The Time-Temperature Superposition of Polymeric Rubber Gels Treated by Means of the Mode-Coupling Theory.

Viscoelastic relaxation measurements on styrene-butadiene rubbers (SBRs) doped with carbon nanotube (CNT) at different concentrations around the sol-gel transition show the time-temperature superposition (TTS). This process is described in terms of the mode coupling theory (MCT) approach to viscoelasticity by considering the frequency behavior of the loss modulus E″(ω) and showing that the corresponding TTS is linked to ω1/2 decay. From the analysis of the obtained data, we observe that the interaction between SBRs and CNT determines different levels of decay according to their concentration. Systems with the lowest CNT concentration are only characterized in the studied T-range by their fragile glass-forming behavior. However, at a specific temperature TL, those with the highest CNT concentration show a crossover towards pure Arrhenius that, according to the MCT, indicates the presence of kinetic glass transition (KGT), where system response functions are characterized by scaling behaviors.

Development of accessible platforms to promote myofibroblast differentiation by playing on hydrogel scaffold composition.

Mechanomimetic materials are particularly attractive for modeling in vitro fibroblast to myofibroblast (Myof) transition, a key process in the physiological repair of damaged tissue, and recognized as the core cellular mechanism of pathological fibrosis in different organs. In vivo, mechanical stimuli from the extracellular matrix (ECM) are crucial, together with cell-cell contacts and the pro-fibrotic transforming growth factor (TGF)-ß1, in promoting fibroblast differentiation. Here, we explore the impact of hydrogels made by polyacrylamide with different composition on fibroblast behavior. By appropriate modulation of the hydrogel composition (e.g. adjusting the crosslinker content), we produce and fully characterize three kinds of scaffolds with different Young modulus (E). We observe that soft hydrogels (E < 1 kPa) induced fibroblast differentiation better than stiffer ones, also in the absence of TGF-ß1. This study provides a readily accessible biomaterial platform to promote Myof generation. The easy approach used and the commercial availability of the monomers make these hydrogels suitable to a wide range of biomedical applications combined with high reproducibility and simple preparation protocols.

The Role of Crosslinker Molecular Structure on Mechanical and Light-Actuation Properties in Liquid Crystalline Networks.

Phase behavior modulation of liquid crystalline molecules can be addressed by structural modification at molecular level. Starting from a rigid rod-like core reduction of the symmetry or increase of the steric hindrance by different substituents generally reduces the clearing temperature. Similar approaches can be explored to modulate the properties of liquid crystalline networks (LCNs)-shape-changing materials employed as actuators in many fields. Depending on the application, the polymer properties have to be adjusted in terms of force developed under stimuli, kinetics of actuation, elasticity, and resistance to specific loads. In this work, the crosslinker modification at molecular level is explored towards the optimization of LCN properties as light-responsive artificial muscles. The synthesis and characterization of photopolymerizable crosslinkers, bearing different lateral groups on the aromatic core is reported. Such molecules are able to strongly modulate the material mechanical properties, such as kinetics and maximum tension under light actuation, opening up to interesting materials for biomedical applications.

The Hydrophobic Effect Studied by Using Interacting Colloidal Suspensions.

Interactions between nanoparticles (NPs) determine their self-organization and dynamic processes. In these systems, a quantitative description of the interparticle forces is complicated by the presence of the hydrophobic effect (HE), treatable only qualitatively, and due to the competition between the hydrophobic and hydrophilic forces. Recently, instead, a sort of crossover of HE from hydrophilic to hydrophobic has been experimentally observed on a local scale, by increasing the temperature, in pure confined water and studying the occurrence of this crossover in different water-methanol solutions. Starting from these results, we then considered the idea of studying this process in different nanoparticle solutions. By using photon correlation spectroscopy (PCS) experiments on dendrimer with OH terminal groups (dissolved in water and methanol, respectively), we show the existence of this hydrophobic-hydrophilic crossover with a well defined temperature and nanoparticle volume fraction dependence. In this frame, we have used the mode coupling theory extended model to evaluate the measured time-dependent density correlation functions (ISFs). In this context we will, therefore, show how the measured spectra are strongly dependent on the specificity of the interactions between the particles in solution. The observed transition demonstrates that just the HE, depending sensitively on the system thermodynamics, determines the hydrophobic and hydrophilic interaction properties of the studied nanostructures surface.

Tuning the Morphology of HDPE/PP/PET Ternary Blends by Nanoparticles: A Simple Way to Improve the Performance of Mixed Recycled Plastics.

Due to a very low mixing entropy, most of the polymer pairs are immiscible. As a result, mixing polymers of different natures in a typical mechanical recycling process leads to materials with multiple interfaces and scarce interfacial adhesion and, consequently, with unacceptably low mechanical properties. Adding nanoparticles to multiphase polymeric matrices represents a viable route to mitigate this drawback of recycled plastics. Here, we use low amounts of organo-modified clay (Cloisite® 15A) to improve the performance of a ternary blend made of high-density polyethylene (HDPE), polypropylene (PP), and polyethylene terephtalate (PET). Rather than looking for the inherent reinforcing action of the nanofiller, this goal is pursued by using nanoparticles as a clever means to manipulate the micro-scale arrangement of the polymer phases. Starting from theoretical calculations, we obtained a radical change in the blend microstructure upon the addition of only 2-wt.% of nanoclay, with the obtaining of a finer morphology with an intimate interpenetration of the polymeric phases. Rather than on flexural and impact properties, this microstructure, deliberately promoted by nanoparticles, led to a substantial increase (>50 °C) of a softening temperature conventionally defined from dynamic-mechanical measurements.

The Interplay between the Theories of Mode Coupling and of Percolation Transition in Attractive Colloidal Systems.

In the recent years a considerable effort has been devoted to foster the understanding of the basic mechanisms underlying the dynamical arrest that is involved in glass forming in supercooled liquids and in the sol-gel transition. The elucidation of the nature of such processes represents one of the most challenging unsolved problems in the field of material science. In this context, two important theories have contributed significantly to the interpretation of these phenomena: the Mode-Coupling theory (MCT) and the Percolation theory (PT). These theories are rooted on the two pillars of statistical physics, universality and scale laws, and their original formulations have been subsequently modified to account for the fundamental concepts of Energy Landscape (EL) and of the universality of the fragile to strong dynamical crossover (FSC). In this review, we discuss experimental and theoretical results, including Molecular Dynamics (MD) simulations, reported in the literature for colloidal and polymer systems displaying both glass and sol-gel transitions. Special focus is dedicated to the analysis of the interferences between these transitions and on the possible interplay between MCT and PT. By reviewing recent theoretical developments, we show that such interplay between sol-gel and glass transitions may be interpreted in terms of the extended F13 MCT model that describes these processes based on the presence of a glass-glass transition line terminating in an A3 cusp-like singularity (near which the logarithmic decay of the density correlator is observed). This transition line originates from the presence of two different amorphous structures, one generated by the inter-particle attraction and the other by the pure repulsion characteristic of hard spheres. We show here, combining literature results with some new results, that such a situation can be generated, and therefore experimentally studied, by considering colloidal-like particles interacting via a hard core plus an attractive square well potential. In the final part of this review, scaling laws associated both to MCT and PT are applied to describe, by means of these two theories, the specific viscoelastic properties of some systems.

Chitosan/Zeolite Composite Aerogels for a Fast and Effective Removal of Both Anionic and Cationic Dyes from Water.

Organic dyes are extensively used in many industrial sectors, and their uncontrolled disposal into wastewaters raises serious concerns for environmental and human health. Due to the large variety of such pollutants, an effective remediation strategy should be characterized by a broad-spectrum efficacy. A promising strategy is represented by the combination of different adsorbent materials with complementary functionalities to develop composite materials that are expected to remove different contaminants. In the present work, a broad-spectrum adsorbent was developed by embedding zeolite 13X powder (ZX) in a chitosan (CS) aerogel (1:1 by weight). The CS-ZX composite adsorbent removes both anionic (indigo carmine, IC) and cationic (methylene blue, MB) dyes effectively, with a maximum uptake capacity of 221 mg/g and 108 mg/g, respectively. In addition, the adsorption kinetics are rather fast, with equilibrium conditions attained in less than 2 h. The composite exhibits good mechanical properties in both dry and wet state, which enables its handling for reusability purposes. In this regard, preliminary tests show that the full restoration of the IC removal ability over three adsorption-desorption cycles is achieved using a 0.1 M NaOH aqueous solution, while a 1 M NaCl aqueous solution allows one to preserve >60% of the MB removal ability.

Tailoring Chitosan/LTA Zeolite Hybrid Aerogels for Anionic and Cationic Dye Adsorption.

Chitosan (CS) is largely employed in environmental applications as an adsorbent of anionic dyes, due to the presence in its chemical structure of amine groups that, if protonated, act as adsorbing sites for negatively charged molecules. Efficient adsorption of both cationic and anionic dyes is thus not achievable with a pristine chitosan adsorbent, but it requires the combination of two or more components. Here, we show that simultaneous adsorption of cationic and anionic dyes can be obtained by embedding Linde Type A (LTA) zeolite particles in a crosslinked CS-based aerogel. In order to optimize dye removal ability of the hybrid aerogel, we target the crosslinker concentration so that crosslinking is mainly activated during the thermal treatment after the fast freezing of the CS/LTA mixture. The adsorption of isotherms is obtained for different CS/LTA weight ratios and for different types of anionic and cationic dyes. Irrespective of the formulation, the Langmuir model was found to accurately describe the adsorption isotherms. The optimal tradeoff in the adsorption behavior was obtained with the CS/LTA aerogel (1:1 weight ratio), for which the maximum uptake of indigo carmine (anionic dye) and rhodamine 6G (cationic dye) is 103 and 43 mg g-1, respectively. The behavior observed for the adsorption capacity and energy cannot be rationalized as a pure superposition of the two components, but suggests that reciprocal steric effects, chemical heterogeneity, and molecular interactions between CS and LTA zeolite particles play an important role.

Mechanically Coherent Zeolite 13X/Chitosan Aerogel Beads for Effective CO2 Capture.

The constant increase of CO2 concentration in the atmosphere is recognized worldwide to severely impact the environment and human health. Zeolites possess a high adsorption capacity for CO2 removal, but their powdery form prevents their use in many practical applications. When binding agents are used, a partial occlusion of the porosity can severely compromise the adsorption capacity. In this regard, a great challenge is producing compact composite adsorbents while maintaining a high specific surface area to preserve the pristine performance of zeolites. Here, this goal was achieved by preparing beads with a high content of zeolite 13X (up to 90 wt %) using a chitosan aerogel as the binding agent. A facile preparation procedure based on the freeze-drying of hydrogel beads obtained by phase inversion led to a peculiar microstructure in which a very fine polymeric framework firmly embeds the zeolite particles, providing mechanical coherence and strength (compressive strain >40% without bead fragmentation, deformation <20% under 1 kgf-load) and yet preserving the powder porosity. This allowed us to fully exploit the potential of the constituents, reaching a high specific surface area (561 m2 g-1) and excellent CO2 uptake capacity (4.23 mmol g-1) for the sample at 90% zeolite. The beads can also be reused after being fully regenerated by means of a pressure swing protocol at room temperature.

High Silica Content Graphene/Natural Rubber Composites Prepared by a Wet Compounding and Latex Mixing Process.

The reduced graphene oxide (rGO) modified natural rubber composite (NR) filled with high contents of silica was prepared by a wet compounding and latex mixing process using a novel interface modifier cystamine dihydrochloride (CDHC) with coagulation ability. CDHC acts as a coagulation agent through electrostatic interaction with rGO, SiO2, and latex rubber particles during the latex-based preparation process, while in the obtained silica/graphene/natural rubber composites, CDHC acts as an interface modifier. Compared with the composites prepared by the conventional mechanical mixing method, the dispersion of both rGO and SiO2 in the composites made by a wet compounding and latex mixing process is improved. As a result, the obtained silica/graphene/natural rubber composite prepared by this new method has good comprehensive properties. A Dynamic Mechanical Test suggests that the tan δ values of the composites at 60 °C decrease, indicating a low rolling resistance with increasing the graphene content at a low strain, but it increases at a higher strain. This unique feature for this material provides an advantage in the rubber tire application.

Some Aspects of the Liquid Water Thermodynamic Behavior: From The Stable to the Deep Supercooled Regime.

Liquid water is considered to be a peculiar example of glass forming materials because of the possibility of giving rise to amorphous phases with different densities and of the thermodynamic anomalies that characterize its supercooled liquid phase. In the present work, literature data on the density of bulk liquid water are analyzed in a wide temperature-pressure range, also including the glass phases. A careful data analysis, which was performed on different density isobars, made in terms of thermodynamic response functions, like the thermal expansion αP and the specific heat differences CP-CV, proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis. The study confirms that supercooled bulk water is a mixture of two liquid "phases", namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the CP-CV isobars behaviors clearly support the existence of both a liquid-liquid transition and of a liquid-liquid critical point.

Light-responsive and self-healing behavior of azobenzene-based supramolecular hydrogels.

HYPOTHESIS: Multi-component supramolecular hydrogels are gaining increasing interest as stimuli-responsive materials. To fully understand and possibly exploit the potential of such complex systems, the hierarchical structure of the gel network needs in-depth investigations across multiple length scales. We show that a thorough structural and rheological study represents a crucial pillar for the exploitation of this class of functional materials. EXPERIMENTS: Supramolecular hydrogels are prepared by self-assembly of hexadecyltrimethylammonium bromide (CTAB) and azobenzene-4,4'-dicarboxylic acid (AZO) in alkaline aqueous solution. The CTAB/AZO concentration was varied from ϕ = 0.25 to 4 wt% keeping the CTAB:AZO molar ratio fixed at 2:1. The systems were thoroughly studied through a combination of X-ray scattering, microscopy, rheological and spectroscopic analyses. FINDINGS: The CTAB/AZO solutions form a self-supporting gel with nanofibrillar structure below ~30 °C. The critical gelation concentration is ϕc = 0.45 wt%. Above this threshold, the gel elasticity and strength increase with CTAB/AZO content as ~(ϕ-ϕc)1. The hydrogels exhibit self-healing ability when left at rest after a stress-induced damage. Moreover, the light-induced isomerization of the AZO moieties provides the gel with light-responsiveness. Overall, the multi-stimuli responsiveness of the studied CTAB/AZO hydrogels makes them a solid starting point for the development of sensors for mechanical vibrations and UV/visible light exposure.

Long-Lasting Efficacy of Coatings for Bronze Artwork Conservation: The Key Role of Layered Double Hydroxide Nanocarriers in Protecting Corrosion Inhibitors from Photodegradation.

The photodegradation kinetics of 2-mercaptobenzothiazole (MBT), a corrosion inhibitor for copper-based alloys, is studied in high amorphous polyvinyl alcohol coatings subjected to either UV irradiation or indoor light exposure. The photodegradation process proceeds rapidly, thus compromising the anticorrosion ability of the coating. The encapsulation of MBT into layered double hydroxide (LDH) nanocarriers slows down its decomposition kinetics by a factor of three. Besides preserving the corrosion inhibitor, such a strategy allows a controlled release of MBT triggered by corrosion-related stimuli, for example, presence of chloride species and acid pH. The developed coating guarantees long-lasting corrosion protection even at low amounts of inhibitor-loaded LDH nanocarriers (ca. 5 wt %). This also reflects in a high transparency, which makes the protective coating suitable for demanding applications, such as the conservation of high-value metal works of art.

Chitosan hydrogels embedding hyper-crosslinked polymer particles as reusable broad-spectrum adsorbents for dye removal.

The removal of dye and toxic ionic pollutants from water is an extremely important issue that requires systematic and efficient adsorbent preparation strategies. To address this challenge, we developed composite chitosan (CS)-based hydrogels containing hyper-crosslinked polymer (HCP) particles to be used as broad-spectrum adsorbents. The goal is to efficiently combine the dye adsorption ability of chitosan and the capacity of the porous particles of trapping pollutant molecules. The HCP particles are well distributed and firmly embedded into the chitosan matrix and the composite hydrogels exhibit improved mechanical properties. Adsorption experiments reveal a synergistic effect between CS and HCP particles, and the samples are able to remove both anionic and cationic dyes (indigo carmine, rhodamine 6G and sunset yellow) from water. The maximum dye uptake is higher than that of comparable biosorbents. Moreover, the mechanical properties of the composite hydrogels are enhanced respect to pure CS, and the samples can be regenerated and reused keeping their adsorption ability unaltered over successive cycles of adsorption, desorption, and washing.

Assembly of plate-like nanoparticles in immiscible polymer blends--effect of the presence of a preferred liquid-liquid interface.

The assembly of lamellar (clay) nanoparticles in a blend of polystyrene (PS) and poly(methyl methacrylate) (PMMA) with drop-matrix morphology is studied combining viscoelastic measurements and morphological analyses. A reference system based on pure PS is used to highlight the effect on the assembly process of the presence of liquid interfaces where the particles are inclined to gather. The filler content is varied in a wide range to cover all the possible structures, from isolated flocs up to space-spanning networks. The goal is to elucidate whether the particles govern the blend morphology or the structural evolutions of the fluids dictate the space arrangement of the filler. The PMMA drops anchor the lamellae frustrating their peculiar mobility in the polymer melt. On the other hand, the clay radically affects the blend morphology, inducing irregularly-shaped drops and drop clustering phenomena even in case of partial coverage of the drop surface. Above the critical filler content for the saturation of the polymer-polymer interface, a space-spanning particle network eventually builds up. Despite the embedding of the PMMA drops, such a superstructure exhibits the same features of those forming in homogeneous mediums, enabling the use of approaches conceived for systems with single-phase matrix. Compared to the latter, the percolation and fractal models reveal subtle and yet meaningful differences in terms of stress-bearing mechanisms and structure of the building blocks which constitute the network.