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.%.     

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.     

Fast speed nano-sized macropore formation on highly-doped n-type silicon via strong oxidizers

The growth of nano-sized macropores at high speed is studied in this work. Nice macropores with diameters of 60–100 nm and aspect ratio up to 2500 were formed by anodic etching on highly-doped n-type silicon without illumination. The HF-containing electrolytes were modulated with strong oxidizer, H₂O₂, which was also attempted by a few other researchers, but did not lead to the expected macropore formation. Our findings reveal that the pore morphology and etching speed are on dependence of HF concentration and the applied current density. The parameter window of macropore formation, corresponding to the HF concentration ranging from 33% to 67% (by volume) in our experiment, is rather large. In addition, the growth speed can be driven up to 1800 μm/h, while the pores are straight, cylindrical and rather smooth. The current-burst-model is applied to interpret the mechanism of such nano-sized macropore formation.     

Mesoporous TiO2−xAy (A = N,S) as a visible-light-response photocatalyst

Mesoporous TiO_2?xA_y (A = N, S) thin films were fabricated using thiourea as a doping resource by a combination of sol-gel and evaporation-induced self-assembly (EISA) processes. The results showed that thiourea could serve two functions of co-doping nitrogen and sulfur and changing the mesoporous structure of TiO₂ thin films. The resultant mesoporous TiO_2?xA_y (A = N, S) exhibited anatase framework with a high porosity and a narrow pore distribution. The formation of the O–Ti–N and O–Ti–S bonds in the mesoporous TiO_2?xA_y (A = N, S) were substantiated by the XPS spectra. A new bandgap in visible light region (520 nm) corresponding to 2.38 eV could be formed by the co-doping. After being illuminated for 3 h, methyl orange could be degraded nearly completely by the co-doped sample under both ultraviolet irradiation and visible light illumination. While pure mesoporous TiO₂ could only degrade 60% methyl orange under UV illumination and showed negligible photodegradation capability in the visible light range. Furthermore, the photo-induced hydrophilic activity of TiO₂ film was improved by the co-doping. The mesoporous microstructure and high visible light absorption could be attributed to their good photocatalytic acitivity and hydrophilicity.     

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.     

Electrochemical and XPS studies of a Nb-containing Ti-based glass-forming alloy system in H2SO4 solution

The corrosion behaviors of Ti₄₀Zr₂₅Ni_12 -xNb_xCu₃Be₂₀ (x = 0, 4, 8, and 12 at.%) alloys in 0.5 mol/L H₂SO₄ solution were studied, aiming to establish the relationship between Nb content and corrosion resistance. The addition of Nb element gives rise to a clear microstructural evolution, from a completely amorphous structure for the alloys without Nb and with 4% Nb alloys to an amorphous/crystalline composite structure for the alloys with 8% and 12% Nb. The alloy with higher Nb content exhibits better corrosion resistance, which can be attributed to the formation of Ti^4 +-, Zr^4 +-, and Nb^5 +-enriched highly protective surface film in corrosive solutions.     

Monte Carlo simulation for chemical reaction equilibrium of ammonia synthesis in MCM-41 pores and pillared clays

Reactive canonical Monte Carlo (RCMC) method was performed to simulate the chemical reaction equilibrium of ammonia synthesis in two important porous materials: MCM-41 pores and pillared clays. First, our results were compared with those in slit pores in the literature. Then, the effect of other factors such as pore size, pressure and temperature on the chemical equilibrium was investigated. A parameter of the absolute increase of ammonia mole fraction in the pores against that in the bulk phase, Δ_abs, is introduced to describe the effect of confinement on the chemical equilibrium. The yield of ammonia increases with the decrease of pore size, but this increase becomes pronounced at pore sizes of 1.5 nm for MCM-41 pores and 1.02 nm for pillared clays. The yield of ammonia also increases with pressure. In addition, the maximum ammonia mole fraction is attained at 100 bar and 573 K in both MCM-41 pores and pillared clays. When the feed mole ratio of N:H of the bulk phase declines from 4:13 to 4:15, the yield of ammonia in the pore phase also decreases. In addition, the effect of porosity in pillared clays on the chemical equilibrium was simulated.     

An understanding of the porosity of residual coal/char/ash samples from an air-blown packed bed reactor operating on inertinite-rich lump coal

The thermal treatment of coal causes a development of internal porosity of the resultant char due to the changes in the coal char pores, i.e. the opening of original closed pores, the formation of new pores, and an increase in pore size of existing and newly formed pores. Furthermore, the porosity formed during de-volatilisation causes changes in pore structural characteristics such as: density, pore size distribution, total open pore volume, porosities and average pore diameter. Much research has been conducted in this area, but was mainly focused on fine particle sizes (<1 mm) and vitrinite-rich coals, particularly from the Northern hemisphere. The objective of this study was to obtain an understanding of both the macro- and micro-porosity development within the de-volatilisation zone of a packed bed consisting of lump inertinite-rich coal (75 mm × 6 mm) from the Highveld coalfield in South Africa. This was achieved by generating samples in an air-blown packed bed reactor and conducting proximate, CO₂ reactivity, mercury intrusion porosimetry, and BET CO₂ surface area analyses on the dissected coal/char/ash samples.From mercury-intrusion porosimetry results obtained for the de-volatilisation reaction zone of the reactor, it was found that although the percentage macro-porosity and average pore diameter increased by 11% and 77% respectively (which confirms pore development), that these developments do not enlarge the surface area, and thus has no significant contribution on the reactivity of the coal/char. On the other hand, the micro-pore surface area, pore volume and pore diameter were all found to increase during de-volatilisation, resulting in an increase in the coal char reactivity. The micro-porosity is thus generally responsible for the largest internal surface area during de-volatilisation, which enables increased reactivity. The CO₂ gasification reactivity (at 1000 °C) increased from 3.8 to 4.5 h⁻¹ in the first stage of de-volatilisation, and then decreased to 3.8 h⁻¹ in a slower de-volatilisation regime. This is due to the maximum pore expansion and volatile matter evolution reached at 4.5 h⁻¹, before coalescence and pore shrinkage occur with a further increase in temperature within the slower de-volatilisation region of the reactor. During de-volatilisation there is thus both an increase and decrease in reactivity which might suggest two distinct intermediate zones within the de-volatilisation zone.     

Computational simulations of pore nucleation in silicon(1 1 1)

Float zone n-Si(1 1 1) was electrochemically etched in diluted NH₄F to form porous nuclei. The experimental results were compared with computational simulations of pore nucleation and growth. Electrochemical etching of silicon(1 1 1) results in pore nucleation preferentially localized on the edges of atomic terraces. The initial pore nuclei have diameter and depth of 17 nm and 0.3 nm, respectively. We find a correlation between H-terminated Si(1 1 1) atomic surface morphology and electric field distribution on pore nucleation and growth mechanism. The H-terminated surface is composed from wide (100–200 nm) atomic terraces with steps of 0.3 nm height. Electric field enhancement occurs at the terrace edges leading to focusing the holes trajectories. This leads to weakening of the Si–Si backbonds resulting in easy atom removing. The maximum electric field was observed at terrace edges and at the semispherical pore bottom.     

Synthesis and magnetoelectric studies on Na0.5Bi0.5TiO3–BiFeO3 solid solution ceramics

Polycrystalline ceramics of 1 ? x[Na_0.5Bi_0.5TiO₃] ? x[BiFeO₃] (NBT–BFO) were synthesized by the modified Pechini's method to study their magnetic and magnetoelectric properties. A series of solid solutions exhibiting magnetoelectric output were formed when two iso-structural compounds Na_0.5Bi_0.5TiO₃ (NBT) and BiFeO₃ (BFO) were combined. Polarization-electric field hysteresis loops revealed that the maximum polarization (～23 μC/cm² for x = 0.1) decreased continuously with the increase of BFO content, following a hard doped effect. Piezoelectric charge coefficient (d₃₃) = 41 pC/N was obtained for the ceramics with x = 0.1 and the value continues to decrease with the composition. Magnetic hysteresis loops represent the canted antiferromagnetic nature for x ≤ 0.6 and ferromagnetic-like behavior for the BFO-rich compositions. Magnetoelectric coupling was determined by measuring the magnetoelectric voltage coefficient which is ～12.4 mV/cm-Oe at an ac magnetic field of 10 Oe (1 kHz), for x = 0.1 sample.     

Preparation and properties of mechanically alloyed and electrochemically etched porous Ti–6Al–4V

Formation of porous Ti–6Al–4V nanostructure biomaterial was described. The alloy was prepared by mechanical alloying followed by pressing, sintering and subsequent anodic electrochemical etching in 1 M H₃PO₄ + 2% HF electrolyte at 10 V for 30 min. Mechanically alloyed Ti–6Al–4V has nanostructure with grain size of about 35 nm and large grain boundaries volume fraction, which essentially improve etching process. The electrolyte penetrates sintered compacts through the grain boundaries, resulting in effective material removing and pores formation. The pore diameter reaches up to 60 μm, which is very attractive for strong bonding with bone. The anodization of the microcrystalline alloy ingot results in selective etching, revealing of the two-phase structure with relatively flat surface. The corrosion properties were investigated in Ringer’s solution. Mechanically alloyed samples shows worse corrosion resistance than the bulk microcrystalline alloy ingot, but electrochemical etching results in improving corrosion resistance.     

Fabrication of through-hole TiO2 nanotubes by potential shock

Through-hole nanotubular membranes of anodic TiO₂ were successfully prepared through the removal of the barrier layer using potential shock. The abrupt increase in the potential at the end of the anodization allowed the pores to homogenously open in the barrier layer within 10 s. The pore opening corresponded to the breakdown of the center of the barrier layer through the massive diffusion of the F^? ions, which were triggered by the significantly high potential (here, > 80 V). The potential shock voltage and time were optimized based on the breakdown mechanism. This method is immediately applicable for preparing the through-hole membranes of anodic TiO₂ because it rapidly produces homogenous pore openings without the need for any complicated processes or dangerous chemicals.     

Electrochemically synthesized CdS nanoparticle-modified TiO2 nanotube-array photoelectrodes: Preparation,characterization, and application to photoelectrochemical cells

A novel electrodeposited CdS nanoparticle-modified highly-ordered TiO₂ nanotube-array photoelectrode and its application to photoelectrochemical cells is reported. Results show formation of a thin, nanoparticulate CdS layer, comprised of sphere-like 10–20 nm diameter nanoparticles, on the anodic synthesized TiO₂ nanotube-array (inner diameter of 70 nm, wall thickness 25 nm and ca. 400 nm length) electrode. The resulting CdS–TiO₂ photoelectrode has an as-fabricated bandgap of 2.53, and 2.41 eV bandgap after sintering at 350 °C in N₂ ambient. Photoelectrochemical properties are described in detail.     

Characteristics and retention properties of a mesoporous γ-Al2O3 membrane for nanofiltration

A mesoporous γ-Al₂O₃ membrane was produced by the sol gel dipping technique, followed by a thermal treatment (calcination and sintering). Different sintering temperatures were applied, which led to membranes with an average pore diameter ranging from 8.7 to 3.4 nm, the latter one corresponding to a MWCO of 900 Da.Salt retention was very much dependent on the pH of the solution as such membranes have an amphoteric character. Minimal salt retention was found at the isoelectric point (pH 7.5). Experiments were carried out with NaCl, MgCl₂ and LaCl₃ at different concentrations and in both single salt solutions and mixtures. The results are interpreted in terms of Donnan exclusion and in terms of the formation of an electrical double layer in the pores.Dynamic corrosion tests showed that some corrosion occurs at a pH of 2 or lower.     

Evaluation of the porous structure development of chars from pyrolysis of rice straw: Effects of pyrolysis temperature and heating rate

The effects of pyrolysis temperature and heating rate on the porous structure characteristics of rice straw chars were investigated. The pyrolysis was done at atmospheric pressure and at temperatures ranging from 600 to 1000 °C under low heating rate (LHR) and high heating rates (HHR) conditions. The chars were characterized by ultimate analysis, field emission scanning electron microscope (FESEM), helium density measurement and N₂ physisorption method. The results showed that temperature had obvious influence on the char porous characteristics. The char yield decreased by approximately 16% with increasing temperature from 600 to 1000 °C. The carbon structure shrinkage and pore narrowing occurred above 600 °C. The shrinkage of carbon skeleton increased by more than 22% with temperatures rising from 600 to 1000 °C. At HHR condition, progressive increases in porosity development with increasing pyrolysis temperature occurred, whereas a maximum porosity development appeared at 900 °C. The total surface area (S_total) and micropore surface area (S_micro) reached maximum values of 30.94 and 21.81 m²/g at 900 °C and decreased slightly at higher temperatures. The influence of heating rate on S_total and S_micro was less significant than that of pyrolysis temperature. The pore surface fractal dimension and average pore diameter showed a good linear relationship.     

A new composite electrode of Ni-Ferrite/TiOx/Si(111): Preparations and photoelectrochemical studies

A composite electrode of Ni-ferrite/TiO_x/Si(111) was synthesized by grafting Ni²⁺Fe²⁺Fe³⁺–LDH–TiCl₃ (LDH: Layered Double Hydroxides) on n-Si(111) surface and calcined under 1100 °C. Photoelectric research results indicated that the electrode had good photovoltaic effects in an electrolyte solution containing 7.6 M HI and 0.05 M I₂, while platinum plate was used as counter-electrode. The observed photo-voltages (U_pv) and photocurrent densities (j_pc) of the electrode were at ?0.75 V and 5.35 mA/cm², respectively. Compared with electrodes of oxidized n-Si(111) crystal and n-Si(111) wafer covered by Ni-ferrites, j_pc of the electrode Ni-ferrite/TiO_x/Si(111) was increased greatly.     

Electrochemically driven intrusion of silver particles into silicon under polarization

The pore formation with the diameter of around 100 nm into a lightly doped p-type Si was achieved with the intrusion of silver particles by electrolysis in HF aqueous solution. The route resembles the metal-catalyzed electroless pore formation, but the present method uses anodic polarization instead of chemical etching in the presence of oxidizing agent. A microporous layer was observed around the pores formed as the tracks of silver particles. Thickness of the microporous layer around the track increased with the increase in current density. The thickness was varied in accordance with the time-programmed variation of current density. Conversely, the intrusion of silver particles seldom occurred in heavily doped p-type silicon, while micropores were formed independently of the location of the particles. The concentration of dopant affects the silver-particle-assisted porosification.     

Rapid anodic growth of TiO2 and WO3 nanotubes in fluoride free electrolytes

In the present work we report on the formation of bundles of high aspect ratio TiO₂ nanotubes and WO₃ nanopores structures with very thin tube or pore walls using anodization under “high voltage” conditions in perchlorate or chloride containing electrolytes. The bundles of TiO₂ nanotubes consist of separated tubes with diameters in the range of approximately 20–40 nm and the WO₃ nanopores consist of pores with diameters in the range of 30–50 nm. Growth occurs locally at specific surface locations. Both the TiO₂ and the WO₃ structures can be grown up to several dozens of micrometers in length within few minutes. We suggest that the growth of these high aspect structures is initiated by localized anodic breakdown event, triggered by a sufficiently high applied anodic field.     

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.     

Standard enthalpy,entropy and Gibbs free energy of formation of “B” type carbonate fluorapatites

The “B” type carbonate fluorapatites Ca_10−x+u(PO₄)_6−x(CO₃)_xF_2−x+2u, with 0 ⩽ x ⩽ 2 and u ⩽ x/2, were synthesized by a double decomposition method. The samples were characterized by X-ray diffraction and infrared spectroscopy. The heat of dissolution of these products in a phosphoric acid solution was measured by a C-80 SETARAM microcalorimeter. A thermochemical cycle was proposed and complementary processes were carried out in order to get the standard enthalpies of formation of these apatites. Estimation of the values of entropy of formation allowed the determination of standard Gibbs free energies of formation of these compounds. The results showed that incorporation of carbonate ions results in a decrease of the stability of the apatite structure.