Formation of porous TiOx biomaterials in H3PO4 electrolytes

In this work, formation of porous TiO_x layers and theirs corrosion behavior were studied. Application of H₃PO₄ electrolytes results in porous TiO_x formation. The process is enhanced by small amount of HF content in the electrolyte. The HF results in higher current density, enhancing dissolution. Small 0.5% HF concentration results in nanopores formation, with pore diameter of about 45 nm. Increase of HF concentration up to 10% results in pores with average diameter of about 5.2 μm. An increase of etching time results in larger pore diameter, but between large 2–5 μm diameter pores smallest ones were observed with diameter below 200 nm. In the initial etching process a remnants of the flat surface are presents with initial cracks in the surface, indicating places for growth of the pores.The TiO_x layers can be used as a biomaterial. The corrosion behavior of the layer investigated in Ringer’s solution, revealed an excellent corrosion resistance, with respect to pure Ti.     

One dimensional macropore-array formation on low doped n-type silicon

Macropores with diameters between 0.1 μm and 0.8 μm show technological significance but become difficult to obtain on low doped n-type silicons. In this study, via anodizing samples with prestructured linear defects, one dimensional (1D) densely arrayed macropores with depths up to 15 μm and diameters between 100 nm and 1 μm were produced with fast speed on low doped n-Si. The pore density increases with reduced current densities: this phenomenon was found to be largely dominated by physics rather than by chemistry. Not least, SCR effects alone were excluded as additional stabilizers of the 1D macropore arrays; the interaction between diffusion and tunneling effects was proved to play a major role instead. Simultaneously, the gradual transition from macropore to mesopore formation, not well understood to date, was experimentally displayed and theoretically interpreted.     

Formation of mesoporous germanium double layers by electrochemical etching for layer transfer processes

We produce uniform mesoporous single- and multilayers on 4 in. p-type Ge wafers by means of electrochemical etching in highly concentrated HF-based electrolytes. Pore formation by anodic etching in germanium leads to a constant dissolution of the already formed porous layer plus substrate. Alternating the etching bias from anodic to cathodic bias enhances the passivation of the pore walls and substrate. The formation of porous multilayers is possible, since the starting layer is not dissolved during the formation of the separation layer. We report on the production of mesoporous double layers in Ge with different porosities. The change in the porosity of the porous layers is achieved by varying the anodic etching current and the HF concentration of the electrolyte. Porosities in the range of 25–65% are obtained for etching current densities of 1–15 mA cm^?2 with the specific resistivity of the Ge substrates lying in the (0.020–0.032) Ω cm range and electrolyte HF concentrations in the range of 35–50 wt.%.     

Macro- and microporous carbon monoliths with high surface areas pyrolyzed from poly(divinylbenzene) networks

Carbon monoliths with well-defined macropores and high surface areas were prepared by carbonization of macroporous poly(divinylbenzene) (PDVB) monoliths. The carbonization reactions of PDVB networks are studied by thermal analysis and FT-IR measurements. According to the measurement results, the PDVB networks are mostly pyrolyzed at 430 °C and their structures dynamically change to graphite-like structure between 600 and 700 °C. The macropore structure retained while the mesopores disappeared after carbonization. In addition, the surface area of the obtained carbons dramatically increased over 900 °C. The typical carbon monolith carbonized at 1000 °C for 2 h had a surface area of 1500 m² g^?1 and uniform macropores with a diameter of 1 μm.     

Shelf-life extension of preservative-free hydrated feed using gamma pasteurization and its effect on growth performance of eel

Hydrated feed (HF) promotes the growth performance and shortens the feeding time of fish by increasing the efficiency of digestion. However, the shelf-life of HF is a concern due to its relatively higher water content. In this study, radiation pasteurization was applied to improve the shelf-life and microbiological quality of HF for fish farming. Preservative-free HF containing 25% moisture was gamma-irradiated and its microbiological and nutritional properties evaluated in addition to a practical feeding trial carried out using eel. The viable counts of bacteria and fungi in HF were 10⁶ and 10⁴ CFU/g, respectively. All coliform bacteria and yeast in HF were eliminated by irradiation at a dose of 5 kGy, and total aerobic bacteria were eliminated at 10 kGy. The shelf-life of the preservative-free and irradiated (10 kGy) HF was estimated as 6 months under ambient conditions. The nutritional composition of HF was stable up to 10 kGy of irradiation. Based on a feeding trial, it was proven that eel fed HF had about 20% higher growth rate than that fed dried feed.     

Mechanoelectrochemical synthesis and properties of porous nano-Ti–6Al–4V alloy with hydroxyapatite layer for biomedical applications

Formation of porous morphology in nanocrystalline mechanically alloyed and electrochemically etched Ti–6Al–4V biomedical alloy was investigated. The alloy was electrochemically etched in a mixture of H₃PO₄ and HF. The electrochemical etching results in broad range from micro(nano)-macropores formation in the surface layer, with diameter in the range of 3 nm–60 µm. On the etched surface hydroxyapatite was electrochemically deposited by using 0.042 M Ca(NO₃)₂ + 0.025 (NH₄)₂HPO₄ + 0.1M HCl electrolyte. In this way bioactive surface was prepared. The pores in the surface acts as anchors for the hydroxyapatite, which grows inside them. Due to the porous morphology, the etched as well as HA deposited surface is promising for hard tissue implant applications. The nanocrystalline alloy has a nanohardness and Young modulus in the range of 993–1275 HV and 137–162 GPa, respectively.     

Mechanoelectrochemical synthesis of porous Ti-based nanocomposite biomaterials

In this work we have synthesized a new class of nanocomposites based on Ti with the addition of hydroxyapatite (HA) and glass 45S5. The nanocomposites were prepared by mechanical alloying of the pure microcrystalline Ti powders with different amount of ceramics. The powder mixture was milled up to 48 h, pressed and sintered, which resulted in nanocomposite structure with the grain size of about 20–36 nm. The ultra low grain size structure improves mechanical properties of the implants in comparison to commonly used microcrystalline Ti-based implants. For example, the hardness of the Ti-HA nanocomposites reaches a value of 1500 HV and is five times greater than the microcrystalline Ti.To improve bonding of the implants with human tissue, the implants were electrochemically etched in 1 M H₃PO₄ + 2–10% HF electrolyte at 10 V vs. OCP for times up to 60 min. The treatment results in highly porous surface covered with Ti-oxide. The nanocrystalline structure is very useful during etching, due to the easy access of the electrolyte to the large volume of the grain boundaries. The nanocomposites with modified surface show very good corrosion resistance in Ringer’s solution.     

Structural evolution during the reaction of Li with nano-sized rutile type TiO2 at room temperature

Rutile type TiO₂ nanoparticles (10 nm × 200 nm in size) were prepared using a precipitation method in aqueous solution. Their lithium reactivities were followed using both classical galvanostatic insertion and in situ XRD measurements, and compared to that of a bulk and commercial nano-sized (50 nm) rutile TiO₂ sample so as to stress the interlink between Li insertion electrochemical capacity and crystallite size. For the highly divided material, we obtained a reversible capacity of 0.5 Li ion per formula unit after a first reduction step during which, the material is irreversibly transformed. Such a reduction step is shown to enlist two solid solution domains followed by the formation of a rocksalt type phase LiTiO₂. Such a specific reactivity of nano-sized rutile TiO₂ is explained in terms of better lattice strains accommodation during the insertion of lithium.     

Photophysical properties of 5-hydroxyflavone

To investigate the role of the excited triplet state in the deactivation process of 5-hydroxyflavone (5HF), the photophysical process of 5HF was studied by transient absorption, phosphorescence spectroscopies, and semiempirical calculations. The triplet–triplet absorption (T–T) spectra of 5HF and 5-methoxyflavone (5MF) were observed upon direct and triplet-sensitized excitation. The T–T spectrum of 5HF (λ_max=350 nm, τ_T=2.8 μs) was different from that of 5MF (λ_max=360 nm, τ_T=6.8 μs). Estimations of the triplet energies of 5HF and 5MF by quenching experiments, phosphorescence, and semiempirical (PM3/CI4) calculation revealed that 5HF underwent an intramolecular hydrogen atom transfer and formed the tautomer in the excited triplet state. The triplet energy of the normal form of 5HF was 260 kJ mol⁻¹, while that of the tautomer form (5HF′) was 197 kJ mol⁻¹. The triplet energy of 5MF, the model compound of the normal form of 5HF, was 261 kJ mol⁻¹. The PM3/CI4 calculation supported the experimental observations and suggested that the most stable conformer in the triplet state of 5HF is the tautomer form.     

An understanding of anomalous capacity of nano-sized CoO anode materials for advanced Li-ion battery

Nanostructured transition metal oxides are of great interest as a new generation of anode materials for high energy density lithium-ion batteries. In this work, research has been focused on the nano-sized (grain size ～7 nm) CoO anode material and this material delivers charge capacity of 900 mAh g^?1 that exceeds the theoretical value of 715 mAh g^?1. Possible reason for this unaccounted and unexplained anomalous capacity of the nano-sized CoO material has been suggested by thermogravimetric analysis. A mechanism for this interesting behavior has been systematically evaluated by using X-ray absorption spectroscopy. The anomalous capacity is proposed to be associated with the formation of oxygen-rich CoO material. The results obtained from the nano-sized CoO material have been compared with relatively larger-sized material (grain size ～32 nm).     

Controlling macropore formation in patterned n-type silicon: Existence of a pitch-dependent etching current density lower bound

Experimental results on back-side illumination electrochemical etching of patterned (hole square-lattices with pitch p from 2 to 50 μm) n-type silicon substrates in HF-based electrolytes are reported. Experiments reveal the existence of a threshold current density J_pitch, which is strictly correlated to the pattern pitch, above which pore formation can be finely controlled beyond commonly accepted state-of-the-art rules. For instance, using the same silicon substrate, pore array with density D spanning over two orders of magnitude (from 0.0025 μm^? 2 up to of 0.25 μm^? 2) can be etched above a minimum porosity P_min, and, in turn, a minimum pore diameter d_min, which depends on the pattern pitch. Etching current densities below such a critical value give rise to uncontrolled pore growth. The occurrence of the threshold current density J_pitch is interpreted in terms of current burst model.     

O2 surface concentration change and its implication on oxygen reduction mechanism and kinetics at platinum in acidic media

O₂ concentration near Pt surface during oxygen reduction reaction (ORR) in 0.1 M HClO₄ has been monitored by rotating ring-disk electrodes system. At 0.8 V < E < 1.0 V (vs. RHE), O₂ concentration near Pt surface increases with potential accompanying with the decrease of ORR current at the disk electrode; O₂ concentration in the negative-going scan is larger than that at the same potential in the positive-going scan, while ORR current shows the opposite trend at ω > 400 rpm. At E > 0.8 V accumulation of O_ad|OH_ad at Pt disk electrode with ORR time is evident, revealing that O_ad|OH_ad formation rate is faster than that for the removal of OH_ad to H₂O under such conditions. At relatively lower rotation speed and faster scan rate, the cathodic current during ORR in the negative-going scan can be larger than that in the positive-going scan with a current peak at ca. 0.8 V, which is attributed to the superimposition of ORR current increase due to change of O₂ concentration near the surface and the additional reduction of O_ad|OH_ad formed from decomposed O₂ at higher potentials.     

High aspect ratio ordered nanoporous Ta2O5 films by anodization of Ta

In this work we report the electrochemical formation of self-organized high aspect ratio Ta₂O₅ porous layers, grown by anodization of Ta in non-aqueous electrolytes consisting of glycerol and small additions of NH₄F. Under optimized electrochemical conditions in these glycerol based electrolytes, the porous layers can be grown up to thickness of 15 μm, with a pore diameter in the range of 10–40 nm. The dimensions and the morphology of the layers can be strongly influenced by the fluoride concentration, the applied potential and the water content in the electrolyte.     

Spectroscopic determination of hypochlorous acid,in chloride brine solutions,featuring 5 MeV proton beam line experiments

The irradiation effects of 4.9 MeV protons on salt repository related brines are investigated spectrophotometrically. The induced formation of hypochlorous acid is determined up to doses of 11 kGy in 3.7 M MgCl₂·6H₂O and in a multicomponent brine of high concentration: Brine G. The build-up of hypochlorous acid to a steady-state concentration is found to be independent on the chloride concentration. The ultimate objective of this experiment is the estimation of the G value for HOCl in which meaningful predictions of long-term redox conditions in a nuclear repository strongly depend on. This paper describes our first steps towards the determination of HOCl.     

Fabrication of a nano-sized ZSM-5 zeolite with intercrystalline mesopores for conversion of methanol to gasoline

Carbon deposition during methanol to hydrocarbons leads to the quick deactivation of ZSM-5 catalyst and it is one of the major problems for this technology. Decreasing the crystal size or introducing mesopores into ZSM-5 zeolites can improve its diffusion property and decrease the coke formation. In this paper, nano-sized ZSM-5 zeolite with intercrystalline mesopores combining the mesoporous and nanosized structure was fabricated. For comparison, the mesoporous ZSM-5 and nano-sized ZSM-5 were also prepared. These catalyst samples were characterized by XRD, BET, NH3-TPD, TEM, Py-IR and TG techniques and used on the conversion of methanol to gasoline in a fixed-bed reactor at T = 405 °C, WHSV = 4.74 h-1and P = 1.0 MPa. It was found that the external surface area of the nano-sized ZSM-5 zeolite with intercrystalline mesopores reached 104 m2/g, larger than that of mesoporous ZSM-5(66 m2/g) and nanosized ZSM-5(76 m2/g). Catalytic lifetime of the nano-sized ZSM-5 zeolite with intercrystalline mesopores was 93 h, which was only longer than that of mesoporous ZSM-5(86 h), but shorter than that of nanosized ZSM-5(104 h). Strong acidity promoted the coke formation and thus decreased the catalytic lifetime of the nano-sized ZSM-5 zeolite with intercrystalline mesopores though it presented large external surface that could improve the diffusion property. The special zeolite catalyst was further dealuminated to decrease the strong acidity. After this, its coke formation rate was slowed and catalytic lifetime was prolonged to 106 h because of the large external surface area and decreased weak acidity. This special structural zeolite is a potential catalyst for methanol to gasoline reaction.     

A microtubular all CNT gas diffusion electrode

We report a microtubular gas diffusion electrodes made of multi-walled carbon nanotubes (MWCNT). The electrodes were prepared by inside-out cake filtration of an aqueous MWCNT suspension onto a microfiltration hollow fiber (HF) membrane, followed by washing out the surfactant, drying and removal of the all CNT microtube from the HF membrane. Length, outer diameter, and wall thickness of the tubular electrodes are: up to 44 cm, ~ 1.7 mm and 275 μm, respectively. The BET surface area is 200 m²/g with a porosity of 48–67% and an electrical conductivity of ~ 20 S/cm. Application of this microtubular Gas Diffusion Electrodes (GDE) was studied for the oxygen reduction reaction (ORR) in divided and undivided electrochemical cells. Oxygen supply into the lumen of the tubular electrodes resulted in much higher current densities for ORR than in experiments where the electrolyte was saturated by bubbling with pure oxygen. Within the 0.25–1.0 bar pressure (gauge) region, higher ORR rates were achieved at lower pressure. We also show that H₂O₂ production is possible using the new GDE. We propose to use such novel electrodes for the fabrication of tubular electrochemical reactors, e.g. fuel cells, H₂O₂ generators, CO₂ reduction and other processes that involve GDE application.     

Competitive adsorption between SDS and carbonate on tetrahydrofuran hydrates

Sodium dodecyl sulfate (SDS) has been well known as a promoter for the formation of hydrates. However, the use of SDS to enhance the formation of CO₂ hydrates has not been effective. This work will present an idea of competitive adsorption that will provide insights into the nonpromoting effect of SDS under high carbonate concentrations. The competitive adsorption is studied between DS^? monomers and carbonate ions on tetrahydrofuran (THF) hydrates. The adsorption is qualitatively investigated by using pyrene fluorescence measurements. The SDS concentration at which hydrophobic domains occur on the hydrate surface increases with the increased carbonate concentration and this trend is less dependent on the order of addition of these two species. This concentration is 0.17 mM at carbonate concentrations less than 2 μM and it shifts to 3.47 mM at carbonate concentrations higher than 2.5 μM. Thus, using carbonate with its concentration higher than 2.5 μM would be enough to displace the hydrophobic domains formed by SDS up to the solubility limit.     

Preparation of spherical silica particles by Stöber process with high concentration of tetra-ethyl-orthosilicate

In this paper, Stöber process with high concentration of tetra-ethyl-orthosilicate (TEOS) up to 1.24 M is used to prepare monodisperse and uniform-size silica particles. The reactions are carried out at [TEOS] = 0.22–1.24 M, low concentrations of ammonia ([NH₃] = 0.81[TEOS]), and [H₂O] = 6.25[TEOS] in isopropanol. The solids content in the resulting suspension achieves a maximum value of 7.45% at 1.24 M TEOS. Various-sized particles in the range of 30–1000 nm are synthesized. The influences of TEOS, NH₃, and H₂O on the size and size distribution of the particles are discussed. A modified monomer addition model combined with aggregation model is proposed to analyze the formation mechanism of silica particles.     

Development of a selective fluorimetric technique for rapid trace determination of zinc using 3-hydroxyflavone

A sensitive and a selective spectrofluorimetric method have been developed for the rapid determination of trace levels of zinc. The method is based on complex formation between zinc and 3-hydroxyflavone (3HF), which displays an intense emission signal around 478 nm. The analytical performance of the method was examined by considering the factors that affect the complex formation such as pH, mole ratio of the metal and solvent type. The optimum conditions for the complex formation were metal to ligand stoichiometric ratio of 1:1 at pH 7.5 with 0.1 M Tris buffer. Under these conditions the detection limit attained was 1.5 ppb. The method was appropriately validated and yielded relative standard deviations of less than 2% (n = 5), which was considered acceptable. It was successfully applied to the trace determination of zinc in drinking water, hair shampoo and pharmaceutical samples.     

Experimental observations on the competing effect of tetrahydrofuran and an electrolyte and the strength of hydrate inhibition among metal halides in mixed CO2 hydrate equilibria

In the present work, experimental data on the equilibrium conditions of mixed CO₂ and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl₂), magnesium chloride (MgCl₂), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO₂ and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (L_W), liquid organic (L_V), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid–liquid phase split of (water + THF) mixture when pressurized with CO₂ and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF < KBr < NaCl < NaBr < CaCl₂ < MgCl₂. Among the cations studied, the strength of hydrate inhibition increases in the following order: K⁺ < Na⁺ < Ca²⁺ < Mg²⁺. Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br^? > Cl^? > F^?. Based on the results, it is suggested that the probability of formation and the strength of ionic–hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water network are the major factors that contribute to hydrate inhibition by electrolytes.