Fourier Transform Rheology Research Articles

Non-linear mechanical behaviour of thermoplastic elastomeric materials and its vulcanizate under tension/tension fatigue deformation by fourier transform rheological studies

Fourier transform (FT) rheology opens up novel frontiers in understanding non-linear mechanical behaviours of polymeric materials under sustained long-term dynamic load. The prediction of the exact point of appearance of a crack in a sample under dynamic mechanical strains of large amplitude and the fatigue analysis has been made possible to such degrees of precision, previously not possible through conventional rheological and mechanical analysis. In this work, the fatigue behaviour of a thermoplastic elastomeric material (TPE) and a thermoplastic vulcanizate (TPV) from thermoplastic polyurethane (TPU) and epichlorohydrin− ethylene oxide−allyl glycidyl ether (GECO) rubber is investigated by Fourier transform studies under oscillatory strain-controlled tensional test to understand the linear and non-linear mechanical behaviour. Fatigue analysis is performed through the fingerprint harmonics of the material’s stress response, i.e., the second and third harmonics, ( I 2/1 and I 3/1) to establish the stress nonlinearity, asymmetry, and the formation of macrocracks. Furthermore, these higher harmonics are fitted with the Neo-Hooke and Mooney-Rivlin model to fundamentally understand the mode of fatigue failure, and a close agreement between theoretical fitting and experimental outcomes is established. Strain-life curves were utilized for the thorough investigation of the fatigue behaviour of the specimens and more than 9-fold enhancement in the strain life of the TPV is observed over TPU at a strain amplitude of ∼1.05 indicating an increasing ductility. Finally, the necessity of FT rheology was further emphasised as it is observed that I 2/1 and I 3/1 harmonics are more sensitive towards fatigue response as compared to the storage modulus and the complex modulus. Henceforth, the FT rheology analysis has enabled the current study to efficiently establish the ductility of each individual specimens and for prediction of the dynamic service lifetime of the developed materials.

Nonlinear viscoelasticity of Melaleuca alternifolia essential oil Pickering emulsion stabilized with cellulose nanofibrils

Pickering emulsions are suitable technological approaches to stabilize the bioactive compounds of essential oils (EOs) with economic interests for the pharmaceutical, cosmetic and food industries using atoxic and renewable stabilizers, such as cellulose nanostructures. The Melaleuca alternifolia essential oil (MaEO) is recognized for its pronounced antimicrobial performance, which has attracted your interest in developing eco-friendly antiseptic products. In this contribution, we report the nonlinear viscoelasticity behavior of MaEO-in-water Pickering emulsions stabilized by cellulose nanofibrils (CNF) using Large Amplitude Oscillatory Shear (LAOS) tests. The rheological characterizations by Fourier Transform (FT) rheology spectroscopy and Lissajous plots enabled the correlation of the viscous and elastic behaviors with the physical processes involving the deformation of the emulsion. Also, the internal structure of the emulsion was elucidated by fluorescence optical microscopy. Several findings relative to the effects of the shear deformation amplitude over the nonlinear viscoelasticity of the emulsified system are reported here, which are essential to the industrial processes used to develop technological products.

Nonlinear oscillatory rheology of aqueous suspensions of cellulose nanocrystals and nanofibrils

In this work, the nonlinear rheological behavior of aqueous suspensions composed of two typical nanocellulose [rod-like cellulose nanocrystals (CNCs) and filamentous cellulose nanofibrils (CNFs)] was examined and compared by using various large-amplitude oscillatory shear (LAOS) analysis methods, such as Fourier-transform rheology, stress decomposition, Chebyshev polynomials, and the sequence of physical processes. From our analysis, the nonlinear rheological parameters of higher harmonics, dissipation ratio, strain hardening ratio, shear thickening ratio, transient modulus, and cage modulus were obtained and quantitatively analyzed. CNCs tend to assemble to form anisotropic structures in an aqueous medium while the CNFs are entangled to form gels. The CNF suspensions demonstrated a significant viscous modulus overshoot and had stronger yield stresses, but the yield of CNC suspensions was more ductile. In the case of low concentrations, the CNF suspensions demonstrated stronger intracycle shear thickening behavior in medium-amplitude oscillatory shear region and lower dissipation ratios at small strain amplitudes. Although both nanocellulose suspensions revealed the existence of four intracycle rheological transition processes (viscoplastic deformation, structural recovery, early-stage yielding, and late-stage yielding), the CNF suspensions exhibited a stronger structural recovery ability. Larger strain amplitudes did not invariably result in a broader range of intracycle rheological transitions, which are also affected by the excitation frequency. The application of the various LAOS analysis methods provided valuable intracycle nonlinear rheological insights into nanocellulose suspensions, which are of great importance for enhancing their industrial perspectives.

Rheo-PIV study of slip effects on oscillatory shear measurements of a yield-stress fluid

The influence of apparent slip on oscillatory shear measurements of a viscoplastic microgel [0.6 wt. % of poly(acrylic acid)] is analyzed by Couette and parallel-plate rheometry and particle image velocimetry (Rheo-PIV). We first provide direct evidence of a critical shear stress for the onset of slip of the microgel under oscillatory (σos) and nonoscillatory measurements (σs). Afterward, we describe the effect of slip on oscillatory measurements via waveforms, Bowditch–Lissajous curves, Fourier transform (FT) rheology, PIV, and as a sequence of physical processes (SPP). The effect of slip is mainly observed at low oscillating frequencies. For amplitudes of the oscillating stresses σ0 ≤ σos, the microgel exhibits linear viscoelastic behavior with in-phase strain response. For σos < σ0 ≤ yield stress (σy), slip introduces a phase shift in the strain response with a forward-tilted waveform and “mango” shape Bowditch–Lissajous curves. Meanwhile, FT rheology shows negligible even harmonics. The strain measured by the rheometer does not match the true strain determined by PIV in the presence of slip, resulting in waveforms that depend on how the displacement distribution is interpreted. This result indicates a break in the symmetry of the flow, that is, the microgel response no longer follows the imposed oscillation, which makes any attempt to correct oscillatory data for slip complex. This behavior arises from recoil of the slipping microgel after reaching its maximum displacement in a cycle. Finally, we provide an overall picture of the kinematics of the process of yielding in the presence of slip as an SPP.

Interplay between yielding, 'recovery', and strength of yield stress fluids for direct ink writing: new insights from oscillatory rheology.

Formulation design and rheology are critical for successful manufacturing via direct ink writing (DIW), thus linking rheology and printability is a growing area of research amongst the DIW and rheology communities. This work provides an extensive rheological investigation into the material strength, yielding and 'recovery' properties of graphite (Gr)-hydrogel based formulations. Using state-of-the-art Large Amplitude Oscillatory Shear (LAOS) techniques, Fourier Transform (FT) rheology and sequence of physical process (SPP) analysis, and 3-step 'recovery' tests we provide new insights on the yielding phenomenon, energy transitions and microstructural changes that the formulations undergo. The insights from the rheology experiments are combined with in situ and continuous monitoring during the printing process. From these analyses, we select rheological metrics or descriptors to quantify flowability, recoverability, and material strength. There is a threshold concentration of Gr powders (30 wt%) at which there is a shift in the yielding process. Below this threshold (for the F127 hydrogel and mixtures with low Gr content), perfect plastic dissipation ratio (ϕ) values are close to 0 in the LVR and then steeply increase to close to 1 after the cross-over in a narrow strain (and stress) space. As Gr concentration increases, and print quality gets worse, ϕ values consistently increase in the LVR and at any given γ0, evidencing an increased energy dissipation throughout the flow transition region. Lissajous-Bowditch curves and SPP Cole-Cole plots illustrate these trends. The extent of the 'recovery' (quantified by the mutation time, λI, and the storage modulus 'recovered' after large deformations ) is also directly related to Gr content, with higher loading resulting in lesser recovery. Our findings provide a comprehensive set of metrics to characterise complex (yield stress) fluids for DIW using three property maps, one for each stage: flowability or yielding process, recoverability and material strength. The results demonstrate that considering these three maps holistically provides insightful trends to guide formulation design and assess performance in DIW.

Linear and nonlinear viscoelasticity of edible o/w emulsions used as saturated fat replacers

A recent strategy for controlling saturated fat intake consists on the design of vegetable oil-based emulsions. The aim was to characterize the linear and nonlinear viscoelastic properties of o/w emulsions formulated with two types of cellulose: MX (methylcellulose, MC) and F4M (hydroxypropyl methylcellulose, HPMC). The emulsions were characterized by steady flow curves and frequency sweeps in SAOS (Small Amplitude Oscillatory Shear) regime. In order to evaluate linear and non-linear response, strain sweeps were performed from 0.01 to 1000% strain amplitude at different frequencies (0.1, 1 and 5 Hz). Fourier Transform rheology and orthogonal stress decomposition were applied and LAOS (Large Amplitude Oscillatory Shear) parameters (G’M, G’L, ηM’, ηL’, S and T) were analysed. The type of cellulose ether significantly affected both flow behaviour and internal structure of the samples. MX emulsion presented greater consistency at rest and higher gel strength in SAOS regime with a lower frequency dependence than F4M emulsion. However, both emulsions presented similar properties at large deformations, showing shear thinning and strain stiffening behaviour. Nonlinear viscoelastic analysis allows to improve the textural characterization of emulsions, providing complementary useful information for establishing the most suitable formulation in experimental conditions closer to real applications and processes.

An investigation into the nonlinear rheological behavior of modified asphalt binders using large amplitude oscillatory shear rheology

ABSTRACT Asphalt binders have been studied extensively with respect to their linear viscoelastic properties. From these properties, performance metrics have been derived and used for specification purposes. However, these materials are used in asphalt concrete pavements where they may experience time-dependent loads in the nonlinear regime. In the past, the vast majority of asphalt binders exhibited strong correlations between their linear and nonlinear properties and so despite this mismatch in characterization and the actual use phase domains, a system based on linear properties could be reliably deployed. More recently though, novel binders and additives have been introduced with differing relationships between linear and nonlinear behaviors. As such there is a need to characterize the asphalt binder response under large strains and use specifications that more explicitly account for the binder nonlinearity. Here, an attempt has been made to characterize the nonlinear rheological properties of asphalt binder using large amplitude oscillatory shear. The response of a single terminal blend, crumb rubber modified binder under large strains is analyzed using Lissajous-Bowditch plots while the contribution of higher harmonics is evaluated using Fourier-transform rheology. Finally, the elastic and viscous contributions are obtained using stress decomposition to an orthogonal set of Chebyshev polynomials. It is found that the relative nonlinearity increases with increasing strain and frequency under the tested conditions. The asphalt binder evaluated in this study predominantly exhibits shear thinning and either strain stiffening or softening behavior depending upon the test conditions. The applicability of time-temperature superposition in the nonlinear regime for asphalt binders is also evaluated.

Isotropic Gels of Cellulose Nanocrystals Grafted with Dialkyl Groups: Influence of Surface Group Topology from Nonlinear Oscillatory Shear

Attractive (non-self-assembling) aqueous cellulose nanocrystal (CNC) suspensions were topologically tailored into isotropic gels through the surface grafting of dialkyl groups. We thus focus on the influence of CNC concentration, including for pristine CNC, surface linker branching, branching degree, and the influence of side group size and branch-on-branch surface-grafted groups. The resulting mobility and strength of interaction in particle-particle interaction mediated by the surface groups was investigated from a rheological point of view. The emphasis is on nonlinear material parameters from Fourier-transform rheology and stress decomposition analysis. The results show that nonlinear material parameters are more sensitive than linear viscoelastic parameters to the onset of weakly interconnected networks in pristine CNC isotropic suspensions. All surface-modified CNC suspensions resulted in isotropic gels. The nonlinear material parameters were found to be broadly sensitive to CNC concentration, branching, degree of branching and surface-grafted linkers' length. However, the length of the grafted chains and the degree of branching were the primary factors influencing the nonlinear material response. Furthermore, the results showed evidence of two strain amplitude ranges with distinct nonlinear signatures that could be attributed to the disruption of weak network connection points and to distortions of more dense (aggregate) network regions, respectively.

Fourier-transform rheology and printability maps of complex fluids for three-dimensional printing

Direct ink writing (DIW) is a three-dimensional (3D) printing technique exploited by researchers working in fields from scaffolds for energy applications to bioprinting. DIW's main strength is that it enables shaping advanced materials, if these materials can be formulated into complex fluids that meet the demands of the printing process. They must be extremely shear thinning soft solids, able to flow through narrow nozzles, recovering their structure upon deposition and retaining the predesigned 3D shape. Formulation design and rheology are critical, but these aspects can be overlooked due to the high specialization required. This work provides insight on the rheology and printability of complex yield-stress fluids through the study of linear and nonlinear behaviors using large-amplitude oscillatory shear rheology. We refine previous protocols and develop tools to understand the behaviors of formulations for DIW. We apply an existing mathematical framework to a library of carbon-based formulations for energy applications. Fourier transform analysis enables quantifying the onset and rising of higher harmonic contributions. Quantitative comparisons between different formulations are established using 3D harmonics maps, stress–strain plots, and material measures of nonlinearities [Fourier and Chebyshev coefficients, elastic moduli (GM′, GL′), and dimensionless index of nonlinearity (S)]. 3D Lissajous plots provide a qualitative alternative to interpretate the yielding transition. We create Ashby-type printability maps to guide formulation design and elucidate that non-printable formulations show distinctive features. This insight on yield-stress fluids for DIW is relevant to other applications and technologies: drilling fluids, gels, colloids, and foods.

Quantitative investigation on the nonlinear viscoelasticity of magnetorheological gel under large amplitude oscillatory shear

Magnetorheological gel (MRG) is a kind of magneto-sensitive smart composite whose nonlinear rheological behavior is highly controllable by external magnetic fields. For filling the gap that most publications studied the nonlinear property of MR materials in a qualitative manner, this work adopts a quantitative analysis method, called Fourier-transform rheology (FTR), to investigate the nonlinear viscoelasticity of MRG under large amplitude oscillatory shear (LAOS) tests. The influences of magnetic field, strain amplitude and frequency on the nonlinearity of MRG are thoroughly discussed. Results indicate that MRG, under a relative smaller magnetic field, appears higher degree of nonlinearity in the high-frequency region. The magneto-mechanical coupling mechanism of microstructures in MRG is also proposed to explain the various nonlinear phenomena under different loading conditions. Furthermore, for remedy the limitation that higher-order harmonics in FTR lack of clear physical meanings, a geometrical nonlinear parameter, S factor, is utilized to disclose the intra-cycle strain stiffening characteristic of MRG. The effects of strain amplitude, frequency and magnetic field on S factor are similar with that on the third-order harmonic in FTR. Moreover, the energy dissipation density is calculated based on Lissajous curve (i.e. hysteretic stress-strain loop) to characterize the damping property or capacity to dissipate energy of MRG. It is found that frequency only has a great effect on energy dissipation density of MRG under relatively large strain amplitude.

Phase transitions of cellulose nanocrystal suspensions from nonlinear oscillatory shear

Cellulose nanocrystals (CNCs) self-assemble in water suspensions into liquid crystalline assemblies. Here, we elucidate the microstructural changes associated with nonlinear deformations in (2–9 wt%) CNC suspensions through nonlinear rheological analysis, that was performed in parallel with coupled rheology—polarized light imaging. We show that nonlinear material parameters from Fourier-transform rheology and stress decomposition are sensitive to all CNC phases investigated, i.e. isotropic, biphasic and liquid crystalline. This is in contrast to steady shear and linear viscoelastic dynamic moduli where the three-region behavior and weak strain overshoot cannot distinguish between biphasic and liquid crystalline phases. Thus, the inter-cycle and intra-cycle nonlinear parameters investigated are a more sensitive approach to relate rheological measurements to CNC phase behavior.

Rheological properties and fractal-rheology analysis of peanut protein isolate suspension

This study focuses on the non-linear rheological property and microstructure of peanut protein isolate (PPI) aggregation suspension. The impact of higher harmonics (I3 and I5) on fundamental stress wave during large amplitude oscillatory shear test was studied. Rheological test show that storage modulus G′ and loss modulus G″ increased with increasing PPI concentration. The non-linear viscoelastic properties of PPI suspension with different concentration were investigated. Using confocal laser-scanning microscopy method, this research explored the microstructure of PPI suspension as well as the fractal dimensions. The new critical strain indirect method combined with Wu-Morbidelli model to calculate the fractal dimension (2.9225) is very close to the actual fractal dimension (2.9206). Fourier Transform Rheology was adopted to get the new critical strain for fractal dimension calculation, which was proved to be feasible. Keywords: peanut protein isolate suspension, rheological property, microstructure, fractal analysis DOI: 10.25165/j.ijabe.20201306.5717 Citation: Bi C H, Chi S Y, Hua Z, Li D, Huang Z G, Liu Y. Rheological properties and fractal-rheology analysis of peanut protein isolate suspension. Int J Agric & Biol Eng, 2020; 13(6): 220–226.

Rheological and structural properties of sodium caseinate as influenced by locust bean gum and κ-carrageenan

The interactions between sodium caseinate and polysaccharide were investigated by choosing both neutral (locust bean gum) and anionic polysaccharides (κ-carrageenan). The linear and non-linear rheological properties, ζ-potential and structures of the sodium caseinate/gum mixtures were evaluated. The mixtures all displayed shear-thinning phenomenon, and the increase of either locust bean gum or κ-carrageenan content led to the increase of storage (G′) and loss (G″) moduli. The large amplitude oscillation shear (LAOS) test and Fourier-transform have been successfully used to detect the slight rheological differences caused by microstructure changes. Increasing levels of κ-carrageenan led to critical strain decreased of the mixture, but not for locust bean gum. The sodium caseinate/locust bean gum mixtures behaved as “hard gel”, while the sodium caseinate/κ-carrageenan mixtures behaved as “soft gel” in Fourier-transform rheology. Changes in viscoelasticity under large strain were illustrated using elastic and viscous Lissajous curves, which were correlated to the microstructural change within the network of the mixtures. The zeta-potential values were significantly decreased in the presence of κ-carrageenan, while the addition of locust bean gum had no significant influence. Phase separation was found more dominant to change the structure than the protein network formation in the sodium caseinate/locust bean gum mixtures. However, protein network formation was the factor to dominate the structure forming of sodium caseinate/κ-carrageenan mixtures with electrostatic forces and hydrogen bonding.

Rheological properties of soy protein isolate – carboxymethyl flaxseed gum mixed dispersions under large amplitude oscillatory shear

Abstract Carboxymethyl flaxseed gum (CMFG) is developed in our laboratory by modifying flaxseed gun through carboxymethylation. The aim of this study is to reveal the rheological properties of soy protein isolate – carboxymethyl flaxseed gum (SPI-CMFG) mixed dispersion in realistic processing conditions by conducting large amplitude oscillatory shear (LAOS) test, with consideration of concentration and degree of substitution (DS) of CMFG. Results showed that increasing CMFG concentration significantly increased storage moduli (Gʹ), loss moduli (Gʺ), and the apparent viscosity of all SPI-CMFG mixed dispersions. LAOS test illustrated that the dispersions experienced a transition from LAOS type IV to type III after increasing the concentration of CMFG, while the behavior converted from LAOS type I to type III by increasing DS. Fourier transform rheology (FTR) exhibited that increasing the concentration or DS of CMFG both induced a conversion from “soft sphere” to “hard sphere” behavior. The strain-stiffening ratio S and the shear-thickening ratio T demonstrated, that all SPI-CMFG dispersions experienced a similar conversion from strain stiffening to strain softening, and from shear thinning to shear thickening behaviors by increasing the concentration of CMFG. Nevertheless, the mixed dispersions presented shear thickening behaviors when DS was no more than 0.520 in the whole range of strain, while a conversion from shear thinning to shear thickening behavior occurred, when DS reached at 0.755 and 0.973.

Nonlinear \u201coddities\u201d at the percolation of 3D hierarchical graphene polymer nanocomposites

The nonlinear rheology of a novel 3D hierarchical graphene polymer nanocomposites was investigated in this study. Based on an isotactic polypropylene, the nanocomposites were prepared using simple melt mixing, which is an industrially relevant and scalable technique. The novel nanocomposites stand out as having an electrical percolation threshold (≈0.94 wt%) comparable to solution mixing graphene-based polymer nanocomposites. Their nonlinear flow behavior was investigated in oscillatory shear via Fourier-transform (FT) rheology and Chebyshev polynomial decomposition. It was shown that in addition to an increase in the magnitude of nonlinearities with filler concentration, the electrical percolation threshold corresponds to a unique nonlinear rheological signature. Thus, in dynamic strain sweep tests, the nonlinearities are dependent on the applied angular frequency, potentially detecting the emergence of a weakly connected network that is being disrupted by the flow. This is valid for both the third relative higher harmonic from Fourier-transform rheology, I3/1, as well as the third relative viscous, v3/1, Chebyshev coefficient. The angular frequency dependency comprised non-quadratic scaling in I3/1 with the applied strain amplitude and a sign change in v3/1. The development of the nonlinear signatures was monitored up to concentrations in the conductor region to reveal the influence of a more robust percolated network.

Nonlinear Viscoelastic Response of Crumb Rubber Modified Asphalt Binder Under Large Strains

Agencies have been increasing their use of polymer modified asphalt binders in recent years to address performance issues and lengthen the useful life of their pavements. When deployed these materials likely experience strain levels exceeding their linear viscoelastic (LVE) limits. The same situation exists in non-polymer modified asphalt binders as well, but the effect may be more pronounced in polymer modified systems because of their bi-phasic nature. In this study, terminally blended crumb rubber (CR-TB) modified asphalt is studied to understand and quantify the nonlinear viscoelastic response under large strains. The CR-TB binders are extensively used in pavements subjected to high vehicular loads and extreme climatic conditions; thereby, their response under large strains becomes more critical. The current standard characterization techniques are based on LVE response using small amplitude oscillatory shear rheology only and do not consider the behavior of binders under large strains. In this study, large amplitude oscillatory shear (LAOS) rheology is used as a framework to more thoroughly investigate the complete response of the CR-TB modified asphalt binder under large strains at 30°C, 40°C, 50°C, and 60°C and at the frequencies of 0.5, 1, and 5 Hz. The LAOS response is analyzed using Fourier-transform rheology and the orthogonal stress decomposition method involving Chebyshev polynomial representation. It is found that nonlinearity manifests greatly in this study material as strain levels increase and frequencies decrease. The relative nonlinearity increases with increasing strain amplitude and is more significant towards lower end of the tested temperature range. The CR-TB binder shows strain-stiffening/softening and shear-thinning/thickening behavior depending upon a specific temperature, strain level, and frequency.

Rheological properties and fractal-rheology analysis of peanut protein isolate suspension

This study focuses on the non-linear rheological property and microstructure of peanut protein isolate (PPI) aggregation suspension. The impact of higher harmonics (I3 and I5) on fundamental stress wave during large amplitude oscillatory shear test was studied. Rheological test show that storage modulus G′ and loss modulus G″ increased with increasing PPI concentration. The non-linear viscoelastic properties of PPI suspension with different concentration were investigated. Using confocal laser-scanning microscopy method, this research explored the microstructure of PPI suspension as well as the fractal dimensions. The new critical strain indirect method combined with Wu-Morbidelli model to calculate the fractal dimension (2.9225) is very close to the actual fractal dimension (2.9206). Fourier Transform Rheology was adopted to get the new critical strain for fractal dimension calculation, which was proved to be feasible. Keywords: peanut protein isolate suspension, rheological property, microstructure, fractal analysis DOI: 10.25165/j.ijabe.20201306.5717 Citation: Bi C H, Chi S Y, Hua Z, Li D, Huang Z G, Liu Y. Rheological properties and fractal-rheology analysis of peanut protein isolate suspension. Int J Agric & Biol Eng, 2020; 13(6): 220–226.

Nonlinear material functions under medium amplitude oscillatory shear (MAOS) flow

Dynamic oscillatory shear flow has been widely used to investigate viscoelastic material functions. In particular, small amplitude oscillatory shear (SAOS) tests have become the canonical method for characterizing the linear viscoelastic properties of complex fluids based on strong theoretical background and plenty of experimental results. Recently, there has been increasing interest in the use of large amplitude oscillatory shear (LAOS) tests for the characterization of complex fluids. However, it is difficult to define material functions in LAOS regime due to an infinite number of higher harmonic contributions. For this reason, many recent studies have focused on intrinsic nonlinearities obtained in medium amplitude oscillatory shear (MAOS) regime, which is a subdivision of the full LAOS regime. In this study, we reviewed recent experimental and theoretical results of nonlinear material functions in the MAOS regime, which contain four MAOS moduli (two first-harmonic moduli and two third-harmonic moduli) from Fourier and power series of shear stress, and a nonlinear material function Q0 and its elastic and viscous parts from Fourier-transform rheology (FT rheology). Furthermore, to identify linear-to-nonlinear transitions in stress response of model polystyrene (PS) solutions, we presented Pipkin diagrams in frequency ranges from the rubbery plateau region to the terminal region.

Aging of natural rubber studied via Fourier-transform rheology and double quantum NMR to correlate local chain dynamics with macroscopic mechanical response

Nowadays mainly the linear rheological properties of natural rubber (NR) vulcanizate during aging are studied, even though NR is rheologically nonlinear under most application conditions. Here, the nonlinearity was quantified via Fourier transform rheology (FT-Rheology) using I3/1, the relative intensity of the 3rd harmonic. The crosslink density and the content of defects were investigated by the 1H double quantum nuclear magnetic resonance (DQ-NMR). For aerobic aging at 120 °C, the crosslink density increases, but later turns into a broader mesh size distribution with more defects. Accordingly, the rheological nonlinearity of the material increases in the earlier stage and then decreases. For mechanical aging, the nonlinearity continuously decreases as a function of the fatigue cycle numbers, whereas the local crosslink density of the polymer network remains constant. This behavior can be assigned to the micro-cracks generated along adjacent network defects, which are larger than the detection scale of DQ-NMR. Compared to the linear rheological parameters, storage modulus G′ and loss factor tanδ, I3/1 exhibits higher sensitivity to the aging of crosslinked NR under both high temperature aerobic and mechanical fatigue conditions.

Interfacial Fourier transform shear rheometry of complex fluid interfaces

Nonlinear rheometry of interfaces is very challenging because of the limits of current day instrumentation and the intricate coupling of flows at interfaces and in the bulk. The use of time periodic flows may constitute a first step in addressing this issue. Fourier transform rheology (FTR) measurements with quasi-monolayers at the air-water interface are used in order to assess the suitability of the different devices to investigate nonlinear interfacial shear viscoelasticity. The probe material was a poly (methyl methacrylate) forming a soft glassy interface, whereas complementary measurements were performed with a polystyrene latex suspension forming a predominantly viscous interface at intermediate surface coverages. The obtained data with the magnetic rod rheometer (ISR) were compared against those obtained with the bicone and the double wall ring geometries attached to standard rotational rheometers. In particular, an unexpected appearance of even in addition to odd harmonics is discussed in terms of flow field asymmetry.