Evolution of TiOx-SiOx nano-composite during annealing of ultrathin titanium oxide films on Si substrate

This paper discusses the formation of the TiO_x-SiO_x nano-composite phase during annealing of ultrathin titanium oxide films (~27 nm). The amorphous titanium oxide films are deposited on silicon substrates by sputtering. These films are important for high-k dielectrics and sensing applications. Annealing of these films at 750 °C in the O₂ environment (for 15–60 min) resulted in the polycrystalline rutile phase. The films exhibit Raman peaks at 150 cm⁻¹ (B_1g), 435 cm⁻¹ (E_g), and 615 cm⁻¹ (A_1g) confirming the rutile phase. The signature TO (1078 cm⁻¹) and LO (1259 cm⁻¹) infrared active vibrational modes of Si–O–Si bond confirms the presence of silicon-oxide. The X-ray photoelectron spectra of the TiO_x films show multiple peaks corresponding to Ti metal (453.8 eV); Ti⁴⁺ state (458.3 eV (Ti 2p_3/2) and 464 eV (Ti 2p_1/2)); and Ti³⁺ state (456.4 eV (Ti 2p_3/2) and 460.8 eV (Ti 2p_1/2)). The O1s XPS spectra peaks at 530–533 eV can be attributed to Ti–O and Si–O bonds of the TiO_x-SiO_x nano-composite phase in the annealed films. The depth profiling XPS study shows that the top surface of the annealed film is mainly TiO_x and the amount of SiO_x increases with the depth.     

Effect of electrolyte concentration on morphology,microstructure and electrochemical impedance of anodic oxide film on titanium alloy Ti-10V–2Fe–3Al

Anodic oxide films were fabricated on titanium alloy Ti-10V–2Fe–3Al in ammonium tartrate solutions at the concentrations: 1, 3, 5, 10 and 15 g L⁻¹. The morphological characteristics and microstructures of the films of the alloy were studied by optical microscopy (OM) and Raman spectroscopy (Raman), respectively. The electrochemical impedances of the films in 0.5 mol L⁻¹ H₂SO₄ solution were investigated by electrochemical impedance spectroscopy (EIS). It was showed that different electrolyte concentrations led to different change rates of anodizing forming voltage. The change rate significantly affected the morphology, microstructure and electrochemical impedance of anodic oxide film. When electrolyte concentration was 5 g L⁻¹, anodic oxide film was the most uniform, exhibited by the least and smallest breakpoints on the film. In addition, the amount of crystal phase of the film was the largest at 5 g L⁻¹, showed by the highest intensity of Raman peaks. Furthermore, the electrochemical impedance of the film of the alloy was the greatest at 5 g L⁻¹, demonstrated by the highest values of polarization resistances and lowest values of capacitances. These phenomenon were associated with the minimum value of the change rate of anodizing forming voltage at 5 g L⁻¹.     

DSA electrochemical treatment of olive mill wastewater on Ti/RuO<Subscript>2</Subscript> anode

The electrochemical oxidation of olive mill wastewater (OMW) over a Ti/RuO₂ anode was studied by means of cyclic voltammetry and bulk electrolysis and compared with previous results over a Ti/IrO₂ anode. Experiments were conducted at 300–1,220 mg L⁻¹ initial chemical oxygen demand (COD) concentrations, 0.05–1.35 V versus SHE and 1.39–1.48 V versus SHE potential windows, 15–50 mA cm⁻² current densities, 0–20 mM NaCl, Na₂SO₄, or FeCl₃ concentrations, 80 °C temperature, and acidic conditions. Partial and total oxidation reactions occur with the overall rate being near first-order kinetics with respect to COD. Oxidation at 28 Ah L⁻¹ and 50 mA cm⁻² leads to quite high color and phenols removal (86 and 84%, respectively), elimination of ecotoxicity, and a satisfactory COD and total organic carbon reduction (52 and 38%, respectively). Similar performance can be achieved at the same charge (28 Ah L⁻¹) using lower current densities (15 mA cm⁻²) but in the presence of various salts. For example, COD removal is less than 7% at 28 Ah L⁻¹ in a salt-free sample, while addition of 20 mM NaCl results in 54% COD reduction. Decolorization of OMW using Ti/RuO₂ anode seems to be independent of the presence of salts in contrast with Ti/IrO₂ where addition of NaCl has a beneficial effect on decolorization.     

The dynamic surface chemistry during the interaction of CO with ceria captured by Raman spectroscopy

The interaction of CO with ceria under conditions typically used to measure the oxygen storage capacity (OSC) of automotive three way catalysts (TWC) has been investigated by in situ Raman spectroscopy. During exposure of the ceria to CO at 623 K vibrational bands at 1582–1600 and 1331–1340 cm⁻¹ appeared; these bands increased with increasing time of exposure to CO. The band positions are consistent with phonon modes of carbon; however, assignment to carboxylate species or carbonate species cannot be excluded. Subsequent exposure to O₂ at room temperature resulted in a decrease in the intensities of the 1582–1600 and 1331–1340 cm⁻¹ bands by more than 90%. As well, exposure to O₂ at room temperature also resulted in the appearance of Raman modes characteristic of formate and peroxide surface species. The mechanism by which formate forms upon room temperature O₂ exposure is discussed in the context of the assignment of the 1582–1600 and 1331–1340 cm⁻¹ bands to carbon phonon modes which result from the disproportionation of CO on reduced ceria.     

Investigation of 12-Tungstophosphoric Acid Supported on Ce0.5Zr0.5O2 Solid Solution

The nature of the Keggin ions of tungstophosphoric acid interacting with Ce_0.5Zr_0.5O₂ solid solution has been investigated. The vibrational study shows additional IR features at 1051 and 957 cm⁻¹ which are correlated to the primary Keggin anions interacting with Lewis sites involving Ce⁴⁺ and Zr⁴⁺ ions, and thus affecting the P–O and W=O_terminal bonds. The IR study indicates the formation of interfacial Ce⁴⁺–O–W and Zr⁴⁺–O–W bonds. The chemisorbed Keggin molecular layers on Ce_0.5Zr_0.5O₂ show activity towards conversion of acetophenone to styrene by Meerwein–Ponndorf–Verley reduction followed by dehydration. The activity is correlated with the relative intensities of IR peaks at 1051 and 957 cm⁻¹ of the perturbed Keggin molecular layers.     

Synthesis of a novel amphiphilic polymer containing nucleobases in the self-organized nanospheres

A simple strategy to achieve molecular recognition in water is to make the polymers self-organized into nanospheres which could incorporate the functional groups containing hydrogen bonding sites into hydrophobic-lipophilic regions. A novel amphiphilic polymer, Poly(polyoxyethylene-600)-oxy-5-(6-(1-thymine)hexyl)) isophthaloyl (PPETHI), has been synthesized. The PPETHI polymer could self-organize into nanospheres in dilute aqueous solution, which were 150–300 nm in diameter as estimated by SEM. The isophthaloyl with side hexyl thymine of the polymer self-organized into hydrophobic regions and the PEG surrounded it. Molecular recognition between thymine in PPETHI polymer and adenine substrate has been studied by FT-IR. The FT-IR studies demonstrate that C₄=O of thymine has recognized with N-H of adenine through complementary nucleobases. It shows that the typical characteristic band at 3,352 cm⁻¹ of N-H stretching vibration of adenine shifted to 3,373 cm⁻¹ and the band at 1,685 cm⁻¹ of C₄=O of thymine shifted to 1,680 cm⁻¹. To confirm the formation of hydrogen bonds, the N-H band at 3,373 cm⁻¹ and C₄=O band at 1,680 cm⁻¹ have retrieved to 3,312 cm⁻¹ and 1,685 cm⁻¹ respectively upon heating to 115 °C or higher by means of variable temperature FT-IR. The formations of hydrogen-bonds between thymine in the polymer and adenine substrate in nanospheres were confirmed. It could enhance their interaction and loading capacity.     

Electrochemical degradation of Reactive Red 120 using DSA and BDD anodes

Electrochemical oxidation of an azo dye (Reactive Red 120) was studied in acidic media (1 M HClO₄) using DSA type (Ti/IrO₂–RuO₂) and boron doped diamond (BDD) anodes. Ti/IrO₂–RuO₂ exhibited low oxidation power with high selectivity to organic intermediates and low TOC removal (10% at 25 °C and 40% at 80 °C). On the other hand BDD was found to be suitable for total mineralization of the organic loading to CO₂. In both cases, the decoloration of the solution was almost 100% achieved very quickly with BDD (2 Ah L⁻¹) but only after long treatment with Ti/IrO₂–RuO₂ (25 Ah L⁻¹). The instantaneous current efficiency (ICE) was up to 0.13 in the case of Ti/IrO₂–RuO₂ and up to 0.45 in the case of BDD.     

Electrodeposition and Capacitive Behavior of Films for Electrodes of Electrochemical Supercapacitors

Polypyrrole films were deposited by anodic electropolymerization on stainless steel substrates from aqueous pyrrole solutions containing sodium salicylate and tiron additives. The deposition yield was studied under galvanostatic conditions. The amount of the deposited material was varied by the variation of deposition time at a constant current density. SEM studies showed the formation of porous films with thicknesses in the range of 0–3 μm. Cyclic voltammetry data for the films tested in 0.5 M Na₂SO₄ solutions showed capacitive behavior and high specific capacitance (SC) in a voltage window of 0.9 V. The films prepared from pyrrole solutions containing tiron showed better capacitive behavior compared to the films prepared from the solutions containing sodium salicylate. A highest SC of 254 F g⁻¹ was observed for the sample with a specific mass of 89 μg cm⁻² at a scan rate of 2 mV s⁻¹. The SC decreased with an increasing film thickness and scan rate. The results indicated that the polypyrrole films deposited on the stainless steel substrates by anodic electropolymerization can be used as electrodes for electrochemical supercapacitors (ES).     

Preparation and evaluation of RuO2–IrO2, IrO2–Pt and IrO2–Ta2O5 catalysts for the oxygen evolution reaction in an SPE electrolyzer

IrO₂–RuO₂, IrO₂–Pt and IrO₂–Ta₂O₅ electrocatalysts were synthesized and characterized for the oxygen evolution in a Solid Polymer Electrolyte (SPE) electrolyzer. These mixtures were characterized by XRD and SEM. The anode catalyst powders were sprayed onto Nafion 117 membrane (catalyst coated membrane, CCM), using Pt catalyst at the cathode. The CCM procedure was extended to different in-house prepared catalyst formulations to evaluate if such a method could be applied to electrolyzers containing durable titanium backings. The catalyst loading at the anode was about 6 mg cm⁻², whereas 1 mg cm⁻² Pt was used at the cathode. The electrochemical activity for water electrolysis was investigated in a single cell SPE electrolyzer at 80 °C. It was found that the terminal voltage obtained with Ir–Ta oxide was slightly lower than that obtained with IrO₂–Pt and IrO₂–RuO₂ at low current density (lower than 0.15 A cm⁻²). At higher current density, the IrO₂–Pt and IrO₂–RuO₂ catalysts performed better than Ir–Ta oxide.     

Long-term behavior of oil-based varnishes and paints I. Spectroscopic analysis of curing drying oils

The curing of drying oils at 60°C has been investigated by Fourier transform infrared spectroscopy and Fourier transform Raman analysis of linseed oil and poppyseed oil. In the first step, hydroperoxides are formed (broad vibration band centered around 3425 cm⁻¹) with concomitant conjugation and cis-trans isomerization of the double bonds (disappearance of cis bands at 3011 and 716 cm⁻¹, appearance of trans conjugated and trans nonconjugated bands at 987 and 970 cm⁻¹). The subsequent decomposition of hydroperoxides in the presence of oxygen leads to the formation of alcohols (nitrite band at 779 cm⁻¹ after nitrogen monoxide treatment), aldehydes (bands at 2810 and 2717 cm⁻¹ in gas phase), ketones (saturated and unsaturated at 1720 and 1698 cm⁻¹, respectively), carboxylic acids (saturated and unsaturated acid fluorides identified at 1843 and 1810 cm⁻¹ after SF₄ treatment), and peresters or γ-lactones (near 1770 cm⁻¹). A rapid decrease in the double-bond concentration is recorded when curing continues, and the formation of epoxides, characterized by a vibration band at 885 cm⁻¹, is observed. Thermolysis experiments have suggested the proposal of a reaction of addition of peroxyl radicals on the conjugated double bonds as a probable mechanism. This mechanism explains both the rapid disappearance of conjugated double bonds and the formation of epoxides as intermediate products observed in the initial step of curing.     

Characteristics of a tungsten film electrodeposited in a KF–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–WO<Subscript>3</Subscript> melt and preparation of W–Cu–W three-layered films for heat sink application

A tungsten film of 13 μm in thickness was obtained on a copper substrate by galvanostatic electrolysis at 30 mA cm⁻² for 40 min in a KF–B₂O₃–WO₃ (67:26:7 mol%) melt at 850 °C. By cross-sectional scanning electron microscopy observation and energy dispersive X-ray analysis, the tungsten layer was found to be compact and free from cracks, voids and melt inclusion. The X-ray diffractometry analysis revealed that the phase was α-tungsten, and that (222) plane was significantly oriented parallel to the substrate. By nanoindentation, its hardness was found to be 8.4 GPa, which was larger than that of single crystal tungsten. Its Young’s modulus was measured to be 410 GPa, which was similar with the reported value of single crystal tungsten. Its coefficient of linear thermal expansion and thermal conductivity were 4.5 × 10⁻⁶ K⁻¹ and 178 W m⁻¹ K⁻¹, respectively, which were similar values for the tungsten produced by a conventional powder metallurgy method. Finally, W–Cu–W three-layered films were prepared for a heat sink application. It was confirmed that a three-layered film having a desired coefficient of linear thermal expansion can be prepared easily by this new molten salt method.     

Raman studies of structural rearrangements induced in human plasma lipoprotein carotenoids by malondialdehyde

Raman and resonance Raman spectra of plasma lipoproteins ± malondialdehyde were studied at concentrations which block the normal receptor-mediated uptake by cells. The strong resonance Raman bands at about 1010, 1162 and 1530 cm⁻¹, due to the presence of carotenoids in the lipoproteins, are envisaged as structural probes. High resolution resonance Raman spectra of the 1500–1600 cm⁻¹ region reveal multiple features suggesting the coexistence of several structural populations of β-carotene whose precise assignment is complex. When plasma lipoproteins are reacted with malondialdehyde, a complex change occurs in the resonance Raman banding of β-carotene in the 1500–1600 cm⁻¹ region. Malonaldehyde (MDA) also modifies the acoustical region (70–200 cm⁻¹ of low density lipoprotein (LDL) lipids. We suggest that malondialdehyde association with plasma lipoproteins alters the lipid structure via apoprotein or apoprotein/lipid associations.     

Spectroscopic Investigation of Quantum Confinement Effects in Ion Implanted Silicon-on-Sapphire Films

Crystalline Silicon-on-Sapphire (SOS) films were implanted with boron (B⁺) and phosphorous (P⁺) ions. Different samples, prepared by varying the ion dose in the range 10¹⁴–5 × 10¹⁵ and ion energy in the range 150–350 keV, were investigated by the Raman spectroscopy, photoluminescence (PL) spectroscopy and glancing angle x-ray diffraction (GAXRD). The Raman results from dose dependent B⁺ implanted samples show red-shifted and asymmetrically broadened Raman line-shape for B⁺ dose greater than 10¹⁴ ions cm⁻². The asymmetry and red shift in the Raman line-shape is explained in terms of quantum confinement of phonons in silicon nanostructures formed as a result of ion implantation. PL spectra shows size dependent visible luminescence at ∼1.9 eV at room temperature, which confirms the presence of silicon nanostructures. Raman studies on P⁺ implanted samples were also carried out as a function of ion energy. The Raman results show an amorphous top SOS surface for sample implanted with 150 keV P⁺ ions of dose 5 × 10¹⁵ ions cm⁻². The nanostructures are formed when the P⁺ energy is increased to 350 keV by keeping the ion dose fixed. The GAXRD results show consistency with the Raman results.     

Properties and mechanism of solar absorber CdTe thin film synthesis by unipolar galvanic pulsed electrodeposition

Electrochemical deposition of CdTe semiconductor thin films over transparent conducting glass substrates by sequential unipolar current pulses is described. The magnitude of pulsed current and pulse periodicity affects the crystalline structure, morphology, optical absorbance and composition of CdTe films. CdTe films formed under high magnitude pulsed current density ~5–15 mA cm⁻² are crystalline with dominant cubic structure having (111) plane oriented parallel to the substrate. Stoichiometric CdTe film growth occurs with current pulses of short 25–300 ms periodicity and 3–50 ms duration. A mechanism of the CdTe growth involving in situ cathodic tellurization process step involving H₂Te formation and reaction with electrochemically deposited Cd monolayer is described. CdTe film growth in the pulsed electrodeposition occurs under mass transport conditions under strong influence of high magnitude pulsed current. This results in much higher growth rates ~5–8 μm h⁻¹ for CdTe films which is attractive for CdTe solar cells in a production environment.     

On the structure of glasses in the Ge-S-Br and Ge-Se-Br systems

The structure of the vitreous GeSBr₂ and GeSeBr₂ compounds has been investigated using Raman scattering spectroscopy. The Raman spectra of the GeSBr₂ compound contain bands at 235 and 113 cm⁻¹, which are attributed to vibrations in the GeBr₄ molecule, and bands at 288, 254, 161, and 147 cm⁻¹, which are absent in the Raman spectra of binary compounds. The Raman spectrum of the GeSeBr₂ glass has common features with the spectra of the GeSe₂ and GeBr₄ compounds but also involves a number of new bands intermediate in position between the bands at 265 cm⁻¹ for the GeSe₂ compound and the bands at 325 cm⁻¹ for the GeBr₄ compound. The spectra obtained confirm the existence of equilibria between the formation and dissociation of ternary structural units in melts of the thiobromide and selenobromide systems.     

Electrochemical properties of amorphous Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript>2</Subscript>O<Subscript>5−<Emphasis Type="Italic">y</Emphasis></Subscript> thin film deposited by r.f.-sputtering

The electrochemical properties of amorphous vanadium pentoxide (V₂O₅) thin films deposited by reactive r.f.-sputtering were investigated using galvanostatic charge/discharge cycling and galvanostatic intermittent titration technique (GITT). As x in Li _x V₂O_5−y increased (x = 0–2.0), the electromotive force of the lithium (Li)∣1 M LiClO₄–propylene carbonate∣Li _x V₂O_5−y cell decreased gradually without a potential plateau or an abrupt potential reduction, demonstrating that an irreversible structural change did not occur in the entire Li content. Chemical diffusivity of the Li ion in the Li _x V₂O_5−y thin film measured using GITT was determined to be 4 × 10⁻¹³–7 × 10⁻¹⁴ cm² s⁻¹ in the Li content range investigated.     

Anodic oxidation of organic pollutants on a Ti/SnO<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>4</Subscript> anode

A Ti/SnO₂–Sb₂O₄ electrode was prepared by alternate Sn and Sb electrodepositions using the thermo-electrochemical method. The chemical, electrochemical, and structural characterization of the electrode was performed and it was tested in the anodic oxidation of several pollutants, phenol, ibuprofen, acid orange 7 (AO7), and diclofenac, all in aqueous 0.035 M Na₂SO₄ solutions at current densities of 10 and 20 mA cm⁻². After the 24 h assay, removal of chemical oxygen demand, total organic carbon (TOC) and absorbance were very high, especially at the higher current density. TOC removals presented the lowest value. However, after 24 h at 20 mA cm⁻², TOC removals were: phenol—94%; ibuprofen—83%; AO7—88%; and diclofenac—73%. Combustion efficiency and instantaneous and mineralization current efficiencies were also determined.     

Composite Electrodes for Electrochemical Supercapacitors

Manganese dioxide nanofibers with length ranged from 0.1 to 1 μm and a diameter of about 4–6 nm were prepared by a chemical precipitation method. Composite electrodes for electrochemical supercapacitors were fabricated by impregnation of the manganese dioxide nanofibers and multiwalled carbon nanotubes (MWCNT) into porous Ni plaque current collectors. Obtained composite electrodes, containing 85% of manganese dioxide and 15 mass% of MWCNT, as a conductive additive, with total mass loading of 7–15 mg cm⁻², showed a capacitive behavior in 0.5-M Na₂SO₄ solutions. The decrease in stirring time during precipitation of the nanofibers resulted in reduced agglomeration and higher specific capacitance (SC). The highest SC of 185 F g⁻¹ was obtained at a scan rate of 2 mV s⁻¹ for mass loading of 7 mg cm⁻². The SC decreased with increasing scan rate and increasing electrode mass.     

Influence of hydrogen on the residual stress in nanocrystalline diamond films

Nanocrystalline films were deposited by microwave-plasma CVD at a pressure of 200 mbar from an Ar/H₂/CH₄ plasma where the hydrogen fraction in the process gas was varied between 2 and 7%.Residual stress is a critical parameter in thin film deposition and especially important for technical applications of nanocrystalline diamond because high residual stress can lead to cracking or even to delamination of the film from the substrate. An ex-situ optical device was used to measure the residual stress of the substrate.It is shown that by controlling the process parameters the residual stress in the NCD films can be adjusted in a wide range even from compressive to tensile.The films were characterized by two wavelength scanning micro Raman spectroscopy and SEM.In this work a correlation is made between the intrinsic stress measurements and the Transpolyacetylene peaks (around 1120 cm^− 1 and 1450 cm^− 1) in the Raman spectra of NCD films. It is shown that the intensity and the FWHM of the peaks correlate with the tensile stress in the films. A model correlating the Raman spectra to the grain size and thus to the intrinsic stress measurements is given in this paper.     

Investigation of N<Subscript>2</Subscript>-fixation on polyaniline electrodes in methanol by electrochemical impedance spectroscopy

The ac response of polyaniline thin films on platinum electrodes was measured at different dc potentials during the N₂-fixation in methanol + LiClO₄ electrolyte with 0.03 mol L⁻¹ H₂SO₄ for the first time. The optimum film thickness was found to be 1.5 μm, N₂-pressure 50 bar and an optimum electrolysis potential of −0.12 V (NHE). The diffusion coefficients for N₂ into the polymer film was found to be (5 ± 2)×10⁻⁹ cm² s⁻¹.