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The incorporation of silica nanoparticles (Si-NPs) into the polymer matrix is a growing area of interest research to produce high-performance polymer nanocomposites (NCs) across a wide range of nanotechnology applications. This improvement is due to the Si-NPs capability to self-assembly giving rise to specific well-organized structures with both short- and long-range order across a hierarchy of spatial scales, determined by both NP-NP and NP-matrix interactions, involving a careful balance among attractive driving forces, repulsive forces, and directional forces. Respect to this, the aim of the present paper is to systematically review the use of Si-NPs in polymer NCs and on the role of NPs self-assembly in determining the final material properties. Firstly, we explored the synthesis and modification of both isotropic and anisotropic Si-NPs in relation with use in NC materials, focusing on NPs dispersion and distribution, as well as on the functionalization strategies of Si-NPs. Besides Si-NPs functionalization with conventional small organic molecules, a large section is devoted to an emerging class of functionalized Si-NPs with macromolecules, namely silica hairy NPs (Si-HNPs), able to give rise a rich variety of complex assemblies and materials with new structures and functionalities. Successively, NCs materials containing Si-NPs and Si-HNPs have been explored in terms of synthetic preparation and properties. The self-organization of Si-NPs and Si-HNPs in polymer matrices has been reported and its effect on the functional materials properties have been evaluated with a critical point of view on the results, limits, and future perspectives. Our review can be considered a tutorial work, aiming at providing useful insights to researchers in the field of nanotechnology and nanoscience, taking into consideration the fundamental role of NPs self-assembly processes in determining the functional material properties.

"Hairy" nanoparticles (HNPs), i.e. inorganic NPs functionalized with polymer chains, are promising building blocks for the synthesis of advanced nanocomposite (NC) materials having several technological applications. Recent evidence shows that HNPs self-organize in a variety of anisotropic structures, resulting in an improvement of the functional properties of the materials, in which are embedded. In this paper, we propose a three-step colloidal synthesis of spherical SiO2-HNPs, with controlled particle morphology and surface chemistry. In detail, the SiO2 core, synthesized by a modified Stöber method, was first functionalized with a short-chain amino-silane, which acts as an anchor, and then covered by maleated polybutadiene (PB), a rubbery polymer having low glass transition temperature, rarely considered until now. An extensive investigation by a multi-technique analysis demonstrates that the synthesis of SiO2-HNPs is simple, scalable, and potentially applicable to different kind of NPs and polymers. Morphological analysis shows the overall distribution of SiO2-HNPs with a certain degree of spatial organization, suggesting that the polymer coating induces a modification of NP-NP interactions. The role of the surface PB brushes in influencing the special arrangement of SiO2-HNPs was observed also in cis-1,4-polybutadiene (cis-PB), since the resulting NC exhibited the particle packing in "string-like" superstructures. This confirms the tendency of SiO2-HNPs to self-assemble and create alternative structures in polymer NCs, which may impart them peculiar functional properties.

The development of effective thermally conductive rubber nanocomposites for heat management represents a tricky point for several modern technologies, ranging from electronic devices to the tire industry. Since rubber materials generally exhibit poor thermal transfer, the addition of high loadings of different carbon-based or inorganic thermally conductive fillers is mandatory to achieve satisfactory heat dissipation performance. However, this dramatically alters the mechanical behavior of the final materials, representing a real limitation to their application. Moreover, upon fillers’ incorporation into the polymer matrix, interfacial thermal resistance arises due to differences between the phonon spectra and scattering at the hybrid interface between the phases. Thus, a suitable filler functionalization is required to avoid discontinuities in the thermal transfer. In this challenging scenario, the present review aims at summarizing the most recent efforts to improve the thermal conductivity of rubber nanocomposites by exploiting, in particular, inorganic and hybrid filler systems, focusing on those that may guarantee a viable transfer of lab-scale formulations to technological applicable solutions. The intrinsic relationship among the filler’s loading, structure, morphology, and interfacial features and the heat transfer in the rubber matrix will be explored in depth, with the ambition of providing some methodological tools for a more profitable design of thermally conductive rubber nanocomposites, especially those for the formulation of tires.

Ladder-like silsesquioxanes (SSQs) and TiO2 have been functionalized with methacryloyloxypropyl chains and embedded in a polybutadiene (PB) matrix giving rise to hybrid (organic–inorganic) nanocomposites (NCs) capable of acting as oxygen scavenging materials. The joint use of infrared spectroscopy, small-angle X-ray scattering, and permittivity measurements highlighted that the presence of TiO2, regardless of its modification, does not significantly alter the structure of the NCs, but just reduces the crosslinking degree and induces a local disorganization of the ladder-like SSQ stacks. The introduction of an optimum amount (0.5 wt%) of modified TiO2 within the polymeric matrix enhanced the oxygen uptake rate of ca. 70% with respect to the sole polymeric material. Moreover, the uptake kinetics changes from the first to second order with respect to the PB amount, clearly indicating different oxidation mechanisms. NCs containing modified TiO2 showed an oxygen uptake rate ranging from 30 to 60% higher than that achievable in the presence of bare TiO2. The superior activity of the materials containing modified TiO2 has been related to mechanistic aspects. Fluorescence and electron spin resonance spectroscopies allowed to underline the role of singlet oxygen within the polymeric matrix, although the known photochemical oxidation of PB and the TiO2 induced hydroxyl radical mediated oxidation cannot be excluded. These results open the route to highly efficient flexible oxygen scavenging materials for the protection of electronic devices such as organic based light emitting diodes, solar cells, and liquid crystal displays, which require high targets of protection from oxygen and water.

Hybrid silica-based nanofillers were synthesised by grafting short chains of poly(ethylene glycol) (PEG) with different molecular weight on the surface of SiO2 porous nanoparticles. Based on this approach, homogeneous poly(ethylene oxide) (PEO)-based ceramic-in-polymer solid-state electrolytes with SiO2 loadings up to 23 wt% were obtained, thanks to the high compatibility between the two phases endowed by the grafted PEG chains. These electrolytes showed satisfying ionic conductivity and excellent resistance against dendrite piercing that enabled long operation, for more than 350 h, under continuous stripping/plating of lithium in symmetric Li/electrolyte/Li cells. Additionally, the operating life of these devices was improved by the self-healing reaction between Li dendrites and silica fillers, being able to reinstate the cycling after short circuit. Finally, a lithium metal full cell, equipped with LiFePO4 positive material and the solid-state electrolyte containing 18 wt% of SiO2, demonstrated high stability against dendrite penetration and discharge capacity at 70 °C comparable to cells based on liquid analogues.

The present study explores the exploitation of ladder-like polysilsesquioxanes (PSQs) bearing reactive functional groups in conjunction with SiO2 nanoparticles (NPs) to produce UV-curable nanocomposite coatings with increased hydrophobicity and good thermal resistance. In detail, a medium degree regular ladder-like structured poly (methacryloxypropyl) silsesquioxane (LPMASQ) and silica NPs, either naked or functionalized with a methacrylsilane (SiO2@TMMS), were blended and then irradiated in the form of a film. Material characterization evidenced significant modifications of the structural organization of the LPMASQ backbone and, in particular, a rearrangement of the silsesquioxane chains at the interface upon introduction of the functionalized silica NPs. This leads to remarkable thermal resistance and enhanced hydrophobic features in the final nanocomposite. The results suggest that the adopted strategy, in comparison with mostly difficult and expensive surface modification and structuring protocols, may provide tailored functional properties without modifying the surface roughness or the functionalities of silsesquioxanes, but simply tuning their interactions at the hybrid interface with silica fillers.

Latex compounding technique is an economic and ecosustainable alternative to melt mixing for preparing nanocomposites in which fillers are directly mixed with natural rubber in the latex aqueous dispersion. Clay minerals are excellent potential fillers to be used in masterbatches prepared exploiting this technique, but their presence is associated to the occurrence of oxidative degradation phenomena of natural rubber. In this work, by exploiting a combination of high- and low-resolution 13C and 1H Solid State Nuclear Magnetic Resonance techniques, with the support of Fourier Transform Infrared spectroscopy and thermal analyses, we characterized for the first time the oxidation phenomena occurring in sepiolite/natural rubber masterbatches obtained by the latex compounding technique. Oxidized species were identified and quantified and the dynamic properties, molecular weight and thermal stability of the rubber were characterized. Moreover, the dependence of degradation phenomena on the filler treatment and on the masterbatch work-up procedure was assessed, identifying freeze-drying as the method able to effectively protect the rubber from oxidation.

In this study, the preparation of polybutadiene/polysilsesquioxane nanocomposites (NCs) having tunable thermomechanical and dielectric properties is reported. This was achieved by using different amounts of a filler consisting of a silsesquioxane with a defined ladder-like molecular structure (LPMASQ) bearing reactive methacrylate functionalities. In detail, solid-state nuclear magnetic resonance (NMR) investigation revealed that an increasing amount of filler leads to a progressive homopolymerization of LPMASQ units resulting in the generation of domains in the composites, which induce a kind of polymer chain confinement in proximity of the hybrid interface. The evolution of the molecular organization of the inorganic nanobuilding blocks as a function of their concentration has been highlighted also by small-angle X-ray scattering (SAXS) experiments. The gradual assembly of LPMASQ units gives rise to peculiar dielectric properties along with enhanced thermal and mechanical stability of the final NCs, thus supplying suitable materials for applications in high performance dielectrics. Furthermore, these outcomes support the idea that a careful control of the molecular architecture and organization of the silsesquioxanes in a polymer matrix allows to simultaneously modulate two or more distinct functional features of polymer NCs

Organic–inorganic nanobuilding blocks (NBBs) based on silsesquioxanes (SSQs) have potential applications as nanofillers, thermal stabilizers, and rheological modifiers, which can improve thermomechanical properties of polymer hosts. The possibility to tune both siloxane structure and pendant groups can promote compatibilization and peculiar interactions with a plethora of polymers. However, the control on SSQs molecular architecture and functionalities is usually delicate and requires careful synthetic details. Moreover, investigating the influence of NBBs loading and structure on the hybrid interface and, in turn, on the polymer chains mobility and mechanical properties, may be challenging, especially for low-loaded materials. Herein, we describe the preparation and characterization of polybutadiene (PB) nanocomposites using as innovative fillers thiol-functionalized SSQs nanobuilding blocks (SH-NBBs), with both tailorable functionality and structure. Swelling experiments and, more clearly, solid-state NMR, enlightened a remarkable effect of SH-NBBs on the molecular structure and mobility of the polymeric chains, envisaging the occurrence of chemical interactions at the hybrid interface. Finally, thermal and DMTA analyses revealed that nanocomposites, even containing very low filler loadings (i.e. 1, 3 wt%), exhibited enhanced thermomechanical properties, which seem to be connected not only to the loading, but also to the peculiar cage or ladder-like architecture of SH-NBBs.

Sepiolite (Sep)&ndash, styrene butadiene rubber (SBR) nanocomposites were prepared by using nano-sized sepiolite (NS-SepS9) fibers, obtained by applying a controlled surface acid treatment, also in the presence of a silane coupling agent (NS-SilSepS9). Sep/SBR nanocomposites were used as a model to study the influence of the modified sepiolite filler on the formation of immobilized rubber at the clay-rubber interface and the role of a self-assembled nanostructure in tuning the mechanical properties. A detailed investigation at the macro and nanoscale of such self-assembled structures was performed in terms of the organization and networking of Sep fibers in the rubber matrix, the nature of both the filler&ndash, filler and filler&ndash, rubber interactions, and the impact of these features on the reduced dissipative phenomena. An integrated multi-technique approach, based on dynamic measurements, nuclear magnetic resonance analysis, and morphological investigation, assessed that the macroscopic mechanical properties of clay nanocomposites can be remarkably enhanced by self-assembled filler structures, whose formation can be favored by manipulating the chemistry at the hybrid interfaces between the clay particles and the polymers.

Global industry is showing a great interest in the field of sustainability owing to the increased attention for ecological safety and utilization of renewable materials. For the scientific community, the challenge lies in the identification of greener synthetic approaches for reducing the environmental impact. In this context, we propose the preparation of novel biocomposites consisting of natural rubber latex (NRL) and sepiolite (Sep) fibers through the latex compounding technique (LCT), an ecofriendly approach where the filler is directly mixed with a stable elastomer colloid. This strategy favors a homogeneous dispersion of hydrophilic Sep fibers in the rubber matrix, allowing the production of high-loaded sepiolite/natural rubber (Sep/NR) without the use of surfactants. The main physicochemical parameters which control Sep aggregation processes in the aqueous medium were comprehensively investigated and a flocculation mechanism was proposed. The uniform Sep distribution in the rubber matrix, characteristic of the proposed LCT, and the percolative filler network improved the mechanical performances of Sep/NR biocomposites in comparison to those of analogous materials prepared by conventional melt-mixing. These outcomes indicate the suitability of the adopted sustainable procedure for the production of high-loaded clay&ndash, rubber nanocomposites with remarkable mechanical features.

The present study reports on a simple preparation strategy of a hybrid catalyst, TiO2/HKUST-1, containing TiO2 anatase nanoparticles (NPs) with tailored morphology and photocatalytic activity coupled with a porous metal-organic framework (MOF), namely HKUST-1, as an advanced material for the CO2 photocatalytic reduction. In detail, TiO2/HKUST-1 catalyst was prepared via an easy slow-diffusion method combined with a step-by-step self-assembly at room temperature. The growth of crystalline HKUST-1 onto titania surface was achieved by functionalizing TiO2 nanocrystals, with phosphoesanoic acid (PHA), namely TiO2-PHA, which provides an intimate contact between MOF and TiO2. The presence of a crystalline and porous shell of HKUST-1 on the TiO2 surfaces was assessed by a combination of analytical and spectroscopic techniques. TiO2/HKUST-1 nanocomposite showed a significant efficiency in reducing CO2 to CH4 under solar light irradiation, much higher than those of the single components. The role of MOF to improve the photoreduction process under visible light was evidenced and attributed either to the relevant amount of CO2 captured into the HKUST-1 porous architecture or to the hybrid structure of the material, which affords enhanced visible light absorption and allows an effective electron injection from TiO2-PHA to HKUST-1, responsible for the photochemical reduction of CO2.

The development of advanced polymer nanocomposites requires a strong filler-polymer interfacial interaction and an optimal filler nanodispersion. The incorporation of the clays into a polymer matrix frequently does not improve the composite mechanical properties, owing to both poor dispersion and macroscopic particle dimensions. In this work, pristine and organically-modified sepiolites (Sep) were structurally modified by an acid treatment, which provides nano-sized sepiolite (NS-Sep) fibers with reduced particle size and increased silanol groups on the surface layer. NS-Sep fibers were used to prepare styrene-butadiene rubber nanocomposites with enhanced mechanical properties. Dynamic-mechanical analysis of clay polymer nanocomposites demonstrated that the NS-Sep fibers provided an excellent balance between reinforcing and hysteretic behavior, compared to the large-sized pristine Sep and isotropic silica. This was related to the enhanced interfacial chemical interaction between NS-Sep and rubber, as well as to the size and self-assembly of anisotropic nanofibers to form filler network structures, as supported by transmission electron microscopy analysis. The preparation of nanocomposites, based on Sep nanofibers obtained by a simple and versatile acid treatment, can thus be considered an alternative approach for the designing of advanced clay polymer nanocomposites.

The present study provides a comprehensive investigation at the micro and nanoscale of the interface between hybrid SiO2@POSS nanofiller, where silica nanoparticles (NPs) and POSS nanocages are intimately interconnected, and Styrene Butadiene Rubber (SBR). SEM and AFM inspection and, more in depth, solid state 1H NMR revealed a remarkable fraction of rigid rubber close to the SiO2@POSS surfaces, which increases with the curing temperature. Instead, a reduced amount of immobilized rubber was detected for SBR/SiO2+POSS nanocomposites, obtained by simply mixing SBR, SiO2 and POSS. The results allowed us to propose a model for the network formation in C-SBR/SiO2@POSS. This is based on the progressive activation by dicumylperoxide (DCP) of the methacryl functionalities of POSS nanounits which, being closely connected to SiO2 NPs in SiO2@POSS, promote crosslinking in proximity of the filler surfaces, and lead to the generation of a tight network strongly bonded to the rubber chains.

A novel hybrid nanofiller, SiO2@POSS, where the silica nanoparticles (NPs) and the POSS belong to the same functional structure, has been synthesized by grafting different loadings of OctaMethacrylPOSS onto silanized commercial SiO2, using a surface reaction mediated by dicumylperoxide (DCP). The peroxide, besides anchoring the nanocages onto the silica surface, ensures the presence of methacryl functionalities in the final structure, which are still available for cross-linking reactions with a polymer host. The hybrid SiO2@POSS NPs were used to prepare, by ex situ blending, SBR nanocomposites. The dynamic-mechanical analysis performed on the cured SBR/SiO2@ POSS composites indicated that the presence of POSS induces a remarkable increase of modulus either at low or at high strain, and a considerable decrease of hysteresis. This has been associated with the peculiar hybrid structure of the SiO2@POSS filler, in which silica NP aggregates are partially interconnected and surrounded by a thin shell of POSS nanounits which, thanks to their high number of reactive functionalities, promote the formation of "sticky regions'' among the silica aggregates and, consequently, a tight filler network wherein rubber is immobilized. This grants a relevant reinforcement and increased hysteretic properties, suggesting SiO2@POSS as a promising filler system for decreasing the energy loss under strain and for leading to a potential reduction of filler utilization in rubber composite formulations.

Silica-styrene butadiene rubber (SBR) nanocomposites were prepared by using shape-controlled spherical and rod-like silica nanoparticles (NPs) with different aspect ratios (AR = 1-5), obtained by a sol-gel route assisted by a structure directing agent. The nanocomposites were used as models to study the influence of the particle shape on the formation of nanoscale immobilized rubber at the silica-rubber interface and its effect on the dynamic-mechanical behavior. TEM and AFM tapping mode analyses of nanocomposites demonstrated that the silica particles are surrounded by a rubber layer immobilized at the particle surface. The spherical filler showed small contact zones between neighboring particles in contact with thin rubber layers, while anisotropic particles (AR > 2) formed domains of rods preferentially aligned along the main axis. A detailed analysis of the polymer chain mobility by different time domain nuclear magnetic resonance (TD-NMR) techniques evidenced a population of rigid rubber chains surrounding particles, whose amount increases with the particle anisotropy, even in the absence of significant differences in terms of chemical crosslinking. Dynamic measurements demonstrate that rod-like particles induce stronger reinforcement of rubber, increasing with the AR. This was related to the self-alignment of the anisotropic silica particles in domains able to immobilize rubber. This journal is

Silica/styrene butadiene rubber (SBR) nanocomposites were prepared by blending method using shape-controlled spherical and rod-like nanoparticles with different aspect ratios as filler for the rubber reinforcement. The differently shaped silica particles were synthesized by sol-gel method using tetraethoxysilane (TEOS) and (3-mercaptopropyl) trimethoxysilane (MPTSM) as silica precursors, and cetyltrimethylammonium bromide (CTAB) as structure directing agent. This strategy allowed to study the influence of the particle morphology on the reinforcing effect independently of the silica surface chemistry and considering the aspect ratio as the only geometrical variance. Spherical and anisotropic rod-like particles, dispersed in the nanocomposites, formed a network of particles bridged by thin rubber layers throughout the SBR matrix. Moreover, differently oriented domains of aligned rods are observed when the aspect ratio of particles increases and is >=2. Dynamic-mechanical properties demonstrated that the rod-like particles with the higher aspect ratio provided stronger reinforcement of the rubber. This was related to the self-alignment of the anisotropic particles and to the consequent larger filler/polymer interface, compared to that of spherical ones. © 2014 Elsevier Ltd. All rights reserved.