Colloids Interfaces, Volume 8, Issue 3 (June 2024) – 8 articles

The authors of numerous measurements of conductivity for suspensions of nanoparticles of various types carried out in the last decade came to the general conclusion that the well-known Maxwell’s theory is not applicable to quantitative explanation of the properties of such systems. In the present work, we demonstrate that the Maxwell’s theory can be still applicable even for such systems, but the specifics of the standard ac measurements have to be correctly taken into account. Namely, the dependence of the capacitance of “metal–electrolyte” cuvette boundaries on nanoparticle adsorption, which in its turn dramatically depends on nanoparticle concentration, has to be taken into account. The latter circumstance strongly (via the $RC$ characteristic of the circuit) affects the results of conductivity measurements. We propose the new algorithm of the impedance measurement data analysis for the particles’ concentration dependence of conductivity $\sigma \left(\varphi \right)$ (where $\varphi$ is the volume fraction of nanoparticles in suspension) for the suspensions of the diamante nanoparticles in alcohol which demonstrates the adequate correspondence of the Maxwell’s theory to the available experimental findings. Full article

The phenomenon of discontinuous shear thickening (DST) is observed in suspensions of solid particles with a very high-volume fraction. It is characterized by an abrupt decrease in the shear rate for critical stress during a ramp of stress. This behavior can be reproduced in numerical simulations by introducing a local friction between two particles above a given local force. We present experimental results showing this DST behavior obtained with suspensions of magnetic (iron) and nonmagnetic (calcium carbonate) particles and different amounts of a superplasticizer molecule used in the cement industry. For both types of particles, the same behavior was observed with first an increase in critical stress with the amount of plasticizer followed by a decrease at higher concentrations but with a larger viscosity before critical stress was reached. At a low concentration of plasticizer, the low critical stress is interpreted by the local sliding of plasticizer molecules on the surface of particles. At higher concentrations, when total coverage is achieved, the critical stress is higher since it has to remove the molecules out of the surface. At still higher concentrations, the increase in viscosity is explained by the formation of multilayers of molecules on the surface of the particles. This interpretation is supported by the measurement of the adsorption isotherm of the plasticizer on the surface of the particles. Full article

Flowable electrodes, a versatile alternative to traditional solid electrodes for electrochemical applications, exhibit challenges of high viscosity and carbon content, limiting flow and device performances. This study introduces colloidal suspensions of thin multiwall carbon nanotubes (MWCNTs) with diameters of 10–15 nm as electrode materials. These thin nanotubes, stabilized in water with a surfactant, form percolated networks, exhibiting high conductivity (50 ms/cm) and stability at a low carbon content (below 2 wt%). Colloidal clustering is enhanced by weak depletion attractive interactions. The resulting suspensions display yield stress and a shear thinning behavior with a low consistency index. They can easily flow at a nearly constant shear over a broad range of shear rates. They remain electrically conductive under shear, making them a promising option for flow electrochemical applications. This work suggests that the use of depletion-induced MWVNT aggregates addresses crucial issues in flow electrochemical applications, such as membrane fragility, operating energy, and pressure. These conductive colloidal suspensions thereby offer potential advancements in device performance and lifespan. Full article

In recent years, the development of nanomaterials with biocidal properties has received considerable attention due to their potential applications in various industries, including food, medicine, and cultural heritage preservation. The growing demand for coatings with antibacterial properties has sparked interest from industrial sectors in exploring the incorporation of biocides into these materials. Coatings are prone to microbial growth, which can cause damage such as cracking, discoloration, and staining. To combat these problems, the integration of biocides into coatings is a crucial strategy. Biocide-embedded nanomaterials offer numerous advantages, including high efficiency in small quantities, ease of application, good chemical stability, low toxicity, and non-bioaccumulation. Encapsulated nanobiocides are particularly attractive to the agro-industry, because they can be less toxic than traditional biocides while still effectively controlling microbial contamination. To fully exploit the benefits of nanobiocides, future research should focus on optimizing their synthesis, formulation, and delivery methods. The purpose of this review is to summarize the current status of biocide nanomaterials, discuss potential future research directions, and highlight research methods, the development of new forms of nanomaterials, and studies of their physico-chemical properties. Biocide nanocapsules of DCOIT (4,5-Dichloro-2-octyl-2H-isothiazol-3-one) are chosen as an example to illustrate the research pathways. Full article

A detailed understanding of the interactions between wax and asphaltenes with other components of crude oils and the effect of treatments with paraffin inhibitors (PIs) and asphaltene dispersants (ADs), with a focus on identifying specific structure-activity relationships, is necessary to develop effective flow assurance strategies. The morphological and rheological consequences of treating wax and asphaltenes in oils of differing composition with a series of ADs having structural features in common with an alpha olefin-maleic anhydride (AO-MA) comb-like copolymer PI were assessed alone and in combination with said PI. Of the four ADs studied, two were identified as being effective dispersants of asphaltenes in heptane-induced instability tests and in a West Texas (WT) crude. The degree to which a low concentration of asphaltenes stabilizes wax in the absence of treatment additives is lessened in oils having greater aromatic fractions. This is because these stabilizing interactions are replaced by more energetically favorable aromatic–asphaltene interactions, increasing oil viscosity. Treatment with AD alone also reduces the extent of wax–asphaltene interactions, increasing oil viscosity. In concert with the PI, treatment with the AD having greater structural similarity with the PI appears to improve wax solubility in both the presence and absence of asphaltenes. However, the viscosity of the treated oils is greater than that of the oil treated with PI alone, while treatment with AD having lesser structural similarity with the PI does not adversely affect oil viscosity. These data suggest that rather than treating both wax and asphaltenes, AD may poison the function of the PI. These data illuminate the pitfalls of designing flow assurance additives to interact with both wax and asphaltenes and developing treatment plans. Full article

Coarse-grained molecular dynamics simulations are employed to investigate the spatiotemporal evolution of vesicles (polymersomes) through the self-assembly of randomly distributed amphiphilic BAB triblock copolymers with hydrophilic A and hydrophobic B blocks in an aqueous solution. The vesiculation pathway consists of several intermediate structures, such as an interconnected network of copolymer aggregates, a cage of cylindrical micelles, and a lamellar cage. The cage-to-vesicle transition occurs at a constant aggregation number and practically eliminates the hydrophobic interfacial area between the B block and solvent. Molecular reorganization underlying the sequence of morphology transitions from a cage-like aggregate to a vesicle is nearly isentropic. The end-to-end distances of isolated copolymer chains in solution and those within a vesicular assembly follow lognormal probability distributions. This can be attributed to the preponderance of folded chain configurations in which the two hydrophobic end groups of a given chain stay close to each other. However, the probability distribution of end-to-end distances is broader for chains within the vesicle as compared with that of a single chain. This is due to the swelling of the folded configurations within the hydrophobic bilayer. Increasing the hydrophobicity of the B block reduces the vesiculation time without qualitatively altering the self-assembly pathway. Full article

Bi₂S₃ has gained considerable attention as a semiconductor for its versatile functional properties, finding application across various fields, and liquid phase exfoliation (LPE) serves as a straightforward method to produce it in nano-form. Till now, the commonly used solvent for LPE has been N-Methyl-2-pyrrolidone, which is expensive, toxic and has a high boiling point. These limitations drive the search for more sustainable alternatives, with water being a promising option. Nonetheless, surfactants are necessary for LPE in water due to the hydrophobic nature of Bi₂S₃, and organic molecules with amphoteric characteristics are identified as suitable surfactants. However, systematic studies on the use of ionic surfactants in the LPE of Bi₂S₃ have remained scarce until now. In this work, we used sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS) and sodium hexadecyl sulfonate (SHS) as representative species and we present a comprehensive investigation into their effects on the LPE of Bi₂S₃. Through characterizations of the resulting products, we find that all surfactants effectively exfoliate Bi₂S₃ into few-layer species. Notably, SDBS demonstrates superior stabilization of the 2D layers compared to the other surfactants, while SHS becomes the most promising surfactant for obtaining products with high yield. Moreover, the resulting nano-inks are used for fabricating films using spray-coating, reaching a fine tuning of band gap by controlling the number of cycles, and paving the way for the utilization of 2D Bi₂S₃ in optoelectronic devices. Full article

The aims of this work are to study the rheological behaviors of a microemulsion of Glucopone–water–hydrocarbon systems and to use a fractional model to describe several experimental results of these systems. Four different types of hydrocarbons were considered. The frequency dependent storage, G′, and loss modulus, G″, were investigated below the critical strain. The critical strain was found to decrease as the alkane chain lengths increased, while the opposite behavior was observed for zero shear viscosity, η₀. Most of the microemulsions exhibited stable elastic fluid behavior (G′ > G″) below 10 rad s⁻¹ angular frequency. For all systems, elastic modulus values were found to be greater than loss modulus in the frequency range studied, indicating more elastic behaviors. Shear-thinning behaviors were observed, and the complex viscosity decreased with an increase in hydrocarbon chain lengths. The effects of hydrocarbon types on the rheological behaviors were more profound in the dodecane systems which showed maximum values of G′ and η₀. The Friedrich–Braun model was introduced and was used to describe several experimental results on Alkyl polyglocoside solutions. Fractional rheology successfully described the viscoelastic phenomena in Glucopone surfactant solutions and the comparisons between the experimental results and the theoretical predictions were found to be satisfactory. Full article