Experimental design in the electrodeposition process of porous composite Ni–P + TiO2 coatings

In this paper, an environmentally friendly electroplating process of the composite Ni–P + TiO₂ coatings was developed. Such coatings were prepared by in situ codeposition of Ni–P with TiO₂ powder (anatase) on a polycrystalline copper substrate from the nickel-plating bath in which titanium dioxide particles were held in suspension. The codeposition was carried out under galvanostatic conditions on a rotating disc electrode. To optimize the production conditions of the Ni–P coatings modified with TiO₂ by the method of mathematical statistics, the Hartley's polyselective quasi D optimum plan of experiments was used. The relationship between the percentage content in the electrodeposited composite Ni–P + TiO₂ coatings (z) and the electrodeposition parameters like cathodic current density (j_dep), bath temperature (T) as well as content of TiO₂ powder suspended in the galvanic bath (c), has been described by the adequate cubic polynomial equation and illustrated graphically. Based on the Hartley's plan it can be stated that the maximal TiO₂ content of 28.7 at.% in the Ni–P + TiO₂ coating can be obtained for the following optimal parameters of the electrodeposition process: j_dep = 0.05 A cm⁻², c = 99 g dm⁻³ and T = 40 °C. The chemical and physical characteristics of the coating obtained under such optimum conditions, have been presented. The deposit exhibits the presence of TiO₂ particles embedded into the amorphous Ni–P matrix. It has been ascertained that embedding of TiO₂ powder to the amorphous Ni–P matrix leads to the production of deposits with large surface area. Such electrochemical codeposition method may be a good alternative in the field of porous composite coatings used in gas evolution.     

Solvo- or hydrothermal fabrication and excellent carbon dioxide adsorption behaviors of magnesium oxides with multiple morphologies and porous structures

MgO nano/microparticles with multiple morphologies and porous structures have been fabricated via the surfactant (poly(N-vinyl-2-pyrrolidone, poly(ethylene glycol) (PEG), cetyltrimethylammonium bromide, oleylamine or triblock copolymer P123 or F127) assisted solvo- or hydrothermal route in a dodecylamine or oleic acid solvent. The as-fabricated MgO samples were characterized by means of numerous techniques. It is shown that the obtained MgO samples were single-phase and of cubic in crystal structure; the particle morphology and pore architecture mainly depended upon the surfactant, solvent, and solvo- or hydrothermal temperature adopted. The solvothermal process resulted in polycrystalline MgO, whereas the hydrothermal one gave rise to single-crystalline MgO. Surface areas (8–169 m² g⁻¹) of the MgO samples derived solvothermally were lower than those (181–204 m² g⁻¹) of the MgO counterparts derived hydrothermally, with the mesoporous MgO generated after the PEG-assisted hydrothermal treatment at 240 °C for 72 h possessing the highest surface area. CO₂ adsorption capacities of the MgO samples were in good agreement with their surface areas, and the mesoporous MgO derived hydrothermally with PEG at 240 °C for 72 h exhibited the largest CO₂ uptake (368 μmol g⁻¹) below 350 °C. We believe that such a high low-temperature adsorption capacity renders the mesoporous magnesia material useful in the utilization of acidic gas adsorption.     

Synthesis of morphology-controlled carbon hollow particles by carbonization of resorcinol–formaldehyde precursor microspheres and applications in lithium-ion batteries

The morphology-controlled carbon hollow particles, derived from resorcinol–formaldehyde (RF) particles, were prepared by using an (oil phase) O/(water phase) W/(oil phase) O inverse-emulsion system which was formed by adding RF precursor (water phase) to n-hexane (oil phase) with Span-80 as surfactant and the following carbonization. This simple method led to the formation of various morphologies of RF carbon precursor particles such as hollow spheres, bowl-like hollow structures, microcapsules, or solid microspheres by adjusting the pH values of the RF precursor. The synthesized carbon particles exhibited porous characters with the surface area of 659 m² g⁻¹ and the total pore volume of 0.44 cm³ g⁻¹. Additionally, the electrochemical behavior of the typical RF carbon particles in lithium-ion batteries revealed that the RF carbon microcapsules displayed a high initial discharge capacity of 1059 mAh g⁻¹ and stabilized at about 330 mAh g⁻¹, indicating its excellent power property and cycle durability.     

Synthesis of (Zn,Mg)TiO3–TiO2 composite ceramics for multilayer ceramic capacitors

(Zn_0.8Mg_0.2)TiO₃–xTiO₂ composite ceramics has been prepared via the solid-phase synthesis method. TiO₂ was employed to tone temperature coefficient of resonant frequency (τ_f) and stabilize hexagonal (Zn, Mg)TiO₃ phase. 3ZnO–B₂O₃ was effective to promote sintering. The movement of grain boundary was obvious because of the liquid phase sintering. The scanning electron microscope (SEM) photographs and energy dispersive spectrometer (EDS) patterns showed that segregation and precipitation of dissociative (Zn, Mg)TiO₃ grains occurred at grain boundary during sintering. SnO₂ was used as inhibitor to prevent the grain boundary from moving. The dielectric behaviors of specimen strongly depended on structural transition and microstructure. We found that 1.0 wt.% 3ZnO–B₂O₃ doped (Zn, Mg)TiO₃–0.25TiO₂ ceramics with 0.1 wt.% SnO₂ additive displayed excellent dielectric properties (at 1000 °C): ?_r = 27.7, Q × f = 65,490 GHz (at 6.07 GHz) and τ_f = −8.88 ppm °C⁻¹. The above-mentioned material was applied successfully to make multilayer ceramic capacitors (MLCCs), which exhibited an excellent electrical property. The self-resonance frequency (SRF) and equivalent series resistance (ESR) of capacitor decreased with capacitance increasing, and the quality factor (Q) of capacitor reduced as frequency or capacity increased.     

An aqueous sol-gel synthesis of chromium(III) doped mesoporous titanium dioxide for visible light photocatalysis

Nanoparticles of titanium dioxide doped with Cr³⁺ ions have been prepared through an aqueous sol-gel method. The mesoporous nature of both pure and Cr³⁺ doped TiO₂ powders, with specific surface area of 7.4 and 6.6 m² g⁻¹, respectively, is maintained even at calcination temperature of 800 °C. The transformation of TiO₂ from the anatase to rutile phase is suppressed up to 800 °C by Cr³⁺ ion doping. Even though surface area values are decreased, the doped materials show improved photocatalytic activity, which may be due to increased crystallinity of the anatase phase without the formation of rutile. Doped materials have a red-shift in the band gap energy and hence, photoactivity under visible light. The rate of photodegradation of methylene blue dye for both pure and doped TiO₂ under visible light has been monitored in this study. The 0.25 mol% Cr(III) doped photocatalyst, calcined at 800 °C, shows the highest photocatalytic activity under visible light with a rate constant of ∼15.8 × 10⁻³ min⁻¹, which is nearly three times higher than that of commercially available Degussa P25 titania (5.8 × 10⁻³ min⁻¹).     

Corrosion behaviour of single (Ti) and duplex (Ti–TiO2) coating on 304L stainless steel in nitric acid medium

Sputter deposited single titanium (Ti) layer, and duplex Ti–TiO₂ coating on austenitic type 304L stainless steel (SS) was prepared, and the corrosion performance was evaluated in nitric acid medium using surface morphological and electrochemical techniques. Morphological analysis using atomic force microscope of the duplex Ti–TiO₂ coated surface showed minimization of structural heterogeneities as compared to single Ti layer coating. The electrochemical corrosion results revealed that, titanium coated 304L SS showed moderate to marginal improvement in corrosion resistance in 1 M, and 8 M nitric acid, respectively. Duplex Ti–TiO₂ coated 304L SS specimens showed improved corrosion resistance as compared to Ti coating from dilute (1 M) to concentrated medium (8 M). The percentage of protection efficiency for base material increases significantly for duplex Ti–TiO₂ coating as compared to single Ti layer coating. The oxidizing ability of nitric acid on both the coatings as well as factors responsible for improvement in protection efficiency are discussed and highlighted in this paper.     

Titanium diffusion in gold thin films

In the present study, diffusion phenomena in titanium/gold (Ti/Au) thin films occurring at temperatures ranging between 200 and 400 °C are investigated.The motivation is twofold: the first objective is to characterize Ti diffusion into Au layer as an effect of different heat-treatments. The second goal is to prove that the implementation of a thin titanium nitride (TiN) layer between Ti and Au can remarkably reduce Ti diffusion.It is observed that Ti atoms can fully diffuse through polycrystalline Au thin films (260 nm thick) already at temperatures as a low as 250 °C. Starting from secondary ion mass spectroscopy data, the overall diffusion activation energy ΔE = 0.66 eV and the corresponding pre-exponential factor D₀ = 5 × 10^− 11 cm²/s are determined. As for the grain boundary diffusivity, both the activation energy range 0.54 < ΔE_gb < 0.66 eV and the pre-exponential factor s₀D_gb0 = 1.14 × 10^− 8 cm²/s are obtained. Finally, it is observed that the insertion of a thin TiN layer (40 nm) between gold and titanium acts as an effective diffusion barrier up to 400 °C.     

Rectangular MgO microsheets with strong catalytic activity

Rectangular hydromagnesite microsheet is prepared by simple solution route through controlled hydrolysis-condensation of magnesium chloride in urea solution using ethylene glycol (EG) as a bifunctional cosolvent. Calcination of the hydromagnesite sheets at 450 °C produces MgO without any alteration in the morphology. The MgO sheets were of 2–3 μ side length and 4–5 nm thickness, and made of highly crystalline MgO nano-particles, which show reasonably high BET surface area of 106 m² g⁻¹. These MgO microsheets showed very strong activity as heterogeneous base catalyst in the solvent free Claisen–Schmidt condensation of benzaldehyde with acetophenone giving 99.0% conversion in less than 4 h with almost no loss of activity in three successive cycles. The strong activity is correlated with its large surface area and presence of oxide ions in low coordination (LC) O_LC²⁻ (where LC = 5C, 4C and 3C for terrace, edge, corner and kink sites, respectively) along with defects, which was revealed by photoluminescence (PL) emission studies. Presence of basic sites of different strength, determined by temperature programmed desorption of carbon dioxide (TPD-CO₂) also supports the strong catalytic activity of the MgO micro-sheets. Increase in calcination temperature to 650 °C destroys the open sheet morphology and enhances crystallite size, which causes decrease in catalytic activity due to low surface area, constrain in mass transport from the core structure and low concentration of active basic sites.     

Dye-sensitized solar cells with TiO2 nanocrystalline films prepared by conventional and rapid thermal annealing processes

Titanium oxide (TiO₂) thin films are prepared by the sol-gel method and annealed at 600 °C by conventional (CTA) and rapid thermal annealing (RTA) processes on fluorine-doped tin oxide -coated glass substrates for application as the work electrode for the dye-sensitized solar cells (DSSC). TiO₂ thin films are crystallized using a conventional furnace and the proposed RTA process at annealing rates of 5 °Cmin⁻¹ and 600 °Cmin⁻¹, respectively. The TiO₂ thin films are characterized by X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller analysis. Based on the results, the TiO₂ films crystallized by RTA show better crystallization, higher porosity and larger surface area than those of CTA. The short-circuit photocurrent and open-circuit voltage values increased from 5.2 mAcm⁻² and 0.6 V for the DSSC with the CTA-derived TiO₂ films to 8.3 mAcm⁻² and 0.68 V, respectively, for the DSSC containing RTA-derived TiO₂ films.     

Annealing effect on the performance of RuO2–Ta2O5/Ti electrodes for use in supercapacitors

The preparation of RuO₂–Ta₂O₅/Ti electrodes, by dip-coating, for use in supercapacitors was investigated. The stability and specific capacitance of the electrodes annealed at various temperatures was examined. The results show that highly stable electrodes with a specific capacitance of 170 F g RuO₂⁻¹ were obtained at approximately 250 °C, while electrodes with a lower capacitance (130 F g RuO₂⁻¹) were obtained at 300 °C. The annealing time needed to obtain a stable RuO₂–Ta₂O₅/Ti electrode at various temperatures correlates well with the Arrhenius’ law: with the activation energy (E) of the annealing reactions for the electrodes being estimated as 73.5 kJ mol⁻¹. SEM images of the electrodes show the coating films to have rough surface morphology with cracks 2–6 μm in width. XRD data indicate that the coating films obtained are composed of crystalline RuO₂ and amorphous tantalum oxide.     

(WO3)x–(TiO2)1−x nano-structured porous catalysts grown by micro-arc oxidation method: Characterization and formation mechanism

Very recently, we fabricated (WO₃)_x–(TiO₂)_1−x layers via micro-arc oxidation process under different applied voltages. Morphological and topographical studies, accomplished by SEM and AFM techniques, revealed that the pores size as well as the surface roughness increased with the voltage. Phase structure and chemical composition of the layers were also investigated by XRD and XPS and the results showed the grown layers consisted of titanium and tungsten oxides. It was found that WO₃ dispersed in the TiO₂ matrix and also doped into the TiO₂ lattice. In addition, optical properties of the synthesized layers were studied employing a UV–vis spectrophotometer. Band gap energy of the layers was approximately determined as 2.87 eV. Finally, methylene blue was selected as a model material and its degradation rate on the surface of the layers was measured to determine the photocatalytic efficiency. The degradation rate constants were measured as 2.2 × 10⁻² and 0.9 × 10⁻² min⁻¹ under ultraviolet and visible irradiations.     

Novel PEO-based composite solid polymer electrolytes incorporated with active inorganic–organic hybrid polyphosphazene microspheres

Inorganic–organic hybrid poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) microspheres with active hydroxyl groups were incorporated in poly(ethylene oxide) (PEO), using LiClO₄ as a dopant salt, to form a novel composite polymer electrolyte (CPE). The polymer chain flexibility and crystallinity properties are studied by DSC. The effects of active PZS microspheres on the electrochemical properties of the PEO-based electrolytes, such as ionic conductivity, lithium ion transference number, and electrochemical stability window are studied by electrochemical impedance spectroscopy and steady-state current method. Maximum ionic conductivity values of 3.36 × 10⁻⁵ S cm⁻¹ at ambient temperature and 1.35 × 10⁻³ S cm⁻¹ at 80 °C with 10 wt.% content of active PZS microspheres were obtained and the lithium ion transference number was 0.34. The experiment results showed that the inorganic–organic hybrid polyphosphazene microspheres with active hydroxyl groups can enhance the ionic conductivity and increase the lithium ion transference number of PEO-based electrolytes more effectively comparing with traditional ceramic fillers such as SiO₂.     

Fabrication and properties of titanium–hydroxyapatite nanocomposites

Titanium–hydroxyapatite nanocomposites with different HA contents (3, 10, 20 vol%) were produced by the combination of mechanical alloying (MA) and powder metallurgical process. The structure, mechanical and corrosion properties of these materials were investigated. Microhardness test showed that the obtained material exhibits Vickers microhardness as high as 1030 and 1500 HV_0.2, which is more than 4–6 times higher than that of a conventional microcrystalline titanium. Titanium nanocomposite with 10 vol% of HA was more corrosion resistant (i_C = 1.19 × 10⁻⁷ A cm⁻², E_C = −0.41 V vs. SCE) than microcrystalline titanium (i_C = 1.31 × 10⁻⁵ A cm⁻², E_C = −0.36 V vs. SCE). Additionally, the electrochemical treatment in phosphoric acid electrolyte results in porous surface, attractive for tissue fixing and growth. Mechanical alloying and powder metallurgy process for the fabrication of titanium–ceramic nanocomposites with a unique microstructure are developed.     

Removal of acid orange 7 by guava seed carbon: A four parameter optimization study

The preparation of carbon from waste materials is a recent and economic alternative for the removal of dyes. In this study four samples of carbon were obtained by thermal treatment at 1000 °C using as precursor the guava seed with different particle sizes. The Taguchi method was applied as an experimental design to establish the optimum conditions for the removal of acid orange 7 in batch experiments. The chosen experimental factors and their ranges were: pH (2–12), temperature (15–35 °C), specific surface area (50–600 m² g⁻¹) and adsorbent dosage (16–50 mg ml⁻¹). The orthogonal array L₉ and the larger the better response category were selected to determine the optimum removal conditions: pH 2, temperature 15 °C, S_esp 600 m² g⁻¹ and dosage 30 mg ml⁻¹. Under these conditions a total removal of acid orange 7 was achieved. Moreover, the most significant factors were the carbon specific surface area and the pH. The influence of the different factors on the adsorption of acid orange 7 from solution is explained in terms of electrostatic interactions by considering the dye species and the character of the surface.     

Spray deposition and property analysis of anatase phase titania (TiO2) nanostructures

Anatase phase titanium dioxide thin films have been deposited at various substrate temperatures by chemical spray pyrolysis of an aerosol of titanyl acetylacetonate. Deposited TiO₂ films were nanocrystalline and preferentially oriented along [101] direction, uniform and adherent to the glass substrate. Best films processed at 450 °C were characterized to analyze its phase composition, texture, roughness, optical and electrical properties. X-ray photoelectron spectroscopy revealed that the surface of the film has only the Ti⁴⁺ cations to form perfect TiO₂ stoichiometry with less amount of hydration. Atomic force microscopy image demonstrated the existence of homogeneous and rough surface, suitable for electrocatalytic applications. The film has an optical transmittance more than 90% and the refractive index of 2.07 was recorded at the wavelength 633 nm. Due to nano-sized grains, obtained optical band gap (3.65 eV) of the TiO₂ thin film was larger than that of the bulk TiO₂ (3.2 eV). Calculated porosity of the films 0.44, revealed the porous nature of the films. Hall measurements indicated that these materials are p-type and yield a carrier density of the order 8.8 × 10²⁰ cm⁻³ and a carrier mobility of 0.48 × 10⁻⁶ cm²/Vs. The dc electrical conductivity was therefore very low (8.91 × 10⁻⁶ S/cm) because of lower value of mean free path of the charge carriers (4.36 × 10⁻¹¹ cm). It gives an impression that the process of spray pyrolysis provides an easy way to tailor make thin films possessing superior properties.     

Preparation of anatase TiO2 thin films by vacuum arc plasma evaporation

Anatase titanium dioxide (TiO₂) thin films with high photocatalytic activity have been prepared with deposition rates as high as 16 nm/min by a newly developed vacuum arc plasma evaporation (VAPE) method using sintered TiO₂ pellets as the source material. Highly transparent TiO₂ thin films prepared at substrate temperatures from room temperature to 400 °C exhibited photocatalytic activity, regardless whether oxygen (O₂) gas was introduced during the VAPE deposition. The highest photocatalytic activity and photo-induced hydrophilicity were obtained in anatase TiO₂ thin films prepared at 300 °C, which correlated to the best crystallinity of the films, as evidenced from X-ray diffraction. In addition, a transparent and conductive anatase TiO₂ thin film with a resistivity of 2.6 × 10^− 1 Ω cm was prepared at a substrate temperature of 400 °C without the introduction of O₂ gas.     

Facile fabrication of SiO2/Al2O3 composite microspheres with a simple electrostatic attraction strategy

SiO₂/Al₂O₃ composite microspheres with SiO₂ core/Al₂O₃ shell structure and high surface area were prepared by depositing Al₂O₃ colloid particles on the surface of monodispersed microporous silica microspheres using a simple electrostatic attraction and heterogeneous nucleation strategy, and then calcined at 600 °C for 4 h. The prepared products were characterized with differential thermal analysis and thermogravimetric analysis (DTA/TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It was found that uniform alumina coating could be deposited on the surface of silica microspheres by adjusting the pH values of the reaction solution to an optimal pH value of about 6.0. The specific surface area and pore volume of the SiO₂/Al₂O₃ composite microspheres calcined at 600 °C were 653 m² g⁻¹ and 0.34 ml g⁻¹, respectively.     

A novel synthetic route to Y2O3:Tb phosphors by bicontinuous cubic phase process

This study applies a novel approach to prepare the terbium-doped yttrium oxide phosphors (Y₂O₃:Tb³⁺) using the bicontinuous cubic phase (BCP) process. The experimental results show that the prepared precursor powder was amorphous yttrium hydroxide Y_1−xTb_x(OH)₃ with a spherical shape and primary size 30–50 nm. High crystallinity phosphors with body-centered cubic structures were obtained after heat treatment above 700 °C for 4 h. The primary size of the phosphors grew to 100–200 nm, and dense agglomerates with a size below 1 μm were formed during the calcination. The obtained Y₂O₃:Tb³⁺ phosphor had a strong green emitting at 542 nm. The optimum Tb³⁺ concentration was 1 mol% to obtain the highest PL intensity. This study indicates that the calcining temperature of 700 °C needed for high luminescence efficiency in this work is much lower than 1000 °C or above needed for the conventional solid-state method.     

Sonochemical preparation of TiO2 nanoparticles in the ionic liquid 1-(3-hydroxypropyl)-3-methylimidazolium-bis(trifluoromethylsulfonyl)amide

Spherical shaped anatase nanoparticles (ø 5 nm) have been synthesized in the ionic liquid 1-(3-hydroxypropyl)-3-methylimidazolium-bis(trifluoromethanesulfonyl)amide from titanium tetraisopropoxide by ultrasound assisted synthesis under ambient conditions. XRD, EDX, TEM, XPS, Raman, UV–vis, PL and BET measurements have been employed for characterization of the nanostructure of as-prepared TiO₂. XRD and Raman measurements both show that the obtained material is crystalline with anatase structure. The morphology of TiO₂ nanoparticles was characterized by transmission electron microscopy (TEM). The bandgap of the TiO₂ nanocrystals estimated from XRD and UV–vis measurements is about 3.3 eV. The surface area of a typical sample is 177 m² g⁻¹. The synthesized anatase nanocrystals show good photocatalytic activity in the degradation of methylorange.