Engineered Ceramics for Extreme Environments

Gel polymer electrolytes (GPEs) are regarded as a promising alternative to conventional electrolytes, combining the advantages of solid and liquid electrolytes. Leveraging the abundance and eco-friendliness of cellulose-based materials, GPEs were produced using methyl cellulose and incorporating various doping agents, either an ionic liquid (1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr14][TFSI]), its polymeric ionic liquid analogue (Poly(diallyldimethylammonium bis(trifluoromethylsulfonyl)imide) [PDADMA][TFSI]), or an anionically charged backbone polymeric ionic liquid (lithium poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino) sulfonyl) imide] LiP[STFSI]). The ion dynamics and molecular interactions within the GPEs were thoroughly analyzed using Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy (ATR-FTIR), Heteronuclear Overhauser Enhancement Spectroscopy (HOESY), and Pulsed-Field Gradient Nuclear Magnetic Resonance Diffusion (PFG-NMR). Li+ transference numbers (tLi+) were successfully calculated. Our study found that by combining slow-diffusing polymeric ionic liquids (PILs) with fast-diffusing lithium salt, we were able to achieve transference numbers comparable to those of liquid electrolytes, especially with the anionic PIL, LiP[STFSI]. This research highlights the influence of the polymer ' s nature on lithium-ion transport within GPEs. Additionally, micro supercapacitor (MSC) devices assembled with these GPEs exhibited capacitive behavior. These findings suggest that further optimization of GPE composition could significantly improve their performance, thereby positioning them for application in sustainable and efficient energy storage systems.

Carbon is a critical material for existing and emerging energy applications and there is considerable global effort in generating sustainable carbons. A particularly promising area is iron-catalyzed graphitization, which is the conversion of organic matter to graphitic carbon nanostructures by an iron catalyst. In this paper, it is reported that iron-catalyzed graphitization occurs via a new type of mechanism that is called homogeneous solid-state catalysis. Dark field in situ transmission electron microscopy is used to demonstrate that crystalline iron nanoparticles “burrow” through amorphous carbon to generate multiwalled graphitic nanotubes. The process is remarkably fast, particularly given the solid phase of the catalyst, and in situ synchrotron X-ray diffraction is used to demonstrate that graphitization is complete within a few minutes.

Laser-induced graphene (LIG) on paper is a popular choice for fabricating flexible micro-supercapacitors (MSCs) as it is a simple and sustainable process. However, carbon-based MSC electrodes have limited energy densities. To address this challenge, this study presents a highly reproducible and cost-effective method for decorating manganese oxide (MnOx) x ) on interdigital LIG MSC electrodes, fabricated via a single-step direct laser writing (DLW) process on paper substrates. The paper fibers embedded with MnOx x precursors are transformed into graphene through laser processing while reducing the salt, resulting in the formation of MnOx-LIG. x-LIG. The resulting MnOx-LIG-MSC x-LIG-MSC exhibits a specific capacitance of 12.30 mF cm- 2 (0.05 mA cm- 2 ) with a 60 % retention at 1000 bending cycles (30 degrees), degrees ), due to the pseudocapacitive contribution of MnOx. x . Furthermore, the devices exhibit high electrochemical stability, retaining 190 % of the initial specific capacitance after 10,000 cycles, and a high energy density of 2.6 mu Wh cm-- 2 (at a power of 0.109 mW cm-- 2 ). The study demonstrates that manganese oxide- based LIG-MSCs have the potential to be used as energy storage devices for portable, low-cost, and flexible paper electronics.

The review provides an overview of the latest innovations, trends, and challenges in the field of 3D-printed metal and metal-ion batteries. It focuses on the materials used in the printing of batteries, including electrodes, electrolytes, and other electroactive components. Compared to other high-quality reviews on the topic, this review provides a broader selection of materials that are expected to gain attention in the next few years, such as redox-active polymers and metal-organic frameworks. This work gives an overview and insight into the latest trends in printing techniques as well as a statistical review of their uses and strengths. We have also gathered the latest works done for each of the material types, and we have taken the opportunity to put them in context and use them to exemplify in which direction is the field going. The review concludes with a critical view of the challenges ahead and a discussion of the direction that the field is taking as well as the external factors that might help to define its future. 

Direct Laser Writing (DLW) has been increasingly selected as a microfabrication route for efficient, cost-effective, high-resolution material synthesis and conversion. Concurrently, lasers participate in the patterning and assembly of functional geometries in several fields of application, of which electronics stand out. In this review, recent advances and strategies based on DLW for electronics microfabrication are surveyed and outlined, based on laser material growth strategies. First, the main DLW parameters influencing material synthesis and transformation mechanisms are summarized, aimed at selective, tailored writing of conductive and semiconducting materials. Additive and transformative DLW processing mechanisms are discussed, to open space to explore several categories of materials directly synthesized or transformed for electronics microfabrication. These include metallic conductors, metal oxides, transition metal chalcogenides and carbides, laser-induced graphene, and their mixtures. By accessing a wide range of material types, DLW-based electronic applications are explored, including processing components, energy harvesting and storage, sensing, and bioelectronics. The expanded capability of lasers to participate in multiple fabrication steps at different implementation levels, from material engineering to device processing, indicates their future applicability to next-generation electronics, where more accessible, green microfabrication approaches integrate lasers as comprehensive tools.
This review covers recent progress and breakthroughs in direct laser writing for multimaterial synthesis and conversion, toward processing and fabrication of electronics. Predominant laser-material processing mechanisms for the writing of conductive and semiconductive materials are discussed, alongside important considerations on laser operation and implementation for both rigid and flexible electronics, including microelectronics, energy harvesting and storage, sensors, and bioelectronics. image

Reinforced films were fabricated by impregnating paper in ethyl cellulose solutions. After solvent evaporation, the infused ethyl cellulose acted as binder of the paper microfibres and occupied the pores and cavities, thus improving the mechanical and barrier properties. To prepare active films, avocado by-products from guacamole industrial production were extracted in ethyl acetate. Then, the extract (optimized to be rich in phenolic compounds and flavonoids and mainly composed by lipids) was incorporated to the paper reinforced with the highest content of ethyl cellulose. In general, the addition of the avocado by-products extract decreased the water uptake and permeability, improved the wettability, and increased the biodegradability in seawater and the antioxidant capacity. In addition, these films acted as barriers and retainers for Escherichia coli and Bacillus cereus. The potentiality of these materials for food packaging was demonstrated by low overall migrations and a similar food preservation to common low-density polyethylene.

Mechanical treatment of porous ceramics, such as porous clay minerals, is a crucial step in ceramic processing. Among clay minerals, design swelling brittle micas have shown exceptional properties for further applications, although they exhibit low surface area and porosity. But, their mechanical activation could improve their textural properties and deserves to be investigated. Thus, the aim of this work was to evaluate the effects of gradual grinding in their surface and framework. At short grinding times, the surface area increases and mesoporous and microporous are generated. Long grinding time provokes particle agglomeration with the consequent change in their colloidal stability. At bulk level, framework defects are observed in both tetrahedral and octahedral sheets and increase with the total layer charge.

Nowadays, solving the problems associated with environmental pollution is of special interest. Therefore, in this work, the morphology and thermal and mechanical properties of extruded fibers based on polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) added to prickly pear flour (PPF) under composting for 3 and 6 months were evaluated. The highest weight loss percentage (92 +/- 7%) was obtained after 6-month degradation of the PLA/PBAT/PPF/CO/AA blend, in which PPF, canola oil (CO), and adipic acid (AA) were added. Optical and scanning electron microscopy (SEM) revealed structural changes in the fibers as composting time increased. The main changes in the absorption bands observed by Fourier transform infrared spectroscopy (FTIR) were related to the decrease in -C=O (1740 cm-1) and -C-O (1100 cm-1) groups and at 1269 cm-1, associated with hemicellulose in the blends with PPF. Differential scanning calorimetry (DSC) showed an increase in the cold crystallization and melting point with degradation time, being more evident in the fibers with PPF, as well as a decrease in the mechanical properties, especially Young's modulus. The obtained results suggest that PPF residues could promote the biodegradability of PLA/PBAT-based fiber composites.

Si3N4/nickel-base superalloy (Inconel-625) and Si3N4/Si3N4 joints with refractory metal (W and Mo) interlayers were vacuum brazed using a Ti-active braze Cu-ABA (92.75Cu-3Si-2Al-2.25Ti) at 1317 K for 30 min with the following interlayered arrangements: Si3N4/Mo/W/Inconel and Si3N4/Mo/W/Si3N4. The joints exhibited Ti segregation at the Si3N4/Cu-ABA interface, elemental interdiffusion across the joint interfaces, and sound metallurgical bonding. Knoop microhardness profiles revealed hardness gradients across the joints that mimicked the interlayered arrangement. The compressive shear strength of Si3N4/Si3N4 joints both with and without W and Mo layers was similar to 142 MPa but the strength of Si3N4/Inconel joints increased from similar to 9 MPa for directly bonded joints without interlayers to 53.5 MPa for joints with Mo and W interlayers.

Clay minerals are ceramics materials that are involved in a wide range of economic uses. But, their structure and composition are modified by heating and, consequently, compromise their final applications. The actual tem-peratures at which changes occur vary greatly from one group to another group and even for different specimens within a given group. The aim of this research has been to evaluate the thermal behaviour of a set of design swelling micas, Na-Mica -n (Mn) and compare them with a set of natural smectites. All samples were heated in the range 200 degrees C to 1000 degrees C; afterwards, they were rehydrated thorough water suspension (0.4% wt). The results have shown that swelling micas have better property of hydration/dehydration than natural clay minerals and those with higher layer charge exhibited higher rehydration ability and dehydration temperature.

High charge mica Na4Al4Si4Mg6O20F4 , Mica-4, is a promising candidate as a filling material to immobilize high-level radioactive waste in deep geological repositories due to its extraordinary adsorption capacity. In contrast to traditional clay materials, the structural composition of this mica, with a high content of alu-minum in the tetrahedral sheet, enhances its chemical reactivity, favoring the formation of new crystalline phases under mild hydrothermal conditions, and thus providing a definitive isolation of the radionuclides in the engineered barrier. Moreover, this synthetic clay has some features that allow its use as an optical sensor by doping with luminescent rare earth cations such as Eu3+. In this paper we discuss the local structure of the nanoclay Mica-4 using Eu3+ as a local probe to track the physical and chemical modifica-tions under hydrothermal conditions. For that purpose, a set of hydrothermal experiments has been carried out heating Mica-4 and an aqueous Eu(NO3)(3) solution in a stainless steel reactor at different temperatures and times. Optical properties of the as-treated samples were characterized by spectroscopic measurements. The fine peak structure of emission and the relative intensity of different Eu3+ transitions as well as the luminescence lifetime have been correlated with the structure and composition of this nanoclay, and the interaction mechanisms between the lanthanide ions and the clay mineral at different temperatures and times. Special attention has been paid to understanding the role of the aluminum content, which may act as either an aggregating or dispersing agent, in the optical features and reactivity of the system.

In this work, we systematically investigate the 'catalytic' graphitization of a biomass precursor (coffee ground) using 10-60 wt.% of the activator iron (III) chloride hexahydrate in a temperature range of 1000 degrees C-2400 degrees C. Special focus is put on the correlation of synthesis conditions, e.g., heat treatment temperature and mass fraction of iron chloride, with the electrochemical performance in carbon vertical bar vertical bar Li metal cells. The structural investigations of the materials reveal a positive impact of an increasing heat treatment temperature and/or mass fraction of inserted activator on the degree of graphitization and the delithiation capacity. However, a saturation point regarding the maximum degree of graphitization at 2000 degrees C and reversible capacity by the 'catalytic' graphitization approach using iron (III) chloride has been found. A maximum degree of graphitization of approximate to 69% could be reached by applying 2000 degrees C and 40 wt.% FeCl3 center dot 6H(2)O, resulting in a reversible capacity of 235 mAh g(-1).

Tridecafluorononanoic acid (TFNA), a C6-fluorinated carboxylic acid, was esterified with cellulose at different molar ratios (0:1, 1:1, 2:1, and 3:1) in a trifluoroacetic acid (TFA):trifluoroacetic anhydride (TFAA):CHCl3 (2:1:1, v:v:v) solvent mixture. Free-standing films were obtained for all formulations and are presented as alternatives to composites and blends of paper with fluorinated molecules. Mechanical properties were investigated by tensile tests, and a plasticizer effect of fluorinated chains was observed. Interestingly, the wettability of these new cellulose derivatives was similar or even better than other common cellulose derivatives and fluorinated poly-mers employed in food packaging. Hydrodynamic properties were also improved by addition of TFNA, resulting in materials with water vapor permeability values comparable to other cellulose-based food packaging materials. In addition, films with the higher amounts of TFNA showed the required oil resistance for papers used in food packaging applications, as determined by the Kit Test. Finally, the biodegradation of these C6-fluorinated cel-lulose esters, assessed by biological oxygen demand (BOD) in seawater, was higher than typical bio-based polymers used in food packaging. The bioplastic synthesized at a molar ratio 1:1 (TFNA:cellulose) showed excellent performances in terms of greaseproof, hydrophobicity, ductility, and biodegradability, representing a sustainable alternative to typical plastics used in food packaging.

Free-standing, robust, and transparent bioplastics were obtained by blending cellulose and naringin at different proportions. Optical, thermal, mechanical, antioxidant, and antimicrobial properties were systematically investigated. In general, the incorporation of naringin produced important UV blocking and plasticizer effects and good antioxidant and antibacterial properties. Moreover, the barrier properties were characterized by determination of their water and oxygen transmission rates, finding that both parameters decreased by increasing the naringin content and reaching values similar to other petroleum-based plastics and cellulose derivatives used for food packaging applications. Finally, the biodegradability of these films was determined by measurement of the biological oxygen demand (BOD) in seawater, demonstrating an excellent decomposition in such conditions.

Little is known about the structure and molecular arrangement of alpha- and beta-amyrin, a class of triterpenoids found within the cuticle of higher plants. Blends of both amyrin isomers with different ratios have been studied taking into consideration a combined methodology of density functional theory (DFT) calculations with experimental data from scanning electron microscopy, differential scanning calorimetry and Raman vibrational spectroscopy. Results indicate that trigonal trimeric aggregations of isomer mixtures are more stable, especially in the 1 : 2 (alpha : beta) ratio. A combination of Raman spectroscopy and DFT calculations has allowed to develop an equation to determine the amount of beta-amyrin in a mixed sample.

Carbons are versatile and diverse materials that have numerous applications across energy and environmental sciences. Carbons with a graphitic structure are particularly appealing due to their high chemical stability, large surface areas and high thermal and electronic conductivity. Numerous methods exist to produce nanostructured graphitic carbons but some of these can be energy-intensive and/or have problems with scalability. One option that is being increasingly explored is the process of iron-catalyzed graphitization. This simply involves the pyrolysis of carbon-rich precursors in the presence of an iron catalyst and has been used to produce carbons with a wide range of structures and properties. This review will examine the current field of iron-catalyzed graphitization, with a focus on molecular organic or biomass precursors. Bio-derived precursors are particularly attractive as a potential option for sustainable production of graphitic carbons. We start with a brief introduction to some key carbon structures, the current applications in which they are employed and some of the key methods that have been developed to produce nanostructured graphitic carbons. We will then review the history of catalytic graphitization before evaluating the wide range of conditions and precursors that have been employed in catalytic graphitization. Finally, this review will investigate the current challenges facing iron-catalyzed graphitization, looking particularly at the limitations of the current understanding of the mechanistic aspects of graphitization, with a view to outlining where research in this field might progress.

The cuticle is the most external layer that protects fruits from the environment and constitutes the first shield against physical impacts. The preservation of its mechanical integrity is essential to avoid the access to epidermal cell walls and to prevent mass loss and damage that affect the commercial quality of fruits. The rheology of the cuticle is also very important to respond to the size modification along fruit growth and to regulate the diffusion of molecules from and toward the atmosphere. The mechanical performance of cuticles is regulated by the amount and assembly of its components (mainly cutin, polysaccharides, and waxes). In tomato fruit cuticles, phenolics, a minor cuticle component, have been found to have a strong influence on their mechanical behavior. To fully characterize the biomechanics of tomato fruit cuticle, transient creep, uniaxial tests, and multi strain dynamic mechanical analysis (DMA) measurements have been carried out. Two well-differentiated stages have been identified. At early stages of growth, characterized by a low phenolic content, the cuticle displays a soft elastic behavior. Upon increased phenolic accumulation during ripening, a progressive stiffening is observed. The increment of viscoelasticity in ripe fruit cuticles has also been associated with the presence of these compounds. The transition from the soft elastic to the more rigid viscoelastic regime can be explained by the cooperative association of phenolics with both the cutin and the polysaccharide fractions.

Sustainable coatings for metal food packaging were prepared from ZnO nanoparticles (obtained by the thermal decomposition of zinc acetate) and a naturally occurring polyhydroxylated fatty acid named aleuritic (or 9,10,16-trihydroxy-hexadecanoic) acid. Both components reacted, originating under specific conditions zinc polyaleuritate ionomers. The polymerization of aleuritic acid into polyaleuritate by a solvent-free, melt polycondensation reaction was investigated at different times (15, 30, 45, and 60 min), temperatures (140, 160, 180, and 200 degrees C), and proportions of zinc oxide and aleuritic acid (0:100, 5:95, 10:90, and 50:50, w/w). Kinetic rate constants calculated by infrared spectroscopy decreased with the amount of Zn due to the consumption of reactive carboxyl groups, while the activation energy of the polymerization decreased as a consequence of the catalyst effect of the metal. The adhesion and hardness of coatings were determined from scratch tests, obtaining values similar to robust polymers with high adherence. Water contact angles were typical of hydrophobic materials with values >= 94 degrees. Both mechanical properties and wettability were better than those of bisphenol A (BPA)-based resins and most likely are related to the low migration values determined using a hydrophilic food simulant. The presence of zinc provided a certain degree of antibacterial properties. The performance of the coatings against corrosion was studied by electrochemical impedance spectroscopy at different immersion times in an aqueous solution of NaCl. Considering the features of these biobased lacquers, they can be potential materials for bisphenol A-free metal packaging.

Small solid biomass combustion systems are among the main contributors to the global particulate emissions share, and cheap, efficient abatement systems are not yet available for them. The placement of inert porous material to confine the combustion region is being recently explored as a possible mitigation system for this kind of pollution. However, given the complexity of biomass thermochemical decomposition processes, it is challenging to justify the performance of these systems on the basis of a physicochemical understanding. A foundational experiment-based study is carried out in this work to understand how combustion confinement affects the particulate emissions production mechanisms. A combustion unit was designed and built to systematically test ceramic foams with different porosities: keeping constant airflow and fuel feed rates. A comprehensive characterisation study was carried out on the solid biomass fuel, the temperature profile, the particulate emissions, and the remaining solid residue. The results evidenced that the use of foams has a substantial impact on the temperature distribution in the combustion chamber. The higher the cell density of the foam, the higher and more homogeneous are the temperatures reached in the combustion bed. This fact improved the thermal decomposition process of the pellets due to a better air-fuel mixture, leading to a reduction of the solid particulate matter emissions by more than 70%. These findings suggest that the use of an inert porous material above the combustion region might be a feasible solution for particulate emission control in small-size biomass combustion technology.

The fabrication of pectin-cellulose nanocrystal (CNC) biocomposites has been systematically investigated by blend-ing both polysaccharides at different relative concentrations. Circular free-standing films with a diameter of 9 cm were prepared by simple solution of these carbohydrates in water followed by drop-casting and solvent evaporation. The addition of pectin allows to finely tune the properties of the biocomposites. Textural characterization by AFM showed fibrous morphology and an increase in fiber diameter with pectin content. XRD analysis demonstrated that pectin incorporation also reduced the degree of crystallinity though no specific interaction between both poly-saccharides was detected, by ATR-FTIR spectroscopy. The optical properties of these biocomposites were character-ized for the first time and it was found that pectin in the blend reduced the reflectance of visible light and increased UV absorbance. Thermal stability, analyzed by TGA, was improved with the incorporation of pectin. Finally, pectin-cellulose nanocrystal biocomposites showed a good biodegradability in seawater, comparable to other common bioplastics such as cellulose and low-molecular weight polylactide, among others.

Despite the recent interest in catalytic graphitization to obtain graphite-like materials from hard-carbon sources, many aspects of its mechanism are still poorly unknown. We performed a series of in situ experiments to study phase transformations during graphitization of a hard-carbon precursor using an iron catalyst at temperatures up to 1100 degrees C and ex situ total scattering experiments up to 2000 degrees C to study the structural evolution of the resulting graphitized carbon. Our results show that upon heating and cooling, iron undergoes a series of reductions to form hematite, magnetite, and wustite before forming a carbide that later decomposes into metallic iron and additional graphite and that the graphitization fraction increases with increasing peak temperature. Structural development with temperature results in decreasing sheet curvature and increased stacking, along with a decrease in turbostratic disorder up to 1600 degrees C. Higher graphitization temperatures result in larger graphitic domains without further ordering of the graphene sheets. Our results have implications for the synthesis of novel biomass-derived carbon materials with enhanced crystallinity.

Acid and thermal treated sepiolite was organophilized by cationic exchange with several alkylammonium cations (octylammonium, hexadecylammonium, tetradecyltrimethylammonium, and hexadecyltrimethylammonium). The adsorption capacity of BTEX from aqueous solutions was evaluated through the adsorption isotherms performed in batch. The results were analysed using three isotherm models: Freundlich, Langmuir and Dubinin-Radushkevich (D-R model). The behaviour of adsorption isotherm suggested the multilayer coverage on a heterogeneous surface, which is according to the Freundlich isotherm model. The thermodynamic analyse using the D-R model show that physical mechanisms govern the process. The maximum adsorption capacity of BTEX on the obtained materials was in the range values of 81.19 mg g(-1) - 1448.42 mg g(-)(1), which are higher than those reported up to now. The organo-sepiolite materials exhibit a high potential in the adsorption of BTEX compounds from aqueous solutions.

Organomica, C8-2-Mica, was obtained from a high charged synthetic mica, Na-2-Mica, by cation exchange reaction with octylammonium cations and these were used to host other bulky guest species such as polyhydroxy aluminium cations, Al(13)20. The hydrolization of 3-mercaptopropyltrimethoxysilane (MPTMS) allowed the covalent attachment with hydroxyl groups of the oligomeric cation, providing thiol groups that create specific adsorption sites, Al(13)20/SH. The structure of the adsorbents was analysed by XRD and Infrared spectroscopy and these were tested as an adsorbent for the removal of zinc and herbicide MCPA from aqueous solutions. C8-2-Mica was the best adsorbent for MCPA and thiol groups favoured the adsorption of Zn2+. Moreover, Al(13)20/SH showed excellent adsorptive properties for the simultaneous adsorption of MCPA and Zn2+.

The structural behavior of some cutin monomers, when deposited on mica support, was extensively investigated by our research group. However, other events, such as esterification reaction (ER), are still a way to explore. In this paper, we explore possible ER that could occur when these monomers adsorb on support. Although classical molecular dynamics simulations are not able to capture reactive effects, here, we show that they become valuable strategies to analyze the initial structural configurations to predict the most favorable reaction routes. Thus, when depositing aleuritic acid (ALE), it is observed that the loss of capacity to form self-assembled (SA) systems favors different routes to occur ER. In pure ALE bilayers systems, an ER is given exclusively through the -COOH and primary -OH groups. In pure ALE monolayers systems, the ER does not happen when the system is self-assembled. However, for disorganized systems, it is able to occur by two possible routes: -COOH and primary -OH (route 1) and -COOH and secondary -OH (route 2). When palmitic acid (PAL) is added in small quantities, ALE SAMs can now form an ER. In this case, ER occurs mostly through the -COOH and secondary -OH groups. However, when the presence of PAL is dominant, ER can occur with either of both possibilities, that is, routes 1 and 2.

Free-standing and flexible biocomposite films formed by a polyaleuritate matrix and nanocellulose fillers (i.e., cellulose nanofibrils) have been fabricated by a sustainable process. For this, 9,10,16-trihydroxyhexadecanoic (aleuritic) acid from shellac and nanocellulose were blended at different ratios in water through a sonication process. Polymerization of the polyhydroxylated fatty acid into polyaleuritate was induced by a solvent-free, melting polycondensation reaction in the oven. These biocomposites were characterized to evaluate their chemical (by ATR-FTIR spectroscopy) and physical (e.g., density, thermal stability, rigidity, gas permeability, surface energy, etc.) properties. The compatibility between the polyester matrix and the polysaccharide fillers was excellent due to the interaction by H bonds of the polar groups of both components. The addition of nanocellulose increased all determined mechanical parameters as well as the wettability and the barrier properties, while the thermal stability and the water uptake were determined by the polyaleuritate matrix. The physical properties of these biocomposites were compared to those of petroleum-based plastics and bio-based polymers, indicating that the developed materials can represent a sustainable alternative for different applications such as packaging.

With a high number of diesel vehicles worldwide, particulate emission control is an urgent issue with a global impact, from the health of citizens to commercial future of this technology in some transport segments. Particulate filters are widely used in automotive engines to comply emissions regulations, but current technologies have room for improvement as they add additional backpressure in the exhaust system, and efficient on-board regeneration process is challenging.
The Fil-Bio-Diesel Project is a R&D initiative to improve current particle filtration systems, based on the development of novel biomorphic substrates. By replicating the biologic tissue of a wood precursor, a biomorphic silicon carbide with hierarchic orthotropic microstructure can be produced. The porosity, the pore size, and pore orientation of this bioceramic material can be tailored through the selection of a suitable precursor, widening the initially narrow relationship between filtration efficiency and pressure drop that characterizes granular ceramic materials. In this paper the methodology and main results of the Fil-Bio-Diesel Project are presented. This work shows the peculiar advantages of biomorphic silicon carbide through several experimental studies. The results show the potential of this novel filter substrate to be used in future particulate abatement systems.

Metals used for food canning such as aluminum (Al), chromium-coated tin-free steel (TFS) and electrochemically tin-plated steel (ETP) were coated with a 2-3-mu m-thick layer of polyaleuritate, the polyester resulting from the self-esterification of naturally-occurring 9,10,16-trihydroxyhexadecanoic (aleuritic) acid. The kinetic of the esterification was studied by FTIR spectroscopy; additionally, the catalytic activity of the surface layer of chromium oxide on TFS and, in particular, of tin oxide on ETP, was established. The texture, gloss and wettability of coatings were characterized by AFM, UV-Vis total reflectance and static water contact angle (WCA) measurements. The resistance of the coatings to solvents was also determined and related to the fraction of unreacted polyhydroxyacid. The occurrence of an oxidative diol cleavage reaction upon preparation in air induced a structural modification of the polyaleuritate layer and conferred upon it thermal stability and resistance to solvents. The promoting effect of the tin oxide layer in such an oxidative cleavage process fosters the potential of this methodology for the design of effective long-chain polyhydroxyester coatings on ETP.

The rational design of electrodes mimicking the cellular structure of natural bio-resources has been a matter of increasing interest for applications in energy storage. Due to their anisotropic and hierarchical porosity, monolithic carbon materials from natural wood precursors are appealing as electrodes for supercapacitor applications due to their interconnected channels, relatively low cost and environmentally friendly synthesis process. In this work, a liquid-phase oxidative treatment with refluxing nitric acid at 100 degrees C for 8 h was performed to enhance the surface properties of beech-derived graphitized carbons treated with an iron catalyst. Microstructural, textural and surface investigations revealed that this strategy was successful in removing amorphous carbon and in functionalizing their surfaces. The crystallinity, accessible surface area, micropore volume and surface functionality of beech-derived carbons were increased upon the reflux treatment. The resulting porous carbon materials were evaluated as binderless monolithic electrodes for supercapacitors applications in aqueous KOH electrolyte. A maximum specific capacitance of 179 F.g(-1) and a volumetric capacitance of 89 Fcm(-3) in galvanostatic charge/discharge experiments were reached. Monolithic electrodes exhibited good cycling stability, with a capacitance retention over 95% after 10,000 cycles.

Heavy metal pollution has become one of the most serious environmental problems, demanding specialized remediation mechanisms. Among the studied treatments, ion-exchange processes have been widely used due to their high remediation capacity, efficiency and fast kinetic. Here, the potential use of a new family of design micas as cation exchanger has been analysed. Micas with a layer charge in the range of brittle micas have been synthesized and their heavy metals cation exchange capacity analysed as a function of the nature of the heavy metal cations (Pb2+, Cd2+ or Hg2+), the nature of the counterions (Cl− or NO3−), concentration of the solutions and the micas layer charge. A cation exchange ratio between 35% and 154% of their cation exchange capacity (CEC) was achieved, being more efficient when mica layer charge diminished. In general, the maximum adsorption capacity followed the trend: Hg2+ > Pb2+ > Cd2+. The efficiency of the cation exchange and adsorption mechanism of the synthetic micas depended on the experimental conditions and they were more efficient than raw and modified natural clay minerals.

Atomic Force Microscopy (AFM) is a versatile technique of surface characterization, providing accurate information about the topography and other wide variety of magnitudes at submicron scale. It is extensively utilized in materials science, but its use in other disciplines such as paleobotany is infrequent. In this review, we introduce the main concepts of AFM to paleobotanists, comparing the characteristics of this technique to common electronic and optical microscopies. Then, main works with extant plants, in particular plant cuticles, are described. Finally, realistic applications with fossils are reviewed and their potential use in the characterization of plant fossils discussed. AFM is proposed as a complementary technique to common microscopies to characterize plant cuticle fine details at nanoscale.

Hard carbons are the material of choice as negative electrode in sodium ion batteries. Despite being extensively studied, there is still debate regarding the mechanisms responsible for storage in low- and high-potential regions. This work presents a comprehensive approach to elucidate the involved storage mechanisms when Na ions insert into such disordered structures. Synchrotron X-ray total scattering experiments were performed to access quantitative information on atomic ordering in these materials at the nanoscale. Results prove that hard carbons undergo an atomic rearrangement as the graphene layers cross-link at intermediate temperatures (1200-1600 degrees C), resulting in an increase of the average interplanar distance up to 1400 degrees C, followed by a progressive decrease. This increase correlates with the positive trend in the reversible capacity of biomass-derived carbons when processed up to 1200-1600 degrees C due to an increased capacity at low potential (<= 0.1 V vs Na/Na+). A decrease in achievable sloping capacity with increasing heat-treatment temperature arises from larger crystalline domains and a lower concentration of defects. The observed correlation between structural parameters and electrochemical properties clearly supports that the main storage of Na ions into a hard-carbon structure is based on an adsorption-intercalation mechanism.

Biodegradable aliphatic polyesters are an alternative to reduce the use of synthetic plastic materials that cause severe damage to the environment. Formulations based on poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT), were mixed in a 60:40 ratio, adding different concentrations of pine essential oil through the use of extrusion technology to obtain biodegradable polymer fibers. Some formulations were coated with chitosan. All the elaborated fibers were characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR), Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD) and mechanical properties. The SEM studies showed that the PBAT improves the tenacity and provides greater elasticity promoting the interaction between the blends phases with fibril formation. In the FTIR-ATR analysis, compatibility between the blends was observed due to a possible interaction of the carbonyl group of PBAT with PLA. The DSC and the mechanical properties showed partial miscibility of the blends, indicating, that the plasticizing action of the essential oil gave greater mobility, flexibility, less rigidity and crystallization in the blends. A lower Young's modulus and greater elongation at break was also observed.

epsilon-caprolactone-p-coumaric acid copolymers at different mole ratios (epsilon-caprolactone: p-coumaric acid 1:0, 10:1, 8:1, 6:1, 4:1, and 2:1) were synthesized by melt-polycondensation and using 4-dodecylbenzene sulfonic acid as catalyst. Chemical analysis by NMR and GPC showed that copolyesters were formed with decreasing molecular weight as p-coumaric acid content was increased. Physical characteristics, such as thermal and mechanical properties, as well as water uptake and water permeability, depended on the mole fraction of p-coumaric acid. The p-coumarate repetitive units increased the antioxidant capacity of the copolymers, showing antibacterial activity against the common pathogen Escherichia coli. In addition, all the synthesized copolyesters, except the one with the highest concentration of the phenolic acid, were cytocompatible and hemocompatible, thus becoming potentially useful for skin regeneration applications.

Bioplastics were prepared from the fatty fraction (i.e., unsaturated and polyhydroxylated fatty acids) of tomato pomace agro-wastes. Aliphatic polyesters were synthesized at different temperatures (125, 150, and 175 °C), reaction times (0.25, 0.5, 0.75, 1, 3, 5, and 7 h), and amounts of tin (II) 2-ethylhexanoate (0, 0.02, 0.05, and 0.10 mmol) used as a catalyst. The rate constants and activation energies were calculated from infrared spectra. The right combination of reaction temperature and amount of catalyst improved the reaction kinetics (apparent k from ∼1 to ∼8.5 h−1), whereas the activation energy was reduced from ∼39 without catalyst to ∼28 kJ/mol when tin (II) 2-ethylhexanoate was present. Glass transitions between ca. −25 and ∼0 °C were measured by differential scanning calorimetry, strictly depending on the degree of polymerization. The amorphous character of the samples was confirmed by X-ray diffraction. Young's modulus and hardness were calculated from indentation tests and were typical of soft materials, although increased as the polycondensation reaction progressed. High water-contact angles (maximum value ∼109°) and low water uptakes (minimum value ∼2.1%) were determined. Physical properties were compared with those of common man-made plastics and polymers, finding that these tomato pomace bioplastics could be their realistic alternatives.

Isolation of high-level radioactive waste (HLW) in deep geological repositories (DGR) through a multibarrier concept is the most accepted approach to ensure long-term safety. Clay minerals are one of the most promising materials to be used as engineered barriers. In particular, high charge micas, as components of the engineered barrier, show superselectivity for some radioactive isotopes and a large adsorption capacity, which is almost twice that of the other low charge aluminosilicates. In addition, high charge micas are optimum candidates for decontamination of nuclear waste through two different mechanisms; namely an ion exchange reaction and a nonreversible mechanism involving the formation of new stable crystalline phases under hydrothermal conditions. In this work, we report a new in situ optical sensor based on the incorporation of Eu3+ in these high charge micas for tracking the long-term physical-chemical behavior of HLW contaminants in DRG under mild hydrothermal conditions. The incorporation of Eu3+ into the interlayer space of the mica originates a well resolved green and red luminescence, from both the 5D1 and 5D0 excited states, respectively. The formation of new crystalline phases under hydrothermal conditions involves important changes in the Eu3+ emission spectra and lifetime. The most interesting features of Eu3+ luminescence to be used as an optical sensor are (1) the presence or absence of the Eu3+ green emission from the 5D1 excited state, (2) the energy shift of the 5D0 → 7F0 transition, (3) the crystal-field splitting of the 7F1 Eu3+ level, and (4) the observed luminescence lifetimes, which are directly related to the interaction mechanisms between the lanthanide ions and the silicate network.

A simple, low-cost and environmentally friendly method has been used to obtain highly porous biomorphic carbon monoliths with a good combination of interconnected macro-, meso- and microporosity, and good electrical conductivity and mechanical strength, making these biocarbon materials interesting for electrochemical applications as binder-free electrodes. Highly porous monolithic biocarbons were obtained from beech wood precursors through pyrolysis and subsequent surface modification in a steam heated to 970 degrees C with different activation times. The obtained biocarbons demonstrated good electrical conductivity and mechanical strength. They were studied as electrodes for supercapacitors in half cell experiments, demonstrating maximum gravimetric capacitance of 200 F g(-1) in a basic media at scan rate 1 mV s(-1). Galvanostatic charge-discharge experiments showed maximum capacitance of 185 F g(-1) at current density of 0.15 A g(-1) and similar to 100 F g(-1) at current density of 0.75 A g(-1). It has been shown that in addition to the developed porous surface, the micropores with diameters exceeding 1 nm play a key role for the enhanced electrochemical capacity. Long-cycling experiments demonstrated excellent stability of the monolithic biocarbon electrodes with no reduction of the initial capacitance values after 600 cycles in voltammetry.

A method consisting of the alkaline hydrolysis of tomato pomace by-products has been optimized to obtain a mixture of unsaturated and polyhydroxylated fatty acids as well as a non-hydrolysable secondary residue. Reaction rates and the activation energy of the hydrolysis were calculated to reduce costs associated with chemicals and energy consumption. Lipid and non-hydrolysable fractions were chemically (infrared (IR) spectroscopy, gas chromatography/mass spectrometry (GC-MS)) and thermally (differential scanning calorimetry (DSC), thermogravimetric analysis (TGA)) characterized. In addition, the fatty acid mixture was used to produce cutin-based polyesters. Freestanding films were prepared by non-catalyzed melt-polycondensation and characterized by Attenuated Total Reflected-Fourier Transform Infrared (ATR-FTIR) spectroscopy, solid-state nuclear magnetic resonance (NMR), DSC, TGA, Water Contact Angles (WCA), and tensile tests. These bio-based polymers were hydrophobic, insoluble, infusible, and thermally stable, their physical properties being tunable by controlling the presence of unsaturated fatty acids and oxygen in the reaction. The participation of an oxidative crosslinking side reaction is proposed to be responsible for such modifications.

Na-Mica-4, a synthetic fluorophlogopite, is an attractive adsorbent. However, the synthesis at large scale demands an economically prized, feasible scalable and sustainable synthesis method, which requires a deep knowledge of the influence of each synthesis step. A set of Na-Mica-4 were synthesized by methods that had one synthesis parameter as variable. The purity, crystallinity and heteroatoms distribution were analysed thorough X-ray diffraction and nuclear magnetic resonance. The results shed a light on the main factors for the design of the final product and indicated that an environmental friendship synthesis could be possible. 

Climatic stressors due to global change induce important modifications to the chemical composition of plant cuticles and their biophysical properties.
In particular, plant cuticles can become heavier, stiffer and more inert, improving plant protection.
The climatic stressors that modify the chemical composition of plant tissues have been recently reviewed by Suseela and Tharayil (2018). In particular, the authors stated that the response of plants to global change effects (viz. increasing temperatures and frequent drought periods) can induce important modifications in plant cuticles such as an increase of the main cuticle components (cutin and polysaccharides), a preponderance of cutan, heavier wax loads, and changes in the chemical composition of waxes, mainly the accumulation of longer aliphatic compounds. In this letter, we would like to emphasize the biophysical consequences that this new scenario involves and how it would affect plant performance.

The most advanced applications of clays depend crucially on their hydration state and swelling is probably the most important feature of expandable 2:1 layered silicate. Sodium Taeniolite, Na-TAE, a swelling trioctahedral fluormica, has been synthesized and studied using thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and infrared and solid state NMR spectroscopies. The results indicated the formation of a swelling 2:1 phyllosilicate with actual layer charge lower than the nominal one. Herein, a new heteroatom distribution and more accurate composition could be deduced.

Biomorphic Silicon Carbide (bioSiC) has been recently introduced in the scope of porous ceramic substrates for hot gas filtration applications, where it has demonstrated to have good thermal and mechanical properties, and a high potential to meet the requirements for current Diesel Particulate Filters (DPF). In this experimental study, a small wall-flow bioSiC diesel filter was characterized using a soot generator, the particle size distribution of which being similar to the one generated by a diesel engine. The bioSiC samples were manufactured from Medium Density Fiberboard (MDF) following a general manufacturing procedure for bioSiC ceramics, but paying special attention in the mechanizing stage to the geometry and optimal design of the honeycomb structure required for diesel engine applications. The samples had a cell density of 57.59 cell/cm(2) (371.6 cpsi), a square cross section of 9.2 x 9.2 mm, and a length of 31 mm. To generate the particle laden stream and perform the filtration tests, a synthetic Soot Generator (SG) was used. Tests were performed under controlled and reproducible conditions, with a fixed gas flow rate of 5 LPM and a soot mass flow rate of 4 mg/h. The filtration efficiency was determined with the aid of a Scanning Mobility Particle Sizer (SMPS) from the measurements of the particle concentration upstream and downstream the filter samples. During the soot loading process, the pressure drop was also monitored. The results show that, in the initial stage (clean filter), bioSiC wall-flow DPFs may have a filtration efficiency between 0.7 and 0.85 and a pressure drop of around 2 kPa for a normalized wall velocity of 0.01 m/s at ambient temperature. The filtration performance of wall-flow bioSiC particle filters showed in this work can help us to better understand their real potential for automotive applications. 

Biomorphic Silicon Carbide (bioSiC) is a novel porous ceramic material with excellent mechanical and thermal properties. Previous studies have demonstrated that it may be a good candidate for its use as particle filter media of exhaust gases at medium or high temperature. In order to determine the filtration efficiency of biomorphic Silicon Carbide, and its adequacy as substrate for diesel particulate filters, different bioSiC-samples have been tested in the flue gases of a diesel boiler. For this purpose, an experimental facility to extract a fraction of the boiler exhaust flow and filter it under controlled conditions has been designed and built. Several filter samples with different microstructures, obtained from different precursors, have been tested in this bench. The experimental campaign was focused on the measurement of the number and size of particles before and after placing the samples. Results show that the initial efficiency of filters made from natural precursors is severely determined by the cutting direction and associated microstructure. In biomorphic Silicon Carbide derived from radially cut wood, the initial efficiency of the filter is higher than 95%. Nevertheless, when the cut of the wood is axial, the efficiency depends on the pore size and the permeability, reaching in some cases values in the range 70–90%. In this case, the presence of macropores in some of the samples reduces their efficiency as particle traps. In continuous operation, the accumulation of particles within the porous media leads to the formation of a soot cake, which improves the efficiency except in the case when extra-large pores exist. For all the samples, after a few operation cycles, capture efficiency was higher than 95%. These experimental results show the potential for developing filters for diesel boilers based on biomorphic Silicon Carbide.

The synthesis of microcrystalline cellulose (MCC) and 9,10,16-hydroxyhexadecanoic (aleuritic) acid ester-based bioplastics was investigated through acylation in a mixed anhydride (trifluoroacetic acid (TFA)/trifluoroacetic acid anhydride (TFAA)), chloroform co-solvent system. The effects of chemical interactions and the molar ratio of aleuritic acid to the anhydroglucose unit (AGU) of cellulose were investigated. The degree of substitution (DS) of new polymers were characterized by two-dimensional solution-state NMR and ranged from 0.51 to 2.60. The chemical analysis by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the presence of aleuritate groups in the structure induces the formation of new H-bond networks. The tensile analysis and the contact angle measurement confirmed the ductile behavior and the hydrophobicity of the prepared bioplastics. By increasing the aleuritate amounts, the glass transition temperature decreased and the solubility of bioplastic films in most common solvents was improved. Furthermore, this new polymer exhibits similar properties compared to commercial cellulose derivatives.

Materials development is driven by microstructural complexity and, in many cases, inspired by biological systems such as bones, shells and wood. In one approach, one selects the main microstructural features responsible for improved properties and design processes to obtain materials with such microstructures (continuous-fibre-reinforced ceramics, porous ceramics, fibrous ceramic monoliths, etc.). In a different approach, it is possible to use natural materials directly as microstructural templates. Biomorphic ceramics are produced from natural and renewable resources (wood or wood-derived products). A wide variety of SiC-based ceramics can be fabricated by infiltration of silicon or silicon alloys into cellulose-derived carbonaceous templates, providing a low-cost route to advanced ceramic materials with near-net shape potential and amenable to rapid prototyping. These materials have tailorable microstructure and properties, and behave like ceramic materials manufactured by advanced ceramic processing approaches. This review aims to be a comprehensive description of the development of bioSiC ceramics: from wood templates and their microstructure to potential applications of bioSiC materials.

The major components of the wastewater from the petroleum refineries are benzene, toluene and phenol and one of the techniques applied to the treatment of effluents is sorption using organo-functionalized clay. The materials exploited in the present study are a family of surface-functionalized synthetic micas and their sorption capacities for non-ionic organic pollutants are analyzed. The organo-functionalization of their surface provides them the capacity to sorb effectively non-ionic pollutants in the interface. Their adsorption performance is a function of the alkylamonium properties such as the chain length, the mass fraction and the organization of the organic cation in the interlayer space of the micas.

The efficiency of thin-film CIGS based cells at the laboratory scale is now getting closer to conventional Silicon technologies. As a consequence, the long-term stability of CIGS is now one of the main challenges left to address in order to assess its potential as an alternative for photovoltaic plants. This paper reports an overview of the critical risks for the commercial viability of the CIGS thin-film technology. The key causes of the potential failures of this technology are determined through the Failure Mode Analysis and Effects (FMEA) methodology. To validate the results obtained from the FMEA, aging tests and outdoor monitoring were also carried out. Based on the results obtained, we argue that the encapsulation material is the main cause of degradation in CIGS modules. 

In article number 1600024, José A. Heredia‐Guerrero, Athanassia Athanassiou, and co‐workers present new, sustainable composite materials inspired by plant cuticles. These materials are fabricated by the impregnation of fibrous cellulose substrates with a naturally occurring polyhydroxylated fatty acid, and subsequent polymerization of the latter into a polyester. In the image a piece of this new material is shown together with tomato and pepper fruits. Cover image created by Dr. Duilio Farina.

Cu(In,Ga)Se-2 (CIGS) technology is one of the best absorber materials with record efficiencies among photovoltaic thin-film technologies (22.3% at lab scale and 16% at large commercial module). Although research on this material was originally motivated by low-cost, glass-glass applications focusing to fixed photovoltaic structures, the high efficiency values make CIGS an interesting alternative for low concentration systems. In this paper a 2D model for Cu(In,Ga)Se-2 (CIGS) solar cells under low solar concentration is described and contrasted with experimental data. Using simulation, the effect of front electric contact design parameters: finger width, finger separation, and number of buses are analyzed for solar concentrations from 1 up to 10 suns. Efficiency maps allowing front contact grid optimization are shown and analyzed for each concentration factor (Cx), assessing the viability of CIGS solar cells for low concentration applications, where commercial CIGS solar cells may exhibit 35% of electrical power increases with proper front grid optimization under low concentration respect to conventional grid design. 

Thin-film PV modules grown on flexible, light weight, thermally stable and low cost substrates such as stainless steel foil, are an attractive product for solar market applications. When metal foils are used as substrate, it is essential to deposit a dielectric barrier layer to isolate electrically and chemically the thin-film solar cells from the substrate. In this work, SiOx stacks deposited on ‘rough’ stainless steel by a combination of a new sol-gel formulation and a Plasma Enhanced Chemical Vapor Deposition (PECVD) deposition step are reported as a suitable dielectric barrier layer candidate. Using these SiOx multilayers, a smooth and homogeneous film was achieved. X-ray diffraction (XRD) analysis showed that back contact of the solar cell (based on Molybdenum) is not affected by the presence of the barrier layer. Moreover, according to X-ray photoelectron spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS) measurements, this approach led to excellent barrier layer properties against the diffusion of impurities from the stainless steel. A complete electrical characterization of these dielectric barrier layers was also carried out showing good electrical insulation.

Biomorphic SiC is a SiC/Si composite made by the reactive infiltration of molten silicon by capillarity into a carbon preform from high-temperature pyrolysis of a wood porous precursor. When excess silicon is removed, a hierarchically porous SiC material with highly interconnected porosity is obtained. By choosing different wood precursors, different pore size distributions can be obtained thus tailoring the resulting properties. 

We study the thermal conductivity of porous biomorphic SiC from five different precursors, including a recycled wood product, in order to determine the microstructure-conductivity correlation. Here, we remove the excess of silicon by a high temperature capillary extraction-evaporation method. We used the laser flash technique to measure thermal diffusivity in the range similar to 300 K to 973 K, in order to determine the thermal conductivity. Thermal conductivities in the range 4-88 W/m K were achieved. The temperature, porosity, pore shape and orientation, and the treatment used to remove the remaining silicon all have a significant impact in the resulting thermal conductivity. We explain this influence in a first approximation in terms of a geometrical model.

Catalytic hydrogen combustion was studied with H-2/air mixtures in conditions that simulate the H-2 concentration of the exhaust gases from fuel cells (3-4% v/v H-2 in air). Pt-impregnated monoliths based on porous biomorphic SiC (bio-SiC) substrates were employed for the first time for this reaction. Capillary forces were exploited for the incipient impregnation of supports with H2PtCl6 solutions. Freeze drying permitted us to obtain a homogeneous distribution of the active phase reducing accumulation at the monolith's outer shell. The supports and catalysts were characterized from a structural and thermal point of view. Catalytic tests were performed in a homemade reactor fed with up to 1000 ml min(-1) H-2/air mixtures and a diffusional regime (non-isothermal) was achieved in the selected conditions. Catalyst loading was tested in the range of 0.25-1.5 wt% Pt and 100% conversion was achieved in all cases. Temperatures were recorded at different points of the monoliths during the reaction showing anisotropic thermal behavior for selected bio-SiC substrates. These effects are of interest for heat management applications and were explained in correlation with thermal conductivity measurements performed on the supports. Pt-impregnated monoliths were also tested in less than 100% conversion conditions (1% v/v H-2 in air) and in powder form in kinetic conditions for comparative purposes.

We report here on the controlled synthesis, characterization, and electrochemical properties of different polymorphs of niobium pentoxide grown by CVD of new single-source precursors. Nb2O5 films deposited at different temperatures showed systematic phase evolution from low-temperature tetragonal (TT-Nb2O5, T-Nb2O5) to high temperature monoclinic modifications (H–Nb2O5). Optimization of the precursor flux and substrate temperature enabled phase-selective growth of Nb2O5 nanorods and films on conductive mesoporous biomorphic carbon matrices (BioC). Nb2O5 thin films deposited on monolithic BioC scaffolds produced composite materials integrating the high surface area and conductivity of the carbonaceous matrix with the intrinsically high capacitance of nanostructured niobium oxide. Heterojunctions in Nb2O5/BioC composites were found to be beneficial in electrochemical capacitance. Electrochemical characterization of Nb2O5/BioC composites showed that small amounts of Nb2O5 (as low as 5%) in conjunction with BioCarbon resulted in a 7-fold increase in the electrode capacitance, from 15 to 104 F g–1, while imparting good cycling stability, making these materials ideally suited for electrochemical energy storage applications.

Graphitic porous carbon materials from pyrolysis of wood precursors were obtained by means of a nanosized Fe catalyst, and their microstructure and electrical and thermal transport properties investigated. Thermal and electrical conductivity of graphitized carbon materials increase with the pyrolysis temperature, indicating a relationship between the degree of graphitization and thus in crystallite size with transport properties in the resulting carbon scaffolds. Evaluation of the experimental results indicate that thermal conductivity is mainly through phonons and increases with the temperature in Fe-catalyzed carbons suggesting that the mean free path of phonons in the material is small and defect scattering dominates over phonon-phonon interactions in the range from room temperature to 800 °C.

The Cavolinioidea are planktonic gastropods which construct their shells with the so-called aragonitic helical fibrous microstructure, consisting of a highly ordered arrangement of helically coiled interlocking continuous crystalline aragonite fibres. Our study reveals that, despite the high and continuous degree of interlocking between fibres, every fibre has a differentiated organic-rich thin external band, which is never invaded by neighbouring fibres. In this way, fibres avoid extinction. These intra-fibre organic-rich bands appear on the growth surface of the shell as minuscule elevations, which have to be secreted differentially by the outer mantle cells. We propose that, as the shell thickens during mineralization, fibre secretion proceeds by a mechanism of contact recognition and displacement of the tips along circular trajectories by the cells of the outer mantle surface. Given the sizes of the tips, this mechanism has to operate at the subcellular level. Accordingly, the fabrication of the helical microstructure is under strict biological control. This mechanism of fibre-by-fibre fabrication by the mantle cells is unlike that any other shell microstructure.

Silicon nitride/silicon nitride joints with refractory metal (W and Mo) interlayers were vacuum brazed using an active braze, Cu-ABA (Cu-3Si-2Al-2.25Ti, wt%), and two interlayer arrangements in a double-lap offset configuration: Si3N4/Cu-ABA/W/Cu-ABA/Mo/Cu-ABA/Si3N4 and Si3N4/Cu-ABA /Si3N4. Titanium segregated at the Si3N4/Cu-ABA and Mo/Cu-ABA interfaces, but not at the W/Cu-ABA interface. The room-temperature compression-shear strength values of Si3N4/Cu-ABA/Si3N4 and Si3N4/Cu-ABA/W/Cu-ABA/Mo/Cu-ABA/Si3N4 joints were 118 +/- 24 MPa and 22 +/- 5 MPa, respectively. Elevated-temperature compression tests showed that Si3N4/Cu-ABA/Si3N4 joints had strength of 31 +/- 6 MPa at 1023 K and 17 +/- 3 MPa at 1073 K. Likewise, Si3N4/Cu-ABA/W/Cu-ABA/Mo/Cu-ABA/Si3N4 joints had strength of 19 +/- 4 MPa at 1023 K and 13 +/- 3 MPa at 1073 K. Knoop microhardness profiles revealed hardness gradients across the joints. The effect of joint microstructure and test configuration on the mechanical behavior is discussed.

The electrical and galvanomagnetic properties of partially graphitized highly porous bioC(Ni) biocarbon matrices produced by pyrolysis (carbonization) of beech wood at temperatures T (carb) = 850-1600A degrees C in the presence of a Ni-containing catalyst have been studied in comparison with their microstructural features. The temperature dependences of the resistivity, the magnetoresistance, and the Hall coefficient have been measured in the temperature range of 4.2-300 K in magnetic fields to 28 kOe. It has been shown that an additional graphite phase introduction into samples with T (carb) a parts per thousand yen 1000A degrees C results in an increase in the carrier mobility by a factor of 2-3, whereas the carrier (hole) concentration remains within similar to 10(20) cm(-3), as in biocarbons obtained without catalyst. An analysis of experimental data has demonstrated that the features of the conductivity and magnetoresistance of these samples are described by quantum corrections related to their structural features, i.e., the formation of a globular graphite phase of nano- and submicrometer sizes in the amorphous matrix. The quantum corrections to the conductivity decrease with increasing carbonization temperature, which indicates an increase in the degree of structure ordering and is in good agreement with microstructural data.

FEBEX clay is considered a reference material in engineered barriers for safe storage of nuclear waste and uranium is a minor component of high-level radioactive waste (HLRW) and a main component of the spent nuclear fuel (SNF). Here, the kinetics of reaction of uranium with FEBEX was investigated in addition to the uranium immobilisation ability and the structural analysis of the reaction products. Hydrothermal treatments were accomplished with UO22+ and tetravalent actinide simulator ZrO2+, also present in HLRW. The quantification of the reaction was performed through gamma spectrometry of uranium. Two mechanisms for UO22+ retention by FEBEX were detected: adsorption and formation of stable and insoluble new phases. The structural analyses performed using ZrO2+, confirmed the uranium adsorption and the presence of new phases, ZrO2 and Zr(SiO4), that emphasise the existence of a chemical reaction with the bentonite. The analysis of the velocity of reaction uranium-clay minerals revealed temperature dependence. An exponential fitting suggested that the removal of uranium from solution at temperatures over 200 °C could be completed in less than a year. For lower temperatures, several years are needed. Milliequivalents of UO22+ immobilised by the clay depended on temperature and time and were over cation exchange capacity (CEC) of FEBEX even at 100 °C (reaching 600% of CEC). The reaction with steel, also temperature dependent, was finally analysed. At 200 °C 40–70% of uranium reacted with steel. But only 30–15% reacted at 300 °C and 100 °C. The reactions provide a stable immobilisation mechanism for uranium even when its sorption and swelling capacities fail. Our experiments will be of particular interest for very deep borehole disposals were higher temperatures and pressures are expected.

Nanoparticles, named cutinsomes, have been prepared from aleuritic (9,10,16-trihidroxipalmitic) acid and tomato fruit cutin monomers (a mixture of mainly 9(10), 16-dihydroxypalmitic acid (85%, w/w) and 16-hydroxyhexadecanoic acid (7.5%, w/w)) with pectin in aqueous solution. The process of formation of the nanoparticles of aleuritic acid plus pectin has been monitored by UV-Vis spectrophotometry, while their chemical and morphological characterization was analyzed by ATR-FTIR, TEM, and non-contact AFM. The structure of these nanoparticles can be described as a lipid core with a pectin shell. Pectin facilitated the formation of nanoparticles, by inducing their aggregation in branched chains and favoring the condensation between lipid monomers. Also, pectin determined the self-assembly of cutinsomes on highly ordered pyrolytic graphite (HOPG) surfaces, causing their opening and forming interconnected structures. In the case of cutin monomers, the nanoparticles are fused, and the condensation of the hydroxy fatty acids is strongly affected by the presence of the polysaccharide. The interaction of pectin with polyhydroxylated fatty acids could be related to an initial step in the formation of the plant biopolyester cutin.

Biomorphic SiC ceramics were fabricated from four different wood precursors and their Knoop hardness and sliding wear resistance when sliding against a Si3N4 ball in air were studied. Tribological experiments were performed using a pin on disk apparatus, under normal loads of 2 and 5 N, at a sliding speed of 100 mm/s. The effects of specimen porosity and microstructure on measured wear were evaluated. A commercial sintered silicon carbide ceramic was also tested for comparison. Small differences in friction coefficient comparable to monolithic SiC ceramics were obtained. Several concurrent wear mechanisms are taking place: microfracture, plastic deformation in the Si phase and oxidation of the Si and/or SiC phase. The presence of an oxide tribolayer was assessed using fluorescence microscopy. Wear rates were found to scale with SiC content and depend on residual porosity in the composite.

Porous graphitic carbons were successfully obtained from wood precursors through pyrolysis using a transition metal as catalyst. Once the catalyst is removed, the resulting material mimics the microstructure of the wood and presents high surface area, open and interconnected porosity and large pore volume, high crystallinity and good electrical conductivity, making these carbons interesting for electrochemical devices. Carbons obtained were studied as electrodes for supercapacitors in half cell experiments, obtaining high capacitance values in a basic media (up to 133 F g−1 at current densities of 20 mA g−1 and 35 F g−1 at current densities of 1 A g−1). Long-cycling experiments showed excellent stability of the electrodes with no reduction of the initial capacitance values after 1000 cycles in voltammetry.

To mimic nontoxic and fully biodegradable biopolymers like the plant cutin, polyester films from a natural occurring fatty polyhydroxyacid like aleuritic (9,10,16-trihydroxyhexadecanoic) acid have been prepared by noncatalyzed melt-polycondensation at moderate temperature (150 degrees C) directly in air. The course of the reaction has been followed by infrared spectroscopy, C-13 magic angle spinning nuclear magnetic resonance spectroscopy, differential scanning calorimetry and X-ray diffraction and well differentiated stages are observed. First, a high conversion esterification reaction leads to an amorphous rubbery, infusible, and insoluble material whose structure is made out of ester linkages mostly involving primary hydroxyls and partially branched by minor esterification with secondary ones. Following the esterification stage, the cleavage of vicinal secondary hydroxyls and further oxidation to carboxylic acid is observed at the near surface region of films. New carboxylic groups created also undergo esterification and generate cross-linking points within the polymer structure. Additionally, and despite the harsh preparation conditions used, very little additional side reaction like peroxidation and dehydration are observed. Results demonstrate the feasibility of polyester films fabrication from a reference fatty polyhydroxyacid like aleuritic acid by noncatalyzed melt-polycondensation directly in air. The methodology can potentially be extended to similar natural occurring hydroxyacids to obtain films and coatings to be used, for instance, as nontoxic and biodegradable food packaging material.

Flexible thin film solar cells are an alternative to both utility-scale and building integrated photovoltaic installations. The fabrication of these devices over electrically conducting low-cost foils requires the deposition of dielectric barrier layers to flatten the substrate surface, provide electrical isolation between the substrate and the device, and avoid the diffusion of metal impurities during the relatively high temperatures required to deposit the rest of the solar cell device layers. The typical roughness of low-cost stainless-steel foils is in the hundred-nanometer range, which is comparable or larger than the thin film layers comprising the device and this may result in electrical shunts that decrease solar cell performance. This manuscript assesses the properties of different single-layer and bilayer structures containing ceramics inks formulations based on Al2O3, AlN, or Si3N4 nanoparticles and deposited over stainless-steel foils using a rotogravure printing process. The best control of the substrate roughness was achieved for bilayers of Al2O3 or AlN with mixed particle size, which reduced the roughness and prevented the diffusion of metals impurities but AlN bilayers exhibited as well the best electrical insulation properties.

Porous graphitic carbons were obtained from wood precursors using Ni as a graphitization catalyst during pyrolysis. The structure of the resulting material retains that of the original wood precursors with highly aligned, hierarchical porosity. Thermal characterization was performed by means of thermogravimetry and differential scanning calorimetry, and the onset temperature for graphitization was determined to be similar to 900 A degrees C. Structural and microstructural characterization was performed by means of electron microscopy, electron and x-ray diffraction, and Raman spectroscopy. The effect of maximum pyrolysis temperature on the degree of graphitization was assessed. No significant temperature effect was detected by means of Raman scattering in the range of 1000-1400 A degrees C, but at temperatures over the melting point of the catalyst, the formation of graphite grains with long-range order was detected.

The structure of high-charged micas, Na-n-micas (n = 2 and 4), a family of synthetic silicates with a wide range of applications, was investigated through the use of 17O solid-state NMR at natural abundance in order to preserve quantitative spectral information. The use of a very high-field and highly sensitive probehead, together with 17O NMR literature data allowed for the detection of an isolated signal at 26 ppm, assigned partially to AlOAl, as evidence of the violation of Lowenstein's rule for Na-4-mica.

The cuticle is one of the most important plant barriers. It is an external and continuous lipid membrane that covers the surface of epidermal cells and whose main function is to prevent the massive loss of water. The spectroscopic characterization of the plant cuticle and its components (cutin, cutan, waxes, polysaccharides and phenolics) by infrared and Raman spectroscopies has provided significant advances in the knowledge of the functional groups present in the cuticular matrix and on their structural role, interaction and macromolecular arrangement. Additionally, these spectroscopies have been used in the study of cuticle interaction with exogenous molecules, degradation, distribution of components within the cuticle matrix, changes during growth and development and characterization of fossil plants.

High-porosity samples of beech wood biocarbon (BE-C) were prepared by pyrolysis at carbonization temperatures T carb = 650, 1300, and 1600°C, and their resistivity ρ and thermal conductivity κ were studied in the 5–300 and 80–300 K temperature intervals. The experimental results obtained were evaluated by invoking X-ray diffraction data and information on the temperature dependences ρ(T) and κ(T) for BE-C samples prepared at T carb = 800, 1000, and 2400°C, which were collected by the authors earlier. An analysis of the κ(T carb) behavior led to the conclusion that the samples under study undergo an amorphous-nanocrystalline phase transition in the interval 800°C < T carb < 1000°C. Evaluation of the electronic component of the thermal conductivity revealed that the Lorentz number of the sample prepared at T carb = 2400°C exceeds by far the classical Sommerfeld value, which is characteristic of metals and highly degenerate semiconductors.

Synthesis of Na-Mica-4 has been achieved by a “mix and calcine” method using sodalite and magnesium fluoride as the only precursors. Previous research found sodalite as a key intermediate reaction product in the formation of Na-Mica-4 when the NaCl melt method was employed. Similarities in structure, chemical composition and cation distribution in products using the proposed method and the NaCl melt method are described and suggest that Na-Mica-4 is a very stable product. The use of sodalite as precursor provokes microporous formation in the final mica. The absence of excess Na leads to a lower particle size and to the presence of less impurity in the calcined product. Different sodalites could be used in the synthesis of different Na-Mica-4 with presumably different physicochemical properties.

Bone loss is still a major problem in orthopedics. The purpose of this experimental study is to evaluate the safety and regenerative potential of a new scaffold based on a bio-ceramization process for bone regeneration in long diaphyseal defects in a sheep model. The scaffold was obtained by transformation of wood pieces into porous biomorphic silicon carbide (BioSiC®). The process enabled the maintenance of the original wood microstructure, thus exhibiting hierarchically organized porosity and high mechanical strength. To improve cell adhesion and osseointegration, the external surface of the hollow cylinder was made more bioactive by electrodeposition of a uniform layer of collagen fibers that were mineralized with biomimetic hydroxyapatite, whereas the internal part was filled with a bio-hybrid HA/collagen composite. The final scaffold was then implanted in the metatarsus of 15 crossbred (Merinos-Sarda) adult sheep, divided into 3 groups: scaffold alone, scaffold with platelet-rich plasma (PRP) augmentation, and scaffold with bone marrow stromal cells (BMSCs) added during implantation. Radiological analysis was performed at 4, 8, 12 weeks, and 4 months, when animals were sacrificed for the final radiological, histological, and histomorphometric evaluation. In all tested treatments, these analyses highlighted the presence of newly formed bone at the bone scaffolds' interface. Although a lack of substantial effect of PRP was demonstrated, the scaffold+BMSC augmentation showed the highest value of bone-to-implant contact and new bone growth inside the scaffold. The findings of this study suggest the potential of bio-ceramization processes applied to vegetable hierarchical structures for the production of wood-derived bone scaffolds, and document a suitable augmentation procedure in enhancing bone regeneration, particularly when combined with BMSCs.

A combined imaging and microdiffraction technique using high-energy synchrotron X-rays is described and used to reveal microstructure, damage and strain evolution around notches in SiC/SiC composites. This technique allows for monitoring the material for cracks while loading and mapping the strain distribution in fibers and matrix with a resolution of tens of microns. We show that at current resolutions this technique is capable of measuring the strain distribution near crack tips in ceramic matrix composites and observe load transfer effects.

Microstructural characteristics and amplitude dependences of the Young modulus E and of internal friction (logarithmic decrement δ) of bio-carbon matrices prepared from beech tree wood at different carbonization temperatures T carb ranging from 600 to 1600°C have been studied. The dependences E(T carb) and δ(T carb) thus obtained revealed two linear regions of increase of the Young modulus and of decrease of the decrement with increasing carbonization temperature, namely, ΔE ∼ AΔT carb and Δδ ∼ BΔT carb, with A ≈ 13.4 MPa/K and B ≈ −2.2 × 10−6 K−1 for T carb < 1000°C and A ≈ 2.5 MPa/K and B ≈ −3.0 × 10−7 K−1 for T carb > 1000°C. The transition observed in the behavior of E(T carb) and δ(T carb) at T carb = 900–1000°C can be assigned to a change of sample microstructure, more specifically, a change in the ratio of the fractions of the amorphous matrix and of the nanocrystalline phase. For T carb < 1000°C, the elastic properties are governed primarily by the amorphous matrix, whereas for T carb > 1000°C the nanocrystalline phase plays the dominant part. The structurally induced transition in the behavior of the elastic and microplastic characteristics at a temperature close to 1000°C correlates with the variation of the physical properties, such as electrical conductivity, thermal conductivity, and thermopower, reported in the literature.

Clay-based minerals are considered to be an important component in backfill barriers due to both their ability to seal and adsorb radioactive waste and to interact chemically with it under subcritical conditions. Herein, we describe a systematic study of the properties of layered silicates that could affect their hydrothermal reactivity, namely type of layers, octahedral occupancy, origin and total amount of the layer charge, and nature of the interlayer cation. The silicates studied were selected on the basis of their different characteristics associated with these properties and were treated hydrothermally at 300 °C for 48 h in a 7.3 · 10− 2 M Lu(NO3)3 · 3.6H2O solution. The final products were analyzed by X-ray diffraction and solid-state NMR spectroscopy. All the layered silicates studied were found to be able to generate a Lu2Si2O7 phase after hydrothermal treatment under subcritical conditions, thereby confirming the participation of a chemical mechanism of the clay barrier generating phases being stables with temperature and pH conditions. However, the extent of this reaction depends to a large extent on the physicochemical properties of the framework and the interlayer space composition, such as the presence or absence of an octahedral sheet, the degree of occupancy of this sheet, and the origin and total layer charge. Therefore, this study allows tuning the clay mineral framework characteristic that favors the rare earth cations (as trivalent actinide simulator) immobilization.

ZrSiO₄ and HfSiO₄ are of considerable interest because of their low thermal expansions, thermal conductivities, and the optical properties of HfSiO₄. In addition, silicate phases of both are studied as model radioactive waste disposal materials. Previous first principles calculations reported near ideal mixing in the Zr_1–xHf_xSiO₄ system, with a very weak propensity for phase separation. Density functional theory (DFT)/cluster-expansion first principles calculations presented in this work indicate near ideal mixing with a very weak propensity for ordering. Zr_1–xHf_xSiO₄ samples (x = 0, 0.25, 0.5, 0.75, and 1.0) were synthesized from intimate stoichiometric mixtures of constituent-oxides and annealing at 1823 K for 20 days in a platinum crucible. Samples were characterized by X-ray diffraction (XRD; Rietveld analysis) and ²⁹Si MAS NMR. The XRD data exhibited a pronounced negative deviation from Vegard’s law in the excess volume of mixing, and the ²⁹Si MAS NMR spectra also suggest nonideal mixing. Given the very weak energetics that favor cation ordering, it is clear that there must be some other cause(s) for the observed deviations from ideal mixing behavior.

An understanding of the interaction mechanisms between exchangeable cations and layered silicates is of interest from both a basic and an applied point of view. Among 2:1 phyllosilicates, a new family of swelling high-charge synthetic micas has been shown to be potentially useful as decontaminant. However, the location of the interlayer cations, their acidity and the water structure in the interlayer space of these silicates are still unknown. The aim of this paper was therefore to study the hydration state of the interlayer cations in the interlayer space of high-charge expandable micas and to evaluate the effect that this hydration has on the swelling and acidity behavior of these new materials. To achieve these objectives, three synthetic micas with different charge density total layer charges (ranging between 2 and 4 per unit cell) and with five interlayer cations (Na+, Li+, K+, Mg2+, and Al3+) were synthesized and their hydration state, interlayer space, and acidity analyzed by DTA/TG, XRD, and 1H MAS NMR spectroscopy. The results showed that the hydration state depends on both the layer charge and the nature of the interlayer cation. A high participation of the inner-sphere complexes in the highly charged confined space has been inferred and proposed to induce Brønsted acidity in the solid.

This paper reports on measurement of the heat capacity at constant pressure C p of silicon bio-carbide prepared within the 5–300 K temperature interval from beech tree wood (bio-SiC(BE)), and within 80–300 K, from tree wood of sapele (bio-SiC(SA)), as well as SiC/Si ecoceramics of beech, sapele, and white eucalyptus wood. It has been shown that in bio-SiC(BE) the measured heat capacity contains a significant contribution of surface heat capacity, whose magnitude decreases with increasing temperature. Of the ecoceramics, only SiC/Si(SA) characterized by a high enough porosity has revealed a small contribution to the heat capacity coming from its surface component. The experimental results obtained are discussed.

Trivalent cation-doped barium cerate perovskites are attractive materials for clean-energy applications, in particular solid oxide fuel cells, due to their singular proton conductivity in wet environments. Furthermore, these devices operate at high temperatures, where creep and other deformation processes determine the lifetime and overall performance. In this work, the structural and microstructural characteristics of undoped and ytterbium-doped (1 to 10 at.%) BaCeO ₃ polycrystals produced by solid state reaction have been investigated. A single orthorhombic perovskite phase was found after sintering in air at 1500 °C for 10 h. The microstructure shows a complex evolution with doping: the average grain size firstly decreases with increasing Yb content up to 5 at.%, and then increases with further Yb additions. The high-temperature mechanical properties have been studied in compression between 1100 and 1250 °C in air at constant initial strain rate. The creep strength increases with increasing Yb content. Extended steady states of deformation were attained at lower strain rates and higher temperatures when increasing doping amount.

NiO/8YSZ (8 mol% Y2O3-stabilized cubic ZrO2) and NiO/3YTZP (3 mol% Y2O3-stabilized tetragonal ZrO2) composites with different NiO contents have been fabricated by a conventional route of mechanical mixing of NiO and zirconia powders and sintering at 1500 °C for 10 h in air. The resulting microstructures have been characterized by electron microscopy. The composites show a duplex microstructure formed by equiaxed grains of NiO and ZrO2, without any intermediate phase. Compressive mechanical tests at constant strain rate were carried out at temperatures between 1150 and 1350 °C under different environments: air, inert (Ar) and reducing (5% H2/95% Ar) atmospheres. The overall creep behavior of the composites is essentially controlled by the zirconia matrix, due to the softness of the NiO phase in the experimental conditions used in this study. The creep strength is not affected by oxygen partial pressure. However, a large decrease in creep resistance under reducing conditions was observed in samples submitted to in situ redox cycling.

Samples of β-SiC/Si ecoceramics with a silicon concentration of ∼21 vol % have been prepared using a series of consecutive procedures (carbonization of sapele wood biocarbon, synthesis of high-porosity biocarbon with channel-type pores, infiltration of molten silicon into empty channels of the biocarbon, formation of β-SiC, and retention of residual silicon in channels of β-SiC). The electrical resistivity ρ and thermal conductivity κ of the β-SiC/Si ecoceramic samples have been measured in the temperature range 5–300 K. The values of ρ Si chan(T) and κ Si chan(T) have been determined for silicon Sichan located in β-SiC channels of the synthesized β-SiC/Si ecoceramics. Based on the performed analysis of the obtained results, the concentration of charge carriers (holes) in Sichan has been estimated as p ∼ 1019 cm−3. The factors that can be responsible for such a high value of p have been discussed. The prospects for practical application of β-SiC/Si ecoceramics have been considered.

NiO/3YTZP (3 mol% Y2O3-stabilized tetragonal ZrO2) composites with 40 mol% NiO (26 vol% NiO) have been fabricated by mechanical mixing of NiO and 3YTZP powders and sintering at 1500 °C for 10 h in air. The resulting microstructures have been characterized by electron microscopy. Compressive mechanical tests at constant strain rate were conducted on these materials at temperatures between 1150 and 1350 °C in air. The σ–ɛ curves display extended secondary creep regimes without signals of macroscopic failure. The composite creep behavior is characterized by a stress exponent n = 2 and an activation energy for flow Q = 490 kJ/mol. The overall creep behavior of the composites is essentially controlled by the zirconia matrix, due to the softness of the NiO phase in the experimental conditions used in this study.

Porous biomorphic silicon carbide (bioSiC) is a structurally realistic, high-strength, and biocompatible material which is promising for application in load-bearing implants. The deposition of an osteoconductive coating is essential for further improvement of its integration with the surrounding tissue. A new strategy towards biomimetic calcium phosphate coatings on bioSiC is described. X-ray photoelectron spectroscopy (XPS) analysis shows that using 10-undecenoic acid methyl ester a covalently bound monolayer can be synthesized on the surface of the bioSiC. After hydrolysis it exposes carboxylic acid groups that promote the selective nucleation and growth of a very well-defined crystalline layer of calcium phosphate. The resulting calcium phosphate coating is characterized by X-ray diffraction and electron microscopy techniques. Further, ion beam imaging is employed to quantify the mineral deposition meanwhile, three-dimensional dual-beam imaging (FIB/SEM) is used to visualize the bioSiC/mineral interface. The monolayer is show to actively induce the nucleation of a well-defined and highly crystalline mixed octacalcium phosphate/hydroxyapatite (OCP/HAP) coating on implantable bioSiC substrates with complex geometry. The mild biomimetic procedure, in principle, allows for the inclusion of bioactive compounds that aid in tissue regeneration. Moreover, the mixed OCP/HAP phase will have a higher solubility compared to HAP, which, in combination with its porous structure, is expected to render the coating more reabsorbable than standard HAP coatings.

A family of organomicas was synthesized using synthetic swelling micas with high layer charge (NanSi8-nAlnMg6F4O20 center dot XH2O, where n = 2, 3, and 4) exchanged with dodecylammonium and octadecylammonium cations. The molecular arrangement of the surfactant was elucidated on the basis on XRD patterns and DTA. The ordering conformation of the surfactant molecules into the interlayer space of micas was investigated by C-13, Al-27, and Si-29 MAS NMR The arrangement of alkylammonium ions in these high-charge synthetic micas depends on the combined effects of the layer charge of the mica and the chain length of the cation. In the organomicas with dodecylammonium, a transition from a parallel layer to a bilayer-paraffin arrangement is observed when the layer charge of the mica increases. However, when octadecylammonium is the interlayer cation, the molecular arrangement of the surfactant was found to follow the bilayer-paraffin model for all values of layer charge. The amount of ordered conformation all-trans is directly proportional of layer charge.

The effect of the addition of materials on the leaching pattern of As and metals (Cu, Zn, Ni, Pb, and Cd) in two contaminated soils was investigated. The examined materials included bentonites, silicates and industrial wastes, such as sugar foam, fly ashes and a material originated from the zeolitization of fly ash. Soil + material mixtures were prepared at 10% doses. Changes in the acid neutralization capacity, crystalline phases and contaminant leaching over a wide range of pHs were examined by using pHstat leaching tests. Sugar foam, the zeolitic material and MX-80 bentonite produced the greatest decrease in the leaching of pollutants due to an increase in the pH and/or the sorption capacity in the resulting mixture. This finding suggests that soil remediation may be a feasible option for the reuse of non-hazardous wastes.

Self-assembled monolayers of n-octadecylamine on mica (ODA/mica SAMs) have been investigated by atomic force microscopy (AFM) and by attenuated total reflectance infrared (ATR-FTIR) and X-ray photoelectron (XPS) spectroscopies. Topographic data characterizes a stable configuration with the alkyl skeleton tilted approximate to 46 degrees from the surface normal that is rationalized according to a well established structural alkyl chain packing model. Extended contact with air increases molecular tilting up to approximate to 58 degrees. ATR-FTIR and XPS reveal the presence of protonated amino groups within the monolayer and its increment upon exposure to air. The transition between both tilted states is explained assuming the protonation reaction as the driving force and introducing a model to evaluate an electrostatic repulsions term in the overall cohesive energy balance of the system. ODA molecules in the self-assembled monolayer respond to their spontaneous protonation by atmospheric water by tilting as a mechanism to relax the repulsions between -NH3+ heads.

The mixing of molecules adsorbed from solution to different interfaces has both industrial and academic relevance and the mixing behaviour at the interface is a key to understanding for example, that the surface tension of a mixture of two surfactants is lower than either of the two pure materials and many other effects. In this paper, we report, for the first time, the application of Solid State NMR to the study of alkane/alcohol mixtures, in a range of relative size ratio between 0 and 0.35, adsorbed onto graphite at high, multilayer coverage. Moreover, this paper evaluated, for the first time, the utility of the combined used of ¹H and ²H NMR for: (i) determining the surface composition and (ii) making a theoretical approach to the sorption isotherm. A variety of preferential adsorption behaviour is reported. Preferential adsorption of the longer molecule (decane vs. heptanol) from a mixture has been observed. However, if both components are of similar length, the alcohol is preferentially adsorbed (heptanol vs. octane and octanol vs. octane). Finally, a linear relation between the relative size ratio and the amount of alcohol at monolayer coverage is observed.

Under pressure and temperature conditions like those found in deep geological repositories (DGRs), rare-earth cations may react with silicates to form rare-earth disilicates. This study establishes the stability range of yttrium disilicates in response to changes in pH. The α, β, γ, and δ polymorphs of Y₂Si₂O₇ were synthesized by the sol-gel process at temperatures between 1100 and 1650 °C and subjected to pH_stat leaching tests. By measuring the Y and Si leaching rates and monitoring the transformation of the crystalline and amorphous phases, we showed that yttrium disilicates were stable at pH > 5. At pH < 5, the pH stability sequence was consistent with the temperature-dependent stabilities of Y₂Si₂O₇ phases, with the δ polymorph showing the lowest leaching rates. Because rare-earth compounds can be used as a proxy for analogous actinide hosts, the results of this study can be used to predict the performance of engineered barriers in DGR.

Na-4-mica, a highly charged fluorophlogopite, has recently attracted much attention because of its unique combination of high charge (four charges per unit cell) and its swelling and cation-exchange properties. The ability to improve the properties of this mica depends on gaining knowledge about its phase evolution during the calcination process. For the synthesis, the stoichiometric powder mixture (4SiO ₂/2Al ₂O ₃/6MgF ₂/8NaCl) was heated to 900 °C for 0-600 h. The obtained solids were characterized by X-ray fluorescence (XRF); X-ray diffraction (XRD); scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) analysis; ²⁹Si, ²⁷Al, and ²³Na magic-angle-spinning MAS NMR spectroscopy; and thermogravimetric/differential thermal analysis (TG/DTA). The results showed that the precursors are rapidly (t < 3 h) transformed into sodalite, Al ₆Na ₈(SiO ₄) ₆Cl ₂, and a 2:1 phyllosilicate. For t = 7.5 h, the amount of 2:1 phyllosilicate increased as a result of the decomposition of sodalite, with a progressive incorporation of aluminum in the 2:1 phyllosilicate being observed. For t = 7.5 h, synthesis of Na-4-mica was considered to be complete, as the material remained essentially unaltered for the next 15 h. For t = 30 h, the mica started to decompose, and for very long reaction times (t ≥ 300 h), only forsterite and a carnegierite phase were present.

Although the structures of pure Sc2Si2O7 and &#914;-Y2Si 2O7 have been described in the literature using the C2/m space group, 29Si magic angle spinning (MAS) NMR measurements of the intermediate members of the Sc2Si2O7-&#914;- Y2Si2O7 system indicate a lowering of the symmetry to the C2 space group. Indeed, these compositions exhibit a unique Si crystallographic site and an Si-O-Si angle lower than 180°, incompatible with the C2/m space group. C2 is the only possible alternative. Space group Cm can be discarded with regard to its two different Si sites per unit cell. Moreover, 89Y MAS NMR data have revealed the existence of two different Y sites in the structure of the intermediate members of the Sc 2Si2O7-&#914;-Y2Si2O 7 system, confirming the lowering of the symmetry to the C2 space group. The viability of the C2 model has therefore been tested and confirmed by refinement of synchrotron and neutron powder diffraction data for the different members of the system. The structural evolutions across the Sc 2Si2O7-&#914;-Y2Si2O 7 system are discussed.

The high-temperature mechanical properties of the mixed ionic-electronic conductor perovskite BaCe_0.95Y_0.05O_3−δ with average grain size of 0.40 μm have been studied in compression between 1100 and 1300 °C in air at different initial strain rates. The true stress–true strain curves display an initial stress drop, followed by an extended steady-state stage. As the temperature decreases and/or the strain rate increases, there is a transition to a damage-tolerant strain-softening stage and eventually to catastrophic failure. Analysis of mechanical and microstructural data revealed that grain boundary sliding is the primary deformation mechanism. The strength drop has been correlated with the growth of ultrafine grains during deformation, already present at grain boundaries and triple grain junctions in the as-fabricated material.

Biomorphic SiC (bioSiC) is a low cost SiC/Si composite obtained by melt infiltration of carbon preforms obtained from the pyrolysis of cellulose precursors. The porosity and pore size distribution of bioSiC can be tailored for specific applications by adequate selection of the wood precursor. Natural and artificial industrial woods were explored as possible bioSiC precursors. Silicon was removed by chemical etching. Relevant microstructural parameters such as pore size distribution, total porosity, and permeability were characterized. Since the filtration process involves large pressure gradients along the material at high temperatures, mechanical properties of porous bioSiC from the different precursors were evaluated at room temperature and 800 °C. The feasibility of porous bioSiC as a filtration material for high temperature gasification processes is discussed in terms of these properties. MDF-bioSiC is shown to be a promising material for such applications because of its good mechanical properties, interconnected porosity, pore sizes, and permeability.

A study has been made of the dependences of the electrical resistivity and the Hall coefficient on the temperature in the range 1.8–1300 K and on magnetic fields of up to 28 kOe for the biomorphic SiC/Si (MDF-SiC/Si) composite and biomorphic porous SiC (MDF-SiC) based upon artificial cellulosic precursor (MDF – medium density fiberboards). It has been shown that electric transport in MDF-SiC is effected by carriers of n-type with a high concentration of ∼10²⁰ cm⁻³ and a low mobility of ∼0.4 cm² V⁻¹ s⁻¹. The specific features in the conductivity of MDF-SiC are explained by quantum effects arising in disordered systems and requiring quantum corrections to conductivity. The TEM studies confirmed the presence of disordering structural features (nanocrystalline regions) in MDF-SiC. The conductivity of MDF-SiC/Si composite originates primarily from Si component in the temperature range 1.8–500 K and since ∼500 to 600 K the contribution of MDF-SiC matrix becomes dominant.

Bentonite is accepted as the best clay material in the engineered barrier of deep geological repositories (DGRs) for radioactive waste disposal. In recent years, the interactions between a wide range of rare-earth (REE) cations and smectites have been studied. A combined study of stable europium and radioactive isotopes is reported here. Saponite was subjected to hydrothermal reactions with stable and radioactive (152Eu) europium ions under subcritical conditions. The structural changes of saponite were evaluated by XRD and SEM. The effect of temperature and reaction time on the changes was quantified by measuring 152Eu through gamma spectrometry. The reaction between europium and saponite was a first-order reaction. The presence of Eu in the precipitate in an amount much higher than the cation exchange capacity of saponite confirmed participation of chemical reactions or surface adsorption in the europium immobilization, even at temperatures as low as 150 °C. The reaction rate constant indicated that an 8- to 9-month period was needed for the completion, without significant changes, of the europium/saponite chemical reaction under the subcritical conditions of 200 °C and 350 °C.

Modifications caused in commercial dense regenerated cellulose (RC) flat membranes by low-dose &#947;-irradiation (average photons energy of 1.23 MeV) are studied. Slight structural, chemical and morphological surface changes due to irradiation in three films with different RC content were determined by ATR-FTIR, XRD, XPS and AFM. Also, the alteration of their mechanical elasticity has been studied. Modification of membrane performance was determined from solute diffusion coefficient and effective membrane fixed charge concentration obtained from NaCl diffusion measurements. Induced structural changes defining new and effective fracture propagation directions are considered to be responsible for the increase of fragility of irradiated RC membranes. The same structural changes are proposed to explain the reduction of the membrane ion permeability through a mechanism involving either ion pathways elongation and/or blocking.

Crystalline monolayers of three aldehydes with an odd number of carbon atoms in the alkyl chain (C₇, C₉ and C₁₁) at low coverages are observed by a combination of X-ray and neutron diffraction. Analysis of the diffraction data is discussed and possible monolayer crystal structures are proposed; although unique structures could not be ascertained for all molecules. We conclude that the structures are flat on the surface, with the molecules lying in the plane of the layer. The C₁₁ homologue is determined to have a plane group of either p2, pgb or pgg, and for the C₇ homologue the p2 plane group is preferred.

Alumina nanoparticles 10-20 nm in diameter were nucleated on alumina particles, 150 nm average diameter, by a colloidal route followed by calcination. It is shown that after sintering, the final grain size is up to 20% smaller due to the addition of the alumina nanoparticles. Electron backscattered diffraction analysis shows that whereas a correlation in the relative crystalline orientations between neighbouring grains exists in the pure materials, the addition of alumina nanoparticles results in a random crystalline orientation.

Aleuritic (9,10,16-trihydroxypalmitic) acid self-assembly on mica from solution has been studied using AFM, ATR-FTIR and MD simulations. The goal of this study is to define the role of hydroxyl groups in the interaction between molecules as reference data to understand the mechanism of formation of synthetic and natural biopolyesters from polyhydroxylated long chain carboxylic acids. In a confined structure, such as the one imposed by a vertically self-assembled layer on mica, aleuritic acid has a tendency to adopt a monolayer configuration ruled by the lateral interactions between molecules via the two secondary hydroxyl groups. This (2D) growth competes with the multilayer formation (3D), which is conditioned by the terminal primary hydroxyl group. As the self-assembly spatial constraint is relaxed, MD has shown that the structure tends to become an amorphous and crosslinked phase that can be characterized by topographic and friction force AFM data.

The aims of the present study is to describe for the first time the Sc-45 MAS NMR spectra of X-2-Sc2SiO5 and C-Sc2Si2O7, to combine the spectroscopic information with the structures published from diffraction data, and to propose a rational interpretation of the chemical shifts and quadrupolar parameters. For that purposed, we have correlated the experimental quadrupole coupling parameters of Sc-45 determined for a number of scandium compounds to those found by a simple electrostatic calculation and we have found that the isotropic chemical shift of the Sc-45 is linearly correlated to the shift parameter, calculated by bond-valence theory. We also show that a simple point charge calculation can approximate the electric field gradient to a sufficiently good approximation that it provides a valuable mean to assign the NMR spectra.

The issue of how to improve product quality and product yield in a short period of time is becoming more critical in many industries. Thus, shorter delay times between laboratory analysis and process correction are important in process control. Elimination of sample handling and operator Manipulation is desirable. The present article proposes micro-X-ray fluorescence (mu XRF) as an economical control method for industrial product quality with a minimum time cost. Samples from different industrial processes have been chosen and analyzed by XRF and mu XRF, The results show that the two techniques give similar results and that mu XRF allows the waste to be classified and is able to detect problems in the production process.

Kalsilite (the low-temperature form of KAlSiO4) is used as the precursor of leucite, an important component in porcelain-fused-to-metal and ceramic-restoration systems, and it has also been proposed as a high-thermal expansion ceramic for bonding to metals. The present study reports the hydrothermal synthesis and characterization of pure kalsilite from kaolinite in subcritical conditions, as well as the characterization of the intermediate products by means of XRD, 29Si and 27Al MAS NMR, IR, SEM, and TEM. Effects of time, temperature, and pH on the reaction products are analyzed. The experimental data indicate that pure kalsilite is obtained after hydrothermal treatment of kaolinite at 300 °C for 12 h in 0.5 M KOH solution. Longer reaction times increase the crystallinity of the structure, whereas lower reaction times give rise to the metastable ABW-type KAlSiO4 polymorph. Lower temperatures are not sufficient to produce kalsilite, but zeolite W is obtained instead as the unique reaction product. Finally, the pH of the aqueous solution in contact with kaolinite is an important parameter for the synthesis of kalsilite, which must be ≥13.70.

This study reports a simple method to synthesize pure kalsilite (KAlSiO4) using readily available precursors, kaolinite and KOH solution, after only 12 h of hydrothermal treatment in mild conditions. A structural refinement has been carried out using the Rietveld method to obtain unit cell parameters, and the 29Si and 27Al magic angle spinning nuclear magnetic resonance spectra have shown the purity and complete Si/Al ordering of the kalsilite structure obtained. Finally, the morphology of the particles has been analyzed by scanning electron microscopy.

Mineralogical changes in a set of phyllosilicates, differing in their layer nature, chemical composition, octahedral character, and Al content of the tetrahedral sheet, were analyzed after hydrothermal reaction in an alkaline solution. The composition of the alkaline solution was selected to simulate the first stage of cement degradation [NaOH-KOH-Ca(OH)2]. The reaction products have been analyzed by XRD, 29Si and 27Al MAS NMR spectroscopy, SEM/EDX, and TEM. The results indicate that the main factor influencing the stability of the clays is the occupation of the octahedral sheet such that all trioctahedral members withstand the alkaline attack, whereas most of the dioctahedral clays suffer a complete dissolution and crystallization of new phases. Second, clays with Al in the tetrahedral sheet of their layers are shown to be less stable than those with a pure Si tetrahedral sheet.

9(10),16-Dihydroxypalmitic acid (diHPA) is a particularly interesting polyhydroxylated fatty acid (1) because it is the main monomer of cutin, the most abundant biopolyester in nature, and (2) because the presence of a terminal and a secondary hydroxyl group in midchain positions provides an excellent model to study their intermolecular interactions in a confined phase such as self-assembled layers. In this study we have combined atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy, as well as molecular dynamics (MD) simulations to conclude that the self-assembling of diHPA molecules on mica is a layer by layer process following a Brunauer−Emmett−Teller (BET) type isotherm and with the first layer growing much faster than the rest. Interactions between secondary hydroxyls reinforce the cohesive energy of the monolayer, while the presence of the terminal hydroxyl group is necessary to trigger the multilayered growth. Besides, XPS and ATR-FT-IR spectroscopies clearly indicate that spontaneous self-esterification occurs upon self-assembling. The esterification reaction is a prerequisite to propose a self-assembly route for the biosynthesis of cutin in nature. Molecular dynamics simulations have shown that internal molecular reorganization within the self-assembled layers provides the appropriate intermolecular orientation to facilitate the nucleophilic attack and the release of a water molecule required by the esterification reaction.

Compounds containing rare earths are of increasing technological interest especially because of their unique mechanical, magnetic, electrical, and optical properties. Among them, rare earth oxyorthosilicates are attractive scintillators for γ- and X-ray spectroscopy and detection. However, there are many structural aspects of those compounds that are not clear. In this research, the structure parameters for Sc2Si2O5, X2-polymorph, have been refined from powder X-ray diffraction (XRD) data and the 29Si MAS NMR spectrum is reported for the first time. X2-Sc2SiO5 polymorph was synthesized by the sol–gel method and characterized by XRD and 29Si MAS NMR. The XRD pattern was indexed in a monoclinic unit cell with space group I2/c; the resulting unit cell parameters were a=9.9674(2) Å, b=6.4264(9) Å, c=12.0636(2) Å, and β=103.938(1)°. The 29Si MAS NMR spectrum showed a unique signal at −79.5 ppm, compatible with the unique Si crystallographic site in the unit cell. Finally, the band valence method has been applied to the calculation of a “shift parameter,” which is correlated with the NMR chemical shift.

Mixing behaviour of solid crystalline monolayers adsorbed onto graphite from different mixtures of undecanoic and dodecanoic acids at submonolayer coverage has been investigated. X-ray diffraction measurements have been collected from a variety of compositions as a function of temperature. An extensive phase separation is found for all the compositions – the scattering patterns characteristic of the pure material crystalline structures being preserved across the entire composition range. The temperature dependence of the monolayer melting points and their depression is also clearly indicative of separation of the two surface components, in clear contrast to that expected if the two carboxylic acids mixed ideally in the monolayer.

Directionally solidified Al2O3-based eutectics are in situ composites grown from the melt. The directional nature of the solidification process makes these materials highly anisotropic and therefore the measurement and quantification of their crystallographic texture is necessary to understand their physical properties. We studied the texture of Al2O3-ZrO2 (12 mol% Y2O3) eutectic rods by means of X-ray and electron backscattering diffraction. The phases grow according to the relationship (10 (1) over bar2}(Al2O3) //{110}(ZrO2) and Al2O3 is oriented with its c-axis approximately parallel to the growth direction. We observed that the c-axis orientation is not constant throughout the sample, but instead changes according to the distance from the growth axis. The c-axis orientation spread was found to be 10 degrees. This spread is a consequence of the curvature of the liquid-solid interface during solidification, whose shape we reconstructed using EBSD data.

Porous NaMgF3 ceramics have been fabricated by leaching a NaF-NaMgF3 eutectic in distilled water, producing NaMgF3 with 53% of connected porosity. The eutectic was fabricated using the Bridgman technique at growth rates of 8, 10 and 15 mm/h. The microstructure and composition of the resulting material has been studied by means of X-ray diffraction and SEM. Compression mechanical tests have been performed at different temperatures up to 750 degrees C, both in constant strain rate and constant stress loading. The microstructure consists of plate-like grains with cylindrical pores in approximately hexagonal packing. Pores are perpendicular in adjacent grains. The compressive strength is found to be rather independent of growth rate, in the range studied. Small differences can be explained using a minimum solid area (MSA) model and differences in the microstructure. In creep experiments, no steady-state regime was observed. Instead, the strain exhibited a series of accelerations that could be associated with damage propagation. 

C-M2Si2O7 (M = RE and In) and crystals of composition X2T2O7 (T = P, As, Ge) with ionic radius of X less than 0.97 angstrom (X = Ni, Cd, Mg, Zn, Cu, Ca) are isostructural with the natural-occurring mineral thortveitite. In those compounds, the T-O bridging distance values vary considerably and there is no explanation to this fact in the literature. This paper will bring their structural characteristics out by the bond-valence model. It has been concluded that T-O bridging distance and mean T-O distance are linearly correlated to the total atomic valence of the bridging oxygen and the T atom (T = Si, P, As, Ge), respectively, and they are a function of the principal quantum number (n) in the valence shell of the atom T. Finally, we have applied successfully the model for the prediction of Ge-O distances of (In,A)(2)Ge2O7 (A = Fe,Y,Gd) compounds.