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.

Multifunctional FFP2 Face Mask for White Light Disinfection and Pathogens Detection using Hybrid Nanostructures and Optical Metasurfaces.

A new generation of an FFP2 (Filtering Face Piece of type 2) smart face mask is achieved by integrating broadband hybrid nanomaterials and a self-assembled optical metasurface. The multifunctional FFP2 face mask shows simultaneously white light-assisted on-demand disinfection properties and versatile biosensing capabilities. These properties are achieved by a powerful combination of white light thermoplasmonic responsive hybrid nanomaterials, which provide excellent photo-thermal disinfection properties, and optical metasurface-based colorimetric biosensors, with a very low limit of pathogens detection. The realized system is studied in optical, morphological, spectroscopic, and cell viability assay experiments and environmental monitoring of harmful pathogens, thus highlighting the extraordinary properties in reusability and pathogens detection of the innovative face mask.

Copper-Decorated Titanium Electrodes: Impact of Surface Modifications of Substrate on the Morphology and Electrochemical Performance.

This study investigates the effect of surface modifications of the titanium substrate on the growth of electrochemically deposited copper. These materials are intended to serve as cathodes in the electroreduction of nitrates in aqueous solutions. Surface modifications included the use of hydrogen fluoride for titanium etching and anodization to promote the growth of a structured titania nanotube array. The effect of an intermediate calcination step for the nanotubes before deposition was assessed along with a comparison to an untreated substrate electrode. The materials were comprehensively characterized by SEM, XRD, contact angle, potentiodynamic tests, EIS, and cyclic voltammetry. Their electrocatalytic ability was tested in the reduction of aqueous solutions containing nitrates. The results reveal that surface finishing impacted the shape and size of the Cu microparticles, as well as the nucleation mechanism enabling a crystal-facet-controllable synthesis. All the materials exhibited microsized copper particles with a spherical shape with some clusters. On the etched titanium surface, a high number of heterogeneous submicroscopic particles were also present. The thermally treated anodized substrate promoted the development of a combination of sparse microparticles corresponding to defect sites in amorphous titanium and the presence of a diffuse coating of octahedral nanosized particles whose growth was promoted by the tetragonal structure of anatase crystals. Electrochemical tests display reduced charge transfer resistance upon copper deposition on the modified substrates, which is indicative of the enhanced conductivity of the coated materials. Additionally, cyclic voltammetry and electrolysis experiments reveal the electrodes' potential for nitrate reduction, showing a better response for the etched titanium substrate (30% nitrate removal, after 2 h at 25 mA cm-2).

Removal of Methylene Blue from Wastewater by Waste Roots from the Arsenic-Hyperaccumulator Pteris vittata: Fixed Bed Adsorption Kinetics.

Phytoremediation of arsenic-contaminated water was successfully conducted by means of the perennial fern Pteris vittate, which is an arsenic-hyperaccumulator plant able to grow in hydroponic cultures. In order to avoid the costs linked to the disposal of As-contaminated biomass, in this work, Pteris vittata waste roots were tested as a low-cost bio-adsorbent for the removal of methylene blue (MB) from water in a fixed-bed adsorption configuration. As a matter of fact, methylene blue can negatively impact the growth and health of algae and plants by blocking light from reaching them in water, which can alter their normal biological processes. Previous works have already shown the potentiality of such material toward the uptake of methylene blue; however, all the studies conducted were just focused on batch-mode experiments. In this work, column runs were carried out at 20 °C, evaluating the bed void fraction for each test and hence estimating the apparent density of the material (300 g/L). The breakthrough curves collected were fitted by means of a mathematical model based on the linear driving force (LDF) approximation to obtain information on the mass transfer mechanism occurring in the system. A relation for the product between the LDF mass transfer coefficient and the solid specific surface (kLDFas) with respect to the Reynolds (Re) dimensionless number was obtained (kLDFas=0.45Re). The range of validity of such expression was Re<0.025. Its applicability was deeply discussed: in such conditions, the technology is ready to be tested at larger scales.

Upscaling of Electrospinning Technology and the Application of Functionalized PVDF-HFP@TiO2 Electrospun Nanofibers for the Rapid Photocatalytic Deactivation of Bacteria on Advanced Face Masks.

In recent years, Electrospinning (ES) has been revealed to be a straightforward and innovative approach to manufacture functionalized nanofiber-based membranes with high filtering performance against fine Particulate Matter (PM) and proper bioactive properties. These qualities are useful for tackling current issues from bacterial contamination on Personal Protective Equipment (PPE) surfaces to the reusability of both disposable single-use face masks and respirator filters. Despite the fact that the conventional ES process can be upscaled to promote a high-rate nanofiber production, the number of research works on the design of hybrid materials embedded in electrospun membranes for face mask application is still low and has mainly been carried out at the laboratory scale. In this work, a multi-needle ES was employed in a continuous processing for the manufacturing of both pristine Poly (Vinylidene Fluoride-co-Hexafluoropropylene) (PVDF-HFP) nanofibers and functionalized membrane ones embedded with TiO2 Nanoparticles (NPs) (PVDF-HFP@TiO2). The nanofibers were collected on Polyethylene Terephthalate (PET) nonwoven spunbond fabric and characterized by using Scanning Electron Microscopy and Energy Dispersive X-ray (SEM-EDX), Raman spectroscopy, and Atomic Force Microscopy (AFM) analysis. The photocatalytic study performed on the electrospun membranes proved that the PVDF-HFP@TiO2 nanofibers provide a significant antibacterial activity for both Staphylococcus aureus (~94%) and Pseudomonas aeruginosa (~85%), after only 5 min of exposure to a UV-A light source. In addition, the PVDF-HFP@TiO2 nanofibers exhibit high filtration efficiency against submicron particles (~99%) and a low pressure drop (~3 mbar), in accordance with the standard required for Filtering Face Piece masks (FFPs). Therefore, these results aim to provide a real perspective on producing electrospun polymer-based nanotextiles with self-sterilizing properties for the implementation of advanced face masks on a large scale.

Chemical, Thermal and Mechanical Characterization of Licorice Root, Willow, Holm Oak, and Palm Leaf Waste Incorporated into Maleated Polypropylene (MAPP).

The effect of four lignocellulosic waste fillers on the thermal and mechanical properties of biocomposites was investigated. Powdered licorice root, palm leaf, holm oak and willow fillers were melt compounded with polypropylene at two different weight contents, i.e., 10 and 30, and then injection molded. A commercially available maleated coupling agent was used to improve the filler/matrix interfacial adhesion at 5 wt.%. Composites were subjected to chemical (FTIR-ATR), thermal (TGA, DSC, DMA) and mechanical (tensile, bending and Charpy impact) analyses coupled with a morphological investigation by scanning electron microscopy. Although similarities among the different formulations were noted, holm oak fillers provided the best combination of thermal and mechanical performance. In particular, at 30 wt.% content with coupling agent, this composite formulation displayed remarkable increases in tensile strength and modulus, flexural strength and modulus, of 28% and 110%, 58% and 111%, compared to neat PP, respectively. The results imply that all these lignocellulosic waste fillers can be used successfully as raw materials for biocomposites, with properties comparable to those featured by other natural fillers.

Recycled Multi-Material Packaging Reinforced with Flax Fibres: Thermal and Mechanical Behaviour.

In this work, the use of a recycled mix stemming from the treatment of multilayer aseptic packaging used in the food and beverage industry is proposed as the matrix for short fibre composites reinforced with flax fibres, to generate value-added materials in contrast to the more common end-of-life scenario including energy recovery. This is expected to be a preferred choice in the waste hierarchy at the European level. A commercially available material (EcoAllene) obtained from multilayer packaging recycling was compounded with short flax fibres up to 30 wt.% by twin screw extrusion, with a view to enhancing its poor mechanical profile and broadening its applications. Composites were in depth analyzed by thermogravimetric analysis and differential scanning calorimetry, which highlighted the complex nature of this recycled product, a limited nucleation ability of flax fibres and a lower thermal stability due to the premature degradation of natural hemicellulose and cellulose, though featuring in any case onset degradation temperatures higher than 300 °C. Composites' mechanical properties were assessed in tension, bending and impact conditions, with remarkable improvements over the neat matrix in terms of stiffness and strength. In particular, at 30 wt.% fibre content and with 5 wt.% of maleated coupling agent, an increase in tensile and flexural strength values by 92% and 138% was achieved, respectively, without compromising the impact strength. The effectiveness of flax fibres confirmed by dynamo-mechanical analysis is beneficial to the exploitation of these composites in automotive interiors and outdoor decking applications.

Effect of Water-Ethanol Extraction as Pre-Treatment on the Adsorption Properties of Aloe vera Waste.

The adsorption properties of Aloe vera (Aloe barbadensis Miller) for the uptake of Methylene Blue (MB) from water were investigated after pre-treating the material with water-ethanol solutions at different ethanol concentrations: 0% v/v (AV0), 25% v/v (AV25), and 50% v/v (AV50). The pre-treated materials were characterized as follows: the pHZC was evaluated to be 6, 5.7, and 7.2 for AV0, AV25, and AV50, respectively; from BET-BJH analysis the mesoporous nature of the material and an increase from 108.2 (AV0) to 331.7 (AV50) m2/kg of its solid surface area was observed; TG analysis revealed a significat increase in volatile compounds from the untreated (5.4%) to the treated materials (8.9%, 10.3%, and 11.3% for AV0, AV25, and AV50, respectively). Adsorption batch tests were then performed to investigate the equilibrium, the kinetics, and the thermodynamics of the process. Results suggested that the Langmuir model was in agreement with the experimental results, and values for qmax of 199 mg/g, 311 mg/g, and 346 mg/g were calculated for AV0, AV25, and AV50, respectively. The kinetic results were used to develop a mathematical model to estimate the effective diffusion coefficient for each type of Aloe adopted. Effective diffusion coefficients of 5.43·10-7 cm2/min, 3.89·10-7 cm2/min, and 5.78·10-7 cm2/min were calculated for AV0, AV25, and AV50, respectively. It was found that pre-treatment, on the one hand, enhances the adsorption capacity of the material and on the other, reduces its affinity toward MB uptake.

Zinc oxide nanostructures and stearic acid as surface modifiers for flax fabrics in polylactic acid biocomposites.

Different surface treatments including mercerization, stearic acid and growth of zinc oxide nanorods as well as their combinations were exploited to address their effects on the properties of green composites based on polylactic acid (PLA) and flax fabrics. The resulting fabrics were morphologically (SEM), crystallographically (XRD) and thermally (TGA) characterized, showing no significant changes with respect to the untreated samples. In contrast, tensile and flexural properties of composites produced by compression moulding were significantly influenced. A combination of mercerization and environmentally friendly stearic acid treatment turned the character of the flax fabric from hydrophilic to hydrophobic, and led to improved bending and tensile strengths by 20% and 12%, respectively, compared to untreated composites. The presence of ZnO nanorods promoted an increase in flexural and tensile stiffness by 58% and 31%, respectively, but at the expense of strength, with reductions ascribed to the degradation of polylactic acid under high-temperature conditions favoured by ZnO, as confirmed by a reduction in the initial thermal degradation temperature up to 26%. These latter composites can be suggested in those applications where a suitable combination of flexural properties and a shorter persistence in the environment is desired.

Functionalization of Commercial Electrospun Veils with Zinc Oxide Nanostructures.

The present research is focused on the synthesis of hexagonal ZnO wurtzite nanorods for the decoration of commercially available electrospun nylon nanofibers. The growth of ZnO was performed by a hydrothermal technique and for the first time on commercial electrospun veils. The growth step was optimized by adopting a procedure with the refresh of growing solution each hour of treatment (Method 1) and with the maintenance of a specific growth solution volume for the entire duration of the treatment (Method 2). The overall treatment time and volume of solution were also optimized by analyzing the morphology of ZnO nanostructures, the coverage degree, the thermal and mechanical stability of the obtained decorated electrospun nanofibers. In the optimal synthesis conditions (Method 2), hexagonal ZnO nanorods with a diameter and length of 53.5 nm ± 5.7 nm and 375.4 nm ± 37.8 nm, respectively, were obtained with a homogeneous and complete coverage of the veils. This easily scalable procedure did not damage the veils that could be potentially used as toughening elements in composites to prevent delamination onset and propagation. The presence of photoreactive species makes these materials ideal also as environmentally friendly photocatalysts for wastewater treatment. In this regard, photocatalytic tests were performed using methylene blue (MB) as model compound. Under UV light irradiation, the degradation of MB followed a first kinetic order data fitting and after 3 h of treatment a MB degradation of 91.0% ± 5.1% was achieved. The reusability of decorated veils was evaluated and a decrease in photocatalysis efficiency was detected after the third cycle of use.

Surface Modification of Basalt Fibres with ZnO Nanorods and Its Effect on Thermal and Mechanical Properties of PLA-Based Composites.

The composites based on basalt fibres and poly(lactic acid) (PLA) show promising applications in biomedical and automotive fields, but their mechanical performance is still largely hindered by poor interfacial properties. Zinc oxide nanorods have been successfully used to tune the PLA/basalt fibre interface by growing them on commercially available basalt fabrics. The hierarchical fibres significantly enhanced the mechanical properties of PLA-based composites, especially their flexural strength and stiffness. These values are 26% and 22% higher than those of unmodified basalt/PLA composites, and 24% and 34% higher than those of glass/PLA composites used as a baseline. The increase in tensile and flexural properties hinges on the mechanical interlocking action promoted by ZnO nanorods and on the creation of a compact transcrystallinity structure. A degradation of PLA matrix was detected but it was positively counteracted by the better interfacial stress transfer. This study offers a novel approach for modifying the fibre-matrix interface of biocomposites intended for high-performance applications.

Remediation of hexavalent chromium contaminated water through zero-valent iron nanoparticles and effects on tomato plant growth performance.

Contaminated water with hexavalent chromium Cr(VI) is a serious environmental problem. This study aimed to evaluate the Cr(VI) removal by zero valent iron nanoparticles (nZVI) reduction process and the impact of Cr(VI), nZVI and combined treatment with nZVI and Cr(VI) on tomato growth performance. To evaluate the Cr(VI) toxic effect on germination capability, seeds were exposed to increasing Cr(VI) concentrations up to 1000 mg L-1. The inhibition of seed germination and the decrease of hypocotyl and root length started from Cr(VI) 5 mg L-1. Under treatment with Cr(VI) + nZVI 5 mg L-1, seed germination, hypocotyl and root length resulted significantly higher compared to Cr(VI) 5 mg L-1 treatment. The impact of only nZVI was investigated on chlorophyll and carotenoid in leaves; iron levels in leaves, roots, fruits and soil; carotenoid, fat-soluble vitamin and nicotianamine in mature fruits. A significant increase of leaf chlorophyll and carotenoids was observed after nZVI 5 mg L-1 treatment compared to controls. No significant variations were observed in carotenoids, fat-soluble vitamins and nicotianamine levels after treatment with nZVI 5 mg L-1 in mature fruits. For their ability to reduce Cr(VI) and to stimulate tomato growth, nZVI might to be considered as alternative for remediation purposes.

Assessment of Alkali-Silica Reactivity of Aggregates by Concrete Expansion Tests in Alkaline Solutions at 38 °C.

A new accelerated concrete prism expansion test at 38 °C (accelerated CPT) is proposed for assessing the alkali-reactivity of concrete aggregates. In this test, concrete prisms with a standardized mix composition and different alkali contents are immersed in alkaline solutions with compositions simulating the pore liquid of hardened concretes. The concrete prism expansion test at 38 °C and RH > 95% (traditional CPT) was taken as a reference test, in order to define the appropriate expansion limit criterion for the proposed accelerated CPT. Three natural aggregates of known field performance and different alkali-silica reactivity were tested. The compositions of alkaline solutions were designed by assuming total dissolution of cement alkalis and taking a ratio between the mass fractions of effective water consumed by cement hydration and of alkalis uptaken by cement hydrates equal to unity. This simplified approach was found in an acceptable agreement with literature empirical equations correlating pore solution alkalinity of hardened Portland cement mixes with total alkali content of cement. Elaboration of expansion data through both pass-fail and threshold alkali level (TAL)-evaluation approaches indicated that, for the accelerated CPT, an expansion limit criterion of 0.04% after 120 days of testing in alkaline solutions is appropriate to evaluate the aggregate alkali reactivity congruently with the traditional CPT. Use of the proposed test method in place of the traditional CPT would reduce the test duration from 365 to 120 days.

Synthesis of Fe/Ni Bimetallic Nanoparticles and Application to the Catalytic Removal of Nitrates from Water.

This work investigated the effectiveness of zerovalent iron and Fe/Ni bimetallic nanoparticles in the treatment of water polluted by a high concentration of nitrates. Nanoparticle synthesis was carried out by a sodium borohydride reduction method in the presence of sodium oleate as a surfactant. The particles were characterized by XRD and SEM. Batch experiments were conducted on water samples contaminated by 300 mg L-1 of nitrate. The parameters investigated were the Fe/Ni dosage (0.05, 0.1, 0.2, 0.3, and 0.4 g L-1) and the reaction pH (unbuffered; buffered at pH = 3; initial pH = 3, 5, and 10). The results showed that almost complete nitrate removal (>99.8%) was always achieved after 15 min at a concentration of bimetallic nanoparticles higher than 0.2 g L-1. The optimization of bimetallic nanoparticle dosage was carried out at a fixed pH. Kinetic study tests were then performed at different temperatures to assess the effect of temperature on the nitrate removal rate. By fixing the pH at acidic values and with an operating temperature of 303 K, nitrates were completely removed after 1 min of treatment.