A SEM-EDX Study on the Structure of Phenyl Phosphinic Hybrids Containing Boron and Zirconium.

The SEM-EDX method was used to investigate the structure and morphology of organic-inorganic hybrids containing zirconium, boron and phosphorus compounds, synthesized by the sol-gel method. We started by using, for the first time together, zirconyl chloride hexa-hydrate (ZrOCl2·6H2O), phenyl phosphinic acid and triethyl borate as precursors and reagents, at different molar ratios. The obtained hybrids showed a very high thermal stability and are not soluble in water or in organic solvents. As a consequence, such hybrid solid materials are suitable for applications at high temperatures. The obtained hybrids have complex 3D structures and form organic-inorganic networks containing Zr-O-Zr, Zr-O-P and Zr-O-B bridges. Such organic-inorganic networks are also expected to form supramolecular structures and to have many potential applications in different fields of great interest such as catalysis, medicine, agriculture, energy storage, fuel cells, sensors, electrochemical devices and supramolecular chemistry.

The Influence of Hydrofluoric Acid Temperature and Application Technique on Ceramic Surface Texture and Shear Bond Strength of an Adhesive Cement.

All-ceramic restorations are the foundation of modern esthetic dentistry. Clinical approaches for preparation, durability, aesthetics, and repair have been reformed by the idea of adhesive dentistry. The aim of the study and the objective question was to evaluate the impact of heated hydrofluoric acid pretreatment and the application technique's influence on the surface morphology and roughness of leucite-reinforced glass-ceramic materials (IPS Empress CAD, Ivoclar Vivadent), which is fundamental for understanding the adhesive cementation process. Scanning electron microscopy was used to observe the effectiveness of the two HF (Yellow Porcelain Etch, Cerkamed) application techniques and the HF's temperature impact on the surface topography of the ceramic. Based on surface conditioning methods, the adhesive cement (Panavia V5, Kuraray Noritake Dental Inc., Tokyo, Japan) was applied to the conditioned ceramic samples and light-cured. Shear bond strength values were correlated with the micro-retentive surface texture of the ceramic. With universal testing equipment at a 0.5 mm/min crosshead speed, SBS values between the resin cement and the ceramic material were assessed until failure. Analyzing the fractured surfaces of the specimens by digital microscopy, the failure modes were divided into three categories: adhesive, cohesive, and mixed failure. Analysis of variance (ANOVA) was used to statistically analyze the collected data. The results show that alternative treatment methods affected the material's surface characteristics and have an influence on the shear bond strength.

Corrosion Behavior of Coated Low Carbon Steel in a Simulated PEMFC Environment.

Here, potential metallic bipolar plate (BP) materials were manufactured by laser coating NiCr-based alloys with different Ti additions on low carbon steel substrates. The titanium content within the coating varied between 1.5 and 12.5 wt%. Our present study focussed on electrochemically testing the laser cladded samples in a milder solution. The electrolyte used for all of the electrochemical tests consisted of a 0.1 M Na2SO4 solution (acidulated with H2SO4 at pH = 5) with the addition of 0.1 ppm F-. The corrosion resistance properties of the laser-cladded samples was evaluated using an electrochemical protocol, which consisted of the open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) measurements, and potentiodynamic polarization, followed by potentiostatic polarization under simulated proton exchange membrane fuel cell (PEMFC) anodic and cathodic environments for 6 h each. After the samples were subjected to potentiostatic polarization, the EIS measurements and potentiodynamic polarization were repeated. The microstructure and chemical composition of the laser cladded samples were investigated by scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDX) analysis.

Functional Surfaces via Laser Processing in Nickel Acetate Solution.

This study presents a novel laser processing technique in a liquid media to enhance the surface mechanical properties of a material, by thermal impact and micro-alloying at the subsurface level. An aqueous solution of nickel acetate (15% wt.) was used as liquid media for laser processing of C45E steel. A pulsed laser TRUMPH Truepulse 556 coupled to a PRECITEC 200 mm focal length optical system, manipulated by a robotic arm, was employed for the under-liquid micro-processing. The study's novelty lies in the diffusion of nickel in the C45E steel samples, resulting from the addition of nickel acetate to the liquid media. Micro-alloying and phase transformation were achieved up to a 30 µm depth from the surface. The laser micro-processed surface morphology was analysed using optical and scanning electron microscopy. Energy dispersive spectroscopy and X-ray diffraction were used to determine the chemical composition and structural development, respectively. The microstructure refinement was observed, along with the development of nickel-rich compounds at the subsurface level, contributing to an improvement of the micro and nanoscale hardness and elastic modulus (230 GPa). The laser-treated surface exhibited an enhancement of microhardness from 250 to 660 HV0.03 and an improvement of more than 50% in corrosion rate.

Microstructure and Mechanical Characteristics of Ti-Ta Alloys before and after NaOH Treatment and Their Behavior in Simulated Body Fluid.

In the present study, the microstructure and mechanical properties of Ti-xTa (x = 5%, 15%, and 25% wt. Ta) alloys produced by using an induced furnace by the cold crucible levitation fusion technique were investigated and compared. The microstructure was examined by scanning electron microscopy and X-ray diffraction. The alloys present a microstructure characterized by the α' lamellar structure in a matrix of the transformed ß phase. From the bulk materials, the samples for the tensile tests were prepared and based on the results and the elastic modulus was calculated by deducting the lowest values for the Ti-25Ta alloy. Moreover, a surface alkali treatment functionalization was performed using 10 M NaOH. The microstructure of the new developed films on the surface of the Ti-xTa alloys was investigated by scanning electron microscopy and the chemical analysis revealed the formation of sodium titanate and sodium tantanate along with titanium and tantalum oxides. Using low loads, the Vickers hardness test revealed increased hardness values for the alkali-treated samples. After exposure to simulated body fluid, phosphorus and calcium were identified on the surface of the new developed film, indicating the development of apatite. The corrosion resistance was evaluated by open cell potential measurements in simulated body fluid before and after NaOH treatment. The tests were performed at 22 °C as well as at 40 °C, simulating fever. The results show that the Ta content has a detrimental effect on the investigated alloys' microstructure, hardness, elastic modulus, and corrosion behavior.

Enhancement of the Catalytic Performance and Operational Stability of Sol-Gel-Entrapped Cellulase by Tailoring the Matrix Structure and Properties.

Commercial cellulase Cellic CTec2 was immobilized by the entrapment technique in sol-gel matrices, and sol-gel entrapment with deposition onto magnetic nanoparticles, using binary or ternary systems of silane precursors with alkyl- or aryl-trimethoxysilanes, at different molar ratios. Appropriate tailoring of the sol-gel matrix allowed for the enhancement of the catalytic efficiency of the cellulase biocatalyst, which was then evaluated in the hydrolysis reaction of Avicel microcrystalline cellulose. A correlation between the catalytic activity with the properties of the sol-gel matrix of the nanobiocatalysts was observed using several characterization methods: scanning electron microscopy (SEM), fluorescence microscopy (FM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA/DTA). The homogeneous distribution of the enzymes in the sol-gel matrix and the mass loss profile as a function of temperature were highlighted. The influence of temperature and pH of the reaction medium on the catalytic performance of the nanobiocatalysts as well as the operational stability under optimized reaction conditions were also investigated; the immobilized biocatalysts proved their superiority in comparison to the native cellulase. The magnetic cellulase biocatalyst with the highest efficiency was reused in seven successive batch hydrolysis cycles of microcrystalline cellulose with remanent activity values that were over 40%, thus we obtained promising results for scaling-up the process.

The Influence of Boron on the Structure and Properties of Hybrid Compounds Containing Zirconium and Phosphorus.

In the present work, novel organic-inorganic hybrid materials containing boron, zirconium, and phosphorus were synthesized at different molar ratios, using the sol-gel method, starting from zirconyl chloride hexa-hydrate, triethyl borate, and phenyl phosphonic acid as the precursors. The sol-gel process is used for the first time in the present work in order to obtain organic-inorganic hybrids (or the so-called inorganic polymers) containing together boron, zirconium, and phosphorus. The sol-gel syntheses were performed at room temperature in ethanol. Zirconium containing compounds are already well known for their applications in medicine in restorative or prosthetic devices, including dental implants, knee and hip replacements, middle-ear ossicular chain reconstruction, and so on. Zirconium is a strong transition metal, which started to replace hafnium and titanium in the last decade in important applications. On the other hand, boron has the capability (similar to carbon) to form stable covalently bonded molecular networks. In addition to this capability, boron also offers mixed metallic and nonmetallic properties, because of its place on the periodic table, at the border between metals and nonmetals. Boron is responsible for the higher thermal stability of synthesized hybrid compounds. In the structure of those hybrid compounds, zirconium, boron, and phosphorus atoms are always connected via an oxygen atom, by P-O-Zr, Zr-O-Zr, or Zr-O-B bridges.

Hybrid Coordination Networks for Removal of Pollutants from Wastewater.

The adsorption properties of two coordination polymers, resulting from the reaction of divalent metal (Ca2+ or Co2+) salts with (2-carboxyethyl)(phenyl)phosphinic acid, are presented in this paper. The structural and textural characterization before and after adsorption experiments is presented. The adsorbent materials were prepared using the hydrothermal procedure. The compound Ca[O2P(CH2CH2COOH)(C6H5)]2 (CaCEPPA) has a layered topology, with the phenyl groups oriented into the interlayer space and crystallizes in the monoclinic system. Compound Co2[(O2P(CH2CH2COO)(C6H5)(H2O)]2·2H2O (CoCEPPA) has a 1D structure composed of zig-zag chains. The adsorption performances of CaCEPPA and CoCEPPA materials were tested in the removal of cadmium and lead from aqueous solutions. The optimum pH of ions adsorption was found to be five for both adsorbent materials. Pseudo-first and second-order kinetic models were used for fitting kinetic experimental data, and Langmuir and Freundlich isotherms were used for modeling the equilibrium experimental data. The pseudo-second-order kinetic model and Langmuir isotherm best described the adsorption of Cd and Pb ions onto the studied materials, judging from the results of the error function (correlation coefficient, sum of square error, chi-square test, and average relative error) analysis. The studied materials present a higher affinity for Cd ions compared with the adsorption capacity developed for the removal of Pb ions from aqueous solutions. CoCEPPA showed the highest adsorption performance in the removal process of metal ions from aqueous solutions compared with CaCEPPA (qm = 54.9 mg Cd2+/g of CoCEPPA, qm = 36.5 mg Cd2+/g of CaCEPPA).

Electrochemical Evaluation of Protective Coatings with Ti Additions on Mild Steel Substrate with Potential Application for PEM Fuel Cells.

In this work, the corrosion behavior of NiCr(Ti) protective coatings deposited on mild steel substrates through laser cladding technology is studied as an alternative new material for metallic bipolar plates used in PEMFC applications. For electrochemical testing, a solution consisting of 0.5 M H2SO4 + 2 ppm F- at room temperature is used as an electrolyte. The fluoride ions are added to simulate the conditions in the PEM fuel cell due to degradation of the proton exchange membrane and fluoride release. A saturated calomel electrode (SCE) is used as a reference electrode and a platinum mesh as the counter electrode. Scanning electron microscopy (SEM) and optical microscopy (OM) are used for studying the morphology of the protective coatings and the effect of Ti addition. The electrochemical evaluation consisted of measuring the open circuit potential (OCP), followed by electrochemical impedance spectroscopy measurements (EIS) and potentiodynamic polarization. It is found that the coatings with 5% Ti, 7% Ti and 10% Ti addition comply with the conditions of the US DOE regarding corrosion performance to be used as materials for the manufacture of the bipolar plates.

Development of a Tailored Sol-Gel Immobilized Biocatalyst for Sustainable Synthesis of the Food Aroma Ester n-Amyl Caproate in Continuous Solventless System.

This study reports the synthesis of a hybrid sol-gel material, based on organically modified silanes (ORMOSILs) with epoxy functional groups, and its application in the stabilization of lipase type B from Candida antarctica (CalB) through sol-gel entrapment. The key immobilization parameters in the sol-gel entrapment of lipase using epoxysilanes were optimized by the design of numerous experiments, demonstrating that glycidoxypropyl-trimethoxysilane can allow the formation of a matrix with excellent properties in view of the biocatalytic esterifications catalyzed by this lipase, at an enzyme loading of 25 g/mol of silane. The characterization of the immobilized biocatalyst and the correlation of its catalytic efficiency with the morphological and physicochemical properties of the sol-gel matrix was accomplished through scanning electron microscopy (SEM), fluorescence microscopy (FM), as well as thermogravimetric and differential thermal analysis (TGA/DTA). The operational and thermal stability of lipase were increased as a result of immobilization, with the entrapped lipase retaining 99% activity after 10 successive reaction cycles in the batch solventless synthesis of n-amyl caproate. A possible correlation of optimal productivity and yield was attempted for this immobilized lipase via the continuous flow synthesis of n-amyl caproate in a solventless system. The robustness and excellent biocatalytic efficiency of the optimized biocatalyst provide a promising solution for the synthesis of food-grade flavor esters, even at larger scales.

Mechanical Properties and Corrosion Behavior of Thermally Treated Ti-6Al-7Nb Dental Alloy.

Ti and its alloys have the most satisfactory properties for biomedical applications due to their specific strength, high corrosion resistance, and high biocompatibility. Ti-6Al-7Nb has been approved for clinical use, proving to be a viable replacement for the Ti-6Al-4V alloy that has been used for many decades in medical applications. In our study, the Ti-6Al-7Nb alloy underwent heat treatment, was cooled in various cooling media such as mineral oil and water, and was then quenched in the oven. The microstructure was investigated, and the mechanical characterization was carried out by Vickers microhardness test. Young's modulus measurements and tensile tests were performed in order to study the effect of cooling media on the material. To study the corrosion behavior, in vitro studies were performed on the Ti-6Al-7Nb samples in simulated body conditions by using artificial saliva. It was observed that the martensitic phase changed as a function of cooling media, and a less intensive cooling medium decreases strength properties' indicators as well as hardness values. The results emphasize that the use of heat treatment improves the passive layer's resistance in the presence of artificial saliva.

Chemical Modification of Chitosan for Removal of Pb(II) Ions from Aqueous Solutions.

Biomacromolecule have a significant contribution to the adsorption of metal ions. Moreover, chitosan is one of the most studied biomacromolecule, which has shown a good performance in the field of wastewater treatment. In this context, a new adsorbent of the aminophosphonic modified chitosan-supported Ni(II) ions type was prepared from the naturally biopolymer, chitosan. In the first step, modified chitosan with aminophosphonic acid groups was prepared using the "one-pot" Kabachnik-Fields reaction. It was characterized by different techniques: FTIR, SEM/EDAX, TGA, and 31P-NMR. In the second step, the modified chitosan with aminophosphonic acid was impregnated with Ni(II) ions using the hydrothermal reaction at different values of pH (5, 6 and 7). The physical-chemical characteristics of final products (modified chitosan carrying aminophosphonic groups and Ni(II) ions) were investigated using FTIR, SEM images, EDAX spectra and thermogravimetric analysis. In this work, the most important objective was the investigation of the adsorbent performance of the chitosan modified with aminophosphonic groups and Ni(II) ions in the process of removing Pb(II) ions from aqueous solutions by studying the effect of pH, contact time, and Pb(II) ions concentration. For removal of Pb(II) ions from the aqueous solution, the batch adsorption method was used.

Influence of the Laser Cladding Parameters on the Morphology, Wear and Corrosion Resistance of WC-Co/NiCrBSi Composite Coatings.

To enhance the sliding wear and corrosion behavior of steels with low carbon content, cermet composite coatings are usually deposited on their surface by various deposition processes. Laser cladding, compared to other deposition techniques such as electroplating, arc welding, and thermal spraying, has numerous advantages to produce such protective coatings. The paper presents the optimization of laser cladding deposition speed versus energy density in order to obtain WC-Co/NiCrBSi coatings with Ni-Al addition free of defects and reduced porosity deposited on low carbon steel substrate. The microstructure and chemical composition were investigated by SEM combined with EDX analysis while XRD was performed in order to examinate the phases within the coatings. In order to investigate the cladding speed influence on the coatings, hardness measurements, POD (pin on disk) wear tests and corrosion tests in 3.5% NaCl solution were carried out. The results showed that an optimal cladding speed has a crucial impact on the microstructure, composition, and hardness. It was found out that optimizing the cladding deposition speed proved to be effective in enhancing the sliding wear resistance and corrosion behavior by controlling the iron content within the coatings.

Carbon Nanotubes for Improved Performances of Endodontic Sealer.

In order to overcome the limitations of current endodontic sealers, especially against resistant bacteria, recent developments in the field of nanotechnology have proved the necessity to reconsider the composition and physico-chemical properties of classical sealers. Nanoparticles with their unique features in terms of small size and high specific surface area, are the best choice for incorporation of antiseptic agents and effective delivery. The aim of our study is to prepare a novel platform for antibacterial drug delivery in dental adhesive systems used in endodontics. For this purpose, multi-walled carbon nanotubes (MWCNTs) encapsulating chlorhexidine (CHX) and colloidal silver nanoparticles (AgNPs) were prepared and incorporated into commercial sealer and investigated in terms of bonding performance to dentin and effectiveness against E. faecalis, S. aureus and Candida albicans, which are responsible for the majority of the failures in endodontic treatments. In this context, the challenges related to the long-term biological effects of CHX/AgNPs loaded MWCNTs are discussed.

Advances in Low-Density Flexible Polyurethane Foams by Optimized Incorporation of High Amount of Recycled Polyol.

An industrially manufactured recycled polyol, obtained by acidolysis process, was for the first time proved to be a possible replacement of the reference fossil-based polyol in a low-density formulation suitable for industrial production of flexible polyurethane foams. The influence of increasing recycled polyol amounts on the properties of the polyurethane foam has been studied, also performing foam emission tests to evaluate the environmental impact. Using 10 pbw recycled polyol in the standard formulation, significant differences of the physical properties were not observed, but increase of the recycled polyol amount to 30 pbw led to a dramatic decrease of the foam air flow and a very tight foam. To overcome this drawback, N,N'-bis[3-(dimethylamino)propyl]urea was selected as tertiary amine catalyst, enabling the preservation of foam properties even at high recycled polyol level (30 pbw). Foam emission data demonstrated that this optimized foam formulation also led to an important reduction of volatile organic compounds. The results open the way for further optimization studies in low-density flexible polyurethane foam formulations, to increase the reutilization of the polyurethane waste and reduce the amount of petroleum-based raw materials.

Pencil Graphite Electrodes Decorated with Platinum Nanoparticles as Efficient Electrocatalysts for Hydrogen Evolution Reaction.

Platinum-based materials are widely known as the most utilized and advanced catalysts for hydrogen evolution reaction. For this reason, several studies have reported alternative methods of incorporating this metal into more economical electrodes with a carbon-based support material. Herein, we report on the performance of pencil graphite electrodes decorated with electrochemically deposited platinum nanoparticles as efficient electrocatalysts for hydrogen evolution reaction. The electrodeposition of platinum was performed via pulsed current electrodeposition and the effect of current density on the electrocatalytic activity was investigated. The obtained electrodes were characterized using cyclic voltammetry, while the electrocatalytic activity was assessed through linear sweep voltammetry. Field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy were utilised to gain an insight into surface morphology and chemical analysis of platinum nanoparticles. The best performing electrocatalyst, at both low and high current densities, was characterized by the highest exchange current density of 1.98 mA cm-2 and an ultralow overpotential of 43 mV at a current density of 10 mA cm-2. The results show that, at low current densities, performances closest to that of platinum can be achieved even with an ultralow loading of 50 µg cm-2 Pt.

Physically Crosslinked Poly (Vinyl Alcohol)/Kappa-Carrageenan Hydrogels: Structure and Applications.

This paper discusses the structure morphology and the thermal and swelling behavior of physically crosslinked hydrogels, obtained from applying four successive freezing-thawing cycles to poly (vinyl alcohol) blended with various amounts of κ-carrageenan. The addition of carrageenan in a weight ratio of 0.5 determines a twofold increase in the swelling degree and the early diffusion coefficients of the hydrogels when immersed in distilled water, due to a decrease in the crystallinity of the polymer matrix. The diffusion of water into the polymer matrix could be considered as a relaxation-controlled transport (anomalous diffusion). The presence of the sulfate groups determines an increased affinity of the hydrogels towards crystal violet cationic dye. A maximum physisorption capacity of up to 121.4 mg/g for this dye was attained at equilibrium.

Synthesis, Characterization and Adsorptive Performances of a Composite Material Based on Carbon and Iron Oxide Particles.

The aim of this paper was to produce a new composite material based on carbon and iron oxides, starting from soluble starch and ferric chloride. The composite material was synthesized by simple thermal decomposition of a reaction mass obtained from starch and iron chloride, in an inert atmosphere. Starch used as a carbon source also efficiently stabilizes the iron oxides particles obtained during the thermal decomposition. The reaction mass used for the thermal decomposition was obtained by simultaneously mixing the carbon and iron oxide precursors, without addition of any precipitation agent. The proper composite material can be obtained by rigorously adhering to the stirring time, temperature, and water quantity used during the preparation of the reaction mass, as well as the thermal regime and the controlled atmosphere used during the thermal decomposition. Synthesized materials were characterized using thermogravimetric analysis, X-Ray Diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infra-red spectroscopy (FT-IR). The performances of the obtained material were highlighted by studying their adsorbent properties and by determining the maximum adsorption capacity for arsenic removal from aqueous solutions.