Microstructure, physical and mechanical properties of dental polychromic multilayer zirconia of uniform composition.

The present study aimed to compare the microstructure, physical, and mechanical properties of three commercially available dental polychromatic multilayer zirconia materials of uniform composition: Dima Mill Zirconia ML, VITA YZ/ST Multicolor, and VITA YZ/XT Multicolor (with 3, 4, and 5 mol% Y2 O3 , respectively); thus, the influence of Y2 O3 content on the above properties of the produced materials was experimentally studied. Homogeneous zirconia ceramics with a dense micro- and nanostructure, without pores or defects, were produced after milling the blocks and sintering, which resulted in yttrium-stabilized tetragonal and cubic zirconia. Statistical analysis of the results of measurable magnitudes was performed by the one-way ANOVA test. The increase of Y2 O3 content (from 3 to 5 mol%) favored larger grain and crystallite sizes and a decrease of the values of the mechanical properties; yet, the differences were statistically insignificant. Clinically, these differences are expected to have no impact on their function in the oral cavity, both in terms of their fracture propensity and the damage that can be caused to the opposing teeth. Accordingly, the experimental results qualify the polychromic multilayer zirconia ceramics of uniform composition fabricated by milling technology for use in dental restorations.

Relationship between the Carbonyl Index (CI) and Fragmentation of Polyolefin Plastics during Aging.

The durability of plastics in the marine environment has emerged as a crucial environmental issue. However, the contribution of several factors and the threshold point after which a plastic product generates secondary micro- and nanoplastics is still unclear. To investigate the interaction of environmental parameters with the physicochemical properties of polyethylene (PE) and polypropylene (PP) films in the marine environment, polyolefin films were subjected to weathering in emulated coastal and marine environments for 12 months, focusing on the relationship between radiation load, alteration on the surface, and subsequent generation of microplastics (MPs). The weight average molecular weight (Mw) was found to be strongly correlated with the generated particles and the Feret diameter, implying the generation of secondary microplastics at decreased Mw. A significant and strong relationship between the carbonyl index (CI) and the Feret diameter for PP films weathered on beach sand was identified. This CI-fragmentation relationship involves three sequential stages and suggests that spontaneous fragmentation occurs at CI values above 0.7.

Microstructural features, physicο-mechanical properties, and wear behavior of dental translucent polychromic multilayer zirconia of hybrid composition prepared by milling technology.

OBJECTIVE: The present study determined the mechanical properties and the wear behavior, as results of the micro(nano)structure, of the enamel, transition, and dentine layers, which comprise the polychromic multilayer zirconia materials of hybrid composition fabricated by milling technology. MATERIALS AND METHODS: Prismatic blocks were fabricated from two commercial pre-sintered dental polychromic multilayer zirconia materials of hybrid composition, IPS e.max ZirCAD Prime (medium and high translucency, from the dentine to the incisal layer) and 3D Pro ML (translucency gradient, from the dentine to the incisal layer) by milling technique, and then, cut into 3 distinct parts to separate the enamel, transition, and dentine layers. The samples were sintered, thermally treated (similarly to the glazing procedure), and polished for characterization. Their microstructure, mechanical properties (determined by nanoindentation and microhardness), and wear behavior (evaluated by scratch test), were examined. RESULTS: The produced materials had a homogeneous and dense nanostructure, where the grain size decreased from the enamel to dentine layer. The mechanical properties decreased from the dentine to enamel layer. However, the three layers manifested similar dynamic friction coefficient. CONCLUSION: The differences in the above properties in the three layers negligibly influenced the wear behavior of the entire multilayer zirconia material. CLINICAL SIGNIFICANCE: The properties of dental restorations produced from polychromic multilayer zirconia of hybrid composition by milling technology (i.e., strong, non-fragile, and esthetic materials), anticipate good performance in oral cavity.

Hydrogen Sulfide Removal via Sorption Process on Activated Carbon-Metal Oxide Composites Derived from Different Biomass Sources.

Biomass exploitation is a global trend due to the circular economy and the environmentally friendly spirit. Numerous applications are now based on the use of biomass-derived products. Hydrogen sulfide (H2S) is a highly toxic and environmentally hazardous gas which is emitted from various processes. Thus, the efficient removal of this toxic hazardous gas following cost-effective processes is an essential requirement. In this study, we present the synthesis and characterization of biomass-derived activated carbon/zinc oxide (ZnO@AC) composites from different biomass sources as potential candidates for H2S sorption. The synthesis involved a facile method for activated carbon production via pyrolysis and chemical activation of biomass precursors (spent coffee, Aloe-Vera waste leaves, and corncob). Activated carbon production was followed by the incorporation of zinc oxide nanoparticles into the porous carbon matrix using a simple melt impregnation method. The synthesized ZnO@AC composites were characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and nitrogen porosimetry. The H2S removal performance of the ZnO@AC composites was evaluated through sorption experiments using a handmade apparatus. Our findings demonstrate that the Aloe-Vera-, spent coffee-, and corncob-derived composites exhibit superior H2S sorption capacity up to 106 mgH2S/gads., 66 mgH2S/gads., and 47 mgH2S/gads., respectively.

Performance of Thyme Oil@Na-Montmorillonite and Thyme Oil@Organo-Modified Montmorillonite Nanostructures on the Development of Melt-Extruded Poly-L-lactic Acid Antioxidant Active Packaging Films.

Today, the use of natural biodegradable materials in the production processes is more and more adopted by industry to achieve cyclic economy targets and to improve environmental and human health indexes. Active packaging is the latest trend for food preservation. In this work, nanostructures were prepared by incorporation of thyme oil with natural natrium-montmorillonite and organo-montmorillonite with two different techniques, direct impregnation and the green evaporation-adsorption process. Such nanostructures were mixed with poly-L-lactic-acid for the first time via an extrusion molding process to develop a new packaging film. Comparisons of morphological, mechanical, and other basic properties for food packaging were carried out via XRD, FTIR, TG, SEM/EDS, oxygen and water vapor permeation, and antimicrobial and antioxidant activity for the first time. Results showed that poly-L-lactic-acid could be modified with clays and essential oils to produce improved active packaging films. The final product exhibits food odor prevention characteristics and shelf-life extension capabilities, and it could be used for active packaging. The films based on OrgMt clay seems to be more promising, while the thyme oil addition improves their behavior as active packaging. The PLLA/3%TO@OrgMt and PLLA/5%TO@OrgMt films were qualified between the tested samples as the most promising materials for this purpose.

Synthesis of a Novel Chitosan/Basil Oil Blend and Development of Novel Low Density Poly Ethylene/Chitosan/Basil Oil Active Packaging Films Following a Melt-Extrusion Process for Enhancing Chicken Breast Fillets Shelf-Life.

An innovative process for the adsorption of the hydrophobic Basil-Oil (BO) into the hydrophilic food byproduct chitosan (CS) and the development of an advanced low-density polyethylene/chitosan/basil-oil (LDPE/CS_BO) active packaging film was investigated in this work. The idea of this study was the use of the BO as both a bioactive agent and a compatibilizer. The CS was modified to a CS_BO hydrophobic blend via a green evaporation/adsorption process. This blend was incorporated directly in the LDPE to produce films with advanced properties. All the obtained composite films exhibited improved packaging properties. The film with 10% CS_BO content exhibited the best packaging properties, i.e., 33.0% higher tensile stress, 31.0% higher water barrier, 54.3% higher oxygen barrier, and 12.3% higher antioxidant activity values compared to the corresponding values of the LDPE films. The lipid oxidation values of chicken breast fillets which were packaged under vacuum using this film were measured after seven and after fourteen days of storage. These values were found to be lower by around 41% and 45%, respectively, compared with the corresponding lipid oxidation values of pure LDPE film.

Carbon Nanostructures Derived through Hypergolic Reaction of Conductive Polymers with Fuming Nitric Acid at Ambient Conditions.

Hypergolic systems rely on organic fuel and a powerful oxidizer that spontaneously ignites upon contact without any external ignition source. Although their main utilization pertains to rocket fuels and propellants, it is only recently that hypergolics has been established from our group as a new general method for the synthesis of different morphologies of carbon nanostructures depending on the hypergolic pair (organic fuel-oxidizer). In search of new pairs, the hypergolic mixture described here contains polyaniline as the organic source of carbon and fuming nitric acid as strong oxidizer. Specifically, the two reagents react rapidly and spontaneously upon contact at ambient conditions to afford carbon nanosheets. Further liquid-phase exfoliation of the nanosheets in dimethylformamide results in dispersed single layers exhibiting strong Tyndall effect. The method can be extended to other conductive polymers, such as polythiophene and polypyrrole, leading to the formation of different type carbon nanostructures (e.g., photolumincent carbon dots). Apart from being a new synthesis pathway towards carbon nanomaterials and a new type of reaction for conductive polymers, the present hypergolic pairs also provide a novel set of rocket bipropellants based on conductive polymers.

Synthesis of Highly Crystalline Graphite from Spontaneous Ignition of In Situ Derived Acetylene and Chlorine at Ambient Conditions.

We exploited a classic chemistry demonstration experiment based on the reaction of acetylene with chlorine to obtain highly crystalline graphite at ambient conditions. Acetylene and chlorine were generated in-situ by the addition of calcium carbide (CaC2) in a concentrated HCl solution, followed by the quick addition of domestic bleach (NaClO). The released gases reacted spontaneously, giving bursts of yellow flame, leaving highly crystalline graphite deposits in the aqueous phase. This was a rather benign alternative towards synthetic graphite, the latter usually being prepared at high temperatures. The synthetic graphite was further utilized to obtain graphene or conductive inks.

Hypergolics in Carbon Nanomaterials Synthesis: New Paradigms and Perspectives.

Recently we have highlighted the importance of hypergolic reactions in carbon materials synthesis. In an effort to expand this topic with additional new paradigms, herein we present novel preparations of carbon nanomaterials, such-like carbon nanosheets and fullerols (hydroxylated fullerenes), through spontaneous ignition of coffee-sodium peroxide (Na2O2) and C60-Na2O2 hypergolic mixtures, respectively. In these cases, coffee and fullerenes played the role of the combustible fuel, whereas sodium peroxide the role of the strong oxidizer (e.g., source of highly concentrated H2O2). The involved reactions are both thermodynamically and kinetically favoured, thus allowing rapid product formation at ambient conditions. In addition, we provide tips on how to exploit the released energy of such highly exothermic reactions in the generation of useful work.

Dendrons and Dendritic Terpolymers: Synthesis, Characterization and Self-Assembly Comparison.

To the best of our knowledge, this is the very first time that a thorough study of the synthetic procedures, molecular and thermal characterization, followed by structure/properties relationship for symmetric and non-symmetric second generation (2-G) dendritic terpolymers is reported. Actually, the synthesis of the non-symmetric materials is reported for the first time in the literature. Anionic polymerization enables the synthesis of well-defined polymers that, despite the architecture complexity, absolute control over the average molecular weight, as well as block composition, is achieved. The dendritic type macromolecular architecture affects the microphase separation, because different morphologies are obtained, which do not exhibit long range order, and various defects or dislocations are evident attributed to the increased number of junction points of the final material despite the satisfactory thermal annealing at temperatures above the highest glass transition temperature of all blocks. For comparison reasons, the initial dendrons (miktoarm star terpolymer precursors) which are connected to each other in order to synthesize the final dendritic terpolymers are characterized in solution and in bulk and their self-assembly is also studied. A major conclusion is that specific structures are adopted which depend on the type of the core connection between the ligand and the active sites of the dendrons.

Self-Assembly of Low-Molecular-Weight Asymmetric Linear Triblock Terpolymers: How Low Can We Go?

The synthesis of two (2) novel triblock terpolymers of the ABC type and one (1) of the BAC type, where A, B and C are chemically different segments, such as polystyrene (PS), poly(butadiene) (PB1,4) and poly(dimethylsiloxane) (PDMS), is reported; moreover, their corresponding molecular and bulk characterizations were performed. Very low dimensions are evident from the characterization in bulk from transmission electron microscopy studies, verified by small-angle X-ray data, since sub-16 nm domains are evident in all three cases. The self-assembly results justify the assumptions that the high Flory-Huggins parameter, χ, even in low molecular weights, leads to significantly well-ordered structures, despite the complexity of the systems studied. Furthermore, it is the first time that a structure/properties relationship was studied for such systems in bulk, potentially leading to prominent applications in nanotechnology and nanopatterning, for as low as sub-10 nm thin-film manipulations.

Magnetic reversal and thermal stability of CoFeB perpendicular magnetic tunnel junction arrays patterned by block copolymer lithography.

Dense arrays of pillars, with diameters of 64 and 25 nm, were made from a perpendicular CoFeB magnetic tunnel junction thin film stack using block copolymer lithography. While the soft layer and hard layer in the 64 nm pillars reverse at different fields, the reversal of the two layers in the 25 nm pillars could not be distinguished, attributed to the strong interlayer magnetostatic coupling. First-order reversal curves were used to identify the steps that occur during switching, and the thermal stability and effective switching volume were determined from scan rate dependent hysteresis measurements.

Νovel Polylactic Acid/Tetraethyl Citrate Self-Healable Active Packaging Films Applied to Pork Fillets' Shelf-Life Extension.

Nowadays, increased food safety and decreased food waste are two of the major global interests. Self-healable active packaging materials are an attractive option to achieve such targets. This property is critical for the hygiene and the consumption appropriateness of the food. Polylactic acid is a very promising polymeric matrix that potentially could replace the widely used low-density polyethylene due to its biobased origin and its easy biodegradable nature. The main drawback of this polymeric matrix is its brittle, fragile nature. On the other hand, tetraethyl citrate is a biobased approved food additive which became an attractive option as a plasticizer for industries seeking alternative materials to replace the traditional petrochemically derived compounds. A novel biobased film exhibiting self-healing behavior suitable for food-active packaging was developed during this study. Polylactic acid's brittleness was reduced drastically by incorporating tetraethyl citrate, and a random cut on the original self-repairing film was fully healed after 120 s. The optimum concentration of tetraethyl citrate in the polylactic acid was around 15% v/w with a water/oxygen barrier close to the relevant of polylactic acid and low migration. According to the EC50 parameter, the antioxidant activity was 300% higher than the relevant of pure polylactic acid, while according to the thiobarbituric acid and heme iron parameters, the film resisted lipid oxidation and deterioration. Finally, the total viable count parameter indicates the strong antimicrobial activity of this sample.

Development and Physicochemical Characterization of Edible Chitosan-Casein Hydrogel Membranes for Potential Use in Food Packaging.

The increasing global concern over plastic waste and its environmental impact has led to a growing interest in the development of sustainable packaging alternatives. This study focuses on the innovative use of expired dairy products as a potential resource for producing edible packaging materials. Expired milk and yogurt were selected as the primary raw materials due to their protein and carbohydrate content. The extracted casein was combined with various concentrations of chitosan, glycerol, and squid ink, leading to the studied samples. Chitosan was chosen due to its appealing characteristics, including biodegradability, and film-forming properties, and casein was utilized for its superior barrier and film-forming properties, as well as its biodegradability and non-toxic nature. Glycerol was used to further improve the flexibility of the materials. The prepared hydrogels were characterized using various instrumental methods, and the findings reveal that the expired dairy-based edible packaging materials exhibited promising mechanical properties comparable to conventional plastic packaging and improved barrier properties with zero-oxygen permeability of the hydrogel membranes, indicating that these materials have the potential to effectively protect food products from external factors that could compromise quality and shelf life.

Thermal and Bulk Properties of Triblock Terpolymers and Modified Derivatives towards Novel Polymer Brushes.

We report the synthesis of three (3) linear triblock terpolymers, two (2) of the ABC type and one (1) of the BAC type, where A, B and C correspond to three chemically incompatible blocks such as polystyrene (PS), poly(butadiene) of exclusively (~100% vinyl-type) -1,2 microstructure (PB1,2) and poly(dimethylsiloxane) (PDMS) respectively. Living anionic polymerization enabled the synthesis of narrowly dispersed terpolymers with low average molecular weights and different composition ratios, as verified by multiple molecular characterization techniques. To evaluate their self-assembly behavior, transmission electron microscopy and small-angle X-ray scattering experiments were conducted, indicating the effect of asymmetric compositions and interactions as well as inversed segment sequence on the adopted morphologies. Furthermore, post-polymerization chemical modification reactions such as hydroboration and oxidation were carried out on the extremely low molecular weight PB1,2 in all three terpolymer samples. To justify the successful incorporation of -OH groups in the polydiene segments and the preparation of polymeric brushes, various molecular, thermal, and surface analysis measurements were carried out. The synthesis and chemical modification reactions on such triblock terpolymers are performed for the first time to the best of our knowledge and constitute a promising route to design polymers for nanotechnology applications.

Synthesis and Structural Insight into poly(dimethylsiloxane)-b-poly(2-vinylpyridine) Copolymers.

In this study, the use of anionic polymerization for the synthesis of living poly(dimethylsiloxane) or PDMS-Li+, as well as poly(2-vinylpyridine) or P2VP-Li+ homopolymers, and the subsequent use of chlorosilane chemistry in order for the two blocks to be covalently joined leading to PDMS-b-P2VP copolymers is proposed. High vacuum manipulations enabled the synthesis of well-defined materials with different molecular weights (Μ¯n, from 9.8 to 36.0 kg/mol) and volume fraction ratios (φ, from 0.15 to 0.67). The Μ¯n values, dispersity indices, and composition were determined through membrane/vapor pressure osmometry (MO/VPO), size exclusion chromatography (SEC), and proton nuclear magnetic resonance spectroscopy (1H NMR), respectively, while the thermal transitions were determined via differential scanning calorimetry (DSC). The morphological characterization results suggested that for common composition ratios, lamellar, cylindrical, and spherical phases with domain periodicities ranging from approximately 15 to 39 nm are formed. A post-polymerization chemical modification reaction to quaternize the nitrogen atom in some of the P2VP monomeric units in the copolymer with the highest P2VP content, and the additional characterizations through 1H NMR, infrared spectroscopy, DSC, and contact angle are reported. The synthesis, characterization, and quaternization of the copolymer structure are important findings toward the preparation of functional materials with enhanced properties suitable for various nanotechnology applications.

Development and Evaluation of a Novel-Thymol@Natural-Zeolite/Low-Density-Polyethylene Active Packaging Film: Applications for Pork Fillets Preservation.

Sustainability, the circular economy, and the "greenhouse" effect have led the food packaging industry to use naturally available bio-compounds. The integration of such compounds in packaging films increases food safety and extends food shelf-life. The development of an active/antioxidant packaging film based on the widely commercially used low-density polyethylene, natural zeolite, and Thymol, a natural extract from thyme oil, is presented in this work. The obtained active films were characterized using X-Ray Diffraction, Fourier-Transform Infrared Spectroscopy, Scanning Electron Microscopy, and Differential Scanning Calorimetry techniques. The tensile strength, water-oxygen barrier properties, and total antioxidant activity were measured. Low-density polyethylene incorporated with Thymol@Natural Zeolite at a proportion of 15 wt% was the most promising material and was used as film to wrap-up pork fillets. The thiobarbituric acid (TBA) method and heme iron measurements indicated a delayed lipids oxidation using this film. A linear correlation between the TBA method and heme iron values seems to be established, which could result in a fast method to determine the degree of lipid oxidation in pork fillets. Finally, a two-stage diffusion process during Thymol release was observed, and the values of the diffusion coefficient was 2.09 × 10-7 and 1.21 × 10-8 cm2/s for each stage. The applied pseudo-second sorption model provided a rate constant k2 = 0.01647 (s-1). These results indicate the strong potential of such films to be used as food packaging materials free of E-number preservatives.

Development, Characterization, and Evaluation as Food Active Packaging of Low-Density-Polyethylene-Based Films Incorporated with Rich in Thymol Halloysite Nanohybrid for Fresh "Scaloppini" Type Pork Meat Fillets Preservation.

A new era is rising in food packaging and preservation, with a consequent focus on transition to "greener" and environmentally friendly techniques. The environmental problems that are emerging nowadays impose use of natural materials for food packaging applications, replacement of chemical preservatives with natural organic extractions, such as essential oils, and targeting of new achievements, such as further extension of food shelf-life. According to this new philosophy, most of the used materials for food packaging should be recyclable, natural or bio-based, and/or edible. The aim of this work was to investigate use and efficiency of a novel food packaging developed based on commercial LDPE polymer incorporated with natural material halloysite impregnated with natural extract of thyme oil. Moreover, a direct correlation between the stiff TBARS method and the easiest heme iron measurements method was scanned to test food lesions easier and faster. The result of this study was development of the LDPE/10TO@HNT film, which contains the optimum amount of a hybrid nanostructure and is capable to be used as an efficient active food packaging film. Furthermore, a linear correlation seems to connect the TBARS and heme iron measurements.

Thymol@activated Carbon Nanohybrid for Low-Density Polyethylene-Based Active Packaging Films for Pork Fillets' Shelf-Life Extension.

Τhe replacement of food packaging additives and preservatives with bio-based antioxidant/antibacterial compounds has been a common practice in recent years following the trend of bioeconomy and nanotechnology. Such bio-additives are often enclosed in nanocarriers for a controlled release process. Following this trend in this work, a thymol (TO)-rich activated carbon (AC) nanohybrid was prepared and characterized physicochemically with various techniques. This TO@AC nanohybrid, along with the pure activated carbon, was extruded with low-density polyethylene (LDPE) to develop novel active packaging films. The codenames used in this paper were LDPE/xTO@AC and LDPE/xAC for the nanohybrid and the pure activated carbon, respectively. X-ray diffractometry, Fourier-transform infrared spectroscopy, and scanning electron microscopy measurements showed high dispersity of both the TO@AC nanohybrid and the pure AC in the LDPE matrix, resulting in enhanced mechanical properties. The active film with 15 wt.% of the TO@AC nanohybrid (LDPE/15TO@AC) exhibited a 230% higher water/vapor barrier and 1928% lower oxygen permeability than the pure LDPE film. For this active film, the highest antioxidant activity referred to the DPPH assay (44.4%), the lowest thymol release rate (k2 ≈ 1.5 s-1), and the highest antibacterial activity were recorded, resulting in a 2-day extension of fresh pork fillets' shelf-life.

Hydrogel Membranes from Chitosan-Fish Gelatin-Glycerol for Biomedical Applications: Chondroitin Sulfate Incorporation Effect in Membrane Properties.

Chondroitin sulfate (ChS), chitosan (Chi), and fish gelatin (FG), which are byproducts of a fish-treatment small enterprise, were incorporated with glycerol (Gly) to obtain dense hydrogel membranes with reduced brittleness, candidates for dressing in wound healing applications. The mechanical properties of all samples were studied via Dynamic Mechanical Analysis (DMA) and tensile tests while their internal structure was characterized using Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) and X-ray Diffraction (XRD) instruments. Their surface morphology was analyzed by ThermoGravimetric Analysis (TGA) method, while their water permeability was estimated via Water Vapor Transmission Rate (WVTR) measurements. Wettability and degradation rate measurements were also carried out. Characterization results indicated that secondary interactions between the natural polymers and the plasticizer create the hydrogel membranes. The samples were amorphous due to the high concentration of plasticizer and the amorphous nature of the natural polymers. The integration of ChS led to decreased decomposition temperature in comparison with the glycerol-free sample, and all the materials had dense structures. Finally, the in vitro endothelial cell attachment studies indicate that the hydrogel membranes successfully support the attachment and survival of primary on the hydrogel membranes and could be appropriate for external application in wound healing applications as dressings.