•FT-IR and NMR spectroscopies were used for the discrimination of samples with different geographical provenance.•T1ρ(H) values, obtained from variable contact time NMR experiments highlighted the ...differences between wood groups.•Principal component analysis of NMR and IR data allowed the most effective discrimination of wood due to provenance.
13C nuclear magnetic resonance and mid-infrared spectroscopies were used for characterizing changes in the chemical structure of wood polymers (cellulose, hemicellulose and lignin) in relation to the tree growth location. Samples of three provenances in Europe (Finland, Poland and Italy) were selected for studies. The requirement was to use untreated solid wood samples to minimize any manipulation to the nanostructure of native wood.
The results confirm that the chemical and physical properties of samples belonging to the same wood species (Picea abies Karst.) differ due to the origin. Both FT-IR and dynamic NMR spectroscopies were able to correctly discriminate samples originating from three different provenances in Europe. Such methods might be very useful for both, research and understanding of wood microstructure and its variability due to the growth conditions.
Organic phase change materials (PCMs) represent an effective solution to manage intermittent energy sources as the solar thermal energy. This work aims at encapsulating docosane in organosilica ...shells and at dispersing the produced capsules in epoxy/carbon laminates to manufacture multifunctional structural composites for thermal energy storage (TES). Microcapsules of different sizes were prepared by hydrolysis-condensation of methyltriethoxysilane (MTES) in an oil-in-water emulsion. X-ray diffraction (XRD) highlighted the difference in the crystalline structure of pristine and microencapsulated docosane, and
C solid-state nuclear magnetic resonance (NMR) evidenced the influence of microcapsules size on the shifts of the representative docosane signals, as a consequence of confinement effects, i.e., reduced chain mobility and interaction with the inner shell walls. A phase change enthalpy up to 143 J/g was determined via differential scanning calorimetry (DSC) on microcapsules, and tests at low scanning speed emphasized the differences in the crystallization behavior and allowed the calculation of the phase change activation energy of docosane, which increased upon encapsulation. Then, the possibility of embedding the microcapsules in an epoxy resin and in an epoxy/carbon laminate to produce a structural TES composite was investigated. The presence of microcapsules agglomerates and the poor capsule-epoxy adhesion, both evidenced by scanning electron microscopy (SEM), led to a decrease in the mechanical properties, as confirmed by three-point bending tests. Dynamic mechanical analysis (DMA) highlighted that the storage modulus decreased by 15% after docosane melting and that the glass transition temperature of the epoxy resin was not influenced by the PCM. The heat storage/release properties of the obtained laminates were proved through DSC and thermal camera imaging tests.
Barium titanate (BT) recently gained new interest in the preparation of dielectric and piezoelectric lead-free materials for applications in sensors, electronics, energy harvesting and storage ...fields. Barium titanate nanocomposites can achieve attractive performance, provided that the compatibility between ceramic particles and polymeric matrices is enhanced to the benefit of the physical properties of the final composite. Tuning the particle–matrix interface through particle functionalization represents a viable solution. In this work, surface functionalization of BT nanoparticles (NPs), obtained by hydrothermal synthesis, with 3-glycidyloxypropyltrimethoxysilane, 2-(acetoxy(polyethyleneoxy)propyltriethoxysilane and triethoxysilylpropoxy(polyethyleneoxy)dodecanoate, was performed after optimizing the hydroxylation process of the NPs to improve their surface reactivity and increase the yield of grafting. Solid-state nuclear magnetic resonance and thermogravimetric analysis were used to quantify the molecules grafted onto the ceramic nanoparticles. Both bare and functionalized particles were employed in the realization of epoxy- and polydimethylsiloxane (PDMS)-based nanocomposites. Functionalization was proven to be beneficial for particle dispersibility and effective for particle alignment in the PDMS matrix. Moreover, the dielectric constant measurements revealed the potential of PDMS-based nanocomposites for applications in the field of dielectric elastomers.
The functional properties displayed by graphene oxide (GO)-polymer nanocomposites are strongly affected by the dispersion ability of GO sheets in the polymeric matrix, which can be largely improved ...by functionalization with organosilanes. The grafting to GO of organosilanes with the general formula RSi(OCH
)
is generally explained by the condensation reactions of silanols with GO reactive groups. In this study, the influence of the organic group on the RSi(OCH
)
grafting ability was analyzed in depth, taking into account the interactions of the R end chain group with GO oxidized groups. Model systems composed of commercial graphene oxide reacted with 3-aminopropyltrimethoxysilane (APTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), and 3-methacryloxypropyltrimethoxysilane, (MaPTMS), respectively, were characterized by natural abundance
C,
N and
Si solid state nuclear magnetic resonance (NMR), x-ray diffraction (XRD), and electron spin resonance (ESR). The silane organic tail significantly impacts the grafting, both in terms of the degree of functionalization and direct interaction with GO reactive sites. Both the NMR and XRD proved that this is particularly relevant for APTMS and to a lower extent for MPTMS. Moreover, the epoxy functional groups on the GO sheets appeared to be the preferential anchoring sites for the silane condensation reaction. The characterization approach was applied to the GO samples prepared by the nitric acid etching of graphene and functionalized with the same organosilanes, which were used as a filler in acrylic coatings obtained by cataphoresis, making it possible to correlate the structural properties and the corrosion protection ability of the layers.
Damages to the intervertebral disc (IVD) due to improper loading or degeneration result in back pain, which is a common disease affecting an increasing number of patients. Different strategies for ...IVD remediation have been developed, from surgical treatment to disc replacement, by using both metallic and non-metallic materials. Hydrogels are very attractive materials due to their ability to simulate the properties of many soft tissues; moreover, their chemical composition can be varied in order to assure performances similar to the natural disc. In particular, for the replacement of the IVD outer ring, namely, the anulus fibrosus, the shear properties are of paramount importance. In this work, we produced hydrogels through the photo-induced crosslinking of different mixtures composed of two hydrophilic monofunctional and difunctional polymers, namely, poly(ethyleneglycol) methyl ether methacrylate (PEGMEMA) and poly(ethyleneglycol) dimethacrylate (PEGDMA), together with a hydrophobic molecule, i.e., tert-butyl acrylate (tBA). By changing the ratio among the precursors, we demonstrated the tunability of both the shear properties and hydrophilicity. The structural properties of hydrogels were studied by solid-state nuclear magnetic resonance (NMR). These experiments provided insights on both the structure and molecular dynamics of polymeric networks and, together with information obtained by differential scanning calorimetry (DSC), allowed for correlating the physical properties of the hydrogels with their chemical composition.
Sepiolite clay is a natural filler particularly suitable to be used with polysaccharide matrices (e.g., in starch-based bio-nanocomposites), increasing their attractiveness for a wide range of ...applications, such as packaging. Herein, the effect of the processing (i.e., starch gelatinization, addition of glycerol as plasticizer, casting to obtain films) and of the sepiolite filler amount on the microstructure of starch-based nanocomposites was investigated by SS-NMR (solid-state nuclear magnetic resonance), XRD (X-ray diffraction) and FTIR (Fourier-transform infrared) spectroscopy. Morphology, transparency and thermal stability were then assessed by SEM (scanning electron microscope), TGA (thermogravimetric analysis) and UV-visible spectroscopy. It was demonstrated that the processing method allowed to disrupt the rigid lattice structure of semicrystalline starch and thus obtain amorphous flexible films, with high transparency and good thermal resistance. Moreover, the microstructure of the bio-nanocomposites was found to intrinsically depend on complex interactions among sepiolite, glycerol and starch chains, which are also supposed to affect the final properties of the starch-sepiolite composite materials.
Ladder-like poly(methacryloxypropyl)-silsesquioxanes (LPMASQ) are photocurable Si-based gels characterized by a double-stranded structure that ensures superior thermal stability and mechanical ...properties than common organic polymers. In this work, these attractive features were exploited to produce, in combination with alumina nanoparticles (NPs), both unmodified and functionalized with methacryloxypropyl-trimethoxysilane (MPTMS), LPMASQ/Al2O3 composites displaying remarkable thermal conductivity. Additionally, we combined LPMASQ with polybutadiene (PB) to produce hybrid nanocomposites with the addition of functionalized Al2O3 NPs. The materials underwent thermal stability, structural, and morphological evaluations via thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance (NMR). Both blending PB with LPMASQ and surface functionalization of nanoparticles proved to be effective strategies for incorporating a higher ceramic filler amount in the matrices, resulting in significant increases in thermal conductivity. Specifically, a 113.6% increase in comparison to the bare matrix was achieved at relatively low filler content (11.2 vol%) in the presence of 40 wt% LPMASQ. Results highlight the potential of ladder-like silsesquioxanes in the field of thermally conductive polymers and their applications in heat dissipation for flexible electronic devices.
Hybrid sol-gel coatings, named U(X):TEOS, based on ureasilicate matrices (U(X)) enriched with tetraethoxysilane (TEOS), were synthesized. The influence of TEOS addition was studied on both the ...structure of the hybrid sol-gel films as well as on the electrochemical properties. The effect of TEOS on the structure of the hybrid sol-gel films was investigated by solid state Nuclear Magnetic Resonance. The dielectric properties of the different materials were investigated by electrochemical impedance spectroscopy. The corrosion behavior of the hybrid coatings on HDGS was studied in chloride-contaminated simulated concrete pore solutions (SCPS) by polarization resistance measurements. The roughness of the HDGS coated with hybrids was also characterized by atomic force microscopy. The structural characterization of the hybrid materials proved the effective reaction between Jeffamine
and 3-isocyanate propyltriethoxysilane (ICPTES) and indicated that the addition of TEOS does not seem to affect the organic structure or to increase the degree of condensation of the hybrid materials. Despite the apparent lack of influence on the hybrids architecture, the polarization resistance measurements confirmed that TEOS addition improves the corrosion resistance of the hybrid coatings (U(X):TEOS) in chloride-contaminated SCPS when compared to samples prepared without any TEOS (U(X)). This behavior could be related to the decrease in roughness of the hybrid coatings (due TEOS addition) and to the different metal coating interaction resulting from the increase of the inorganic component in the hybrid matrix.
The hydrolysis-condensation of trialkoxysilanes under strictly controlled conditions allows the production of silsesquioxanes (SSQs) with tunable size and architecture ranging from ladder to ...cage-like structures. These nano-objects can serve as building blocks for the preparation of hybrid organic/inorganic materials with selected properties. The SSQs growth can be tuned by simply controlling the reaction duration in the in situ water production route (ISWP), where the kinetics of the esterification reaction between carboxylic acids and alcohols rules out the extent of organosilane hydrolysis-condensation. Tunable SSQs with thiol functionalities (SH-NBBs) are suitable for further modification by exploiting the simple thiol-ene click reaction, thus allowing for modifying the wettability properties of derived coatings. In this paper, coatings were prepared from SH-NBBs with different architecture onto cotton fabrics and paper, and further functionalized with long alkyl chains by means of initiator-free UV-induced thiol-ene coupling with 1-decene (C10) and 1-tetradecene (C14). The coatings appeared to homogeneously cover the natural fibers and imparted a multi-scale roughness that was not affected by the click functionalization step. The two-step functionalization of cotton and paper warrants a stable highly hydrophobic character to the surface of natural materials that, in perspective, suggests a possible application in filtration devices for oil-water separation. Furthermore, the purification of SH-NBBs from ISWP by-products was possible during the coating process, and this step allowed for the fast, initiator-free, click-coupling of purified NBBs with C10 and C14 in solution with a nearly quantitative yield. Therefore, this approach is an alternative route to get sol-gel-derived, ladder-like, and cage-like SSQs functionalized with long alkyl chains.
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