Modification of Epoxides with Metallic Fillers-Mechanical Properties after Ageing in Aqueous Environments.

The aim of this research was a comparative analysis of selected mechanical properties of epoxy compounds that were modified with metallic fillers and aged in aqueous environments. The tested epoxy compounds consisted of three components: styrene modified epoxy resin based on Bisphenol A, triethylenetetramine curing agent (resin/curing agent ratio of 100:10) and two types of metallic fillers in the form of particles: aluminum alloy (EN AW-2024-AlCu4Mg1) and tin-phosphor bronze (CuSn10P). Samples were subjected to ageing in 4 water environments: low-, medium- and high-mineralized natural water and in a sugar-containing solution for 1, 2 and 3 months. The epoxy samples were subjected to compressive strength tests in accordance with the ISO 604:2002 standard. It was observed that, among others, the compositions seasoned in low-mineralized water usually achieved the highest average compressive strength. As for filler type, using the bronze filler (CuSn10P) usually achieved the highest average compressive strength results.

Physico-Chemical Properties and Valorization of Biopolymers Derived from Food Processing Waste.

The widespread use of synthetic plastics, as well as the waste produced at the end of their life cycle, poses serious environmental issues. In this context, bio-based plastics, i.e., natural polymers produced from renewable resources, represent a promising alternative to petroleum-based materials. One potential source of biopolymers is waste from the food industry, the use of which also provides a sustainable and eco-friendly solution to waste management. Thus, the aim of this work concerns the extraction of polysaccharide fractions from lemon, tomato and fennel waste. Characterizing the chemical-physical and thermodynamic properties of these polysaccharides is an essential step in evaluating their potential applications. Hence, the solubility of the extracted polysaccharides in different solvents, including water and organic solvents, was determined since it is an important parameter that determines their properties and applications. Also, acid-base titration was carried out, along with thermoanalytical tests through differential scanning calorimetry. Finally, the electrospinning of waste polysaccharides was investigated to explore the feasibility of obtaining polysaccharide-based membranes. Indeed, electrospun fibers are a promising structure/system via which it is possible to apply waste polysaccharides in packaging or well-being applications. Thanks to processing feasibility, it is possible to electrospin waste polysaccharides by combining them with different materials to obtain porous 3D membranes made of nanosized fibers.

Valorization of Waste from Argan Seeds for Polyhydroxybutyrate Production Using Bacterial Strains Isolated from Argan Soils.

The aim of this work was to study the valorization of argan seed pulp, a waste material obtained from argan oil extraction, for the biosynthesis of polyhydroxybutyrate (PHB). A new species that showed the metabolic capacity for the conversion of argan waste into the bio-based polymer was isolated from an argan crop located in Teroudant, a southwestern region of Morocco, where the arid soil is exploited for goat grazing. The PHB accumulation efficiency of this new species was compared to the previously identified species 1B belonging to the genus Sphingomonas, and results were reported as dry cell weight residual biomass and PHB final yield measured. Temperature, incubation time, pH, NaCl concentration, nitrogen sources, residue concentrations, and culture medium volumes were analyzed with the aim of obtaining a maximum accumulation of PHB. UV-visible spectrophotometry and FTIR analysis confirmed that PHB was present in the material extracted from the bacterial culture. The results of this wide investigation indicated that the new isolated species 2D1 had a higher efficiency in PHB production compared to the previously identified strain 1B, which was isolated from a contaminated argan soil in Teroudant. PHB final yield of the two bacterial species, i.e., the new isolated and 1B, cultivated under optimal culture conditions, in 500 mL MSM enriched with 3% argan waste, were 21.40% (5.91 ± 0.16 g/L) and 8.16% (1.92 ± 0.23 g/L), respectively. For the new isolated strain, the result of the UV-visible spectrum indicates the absorbance at 248 nm, while the FTIR spectrum showed peaks at 1726 cm-1 and 1270 cm-1: these characteristic peaks indicated the presence of PHB in the extract. The data from the species 1B UV-visible and FTIR spectra were previously reported and were used in this study for a correlation analysis. Furthermore, additional peaks, uncharacteristic of standard PHB, suggest the presence of impurities (e.g., cell debris, solvent residues, biomass residues) that persisted after extraction. Therefore, a further enhancement of the sample purification during extraction is recommended for more accuracy in the chemical characterization. If 470,000 tons of argan fruit waste can be produced annually, and 3% of waste is consumed in 500 mL culture by 2D1 to produce 5.91 g/L (21.40%) of the bio-based polymer PHB, it can be estimated that the amount of putative PHB that can be extracted annually from the total argan fruit waste is about 2300 tons.

A Novel Sphingomonas sp. Isolated from Argan Soil for the Polyhydroxybutyrate Production from Argan Seeds Waste.

Polyhydroxybutyrate (PHB) is a biodegradable bio-based polymer synthesized by microorganisms under unfavorable conditions from agro-industrial residues as a source of carbon. These aspects make the bio-based polymer attractive for the mass production of biodegradable plastics, and a definitive replacement for petroleum-based plastics. The aim of this work was to characterize the putative PHB-producing bacterium 1B isolated from the argan soil, to identify the polymer produced, and quantify the PHB production using argan seeds waste. DNA extraction, PCR, and Sanger sequencing were conducted for the molecular identification of strain 1B; the residual biomass and the PHB quantification were measured and compared in the presence of simple sugars and pretreated argan seeds waste. The 1B growth and PHB synthesis were optimized by selecting physical and nutritional parameters: temperature, incubation time, pH, NaCl concentration, and nitrogen sources concentrations. A preliminary characterization of the bio-based polymer extracted was conducted by UV-Visible spectrophotometry and FTIR analysis. The strain 1B was identified as belonging to the genus Sphingomonas. The PHB final yield was higher in a growth culture enriched with argan waste (3.06%) than with simple sugars. The selected conditions for the bacterial optimal growth incremented the PHB final yield to 6.13%, while the increase in the argan residue concentration from 1 to 3% in a larger culture volume led to the PHB final yield of 8.16%. UV-Visible spectrophotometry of the extracted sample reported a remarkable peak at 248 nm, as well as FTIR spectra analysis, showed peaks at 1728 and 1282 wavenumber/cm. Both preliminary characterizations demonstrated that the extracted sample is the bio-based polymer polyhydroxybutyrate. The results reported in this work reveal how the costless available argan seeds can be used for polyhydroxybutyrate production using a novel Sphingomonas species.

Biological Effects and Toxicity of Compounds Based on Cured Epoxy Resins.

The aim of this work was to investigate selected biological and toxicity properties of cured epoxy resin-based compounds based on a bisphenol A epoxy resin, cold-cured by a polyamide and containing two types of metal powders (aluminum and copper). This study involved cytotoxicity analysis, pH measurements, absorbance measurements and sterilization. The cytotoxicity analysis was conducted to determine the harmful degree of the cured epoxy resin. Aimed at identifying toxic agents in cured compounds, the cytotoxicity analysis involved absorbance measurements in an entire wavelength range. Cytotoxicity and absorbance results demonstrated that the extracts of all the tested resin samples had no cytotoxic effects on the cells of living organisms. The absorbance values obtained over the entire wavelength range did not point to the formation of aggregations, which proved that no toxic agents harmful to living organisms were extracted from the resin samples. Based on the results obtained, it can be concluded that all tested compounds, based on epoxy resins, which are also used as adhesives in various applications, are essentially safe materials when using such formulations in a cured state.

Does Size Matter? The Case of Piezoresistive Properties of Carbon Nanotubes/Elastomer Nanocomposite Synthesized through Mechanochemistry.

The growing interest in piezoresistive sensors has favored the development of numerous approaches and materials for their fabrication. Within this framework, carbon nanotubes (CNTs) are often employed. However, CNTs are a heterogeneous material with different morphological characteristics in terms of length and diameter, and, so far, experimental studies have not usually considered the effect of these parameters on the final sensor performances. Here, we observe how, by simply changing the CNTs length in a solvent-free mechanochemistry fabrication method, different porous 3D elastomeric nanocomposites with different electrical and mechanical properties can be obtained. In particular, the use of longer carbon nanotubes allows the synthesis of porous nanocomposites with better mechanical stability and conductivity, and with a nine-times-lower limit of detection (namely 0.2 Pa) when used as a piezoresistive sensor. Moreover, the material prepared with longer carbon nanotubes evidenced a faster recovery of its shape and electrical properties during press/release cycles, thus allowing faster response at different pressures. These results provide evidence as to how CNTs length can be a key aspect in obtaining piezoresistive sensors with better properties.

Adhesive Joint Degradation Due to Hardener-to-Epoxy Ratio Inaccuracy under Varying Curing and Thermal Operating Conditions.

This paper presents the results of an experimental study of adhesive joint strength with consideration of the inaccuracy of the hardener dosage, in the context of evaluating the degradation of joints when used either at ambient or elevated temperatures. The butt joint strength characteristics were assessed for two types of adhesives-rigid and flexible-and two curing scenarios-with and without heat curing. An excess hardener was shown to be significantly more unfavourable than its deficiency, which can ultimately be considered as a recommendation for forming epoxy adhesive joint assemblies. In order to fully understand the relationship between the analysed mechanical properties of the material and the influence of component ratio excesses and heating, a process of fitting basic mathematical models to the obtained experimental data was also performed.

Effect of Diluents on Mechanical Characteristics of Epoxy Compounds.

The aim of this work is to assess the influence of different commercial diluents on some mechanical properties of two bisphenolic epoxy compounds, cold-cured by a polyamide curing agent, to be employed as epoxy structural adhesives for building and industrial applications. The diluents under analysis were epoxy, bituminous, nitro, acrylic and extraction. The choice of these products was made on the basis of their wide commercial availability as diluents for epoxies used as adhesives and in different industrial and construction applications. The diluents were all added in small proportions, i.e., from 1 to 10 g per 100 g of epoxy resin. The cold-cured epoxy compounds were subjected to compressive (according to ISO 604) and static tensile (according to ISO 527-1) tests. The same mechanical tests were performed on both unmodified epoxy resins, for comparison purposes. On the basis of the obtained results, it was concluded that the influence of the presence of a diluent, and of its amount, on the mechanical properties of epoxy compounds depends on the type of resin and of diluent, as well as on the mechanical characteristics analyzed.

Assessment of the Ageing and Durability of Polymers.

As any other natural or industrial material, polymers can experience some kind of degradation during their service life, resulting in minor to severe changes in their properties [...].

Physical Properties of Eco-Sustainable Form-Stable Phase Change Materials Included in Mortars Suitable for Buildings Located in Different Continental Regions.

Starting from two low-cost, low-environmental-impact polymers belonging to the Polyethylene Glycol (PEG) family, i.e., PEG 800 and PEG 1000, two form-stable phase change materials were produced. The two PEGs differ in molecular weight and, as a consequence, the melting and crystallization range of temperatures. The PCMs were obtained, including the PEG, in a liquid state, inside the pores of Lecce Stone flakes, obtained as waste pieces from its processing. A simple and inexpensive impregnation process was selected to produce the PCMs, thus adopting low-environmental-impact materials and cheap processes, and respecting circular economy principles. The two PCMs, the first composed of PEG 800, namely LS/PEG800, and the second composed of a 50/50%wt. mix of the different LS/PEGs, i.e., LS/PEG800_LS/PEG1000, were added as aggregates to four types of mortars, based on aerial and hydraulic lime, gypsum, and cement. The obtained mortars were characterized in their fresh state to assess their workability, and in a solid state after a proper cure to determine their characteristic Latent Heat Thermal Energy Storage (LHTES) properties and mechanical properties in both flexural and compressive modes, taking the mortars not containing any PCM as the reference. The results revealed that, with the proper selection of mortar formulations, it was possible to achieve suitable workability and adequate mechanical characteristics. The selection of a PEG with a low range of phase change temperatures, such as PEG 800, allows one to obtain mortars characterized by a melting/crystallization range that can be considered appropriate in applications characterized by cold climates. The production of a mixed PCM, composed of both PEGs, led to mortars displaying a large interval of melting/crystallization temperatures, which could be suitable in both warm and cold climates.

Physical Properties of an Eco-Sustainable, Form-Stable Phase Change Material Included in Aerial-Lime-Based Mortar Intended for Different Climates.

The aim of this experimental investigation was to produce a form-stable phase change material (PCM) able to reduce the need for nonrenewable energy resources required for the heating/cooling of buildings located in regions characterized by different climatic conditions. The innovative PCM must also be sustainable and must be produced according to the principles of the circular economy. To achieve such ambitious goals, a form-stable, sustainable PCM was produced through vacuum impregnation. The form-stable PCM was produced starting from a low-toxicity, low-flammability polyethylene glycol of medium molecular weight (PEG 800), which was included in porous stone granules obtained as waste products of the cutting/processing of local (Lecce) stone. The thermal properties and thermal stability of PEG 800 and of its PCM-composite were evaluated by employing differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA). The appropriate parameters to perform the impregnation procedure were identified through rheological and calorimetric analyses. A simple leakage test was performed to assess if the PEG polymer can leak from the stone flakes. Finally, the new PCM was added as an aggregate in aerial-lime-based mortars, and the mortar's properties were analyzed in fresh (workability) and hardened (flexural and compressive strength and thermal characteristics) states for potential applications, particularly in ancient buildings.

Nanoarchitectonics of highly sensitive and with large working range 3D piezoresistive microporous foam based on carbon nanotubes and elastomer.

HYPOTHESIS: Nanocarbon/polymeric 3D porous composites have been widely developed as piezoresistive sensors due to their improved performances. Functionalized nanocarbon is usually used to allow its adsorption on the surface of porous polymeric material. However, both the functionalization and the surface localized distribution of the nanomaterial can limit the nanocarbon effect on conductivity and mechanical stability of the material thus affecting piezoresistive performances. EXPERIMENTS: A novel nanoarchitectonics strategy to prepare an elastomeric/carbon nanotubes (CNTs) 3D porous piezoresistive nanocomposite is developed. The fabrication route does not require complex apparatus and CNTs chemical functionalization. Moreover, foams of any shape and dimensions can be produced with neither complex machinery and procedures nor wastes production. FINDINGS: The obtained material is characterized by the presence of well dispersed pristine CNTs on both surface and bulk of the polymeric matrix. The foam exhibited improved piezoresistive properties with excellent compressive stress (>150 kPa), sensitivity at low displacement (29 kPa-1) and limit of detection for both pressure (2 Pa) and extension (130 nm). These excellent features could allow the use of the as prepared nanocomposite in different applications ranging from wearable devices to robotic or infrastructure monitoring with outstanding flexibility.

Can Accelerated Aging Procedures Predict the Long Term Behavior of Polymers Exposed to Different Environments?

During their useful life, polymers are subject to degradation processes due to exposure to specific environmental conditions over long times. These processes generally lead to changes, almost always irreversible, of properties and performances of polymers, changes which would be useful to be able to predict in advance. To meet this need, numerous investigations have been focused on the possibility to predict the long-term performance of polymers, if exposed to specific environments, by the so called "accelerated aging" tests. In such procedures, the long-term behavior of polymeric materials is typically predicted by subjecting them to cycles of radiations, temperatures, vapor condensation, and other external agents, at levels well above those found in true conditions in order to accelerate the degradation of polymers: this can produce effects that substantially deviate from those observable under natural exposure. Even following the standard codes, different environmental parameters are often used in the diverse studies, making it difficult to compare different investigations. The correlation of results from accelerated procedures with data collected after natural exposure is still a debated matter. Furthermore, since the environmental conditions are a function of the season and the geographical position, and are also characteristic of the type of exposure area, the environmental parameters to be used in accelerated aging tests should also consider these variables. These and other issues concerning accelerated aging tests applied to polymers are analyzed in the present work. However, bearing in mind the limitations of these practices, they can find useful applications for rating the durability of polymeric materials.

Isolation of Two Bacterial Species from Argan Soil in Morocco Associated with Polyhydroxybutyrate (PHB) Accumulation: Current Potential and Future Prospects for the Bio-Based Polymer Production.

The environmental issues caused by the impacts of synthetic plastics use and derived wastes are arising the attention to bio-based plastics, natural polymers produced from renewable resources, including agricultural, industrial, and domestic wastes. Bio-based plastics represent a potential alternative to petroleum-based materials, due to the insufficient availability of fossil resources in the future and the affordable low cost of renewable ones that might be consumed for the biopolymer synthesis. Among the polyhydroxyalkanoates (PHA), the polyhydroxybutyrate (PHB) biopolymer has been synthesized and characterized with great interest due to its wide range of industrial applications. Currently, a wide number of bacterial species from soil, activated sludge, wastewater, industrial wastes, and compost have been identified as PHB producers. This work has the purpose of isolating and characterizing PHB-producing bacteria from the agricultural soil samples of Argania spinosa in the south region of Morocco where the plant species is endemic and preserved. During this research, four heat-resistant bacterial strains have been isolated. Among them, two species have been identified as endospore forming bacteria following the Schaffer-Fulton staining method with Malachite green and the Methylene blue method. Black intracellular granules have been appreciated in microscopy at 100× for both strains after staining with Sudan black B. The morphological and biochemical analyses of the isolates, including sugar fermentation and antibiotic susceptibility tests, preliminarily identified the strains 1B and 2D1 belonging to the genus Serratia and Proteus, respectively.

Reliability Prediction of Acrylonitrile O-Ring for Nuclear Power Applications Based on Shore Hardness Measurements.

The degradation of polymeric components is of considerable interest to the nuclear industry and its regulatory bodies. The objective of this work was the development of a methodology to determine the useful life-based on the storage temperature-of acrylonitrile O-rings used as mechanical sealing elements to prevent leakages in nuclear equipment. To this aim, a reliability-based approach that allows prediction of the use-suitability of different storage scenarios (that involve different storage times and temperatures) considering the further required in-service performance, is presented. Thus, experimental measurements of Shore A hardness have been correlated with storage variables (temperature and storage time). The storage (and its associated hardening) was proved to have a direct effect on in-service durability, reducing this by up to 60.40%. Based on this model, the in-service performance was predicted; after the first three years of operation the increase in probability of failure (POF) was practically insignificant. Nevertheless, from this point on, and especially, from 5 years of operation, the POF increased from 10% to 20% at approximately 6 years (for new and stored). From the study, it was verified that for any of the analysis scenarios, the limit established criterion was above that of the storage time premise considered in usual nuclear industry practices. The novelty of this work is that from a non-destructive test, like a Shore A hardness measurement, the useful life and reliability of O-rings can be estimated and be, accordingly, a decision tool that allows for improvement in the management of maintenance of safety-related equipment. Finally, it was proved that the storage strategies of our nuclear power plants are successful, perfectly meeting the expectations of suitability and functionality of the components when they are installed after storage.

Cold-Cured Bisphenolic Epoxy Adhesive Filled with Low Amounts of CaCO3: Effect of the Filler on the Durability to Aqueous Environments.

The effects of aging exposures to three non-saline aqueous environments on the compressive mechanical properties of a calcium carbonate-filled bisphenolic epoxy adhesive, cold-cured with the addition of two curing agents suitable for the cure at ambient temperature (i.e., Mannich base and triethylenetetramine), were assessed. The amount of the added filler (CaCO3) varied from 1 to 3 g per 100 g of resin; the immersion times in each of the selected medium varied from 1 to 10 months. It was found that the mechanical properties measured in compression mode on cylindrical specimens of unfilled and CaCO3-loaded epoxy were scarcely influenced by the kind of curing agent employed; only the compressive modulus was limitedly affected by this parameter. Referring to the behavior when aged in water, the CaCO3-filled epoxies displayed noticeable growths in modulus, small reductions in strength, and limited variations in strain, with a certain influence of the exposure time, especially when comparing the properties at the lowest time with those at medium-long times. On the basis of the results of statistical MANOVA analysis, it can be concluded that among the compositional factors (i.e., the type of curing agent employed to cure the epoxy compounds and the micro-filler content), only the amount of CaCO3 filler significantly affects the compressive modulus.

Novel Nano-Filled Coatings for the Protection of Built Heritage Stone Surfaces.

An experimental nano-filled coating, based on a fluorine resin containing SiO2 nano-particles, was applied on calcareous stones, representative of materials used in buildings and monuments of the Mediterranean basin; for comparison purposes, two commercial products were applied on the same substrates. The efficacy of the protective treatments was assessed by analyzing different characteristics of the three experimental/commercial products, i.e., color changes and permeability to water vapor to evaluate the treatments' harmlessness; capillary water absorption and water stone contact angle to evaluate the protection against water ingress; oleophobicity of the treated surfaces and the behavior under staining by acrylic blue-colored spray paint and felt-tip marker to verify the anti-graffiti action. Finally, the properties of the treated stone surfaces were analyzed also after the application of pancreatin, used to simulate bird excreta (guano). The protective coatings were found to promote graffiti removal, reducing also the detrimental effects due to simulated guano. The experimental nano-filled product, in addition, was able to provide outstanding performance but using smaller amounts of product in comparison to commercial systems.

Innovative Materials for Construction.

Academic and industrial efforts around the world are continuously engaged to develop new smart materials that can provide efficient alternatives to conventional construction materials and improve the energy-efficiency in buildings or are able to upgrade, repair, and protect existing infrastructures [...].

Aging Effects of Aqueous Environment on Mechanical Properties of Calcium Carbonate-Modified Epoxy Resin.

The purpose of this study was to assess the effects of different aqueous environments (i.e., demineralised, distilled and spring water) on the mechanical properties of a cold-cured bisphenolic epoxy resin modified with the addition of calcium carbonate filler, typically employed as structural adhesive. The parameters selected for the analysis have been; the kind of curing agent employed to cure the epoxy resin at ambient temperature (i.e., Mannich base and triethylenetetramine); the load of calcium carbonate added to liquid epoxy (i.e., from 1 to 3 g per 100 g of resin) and; the duration of the exposure to the different aging conditions (i.e., from 1 to 10 months). Cylindrical specimens of calcium carbonate-modified epoxy systems were tested in compression mode, before and after each of the aging regimes. The effect of the selected curing agents is very small, and they are both suitable for a cure at ambient temperature, on the unfilled epoxy on compressive maximum strength and strain at break; the choice of the hardener affects instead the compressive modulus. The CaCO3 amount was demonstrated to have a significant effect on the mechanical characteristics of un-aged epoxy systems, leading to growth in compressive modulus and maximum strength with reductions in strain at break. Generally speaking, the aging time noticeably affects the compressive properties of calcium carbonate-modified epoxies while almost negligible is the kind of water employed in each exposure regime. Notwithstanding the adverse effects of an aqueous environment on compressive mechanical properties of CaCO3-filled epoxies, these systems keep compressive modulus and maximum strength greater than, and close to, respectively, the same characteristics measured on unaged unfilled control epoxies, demonstrating the positive effect of the addition of this kind of filler to epoxy-based structural adhesives, especially with the addition of 2 and 3 g of CaCO3 per 100 g resin. The results obtained in this study demonstrated that it is possible to contrast the detrimental effects observed in cold-cured epoxy-based structural adhesives due to their aging in water upon the addition of limited amounts (particularly at 2 and 3 g per 100 g resin) of a cheap CaCO3 filler.

Tomato Oil Encapsulation by α-, ß-, and γ-Cyclodextrins: A Comparative Study on the Formation of Supramolecular Structures, Antioxidant Activity, and Carotenoid Stability.

Cyclodextrins (CDs) are oligosaccharides, comprising 6 (α), 7 (ß), or 8 (γ) glucose residues, used to prepare oil-in-water emulsions and improve oil stability towards degradation. In this research, the aptitude of α-, ß-, and γ-CDs to form complexes with a supercritical CO2 extracted lycopene-rich tomato oil (TO) was comparatively assessed. TO/CD emulsions and the resulting freeze-dried powders were characterized by microscopy, Fourier transform infrared-attenuated total reflection (FTIR-ATR), and differential scanning calorimetry (DSC), as well as for their antioxidant activity. Furthermore, carotenoid stability was monitored for 90 days at 25 and 4 °C. Confocal and SEM microscopy revealed morphological differences among samples. α- and ß-CDs spontaneously associated into microcrystals assembling in thin spherical shells (cyclodextrinosomes, Ø ≈ 27 µm) at the oil/water interface. Much smaller (Ø ≈ 9 µm) aggregates were occasionally observed with γ-CDs, but most TO droplets appeared "naked". FTIR and DSC spectra indicated that most CDs did not participate in TO complex formation, nevertheless structurally different interfacial complexes were formed. The trolox equivalent antioxidant capacity (TEAC) activity of emulsions and powders highlighted better performances of α- and ß-CDs as hydrophobic antioxidants-dispersing agents across aqueous media. Regardless of CDs type, low temperature slowed down carotenoid degradation in all samples, except all-[E]-lycopene, which does not appear efficiently protected by any CD type in the long storage period.