Novel Method for the Production of Titanium Foams to Reduce Stress Shielding in Implants.

Titanium foams have potential applications in orthopedic and dental implants because of their low elastic modulus and good bone in-growth properties. In the present study, a novel method for the preparation of three-dimensional interconnected microporous titanium foams has been developed. This method is based on the insertion of a filler metal into the titanium metal by arc melting, followed by its removal by an electrochemical dealloying process for the development of foams. Complete removal of the filler metal by the electrochemical dealloying process was confirmed by an X-ray diffractometry (XRD) analysis, whereas scanning electron microscopy (SEM) analysis of the developed foams showed the development of interconnected porosity. Ti foams with different levels of porosities were successfully developed by varying the amount of the filler metal. Mechanical and thermal characterizations of the developed foams were carried out using compression testing and laser flash apparatus, respectively. The yield strength and elastic modulus of the developed foams were found to decrease by increasing the volume fraction of pores. The elastic modulus of the developed titanium foams (15.5-36 GPa) was found to be closer to that of human bones, whereas their yield strength (147-170 MPa) remained higher than that of human bones. It is therefore believed that the developed Ti foams can help in reducing the problem of stress shielding observed in orthopedic implants. The thermal diffusivity of the developed foams (4.3-0.69 mm2/s) was found to be very close to that of human dentine.

Ceramic-reinforced HEA matrix composites exhibiting an excellent combination of mechanical properties.

CoCrFeNi is a well-studied face centered cubic (fcc) high entropy alloy (HEA) that exhibits excellent ductility but only limited strength. The present study focusses on improving the strength-ductility balance of this HEA by addition of varying amounts of SiC using an arc melting route. Chromium present in the base HEA is found to result in decomposition of SiC during melting. Consequently, interaction of free carbon with chromium results in the in-situ formation of chromium carbide, while free silicon remains in solution in the base HEA and/or interacts with the constituent elements of the base HEA to form silicides. The changes in microstructural phases with increasing amount of SiC are found to follow the sequence: fcc → fcc + eutectic → fcc + chromium carbide platelets → fcc + chromium carbide platelets + silicides → fcc + chromium carbide platelets + silicides + graphite globules/flakes. In comparison to both conventional and high entropy alloys, the resulting composites were found to exhibit a very wide range of mechanical properties (yield strength from 277 MPa with more than 60% elongation to 2522 MPa with 6% elongation). Some of the developed high entropy composites showed an outstanding combination of mechanical properties (yield strength 1200 MPa with 37% elongation) and occupied previously unattainable regions in a yield strength versus elongation map. In addition to their significant elongation, the hardness and yield strength of the HEA composites are found to lie in the same range as those of bulk metallic glasses. It is therefore believed that development of high entropy composites can help in obtaining outstanding combinations of mechanical properties for advanced structural applications.

Effect of Annealing Heat Treatment on the Composition, Morphology, Structure and Mechanical Properties of the W-S-N Coatings.

Alloyed-transition metal dichalcogenide (TMD) coatings have been under investigation as multi-environment lubricants for the past few decades. These coatings display very low coefficient of friction properties at elevated temperatures. Studies on the annealing of these low-friction coatings are missing in the literature. For the first time, in this study, the annealing of the W-S-N dry lubricant coatings was carried out to study its effects on the composition, morphology, crystal structure and hardness of the coatings. The W-S-N coatings were deposited by direct current (DC) reactive magnetron sputtering. The analysis was carried out for as-deposited, 200 °C and 400 °C annealed coatings. The as-deposited coatings have N content in the range of 0-25.5 at. %. The coatings are compact and the densification increased with the increase in N-alloying. All the coatings are crystalline except the highest N-alloyed coating which is X-ray amorphous. A maximum hardness of 8.0 GPa was measured for the coating alloyed with 23 at. % N. Annealing did not affect the composition and morphology of the coatings, while some variations were observed in their crystal structure and hardness. The maximum hardness increased from 8 GPa to 9.2 GPa after 400 °C annealing of the 23 at. % N-alloyed coating.

Microstructural evolution and mechanical characterization of a WC-reinforced CoCrFeNi HEA matrix composite.

High entropy alloys (HEAs) are a relatively new class of material that have shown the potential to exhibit excellent combinations of mechanical properties. Various microstructural modifications have been explored to further enhance their mechanical properties for use in demanding structural applications. The main focus of the present work is an investigation of the effect of adding varying amounts of hard ceramic material (WC) to a tough HEA matrix (CoCrFeNi) by arc melting under an argon atmosphere, including microstructural changes, and evaluation of the WC additions on mechanical properties. X-ray diffraction analysis of the HEA-WC composites showed the presence of both fcc and carbide phases. Scanning electron microscope investigations, including energy dispersive spectroscopy, reveal that chromium diffuses from the matrix and interacts with WC to form an alloyed carbide phase. The amount of alloyed carbide was found to increase with increasing amount of WC addition to the HEA matrix. Mechanical characterization revealed that hardness and yield strength of the HEA-WC composites increase with increasing amount of the carbide phase in the matrix. The hardness of HEA-20wt.% WC sample was found to be as high as 3.3 times (593 HV) the hardness of the base HEA (180 HV), while the yield strength increased from 278 MPa for the base HEA to 1098 MPa for the CoCrFeNi-20 wt.% WC composite. The investigated composites also showed excellent values of ductility (~ 50% strain for CoCrFeNi-10 wt% WC and ~ 20% strain for CoCrFeNi-20 wt% WC). It is therefore believed that ceramic-reinforced high entropy matrix composites have the potential to provide outstanding combinations of mechanical properties for demanding structural applications.

Removal of levofloxacin from aqueous solution by green synthesized magnetite (Fe3O4) nanoparticles using Moringa olifera: Kinetics and reaction mechanism analysis.

Levofloxacin antibiotic is frequently being detected in the environment and regarded as an emerging contaminant. The present study was focused on the green synthesis of magnetite (Fe3O4 - gINPs) nanoparticles from Moringa olifera and its efficiency for removal of levofloxacin from aqueous solution. The adsorbent magnetite nanoparticles (Fe3O4) were prepared by green synthesis using Moringa olifera and coprecipitation method. Characterizations analyses of both chemically and green synthesized nanoparticles were performed by SEM, XRD, and FTIR. The average crystallite size of gINPs was 14.34 nm and chemically synthesized was 18.93 nm. The performance of the synthesized product was evaluated by adsorption capacity and removal efficiency. The parameters considered included adsorbent (gINPs) dosage, initial concentration of adsorbate, pH, contact time, and temperature. The obtained data were fitted to kinetic and isotherm models to determine the mechanism. Adsorption batch experiments were conducted to determine the reaction mechanism by studying kinetics while fitting isotherm models for samples analyzed using HPLC at 280 nm. Results showed that 86.15% removal efficiency of 4 mg L-1 levofloxacin was achieved by 100 mg L-1 gINPs in 24 h contact time when all other parameters (pH 7, temperature 25 °C) were kept constant. The maximum adsorption capacity achieved at equilibrium was 22.47 mg/g. Further, it was identified as a pseudo-second-order model with R2 = 0.965 for adsorption kinetics while isotherm data better fitted to the Freundlich model compared to Langmuir isotherm with R2 = 0.994. The potential pathway determined for levofloxacin removal was chemisorption with minor diffusion, multilayer, spontaneous and exothermic processes on the gINPs (Fe3O4). Reusability experiments were conducted in four cycles and removal efficiency varied from 85.35% to 80.47%, indicating very high potential of the adsorbent for re-use.

TiO2 nanoparticles dose, application method and phosphorous levels influence genotoxicity in Rice (Oryza sativa L.), soil enzymatic activities and plant growth.

The present study focused on investigating the effect of titanium dioxide nanoparticles (TiO2NPs) on rice (Oryza sativa L.) growth and changes in soil health in two contrasting soil textures (silt-loam and clay). Moreover, response of rice to different methods of TiO2NPs application and phosphorous fertilizer levels were also evaluated. For toxicity assessment, pot experiment was carried out. TiO2NPs (0, 500, 750 mg kg-1) were applied and plants were grown till vegetative stage. After harvesting, physiological parameters, stress assay, soil microbial and enzymatic activities were determined. Based on the results of toxicity study, impact of three methods of TiO2NPs application (foliar, irrigation, soil) and four phosphorous fertilizer levels (0, 10, 20, 40 mg kg-1) on rice growth were assessed. During the 1st phase, results showed an adverse effect of TiO2NPs on plant growth and soil microorganisms in both soil textures at 750 mg kg-1. The H2O2 production, lipid peroxidation and leaf membrane injury index were increased by 4.3-, 2.4-, and 1.9-folds in clay soil upon 750 mg kg-1 TiO2NPs application. Likewise, at the same level of TiO2NPs; microbial biomass, dehydrogenase, and respiration were decreased by 0.91-, 0.79-, and 0.78- folds respectively. In 2nd phase, maximum shoot length, biomass, phosphorous uptake and rice grain protein content were observed under application of TiO2NPs (500 mg kg-1) through irrigation method in combination with 40 mg P kg-1. However, 20 and 40 mg P kg-1 performed equally well upon TiO2NPs application and the results were not statistically significant. The results suggest that 750 mg kg-1 of TiO2NPs negatively affect plant growth and soil enzymatic activities. Moreover, combined application of TiO2NPs (500 mg kg-1) through irrigation and 20 mg P kg-1 is recommended to be the optimum for growth of rice plant.

Lead phytoextraction by Pelargonium hortorum: Comparative assessment of EDTA and DIPA for Pb mobility and toxicity.

Soil amendments like ethylene-diamine-tetraacetic-acid (EDTA) have extensively been used for enhancing lead (Pb) phytoextraction. But due to its toxic effects, environment friendly substitute is required. Therefore, the present study was conducted to investigate the effect of EDTA and Di-iso-propanol-amine (DIPA) to enhance Pb phytoavailability and uptake by Pelargonium hortorum along with comparative toxicities of both organic amendments. For this purpose, soil was spiked with Pb concentrations (0, 500, 750, 1000 and 1500 mg kg1) and amended with EDTA and DIPA at dosage levels (0, 1.5, 3, 5, 7.5, 10 mmol kg-1) for plantation of Pelargonium hortorum. Soil samples were extracted with MgCl2, plant samples were acid digested and analyzed for metal content. Biomass and root/shoot length of Pelargonium hortorum was decreased with increase in concentration of Pb and chelating agents. Phytoavailability of Pb at 1500 mg kg-1 with EDTA 10 mmol kg-1 was 0.3-folds in comparison to DIPA at the same dosage. Pelargonium hortorum plants amended with EDTA and DIPA at 10 mmol kg-1 with Pb 1000 mg kg-1 were found to uptake Pb 5.3-fold and 2.5-folds, respectively in comparison to Pb 1000 mg kg-1 alone. Pb uptake decreased at 1500 mg kg-1 with both chelating agents. The EDTA alone and in combination with 1500 mg Pb kg-1 showed maximum genotoxicity by reducing the mitotic index and increasing the micronuclei formation. EDTA+Pb showed maximum toxicity followed by Pb and DIPA. Overall, 10 mmol kg-1 of EDTA and DIPA performed better among all dosages in enhancing phytoavailability and uptake of Pb. DIPA showed less toxicity than that caused by EDTA, with comparable ability to promote Pb phytoextraction.

Phosphoric Acid Activated Carbon from Melia azedarach Waste Sawdust for Adsorptive Removal of Reactive Orange 16: Equilibrium Modelling and Thermodynamic Analysis.

Waste wood biomass as precursor for manufacturing activated carbon (AC) can provide a solution to ever increasing global water quality concerns. In our current work, Melia azedarach derived phosphoric acid-treated AC (MA-AC400) was manufactured at a laboratory scale. This novel MA-AC400 was tested for RO16 dye removal performance as a function of contact time, adsorbent dosage, pH, temperature and initial dye concentration in a batch scale arrangement. MA-AC400 was characterized via scanning electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, dynamic light scattering (DLS) and fluorescence spectroscopy. MA-AC400 is characterized as mesoporous with BET surface area of 293.13 m2 g-1 and average pore width of 20.33 Å. pHPZC and Boehm titration confirm the acidic surface charges with dominance of phenolic functional groups. The average DLS particle size of MA-AC400 was found in the narrow range of 0.12 to 0.30 µm and this polydispersity was confirmed with multiple excitation fluorescence wavelengths. MA-AC400 showed equilibrium adsorption efficiency of 97.8% for RO16 dye at its initial concentration of 30 mg L-1 and adsorbent dose of 1 g L-1. Thermodynamic study endorsed the spontaneous, favorable, irreversible and exothermic process for RO16 adsorption onto MA-AC400. Equilibrium adsorption data was better explained by Langmuir with high goodness of fit (R2, 0.9964) and this fitness was endorsed with lower error functions. The kinetics data was found well fitted to pseudo-second order (PSO), and intra-particle diffusion kinetic models. Increasing diffusion constant values confirm the intraparticle diffusion at higher RO16 initial concentration and reverse was true for PSO chemisorption kinetics. MA-AC400 exhibited low desorption with studied eluents and its cost was calculated to be $8.36/kg.

A novel strategy for synthesis of Al powder comprising of Al nanoflakes via ultrasonication of Al foil.

Aluminum (Al) nanopowders have potential applications as hydrogen storage medium, energetic materials, pigments, and for production of metal matrix parts via powder metallurgy, to name a few. They are synthesized by methods which are either expensive or result in the product with impurities. A novel methodology based on ultrasonication of commercially available Al foil has been developed for synthesis of Al powders. Al foil was immersed in an organic medium and subjected to ultrasonication in a 160-watt bath ultrasonicator operated at 35 kHz frequency. Morphological, crystal structural, and dimensional characterization of ultrasonicated Al was carried out with the help of scanning electron microscopy (SEM), X-ray diffraction (XRD), and atomic forces microscopy (AFM) respectively. Characterization results revealed that Al foil was eroded laterally as well as axially, resulting in the formation of micro and nanosized flake-like pure Al powder.

Comparison of the site occupancies determined by combined Rietveld refinement and density functional theory calculations: example of the ternary Mo-Ni-Re σ phase.

The site occupancies of the Mo-Ni-Re σ phase have been studied as a function of the composition in the ternary homogeneity domain by both experimental measurements and calculations. Because of the possible simultaneous occupancy of three elements on the five sites of the crystal structure, the experimental determination of the site occupancies was achieved by using combined Rietveld refinement of X-ray and neutron diffraction data, whereas calculation of the site occupancies was carried out by using the density functional theory results of every ordered (i.e., 3(5) = 243) configuration appearing in the ternary system. A comparison of the experimental and calculation results showed good agreement, which suggests that the topologically close-packed phases, such as the σ phase, could be described by the Bragg-Williams approximation (i.e., ignoring the short-range-order contributions). On the other hand, the atomic distribution on different crystallographic sites of the Mo-Ni-Re σ phase was found to be governed by the atomic sizes. Ni, having the smallest atomic size, showed a preference for low-coordination-number (CN) sites, whereas Mo, being the largest in atomic size, preferred occupying high-CN sites. However, the preference of Re, having intermediate atomic size, varied depending on the composition, and a clear reversal in the preference of Re as a function of the composition was evidenced in both the calculated and experimental site-occupancy results.