Natural mud usually exhibits non-Newtonian rheological behaviors like viscoelasticity, thixotropy and yield stress. The history of each mud sample is also an important factor influencing the rheological behavior, as the state of the clay fabric – for a same composition – is dependent on the shear stresses experienced previously by the sample. Several rheological tests including stress ramp-up, oscillatory frequency sweep and structural recovery tests were performed, in order to analyse the rheological fingerprint of the mud samples collected from two different locations of the Port of Hamburg. The yield stress, storage moduli and structural recovery of mud from the same location was studied as a function of density for two series of samples. One series consisted of samples (“natural samples”) taken in-situ as a function of depth (with increasing density as a function of depth) whereas the other one (“diluted samples”) consisted of samples whereby the density was varied by adding in-situ water to the natural sample having the highest density. Significant differences in rheological characteristics were found between the natural and diluted mud samples, that were attributed to the state/composition of the mud's fabric in each situation but also to the structural rearrangements caused by the preparation of diluted samples.@en

Purpose: Fluid mud layers can be substantial in waterways and they can jeopardise navigation when the ship’s keel comes in its vicinity. The nautical bottom has therefore to be properly characterised. Mud density and yield stress are used as criteria to characterise the nautical bottom. For a decade, measuring these parameters in situ has been a challenging task. The goal of this paper is to compare the parameters obtained from recently developed in situ measuring instruments. Materials and methods: Two vertical profilers (Graviprobe and Rheotune) were used in this study. The Graviprobe measures the undrained shear strength, whereas the Rheotune measures the Bingham yield stress and density of mud layers. Four different locations at the Port of Hamburg were used to test the Rheotune. Bingham yield stresses obtained from Rheotune measurements were compared with the laboratory rheological measurements. The mud layer thicknesses profiled by Graviprobe and Rheotune at the Port of Hamburg and at the Port of Rotterdam were compared. The measurements were also compared with a model that predicts the consolidation of weak mud. Results and discussion: The Rheotune data match well with the laboratory experiments at two of the four tested locations at the Port of Hamburg. For the other two locations, the Rheotune data underestimates the Bingham yield stress, as compared with the laboratory data. The reason for the discrepancy is discussed. The comparison between the Graviprobe’s and Rheotune’s profiles showed that the thickness of the fluid mud layer, found from each device, for all locations, is similar. The in situ density measurements were confirmed by the laboratory experiments. It was found that the standard model for consolidation of mud could reproduce the in situ strength and density measurements as a function of time relatively well. The mismatch between model and experimental data is most probably due to a change in constitutive parameters over time. Conclusions: Our results show that the correlation between density and yield stress measurements, as a function of different measuring equipment, strongly depends on the type of mud. Therefore, a proper calibration should be performed by establishing a reference database for each equipment. In order to decrease the amount of in situ survey, it is also necessary to develop models that can accurately predict the consolidation over time.

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In this work, the effects of chemical pretreatment and different fiber loadings on mechanical properties of the composites at the sub-micron scale were studied through nanoindentation. The composites were prepared by incorporating choline chloride (ChCl) pretreated rice husk waste (RHW) in low-density polyethylene (LDPE) using melt processing, followed by a thermal press technique. Nanoindentation experiments with quasi continuous stiffness mode (QCSM) were performed on the surface of produced composites with varying content of pretreated RHW (i.e., 10, 15, and 20 wt.%). Elastic modulus, hardness, and creep properties of fabricated composites were measured as a function of contact depth. The results confirmed the appreciable changes in hardness, elastic modulus, and creep rate of the composites. Compliance curves indicated that the composite having 20 wt.% of pretreated RHW loading was harder compared to that of the pure LDPE and other composite samples. The values of elastic modulus and hardness of the composite containing 20 wt.% pretreated RHW were increased by 4.1% and 24% as compared to that of the pure LDPE, respectively. The creep rate of 42.65 nm/s and change in depth of 650.42 nm were also noted for the composite with RHW loading of 20 wt.%, which showed the substantial effect of holding time at an applied peak load of 100 mN. We believe that the developed composite could be a promising biodegradable packaging material due to its good tribo-mechanical performance.

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Oil/water emulsions are usually stabilized either by interfacial modification using nanoparticles and surfactants (stated as pickering emulsion or bijels) or by bulk stabilization with the help of low‐molecular‐weight or polymeric gelators (known as bigels) in response to some external stimuli (e.g., pH, temperature). Both these approaches result in different systems that are quite useful for different applications, including catalysis, pharmaceutical and agrochemicals. However, these systems also possess some inherent drawbacks that need to be addressed, like difficulty in fabrication and ensuring the permanent binding of nanoparticles at the oil/water interface, in case of nanoparticles stabilized emulsions (i.e., interfacial stabilization). Similarly, the long‐term stability of the oil/water systems produced by using (hydro/organo) gelators (i.e., bulk stabilization) is a major concern. Here, we show that the oil/water system with improved mechanical and structural properties can be prepared with the synergistic effect of interfacial and bulk stabilization. We achieve this by using nanoparticles to stabilize the oil/water interface and polymeric gelators to stabilize the bulk phases (oil and water). Furthermore, the proposed strategy is extremely adaptable, as the properties of the resultant system can be finely tuned by manipulating different parameters such as nanoparticles content and their surface functionalization, solvent type and its volume fraction, and type and amount of polymeric gelators.

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The characteristics of clayey suspensions, majorly composed of quartz microparticles, in the presence of anionic and cationic polyelectrolytes were investigated using different techniques. A wide range of clay concentrations was used, i.e., from 0.07 to 1000 g/L for different experimental techniques, based on the fact that the clay concentration possible to analyze with selected experimental methods was significantly different. The optimum flocculant to clay ratio was defined as the ratio that gives the fastest initial floc growth by static light scattering or fastest initial settling velocity by settling column experiments. In case of anionic polyelectrolyte, it was observed that the optimum flocculant dose depends on the amount of cations present in the system. For suspensions made with demi-water, a lower optimum flocculant dose (<1 mg/g) than for suspensions prepared in tap water (2.28 mg/g) was observed. At these lower salinities, the supernatant remained turbid in all the experiments and was, therefore, not a good measure for optimal anionic based flocculation. The equilibrium floc size at a given shear rate was found to be independent on the shear history of the floc and only dependent on the current applied shear. This was confirmed by both light scattering and rheological analysis. In case of cationic polyelectrolyte, the optimum flocculant ratio (5–6 mg/g) corresponded to the ratio that gives the lowest electrophoretic mobility for each clay concentration and to the ratio that gives the fastest settling velocity for the highest clay concentrations (12–15 g/L), where static light scattering measurements were not possible. All investigation techniques, therefore, proved to be good indicators for predicting the optimum flocculant to clay ratio. For the lowest concentrations (1.75–8.7 g/L) studied by settling column measurements, the optimum flocculant ratio was observed to increase with decreasing clay concentration, for fixed mixing conditions. The optimum flocculant to clay ratio was not always corresponding to the clearest supernatant and the size of flocs at optimum dosage was dependent on the mixing efficiency. The equilibrium floc size at a given shear rate was found to be dependent on the shear history of the floc and the current applied shear. This was confirmed by both light scattering and rheological analysis.

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Yield stress materials have a wide range of commercial applications. Yet, the suitable way of determining the yield stress values of a given material has been the subject of many studies and debates. Yield stresses are dependent on the material (shear) history and composition, which implies that robust protocols should be developed to study the yield stress dependence on a given parameter. In this study, three natural mud samples from a port having different densities were chosen for analysis. Four different geometries including concentric cylinders (Couette), cone and plate, parallel plates, and vane geometries were used. Our aim was to find the geometry and measurement protocol that best adapted to natural mud samples: the measurement should be reasonably fast and the major changes in sample structure (two-step yielding) should be recorded within the same measurement. Various rheological experiments such as stress sweep, oscillatory amplitude sweep, creep and stress growth tests were tested. Two-step yielding behavior was observed for the mud samples in stress sweep and amplitude sweep tests. The first yield point was linked with the breakage of interconnected network of aggregates/flocs while the second one was attributed to the collapse of aggregates into the smaller flocs or individual particles. Stress sweep tests proved to be practical, time efficient, and reliable tests for measuring yield stress values. Our study showed that Couette and parallel plate geometries are the most suitable geometries for analyzing the two yield stresses of the samples. Vane geometry is appropriate to study consolidated (solid-like) systems as for these samples a Couette geometry cannot be used because the bob could get stuck during the experiment.

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Mud sediments can exhibit a complex rheological behaviour particularly a thixotropic character or structural recovery after breakup due to the presence of organic matter/biopolymer. Such biopolymers can lead towards the development of flocculated structures having multiple length scales which are sensitive to shearing rate and history. In this study, the extent and rate of structural recovery of mud sediments was studied by measuring the storage modulus as a function of time using small amplitude oscillatory tests after a destructive steady shearing. This linear viscoelastic response of the sediments was further investigated as a function of several parameters including pre-shear rate, pre-shear time, measuring geometry, mud density and organic matter content. The equilibrium storage modulus (G_∞ ^') and the characteristic time (t_r) for the structural recovery of the sediment matrix were estimated by fitting the experimental data to a stretched exponential function. The normalized storage modulus, G^'/G₀ ^' (i.e., structural parameter) was used to relate it with the yield stresses of mud sediments. The results showed that the recovery of structure after shearing was instantaneous (t_r being of the order of seconds), however, the extent of recovery was highly dependent on the studied parameters. The extent of recovery was higher for the samples with lower density and lower organic matter content. The effect of the shearing time on t_r and G_∞ ^' was almost negligible, which implies that the destruction of the structure was achieved within seconds. Using vane geometry, the extent of recovery was higher than using Couette geometry which is linked with the distribution of shear stresses within the cell for each geometry. Yield stresses showed a strong dependency on structural parameter, until it reaches very small values. At low values of structural parameter, the yield stresses were constant as the structural recovery was even faster than the time required to perform the amplitude sweep tests. This study provides an extensive knowledge about the structural recovery in mud sediments under different shearing conditions which can be useful for sediment management.

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Nanostructured (hybrid) membranes combining properties of inorganic and polymeric materials is an integral part of the field of separation technology. Mixed matrix membranes were prepared from oppositely charged inorganic (INPs) and polymeric (PNPs) nanoparticles using spin coating method. Four different types of PNPs were prepared. Poly(2-dimethylaminoethyl methacrylate)-b-(methyl methacrylate)) and poly((methacrylic acid)-b-(methyl methacrylate)) diblock copolymers were prepared via RAFT dispersion polymerization in ethanol at 70 °C. Quaternized poly(2-(dimethylamino) ethyl methacrylate)-b-poly (benzyl methacrylate) and poly(potassium 3-sulfopropyl methacrylate)-b-poly (benzyl methacrylate) block copolymers were prepared using aqueous RAFT emulsion polymerization method at 70 °C. The inorganic iron oxide nanoparticles (INPs) were either coated with [3-(2-Aminoethylamino)propyl] trimethoxysilane (TPED) via Dimercaptosuccinic acid (DMSA) using stab exchange. Transmission electron microscopy (TEM) and Dynamic light scattering (DLS) analysis were performed to examine the size and morphology of the prepared polymeric and inorganic nanoparticles. Scanning electron microscope (SEM) and Atomic Force Microscope (AFM) images were obtained to analyze the topography and thin film formation on the nylon support. Detailed filtration experiments were carried out to evaluate the effect of pH on the performance of the membrane.

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Ionic liquids (ILs) are liquid salts at ambient or lower temperatures and consist of ions and short-lived ion pairs. They are potential alternatives to toxic, hazardous, highly flammable, and volatile solvents for preparing solutions, dispersions, gels, composites, and polymeric melts. ILs have some very interesting and unique characteristics like good chemical and thermal stability and very low vapor pressures. They have good solvation interactions with a wide range of organic, inorganic, and polymeric compounds. They can enhance colloidal stability and the elasticity range of polymers. ILs are environmental friendly, easily recyclable, and structurally similar to the conventional solvents. For optimal performance, it is necessary to fully understand the rheological properties of ILs and their different systems for academic interests such as understanding the ability of ILs as processing AIDS particularly in film casting, fiber spinning and spraying, comprehension of thermodynamics and dynamics of polymer chains in ILs, analyzing the hydrodynamic volume of dispersed polymer, polymer-ILs interactions, characterizing the viscoelastic properties and nanophase-ILs interactions in nanocomposite systems, analyzing the plasticization efficiency, and the final properties of the composite system. The rheological analysis is also important for industrial purposes particularly for designing processing techniques and suitable operating conditions for IL based systems. The aim of this review is to give an overview of the rheological properties of pure ionic liquids and solutions, dispersions, gels, composites, and melts based on ionic liquids.@en

Purpose: An innovative way to define navigable fluid mud layers is to make use of their rheological properties, in particular their yield stress. In order to help the development of in situ measurement techniques, it is essential that the key rheological parameters are estimated beforehand. Is there only one yield stress? In which shear rate/shear stress range is yield expected to occur? How is yield stress dependent on depths and locations in the harbor? In order to answer these questions, we investigated the changes in the rheological properties of mud from along the river stream in the Port of Hamburg, Germany, using a recently developed laboratory protocol. Materials and methods: In this study, a detailed rheological analysis was carried out on the mud samples collected from different locations and depths of the Port of Hamburg. A variety of rheological tests was performed including: stress sweep tests, flow curves, thixotropic tests, oscillatory amplitude, and frequency sweep tests. Results and discussion: The yield stresses of sediments from different locations were significantly dissimilar from each other due to differences in densities and organic matter content. Two yield stresses (termed static and fluidic) were observed for every sample and linearly correlated to each other. The thixotropic studies showed that all mud samples, except from one location, displayed a combination of thixotropic and anti-thixotropic behaviors. The results of frequency sweep tests showed the solid-like character of the sediments within the linear viscoelastic limit. The yield stresses, thixotropy, and moduli of the mud samples increased by going deeper into the sediment bed due to the increase in density of the sediments. Conclusions: This study confirmed the applicability of the recently developed protocol as a fast and reliable tool to measure the yield stresses of sediments from different locations and depths in the Port of Hamburg. The fluid mud layer, in all the locations it was observed, exhibited relatively small yield stress values and weak thixotropic behavior. This confirms that despite the fact that rheology of fluid mud is complex, this layer can be navigable.

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Fluid mud can be described as a mixture of water, organic matter and mainly cohesive mineral sediment that is usually found in estuaries and in rivers with low-intensity currents. It is in a transient state and can densify over time unless mixing (produced by mechanical and/or natural forces) prevents its gelling. Typically, fluid mud exhibits bulk densities between 1080 and 1200 kg/m3. It has a weak strength that, in low energetic conditions, develops over time forming a structured bed of considerably higher rigidity. The current definitions of fluid mud are based on the density of the sediment. These definitions are ambiguous since the proposed critical parameters do not account for the possible strength developments in fluid mud. We propose to use rheological properties for distinguishing the fluid mud layer from the suspension layer above and the consolidated mud layer underneath. The protocols involve the use of a rotational bob (Couette) rheometer that can perform oscillations, shear stress and shear rate controlled experiments. A number of natural mud samples were used for testing the protocols.

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Bigels are interesting semisolid formulations with better properties for different applications such as cosmetics and pharmaceutical systems. Due to the mixing of two phases of different nature (polar and apolar), bigels possess some interesting features like ability to deliver hydrophilic and hydrophobic drugs, better spreadability and water washability, improved permeability of drugs, enhanced hydration of stratum corneum and ability to manipulate the drug release rate. The main objective of this review article is to provide a thorough insight into the important characteristics of bigels together with the discussion on modelling of bigel systems to relate their properties with individual constituents and different parameters. Moreover, some important applications of bigels are also discussed by considering some examples from the literature.@en

Polyether ether ketone (PEEK) is a semi-crystalline thermoplastic polymer having excellent mechanical and thermal properties. Exposure of this polymer to aliphatic and aromatic solvents can lead to degradation or swelling of the polymeric material. The present work described the plasticization and stability analysis of semi-crystalline PEEK under different aromatic and aliphatic solvent environment. A variety of solvents (acetone, benzene, benzyl alcohol, chloroform, methanol, and toluene), based on their Hildebrand’s Solubility Parameter, were chosen for investigation. The physico-chemical characteristics of virgin and treated polymeric samples were investigated using Gas Chromatography–Mass Spectrometry (GC–MS), Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and Fourier Transform Infrared Spectroscopy (FTIR) techniques. The results indicated that the solvent exposure did not significantly affect the thermal behavior and chemical structure of the polymer. However, it seems that certain components of the polymer were leached into the solvent phase as revealed by the GC–MS analysis. The present study identified PEEK as a potentially suitable polymer for the applications where high resistance to aliphatic and aromatic solvents is needed.@en

Mud is a cohesive material which contains predominantly clay minerals, water, organic matter and some amounts of silt and sand. Mud samples can have complex rheological behaviour, displaying viscoelasticity, shear-thinning, thixotropy and yield stress. In this study, influence of organic matter on the rheological behaviour of different mud samples having similar densities is investigated. Four samples, collected from different locations and depths of Port of Hamburg (Germany) were selected. Two samples with the density of about 1210 kg/m3 and two samples with the density of about 1090 kg/m3 were analysed by different rheological tests, including stress ramp-up tests, flow curves, thixotropic tests, oscillatory amplitude and frequency sweep tests. Two yield stress regions (with two yield stress values stated as “static” and “fluidic” yield stresses) were identified for all the samples, and these regions, corresponding to a structural change of the samples were significantly different from sample to sample due to the differences in organic matter content. For lower density samples, the ratio of fluidic to static yield stress increased from 3 to 4.4 while it increased from 4.4 to 5.2 in case of higher density samples, by increasing the organic matter content. The thixotropic studies showed that the mud samples having lowest organic matter content (VH and KBZ) exhibit a combination of thixotropic and anti-thixotropic behaviours. The results of frequency sweep tests revealed the solid-like character of the mud within the linear viscoelastic regime. Mud samples having higher organic matter content (RV and RT) had a higher complex modulus (417 Pa and 7909 Pa) than the ones with lower organic matter content (13 Pa and 1774 Pa), for a given density. This study demonstrated that the density only is not a sufficient criterion to predict the rheology of different mud. Furthermore, even small amounts of organic matter content change significantly the mud rheological behaviour.@en

Nano-indentation is an interesting tool for analyzing nano-scale mechanical properties. The analysis of nano-mechanical properties as a function of experimental conditions is very critical for designing engineering components. In this study, nano-indentation experiments were performed by considering different values of amplitude (1, 5, 10 nm), frequency (11.2, 22.5, 45 Hz), strain rate (0.02, 0.05, 0.1, 0.2, 1 s ⁻¹ ), peak load (10, 30, 100 mN) and hold time (1, 3, 5, 10, 20, 50, 100 sec) to analyze their effect on the mechanical properties of LDPE. The results showed that the effect of amplitude and frequency on the nano-mechanical properties of LDPE were negligible. Load-displacement curves displayed a shift towards higher indentation depths along with a decrease in peak load from 20.6 to 14.8 mN by having a decrease in strain rate from 1 to 0.02 s ⁻¹ . Elastic modulus and hardness values exhibited a decrease with an increase in hold time. Logarithmic creep model was used to fit the experimental data of creep as a function of holding time which showed good agreement (r ² ≥ 0.97) with the experimental values. Recommended holding times are also suggested to eliminate the creep and nose problem in order to achieve high accuracy in measurements.

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A modified version of the commercially available RheOptiCAD® was developed to visualize the microscopic structural changes occurring in concentrated suspensions, such as the break-up of flocs in clay suspensions, under shearing action. This is made possible by replacing the inverted microscope used in the traditional RheOptiCAD® set-up by an upright modular microscope equipped with a CMOS camera and epi-illumination. Our device retains the following features of the previous version of RheOptiCAD®: [i] uniaxial translational motion of two parallel plates, [ii] three modes of shear straining, [iii] controlled thermal environment, and [iv] vacuum joining of microscopy glass slides. The validation of the new design was done using a model system of un-flocculated and flocculated kaolin suspensions and concentrated natural mud suspension. The results showed that the constructed device is a promising tool for studying, from fundamental and industrial perspectives, the microstructural behaviour of complex suspended systems under controlled thermal and mechanical conditions.

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A primitive element for the development of sustainable pyrolysis processes is the study of thermal degradation kinetics of lignocellulosic waste materials for optimal energy conversion. The study presented here was conducted to predict and compare the optimal kinetic parameters for pyrolysis of various lignocellulosic biomass such as wood sawdust, bagasse, rice husk, etc., under both isothermal and non-isothermal conditions. The pyrolysis was simulated over the temperature range of 500–2400 K for isothermal process and for heating rate range of 25–165 K/s under non-isothermal conditions to assess the maximum pyrolysis rate of virgin biomass in both cases. Results revealed that by increasing the temperature, the pyrolysis rate was enhanced. However, after a certain higher temperature, the pyrolysis rate was diminished which could be due to the destruction of the active sites of char. Conversely, a decrease in the optimum pyrolysis rate was noted with increasing reaction order of the virgin biomass. Although each lignocellulosic material attained its maximum pyrolysis rate at the optimum conditions of 1071 K and 31 K/s for isothermal and non-isothermal conditions, respectively, but under these conditions, only wood sawdust exhibited complete thermal utilization and achieved final concentrations of 0.000154 and 0.001238 under non-isothermal and isothermal conditions, respectively.

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