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This work aims at improving and disclosing new properties of films based on polylactic acid (PLA) and a star-shaped polycaprolactone (PCL). Indeed, previous works demonstrated that the presence of ad-hoc synthesized PCL, characterized by low molecular weight and carboxyl end groups (coded as PCL-COOH), improves the elongation at break of the films compared to that of neat PLA and increases their functionality. To further improve the properties of the system, alternating layers of chitosan (CH) and DNA were deposited on the surface applying a Layer-by-Layer (LbL) technique. This method was chosen because it allows the properties of the system to be modified without affecting the specific features of the bulk. In addition, the LbL technique is easily scalable and environmentally friendly because it is based on the use of an aqueous solution of two biomaterials, namely DNA and CH, which are not only derived from renewable sources but are also biocompatible and biodegradable. IR measurements on model silicon substrates subjected to the same treatment as the films, pointed out a linear growth of the proposed LbL assembly. Indeed, FE-SEM measurements highlighted the deposition of a uniform coating. The presence of the CH/DNA assembly reduced the oxygen permeability under both dry and humid (50% R.H.) conditions when compared to the uncoated film. In addition, the coating had no relevant effect on the hydrolytic and enzymatic degradation of the system, so that the biodegradability of the film was maintained., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A novel polyamidoamine (M-PCASS) bearing a disulfide group and two phosphonate groups per repeat unit was obtained by reacting N , N '-methylenebisacrylamide with a purposely designed bis-sec-amine monomer, namely, tetraethyl(((disulfanediylbis(ethane-2,1-diyl))bis(azanediyl))bis(ethane-2,1-diyl))bis(phosphonate) (PCASS). The aim was to ascertain whether the introduction of phosphonate groups, well-known for inducing cotton charring in the repeat unit of a disulfide-containing PAA, increased its already remarkable flame retardant efficacy for cotton. The performance of M-PCASS was evaluated by different combustion tests, choosing M-CYSS, a polyamidoamine containing a disulfide group but no phosphonate groups, as a benchmark. In horizontal flame spread tests (HFSTs), M-PCASS was a more effective flame retardant than M-CYSS at lower add-ons with no afterglow. In vertical flame spread tests, the only effect was afterglow suppression with no self-extinguishment even at add-ons higher than in HFSTs. In oxygen-consumption cone calorimetry tests, M-PCASS decreased the heat release rate peak of cotton by 16%, the CO 2 emission by 50%, and the smoke release by 83%, leaving a 10% residue to be compared with a negligible residue for untreated cotton. Overall, the set of results obtained envisage that the newly synthesized phosphonate-containing PAA M-PCASS may be suitable for specific applications as flame retardant, where smoke suppression or reduction of total gas released is a key requirement.

Linear amphoteric polyamidoamines (PAAs) are usually water-soluble, biodegradable and biocompatible. Crosslinked PAAs form in water hydrogels, retaining most of the favorable properties of their linear counterparts. The hydrogels prepared by the radical post-polymerization of the oligo-α,ω-bisacrylamido-terminated PAA called AGMA1, obtained by the polyaddition of 4-aminobutylguanidine (agmatine) with 2,2-bis(acrylamido)acetic acid, exhibit excellent cell-adhesion properties both in vitro and in vivo. However, due to their low mechanical strength, AGMA1 hydrogels cannot be sewn to biological tissues and need to be reinforced with fibrous materials. In this work, short silk fibers gave excellent results in this sense, proving capable of establishing covalent bonds with the PAA matrix, thanks to their lysine content, which provided amino groups capable of reacting with the terminal acrylamide groups of the AGMA1 precursor in the final crosslinking phase. Morphological analyses demonstrated that the AGMA1 matrix was intimately interconnected and adherent to the silk fibers, with neither visible holes nor empty volumes. The silk/H-AGMA1 composites were still reversibly swellable in water. In the swollen state, they could be sewn and showed no detachment between fibers and matrix and exhibited significantly improved mechanical properties compared with the plain hydrogels, particularly as regards their Young's modulus and elongation at break.

The polyelectrolyte (PE)-based water dispersion of graphene-related materials (GRMs) represents an interesting intermediate for the development of advanced materials by sustainable processes. Although the proof of concept has been demonstrated, there is a lack of knowledge for what concerns the effects of parameters typical of PEs such as functionalization, molecular weight, and charge density. In this work, we evaluate the effects of such parameters on the quality and long-term stability of reduced graphite oxide (rGO) dispersion in aqueous media prepared by ultrasound sonication in the presence of different PEs. Four PEs were evaluated: polyacrylic acid (PAA), branched poly(ethylenimine) (BPEI), sodium carboxymethyl cellulose (CMC), and poly(sodium 4-styrenesulfonic acid) (PSS). The prepared dispersions were thoroughly characterized by means of UV-visible spectroscopy, thermogravimetric analysis, dynamic light scattering, and Raman spectroscopy. The highest concentrations of rGO were achieved by BPEI with a molecular weight of 25,000 and 270,000 Da (33 and 26 µg/mL, respectively). For other PEs, the rGO concentration was found to be independent of the molecular weight. The PAA-based dispersions displayed the best through-time stability while yielding homogeneous dispersion with a smaller average size and narrower size distribution.

Linear polyamidoamines (PAAs) derived from the polyaddition of natural α-amino acids and N , N '-methylene bis(acrylamide) are intumescent flame retardants for cotton. Among them, the glycine-derived M-GLY extinguished the flame in horizontal flame spread tests at 4% by weight add-on. This paper reports on an extensive study aimed at understanding the molecular-level transformations of M-GLY-treated cotton upon heating in air at 300 °C, 350 °C and 420 °C. Thermogravimetric analysis (TGA) identified different thermal-oxidative decomposition stages and, coupled to Fourier transform infrared spectroscopy, allowed the volatile species released upon heating to be determined, revealing differences in the decomposition pattern of treated and untreated cotton. XPS analysis of the char residues of M-GLY-treated cotton revealed the formation of aromatic nanographitic char at lower temperature with respect to untreated cotton. Raman spectroscopy of the char residues provided indications on the degree of graphitization of treated and untreated cotton at the three reference temperatures. Solid state 13 C nuclear magnetic resonance spectroscopy (NMR) provided information on the char structure as a function of the treatment temperature, clearly indicating that M-GLY favors the carbonization of cotton with the formation of more highly condensed aromatic structures.

In the field of bone regeneration, considerable attention has been addressed towards the use of mesoporous bioactive glasses (MBGs), as multifunctional therapeutic platforms for advanced medical devices. In fact, their extremely high exposed surface area and pore volume allow to load and the release of several drugs, while their framework can be enriched with specific therapeutic ions allowing to boost the tissue regeneration. However, due to the open and easily accessible mesopore structure of MBG, the release of the incorporated therapeutic molecules shows an initial burst effect leading to unsuitable release kinetics. Hence, a still open challenge in the design of drug delivery systems based on MBGs is the control of their release behavior. In this work, Layer-by-layer (LbL) deposition of polyelectrolyte multi-layers was exploited as a powerful and versatile technique for coating the surface of Cu-substituted MBG nanoparticles with innovative multifunctional drug delivery systems for co-releasing of therapeutic copper ions (exerting pro-angiogenic and anti-bacterial effects) and an anti-inflammatory drug (ibuprofen). Two different routes were investigated: in the first strategy, chitosan and alginate were assembled by forming the multi-layered surface, and, successively, ibuprofen was loaded by incipient wetness impregnation, while in the second approach, alginate was replaced by ibuprofen, introduced as polyelectrolyte layer. Zeta-potential, TGA and FT-IR spectroscopy were measured after the addition of each polyelectrolyte layer, confirming the occurrence of the stepwise deposition. In addition, the in vitro bioactivity and the ability to modulate the release of the cargo were evaluated. The polyelectrolyte coated-MBGs were proved to retain the peculiar ability to induce hydroxyapatite formation after 7 days of soaking in Simulated Body Fluid. Both copper ions and ibuprofen were co-released over time, showing a sustained release profile up to 14 days and 24 h, respectively, with a significantly lower burst release compared to the bare MBG particles.

During the past 50 years, the aim to reduce the eddy current losses in magnetic cores to a minimum led to the formulation of new materials starting from electrically insulated iron powders, today called Soft Magnetic Composites (SMC). Nowadays, this promising branch of materials is still held back by the mandatory tradeoff between energetic, electrical, magnetic, and mechanical performances. In most cases, the research activity focuses on the deposition of an insulating/binding layer, being one of the critical points in optimizing the final composite. This insulation usually is achieved by either inorganic or organic layer constituents. The main difference is the temperature limit since most inorganic materials typically withstand higher treatment temperatures. As a result, the literature shows many materials and process approaches, each one designed to meet a specific application. The present work summarizes the recent advances in state of the art, analyzing the relationship among material compositions and magnetic and mechanical properties. Each coating shows its own processing sets, which vary from simple mechanical mixing to advanced chemical methods to metallurgical treatments. From state of the art, Aluminum coatings are characterized by higher current losses and low mechanical properties. In contrast, higher mechanical properties are obtained by adopting Silicon coatings. The phosphates coatings show the best-balanced overall properties. Each coating type was thoroughly investigated and then compared with the literature background highlighting. The present paper thus represents a critical overview of the topic that could serve as a starting point for the design and development of new and high-performing coating solutions for SMCs. However, global research activity continuously refines the recipes, introducing new layer materials. The following steps and advances will determine whetherthese materials breakthrough in the market.

In this paper, bioinspired polyamidoamines (PAAs) were synthesized from N,N '-methylenebisacrylamide and nine natural α-amino acids: L -alanine, L -valine, L -leucine (M-LEU), L -histidine, L -serine, L -asparagine, L -glutamine (M-GLN), L -aspartic acid and L -glutamic acid (M-GLU) and their performance as flame retardants (FRs) for cotton were determined. The aim was to ascertain if the ability to protect cotton from fire by the process of intumescing, previously found for the glycine-derived M-GLY, was a general feature of α-amino acid-derived PAAs. None of the PAAs ignited by flame impingement, apart from M-LEU, which burned for a few seconds leaving 93% of residue. All of them formed carbon- and oxygen-rich, porous chars with a graphitic structure in the air at 350 °C, as revealed by X-ray photoelectron spectroscopy. All samples were tested as FRs for cotton by horizontal flame spread tests. At a 5% add-on, M-GLU and M-GLN extinguished the flame. The same results were obtained with all the other PAAs at a 7% add-on. The α-amino acid residues influenced the FR performance. The most effective were those that, by heating, were most suitable for producing thermally stable cyclic aromatic structures. All PAA-treated cotton samples, even when burning, left significant residues, which, according to scanning electron microscopy analysis, maintained the original cotton texture.

The exploitation of self-assembled coatings comprising graphite oxide (GO) nanoplates has been recently demonstrated as a promising route to improve the fire safety of flexible polyurethane (PU) foams. However, limited knowledge has been gathered on the correlations between the physical and chemical properties of different GO grades and the performance obtained in this application. This work addresses the effects of the nanoparticle dimensions on the layer-by-layer (LbL) assembly and flame-retardant properties of GO-based coatings deposited on PU foams. To this aim, three GO bearing different lateral sizes and thicknesses were selected and LbL-assembled with chitosan (CHIT). Coating growth and morphology were evaluated by FTIR and FESEM, respectively. The resulting CHIT/GO assemblies were demonstrated to be capable of slowing down the combustion of the PU both in flammability and forced combustion tests. In addition, compressive stress/strain tests pointed out that the LbL-coated foams (22-24 kg/m 3 ) could easily replace denser commercial PU foam (40-50 kg/m 3 ) with weight reduction potentials in the transport field. These results are correlated with the properties of the employed GO. The production of assemblies characterized by a high density of CHIT/GO interfaces is identified as the main parameter controlling the FR efficiency and the mechanical properties of the coatings.

This manuscript reports the development of functional 3D scaffolds based on chitosan (CHI) and graphite oxide nanoplatelets (GO) for neuronal network growth. To this aim, CHI microparticles, produced by alkaline gelation method, were coated with GO exploiting a simple template-assisted assembly based on the electrostatic attraction in an aqueous medium. The optimal deposition conditions were evaluated by optical microscopy and studied by quartz crystal microbalance. FE-SEM observations highlight the formation of a core-shell structure where the porous chitosan core is completely wrapped by a uniform GO layer. This outer shell protects the inner chitosan from enzymatic degradation thus potentially extending the scaffold viability for in vivo applications. The presence of hydrophilic oxygen-containing functionalities on the outermost layer of GO and its inner conductive graphitic core maintained the bioactivity of the scaffold and promoted neuronal cell adhesion and growth. The proposed approach to modify the surface of CHI microparticles makes it possible for the design of 3D scaffolds for advanced neuronal tissue engineering applications., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The polyamidoamine derived from N,N'-methylenebisacrylamide (M) and glycine (G), M-G, has been shown to be an effective flame-retardant (FR) for cotton in horizontal flame spread tests (HFST), extinguishing the flame at 5% add-on. Its activity was attributed to its intrinsic intumescence. In vertical flame spread tests (VFST), M-G failed to extinguish the flame even at 30% add-on. Conversely, in VFST, the polyamidoamine derived from M and cystine (C), M-C, inhibited cotton combustion at 16% add-on, but in HFST failed to extinguish the flame below 12% add-on. Its activity was ascribed to the release of sulfur-containing volatiles acting as radical scavengers. In this work, the FR effectiveness of M-G m -C n copolymers with different G/C ratio was compared with that of the M-G and M-C homopolymers and of M-G/M-C blends of the same compositions. In HFST, both copolymers and blends extinguished the flame. In particular, M-G 50 -C 50 and (M-G/M-C) 50/50 extinguished the flame, even at 7% add-on. In VFST, the copolymers with ≥50% M-C units, similar to M-C, inhibited cotton combustion at 16% add-on. At the same add-on, the M-G/M-C blends failed to extinguish the flame. It may be concluded that, in contrast to blends, copolymers combined the merits of both homopolymers in all tests.

The high flame-retardant loading required for ethylene-vinyl acetate copolymer blends with polyethylene (EVA-PE) employed for insulation and sheathing of electric cables represents a significant limitation in processability and final mechanical properties. In this work, melamine triazine (TRZ) and modified bentonite clay have been investigated in combination with aluminum trihydroxide (ATH) for the production of EVA-PE composites with excellent fire safety and improved mechanical properties. Optimized formulations with only 120 parts per hundred resin (phr) of ATH can achieve self-extinguishing behavior according to the UL94 classification (V0 rating), as well as reduced combustion kinetics and smoke production. Mechanical property evaluation shows reduced stiffness and improved elongation at break with respect to commonly employed EVA-PE/ATH composites. The reduction in filler content also provides improved processability and cost reductions. The results presented here allow for a viable and halogen-free strategy for the preparation of high performing EVA-PE composites., Competing Interests: The authors declare no conflicts of interest.

Hydrated salt thermochemical energy storage (TES) is a promising technology for high density energy storage, in principle opening the way for applications in seasonal storage. However, severe limitations are affecting large scale applications, related to their poor thermal and mechanical stability on hydration/dehydration cycling. In this paper, we report the preparation and characterization of composite materials manufactured with a wet impregnation method using strontium bromide hexahydrate (SBH) as a thermochemical storage material, combined with expanded natural graphite (G). In addition to these fully inorganic formulations, an organic polyelectrolyte (PDAC, polydiallyldimethylammonium chloride) was exploited in the structure, with the aim to stabilize the salt, while contributing to the sorption/desorption process. Different formulations were prepared with varying PDAC concentration to study its contribution to material morphology, by electron microscopy and X-ray diffraction, as well as water sorption/desorption properties, by thermogravimetry and differential calorimetry. Furthermore, the SBH/G/PDAC powder mixture was pressed to form tabs that were analyzed in a climatic chamber, which is evidence for an active role of PDAC in the improvement of water sorption, coupled with a significant enhancement of mechanical resistance upon hydration/dehydration cycling. Therefore, the addition of the polyelectrolyte is proposed as an innovative approach in the fabrication of efficient and durable TES devices.

This work deals with the Layer by Layer (LbL) assembly of hybrid organic/inorganic flame retardant coatings made of Octa-ammonium POSS (polyhedral oligomeric silsesquioxane) and sodium montmorillonite clay on polyester (PET) fabrics. The effects of ionic strength on the achieved flame retardancy properties were investigated. The coating growth asa function of different ionic strengths was evaluated by infrared spectroscopy. 0.10M NaCl was found able to promote the highest adsorption of each coating species at each deposition step strongly affecting clay stacking as evaluated by X-ray diffraction measurements. The coatings on PET assembled at high ionic strength turned out to be more homogeneous and thicker than the reference one. Thanks to the increased thickness and better surface coverage, the same coatings efficiently suppressed the melt dripping phenomenon and significantly slowed down flame spread rate in horizontal flammability tests with only 2wt% of coating mass added. Furthermore, the same performances were maintained after 1h washing at 70°C. By cone calorimetry, coated fabrics showed a strong reduction in the combustion kinetics by nearly halving the peak of heat release rate. This paper provides an important insight on the viability of tuning deposition of LbL coatings on fabrics employing industrial-like processes by simple modification of ionic strength., (Copyright © 2017 Elsevier Inc. All rights reserved.)

This work deals with the use of hydrotalcite nanoparticle post-diffusion in layer by layer (LbL) coatings with the aim of improving their flame retardant action on cotton. The selected LbL components, which encompass polydiallyldimethylammonium chloride and deoxyribonucleic acid, aim at the deposition of an intumescent coating. Infrared spectra pointed out a super-linear growth of the investigated assembly, indicating the ability to deposit thick coatings while maintaining a relatively low deposition number. A post-diffusion process, performed by exposing the LbL-treated fabrics to two different concentrations of hydrotalcite water suspensions (0.1 or 1 wt %), was carried out to improve the fireproofing efficiency of these coatings. Coatings treated with the lowest concentration suspension partially swelled as a consequence of their structural rearrangements while the use of the highest concentration led to nanoparticle aggregates. Horizontal flame spread tests were used for assessing the achieved flame retardant properties. The post-diffusion performed at the lowest hydrotalcite concentration lowers the minimum number of Bi-Layers required for obtaining cotton self-extinguishment while samples treated with the highest concentration showed detrimental effects on the performances of treated fabrics. This behavior is ascribed to the effects of hydrotalcite particles on the intumescence of LbL coatings, as evidenced by the morphological analyses of post-combustion residues., Competing Interests: The authors declare no conflict of interest.

In the present manuscript a new concept of completely inorganic intumescent flame retardant nanocoating comprised of sodium montmorillonite nanoplatelets embedded in an ammonium polyphosphate matrix has been investigated using cotton as model substrate. The coating, deposited by multistep adsorption from diluted water-based suspensions/solutions, homogenously cover each cotton fibers with average thicknesses below 50 nm and add-on up to 5% in weight. Combustion characterization evidences the interesting properties: indeed, the so-treated fabrics reached self-extinguishing during horizontal flame spread tests. Furthermore, when the coating add-on reaches 5%, no ignition has been observed during cone calorimetry tests under 35 kW/m² heat flux. Residue analyses pointed out the formation of an expanded all-inorganic coating capable of greatly improving char formation by exerting barrier function towards volatile release and heat transfer.

Over the last ten years a new trend of research activities regarding the flame retardancy of polymeric materials has arisen. Indeed, the continuous search for new flame retardant systems able to replace the traditional approaches has encouraged alternative solutions, mainly centred on nanotechnology. In this context, the deposition of nanostructured coatings on fabrics appears to be the most appealing and performance suitable approach. To this aim, different strategies can be exploited: from the deposition of a single monolayer consisting of inorganic nanoparticles (single-step adsorption) to the building-up of more complex architectures derived from layer by layer assembly (multi-step adsorption). The present paper aims to review the application of such systems in the field of polyester and polyester-cotton blend fabrics. The results collated by the authors are discussed and compared with those published in the literature on the basis of the different deposition methods adopted. A critical analysis of the advantages and disadvantages exhibited by these approaches is also presented.

This study focuses on the dielectrical characterization of polycarbonate films coated with silica nanoparticle bilayers assembled through the Layer-by-Layer (LbL) technique. This is the first attempt of dielectric characterization performed on LbL-treated plastic substrates. To this aim, LbL coatings consisting of oppositely charged colloidal silica have been built on a polymeric substrate (polycarbonate). Then, dielectric features such as space charge accumulation, electrical voltage breakdown, and resistance to corona discharge (through laser ablation) have demonstrated that the colloidal silica nanoparticle assemblies can influence the nature of the trapped space charges and affect the resistance of polycarbonate to corona discharge, changing the distribution of the laser energy on impact., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Thin films of colloidal silica were deposited on cotton fibers via layer-by-layer (LbL) assembly in an effort to reduce the flammability of cotton fabric. Negatively charged silica nanoparticles of two different sizes (8 and 27 nm) were paired with either positively charged silica (12 nm) or cationic polyethylenimine (PEI). PEI/silica films were thicker due to better (more uniform) deposition of silica particles that contributed to more than 90% of the film weight. Each coating was evaluated at 10 and 20 bilayers (BL). All coated fabrics retained their weave structure after being exposed to a vertical flame test, while uncoated cotton was completely destroyed. Micro combustion calorimetry confirmed that coated fabrics exhibited a reduced peak heat release rate, by as much as 20% relative to the uncoated control. The 10 BL PEI-8 nm silica recipe was the most effective because the coating is relatively thick and uniform relative to the other systems. Soaking cotton in basic water (pH 10) prior to deposition resulted in better assembly adhesion and flame-retardant behavior. These results demonstrate that LbL assembly is a useful technique for imparting flame retardant properties through conformal coating of complex substrates like cotton fabric., (Copyright © 2010 Elsevier Inc. All rights reserved.)