Rheological and dielectric behavior of sodium carboxymethyl cellulose (NaCMC)/Ca2+ and esterified NaCMC/Ca2+ hydrogels: Correlating microstructure and dynamics with properties.

Polyelectrolyte-based conductive hydrogels are being extensively explored for applications in energy storage and as electrode materials for batteries. We synthesized ionically crosslinked sodium carboxymethyl cellulose (NaCMC), esterified NaCMC, and Ca2+ doped esterified NaCMC hydrogels. This work aims to understand the effect of Ca2+ ions on the NaCMC and esterified NaCMC. FTIR, SEM, Rheology and EIS studies were performed to understand the structure and dynamics of hydrogels. Results confirmed that Ca2+ ions have an important role in determining the rheological and dielectric response of hydrogels. Power law behavior was observed in their rheological response with exponent (n) of 0.81 for G' and 0.76 for G″ of ionically crosslinked NaCMC, 5.38 for G' and 4.70 for G″ of esterified NaCMC, whereas, negative exponents -1.44 for G' and -1.10 for G″ of Ca2+ ion doped esterified NaCMC. Ionically crosslinked NaCMC hydrogels have relaxation times (τ) in the range of 8.9 × 10-5 s-2.8 × 10-5 s may be due to the formation of temporary dipoles by electrostatic bridge formations with dc conductivity of (0.1 S/cm-5 S/cm), whereas, esterified NaCMC showed relaxation times (10-3 s-8.9 × 10-5 s) with increasing ester crosslinks and dc conductivity of (0.05 S/cm-0.8 S/cm). Interestingly, Ca2+ ion doped esterified hydrogels showed multiple dielectric relaxations on Ca2+ ion addition with different relaxation times may be due to change in ionic environment. The understanding obtained from this work may be useful for designing tuneable hydrogels with optimum electrical and mechanical properties.

A Unique Temperature-Induced Reverse Supramolecular Chirality-Assisted Gel-to-Gel Transition.

Supramolecular hydrogels typically undergo a gel-to-sol transition with heat, as intermolecular interactions within the gel weaken. Although gel-to-gel transitions during heating are rare, they may occur due to minor rearrangements caused by thermal forces in the supramolecular self-assembled structure. Here, an unprecedented temperature-induced gel-to-gel transition assisted by supramolecular chiral inversion in a hydrogel system is presented. The transition results from a left-handed M-type helix to a right-handed P-type helix, attributed to the π-system-conjugated amino acid, l-Tyrosine (Fm- l-Tyr). Upon solvent dilution, Fm-l-Tyr induces translucent hydrogel formed by entangled fibers with a kinetically stable left-handed M-type supramolecular helix. At 70 °C, hydrogel transforms into an opaque gel with a reverse supramolecular chirality yielding a thermodynamically stable right-handed P-type helix. Supramolecular chiral inversion is substantiated by two chiroptical methods. This unique gel-to-gel transition, accompanied by chiral inversion, is anticipated to attract attention, especially for applications sensitive to chirality.

The Personality and Resilience of Competitive Athletes as BMW Drivers-Data from India, Latvia, Lithuania, Poland, Romania, Slovakia, and Spain.

BACKGROUND: Individual differences in personality and resilience are related to a variety of social behaviors. The current study sought to answer the question of whether BMW drivers exhibit different personality profiles and resilience levels compared with drivers of other car brands. PARTICIPANTS AND PROCEDURE: An international study was carried out in India, Latvia, Lithuania, Poland, Romania, Slovakia, and Spain on a sample of 448 athletes using the 20-item Mini-IPIP and the Resilience Scale. The results of BMW drivers (n = 91) were compared with the results of drivers of other German car brands (n = 357). RESULTS: BMW drivers were characterized by higher neuroticism compared with drivers of other German car brands. They also showed higher resiliency, both in terms of total score and scores on the subscales of: personal coping competences and tolerance of negative emotions, tolerance of failures and perceiving life as a challenge, and optimistic attitude towards life and capacity for self-mobilization in difficult situations. The greatest difference was observed for the factor of tolerance of failures and perceiving life as a challenge. Using the Dwass-Steel-Critchlow-Fligner (DSCF) pairwise comparison test, gender differences between athletes (as BMW drivers and drivers of other German car brands, respectively) were discussed. Additionally, the results of the main logistic regression analyses emphasized that neuroticism represents a better predictor of BMW preference in the case of athletes (as drivers) than the scores obtained for resilience. CONCLUSIONS: BMW drivers differed from drivers of other German car brands only with regard to neuroticism. A higher level of neuroticism can affect mental health and the overall quality of life in athletes; aggression and distress management are essential. Athletes (as BMW drivers) also showed differences in resiliency levels. Understanding the mechanisms of behavior among BMW drivers is possible through considering their personality and individual differences.

Electrostatic Heteroaggregation: Fundamentals and Applications in Interfacial Engineering.

The aggregation of oppositely charged soft materials (particles, surfactants, polyelectrolytes, etc.) that differ in one or more physical or chemical attributes, broadly referred to as electrostatic heteroaggregation, has been an active area of research for several decades now. While electrostatic heteroaggregation (EHA) is relevant to diverse fields such as environmental engineering, food technology, and pharmaceutical formulations, more recently there has been a resurgence to explore various aspects of this phenomenon in the context of interface stabilization and the development of functional materials. In this Feature Article, we provide an overview of the recent contributions of our group to this exciting field with particular emphasis on fundamental studies of electrostatic heteroaggregation between oppositely charged systems in the bulk, at interfaces, and across the bulk/interface. The influence of the size and shape of particles and the surface charge of heteroaggregates on the formation of Pickering emulsions and their utilization in the development of porous ceramics is discussed.

π-System Functionalization Transforms Amyloidogenic Peptide Fragment of Human Islet Amyloid Polypeptide into a Super Hydrogelator.

While a considerable number of ultra-short/short amyloid peptides have been reported to form 3D supramolecular hydrogels, they all possess high minimum gelation concentration (MGC) (≥1 wt%), which preclude their applications. In this context, we demonstrate that functionalisation of a well-known amyloidogenic ultra-short peptide fragment NFGAIL (IAPf) of human Islet amyloid polypeptide with a π-system (Fluorenyl, Fm) at the N-terminus of the peptide (Fm-IAPf) yield not only highly thermostable hydrogel at physiological pH but also exhibited super gelator nature as the MGC (0.08 wt%) falls below 0.1 wt%. Various experimental results confirmed that aromatic π-π interactions from fluorenyl moieties and hydrogen bonding interactions between the IAPf drive the self-assembly/fibril formation. Fm-IAPf is the first super hydrogelator derived from amyloid-based ultra-short peptides, to the best of our knowledge. We strongly believe that this report, i. e., functionalization of an amyloid peptide with π-system, provides a lead to develop super hydrogelators from other amyloid-forming peptide fragments for their potential applications.

Multiscale Approach to Studying Biomolecular Interactions in Cellulose-Casein Adhesion.

Casein finds application as an eco-friendly adhesive for paper, wood, glass, etc. Casein being a protein can undergo conformational and microstructural changes during various processing steps involved in interfacial bonding. This study aims at understanding the multiscale contributions of these changes in casein to its adhesion to cellulose pressboards. Investigations spanning from molecular structure to macroscopic adhesion characteristics have been used in this work. The lap shear strength of casein bonded cellulose pressboards is found to increase with the increase in casein concentration. It was observed from Fourier transform infrared spectroscopy (FTIR) investigations along with microscopy and rheological studies that casein dispersions result in more α-helical conformations during the preconcentration process of casein dispersions. This results in increased hydrophobicity of the casein particles/aggregates, which in turn affects the wetting characteristics and the adhesion behavior. Casein compositions lacking α-helices were found to enhance the bonding strength of casein with cellulose. The present study shows that the adhesion between casein and microporous cellulose substrate has contributions at the multiscale originating from the polar-polar interactions of casein and cellulose molecules, conformational changes in the protein structure of casein during drying, microstructure of casein particles in the dispersion, and the microporous nature of the cellulose boards. These interactions at multiple scales can be tuned to suit different adhesive applications using casein.

A "self-shrinking" supramolecular hydrogel with a 3D shape memory performance from an unnatural amino acid derivative.

A supramolecular hydrogel with 3D self-shrinking, without any assistance, and a shape memory performance at room temperature is discovered from an unnatural amino acid derivative, i.e. fluorenylmethoxycarbonyl-L-ß-phenylalanine, as a minimalistic model. The self-shrinking properties of this hydrogel can be explored for potential applications.

Pectin self-assembly and its disruption by water: insights into plant cell wall mechanics.

Plant cell walls undergo multiple cycles of dehydration and rehydration during their life. Calcium crosslinked low methoxy pectin is a major constituent of plant cell walls. Understanding the dehydration-rehydration behavior of pectin gels may shed light on the water transport and mechanics of plant cells. In this work, we report the contributions of the microstructure to the mechanics of pectin-Ca gels subjected to different extents of dehydration and subsequent rehydration. This is investigated using a pectin gel composition that forms 'egg-box bundles', a characteristic feature of the microstructure of low methoxy pectin-Ca gels. Large amplitude oscillatory shear (LAOS) rheology along with small angle neutron scattering and near infrared (NIR) spectroscopy on pectin gels is used to elucidate the mechanical and microstructural changes during dehydration-rehydration cycles. As the extent of dehydration increases, the reswelling ability, strain-stiffening behavior and yield strain decrease. These effects are more prominent at faster rates of dehydration and are not completely reversible upon rehydration to the initial undried state. Microstructural changes due to the aggregation of egg-box bundles and single chains and the associated changes in the water configurations lead to these irreversible changes.

Contributions from microstructural changes to the rheological behavior of casein dispersions during drying.

In several applications, a protein such as casein in dispersion form undergoes multiple processing steps including drying. In this work, the rheological and microstructural features of casein dispersions concentrated by evaporation of the solvent (drying dispersions) were studied in comparison with those of equal concentrations of the as-prepared dispersions without drying. The molecular assembly of casein is affected by drying along with the conformational composition changes in the secondary structures such as α-helix, ß-sheets, turns and random structures of the protein. Modeling of the rheological data indicates that these changes also affect the packing of casein molecular assemblies and these molecular assemblies in alkaline dispersions can behave as soft deformable particles. During drying, casein dispersions show prominent shear thinning for concentrations higher than 20 wt% along with the prevalence of α-helices and ß-sheets. In comparison, the as-prepared dispersions show different microstructural features, and therefore different rheological responses. A detailed analysis shows that alkalinity changes during drying is the crucial factor controlling the microstructural changes of the soft casein particles and hence the rheology.

Fibrillar Network Dynamics during Oscillatory Rheology of Supramolecular Gels.

Supramolecular gels are three-dimensional network structures formed by the hierarchical self-assembly of small molecules through weak noncovalent interactions. On the basis of the various interactions contributed by specific functional groups/moieties, gels with different architectures can be constructed that are smart to the external stimuli such as pH, type of solvent, stress, temperature, etc. In the present work, we explore the oscillatory shear response of supramolecular self-assembled systems formed by the low-molecular-weight (LMW) gelator based on difunctionalized amino acid, florenylmethoxycarbonyl (Fmoc)-lysine(Fmoc), Fm-K(Fm) in aqueous buffer solution, at two different pH (6 and 7.4). Small amplitude oscillatory shear (SAOS) reported weak frequency dependence of moduli indicating a gel-like network structure. Large amplitude oscillatory shear (LAOS) indicated flow regimes dictated by yielding and subsequent network dynamics analogous to cagelike soft glassy events reported for colloidal systems. The three interval thixotropy test (3iTT) indicated recovery of moduli due to regelation contributed by the reversible interactions. A generalized network model framework is utilized to investigate the transient network characteristics of the Fm-K(Fm) gels. The "network creation" and "network loss" rates were chosen as exponential functions of scaled shear stress (= |τ12(t)G|) to effectively describe the complex response. On the basis of the insights, possible mechanisms to explain the differences/similarities in the response at different pH are speculated. It is further illustrated that the modeling strategy can be extended to supramolecular gels of different classes because of the commonality/universality of their response features under oscillatory shear.

Self-healing microcapsules encapsulated with carbon nanotubes for improved thermal and electrical properties.

Microcapsules are widely used by researchers in self-healing composites. In this study, multi-walled carbon nanotubes (CNT) were incorporated into the core of the microcapsules, along with the self-healing agent. Dicyclopentadiene (DCPD) and urea-formaldehyde (UF) were chosen as the core and shell materials respectively, and DCPD-CNT-UF based dual core microcapsules were synthesized. Two types of microcapsules, namely, DCPD-UF and DCPD-CNT-UF were successfully synthesized by the in situ polymerization technique. The novelty of this work is the development of dual core microcapsules with DCPD-CNT-UF combination. Surface morphology characterization and elemental analysis of the microcapsules were carried out using a scanning electron microscope (SEM-EDX). TGA and DSC analysis show that DCPD-CNT-UF microcapsules have better thermal stability than DCPD-UF microcapsules. These novel DCPD-CNT-UF microcapsules were found to be compatible with epoxy base resin for making resin castings. The presence of CNT is found to improve the mechanical, thermal and electrical properties of the resin cast specimens without compromising on self-healing efficiency.

Influence of reduced graphene oxide on flow behaviour, glass transition temperature and secondary crystallinity of plasticized poly(vinyl chloride).

Understanding the rheological behaviour of thermoplastic nanocomposites is important to obtain a concrete knowledge of their processability. The viscoelastic properties of nanocomposites are a reflection of their morphology. The study of flow and deformation of nanocomposites provides essential information related to prevalent interactions in the system as well as contribution from the dispersion of incorporated nanofillers. In the present study, plasticized polyvinyl chloride/reduced graphene oxide nanocomposites (PPVC/RGO) were fabricated using melt mixing technique with different filler concentration. Flow behaviour of the nanocomposites was analyzed using small amplitude oscillatory shear (SAOS) measurements and it indicated an enhancement in the storage modulus (G'), loss modulus (G'') and complex viscosity (η*) with RGO content. This can be attributed to very good dispersion and reinforcing effect of RGO in PPVC matrix as supported by TEM and FTIR results. Weak gel model is used to fit the rheological parameters and is found to be in excellent agreement with the SAOS experiments. Thermal history of the prepared nanocomposites was learned using differential scanning calorimetry. A shift in glass transition temperature (T g) to higher temperature region could be seen, that manifest the effect of RGO in the amorphous portion of PPVC. An interesting property called secondary crystallinity was also found in these materials.

Non-proteinogenic amino acid based supramolecular hydrogel material for enhanced cell proliferation.

Supramolecular gel material built from low-molecular-weight (LMW) gelators finds potential applications in various fields, especially in drug delivery, cell encapsulation and delivery, and tissue engineering. The majority of the LMW gelators in these applications are based on functionalized peptides/amino acids consisting of proteinogenic amino acids which are proteolytically unstable. Herein, we have developed a new LMW gelator containing non-proteinogenic amino acid namely 2,3-diaminopropionic acid (Dap), a key precursor in the synthesis of many antibiotics namely viomycin and capreomycin, by functionalizing with fluorenylmethoxycarbonyl at both amino terminals of Dap [Fm-Dap(Fm)]. Hydrogelation test at different pH indicates that Fm-Dap(Fm) can form a hydrogel in a wide range of pH (4.9 to 9.1) with minimum hydrogelation concentration depends on the pH. The mechanical strength and thermal stability of the Fm-Dap(Fm) hydrogel material are found to decrease with increasing pH (acidic > neural/physiological > basic). The thermal stability of Fm-Dap(Fm) hydrogels is pH-dependent and elicits high stability at acidic pH. Also, Fm-Dap(Fm) hydrogels exhibit strong thixotropic property where regelation (self-healing) occurs upon release of stress. Morphological analysis indicates the formation of fibrils, which are entangled to form three dimensional network structures. Several spectroscopic measurements provided evidence for the self-assembly of Fm-Dap(Fm) molecules through intermolecular aromatic π-π stacking and hydrogen bonding interactions during hydrogelation. Interestingly, Fm-Dap(Fm) not only exhibits hydrogel formation but also shows cell viability and enhanced cell proliferation at physiological pH (7.4). Further, Fm-Dap(Fm) forms a hydrogel upon co-incubation with vitamin B12 and also exhibits release of vitamin B12 over a period. The current study thus demonstrates the development of a new hydrogel material, based on LMW gelator containing the non-proteinogenic amino acid, which can elicit cell viability, enhanced cell proliferation, drug encapsulation, and drug release properties. Hence, Fm-Dap(Fm) hydrogel could be an ideal material for biomedical applications, especially in tissue engineering and drug delivery.

Dissipation and strain-stiffening behavior of pectin-Ca gels under LAOS.

Non-linear mechanical responses observed in networks of many biopolymers such as pectin are important for their functioning as biological systems. Additionally, pectins derived from plant sources are also used for several food and biomedical applications. In the present work, the possible contributions of egg-box bundles in the large deformation response of calcium crosslinked gels of low methoxy pectin are explored using large amplitude oscillatory shear (LAOS). The gels exhibit a significant overshoot in the loss modulus (G'') and intra-cycle strain-stiffening, more prominent at greater extents of egg-box bundling. This observation signifies the dissipation characteristics of the egg-box bundles in pectin gels, hitherto not reported. The observed non-linear signatures diminish when the extent of bundling as well as the bundle radius decreases below a critical value. We identify different pectin/Ca concentration regimes based on the semi-flexible/flexible nature of the gel network and the non-linear signatures. Monovalent salt addition prior to crosslinking is shown to modify the extent of bundling, thereby influencing the magnitude of G'' overshoot and strain-stiffening. The intensity of the G'' overshoot and the extent of strain-stiffening are correlated with the radius of the egg-box bundles obtained from small angle neutron scattering (SANS) data. However, analysis using strain-stiffening models indicates the possible contributions from the semi-flexible nature of egg-box bundles and single chains.

Rheology and microstructure of concentrated microcrystalline cellulose (MCC)/1-allyl-3-methylimidazolium chloride (AmimCl)/water mixtures.

Water added to a solution of microcrystalline cellulose (MCC) in 1-allyl-3-methylimidazolium chloride (AmimCl) reduces the solvent quality and causes significant changes in the flow properties and microstructure due to restructuring and aggregation of cellulose molecules. We report an experimental investigation by means of polarization optical microscopy (POM) and rheology of the distinct phases formed in 5-20 wt% MCC/AmimCl solutions due to the addition of water. With increase in the cellulose concentration, the MCC/AmimCl/water mixtures showed different morphologies such as the non-aligned cholesteric liquid crystalline (LC) domain, the coexistence of spherulite-like structures within the LC domain and a space-spanning network of spherulite-like structures at high concentrations of water. In situ microscopy during shear and POM observations pre and post shear revealed a significant increase in the size of the birefringent domains as the shear rate is increased, which continued to exist even after the cessation of shear. With an increase in the concentration of water, the zero shear viscosity of the MCC/AmimCl/water mixtures was found to go through a minimum, beyond which the aggregation of cellulose commenced. The corresponding oscillatory shear response showed a sol-gel transition with an increase in water concentration. Moreover, at high cellulose concentrations (12-20 wt%), the MCC/AmimCl/water gels exhibited self-similarity and followed the Chambon-Winter (CW) criterion. The similar phase behavior and rheological response observed for MCC dissolved in 1-butyl-3 methylimidazolium chloride (BmimCl) indicated the generality of the presented results.

Kosmotropic effect leads to LCST decrease in thermoresponsive polymer solutions.

We study the phenomena of decrease in lower critical solution temperature (LCST) with addition of kosmotropic (order-making) cosolvents in thermoresponsive polymer solutions. A combination of explicit solvent coarse-grained simulations and mean-field theory has been employed. The polymer-solvent LCST behavior in the theoretical models has been incorporated through the Kolomeisky-Widom solvophobic potential. Our results illustrate how the decrease in the LCST can be achieved by the reduction in the bulk solvent energy with the addition of cosolvent. It is shown that this effect of cosolvent is weaker with an increase in polymer hydrophilicity which can explain the absence of a LCST decrease in poly(N,N-diethylacrylamide), water, and methanol systems. The coarse-grained nature of the models indicates that a mean energetic representation of the system is sufficient to understand the phenomena of LCST decrease.

Enhanced mobility of non aqueous phase liquid (NAPL) during drying of wet sand.

Enhanced upward mobility of a non aqueous phase liquid (NAPL) present in wet sand during natural drying, and in the absence of any external pressure gradients, is reported for the first time. This mobility was significantly higher than that expected from capillary rise. Experiments were performed in a glass column with a small layer of NAPL-saturated sand trapped between two layers of water-saturated sand. Drying of the wet sand was induced by flow of air across the top surface of the wet sand. The upward movement of the NAPL, in the direction of water transport, commenced when the drying effect reached the location of the NAPL and continued as long as there was significant water evaporation in the vicinity of NAPL, indicating a clear correlation between the NAPL rise and water evaporation. The magnitude and the rate of NAPL rise was measured at different water evaporation rates, different initial locations of the NAPL, different grain size of the sand and the type of NAPL (on the basis of different NAPL-glass contact angle, viscosity and density). A positive correlation was observed between average rate of NAPL rise and the water evaporation while a negative correlation was obtained between the average NAPL rise rate and the NAPL properties of contact angle, viscosity and density. There was no significant correlation of average NAPL rise rate with variation of sand grain size between 0.1 to 0.5mm. Based on these observations and on previous studies reported in the literature, two possible mechanisms are hypothesized -a) the effect of the spreading coefficient resulting in the wetting of NAPL on the water films created and b) a moving water film due to evaporation that "drags" the NAPL upwards. The NAPL rise reported in this paper has implications in fate and transport of chemicals in NAPL contaminated porous media such as soils and exposed dredged sediment material, which are subjected to varying water saturation levels due to drying and rewetting.

A Low-Molecular-Weight Gelator Composed of Pyrene and Fluorene Moieties for Effective Charge Transfer in Supramolecular Ambidextrous Gel.

Charge-transfer (CT) gel materials obtained from low-molecular-weight (LMW) compounds through a supramolecular self-assembly approach have received fascinating attention by many researchers because of their interesting material property and potential applications. However, most of the CT gel materials constructed were of organogels while the construction of CT gels in the form of a hydrogel is a challenge because of the solubility issue in water, which considerably limits the use of CT hydrogels. Herein, for the first time, we report a new LMW gelator [Nα-(fluorenylmethoxycarbonyl)-Nε-(δ-butyric-1-pyrenyl)-l-lysine, (FmKPy)], composed of two functional moieties such as fluorenylmethoxycarbonyl and pyrene, which not only parade both hydro and organo (ambidextrous) supramolecular gel formation but also exhibit CT ambidextrous gels when mixed with an electron acceptor such as 2,4,7-trinitro-9-fluorenone (TNF). This finding is significant as the established CT organogelator in the literature did not form an organogel in the absence of an electron acceptor or lose their gelation property upon the addition of the acceptor. CT between pyrene and TNF was confirmed by the color change as well as the appearance of the CT band in the visible region of the absorption spectrum. CT between FmKPy and TNF was supported by the solvent dilution method using tetrahydrofuran as the gel breaker and pyrene fluorescence quenching in the case compound containing pyrene and TNF. The morphology of FmKPy ambidextrous gels indicates the fibrous nature while the self-assembled structure is primarily stabilized by π-π stacking among fluorenyl and pyrenyl moieties and hydrogen bonding between amide groups. The FmKPy-TNF CT ambidextrous gel retains the fibrous nature; however, the size of the fibers changed. In FmKPy-TNF CT gels, TNF is intercalated between pyrene moieties in the self-assembled structure as confirmed by fluorescence quenching and powder X-ray diffraction. The FmKPy ambidextrous gel exhibits significant properties such as low minimum gelation concentration (MGC), thixotropic nature, pH stimuli response, and high thermal stability. Upon the addition of TNF, the FmKPy-TNF CT ambidextrous gel maintains all these properties except MGC which increased for FmKPy-TNF. Because pyrene-based LMW organogels have been developed widely for many applications while their hydrogels were limited, the current finding of the pyrene-based ambidextrous fluorescent gel with the CT property provides a wide opportunity to use FmKPy as a soft material maker and also for potential applications in fields like surface coating, three-dimensional printing, and so forth.

Molecular Structuring and Percolation Transition in Hydrated Sulfonated Poly(ether ether ketone) Membranes.

The extent of phase separation and water percolation in sulfonated membranes are the key to their performance in fuel cells. Toward this, the effect of hydration on the morphology and transport characteristics of sulfonated poly(ether ether ketone), sPEEK, membrane is investigated using atomistic molecular dynamics simulation at various hydration levels(λ: number of water molecules per sulfonate group). The evolution of local morphology is investigated using structural correlations and minimum pair distances. Transport properties are probed using mean squared displacements and diffusion coefficients. The water-sulfonate interaction in sPEEK is found to be stronger than that in Nafion, as observed in experiments. Analyses indicate the presence of narrow connected path of water and hydronium at λ = 4 and large domains, spanning half the simulation box, at λ = 15. The behavior of membrane water remains far from bulk as indicated by its diffusion coefficient. The persistence of small isolated water clusters demonstrates the extent of phase separation in sPEEK to be lesser than that in Nafion. Analyses at molecular and collective levels suggest the occurrence of a percolation transition between λ = 8 and 10, which leads to a connected network of water channels in the membrane, thereby boosting the hydronium mobility.

Hetero-aggregation of oppositely charged nanoparticles.

Hetero-aggregation refers to aggregation of particles that are not identical i.e. particles of different physical-chemical properties. The investigation of this phenomenon is important because of the fascinating structures that can be formed and their application in several fields including the synthesis of porous materials and particle stabilized emulsions. We report an experimental study of hetero-aggregation behaviour of oppositely charged nanoparticles of similar size. In this study, the hetero-aggregation phenomenon is investigated using a combination of visual observation, zeta potential measurements, dynamic light scattering, scanning electron microscopy and rheology measurements. We report details of aggregate size, structure, flow properties to provide understanding of hetero-aggregation by a careful examination of different phases formed upon mixing oppositely charged particles. The experiments were carried out at different mixing fraction (defined as the mass of positive particle in the dispersion divided by total mass of particles in the dispersion) varying from 0 to 1 with total concentration of particles ranging from 0.05 to 30wt% (0.023-13.82vol%). At low total particle concentration, four different states of the mixture were observed which includes sediment with turbid supernatant, sediment with clear supernatant, turbid sample with no sediment and a clear dispersion. However, at higher concentration above ∼7.5wt% (3.45vol%), the mixture of oppositely charged particles form - a particulate gel with turbid supernatant at low mixing fraction (from 0.1 to 0.3), a solid-like gel at intermediate mixing fraction (from ∼0.3 to 0.7) and a turbid sample at high mixing fractions from 0.7 to 1.0.