Effects of PTFE activation and carbon sources on combustion synthesis of Cr2AlC/Al2O3 composites

Formation of Cr₂AlC/Al₂O₃ in situ composites was investigated by self-propagating high-temperature synthesis (SHS) involving both PTFE activation and aluminothermic reduction. In addition to Al and Cr₂O₃ as the starting materials, carbon black, graphite, and Al₄C₃ were used as the carbon sources. PTFE was employed not only as a reaction promoter, but also as a carburizing agent. Depending on different sources of carbon, the threshold amounts of PTFE for inducing self-sustaining combustion were 1.5, 4.0, and 3.0 wt% for the samples adopting carbon black, graphite, and Al₄C₃, respectively. The combustion front velocity and temperature increased with increasing PTFE content. Moreover, the sample using carbon black was the most exothermic, while the Al₄C₃-based sample was the least. For the powder compacts adopting carbon black or graphite, Cr₂AlC/Al₂O₃ composites were produced with no impurities. Due to relatively weak reaction exothermicity, however, the synthesized composites containing small amounts of Cr₇C₃ and Al₄C₃ were obtained from the Al₄C₃-based reaction scheme.     

Electrochemical oxidation of organics at metal oxide electrodes: The incineration of oxalic acid at IrO2-Ta2O5 (DSA-O2) anode

The electrochemical incineration of oxalic acid (OA) at Ti/IrO₂-Ta₂O₅ (DSA-O₂) anode was investigated to find the influence of the operative parameters on the performances of the process. Polarization curves and chronoamperometric measurements indicate the probable occurrence of a direct electrochemical oxidation of OA at the surface of the DSA anode. In incineration electrolyses, the performances of the process in terms of OA conversion and current efficiency dramatically depend on the adopted operative conditions. Interestingly, very high OA removal and current efficiency were obtained when the process was performed at relatively high temperatures (50 °C) or in the presence of NaCl. The experimental results are in good agreement with the previsions of a simple theoretical model previously developed.     

Fe2O3/Al2O3 catalysts for the N2O decomposition in the nitric acid industry

Fe₂O₃ catalysts supported on Al₂O₃ were used to remove nitrous oxide from the nitric acid plant simulated process stream (containing O₂, NO and H₂O). Catalysts were prepared by the coprecipitation method and were characterized for their physico-chemical properties by BET, XRD, AFM and TPR analysis. A strong influence of the post-preparation heating conditions on the structural and catalytic properties of the catalysts has been evidenced. Laboratory tests revealed 95% conversion of N₂O at temperature 750 °C and a slight decrease in activity in the presence of H₂O and NO. The catalysts were inert towards decomposition of NO. The pilot-plant reactor and real plant studies (up to 3300 h time-on-stream) confirmed high activity and very good mechanical stability of the catalysts as well as no decomposition of nitric oxide.     

N2O5/HNO3体系中硝解DADN的反应动力学

采用高效液相色谱跟踪检测了不同温度条件下N₂O₅/HNO₃体系硝解DADN时反应底物、中间体和产物浓度随时间的变化情况。通过对303、313、323、333 K温度下实验数据的分析,计算得到各步的反应速率常数,并最终求得DADN到SEX和SEX到HMX两步的反应活化能分别为2.3996×10⁴ J·mol^-1和1.6598×10⁴ J·mol^-1,指前因子分别为2.2000×10⁴ h^-1和6.5178×10² h^-1。同时,通过柱分离得到的中间产物经结构鉴定为SEX,对其硝基机理进行了分析,实验证明DADN的硝解反应分两步进行,是一级连串反应过程,控制步骤是SEX到HMX。     

Electrochemical properties of bare and Ta-substituted Nb2O5 nanostructures

In this work, bare and Ta-substituted Nb₂O₅ nanofibers are prepared by electrospinning followed by sintering at temperatures in the 800–1100 °C range for 1 h in air. Obtained bare and Ta-substituted Nb₂O₅ polymorphs are characterized by X-ray diffraction, scanning electron microscopy, density measurement, and Brunauer, Emmett and Teller surface area. Electrochemical properties are evaluated by cyclic voltammetry and galvanostatic techniques. Cycling performance of Nb₂O₅ structures prepared at temperature 800 °C, 900 °C, and 1100 °C shows following discharge capacity at the end of 10th cycle: 123, 140, and 164 (±3) mAh g⁻¹, respectively, in the voltage range 1.2–3.0 V and at current rate of 150 mA g⁻¹ (1.5 C rate). Heat treated composite electrode based on M-Nb₂O₅ (1100 °C) in argon atmosphere at 220 °C, shows an improved discharge capacity of 192 (±3) mAh g⁻¹ at the end of 10th cycle. The discharge capacity of Ta-substituted Nb₂O₅ prepared at 900 °C and 1100 °C showed a reversible capacity of 150, 202 (±3) mAh g⁻¹, respectively, in the voltage range 1.2–3.0 V and at current rate of 150 mA g⁻¹. Anodic electrochemical properties of M-Nb₂O₅ deliver a reversible capacity of 382 (±5) mAh g⁻¹ at the end of 25th cycle and Ta-substituted Nb₂O₅ prepared at 900 °C, 1000 °C and 1100 °C shows a reversible capacity of 205, 130 and 200 (±3) mAh g⁻¹ (at 25th cycle) in the range, 0.005–2.6 V, at current rate of 100 mA g⁻¹.     

XPS study of Li ion intercalation in V2O5 thin films prepared by thermal oxidation of vanadium metal

The intercalation and deintercalation mechanisms of lithium into V₂O₅ thin films prepared by thermal oxidation of vanadium metal have been studied by X-ray photoelectron spectroscopy (XPS) using a direct anaerobic and anhydrous transfer from the glove box (O₂ and H₂O < 1ppm), where the samples were electrochemically treated, to the XPS analysis chamber. Vanadium in the as-prepared oxide films is mostly (from 93 to 96% depending on samples) in a pentavalent state (V⁵⁺) with a stoichiometric O/V concentration ratio fitting that of V₂O₅. Four to seven percent of VO₂ is also observed. After the 1st and the 2nd intercalation steps at E = 3.3 and 2.8 V versus Li/Li⁺, respectively, the V2p core level spectra evidence a partial reduction to V⁴⁺ states with a remaining concentration of 73 and 56% of V⁵⁺, in agreement with the intercalation of about 1/2 mol of Li per V₂O₅ mol at each intercalation step. Intercalated lithium was observed at a binding energy of 56.1 eV for Li1s. Changes of the electronic structure of the V₂O₅ thin film after intercalation are evidenced by the observation, at a binding energy of 1.3 eV, of occupied V3d states (V⁴⁺) originally empty in the pristine film (V⁵⁺). The V2p and Li1s core level spectra show that the process of Li intercalation is partially irreversible. In the first cycle, 34 and 14% of the vanadium ions remain in the V⁴⁺ state after deintercalation at E = 3.4 and 3.8 V versus Li/Li⁺, respectively, indicating a partially irreversible process already after the 1st deintercalation. The analyses of C1s and O1s XP spectra show the formation of a solid-electrolyte interface (SEI). The analyzed surface layer includes lithium carbonate and Li-alkoxides.     

Solid-phase combustion synthesis of calcium aluminate with CaAl2O4 nanofiber structures

Calcium aluminate with CaAl₂O₄ (CA) nanofiber structures was fabricated through a facile solid-phase combustion synthesis method with raw materials of CaO₂, CaCO₃, Al, and Al₂O₃ in Ar atomosphere at a pressure of 0.1 MPa. The results indicated that the relative content of CA decreased, but that of Ca₁₂Al₁₄O₃₃ (C₁₂A₇) increased with the increase of r-value from 0 to 0.5 (r is molar substitution coefficient of CaCO₃ for CaO₂). Interestingly, CA nanofibers with tens of micrometers in length and about 200 nm in diameter were observed in the combustion products with r = 0.2, 0.3, 0.4, respectively. The more nanofibers can be found in the products, as the content of CaCO₃ in raw material ratios increased. And the yield of nanofibers in the combustion product with r = 0.4 is the highest. The typical round droplet on head of nanofiber indicated that the growth process of nanofibers was governed by vapor-liquid-solid (VLS) mechanism with base growth mode. It is proposed that both higher reaction temperature and reducing atmosphere are requirements for the growth of CA nanofiber during the process of combustion synthesis. The nanofiber cannot be generated in the samples r0, and r5, because the gaseous Ca is absent due to oxidizing atmosphere and lower reaction temperature, respectively.     

Hydrothermal synthesis of vanadium oxide nanotubes from V2O5 gels

Vanadium oxide nanotubes (VO_x-NT) have been synthesized in high yield by adding hexadecylamine to V₂O₅·nH₂O gels, followed by a hydrothermal treatment (150–180 °C, 2–7 days). Scanning electron microscopy (SEM) and X-ray diffraction analysis have been performed to optimize the temperature and reaction time required for formation of VO_x-NT and the morphology of the nanotubes investigated by transmission electron microscopy (TEM).     

Hydrophobicity and transparency of Al2O3-based poly-tetra-fluoro-ethylene composite thin films using aerosol deposition

Alumina and polytetrafluoroethylene (Al₂O₃-PTFE) composite films were fabricated by a simple aerosol deposition (AD) process, to confirm its applicability for various display screens requiring water resistant, anti-smudge and easy-to-clean properties. The surface morphologies, hydrophobic properties, and transparencies of the composite films with different PTFE contents, varying from 0.01 to 1?wt% were investigated. As a result, the composite films with over 0.3?wt% PTFE showed a sudden rise in surface roughness and low transmittance, despite having the highest contact angle of 128° at a PTFE content of 0.3?wt%. From the energy dispersive spectrometer analysis, the crash-cushioning effect of PTFE and agglomerated PTFE particles were determined to be major causes of surface roughness and opacity. In contrast, the transmittance showed a tendency to be enhanced, with an increasing PTFE content in the range of 0.01, 0.05, and 0.1?wt% PTFE, respectively. Especially, the film with 0.1?wt% of PTFE had contact angle of 111° and exhibited a high transmittance of over 75%, which was inferred to be an appropriate amount of PTFE, with a high elongation filling up the surface and the internal defects, leading to an enhancement of transparency. Consequently, these results implied that the AD-prepared Al₂O₃-PTFE composite coatings are promising candidates for various display applications.     

Sol-gel synthesis and characterization of ZnAl2O4 powders for transparent ceramics

The sol-gel synthesis of ZnAl₂O₄ ceramic powders from alkoxide and acetate sources of metals, as well as the microstucture and the hardness of the hot-pressed ZnAl₂O₄ specimens were considered. ZnAl₂O₄ powders were prepared by the hydrolysis of an alcohol solution of aluminium isopropoxide using an aqueous solution of zinc acetate followed by heat treatment. The thermal evolution of the ZnAl₂O₄ precursor was investigated. The effect of calcination temperature on the morphology and the specific surface area of ZnAl₂O₄ powders were also studied. The sintering of the resultant powders to the high transparent ceramic using a hot pressing with 1?wt% ZnF₂, as a sintering additive was successfully demonstrated. The in-line transmittance of ZnAl₂O₄ ceramics (1?mm thickness) achieved 80% in the visible region and 85% at 5?µm; Vickers hardness was 11.6?GPa.     

Electrochemical modification of the catalytic properties of composite membranes of substituted Bi4V2O11 (BIMEVOX) for propane oxidation in a catalytic dense membrane reactor

Dense BICOVOX membrane, bulk BICOVOX/Au cermet membrane and BICOVOX membrane with a BICOVOX/Au cermet on its surfaces are investigated in the partial oxidation of propane under open circuit voltage (OCV) and under electrical bias at 700 °C. The propane conversion remains in the range 10–12% whatever the conditions of polarisation. Mostly cracking products are observed. Hydrogen is the main product with a selectivity around 55–60%. At OCV, no product of oxidation is detected except water which can not be quantified. On the membrane with BICOVOX/Au cermet electrodes on surface, traces of CO are observed as well as a small increase of propylene content under anodic polarisation. This can be explained by partial oxidation and oxidative dehydrogenation of propane, respectively. An anodic polarisation leads to a decrease of hydrogen due to its oxidation into water. In contrast, an increase of the hydrogen content is observed under cathodic polarisation. The effects on the membrane are modest, but they show the possibility that such a system offers for modifying the catalytic properties of membrane materials in a CDMR.     

Self-organized porous titanium oxide prepared in Na2SO4/NaF electrolytes

The anodic formation of nanoporous TiO₂ on titanium was investigated in Na₂SO₄ electrolytes containing low concentrations of NaF (0.1-1 wt.%). It was found that under optimized electrolyte conditions and extended polarization, a self-organized nanostructure consisting of porous TiO₂ is obtained. The porous structure is arranged in sections of arrays with single pore diameters of typically 100 nm and an average spacing of 150 nm. The pores are open at the top and covered by oxide at the bottom. Compared with earlier work, we show that using a neutral NaF electrolyte significantly thicker porous layers can be obtained than in acidic solutions.     

Limonene oxidation over V2O5/TiO2 catalysts

Vanadia-titania catalysts prepared by different sol–gel procedures were studied as heterogeneous catalysts for the liquid phase oxidation of limonene. The catalysts were characterized by XRD, XPS, ICP and nitrogen adsorption. According to the XRD results the catalyst samples can be divided in two different groups: anatase samples and anatase + rutile samples. XRD signals of vanadia are not found in the diffractograms.

The main reaction products are polymers. Limonene oxide, limonene glycol, carveol and carvone are obtained in small amounts. A number of autoxidation products, alcohols, aldehydes and ketones, are also obtained.

The effects of titania composition on the reaction orientation are discussed.     

Electrochemical performance of single crystalline spinel LiMn2O4 nanowires in an aqueous LiNO3 solution

Single crystalline cubic spinel LiMn₂O₄ nanowires were synthesized by hydrothermal method and the precursor calcinations. The phase structures and morphologies were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). Galvanostatic charging/discharging cycles of as-prepared LiMn₂O₄ nanowires were performed in an aqueous LiNO₃ solution. The initial discharge capacity of LiMn₂O₄ nanowires was 110 mAh g⁻¹, and the discharge capacity was still above 100 mAh g⁻¹ after 56 cycles at 10C-rate, and then 72 mAh g⁻¹ was registered after 130 cycles. This is the first report of a successful use of single crystalline spinel LiMn₂O₄ nanowire as cathode material for the aqueous rechargeable lithium battery (ARLB).     

The distribution of lithium intercalated in V2O5 thin films studied by XPS and ToF-SIMS

The distribution of lithium in V₂O₅/V lower oxide duplex thin films prepared by thermal oxidation of V metal was analysed by XPS and ToF-SIMS after intercalation at 2.8 V versus Li/Li⁺ and de-intercalation at 3.8 V following cycling between 3.8 and 2.8 V in 1 M LiClO₄-PC. XPS analysis of the intercalated thin film evidenced a partial reduction (43 at.% V⁴⁺) of the V₂O₅ surface, the modification of its electronic structure and the presence of Li, consistent with the formation of the δ-Li_xV₂O₅ (0.9 ≤ x ≤ 1) phase. The Li in-depth distribution measured by ToF-SIMS shows a maximum in the outer layer of V₂O₅, but Li is also found at the oxide film/metal substrate interface indicating its diffusion across the inner layer of V lower oxides. The analyses performed after de-intercalation on the samples cycled 12, 120 and 300 times reveal the effect of aging on the trapping of lithium. A significant reduction (17-22 at.% V⁴⁺) of the V₂O₅ surface was measured after 300 cycles. The Li in-depth distribution shows a maximum at the interface between the outer layer of V₂O₅ and the inner layer of lower oxides. Aging favours the accumulation of lithium at this interface with a resulting enlarged distribution enriching the sub-surface of the outer layer of V₂O₅ and the inner layer of lower oxides after 300 cycles. Lithium is also found, but in smaller quantities, at the oxide film/metal substrate interface. Measurements performed in the non-electrochemically treated surface areas of the de-intercalated samples revealed the same type of modifications, evidencing the diffusion of lithium along the interfaces where it is trapped.     

Evidence of redox interactions between polypyrrole and Fe3O4 in polypyrrole-Fe3O4 composite films

The electrical properties of conducting polymers make them useful materials in a wide number of technological applications. In the last decade, an important effect on the properties of the conducting polymer when iron oxides particles are incorporated into the conductive matrix was shown. In the present study, films of polypyrrole were synthesized in the presence of magnetite particles. The effect of the magnetite particles on the structure of the polymer matrix was determined using Raman spectroscopy. Mass variations at different concentrations of Fe₃O₄ incorporated into the conducting matrix were also measured by means of quartz crystal microbalance. Additionally, the changes in the resistance of the films were evaluated over time by electrochemical impedance spectroscopy in solid state. These results show that the magnetite incorporation decreases polymeric film resistance and Raman experiments have evidenced that the incorporation of magnetite into polymeric matrix not only stabilizes the polaronic form of the polypyrrole, but also preserves the polymer from further oxidation.     

Crystal structure and electrochemical performance of Li3V2(PO4)3 synthesized by optimized microwave solid-state synthesis route

To investigate the crystal structure and electrochemical performance of samples synthesized under different microwave solid-state synthesis condition, a series of Li₃V₂(PO₄)₃ samples has been synthesized at five different temperatures for 3-5 min and at 750 °C for various time. The as-synthesized Li₃V₂(PO₄)₃ samples are characterized and studied by ICP-AES analysis, X-ray diffraction (XRD), Rietveld analysis, scanning and transmission electron microcopy (SEM and TEM). At relatively lower temperature (650 °C) and very short reaction time (3 min), pure phase of Li₃V₂(PO₄)₃ could be synthesized in microwave irradiation field. The crystal structure and Li atomic fractional coordinate present a significant deviation upon the change of microwave irradiation temperature and time. Relatively, the diffusion ability of lithium cations and the electrochemical performance are affected. Under the proper reaction temperature and time, the carbon-free samples MW750C5m and MW850C3m show the best specific discharge capacity 126.4 and 132 mAh g⁻¹ at the voltage range of 3.0-4.3 V, near the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹). At the voltage range of 3-4.8 V, the sample MW750C5m presents the best initial specific charge capacity of 197 mAh g⁻¹, equivalent to the reversible cycling of three lithium ions per Li₃V₂(PO₄)₃ formula unit (197 mAh g⁻¹). The initial discharge capacity, the samples MW750C5m and MW850C3m present high specific discharge capacity 183.4 and 175.7 mAh g⁻¹, respectively. The relationship among microwave irradiation condition, crystal structure, lithium atomic fractional coordinates and the electrochemical performance have been discussed in detail.     

Corrosion mechanisms of Al2O3/MgAl2O4 by V2O5, NiO, Fe2O3 and vanadium slag

The effects of V₂O₅, NiO, Fe₂O₃ and vanadium slag on the corrosion of Al₂O₃ and MgAl₂O₄ have been investigated. The specimens of Al₂O₃ and MgAl₂O₄ with the respective oxides above mentioned were heated at 10 °C/min from room temperature up to three different temperatures: 1400, 1450 and 1500 °C. The corrosion mechanisms of each system were followed by XRD and SEM analyses. The results obtained showed that Al₂O₃ was less affected by the studied oxides than MgAl₂O₄. Alumina was only attacked by NiO forming NiAl₂O₄ spinel, while the MgAl₂O₄ spinel was attacked by V₂O₅ forming MgV₂O₆. It was also observed that Fe₂O₃ and Mg, Ni, V and Fe present in the vanadium slag diffused into Al₂O₃. On the other hand, the Fe₂O₃ and Ca, S, Si, Na, Mg, V and Fe diffused into the MgAl₂O₄ structure. Finally, the results obtained were compared with those predicted by the FactSage software.     

Synthesis of a TiO2 ceramic membrane containing SrCo0.8Fe0.2O3 by the sol-gel method with a wet impregnation process for O2 and N2 permeation

A SrCo_0.8Fe_0.2O₃ impregnated TiO₂ membrane (TiO₂-SrCo_0.8Fe_0.2O₃ membrane) was successfully prepared using a sol-gel method in combination with a wet impregnation process. The membrane was subjected to a single gas permeance test using oxygen (O₂) and nitrogen (N₂). The TiO₂ membrane was immersed in the SrCo_0.8Fe_0.2O₃ solution, dried and then calcined to affix SrCo_0.8Fe_0.2O₃ into the membrane. The effect of the acid/alkoxide (H⁺/Ti⁴⁺) molar ratio of the TiO₂ sol on the TiO₂ phase transformation was investigated. The optimal molar ratio was found to be 0.5, which resulted in nanoparticles with a mean size of 5.30 nm after calcination at 400 °C. The effect of calcination temperature on the phase transformation of TiO₂ and SrCo_0.8Fe_0.2O₃ was investigated by varying the calcination temperature from 300 to 500 °C. X-ray diffraction spectroscopy (XRD) and Fourier transform infrared (FTIR) analysis confirmed that a calcination temperature of 400 °C was preferable for preparing a TiO₂-SrCo_0.8Fe_0.2O₃ membrane with fully crystallized anatase and SrCo_0.8Fe_0.2O₃ phases. The results also showed that polyvinyl alcohol (PVA) and hydroxypropyl cellulose (HPC) were completely removed. Field emission scanning electron microscopy (FESEM) analysis results showed that a crack-free and relatively dense TiO₂ membrane (∼0.75 μm thickness) was created with a multiple dip-coating process and calcination at 400 °C. The gas permeation results show that the TiO₂ and TiO₂-SrCo_0.8Fe_0.2O₃ membranes exhibited high permeances. The TiO₂-SrCo_0.8Fe_0.2O₃ membrane developed provided greater O₂/N₂ selectivity compared to the TiO₂ membrane alone.     

Electrochemical performance of carbon-coated Li3V2(PO4)3 cathode materials derived from polystyrene-based carbon-thermal reduction synthesis

Li₃V₂(PO₄)₃ cathode materials were synthesized by a simple carbon-thermal reduction method using polystyrene as a carbon source. The residual carbon produced by the pyrolysis of polystyrene produced fine particle sizes and uniform carbon distribution on the Li₃V₂(PO₄)₃ particle surface. By increasing the amount of polystyrene added in the range of 0-16 wt.%, the thickness of the carbon coating increased, and the coating thickness was found to influence the electrochemical performance of the Li₃V₂(PO₄)₃ significantly. Our results indicate that the 6 wt.% polystyrene added Li₃V₂(PO₄)₃ with a 0.5-1 nm thick carbon coating possesses the highest initial discharge capacity of 132.7 mAh g⁻¹ between 3.0 and 4.3 V at 0.1 C. However, at high current densities, the higher polystyrene added Li₃V₂(PO₄)₃/C with a thicker carbon coating shows better performance in terms of the discharge capacity and cycling stability than that with the thin carbon coating. The improved cycling performance at higher current densities is attributed to the relatively small particle size and the suppressed impedance increase because of the thicker carbon coating.