Facile and Bioinspired Approach from Gallic Acid for the Synthesis of Biobased Flame Retardant Coatings of Basalt Fibers.

A sustainable, bioinspired approach to functionalize basalt fibers with an innovative gallic acid (GA)-iron phenyl phosphonate complex (BF-GA-FeP), for the purpose of improving the flame retardancy in composite materials, is developed. BFs were at first pretreated with O3, obtaining surface free hydroxyl groups that allowed the subsequent covalent immobilization of biosourced GA units on the fiber through ester linkages. Phenolic -OH groups of the GA units were then exploited for the complexation of iron phenyl phosphonate, resulting in the target-complex-coated BF fiber (BF-GA-FeP). Microwave plasma atomic emission spectroscopy and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy analyses of BF-GA-FeP highlighted an increase in iron content, modification of fiber morphology, and occurrence of phosphorus, respectively. BFs, modified with a low amount of the developed complex, were used to reinforce a poly(lactic acid) (PLA) matrix in the production of a biocomposite (PLA/BF-FeP). PLA/BF-FeP showed a higher thermal stability than neat PLA and PLA reinforced with untreated BFs (PLA/BF), as confirmed by thermogravimetric analysis. The cone calorimeter test highlighted several advantages for PLA/BF-FeP, including a prolonged time to ignition, a reduced time to flame out, an 8% decrease in the peak heat release rate, and a 15% reduced fire propagating index compared to PLA/BF.

Hybrid Hemp Particles as Functional Fillers for the Manufacturing of Hydrophobic and Anti-icing Epoxy Composite Coatings.

The development of hydrophobic composite coatings is of great interest for several applications in the aerospace industry. Functionalized microparticles can be obtained from waste fabrics and employed as fillers to prepare sustainable hydrophobic epoxy-based coatings. Following a waste-to-wealth approach, a novel hydrophobic epoxy-based composite including hemp microparticles (HMPs) functionalized with waterglass solution, 3-aminopropyl triethoxysilane, polypropylene-graft-maleic anhydride, and either hexadecyltrimethoxysilane or 1H,1H,2H,2H-perfluorooctyltriethoxysilane is presented. The resulting epoxy coatings based on hydrophobic HMPs were cast on aeronautical carbon fiber-reinforced panels to improve their anti-icing performance. Wettability and anti-icing behavior of the prepared composites were investigated at 25 °C and -30 °C (complete icing time), respectively. Samples cast with the composite coating can achieve up to 30 °C higher water contact angle and doubled icing time than aeronautical panels treated with unfilled epoxy resin. A low content (2 wt %) of tailored HMPs causes an increase of ∼26% in the glass transition temperature of the coatings compared to pristine resin, confirming the good interaction between the hemp filler and epoxy matrix at the interphase. Finally, atomic force microscopy reveals that the HMPs can induce the formation of a hierarchical structure on the surface of casted panels. This rough morphology, combined with the silane activity, allows the preparation of aeronautical substrates with enhanced hydrophobicity, anti-icing capability, and thermal stability.

Solvent-Free One-Pot Synthesis of Epoxy Nanocomposites Containing Mg(OH)2 Nanocrystal-Nanoparticle Formation Mechanism.

Epoxy nanocomposites containing Mg(OH)2 nanocrystals (MgNCs, 5.3 wt %) were produced via an eco-friendly "solvent-free one-pot" process. X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and thermogravimetric analysis (TGA) confirm the presence of well-dispersed MgNCs. HRTEM reveals the presence also of multisheet-silica-based nanoparticles and a tendency of MgNCs to intergrow, leading to complex nanometric structures with an intersheet size of ∼0.43 nm, which is in agreement with the lattice spacing of the Mg(OH)2 (001) planes. The synthesis of MgNCs was designed on the basis of a mechanism initially proposed for the preparation of multisheet-silica-based/epoxy nanocomposites. The successful "in situ" generation of MgNCs in the epoxy via a "solvent-free one-pot" process confirms the validity of the earlier disclosed mechanism and thus opens up possibilities of new NCs with different fillers and polymer matrix. The condition would be the availability of a nanoparticle precursor soluble in the hydrophobic resin, giving the desired phase through hydrolysis and polycondensation.

Co-immobilization of Cellulase and ß-Glucosidase into Mesoporous Silica Nanoparticles for the Hydrolysis of Cellulose Extracted from Eriobotrya japonica Leaves.

Fungal cellulases generally contain a reduced amount of ß-glucosidase (BG), which does not allow for efficient cellulose hydrolysis. To address this issue, we implemented an easy co-immobilization procedure of ß-glucosidase and cellulase by adsorption on wrinkled mesoporous silica nanoparticles with radial and hierarchical open pore structures, exhibiting smaller (WSN) and larger (WSN-p) inter-wrinkle distances. The immobilization was carried out separately on different vectors (WSN for BG and WSN-p for cellulase), simultaneously on the same vector (WSN-p), and sequentially on the same vector (WSN-p) in order to optimize the synergy between cellulase and BG. The obtained results pointed out that the best biocatalyst is that prepared through simultaneous immobilization of BG and cellulase on the same vector (WSN-p). In this case, the adsorption resulted in 20% yield of immobilization, corresponding to an enzyme loading of 100 mg/g of support. 82% yield of reaction and 72 µmol/min·g activity were obtained, evaluated for the hydrolysis of cellulose extracted from Eriobotrya japonica leaves. All reactions were carried out at a standard temperature of 50 °C. The biocatalyst retained 83% of the initial yield of reaction after 9 cycles of reuse. Moreover, it had better stability than the free enzyme mixture in a wide range of temperatures, preserving 72% of the initial yield of reaction up to 90 °C.

Structure and Bottom-up Formation Mechanism of Multisheet Silica-Based Nanoparticles Formed in an Epoxy Matrix through an In Situ Process.

Organic/inorganic hybrid composite materials with the dispersed phases in sizes down to a few tens of nanometers raised very great interest. In this paper, it is shown that silica/epoxy nanocomposites with a silica content of 6 wt % may be obtained with an "in situ" sol-gel procedure starting from two precursors: tetraethyl orthosilicate (TEOS) and 3-aminopropyl-triethoxysilane (APTES). APTES also played the role of a coupling agent. The use of advanced techniques (bright-field high-resolution transmission electron microscopy, HRTEM, and combined small- and wide-angle X-ray scattering (SAXS/WAXS) performed by means of a multirange device Ganesha 300 XL+) allowed us to evidence a multisheet structure of the nanoparticles instead of the gel one typically obtained through a sol-gel route. A mechanism combining in a new manner well-assessed knowledge regarding sol-gel chemistry, emulsion formation, and Ostwald ripening allowed us to give an explanation for the formation of the observed lamellar nanoparticles.

Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride.

Thermosetting polymers have been widely used in many industrial applications as adhesives, coatings and laminated materials, among others. Recently, bisphenol A (BPA) has been banned as raw material for polymeric products, due to its harmful impact on human health. On the other hand, the use of aromatic amines as curing agents confers excellent thermal, mechanical and flame retardant properties to the final product, although they are toxic and subject to governmental restrictions. In this context, sugar-derived diepoxy monomers and anhydrides represent a sustainable greener alternative to BPA and aromatic amines. Herein, we report an "in-situ" sol-gel synthesis, using as precursors tetraethylorthosilicate (TEOS) and aminopropyl triethoxysilane (APTS) to obtain bio-based epoxy/silica composites; in a first step, the APTS was left to react with 2,5-bis[(oxyran-2-ylmethoxy)methyl]furan (BOMF) or diglycidyl ether of bisphenol A (DGEBA)monomers, and silica particles were generated in the epoxy in a second step; both systems were cured with methyl nadic anhydride (MNA). Morphological investigation of the composites through transmission electron microscopy (TEM) demonstrated that the hybrid strategy allows a very fine distribution of silica nanoparticles (at nanometric level) to be achieved within a hybrid network structure for both the diepoxy monomers. Concerning the fire behavior, as assessed in vertical flame spread tests, the use of anhydride curing agent prevented melt dripping phenomena and provided high char-forming character to the bio-based epoxy systems and their phenyl analog. In addition, forced combustion tests showed that the use of anhydride hardener instead of aliphatic polyamine results in a remarkable decrease of heat release rate. An overall decrease of the smoke parameters, which is highly desirable in a context of greater fire safety was observed in the case of BOMF/MNA system. The experimental results suggest that the effect of silica nanoparticles on fire behavior appears to be related to their dispersion degree.

A New Strategy to Produce Hemp Fibers through a Waterglass-Based Ecofriendly Process.

Natural fibers such as kenaf, hemp, flax, jute, and sisal have become the subject of much research as potential green or eco-friendly reinforcement composites, since they assure the reduction of weight, cost, and CO2 release with less reliance on oil sources. Herein, an inexpensive and eco-friendly waterglass treatment is proposed, allowing the production of silica-coated fibers that can be easily obtained in micro/nano fibrils through a low power mixer. The silica coating has been exploited to improve the chemical compatibility between fibers and the polymer matrix through the reaction of silanol groups with suitable coupling agents. In particular, silica-coated fibers easily functionalized with (3-Aminopropyl) triethoxysilane (APTS) were used as a filler in the manufacturing of epoxy-based composites. Morphological investigation of the composites through Scanning Electron Microscopy (SEM) demonstrated that the filler has a tendency to produce a web-like structure, formed by continuously interconnected fibrils and microfibrils, from which particularly effective mechanical properties may be obtained. Dynamic Mechanical Analysis (DMA) shows that the functionalized fibers, in a concentration of 5 wt%, strongly affect the glass transformation temperature (10 °C increase) and the storage modulus of the pristine resin. Taking into account the large number of organosilicon compounds (in particular the alkoxide ones) available on the market, the new process appears to pave the way for the cleaner and cheaper production of biocomposites with different polymeric matrices and well-tailored interfaces.

Water Resistant Self-Extinguishing Low Frequency Soundproofing Polyvinylpyrrolidone Based Electrospun Blankets.

This paper shows that an eco-friendly electrospinning process allows us to produce water resistant sound absorbers with reduced thickness and excellent sound-absorption properties in the low and medium frequency range (250-1600 Hz) for which which human sensitivity is high and traditional materials struggle to match, that also pass the fire tests which are mandatory in many engineering areas. The structure and composition were studied through Scanning Electron Microscopy (SEM), Fourier Transform InfraRed (FTIR) Spectroscopy and ThermoGravimetric Analysis (TGA). The density, porosity and flow resistivity were measured. Preliminary investigation of the thermal conductivity through Differential Scanning Calorimetry (DSC) shows that they have perspectives also for thermal insulation. The experimental results indicate that the achievements are to be ascribed to the chemical nature of Polyvinylpyrrolidone (PVP). PVP is, in fact, a polymeric lactam with a side polar group that may be easily released by a thermooxidative process. The side polar groups allow for using ethanol for electrospinning than relying on a good dispersion of silica gel particles. The silica particles dimensionally stabilize the mats upon thermal treatments and confer water resistance while strongly contributing to the self-extinguishing property of the materials.

Non Monotonous Effects of Noncovalently Functionalized Graphene Addition on the Structure and Sound Absorption Properties of Polyvinylpyrrolidone (1300 kDa) Electrospun Mats.

Graphene is an attractive component for high-performance stimuli-responsive or 'smart' materials, shape memory materials, photomechanical actuators, piezoelectric materials and flexible strain sensors. Nanocomposite fibres were produced by electrospinning high molecular weight Polyvinylpyrrolidone (PVP-1300 kDa) in the presence of noncovalently functionalised graphene obtained through tip sonication of graphite alcoholic suspensions in the presence of PVP (10 kDa). Bending instability of electrospun jet appears to progressively increase at low graphene concentrations with the result of greater fibre stretching that leads to lower fibre diameter and possibly conformational changes of PVP. Further increase of graphene content seams having the opposite effect leading to greater fibre diameter and Raman spectra similar to the pure PVP electrospun mats. All this has been interpreted on the basis of currently accepted model for bending instability of electrospun jets. The graphene addition does not lower the very high sound absorption coefficient, α, close to unity, of the electrospun PVP mats in the frequency range 200⁻800 Hz. The graphene addition affects, in a non-monotonous manner, the bell shaped curves of α versus frequency curves becoming sharper and moving to higher frequency at the lower graphene addition. The opposite is observed when the graphene content is further increased.