Effects of Sintering Conditions on Giant Dielectric and Nonlinear Current-Voltage Properties of TiO2-Excessive Na1/2Y1/2Cu3Ti4.1O12 Ceramics.

The effects of the sintering conditions on the phase compositions, microstructure, electrical properties, and dielectric responses of TiO2-excessive Na1/2Y1/2Cu3Ti4.1O12 ceramics prepared by a solid-state reaction method were investigated. A pure phase of the Na1/2Y1/2Cu3Ti4.1O12 ceramic was achieved in all sintered ceramics. The mean grain size slightly increased with increasing sintering time (from 1 to 15 h after sintering at 1070 °C) and sintering temperature from 1070 to 1090 °C for 5 h. The primary elements were dispersed in the microstructure. Low dielectric loss tangents (tan δ~0.018-0.022) were obtained. Moreover, the dielectric constant increased from ε'~5396 to 25,565 upon changing the sintering conditions. The lowest tan δ of 0.009 at 1 kHz was obtained. The electrical responses of the semiconducting grain and insulating grain boundary were studied using impedance and admittance spectroscopies. The breakdown voltage and nonlinear coefficient decreased significantly as the sintering temperature and time increased. The presence of Cu+, Cu3+, and Ti3+ was examined using X-ray photoelectron spectroscopy, confirming the formation of semiconducting grains. The dielectric and electrical properties were described using Maxwell-Wagner relaxation, based on the internal barrier layer capacitor model.

A compact furnace for in situ X-ray absorption spectroscopy: design, fabrication and study of cationic oxidation states in Pr6O11 and NiO.

A well designed compact furnace has been designed for in situ X-ray absorption spectroscopy (XAS). It enables various heat ramps from 300 K to 1473 K. The furnace consists of heaters, a quartz tube, a circulated refrigerator and a power controller. It can generate ohmic heating via an induction process with tantalum filaments. The maximum heating rate exceeds 20 K min-1. A quartz tube with gas feedthroughs allows the mixing of gases and adjustment of the flow rate. The use of this compact furnace allows in situ XAS investigations to be carried out in transmission or fluorescence modes under controlled temperature and atmosphere. Moreover, the furnace is compact, light and well compatible to XAS. The furnace was used to study cationic oxidation states in Pr6O11 and NiO compounds under elevated temperature and reduced atmosphere using the in situ X-ray absorption near-edge structure (XANES) technique at beamline 5.2 SUT-NANOTEC-SLRI of the Synchrotron Light Research Institute, Thailand. At room temperature, Pr6O11 contains a mixture of Pr3+ and Pr4+ cations, resulting in an average oxidation state of +3.67. In situ XANES spectra of Pr (L3-edge) show that the oxidation state of Pr4+ cations was totally reduced to +3.00 at 1273 K under H2 atmosphere. Considering NiO, Ni2+ species were present under ambient conditions. At 573 K, the reduction process of Ni2+ occurred. The Ni0/Ni2+ ratio increased linearly with respect to the heating temperature. Finally, the reduction process of Ni2+ was completely finished at 770 K.

Structural and Compositional Characteristics of Ball-Milled Lepidocrocite Alkali Titanate and the Correlation to Its Surface Acidic-Basic Properties.

The studies on mechanical treatments of layered alkali metal oxides are limited despite their diverse compositions/structures and potential for property tuning. In this work, we vibratory mill Cs0.7Zn0.35Ti1.65O4, K0.8Zn0.4Ti1.6O4, and Cs2Ti6O13 for up to 4 h, during which the lepidocrocite-type structure and the plate-like morphology are well preserved. X-ray diffraction (XRD) indicates a tiny (≤0.6 Å) interlayer expansion accompanied by the enhancement of the preferred orientation along the stacking direction. Chemical analyses across multiple length scales suggest Cs deintercalation, elemental redistributions, and bulk-to-surface (or crystal edge) Cs migration. This ball-milling-induced Cs-rich moiety partially blocks the surface acid sites, although the solids still show a dominating acidic character. The ball-milled samples Cs0.7-pZn0.35-qTi1.65O4-δ contain vacancies between the sheets (p) and at the sheets (q and δ). It is deduced from Sanderson's electronegativity equalization principle and experimentally verified by X-ray photoelectron spectroscopy (XPS) that ball milling increases (decreases) the partial charge at the surface acidic Ti4+/Zn2+ (basic O2-) sites. These nonporous solids (≤20 m2·g-1) contain water sorbed on the external surface as high as 1.1 mol·mol-1, which is comparable to that in a water-intercalated sample. Our work expands the current understanding of the reactivity vs robustness in layered alkali titanates under physically demanding conditions, complementing knowledge gathered via the soft chemistry approach.

Origins of Giant Dielectric Properties with Low Loss Tangent in Rutile (Mg1/3Ta2/3)0.01Ti0.99O2 Ceramic.

The Mg2+/Ta5+ codoped rutile TiO2 ceramic with a nominal composition (Mg1/3Ta2/3)0.01Ti0.99O2 was synthesized using a conventional solid-state reaction method and sintered at 1400 °C for 2 h. The pure phase of the rutile TiO2 structure with a highly dense microstructure was obtained. A high dielectric permittivity (2.9 × 104 at 103 Hz) with a low loss tangent (<0.025) was achieved in the as-sintered ceramic. After removing the outer surface, the dielectric permittivity of the polished ceramic increased from 2.9 × 104 to 6.0 × 104, while the loss tangent also increased (~0.11). The dielectric permittivity and loss tangent could be recovered to the initial value of the as-sintered ceramic by annealing the polished ceramic in air. Notably, in the temperature range of -60-200 °C, the dielectric permittivity (103 Hz) of the annealed ceramic was slightly dependent (<±4.4%), while the loss tangent was very low (0.015-0.036). The giant dielectric properties were likely contributed by the insulating grain boundaries and insulative surface layer effects.

Influences of Sr2+ Doping on Microstructure, Giant Dielectric Behavior, and Non-Ohmic Properties of CaCu3Ti4O12/CaTiO3 Ceramic Composites.

The microstructure, dielectric response, and nonlinear current-voltage properties of Sr2+-doped CaCu3Ti4O12/CaTiO3 (CCTO/CTO) ceramic composites, which were prepared by a solid-state reaction method using a single step from the starting nominal composition of CCTO/CTO/xSrO, were investigated. The CCTO and CTO phases were detected in the X-ray diffraction patterns. The lattice parameter increased with increasing Sr2+ doping concentration. The phase compositions of CCTO and CTO were confirmed by energy-dispersive X-ray spectroscopy with elemental mapping in the sintered ceramics. It can be confirmed that most of the Sr2+ ions substituted into the CTO phase, while some minor portion substituted into the CCTO phase. Furthermore, small segregation of Cu-rich was observed along the grain boundaries. The dielectric permittivity of the CCTO/CTO composite slightly decreased by doping with Sr2+, while the loss tangent was greatly reduced. Furthermore, the dielectric properties in a high-temperature range of the Sr2+-doped CCTO/CTO ceramic composites can be improved. Interestingly, the nonlinear electrical properties of the Sr2+-doped CCTO/CTO ceramic composites were significantly enhanced. The improved dielectric and nonlinear electrical properties of the Sr2+-doped CCTO/CTO ceramic composites were explained by the enhancement of the electrical properties of the internal interfaces.

The Primary Origin of Excellent Dielectric Properties of (Co, Nb) Co-Doped TiO2 Ceramics: Electron-Pinned Defect Dipoles vs. Internal Barrier Layer Capacitor Effect.

(Co, Nb) co-doped rutile TiO2 (CoNTO) nanoparticles with low dopant concentrations were prepared using a wet chemistry method. A pure rutile TiO2 phase with a dense microstructure and homogeneous dispersion of the dopants was obtained. By co-doping rutile TiO2 with 0.5 at.% (Co, Nb), a very high dielectric permittivity of ε' ≈ 36,105 and a low loss tangent of tanδ ≈ 0.04 were achieved. The sample-electrode contact and resistive outer-surface layer (surface barrier layer capacitor) have a significant impact on the dielectric response in the CoNTO ceramics. The density functional theory calculation shows that the 2Co atoms are located near the oxygen vacancy, creating a triangle-shaped 2CoVoTi complex defect. On the other hand, the substitution of TiO2 with Nb atoms can form a diamond-shaped 2Nb2Ti complex defect. These two types of complex defects are far away from each other. Therefore, the electron-pinned defect dipoles cannot be considered the primary origins of the dielectric response in the CoNTO ceramics. Impedance spectroscopy shows that the CoNTO ceramics are electrically heterogeneous, comprised of insulating and semiconducting regions. Thus, the dielectric properties of the CoNTO ceramics are attributed to the interfacial polarization at the internal insulating layers with very high resistivity, giving rise to a low loss tangent.

Microstructural Evolution and High-Performance Giant Dielectric Properties of Lu3+/Nb5+ Co-Doped TiO2 Ceramics.

Giant dielectric (GD) oxides exhibiting extremely large dielectric permittivities (ε' > 104) have been extensively studied because of their potential for use in passive electronic devices. However, the unacceptable loss tangents (tanδ) and temperature instability with respect to ε' continue to be a significant hindrance to their development. In this study, a novel GD oxide, exhibiting an extremely large ε' value of approximately 7.55 × 104 and an extremely low tanδ value of approximately 0.007 at 103 Hz, has been reported. These remarkable properties were attributed to the synthesis of a Lu3+/Nb5+ co-doped TiO2 (LuNTO) ceramic containing an appropriate co-dopant concentration. Furthermore, the variation in the ε' values between the temperatures of -60 °C and 210 °C did not exceed ±15% of the reference value obtained at 25 °C. The effects of the grains, grain boundaries, and second phase particles on the dielectric properties were evaluated to determine the dielectric properties exhibited by LuNTO ceramics. A highly dense microstructure was obtained in the as-sintered ceramics. The existence of a LuNbTiO6 microwave-dielectric phase was confirmed when the co-dopant concentration was increased to 1%, thereby affecting the dielectric behavior of the LuNTO ceramics. The excellent dielectric properties exhibited by the LuNTO ceramics were attributed to their inhomogeneous microstructure. The microstructure was composed of semiconducting grains, consisting of Ti3+ ions formed by Nb5+ dopant ions, alongside ultra-high-resistance grain boundaries. The effects of the semiconducting grains, insulating grain boundaries (GBs), and secondary microwave phase particles on the dielectric relaxations are explained based on their interfacial polarizations. The results suggest that a significant enhancement of the GB properties is the key toward improvement of the GD properties, while the presence of second phase particles may not always be effective.

Significantly Improved Colossal Dielectric Properties and Maxwell-Wagner Relaxation of TiO2-Rich Na1/2Y1/2Cu3Ti4+xO12 Ceramics.

In this work, the colossal dielectric properties and Maxwell-Wagner relaxation of TiO2-rich Na1/2Y1/2Cu3Ti4+xO12 (x = 0-0.2) ceramics prepared by a solid-state reaction method are investigated. A single phase of Na1/2Y1/2Cu3Ti4O12 is achieved without the detection of any impurity phase. The highly dense microstructure is obtained, and the mean grain size is significantly reduced by a factor of 10 by increasing Ti molar ratio, resulting in an increased grain boundary density and hence grain boundary resistance (Rgb). The colossal permittivities of ε' ~ 0.7-1.4 × 104 with slightly dependent on frequency in the frequency range of 102-106 Hz are obtained in the TiO2-rich Na1/2Y1/2Cu3Ti4+xO12 ceramics, while the dielectric loss tangent is reduced to tanδ ~ 0.016-0.020 at 1 kHz due to the increased Rgb. The semiconducting grain resistance (Rg) of the Na1/2Y1/2Cu3Ti4+xO12 ceramics increases with increasing x, corresponding to the decrease in Cu+/Cu2+ ratio. The nonlinear electrical properties of the TiO2-rich Na1/2Y1/2Cu3Ti4+xO12 ceramics can also be improved. The colossal dielectric and nonlinear electrical properties of the TiO2-rich Na1/2Y1/2Cu3Ti4+xO12 ceramics are explained by the Maxwell-Wagner relaxation model based on the formation of the Schottky barrier at the grain boundary.

Effects of catalyst surfaces on adsorption revealed by atomic force microscope force spectroscopy: photocatalytic degradation of diuron over zinc oxide.

Controlling adsorption of a heterogeneous catalyst requires a detailed understanding of the interactions between reactant molecules and the catalyst surface. Various characteristics relevant to adsorption have been theoretically predicted but have yet to be experimentally quantified. Here, we explore a model reaction based on diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] photo-degradation over a ZnO particle catalyst. We used atomic force microscope (AFM)-based force spectroscopy under ambient conditions to investigate interactions between individual functional groups of diuron (NH2, Cl, and CH3) and surfaces of ZnO particles (polar Zn and O-terminated, and nonpolar Zn-O terminated). We were able to distinguish and identify the two polar surfaces of conventional ZnO particles and the nonpolar surface of ZnO nanorods based on force-distance curves of functionalized probe/surface pairs. We posit that the reaction involved physisorption and could be described in terms of Hamaker constants. These constants had an order-of-magnitude difference among the probe/surface interacting pairs based on polarity. Hence, we confirmed that van der Waals interactions determined the adsorption behavior. We interpreted the electronic distribution models of the probe-modifying molecules. The functional group configurations inferred the diuron adsorption configurations during contact with each ZnO facet. The adsorption affected characteristics of the reaction intermediates and the rate of degradation.

An Unusually Acidic and Thermally Stable Cesium Titanate Cs xTi2- yM yO4 ( x = 0.67 or 0.70; M = vacancy or Zn).

Proton-free, alkali-containing layered metal oxides are thermally stable compared to their protonic counterparts, potentially allowing catalysis by Lewis acid sites at elevated temperatures. However, the Lewis acidic nature of these materials has not been well explored, as alkali ions are generally considered to promote basic but to suppress acidic character. Here, we report a rare example of an unusually acidic cesium-containing oxide Cs xTi2- yM yO4 ( x = 0.67 or 0.70; M = Ti vacancy □ or Zn). These lepidocrocite-type microcrystals desorbed NH3 at >400 °C with a total acidity of ≲410 µmol g-1 at a specific surface area of only 5 m2 g-1, without the need for lengthy proton-ion exchange, pillaring, delamination, or restacking. The soft and easily polarized Cs+ ion essentially drives the formation of the Lewis acidic site on the surfaces as suggested by IR of sorbed pyridine. The two-dimensional layered structure was preserved after the oxide was employed in the ethanol conversion at 380 °C, the temperature at which the protonic form could have converted to anatase. The structure was also retained after the NH3 temperature-programmed desorption measurement up to 700 °C. The production of ethylene from ethanol, well-known to occur over acid sites, unambiguously confirmed the acidic nature of this cesium titanate.

Ag/Au/Pt trimetallic nanoparticles with defects: preparation, characterization, and electrocatalytic activity in methanol oxidation.

Two series of Ag x /Au/Pt y trimetallic nanoparticles (Ag x Au1Pt2 with x ranging from 1-5 and Ag4Au1Pt y with y ranging from 1-3) were prepared by a sequential chemical reduction method that involved the deposition of Pt on preformed Ag/Au core-shell particles by systematically controlling the amount of Ag, Au, and Pt metal precursor solutions. The structural changes (the diameters and increased surface roughness from the defective features) and absorption patterns (the significant reduction of the peak intensities) of the nanoparticles examined with TEM and UV-vis spectroscopy indicated the selective incorporation of Pt on the Ag/Au nanoparticles regardless of their compositions. In addition, a combination of WDX, XRD, and XPS analyses quantitatively and qualitatively confirmed the successful formation of the Ag x Au1Pt2 and Ag4Au1Pt y trimetallic nanoparticles. Subsequently, these series of nanoparticles were deposited on multi-wall carbon nanotubes (MWCNTs) to evaluate their electrocatalytic property in the methanol oxidation reaction (MOR) as a function of their metal compositions. The results showed that the electrocatalytic activities of all Ag4/Au1/Pt y systems were higher than those of typical Pt on the MWCNTs. In particular, the Ag4Au1Pt2 nanoparticles exhibited the highest electrocatalytic property for the MOR, suggesting the importance of the proper combination of metal constituents and structures to regulate the activity in electrocatalytic systems.

Probing capping mechanisms and polymer matrix loading of biogenic vaterite CaCO3-Ag hybrid through X-ray photoelectron spectroscopy (XPS).

Despite extensive research in the literature, the synthesis of silver nanoparticles (AgNPs) via capping mechanisms remains incompletely understood. This study employs a mechanistic approach to unravel the underlying molecular interactions driving the capping process of biogenic vaterite CaCO3-Ag and explores their interactions with different polymer matrices. X-ray photoelectron spectroscopy (XPS) was used to reveal the capping mechanisms, surface composition alterations, and vaterite polymorph transitions. The oxidation states of AgNPs exhibited distinct changes under different capping agents. The Ag3d spin-orbit splitting profiles revealed the coexistence of Ag+ and Ag0 within CaCO3-Ag, with a significant presence of Ag0 when poly(sodium 4-styrene sulfonate) was employed as the capping agent. Conversely, the use of carboxy methyl cellulose as the capping agent resulted in Ag+ dominance. XPS analysis illuminated the transformation of CaCO3 polymorphs from calcite to vaterite structure, which remained stable following embedding within polymer matrices. Integrating CaCO3-Ag microspheres into polymer matrices and investigating their surface characteristics represents a strategic step toward tailoring material properties for potential applications in active packaging and biomedicine.

Pioneering dielectric materials of Sn-doped Nb0.025Ti0.975O2 ceramics with excellent temperature and humidity stability for advanced ceramic capacitors.

In this study, the rutile TiO2 system, widely acclaimed for its superior properties, was enhanced through co-doping with isovalent Sn4+ ions and 2.5% Nb5+ donor ions, diverging from traditional acceptor doping practices. This novel doping strategy was implemented by employing a conventional solid-state reaction method, resulting in the synthesis of Sn-doped Nb0.025Ti0.975O2 (Sn-NTO) ceramics. These ceramics demonstrated remarkable dielectric characteristics, with a high dielectric constant (ε') ranging from ∼27 000 to 34 000 and an exceptionally low loss tangent between 0.005 and 0.056 at ∼25 °C and 1 kHz. Notably, the temperature coefficient of ε', , aligned with the stringent specifications for X7/8/9R capacitors. Furthermore, the Sn-NTO ceramics exhibited a stable Cp response across various frequencies within a humidity range of 50 to 95% RH, with ΔCp (%) values within ±0.3%, and no hysteresis loop was detected, suggesting the absence of water molecule adsorption and desorption during humidity assessments. This behavior is primarily attributed to the effective suppression of oxygen vacancy formation by the Sn4+ ions, which also affects the grain growth diffusion process in the Sn-NTO ceramics. The observed heterogeneous electrical responses between semiconducting grains and insulating grain boundaries in these polycrystalline ceramics are attributed to the internal barrier layer capacitor effect.

Hydroxy and surface oxygen effects on 5-hydroxymethylfurfural oxidation to 2,5-furandicarboxylic acid on ß-MnO2: DFT, microkinetic and experiment studies.

Manganese dioxide, ß-MnO2, has shown potential in catalyzing the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a monomer of bioplastic polyethylene furanoate (PEF). Herein, the insight into the hydroxy (OH) and surface oxygen effects on the HMF-to-FDCA reaction over ß-MnO2 is clarified through a comprehensive investigation using density functional theory (DFT) calculations, microkinetic modeling, and experiment. Theoretical analyses revealed that both active surface oxygen and OH species (from either base or solvent) facilitate C-H bond breaking and OH insertion, promoting the catalytic activity of ß-MnO2. Microkinetic modeling demonstrated that the FFCA-to-FDCA and DFF-to-FFCA steps are the rate-limiting steps of the hydroxylated and non-hydroxylated surfaces, respectively. These theoretical results agree well with the experiment when water and dimethyl sulfoxide (DMSO) were used as solvents. In addition, the synthesized ß-MnO2 catalyst showed high stability and activity, maintaining stable HMF conversion (≥99 mol%) and high FDCA yield (85-92 mol%) during continuous flow oxidation for 72 hours at pO2 of 1 MPa, 393 K and LHSV of 1 h-1. Thus, considering both hydroxy and surface oxygen species is a new strategy for enhancing the catalytic activity of Mn oxides and other metal oxide catalysts for the HMF-to-FDCA reaction.

Comparison of potassium catalysts on zeolite sodium A and X in transesterification of palm oil and active species specification.

Heterogeneous catalysts consisting of potassium supported on zeolites are active for transesterification, but the effect of zeolite properties is not clearly understood. This work compares catalysts containing 12 wt.% potassium on zeolite sodium A and X (12K/NaA and 12K/NaX) in terms of performance and physicochemical properties. Both catalysts were prepared by ultrasound-assisted impregnation with potassium acetate buffer. 12K/NaA is a better catalyst in transesterification of palm oil, giving a higher biodiesel yield than 12K/NaX in the first run (99.1 ± 0.3 % and 77.9 ± 2.2 %, respectively). From characterization by CO2-TPD, XRD, FTIR, XPS, and SEM-EDS, both catalysts have similar basicity but different dispersion of carbonates and interaction on the zeolites. The 12K/NaA has those species on external surfaces and more monodentate carbonate than 12K/NaX. Ion exchange occurs between potassium ions from the precursor and sodium ions from the zeolite. Moreover, 12K/NaA is more stable, providing higher biodiesel yields in the second and third catalytic cycles.

Magnetic Graphene Oxide Nanocomposites for Selective miRNA Separation and Recovery.

In this study, we developed magnetic graphene oxide composites by chemically attaching Fe3O4 nanoparticles to graphene oxide nanosheets. Characterization techniques, including Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and transmission electron microscopy (TEM), confirmed the successful synthesis of Fe3O4@GO composites with desirable properties. The resulting composites exhibited superparamagnetic behavior, solubility, and compatibility for efficient miRNA separation. Using miR-29a as a model, we demonstrated the effective binding of miR-29a to the magnetic graphene oxide (GO) composites at an optimal concentration of 1.5 mg/mL, followed by a simple separation using magnetic forces. Additionally, the addition of 5.0 M urea enhanced the miRNA recovery. These findings highlight the potential use of our magnetic graphene oxide composites for the efficient separation and recovery of miR-29a, suggesting their broad applicability in various miRNA-based studies. Further exploration can focus on investigating endogenous miRNAs with aberrant expression patterns, contributing to the advancements in precision medicine.

Extremely reduced loss tangent with retaining ultra high dielectric permittivity in Mg2+-doped La1.9Sr0.1NiO4 ceramics.

An extremely reduced loss tangent while retaining ultrahigh dielectric permittivity can be successfully obtained in La1.9Sr0.1NiO4 ceramics by doping with Mg2+ ions. A single phase of La1.9Sr0.1NiO4 was detected in all the sintered ceramics, while the lattice parameters increased with increasing doping concentration, indicating that Mg2+ ions can enter the Ni2+ sites. A highly dense microstructure is achieved. Microstructural analysis revealed that Mg2+ ions disperse well in the microstructure of La1.9Sr0.1NiO4 ceramics. Interestingly, ultra-high dielectric permittivity of approximately 8.11 × 105 at 1 kHz is achieved in the La1.9Sr0.1Ni0.6Mg0.4O4 ceramic, while the loss tangent is significantly reduced by two orders of magnitude compared to the undoped La1.9Sr0.1NiO4 ceramic. The DC conductivity significantly decreased by three orders of magnitude. The giant dielectric responses are described by Maxwell-Wagner polarization and small polaron hopping mechanisms. Thus, the significant reduction in the loss tangent can be attributed to the significantly enhanced resistance of the grain boundaries.

Correction: Effects of Ni precursors on the formation of Mg-Fe-Ni intermetallic hydrides, kinetics, and reversibility.

[This corrects the article DOI: 10.1039/D3RA01914D.].

Fabrication and Characterization of a Polydopamine-Modified Bacterial Cellulose and Sugarcane Filter Cake-Derived Hydroxyapatite Composite Scaffold.

The search for environmentally friendly and sustainable sources of raw materials has been ongoing for quite a while, and currently, the utilization and applications of agro-industrial biomass residues in biomedicine are being researched. In this study, a polydopamine (PDA)-modified bacterial cellulose (BC) and hydroxyapatite (HA) composite scaffold was fabricated using the freeze-drying method. The as-prepared hydroxyapatite was synthesized via the chemical precipitation method using sugarcane filter cake as a calcium source, as reported in a previous study. X-ray diffraction analysis revealed a carbonated phase of the prepared hydroxyapatite, similar to that of the natural bone mineral. Wide-angle X-ray scattering analysis revealed the successful fabrication of BC/HA composite scaffolds, while X-ray photoelectron spectroscopy suggested that PDA was deposited on the surface of the BC/HA composite scaffolds. In vitro cell viability assays indicated that BC/HA and PDA-modified composite scaffolds did not induce cytotoxicity and were biocompatible with MC3T3-E1 preosteoblasts. PDA-modified composite scaffolds showed enhanced protein adsorption capacity in vitro compared to the unmodified scaffolds. On a concluding note, these results demonstrate that agro-industrial biomass residues have the potential to be used in biomedical applications and that PDA-modified BC/HA composite scaffolds are a promising biomaterial for bone tissue engineering.

Effects of Ni precursors on the formation of Mg-Fe-Ni intermetallic hydrides, kinetics, and reversibility.

This work focuses on the effects of Ni precursors (metallic Ni or Mg2NiH4) on the formation of Mg-Fe-Ni intermetallic hydrides as well as their de/rehydrogenation kinetics and reversibility. After ball milling and sintering, the formation of Mg2FeH6 and Mg2NiH4 are found in both samples, while MgH2 is observed only in the sample with metallic Ni. Both samples show comparable hydrogen capacities of 3.2-3.3 wt% H2 during the 1st dehydrogenation, but the sample with metallic Ni decomposes at a lower temperature (ΔT = 12 °C) and shows faster kinetics. Although phase compositions after dehydrogenation of both samples are comparable, their rehydrogenation mechanisms are different. This affects the kinetic properties upon cycling and reversibility. Reversible capacities of the samples with metallic Ni and Mg2NiH4 during the 2nd dehydrogenation are 3.2 and 2.8 wt% H2, respectively, while those during the 3rd-7th cycles reduce to ∼2.8 and 2.6 wt% H2, respectively. Chemical and microstructural characterizations are carried out to explain de/rehydrogenation pathways.