Among numerous biologically important metal cations, strontium (Sr2+) has received much attention in bone tissue regeneration because of its osteoinductive properties combined with its ability to inhibit osteoclast activity. In this study, strontium-doped hydroxyapatite (Sr-HAp) nanorods with varying molar ratios of Ca : Sr (10 : 0, 9 : 1, 5 : 5, 3 : 7 and 0 : 10) were synthesized using the chemical precipitation technique. The synthesized Sr-HAp nanostructures were characterized using powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy, energy dispersive X-ray spectroscopy, and Raman and Fourier transform infrared (FTIR) spectroscopies to understand their structural and morphological features, and composition. XRD results revealed the formation of HAp nanostructures, whose unit cell volume increased as a function of the dopant level. The reaction process investigation showed the formation of hydroxyapatite (HAp), strontium apatite (SAp) and various Sr-HAp phases. FESEM micrographs displayed the morphological transformation of Sr-HAp from nanorods to nanosheets upon increasing the dopant level. In the FTIR spectra, the bands of the PO43- group shifted towards a lower wavenumber upon increasing the dopant concentration in Sr-HAp that signifies the structural distortion due to the presence of a large amount of strontium ions. The peaks of PO43- and OH- vibrations in the Raman spectra were further analysed to corroborate the structural distortion of Sr-HAp. Selected area electron diffraction patterns obtained using TEM reveal the reduced crystallinity of Sr-HAp due to Sr-doping, which is in line with the XRD results. Finally, the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay showed that the synthesized Sr-HAp has no toxic effect on the survival and growth of mesenchymal stem cells. In summary, the synthesized novel Sr-HAp nanorods exhibit great promise for bone tissue engineering applications. The morphology and crystalline parameters of Sr-doped HAp were fine-tuned by varying the dopant concentration and annealing temperature, and the Sr-doped HAp exhibited excellent biocompatibility.
Aging populations and the increase in chronic diseases worldwide demand efficient healthcare tools for simple, rapid, and accurate diagnosis and monitoring the human health. In this context, gas sensors are used to analyze the type of gas in the breath to diagnose chronic diseases. Metal oxide and ceramic nanofibers (NFs) produced by the electrospinning (ES) method have been investigated for potential use as gas sensors in the engineering and medical sectors. The material and process parameters are the main influencing factors on the functional performance of electrospun metal oxide NFs. Zinc oxide (ZnO) based NFs are used in various gas sensors due to the wide band gap (3.37eV), large exciton binding energy, and high mobility of charge carriers of ZnO. In this research, we made an attempt to study the effect of poly(vinyl alcohol) (PVA) and zinc acetate dihydrate (ZnAc 2 ) concentrations and feed rate, voltage, spinneret tip-to-collector distance (TCD), and pyrolysis temperature on the physical properties of ZnO NFs. An average fiber diameter of 119 nm was obtained after pyrolysis at 600 °C of electrospun fiber produced from an aqueous PVA solution of concentration 15 w% with 7.5 w% ZnAc 2 based on the weight of PVA. The grain size, transmittance, structural defects, and band gap energy of NFs were found to increase as a function of the pyrolysis temperature, which could be beneficial for the functional applications of these NFs.
Robots in 3D spaces with more than six degrees of freedom are redundant. A redundant robot allows multiple configurations of the robot for the given target point in the dexterous workspace. The presence of multiple solutions helps in resolving constraints in workspace such as object avoidance and energy minimization during trajectory planning. Inverse kinematics solutions of such redundant robotics are intricate. The present study involves comparison of different metaheuristic optimization algorithms (MOA), which have a positional error, and identify a MOA for high precision of positioning of the end effector of the robot. This study applies recent MOA for the inverse kinematics of hyper redundant nine degrees of freedom (DOF) robot arm by using forward kinematics of the Denavit-Hartenberg (DH) parameters and compares the performance of these algorithms. The comparative study shows Bald Eagle Search (BES) algorithm has better performance over other metaheuristic algorithms. BES algorithm outperforms the other MOA in achieving the desired position with very high precision and least positional error for a 9-DOF robot arm.
In this pilot study, we analyzed the response of magnetic fabrics and X-ray diffraction to low strains (≤ 0.0103) applied during quasi-static and dynamic deformation. Four cylindrical samples of Maggia gneiss were deformed under uniaxial compression oriented parallel to the foliation of the gneiss. Out of these four, two cylinders were deformed at dynamic strain rates (> 50/s) with a split Hopkinson pressure bar and two at quasi-static strain rates (< 10–4/s) using a hydraulic press. From each deformed cylinder, five to six specimens were retrieved. Under the polarizing microscope, the original samples and those deformed in the laboratory do not show any difference in microstructures. However, X-ray diffraction reveals gradual straining of the quartz and biotite lattice with increasing experimental strain. Moreover, after the experimental deformation, the maximum and intermediate principal magnetic susceptibility axes (K1 and K2) form a girdle, which is clearly different from the triaxial distribution in the undeformed samples. The corrected degree of anisotropy and the oblateness of the magnetic fabrics increase. The magnitude of the intermediate susceptibility axis (K2) increases, and of the minimum susceptibility axes (K3) decreases. In this pilot study, we are able to show that XRD and magnetic fabrics are very sensitive to strain and capable of recording even low strains which do not present any other apparent evidence of deformation. With further studies, XRD can be established as a practical technique for measuring low mechanical strain in rocks.
Synergetic effect of nickel ion-rich spinel phase and morphology of nickel titanate (NTO) nanofiber on magnetic properties.
Dye-Sensitized Solar Cells (DSSCs) are the promising low-cost solar cells to convert solar energy into electric energy. In this study, TiO2 based Dye-Sensitized Solar Cell is fabricated. TiO2 paste is prepared by using ethanol as a solvent. A thin layer of TiO2 paste is coated on ITO conducting glass, which acts as a working electrode. The counter electrode is prepared by pencil graphite paste using ethanol as a solvent and coated on ITO conducting glass. The dye solution is prepared by adding commercially available methylene blue dye to ethanol and deionized water. From XRD studies, the average crystallite size of TiO2 powder is found to be 88.46 nm. This indicates that the nanostructure of the TiO2 having a large surface to volume ratio playing a vital role in the absorption of solar radiations by the material. J-V characteristics of fabricated DSSC were studied to evaluate its performance in terms of a short circuit current, open-circuit voltage, and fill factor. The performance of DSSC may be enhanced by decreasing the crystallite size of TiO2.
High impact polystyrene (HIPS) material is widely used for low-strength structural applications. To ensure proper function, dimensional accuracy and porosity are at the forefront of industrial relevance. The dimensional accuracy cylindricity error (CE) and porosity of printed parts are influenced mainly by the control variables (layer thickness, shell thickness, infill density, print speed of the fused deposition modeling (FDM) process). In this study, a central composite design (CCD) matrix was used to perform experiments and analyze the complete insight information of the process (control variables influence on CE and porosity of FDM parts). Shell thickness for CE and infill density for porosity were identified as the most significant factors. Layer thickness interaction with shell thickness, infill density (except for CE), and print speed were found to be significant for both outputs. The interaction factors, i.e., shell thickness and infill density, were insignificant (negligible effect) for both outputs. The models developed produced a better fit for regression with an R-2 equal to 94.56% for CE, and 99.10% for porosity, respectively. Four algorithms (bald eagle search optimization (BES), particle swarm optimization (PSO), RAO-3, and JAYA) were applied to determine optimal FDM conditions while examining six case studies (sets of weights assigned for porosity and CE) focused on minimizing both CE and porosity. BES and RAO-3 algorithms determined optimal conditions (layer thickness: 0.22 mm; shell thickness: 2 mm; infill density: 100%; print speed: 30 mm/s) at a reduced computation time equal to 0.007 s, differing from JAYA and PSO, which resulted in an experimental CE of 0.1215 mm and 2.5% of porosity in printed parts. Consequently, BES and RAO-3 algorithms are efficient tools for the optimization of FDM parts.
Nickel cobaltite (NCO) attains the apex of Sabatier-type volcano plot for electrochemical reaction compared to simple oxides due to synergetic effect of mixed transition metal cations. The combination of high surface area, aspect ratio, and porosity of electrospun NCO nanofibers (NCO-NF) enhance their electrocatalytic performance by improved electron mobility and more active sites. In the present study, NCO-NF fabricated using poly (styrene-co-acrylonitrile) (SAN) as a sacrificial polymer, were embellished with graphene nanoclusters (GNC), which augment the electrocatalytic performance of the NCO-NF. The in situ formed GNC along the NCO-NF are result of the interaction between the polar functional groups of the polymer, and the cations of precursor salts during the calcination of precursor nanofibers. The GNC/NCO-NF with least crystallite size and high aspect ratio having porous NCO nanoparticles and in situ grown GNC were developed using sol-gel electrospinning process assisted by calcination of precursor nanofibers. This simple, eco-friendly, and economical synthesis route with unique structure chemistry of SAN to form GNC and the presence of dual cations (Ni and Co) provides enhanced performance and multifunctionality to GNC/NCO-NF electrodes for electrocatalytic applications, such as biosensors and water-splitting. In the present study, the modified electrodes (GNC/NCO-NF/graphite electrode) exhibited excellent non-enzymatic glucose detection over a wide range of concentration with a lower limit of 1.2 mu M and sensitivity of 1827.5 mu A mM(-1) mg(-1) in 0.1 M NaOH. Further, the modified electrodes were also tuned for H2O2 detection to aid enzymatic glucose sensing. When examined for bifunctional water-splitting in 1 M NaOH, the electrode reached an onset potential of -0.537 V and 0.735 V against reversible hydrogen reference electrode and a Tafel slope of 37.6 mV.dec(-1) and 67.0 mV.dec(-1) for hydrogen and oxygen evolution reactions, respectively. The results prove that GNC/NCO-NF are promising candidates as multifunctional electrocatalyst.
S2. FESEM-EDS analysis of NTO nanofibers FESEM images were used to measure the average fibre diameter (AFD) and standard deviation (SD) of nickel titanate (NTO) nanofibers using Image J software as shown in Figure S2. The mosaic structured nanoparticles in NTO nanofibers obtained at 773 K transforms to bamboo like structure NTO nanofibers with increasing pyrolysis soaking temperature to 1173 K. EDS spectra was acquired for the selected area on the NTO nanofiber. The weight and atomic percentage of each element is shown in Figure S2.
Producing pure H-2 and O-2 to sustain the renewable energy sources with minimal environmental damage is a key objective of photo/electrochemical water-splitting research. Metallic Ni-based electrocatalysts are expensive and eco-hazardous. This has rendered the replacement or reduction of Ni content in Ni-based electrocatalysts a decisive criterion in the development of bifunctional electrocatalytic materials. In the current study, spinel/ilmenite composite nickel titanate (NTO) nanofibers were synthesised using sol-gel assisted electrospinning followed by pyrolysis at different soaking temperatures (viz., 773, 973, and 1173 K). The presence of a defective spinel NTO phase (SNTO) distributed uniformly along the nanofibers was confirmed by X-ray photoelectron and Raman spectroscopy. The electron micrographs revealed the morphological change of NTO nanofibers from a mosaic to bamboo structure with an increase in pyrolysis soaking temperature. The electrocatalytic activity of NTO nanofibers obtained at different pyrolysis soaking temperatures for alkaline water-splitting was studied. The highly defective SNTO manifests properties similar to metallic Ni and favours H-2 evolution through the hydrogen evolution reaction (HER) by adsorbing more H+ ions on active sites. In contrast, the ilmenite NTO favours O-2 discharge. These results are explained based on the morphology of the NTO nanofibers. The mosaic structure which has higher porosity and greater SNTO content shows excellent HER performance. In contrast, the large bamboo structured NTO nanofibers which have lesser porosity and SNTO content cage the bigger (OH)(ads) ions at their catalytic sites to facilitate OER performance.
The solution electrospinning of polyolefins has not been deeply studied mainly due to the difficulty in dissolving these polymers in appropriate solvents. In this study, composite nanofibers of organically modified montmorillonite/ethylene-octene random copolymer were produced for the first time with a mixture of cyclohexane and xylene as a solvent by solution electrospinning. Montmorillonite was used as an additive to increase the electrical charge density of the polymer solution. The influence of solution and process parameters on the electrospun ethylene-octene copolymer fibers' morphology and diameter was investigated using the design of experiment. Multiple regression analysis was used for the optimization of the electrospinning parameters. Ultrafine fibers, with diameters in the range of 150-350nm were obtained; these nanofibers exhibited an excellent hydrophobicity over a period of 10min as revealed by contact angle measurements.
Nickel cobaltite (NCO) is a binary transition-metal oxide, which is extensively used as an electrocatalyst and magnetic material. NCO nanofibers and NCO/graphene composite exhibit high electrochemical reactivity due to the directional bridging of NCO particles. This makes NCO a promising candidate electrode material for use in supercapacitors and batteries. Besides, NCO is also a promising magnetic material due to its unique structural composition, where the cations are seated in octahedral sites surrounded by oxygen vacancies. In the present work, a simple and reliable method was discovered for tuning the morphological and structural changes of nickel cobaltite (NCO) nanoparticles, which were reshaped along the NCO nanofibers, by controlling the pyrolysis soaking time. As the pyrolysis soaking time increases, NCO transforms from inverse spinel to normal spinel; and the morphology of NCO nanoparticles changes from spherical to rod-like. These changes were validated by the hypsochromic peak shifts in Raman, and FTIR spectroscopies. The magnetic measurements reveal changes in the shape of the hysteresis loop, which are explained on the basis of structural and morphological changes in the nanostructure. The net magnetisation increases and coercivity decreases, with an increase in pyrolysis soaking time. These changes in magnetic parameters are attributed to structural changes caused by the formation of oxygen vacancies, and surface effects due to switching in morphology of the NCO nanoparticle.
Randomly oriented nanofibers of nickel cobaltite (NCO) were fabricated using sol-gel electrospinning followed by calcination. The precursor fibers were collected on rotating disc (RDI) and rotating drum (RDR) collectors. Variable fictitious forces produce continuous deflection at each fiber landing position on the RDI collector, which subjects the nanofibers to non-bundling. On the other hand, in the case of the RDR collector, the fictitious forces act just at the surface, and these forces merely cause slip of the fibers along the rotational axis of the RDR. This slip along with the retained Columbic charges on the surface of the fibers produces fiber bundling, which affects the morphological and structural properties of the NCO nanofibers obtained by calcining the precursor fibers. The use of the RDI collector in sol-gel electrospinning is a simple and optimal method of fabricating precursor nanofibers, which yields non-agglomerated and impurity-free inorganic nanofibers.
Nickel cobaltite (NCO) nanofibers were synthesized using poly(styrene-co-acrylonitrile) (SAN) as the polymeric binder through sol–gel assisted electrospinning. Defect-free precursor nanofiber mats were pyrolyzed at 773 K at three different pyrolysis soaking times t = 2, 4, and 6 h. The SAN present in the precursor nanofibers caused morphological changes in the NCO nanofibers during their thermochemical degradation. Consequently, fractal aggregates of NCO nanoparticles were formed along the length of the nanofibers. X-ray photoelectron spectroscopy (XPS) revealed both + 2 and + 3 oxidation states for Ni and Co, with spinel crystal defects due to oxygen rich atmosphere. XPS, high-resolution transmission microscopy, and optical analysis showed graphene-like structures embedded within the NCO nanofibers. With increase in pyrolysis soaking time, the morphology of the NCO particles markedly changed from spherical to rod-like. We propose a mechanism for the morphological change of NCO nanoparticles on the basis of crystallite splitting accompanied by particle splitting and reordering.
In this study, we report for the first time the synthesis of nickel titanate (NTO) nanofibers containing a mixture of ilmenite and spinel phases of NTO, at an atypical low temperature. Precursor nanofibers produced by sol-gel electrospinning were calcined at three different temperatures to produce the NTO nanofibers. Thermal analysis along with X-ray photoelectron spectroscopy confirmed the formation of non-crystalline stable phases of TiN and Ti-O-N that restrained the formation of ilmenite NTO, and the Ni-rich environment pushed the Ti atoms to tetrahedral sites to form a defective spinel structure. The crystallite size of spinel NTO was observed to increase as a function of the calcination temperature above 700°C, as the activation energy for coalescence and growth of spinel NTO was favorable. NTO nanofibers obtained above the calcination temperature of 700°C exhibited new band gap energy around 2.5eV in Tauc plot. Oxygen vacancies in these ceramic nanofibers decreased as the calcination temperature was increased. A hypsochromic shift of 20nm in the photoluminescence spectra suggested that the material had a Ni2+ rich NTO (spinel).
ZnMn2O4 has application potential in lithium ion batteries, supercapacitors, sensors, and thermistors. In this study, mesoporous spinel ZnMn2O4 nanofibers were synthesized by sol–gel assisted electrospinning combined with calcination, using poly(styrene-co-acrylonitrile) as sacrificial polymeric binder. Structural, morphological and optical properties of these ceramic nanofibers were characterized. X-ray diffraction and X-ray photoelectron spectroscopy results revealed the presence of hexagonal ZnMnO3 and MnO phases in the ZnMn2O4 nanofibers produced. Based on these observations we propose a plausible mechanism of formation of ZnMn2O4 nanofibers. The nanofibers calcined at 773 K exhibit a specific surface area of 79.5 m2 g−1, which is higher than that of the zinc manganite nanofibers synthesized hitherto by sol–gel electrospinning. Moreover, this material exhibits four bandgaps, which is believed to be the first observation in ZnMn2O4 nanofibers.