Exploring the Effect of Resins of Different Origin on the Structure, Dynamics and Curing Characteristics of SBR Compounds.

The replacement of synthetic and petroleum-based ingredients with greener alternatives of natural origin is an imperative issue in rubber technology for the tire industry. In this study, a glycerin-esterified maleated rosin resin, derived from natural resources, is examined as a potential tackifier in styrene-butadiene rubber (SBR) formulations. A comparison is made with two synthetic resins commonly used as tackifiers in tire manufacturing: a petroleum-derived aromatic resin and a phenolic resin. Specifically, this research investigates how these resins affect the structure, dynamics, and curing characteristics of SBR compounds, which are strictly related to the mechanical and technological properties of the final products. Moving die rheometer and equilibrium swelling experiments are employed to analyze vulcanization kinetics and crosslink density, which are differently influenced by the different resins. Information on the polymer-resin compatibility is gained by differential scanning calorimetry and dynamo-mechanical analysis, while solid-state NMR methods offer insights into the structure and dynamics of both cured and uncured SBR compounds at the molecular level. Overall, our analysis shows that the resin of vegetal origin has a comparable impact on the SBR compound to that observed for the synthetic resins and could be further tested for industrial applications.

Thermally Activable Bistetrazoles for Elastomers Crosslinking.

Sulfur vulcanization is the most used method for curing of natural and synthetic rubbers. The crosslinking degree achieved is usually controlled by adding proper quantities of accelerants, activators, co-activators, retardants, and inhibitors, and influences the hardness, elasticity, hysteresis of elastomers and, consequently, the properties and behavior of the materials that incorporate them. Despite the fine tuning pursued over the years, sulfur crosslinking is still difficult to control both in terms of degree and homogeneity of cross-link. Addition of thermally activable bifunctional reagents able to crosslink the polymer matrix through covalent bonds could be a strategy to modulate and control finely the reticulation grade of elastomers. Tetrazoles can form highly reactive nitrilimines by thermal treatment at appropriate temperature, which can react with the vinyl double bonds present in the rubber. In this work a set of bis-tetrazoles were synthesized and those with the right activation temperatures were used for the curing of styrene-butadiene rubber, acting both as single crosslinkers and together with classic sulfur-based ones. The addition of bistetrazoles simplified and made more efficient the compounding process, allowing to prolong the mixing until optimum dispersion and homogeneity were obtained. Moreover, they led to an improvement in the hysteretic properties of the compound and to the reduction of the non-linearity of the dynamic behavior (Payne effect).

Influence of Sulfur-Curing Conditions on the Dynamics and Crosslinking of Rubber Networks: A Time-Domain NMR Study.

The characterization of the structural and dynamic properties of rubber networks is of fundamental importance in rubber science and technology to design materials with optimized mechanical properties. In this work, natural and isoprene rubber networks obtained by curing at three different temperatures (140, 150, and 170 °C) and three different sulfur contents (1, 2, and 3 phr) in the presence of a 3 phr accelerator were studied using a combination of low-field time-domain NMR (TD-NMR) techniques, including 1H multiple-quantum experiments for the measurement of residual dipolar couplings (Dres), the application of the Carr-Purcell-Meiboom-Gill pulse sequence for the measurement of the transverse magnetization decay and the extraction of 1H T2 relaxation times, and the use of field cycling NMR relaxometry for the determination of T1 relaxation times. The microscopic properties determined by TD-NMR experiments were discussed in comparison with the macroscopic properties obtained using equilibrium swelling, moving die rheometer, and calorimetric techniques. The obtained correlations between NMR observables, crosslink density values, maximum torque values, and glass transition temperatures provided insights into the effects of the vulcanization temperature and accelerator/sulfur ratio on the structure of the polymer networks, as well as on the effects of crosslinking on the segmental dynamics of elastomers. Dres and T2 were found to show linear correlations with the crosslink density determined by equilibrium swelling, while T1 depends on the local dynamics of polymer segments related to the glass transition, which is also affected by chemical modifications of the polymer chains occurring during vulcanization.

Silica hairy nanoparticles: a promising material for self-assembling processes.

"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.

Glassy and Polymer Dynamics of Elastomers by 1H-Field-Cycling NMR Relaxometry: Effects of Fillers.

1H spin-lattice relaxation rate (R1) dispersions were acquired by field-cycling (FC) NMR relaxometry between 0.01 and 35 MHz over a wide temperature range on polyisoprene rubber (IR), either unfilled or filled with different amounts of carbon black, silica, or a combination of both, and sulfur cured. By exploiting the frequency-temperature superposition principle and constructing master curves for the total FC NMR susceptibility, χ″(ω) = ωR1(ω), the correlation times for glassy dynamics, τs, were determined. Moreover, the contribution of polymer dynamics, χpol″(ω), to χ″(ω) was singled out by subtracting the contribution of glassy dynamics, χglass″(ω), well represented by the Cole-Davidson spectral density. Glassy dynamics resulted moderately modified by the presence of fillers, τs values determined for the filled rubbers being slightly different from those of the unfilled one. Polymer dynamics was affected by the presence of fillers in the Rouse regime. A change in the frequency dependence of χpol″(ω) at low frequencies was observed for all filled rubbers, more pronounced for those reinforced with silica, which suggests that the presence of the filler particles can affect chain conformations, resulting in a different Rouse mode distribution, and/or interchain interactions modulated by translational motions.

Radiographic evaluation of the tunnel position in single and double bundle anterior cruciate ligament reconstruction.

Aim To evaluate tunnel positioning on radiographs in singlebundle (SB) and double-bundle (DB) anterior cruciate ligament (ACL) reconstruction, to evaluate if measurement is accurate and reproducible. Methods Radiographs of 30 SB and 30 DB ACL reconstruction were reviewed by two examiners who measured tunnel positioning with the quadrant method on the femur (a=depth, b=height) and the Amis and Jakob method on the tibia. Intra- and inter-observer reliability were evaluated with intra-class correlation coefficient (ICC). Results A radiographic analysis was completed in all patients in a SB-group and in 27 in a DB-group (p>0.05). Intra-observer reliability was almost perfect on femoral (ICC: a=0.85, b=0.83) and tibial (ICC=0.87) side in the SB-group. In the DB-group, it was almost perfect for tibial anteromedial (AM) and posterolateral (PL) bundles (ICC: AM=0.84, PL=0.81) and for femoral PL bundle (ICC: a=0.83, b=0.82), and substantial for femoral AM bundle (ICC: a=0.78, b=0.74). Inter-observer reliability was almost perfect on tibial (ICC=0.81) and femoral (ICC: a=0.81, b=0.87) side in the SB-group, and substantial on tibial (ICC: AM=0.71, PL=0.77) and femoral (ICC: AM a=0.73, b=0.78; PL a=0.74, b=0.76) side in the DB-group. Standard deviation (SD) was low (±9%) with respect to the centre of tunnel(s). Conclusion The quadrant method and the Amis and Jakob method are accurate and reproducible measurement methods. Also, as SD was low, an outside-in approach with a front-entry guide, which is free-hand positioned, can be postulated as a reliable method to locate the femoral tunnel in SB reconstruction and the AM bundle in DB reconstruction.

Enzymatic Modification of Cellulose To Unlock Its Exploitation in Advanced Materials.

Nowadays natural biopolymers have a wide variety of uses in various industrial applications, such as food, adhesives and composite materials. Among them, cellulose has attracted the interest of researchers due to its properties: high strength and flexibility, biocompatibility and nontoxicity. Despite that, in many cases its practical use is limited because of poor solubility and/or an unsuitable hydrophilic/hydrophobic balance. In this context, enzymatic modification appears as a powerful strategy to overcome these problems through selective, green and environmentally friendly processes. This minireview discusses the different methods developed for the enzymatic modification of cellulose, emphasizing the type of reaction, the enzymes used (laccases, esterases, lipases, hexokinases, etc.), and the properties and applications of the cellulose derivatives obtained. Considering that cellulose is the most abundant natural polymer on Earth and can be derived from residual lignocellulosic biomass, the impact of its use in bio-based process following the logic of the circular economy is relevant.

Graphene Oxide and Oxidized Carbon Black as Catalyst for Crosslinking of Phenolic Resins.

Influence of different graphite-based nanofillers on crosslinking reaction of resorcinol, as induced by hexa(methoxymethyl)melamine, is studied. Curing reactions leading from low molecular mass compounds to crosslinked insoluble networks are studied by indirect methods based on Differential Scanning Calorimetry. Reported results show a catalytic activity of graphene oxide (eGO) on this reaction, comparable to that one already described in the literature for curing of benzoxazine. For instance, for an eGO content of 2 wt %, the exothermic crosslinking DSC peak (upon heating at 10 °C/min) shifted 6 °C. More relevantly, oxidized carbon black (oCB) is much more effective as catalyst of the considered curing reaction. In fact, for an oCB content of 2 wt %, the crosslinking DSC peak can be shifted more than 30 °C and a nearly complete crosslinking is already achieved by thermal treatment at 120 °C. The possible origin of the higher catalytic activity of oCB with respect to eGO is discussed.

Hybrid Interface in Sepiolite Rubber Nanocomposites: Role of Self-Assembled Nanostructure in Controlling Dissipative Phenomena.

Sepiolite (Sep)⁻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⁻filler and filler⁻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.

A Green Approach for Preparing High-Loaded Sepiolite/Polymer Biocomposites.

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⁻rubber nanocomposites with remarkable mechanical features.

Femoral tunnel in revision anterior cruciate ligament reconstruction.

The failure rate after anterior cruciate ligament (ACL) reconstruction performed by expert surgeons is estimated to be in the range of 10-15%, and only 60% of patients undergoing this surgery are able to resume sporting activities comparable to those they engaged in prior to the traumatic incident. Incorrect femoral tunnel placement is one of the main causes of failed ACL reconstruction and this must be remembered when undertaking revision surgery. There are various possible errors that can be committed and, to plan revision surgery correctly, it is fundamental to study the position of the existing femoral tunnel(s) both on classic anteroposterior and lateral plain radiographs and on computed tomography scans with frontal, sagittal, and coronal sections, and also using three-dimensional reconstruction. In-depth anatomical knowledge and familiarity with the various possible surgical techniques are also mandatory for a successful surgical outcome.

Neutral, Cationic, and Anionic Alkyl Derivatives of Tungsten Bonded to a Calix[4]arene Oxo Surface.

The chemically reversible reduction of [(Me)2 W(calix)] to the diamagnetic [(Me)2 W(calix)Na2 ] [Eq. (1)], without major changes in the connectivity of the molecule, illustrates the flexibility of the calixarene ligand and stresses its potential as a molecular functional model of heterogeneous oxo surfaces.