Type-A zeolites with hydroxyapatite surface layers formed by an ion exchange reaction

To enhance adsorption of harmful ions on type-A zeolites (LTA), hydroxyapatite (HAp) thin layers were synthesized on the LTA surface by an ion exchange reaction of Ca²⁺ for NH₄⁺ under hydrothermal treatment. The temperatures and durations in the reactions were varied ranging from 25 to 200 °C and from 1 to 168 h. The samples synthesized were characterized by X-ray diffraction method (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer–Emmet–Teller method (BET). The structure of LTA was not destroyed by the hydrothermal treatments at 25 to 160 °C for 8 h and also at 120 °C for 1 to 72 h. The yield of HAp grown on the LTA surface, synthesized at 120 °C for 8 h, showed a maximum value of 0.82. The morphologies of HAp were dependent mainly on the temperatures. The specific surface area remained unchanged in the treatments at 25 to 40 °C for 8 h, as compared to the specific surface area of Ca-LTA, however up to 80 °C, the value decreased with an increase of exchange temperature.     

Synthesizing carbon nanotubes and carbon nanofibers over supported-nickel oxide catalysts via catalytic decomposition of methane

Supported-NiO catalysts were tested in the synthesis of carbon nanotubes and carbon nanofibers by catalytic decomposition of methane at 550 °C and 700 °C. Catalytic activity was characterized by the conversion levels of methane and the amount of carbons accumulated on the catalysts. Selectivity of carbon nanotubes and carbon nanofiber formation were determined using transmission electron microscopy (TEM). The catalytic performance of the supported-NiO catalysts and the types of filamentous carbons produced were discussed based on the X-ray diffraction (XRD) results and the TEM images of the used catalysts. The experimental results show that the catalytic performance of supported-NiO catalysts decreased in the order of NiO/SiO₂ > NiO/HZSM-5 > NiO/CeO₂ > NiO/Al₂O₃ at both reaction temperatures. The structures of the carbons formed by decomposition of methane were dependent on the types of catalyst supports used and the reaction temperatures conducted. It was found that Al₂O₃ was crucial to the dispersion of smaller NiO crystallites, which gave rise to the formation of multi-walled carbon nanotubes at the reaction temperature of 550 °C and a mixture of multi-walled carbon nanotubes and single-walled carbon nanotubes at 700 °C. Other than NiO/Al₂O₃ catalyst, all the tested supported-NiO catalysts formed carbon nanofibers at 550 °C and multi-walled carbon nanotubes at 700 °C except for NiO/HZSM-5 catalyst, which grew carbon nanofibers at both 550 °C and 700 °C.     

Decomposition of nonionic surfactant on a nitrogen-doped photocatalyst under visible-light irradiation

A visible-light-active N-containing TiO₂ photocatalysts were prepared from crude amorphous titanium dioxide by heating amorphous TiO₂ in gaseous NH₃ atmosphere. The calcination temperatures ranged from 200 to 1000 °C, respectively. UV–vis/DR spectra indicated that the N-doped catalysts prepared at temperatures <400 °C absorbed only UV light (E_g = 3.3 eV), whereas samples prepared at temperatures ≥400 °C absorbed both, UV (E_g = 3.10–3.31 eV) and vis (E_g = 2.54–2.66 eV) light. The chemical structure of the modified photocatalysts was investigated using FT-IR/DRS spectroscopy. All the spectra exhibited bands indicating nitrogen presence in the catalysts structure. The photocatalytic activity of the investigated catalysts was determined on a basis of a decomposition rate of nonionic surfactant (polyoxyethylenenonylphenol ether, Rokafenol N9). The most photoactive catalysts were those calcinated at 300, 500 and 600 °C. For the catalysts heated at temperatures of 500 and 600 °C Rokafenol N9 removal was equal to 61 and 60%, whereas TOC removal amounted to 40 and 35%, respectively. In case of the catalyst calcinated at 300 °C surfactant was degraded by 54% and TOC was removed by 35%. The phase composition of the most active photocatalysts was as follows: (a) catalyst calcinated at 300 °C—49.1% of amorphous TiO₂, 47.4% of anatase and 3.5% of rutile; (b) catalyst calcinated at 500 °C—7.1% of amorphous TiO₂, 89.4% of anatase and 3.5% of rutile; (c) catalyst calcinated at 600 °C—94.2% of anatase and 5.8% of rutile.     

Microwave enhanced synthesis of MOF-5 and its CO2 capture ability at moderate temperatures across multiple capture and release cycles

The metal-organic framework, MOF-5 (Zn₄O(BDC)₃), was prepared using solvothermal synthesis under microwave irradiation, followed by solvent exchange to improve molecular stability at high temperatures, and assessed for its ability to capture CO₂ at ambient pressure and temperatures up to 300 °C. The reaction product was characterised by X-ray diffraction, scanning electron microscope, N₂ physisorption, thermogravimetric analysis and CO₂ physisorption. Cyclic CO₂ physisorption showed the capacity of the MOF-5 crystals to be 3.61 wt% when cycled between 30 °C and 300 °C through 10 separate capture and release cycles. Above 400 °C MOF-5 underwent thermal decomposition and was no longer capable of capturing CO₂.     

Production of hydrogen and MWCNTs by methane decomposition over catalysts originated from LaNiO3 perovskite

LaNiO₃ type perovskite was prepared by the “self-combustion” method and was used as catalyst precursor for the methane decomposition reaction at 600 and 700 °C. CH₄ conversion reaches 80% at 700 °C and 65% at 600 °C using pure CH₄. The yield of CNT and H₂ were 2.2 g_CNT g^?1 h^?1 and 8.2 L g^?1 h^?1 at 700 °C respectively after 4 h of reaction. When the reaction is prolonged to 22 h the catalytic activity decreases but the catalyst is still active, the production of hydrogen reaches 63.5 L (STP) per gram of catalyst and the production of MWCNT was equal to 17 g per gram of catalyst.Multi-wall carbon nanotubes were characterized by X-ray diffraction (XRD), surface area (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and Raman spectroscopy. TEM micrographs showed that MWCNT longer than 20 μm were formed with inner diameters ranging from 5 to 16 nm and outer diameters up to about 40 nm.The results obtained here clearly show that the use of the perovskite LaNiO₃ as catalytic precursor is very effective for the simultaneous production of carbon nanotubes and hydrogen.     

Experimental study on the stability of graphitic C3N4 under high pressure and high temperature

The stability and decomposition of graphitic C₃N₄ (g-C₃N₄) were studied in the pressure and temperature range of 10–25 GPa and up to 2000 °C by multi-anvil experiments and phase characterization of the quenched products. g-C₃N₄ was found to remain stable at relatively mild temperatures, but decomposes to graphite and nitrogen at temperatures above 600–700 °C and up to 15 GPa, while it decomposes directly to diamond (plus nitrogen) above 800–900 °C and between 22 and 25 GPa. The estimated decomposition curve for g-C₃N₄ has a positive slope (~ 0.05 GPa/K) up to ~ 22 GPa, but becomes inverted (negative) above this pressure. The diamond formed through decomposition is characterized by euhedral crystals which are not sintered to each other, but loosely aggregated, suggesting the crystallization in a liquid (nitrogen) medium. The nitrogen release from the graphitic CN framework may also play an important role in lowering the activation energy required for diamond formation and enhancing the grain growth rate. No phase transition of g-C₃N₄ was found in the studied P–T range.     

Effect of NiS addition on nitridation of alumina to aluminum nitride using polymeric carbon nitride as a nitridation reagent

We investigated the effect of adding nickel(II) sulfide (NiS) on nitridation of alumina (Al₂O₃) to aluminum nitride (AlN) using polymeric carbon nitride (PCN), which was synthesized by polymerization of dicyandiamide at 500 °C. The product powders obtained from nitridation of a mixture of δ-Al₂O₃ and NiS powders (mole ratio of 1:0.01) at various reaction temperatures were characterized by powder X-ray diffraction, ²⁷Al magic-angle spinning nuclear magnetic resonance, and Raman spectroscopy. δ-Al₂O₃ began to convert to AlN at 900 °C and completely converted to AlN at 1300 °C. The as-synthesized sample powders contained nitrogen-doped carbon microtubes (N-doped CMTs) with a length of several tens of mm and thickness of ca. 3 µm. The addition of NiS to δ-Al₂O₃ resulted in the enhancement of the amount of N-doped CMTs and nitridation rate, which might be due to the catalytic action of Ni particles on the thermal decomposition of vaporized PCN. The change in Raman spectra with reaction temperatures indicated that the crystallinity of N-doped CMTs was increased by calcining at higher reaction temperatures.     

Wear damage of Si3N4-graphene nanocomposites at room and elevated temperatures

Mechanical and tribological properties of nanocomposites with silicon nitride matrix with addition of 1 and 3 wt.% of multilayered graphene (MLG) platelets were studied and compared to monolithic Si₃N₄. The wear behavior was observed by means of the ball-on-disk technique with a silicon nitride ball used as the tribological counterpart at temperatures 25 °C, 300 °C, 500 °C, and 700 °C in dry sliding. Addition of such amounts of MLG did not lower the coefficient of friction. Graphene platelets were integrated into the matrix very strongly and they did not participate in lubricating processes. The best performance at room temperature offers material with 3 wt.% graphene, which has the highest wear resistance. At medium temperatures (300 °C and 500 °C) coefficient of friction of monolithic Si₃N₄ and composite with 1%MLG reduced due to oxidation. Wear resistance at high temperatures significantly decreased, at 700 °C differences between the experimental materials disappeared and severe wear regime dominated in all cases.     

Microstructure and mechanical properties of the spark plasma sintered Ta2C ceramics

Single phase hexagonal α-Ta₂C ceramics were synthesized by spark plasma sintering and using TaC and Ta as the starting powders. Effects of sintering temperatures and holding times on the densification process, phase formation, microstructure development, and mechanical properties of the α-Ta₂C ceramics were investigated. Densification occurred in the temperature range of 1520–1675 °C in less than 2.5 min. But completion of the Ta₂C formation took about 40 min at 1500 °C, and 5 min at 1900 °C. The materials sintered at 1500 °C consisted of fine equiaxed grains. The Ta₂C grains grew anisotropic to form an elongated self-toughening microstructure at 1700 °C. At 1900 °C, the neighboring Ta₂C individual crystals coalesced to form large Ta₂C blocks to entrap the residual pores. Although higher flexural strength and fracture toughness were reached at 1700 °C, the unstable microstructures of the Ta₂C materials indicated limited applications at high temperatures.     

Non-catalytic vanadium removal from vanadyl etioporphyrin (VO-EP) using a mixed solvent of supercritical water and toluene: A kinetic study

Reaction kinetics and mechanisms of the decomposition of vanadyl etioporphyrin (VO-EP), the most common metal compounds present in heavy crude, were studied in a mixed solvent of supercritical water (SCW) and toluene without the addition of any catalyst, H₂ or H₂S to remove vanadium. The aim of this study was to remove vanadium an environmentally benign way from VO-EP at a high extent and in a short reaction time. The experiments were conducted in an 8.8 mL batch reactor fabricated from Hastelloy C-276. The capability of SCW to remove vanadium from VO-EP was discovered at temperatures of 410–490 °C and a water partial pressure (WPP) of 25 MPa. Experimental results revealed that the overall VO-EP conversion was 90.51% at a temperature of 490 °C, WPP of 25 MPa and reaction time of 180 min. Under the same reaction conditions, approximately 80.26% vanadium was removed by reaction with SCW. The global reaction followed first order kinetics, with Arrhenius parameters of activation energy 8.93 kcal/mol and a pre-exponential factor 5.66 s^?1. A kinetic model of demetallation that well-fit the experimental results, was proposed. The reaction kinetics may be critically explained in terms of free radical mechanism. The obtained results suggest that SCW is capable of removing vanadium from VO-EP.     

Thermal cycling induced capacity enhancement of graphite anodes in lithium-ion cells

Graphite electrodes were electrochemically cycled in Li-ion cells at 50 and 60 °C in order to determine the changes in their surface properties in comparison to the electrodes tested at 25 °C. A 17% drop in planar capacity occurred during the first cycle at 60 °C compared to a 40% at 25 °C and reduced the amount of damage that occurred to graphite due to a rapidly formed solid electrolyte interphase (SEI). During the following cycles, a planar capacity of 3.11 ± 0.12 mAh cm⁻² was attained at 60 °C rather than 0.53 ± 0.03 mAh cm⁻² at 25 °C. The SEI layer formed at 60 °C predominantly consisted of Li₂CO₃ and was devoid of residual LiClO₄ detected at 25 °C. At 25 °C, the diffusion coefficient of Li⁺ (D_Li⁺) was calculated as 1.07 × 10⁻⁸ cm² s⁻¹, whereas at 60 °C, D_Li⁺ increased to 3.25 × 10⁻⁸ cm² s⁻¹. A pre-treatment conducted at 60 °C enhanced the cyclic performance of graphite subsequently cycled at 25 °C; a Li₂CO₃-enriched SEI, generated during the 60 °C pre-treatment, covered the graphite surface uniformly and resulted in a 28% increase in battery capacity at 25 °C.     

Degradation of plasma-sprayed yttria-stabilized zirconia coatings via ingress of vanadium oxide

V₂O₅ reaction and melt infiltration in plasma-sprayed 7 wt% Y₂O₃–ZrO₂ (YSZ) coatings were investigated at temperatures ranging from 750 °C to 1200 °C using SEM and TEM combined with EDS. The interlamellar pores and intralamellar cracks, common in plasma-sprayed materials, provide pathway for the molten species. The microstructure of the contaminated coatings is therefore the result of the interplay between the dissolution/reaction rates of the V₂O₅ with YSZ coating and the infiltration rates of the molten species. Near the coating surface, the reaction front proceeds in a planar fashion, via dissolution of the lamella and precipitation of fine-grained reaction products composed of ZrV₂O₇ (for reactions at 750 °C and below), m-ZrO₂ and YVO₄. The thickness of this planar reaction zone or PRZ was found to increase as reaction time and temperature increased. The melted V₂O₅ was observed to infiltrate along the characteristic microstructure of plasma-sprayed coatings, i.e. the interconnected pores and cracks, and react with the YSZ. The thickness of this melt infiltrated reaction zone or MIRZ ranged from 5 μm for reactions at 750 °C for 30 min to 130 μm for reactions at 1000 °C for 90 min. At 1200 °C, only a PRZ was observed (i.e. the thickness of the MIRZ was nominally zero), suggesting that the dissolution reaction within the pores/cracks and subsequent formation of reaction products may limit infiltration. Fifty-hour heat-treatments at 1000 °C and 1200 °C prior to reaction with the V₂O₅ at 800 °C for 90 min were used to change the microstructural features of the coating, such as crack connectivity and pore size. The heat-treatment at 1000 °C was found most deleterious to the coating due to large cracks created via a desintering process that afforded deep penetration of the molten V₂O₅.     

The resistance to oxidation of an HfB2–SiC composite

The oxidation resistance of an hot-pressed HfB₂–SiC composite was studied through non-isothermal and isothermal treatments at temperatures up to 1600 °C in air. The most severe oxidation conditions consisted of repeated heating-cooling cycles at 1600 °C for up to 80 min of exposure. A thermogravimetric test for over 20 h at 1450 °C provided evidence that, at this temperature, the oxidation kinetics fits a paralinear law until 10 h, when a partial rupture of external oxide scale occurs (i.e. a break-away reaction). Afterwards, the weight gain data fit a linear law. The main secondary phases formed in the composite during hot-pressing, namely BN, Hf(C,N) and a Si-based compound, although in limited amounts, influenced the oxidation resistance at temperatures below 1350 °C. At temperatures higher than about 1400 °C, the presence of SiC particles markedly improved the oxidation resistance due to the formation of a protective borosilicate glassy coating on the exposed surfaces.     

Effects of precursor chemistry and thermal treatment conditions on obtaining phase pure bismuth ferrite from aqueous gel precursors

Phase pure BiFeO₃ powders are synthesized by an entirely aqueous solution–gel route, starting from water soluble Fe(III) nitrate or citrate, and Bi(III) citrate as precursors. In order to obtain stable solutions, which transform to homogeneous gels upon drying, the pH is adjusted to 7 and a citric acid content equimolar to the metal ions is selected.The presence of nitrate strongly accelerates the thermo-oxidative decomposition step of the precursor gel around 200 °C, and the decomposition is finished at a lower temperature for the nitrate containing precursor (460 °C) than without nitrates (500 °C) in dynamic dry air. An oxidative ambient is required to fully decompose the precursor.The presented synthesis allows very low temperature (400 °C) crystallization of BiFeO₃ together with a secondary phase, as shown by high temperature XRD. This parasitic phase remains up to high temperatures, where decomposition of BiFeO₃ is observed from 750 °C onwards, and Bi₂Fe₄O₉ is formed. However, optimization of the furnace treatment, considering anneal temperatures and heating rates showed that phase pure BiFeO₃ can be obtained, with the heating rate being the crucial factor (5 °C/min). The chemical purity of the powders is confirmed by FTIR, and the antiferromagnetic to paramagnetic phase transition is demonstrated by DSC measurements.     

Reaction joining of SiC ceramics using TiB2-based composites

SiC ceramics were reaction joined in the temperature range of 1450–1800 °C using TiB₂-based composites starting from four types of joining materials, namely Ti–BN, Ti–B₄C, Ti–BN–Al and Ti–B₄C–Si. XRD analysis and microstructure examination were carried out on SiC joints. It is found that the former two joining materials do not yield good bond for SiC ceramics at temperatures up to 1600 °C. However, Ti–BN–Al system results in the connection of SiC substrates at 1450 °C by the formation of TiB₂–AlN composite. Furthermore, nearly dense SiC joints with crack-free interface have been produced from Ti–BN–Al and Ti–B₄C–Si systems at 1800 °C, i.e. joints TBNA80 and TBCS80, whose average bending strengths are measured to be 65 MPa and 142 MPa, respectively. The joining mechanisms involved are also discussed.     

Hierarchically structured polymer-derived ceramic fibers by electrospinning and catalyst-assisted pyrolysis

Hierarchically structured polymer-derived ceramic fibers were successfully produced by electrospinning a commercially available preceramic polymer to which a cobalt-based catalyst precursor was added, followed by pyrolysis in nitrogen at temperatures ranging from 1250 to 1400 °C. The nanowires formed via the vapor–liquid–solid (VLS) mechanism, involving the reaction of SiO and CO gases, generated from the decomposition of the polymer-derived-ceramic at high temperature, with the heating atmosphere assisted by the presence of nano-sized CoSi droplets. The main crystalline phase for the nanowires was Si₃N₄ below 1350 °C, and Si₂N₂O at 1400 °C, and the amount of nanowires increased with increasing heating temperature. Hierarchically structured fiber mats possessed a higher specific surface area (14.45 m²/g) than that of a sample produced without the cobalt catalyst (4.37 m²/g).     

Microstructure evolution during air bonding of Al2O3 to Al2O3 joints using bismuth–borate–zinc glass

Alumina ceramics with 95 wt.% purity were sealed together using a bismuth based glass, 40Bi₂O₃–40B₂O₃–20ZnO (mol.%). The wettability of the glass on the Al₂O₃ substrate was investigated. The results showed a contact angle of ≤36.5° was achieved when the temperature was ≥630 °C. Subsequently, sealing cycles were performed at temperatures of 520–700 °C for 30 min. The dependence of microstructure evolution of the joints on temperature was investigated. Bi₂₄B₂O₃₉ was detected to be the product in the joints sealed at 530–580 °C, while ZnAl₂O₄ was identified to be the main product when sealing at temperature of ≥650 °C due to the reaction between the Al₂O₃ substrate and ZnO from the glass. The influence of dwelling time at 700 °C on microstructure evolution of the joints was also studied. The results showed that the size of ZnAl₂O₄ increased with increasing holding time.     

Spontaneous nucleation of diamond in the system MgCO3–CaCO3–C at 7.7 GPa

High-pressure and high-temperature experiments were carried out to determine the minimum temperature required for spontaneous nucleation of diamond in the system comprising a carbonate mixture (60 mol% MgCO₃ and 40 mol% CaCO₃) and graphite at 7.7 GPa, for 1 h and longer reaction times up to 12.5 h, and also in the systems MgCO₃–graphite and CaCO₃–graphite for comparison. The above carbonate mixture melted at a temperature between 1600°C and 1700°C. The minimum temperature for spontaneous nucleation of diamond was 1900°C for a reaction time of 1 h; it was lowered to 1700°C for 11 h, but no diamond was formed at 1600°C for 12.5 h. These results indicate that the molten state of the solvent-catalyst and enough reaction time are necessary for diamond nucleation in the systems examined at 7.7 GPa.     

Micronization and characterization of squid lecithin/polyethylene glycol composite using particles from gas saturated solutions (PGSS) process

Lecithin was isolated from squid viscera residues after supercritical carbon dioxide (SC-CO₂) extraction at 25 MPa and 45 °C. The particle formation of squid lecithin with biodegradable polymer, polyethylene glycol (PEG) was performed by PGSS using SC-CO₂ in a thermostatted stirred vessel. By applying different temperatures (40 and 50 °C) and pressures (20–30 MPa), conditions were optimized. Two nozzles of different diameters (250 and 300 μm) were used for PGSS and the reaction time was 1 h. The average diameter of the particles obtained by PGSS at different conditions was about 0.74–1.62 μm. The lowest average size of lecithin particle with PEG was found by the highest SC-CO₂ density conditions with the stirring speed of 400 rpm and nozzle size of 250 μm. The inclusion of lecithin in PEG was quantified by HPLC. Acid value and peroxide value was measured after micronization of lecithin.     

Synthesis and characterization of nanometric gadolinia powders by room temperature solid-state displacement reaction and low temperature calcination

Nanometric-sized gadolinia (Gd₂O₃) powders were obtained by applying solid-state displacement reaction at room temperature and low temperature calcination. The XRD analysis revealed that the room temperature product was gadolinium hydroxide, Gd(OH)₃. In order to induce crystallization of Gd₂O₃, the subsequent calcination at 600 ∼ 1200 °C of the room temperature reaction products was studied. Calculation of average crystallite size (D) as well as separation of the effect of crystallite size and strain of nanocrystals was performed on the basic of Williamson-Hall plots. The morphologies of powders calcined at different temperatures were followed by scanning electron microscopy. The pure cubic Gd₂O₃ phase was made at 600 °C which converted to monoclinic Gd₂O₃ phase between 1400° and 1600 °C. High-density (96% of theoretical density) ceramic pellet free of any additives was obtained after pressureless sintering at 1600 °C for 4 h in air, using calcined powder at 600 °C.