Small Amplitude Oscillatory Shear Experiments Research Articles

Effect of specific surface area on the rheological properties of graphene nanoplatelet/poly(ethylene oxide) composites

The rheological properties of poly(ethylene oxide) containing graphene nanoplatelets (GNPs) having different specific surface areas (SSAs) are studied using steady shear and small amplitude oscillatory shear experiments. A series of GNPs having SSAs ranging from 175 ± 5 to 430 ± 13 m2/g was prepared using a thermomechanical exfoliation process. The complex viscosity, moduli, and yield stress of the composites increase with SSA, whereas electrical and rheological percolation threshold concentrations decrease, suggesting that higher SSAs promote filler network formation. Modeling of small amplitude oscillatory shear data using a two-phase model confirms that hydrodynamic effects dominate at low concentrations below 8 wt. %, where the particles are noninteracting. At higher concentrations, the response is dominated by filler-phase contributions. We demonstrate that the two-phase model parameters can be used to track the exfoliation of graphite into GNPs. Fitting of rheological percolation curves using Utracki and Lyngaae–Jørgensen models at low concentrations (noninteracting regime) resulted in aspect ratios between 19 and 76. At high concentrations (interacting particles), the aspect ratios determined by the Krieger–Daugherty model ranged between 5 and 24 due to aggregation. The highest aspect ratios (defined as the ratio of major dimension to minor dimension) were associated with GNPs that had the highest SSA of 430 m2/g. Strain sweeps revealed that the critical strain for the onset of nonlinear viscoelasticity scaled with SSA above the percolation threshold. The scaling relationships of the critical strain and storage modulus with volume fraction were used to infer the fractal dimensions of filler networks.

Concentration Scaling on Linear Viscoelastic Properties of Cellular Suspensions and Effects of Equilibrium Phase Behavior.

Concentration scaling on linear viscoelastic properties of cellular suspensions has been studied by rheometric characterisation of Phormidium suspensions and human blood in a wide range of volume fraction under small amplitude oscillatory shear experiments. The rheometric characterisation results are analysed by the time-concentration superposition (TCS) principle and show a power law scaling of characteristic relaxation time, plateau modulus and the zero-shear viscosity over the concentration ranges studied. The results show that the concentration effect of Phormidium suspensions on their elasticity is much stronger than that of human blood due to its strong cellular interactions and a high aspect ratio. For human blood, no obvious phase transition could be observed over the range of hematocrits studied here and with respect to a high-frequency dynamic regime, only one concentration scaling exponent could be identified. For Phormidium suspensions with respect to a low-frequency dynamic regime, three concentration scaling exponents in the volume fraction Region I (0.36≤ϕ/ϕref≤0.46), Region II (0.59≤ϕ/ϕref≤2.89) and Region III (3.11≤ϕ/ϕref≤3.44) are identified. The image observation shows that the network formation of Phormidium suspensions occurs as the volume fraction is increased from Region I to Region II; the sol-gel transition takes place from Region II to Region III. In combination with analysis of other nanoscale suspensions and liquid crystalline polymer solutions reported in the literature, it is revealed that such a power law concentration scaling exponent depends on colloidal or molecular interactions mediated with solvent and is sensitive to the equilibrium phase behaviour of complex fluids. The TCS principle is an unambiguous tool to give a quantitative estimation.

Melt State Reinforcement of Polyisoprene by Silica Nanoparticles Grafted with Polyisoprene.

We systematically vary the nanoparticle (NP) dispersion state in composites formed by mixing polyisoprene homopolymers with polyisoprene grafted silica particles, and demonstrate how creep measurements allow us to overcome the limitations of small amplitude oscillatory shear (SAOS) experiments. This allows us to access nearly 13 orders in time in the mechanical response of the resulting composites. We find that a specific NP morphology, a percolating particle network achieved at intermediate graft densities, significantly reinforces the system and has a lower NP percolation loading threshold relative to other morphologies. These important effects of morphology only become apparent when we combine creep measurements with SAOS re-emphasizing the role of synergistically combining methods to access the mechanical properties of polymer nanocomposites over broad frequency ranges.

Measuring and understanding blocking resistance in films cast from polymer latexes

Good blocking resistance is a pre-requisite for the practical use of films cast from aqueous polymer dispersions in coating applications. However, most blocking resistance measurements are highly subjective and therefore differentiating between samples is a challenge and does not always represent performance in real situations. In this work, we report a method for the quantitative measurement of blocking resistance of films cast from emulsion polymers using a universal testing machine. A number of representative polymer latexes are prepared and the blocking resistance is measured using the technique. It is demonstrated that effects of time, temperature and pressure on blocking resistance can largely be understood from the rheological master curves of the films as determined by small amplitude oscillatory shear experiments. It is shown that samples with higher Young's modulus and higher terminal relaxation times result in improved blocking resistance.

Viscoelastic properties of pNIPAM-hydrogels: A mode-coupling theory study

We investigate the viscoelastic properties of poly(N-isopropylacrylamide) (pNIPAM) hydrogels cross-linked with glutaraldehyde by means of small amplitude oscillatory and steady shear experiments in dependence on the frequency and shear rate. These properties are strongly influenced by the ratio of monomer and glutaraldehyde as a cross-linker. Due to the thermosensitivity of pNIPAM, the rheological properties of these hydrogels can be tuned by the temperature as an external stimulus. The experimentally obtained viscosities and linear viscoelastic moduli are analyzed by a schematic mode-coupling ansatz employing a rescaled F12-model.

Extracellular Matrix Modulates Outgrowth Dynamics in Ovarian Cancer.

Ovarian carcinoma (OC) forms outgrowths that extend from the outer surface of an afflicted organ into the peritoneum. OC outgrowth formation is poorly understood due to the limited availability of cell culture models examining the behavior of cells that form outgrowths. Prompted by immunochemical evaluation of extracellular matrix (ECM) components in human tissues, laminin and collagen-rich ECM-reconstituted cell culture models amenable to studies of cell clusters that can form outgrowths are developed. It is demonstrated that ECM promotes outgrowth formation in fallopian tube non-ciliated epithelial cells (FNE) expressing mutant p53 and various OC cell lines. Outgrowths are initiated by cells that underwent outward translocation and retained the ability to intercalate into mesothelial cell monolayers. Electron microscopy, optical coherence tomography, and small amplitude oscillatory shear experiments reveal that increased ECM levels led to increased fibrous network thickness and high shear elasticity of the microenvironment. These physical characteristics are associated with outgrowth suppression. The low ECM microenvironment mimicks the viscoelasticity of malignant peritoneal fluid (ascites) and supports cell proliferation, cell translocation, and outgrowth formation. These results highlight the importance of the ECM microenvironment in modulating OC growth and can provide additional insights into the mode of dissemination of primary and recurrent ovarian tumors.

Nanoclay Migration and the Rheological Response of PBAT/LDPE Blends

Abstract Blends of a poly(butylene adipate-co-terephthalate) (PBAT) and a low density polyethylene (LDPE) (80 wt%/20 wt%) were prepared through a twin screw extruder while incorporating 3 wt% Cloisite 30B (C30B) nanoclay that possessed a much higher affinity with PBAT. The blends were processed through three melt mixing strategies: ( i) direct mixing of all three components, (ii) mixing C30B and PBAT followed by mixing with LDPE, and (iii) mixing C30B and LDPE followed by mixing with PBAT. The rheological properties of each system were determined in small amplitude oscillatory shear (SAOS) experiments. The migration of C30B nanoparticles from the LDPE minor phase towards the PBAT matrix was then monitored in the blend nanocomposites prepared through strategy (iii) via SAOS time sweep experiments. It was firstly understood that the C30B migration could be detected during time sweep SAOS experiments. The migration time was observed to be frequency dependent due to the smaller length scales probed at larger frequencies. Such migration occurred even faster when the SAOS time sweep experiments were conducted at a higher temperature due to the viscosity reduction.

Development of CNC-reinforced PBAT nanocomposites with reduced percolation threshold: a comparative study on the preparation method

Cellulose nanocrystal (CNC)-reinforced poly(butylene adipate-co-terephthalate) (PBAT) nanocomposites with CNC contents of 1, 3, and 5 wt% were prepared through either solution casting or dilution of a PBAT/CNC masterbatch through melt mixing. The efficiency of these preparation approaches on CNC dispersion quality was examined using transmission electron microscopy and rheological analysis. It was found that solution-casted nanocomposites possessed a much finer CNC dispersion, while melt mixing could cause the formation of CNC agglomerates. In the nanocomposites, the rheological percolation threshold through small-amplitude oscillatory shear experiments was determined to be around 2.18 and 3.15 wt% CNC, respectively. The PBAT melt crystallization was also promoted with CNC regardless of the preparation method. The oxygen permeability of PBAT remarkably reduced with the CNC incorporation, specifically in the solution-casted nanocomposites with finer CNC dispersion. The thermal degradation, thermomechanical, and mechanical properties of the nanocomposites were also compared although no significant differences were observed.

Rheological measurement of the nonlinear viscoelasticity of the ABS polymer and numerical simulation of thermoforming process

The thickness distribution of thermoformed products is greatly affected by the viscoelastic behavior of the extruded polymer sheet. In this work, linear and nonlinear rheological experiments are carried out to characterize the viscoelastic properties of acrylonitrile-butadiene-styrene sheets under thermoforming conditions including a wide range of temperatures, strains, and strain rates. First, aspects of linear viscoelasticity such as the storage modulus and loss modulus are measured by small-amplitude oscillatory shear experiments. The discrete relaxation spectra and the Williams-Landel-Ferry parameters are obtained from the constructed linear master curves. Then, nonlinear time-dependent extensional viscosity is measured by uniaxial extensional experiments. The parameters of the damping function are evaluated using an optimization method. In addition, the effect of the orientation of the polymer is analyzed. The uniaxial extensional stress and viscosity in the extruder direction demonstrate higher resistance against tearing and extreme thickness reduction during processing. Finally, the linear and nonlinear input parameters for the numerical simulation are prepared. Numerical simulations are performed using the Wagner model with the obtained nonlinear viscoelasticity. The thickness distribution in thermoformed ABS sheets, obtained numerically, shows good agreement with the experimentally obtained values.

Rheological Properties and Age-Related Changes of the Human Vitreous Humor.

The vitreous humor is a fragile, transparent hydrogel situated between the lens and the retina, occupying 80% of the eye's volume. Due to its viscoelastic behavior, the vitreous serves as a mechanical damper for the eye, absorbing impacts, and protecting the lens and retina. The vitreous liquefies with age, which compromises its function as a shock absorber and causes complications including retinal detachment, macular holes, and vitreous hemorrhage. Studies on the viscoelastic properties of the vitreous have been limited. Rheological testing of the vitreous has commonly been done on non-primate mammalian species. Human vitreous rheological properties have been previously reported; however, various measurement techniques were used, resulting in data that differed by orders of magnitude. Shear rheometry is commonly used to characterize soft tissues and hydrogels such as the vitreous humor. However, no human vitreous rheological data have been reported using this technique, preventing direct comparison to other published work. Additionally, no age-related changes in the mechanical properties of the human vitreous humor have been reported. Human vitreous samples (n = 39, aged 62 ± 15 years) were tested using a shear rheometer. Small amplitude oscillatory shear and creep experiments were performed. The linear viscoelastic region of the human vitreous was found to be below 1% strain. The solid phase of the old human vitreous was found to be stiffer than the young human vitreous and the porcine vitreous. The stiffness of the human vitreous gel also appeared to be positively correlated with age. Vitreous dehydration due to a decrease in hyaluronic acid concentration with age was proposed to cause the stiffening of the solid phase of the vitreous gel. Vitreous liquefaction, therefore, might be characterized as a simultaneous increase in liquid volume and localized stiffening of the vitreous gel. The phase separation of the vitreous humor with age has been hypothesized as the cause of many vitreous-related complications. This study provides viscoelastic properties and age-related changes of the human vitreous humor, which will aid in the design of biomimetic vitreous substitutes, enhancement in analyzing intravitreal transport of therapeutics, and understanding the pathological conditions of the vitreous humor.

Effect of Shear Flow on Crystallization of Sydiotactic Polypropylene/Clay Composites

The high sensitivity of crystallization to shear flow is a subject of great research interest the last several years. A set of syndiotactic polypropylene/clay composite samples were used to examine the effect of shear flow on crystallization kinetics. This phenomenon alters both processing and material final properties. In the present work, the effects of clay contents and shear flow on the rate of flow induced crystallization were investigated using rheological technique. Small amplitude oscillatory shear experiments were performed using advanced rheometric expansion system (ARES). The crystallization rate is found to alter by both shear and clay contents in the polymer composites.

Solid State Viscoelastic Properties, Morphological and Melt Rheological Studies on PLA/TPU/POSS Nanocomposites

ABSTRACTEffects of trifluoropropyl-substituted polyhedral oligomeric Silsesquioxane (POSS), on the morphological, rheological and dynamic mechanical properties of a series of poly(lactic acid)(PLA)/thermoplastic polyurethane (TPU) blends were explored, thoroughly. Microscopic techniques including scanning electron microscope (SEM) and transmission electron microscope (TEM) utilized in conjunction with viscosity measurements to explain morphological dissimilarities between different samples. A remarkable morphological refinement was observed upon addition of POSS into the 50/50 PLA/TPU blend. This morphological change was detected by means of frequency sweep rheological experiments, where the shoulder-like plateau appears as a result of increase in the contribution from the interfacial component of elasticity in the enhancement of storage modulus. Based on the results of the dynamic time sweep small amplitude oscillatory shear (SAOS) experiments, a scaling relation was proposed to quantify the kinetics of phase separation and the associate time evolution of elasticity. It turned out that POSS particles can slow down the rate of morphological coarsening up to the 50%. Using dynamic mechanical thermal analysis (DMTA) and rheological experiments, the differences in the rate of undergoing dynamics in all the length scales, starting from segmental up to the chain level, were compared for various compositions and the discrepancies were fully described based on the dissimilarities in the entanglement densities, combinatorial effects of soft and hard segments of TPU, lubricating role of POSS particles, crystallinity, and morphological characteristics of samples.

A general method for obtaining diffusion coefficients by inversion of measured torque from diffusion experiments under small amplitude oscillatory shear

A numerical approach based on Tikhonov regularization is developed to invert torque curves from time-dependent small amplitude oscillatory shear (SAOS) experiments in which diffusion occurs to determine the diffusion coefficient. Diffusion of a solvent into a polymer melt for example causes the measured torque to decrease over time and is thus dependent on diffusion kinetics and the concentration profile. Our numerical approach provides a general method for retrieving local viscosity profiles during diffusion with reasonable accuracy, depending only on the linear viscoelastic constitutive equation and a general power law dependency of the diffusion process on time. This approach also allows us to identify the type of diffusion (Fickian, pseudo-Fickian, anomalous, and glassy) and estimate the diffusion coefficient without the a priori identification of a specific diffusion model. Retrieving local viscosity profiles from torque measurements in the presence of a concentration gradient is an ill-posed problem of the second type and requires Tikhonov regularization. The robustness of our approach is demonstrated using a number of virtual experiments, with data sets from Fickian and non-Fickian theoretical concentration and torque profiles as well as real experimental data.

Influence of the molar masses on compatibilization mechanism induced by two block copolymers in PMMA/PS blends

The compatibilization mechanism of poly(methylmethacrylate) (PMMA)/polystyrene (PS) blends induced by PMMA-b-PS block copolymers of different molar masses (30 and 104 kg/mol) was studied. The blend morphologies with and without copolymers were observed by scanning electron microscopy. The rheological behavior was studied performing small amplitude oscillatory shear experiments. The experimental results were compared to Palierne's model predictions. Shear induced coalescence tests were also conducted. Contrary to what was expected, adding block copolymers did not result in a refinement of the droplet size. However, it induced Marangoni stresses, a decrease in interfacial tension and an inhibition of coalescence of the dispersed phase. During coalescence tests, a decrease in the relaxation time due to Marangoni stresses with time was revealed. This interesting behavior contradicts previous works on the subject, and is believed to be due to a migration of block copolymers to the interface during the tests rather than droplets' coalescence. As such, the morphology was explained by the fact that block copolymers are not entirely at the interface initially. Also, the block copolymer with a higher molecular mass was shown more efficient at inhibiting coalescence, indicating that the compatibilization mechanism is a combination of Marangoni stresses and steric hindrance.

Properties and phase structure of melt-processed PLA/PMMA blends

This study examines the rheological, mechanical and thermal behavior of Poly(lactic acid)/Poly(methyl methacrylate) (PLA/PMMA) blends and takes a look at the phase structure evolution during their melt processing. Semi-crystalline or amorphous PLA grades were combined with PMMA of different molecular weight to prepare the blends. The rheological properties and phase structure was first assessed using small-amplitude oscillatory shear experiments. The blends were injection molded into bars and characterized in terms of their tensile properties and of their dynamic mechanical behavior. Differential scanning calorimetry was also used to study the miscibility and crystallization behavior of prepared blends. Tensile properties of the blends nearly followed a linear mixing rule with no detrimental effect that could have been associated with an uncompatibilized interface. However, dynamic mechanical analysis and calorimetric experiments showed that some phase separation was present in the molded parts. Nevertheless, a single Tg was found if sufficient time was given in quiescent conditions to achieve miscibility. The Gordon-Taylor equation was used to assess the polymer interactions, suggesting that miscibility is the thermodynamically stable state. The ability of PLA to crystallize was strongly restricted by the presence of PMMA and little or no crystallinity development was possible in the blends with more than 30% of PMMA. Results showed an interesting potential of these blends from an application point of view, whether they are phase separated or not.

Analysis of network formation and long-term stability in silica nanoparticle stabilized emulsions.

Emulsions are widely used in industrial applications, including in food sciences, cosmetics, and enhanced oil recovery. For these industries, an in depth understanding of the stability and rheological properties of emulsions under both static and dynamic conditions is vital to their successful application. Presented here is a thorough assessment of a model nanoparticle (NP) stabilized dodecane-in-water emulsion as a route to improved understanding of the relationship between NP properties, microstructure and droplet-droplet interactions on the stability and rheological properties of emulsions. Emulsions are obtained here with low NP loadings without the need for added electrolyte through the use of an optimized silica NP (SNP) surface modification procedure. The prepared emulsions were characterized via optical microscopy, cryo-scanning electron microscopy (cryo-SEM), zeta potential analysis and laser scanning confocal microscopy (LSCM), enabling quantification of the emulsion droplet size, SNP interfacial coverage/morphology and surface charge. The correlation of these properties with the rheology of the emulsions is investigated through small amplitude oscillatory shear experiments which provide significant insight into the origins of the emulsions' rheological behavior and their stability. In addition, long-term stability, droplet-droplet network formation and microstructural evolution are found to be readily detectable shortly after preparation through measured progression of the emulsion's rheological properties.

Thermo-Mechanical Properties of Soft Candy: Application of Time-Temperature Superposition to Mimic Response at High Deformation Rates

Soft candy primarily consists of an amorphous sugar matrix with highly adhesive and cohesive characteristics, which is generated by rapid cooling of a supersaturated sugar solution. The integration of fondant in soft candy leads to a partial recrystallization of the amorphous sugar so that the dispersed sugar crystals disrupt the continuous amorphous phase; this lowers cohesiveness, and creates a short texture that is responsible for a more brittle fracture. Final processing (e.g., cutting and packaging) is usually done at temperatures between 25 and 45 °C and short time scale. This study analyzed the effects of temperature and time scale on thermo-mechanical properties of different types of soft candy. The application of time-temperature superposition principle on small amplitude oscillatory shear experiments resulted in master curves that covered a frequency window up to 105 rad/s, hence a time scale that is relevant in rapid processing. The respective shift factors depend on material properties, and a main factor of influence is the presence of a crystalline phase. Simple penetration and tensile tests give additional information on material behavior, especially with respect to effects of temperature on adhesiveness and cohesiveness. The results of the study provide support for further optimizing soft candy formulations to ensure rapid and undisturbed processing.

Strain accumulation in bituminous binders under repeated creep-recovery loading predicted from small-amplitude oscillatory shear (SAOS) experiments

The creep-recovery (CR) test starts out with a period of shearing at constant stress (creep) and is followed by a period of zero-shear stress where some of the accumulated shear strain gets reversed. Linear viscoelasticity (LVE) allows one to predict the strain response to repeated creep-recovery (RCR) loading from measured small-amplitude oscillatory shear (SAOS) data. Only the relaxation and retardation time spectra of a material need to be known and these can be determined from SAOS data. In an application of the Boltzmann superposition principle (BSP), the strain response to RCR loading can be obtained as a linear superposition of the strain response to many single creep-recovery tests. SAOS and RCR data were collected for several unmodified and modified bituminous binders, and the measured and predicted RCR responses were compared. Generally good agreement was found between the measured and predicted strain accumulation under RCR loading. However, in the case of modified binders, the strain accumulation was slightly overestimated (≤20% relative error) due to the insufficient SAOS information at long relaxation times. Our analysis also demonstrates that the evolution in the strain response under RCR loading, caused by incomplete recovery, can be reasonably well predicted by the presented methodology. It was also shown that the outlined modeling framework can be used, as a first approximation, to estimate the rutting resistance of bituminous binders by predicting the values of the Multiple Stress Creep Recovery (MSCR) test parameters.

Rheological properties of synthetic mucus for airway clearance.

In this work, a complete rheological characterization of bronchial mucus simulants based on the composition proposed by Zahm et al. (Eur Respir J 1991; 4:311-315) is presented. Dynamic small amplitude oscillatory shear (SAOS) experiments, steady state (SS) flow measurements and three intervals thixotropy tests (3ITT), are carried out to investigate the global rheological complexities of simulants (viscoelasticity, viscoplasticity, shear-thinning, and thixotropy) as a function of scleroglucan concentrations (0.5-2 wt %) and under temperatures of 20 and 37°C. SAOS measurements show that the limit of the linear viscoelastic range as well as the elasticity both increase with increasing sclerogucan concentrations. Depending on the sollicitation frequency, the 0.5 wt % gel response is either liquid-like or solid-like, whereas more concentrated gels show a solid-like response over the whole frequency range. The temperature dependence of gels response is negligible in the 20-37°C range. The Herschel-Bulkley (HB) model is chosen to fit the SS flow curve of simulants. The evolution of HB parameters versus polymer concentration show that both shear-thinning and viscoplasticity increase with increasing concentrations. 3ITTs allow calculation of recovery thixotropic times after shearings at 100 or 1.6 s-1 . Empiric correlations are proposed to quantify the effect of polymer concentration on rheological parameters of mucus simulants. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 386-396, 2018.

Rheology and morphology study of immiscible linear low‐density polyethylene/poly(lactic acid) blends filled with nanosilica particles

ABSTRACTThe objectives of this study are to investigate the effect of silica nanoparticles on the morphology and rheological behavior of immiscible linear low‐density polyethylene/poly(lactic acid) (LLDPE/PLA) blends. Melt blending method is applied to prepare the blends and their nanocomposites. Scanning electron microscope and parallel plate rheometer were used to investigate morphology and rheological behavior of the blend nanocomposites. Scanning electron microscope results demonstrated a significant change in morphology behavior by incorporation of silica nanoparticles. A significant reduction in the PLA droplet for LLDPE/PLA (75/25) with 8 wt % silica was observed. The rheological studies illustrated that for all samples storage modulus and complex viscosity of blend nanocomposites are higher than neat blends. Finally, melt rigidity of blend nanocomposites was estimated by measurement of rheological properties using a rotational rheometer through small amplitude oscillatory shear experiments. As a result, through the shear data, a high value quantity as a criteria for melt rigidity is obtained for the LLDPE/PLA (75/25) with 8 wt % silica in comparing to the other samples. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45526.