength and response rate, resulting in good recoverability after high-speed shear. The viscosity changed with temperature and also displayed a thermo-responsive behavior, which significantly alleviated the effect of shear thinning on the viscosity under high temperature. This study presented a new strategy for effectively tuning the fluid characters and modifying the viscosity of lubricating oils by adding highly concentrated inorganic nanoparticles.     

ELECTRORHEOLOGICAL PROPERTIES OF TALC POWDER/SILICONE OIL SUSPENSIONS UNDER DC FIELDS

In this study, the electrorheological （ER） behavior of suspensions prepared from d50 = 2.4 lam talc powder, dispersed in insulating silicone oil （SO） medium was investigated. Sedimentation stabilities of suspensions （c = 5 wt%） prepared using these talc powder powders were determined to be 78 days. The ER activity of all the suspensions was observed to increase with increasing electric field strength, concentration and decreasing shear rate. The shear stress of talc powder suspensions increased linearly with increasing concentrations of the particles and with the applied electric field strength. Electric field viscosity of all the suspensions decreased sharply with increasing shear rate and showed a typical shear thinning non-Newtonian visco-elastic behavior. Effects of frequency on the ER activity of talc powder/SO system were also investigated.     

Flow and Dynamic Viscoelastic Characterization of Non-Purified and Purified Mucin Dispersions

This study demonstrated that the rheological behavior of mucin, a glycoprotein, mainly depends on the concentration of its dispersions and purity of the sample. Rheological properties were studied under rotational and oscillatory shear and creep curves. The results showed that mucin dispersions display non-Newtonian behavior of the shear thinning type. The mucin dispersion showed an apparent viscosity ranging from 0.22 to 29.29 Pa.s; at 10% concentration it formed macromolecular solutions with G″>G′; these showed viscoelastic liquid behavior, while at 40% it showed viscoelastic solid behavior, characteristic of weak gels, G′>G″. Atomic force microscopy revealed topographical differences on the commercial mucin surface, as in non-purified and purified mucin gels.     

Diffusing wave spectroscopy used to study the influence of shear on aggregation

In this study, diffusing wave spectroscopy (DWS) is used to investigate the effect of shear on a food-related aggregating emulsion. The principle of the method is validated using a nonaggregating, nearly monodisperse latex suspension. In general, with increasing shear rate the diffusive motion of the scatterers becomes negligible compared to the convective motion. This causes a decrease in the decay time of the autocorrelation curves and a change in the form of the autocorrelation curves from nearly exponential to Gaussian. This is reflected in the exponent of the mean square displacement that changes from 1 to 2. The effect of shear on the acidification of a sodium caseinate-stabilized emulsion was studied by DWS and by rheometry. The emulsion droplets in the food-related emulsion were uniformly dispersed at neutral pH. Upon acidification down to a pH of 5.2 +/- 0.05, the emulsion showed Newtonian behavior with constant viscosity over the whole pH range. At pH 5.17 +/- 0.05, independent of the applied shear rate during acidification, the viscosity suddenly increased. From this point on, the emulsion showed shear-thinning behavior. The photon-transport mean free path ( l*) was not influenced by the applied shear rate and did not change down to pH 5.2 +/- 0.05. Close to this pH, l* increased, and the decay of the autocorrelation curves shifted to longer correlation times when shear rates smaller than 1 s (-1) were applied. At lower pH (5.05 +/- 0.05), l* started to fluctuate, and the autocorrelation curves no longer decayed to zero, indicating that at these shear rates the system behaved nonergodicly. Assuming that the convective motion and the Brownian motion are independent of each other, the mean square displacement as a result of Brownian motion was determined. From this, the sol-gel point and the radius of the aggregates at this point as a function of the shear rate was determined. The results indicated that the radius of the aggregates at the sol-gel transition decreased with increasing shear rate and suggested that shear will result in a more open structure of the network formed by the aggregates.     

利用大幅振荡剪切研究Laponite 凝胶的流变性质

通过大幅振荡剪切(LAOS)流变学方法, 研究了NaCl浓度对Laponite悬浮体系的结构及非线性黏弹性的影响. 在线性黏弹性区, Laponite体系的储能模量G′随着NaCl浓度的增加而逐渐增大. 体系的非线性黏弹性用响应应力的Fourier变换三次谐波的相对振幅I_3/1与Lissajous曲线的定量参数G_M, G_L, η_M和η_L描述. 当NaCl浓度较低时, I_3/1随应变振幅γ₀的增加而缓慢增加; 当NaCl浓度较高时, I_3/1随γ₀的增加迅速增大, 达到平台值. 不同NaCl浓度试样的G_M和G_L随γ₀变化的曲线区别不大, 但η_M和η_L随γ₀变化曲线在非线性区域出现峰值且区别较大. NaCl浓度越高, η_M和η_L出现峰值的γ₀越小, 峰值越大. 结果表明, Laponite凝胶的非线性黏弹性与凝胶网络结构有关, 随着NaCl浓度的增加, 粒子间的静电相互作用距离缩短, 粒子间距减小, 形成了更紧密的网络结构. 但这种网络在较大的应变下很容易被破坏, 出现非线性黏弹性.