Electrochemical and SERS spectroscopic investigations of 4-methyl-4H-1,2,4-triazole-3-thiol monolayers self-assembled on copper surface

Electrochemically anticorrosive behaviors of 4-methyl-4H-1,2,4-triazole-3-thiol (4-MTTL) monolayers self-assembled on copper surface have been investigated by electrochemical impedance spectroscopy (EIS), electrochemical polarization measurement and surface-enhanced Raman scattering (SERS) spectroscopy. The EIS mechanism of the copper surface adsorbed with 4-MTTL monolayers was fitted with the mode of R(QR)(QR)(CR). The electrochemical polarization experimental results indicated the high inhibitive efficiency of about 81.1%. Potential dependent SERS result suggests that 4-MTTL molecule was anchored at the copper surface via S⁶ and N² atoms with a tilted orientation, which resulting in a strong interaction between the 4-MTTL molecule and copper surface. The molecule tended to experience a transition state of the adsorption at the copper surface via S⁶ atom only as the potential applied at −0.5 V vs. SCE.     

Structure and properties of (AlCrMnMoNiZrB0.1)Nx coatings prepared by reactive DC sputtering

The microstructure and properties of AlCrMnMoNiZrB_0.1 nitride films prepared by reactive direct current sputtering at various N₂-to-Ar flow ratios (R_N) were investigated. The films had an amorphous structure at low R_N and a face-centered cubic structure at a high R_N. As the R_N increased, the decrease in clusters and defects resulted in a dense columnar structure and low surface roughness. The peak hardness and modulus of the nitride films were 10.3 and 180 GPa, respectively. The enhanced hardness is ascribed to the increased metal-nitrogen bonding, solid solution strengthening of several metallic nitrides, and lattice strain. The nitride films deposited at R_N = 0.2, 0.5, and 0.8 had friction coefficients of 0.16, 0.12 and 0.15, respectively. Wear-out failure occurred within 400 s when R_N = 0 and 1.0. Adhesive wear was the dominant wear mechanism.     

Tribological characterization of chromium nitride coating deposited by filtered cathodic vacuum arc

CrN coatings were prepared by filtered cathodic vacuum arc (FCVA) technique. The influence of the deposition parameters (nitrogen partial pressure PN₂, substrate bias voltage V_s and preheating of the substrate) on the structural, mechanical and tribological properties of the FCVA CrN coatings was investigated. Further, the FCVA CrN coating was compared in dry reciprocating sliding with commercial multi-arc ion plating (MAIP) CrN coating as to friction and wear properties. Profilometer, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDX) were used to evaluate the wear scars and the wear mechanisms were discussed. The results showed that the structural, mechanical and tribological properties of the FCVA CrN coatings were significantly dependent on the deposition parameters. The FCVA CrN coating deposited with PN₂ of 0.1 Pa, V_s of −100 V and without preheating exhibited the optimal mechanical and tribological properties. The FCVA CrN coating exhibited much better anti-abrasive and anti-spalling properties than the MAIP CrN coating, which was resulted from significant reduction of macroparticles and pitting defects by the FCVA technique. The MAIP CrN coating suffered severe concentrated wear by a combination wear mechanisms of delamination, abrasive and oxidative wear when high normal load was applied, while for the FCVA CrN coating the wear mechanisms were ultra-mild abrasive and oxidative wear.     

Defect-controlled growth of ZnO nanostructures using its different zinc precursors and their application for effective photodegradation

Various zinc precursors, such as zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride, have been used to control the formation of zinc oxide (ZnO) nanostructures onto aluminum substrate by chemical means. FESEM images of the ZnO nanostructures showed the formation of different morphologies, such as flakes, nanowalls, nanopetals, and nanodisks, when the nanostructures were synthesized using zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride precursors, respectively. The TEM image of disk-like ZnO nanostructures formed using zinc chloride as a precursor revealed hexagonally shaped particles with an average diameter of 0.5 μm. Room-temperature photoluminescence (PL) spectra revealed a large quantity of surface oxygen defects in ZnO nanodisks grown from zinc chloride compared with those using other precursors. Furthermore, the ZnO nanostructures were evaluated for photocatalytic activity under ultraviolet (UV) light illumination. Nanostructures having a disk-like shape exhibited the highest photocatalytic performance (k = 0.027 min⁻¹) for all the ZnO nanostructures studied. Improved photocatalytic activity of ZnO nanodisks was attributed to their large specific surface area (4.83 m² g⁻¹), surface oxygen defects, and super-hydrophilic nature of their surface, which is particularly suitable for dye adsorption.     

Tailoring the wettability of nanocrystalline TiO2 films

The water contact angle (WCA) of nanocrystalline TiO₂ films was adjusted by fluoroalkylsilane (FAS) modification and photocatalytic lithography. FAS modification made the surface hydrophobic with the WCA up to ∼156°, while ultraviolet (UV) irradiation changed surface to hydrophilic with the WCA down to ∼0°. Both the hydrophobicity and hydrophilicity were enhanced by surface roughness. The wettability can be tailored by varying the concentration of FAS solution and soaking time, as well as the UV light intensity and irradiation time. Additionally, with the help of photomasks, hydrophobic-hydrophilic micropatterns can be fabricated and manifested via area-selective deposition of polystyrene particles.     

Work function of the adsorption system of potassium on tungsten

The work functions φ_hklof tungsten single crystal planes as functions of the surface densities N_hkl of the adsorbed potassium have been measured by means of the field emission method. Sealed-off field emission tubes with a Faraday collector and rotatable emitter were used. Another, special tube was made in order to determine the surface density of potassium. The unequilibrated adlayers on {110}, {112}, {100} and {111} tungsten single crystal planes have been investigated. For all the planes investigated the φ_hkl(N_hkl) dependence exhibited a distinct minimum. An attempt has been made to compare the experimental results with the theoretical models suggested recently.     

A calculation of the intrinsic {111} surface states of the zinc blende ANB8−N compounds

The electronic structure of polar {111} faces of zinc blende A^NB^8?N compounds is studied using a LCAO approximation. Within a molecular model a selfconsistent solution is achieved, taking into account the charge accumulation near the surface necessary to stabilize the system. It is found that stabilization by intrinsic surface states associated with unreconstructed surfaces is easier in large gap systems, which is supported by experimental evidence. The gap between electronegative and electropositive surface states is found to be in agreement with recent photoemission measurements for GaAs.     

Sonication-assisted synthesis of a new cationic zinc nitrate complex with a tetradentate Schiff base ligand: Crystal structure,Hirshfeld surface analysis and investigation of different parameters influence on morphological properties

A nanostructured cationic zinc nitrate complex with a formula of [ZnLNO₃]NO₃ (where L = (N²E,N^2′E)-N¹,N^1′-(ethane-1,2-diyl)bis(N²-((E)-3-phenylallylidene)ethane-1,2-diamine)) was prepared by sonochemical process and characterized by single crystal X-ray crystallography, scanning electron microscopy (SEM), FT-IR and NMR spectroscopy and X-ray powder diffraction (XRPD). The X-ray analysis demonstrates the formation of a cationic complex that metal center is five-coordinated by four nitrogen atom from Schiff base ligand and one oxygen atom from nitrate group. The crystal packing analysis demonstrates the essential role of the nitrate groups in the organization of supramolecular structure. The morphology and size of ultrasound-assisted synthesized zinc nitrate complex have been investigated using scanning electron microscopy (SEM) by changing parameters such as the concentration of initial reactants, the sonication power and reaction temperature. In addition the calcination of zinc nitrate complex in air atmosphere led to production of zinc oxide nanoparticles.     

Self-assembled monolayer growth on chemically modified polymer surfaces

We report a study of the self-assembled monolayer (SAM) growth of bis[3(triethoxysilane)propyl]tetrasulfide (Tetrasulfide) on low dielectric constant (low-k) aromatic hydrocarbon SiLK whose surface chemistry was modified using sulfuric acid, He plasma treatment, and N₂ plasma treatment. X-ray photoelectron spectroscopy (XPS) spectra show that there is no detectable growth of Tetrasulfide SAM on untreated SiLK surfaces. After the SiLK surfaces have been treated with sulfuric acid, He plasma, or N₂ plasma, the original chemically inert polymer surfaces are functionalized with polar groups resulting in a significant improvement of their wettability, which is confirmed by their reduction of water droplet contact angles. The introduction of polar functional groups thus facilitates the formation of Tetrasulfide SAM on the polymer surfaces. Atomic force microscopy (AFM) analysis shows an insignificant change in the surface morphology after the growth of Tetrasulfide SAM on the chemically modified SiLK surfaces. Quantitative XPS analysis also showed that Tetrasulfide SAM growth is more prominent on He and N₂ plasma treated surfaces than those treated by sulfuric acid.     

Generation of widely tunable Fourier-transform-limited terahertz pulses using narrowband near-infrared laser radiation

Widely tunable, Fourier-transform-limited pulses of terahertz (THz) radiation have been generated using (i) crystals of the highly nonlinear organic salt 4-N,N-dimethylamino-4′-N′-methyl stilbazolium tosylate (DAST), (ii) zinc telluride (ZnTe) crystals, (iii) gallium phosphide (GaP) crystals, and (iv) low-temperature-grown gallium arsenide (LTG-GaAs) photomixers with THz spiral antennas. Outputs from two narrowband (Δν < 1 MHz, λ ∼ 800 nm) cw titanium-doped sapphire (Ti:Sa) ring lasers with a well-controlled frequency difference were shaped into pulses using acousto-optic modulators (AOM), coupled into an optical fiber, pulse amplified in Nd:YAG-pumped Ti:Sa crystals and used as optical sources to pump the THz emitters. The THz radiation was detected over a broad frequency range and its bandwidth was determined to be ∼10 MHz. The spectroscopic potential of the THz source is illustrated by the absorption spectrum of a pure rotational transition of OCS.     

Dry sliding wear characteristics of in situ synthesized Al-TiC composites

Abstract

Aluminum-based composites containing 0.06, 0.09, 0.12 fractions of in situ-synthesized TiC (Titanium carbide) particles have been prepared through in-melt reaction from Ai–SiC–Ti system following a simple and cost-effective stir-casting route. The TiC forms by the reaction of Ti with carbon which is released by SiC at temperatures greater than 1073 K. However, some amount of titanium aluminide (Al₃Ti) is also formed. The formation of TiC has been confirmed through X-ray diffraction studies of the composite. The hardness and tensile strength have been found to increase with increasing amount of TiC. The friction and wear characteristics of the composites have been determined by carrying out dry sliding tests on pin-on-disc machine at different loads of 9.8 N, 19.6 N, 29.4 N, 39.2 N at a constant sliding speed of the 1 m/s speed. The wear rate i.e. volume loss per unit sliding distance has been found to increase linearly with increasing load following Archard’s law. However, both the wear rate and friction coefficient have been observed to decrease with increasing amount of TiC in the composite. This has been attributed to (i) a relatively higher hardness of composites containing relatively higher amount of TiC resulting in a relatively lower real area of contact and (ii) the formation of a well-compacted mechanically mixed layer of compacted wear debris on the worn surface which might have inhibited metal–metal contact and resulted in a lower wear rate as well as friction coefficient.     

Friction,adhesion and wear durability of an ultra-thin perfluoropolyether-coated 3-glycidoxypropyltrimethoxy silane self-assembled monolayer on a Si surface

The tribological properties, such as coefficient of friction, adhesion and wear durability of an ultra-thin (<10?nm) dual-layer film on a silicon surface were investigated. The dual-layer film was prepared by dip-coating perfluoropolyether (PFPE), a liquid polymer lubricant, as the top layer onto a 3-glycidoxypropyltrimethoxy silane self-assembled monolayer (epoxy SAM)-coated Si substrate. PFPE contains hydroxyl groups at both ends of its backbone chain, while the SAM surface contains epoxy groups, which terminate at the surface. A combination of tests involving contact angle measurements, ellipsometry, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) was used to study the physical and chemical properties of the film. The coefficient of friction and wear durability of the film were investigated using a ball-on-disk tribometer (4?mm diameter Si₃N₄ ball as the counterface at a nominal contact pressure of ～330?MPa). AFM was used to investigate the adhesion forces between a sharp Si₃N₄ tip and the film. This dual-layer film had a very low coefficient of friction, adhesion and wear when compared to epoxy SAM-coated Si only or bare Si surface. The reasons for the improved tribological performance are explained in terms of the lubrication characteristics of PFPE molecules, low surface energy of PFPE, covalent bonding between PFPE and epoxy SAM coupled with reduced mobile PFPE. The low adhesion forces coupled with high wear durability show that the film has applications as a wear resistant and anti-stiction film for microcomponents made from Si.     

Optical emission studies of sulphur plasma using laser induced breakdown spectroscopy

We present the optical emission studies of sulphur (S) plasma generated by the first (1064 nm) and second (532 nm) wavelengths of a Q-switched Nd:YAG laser. The target material was placed in front of laser beam in air at atmospheric pressure. The experimentally observed line profiles of neutral sulphur have been used to extract the electron temperature (T _e ) using the Boltzmann plot method, whereas the electron number density (N _e ) has been determined from the Stark broadening. The electron temperature is calculated by varying, distance from, the target surface along the line of propagation of plasma plume and also by varying the laser irradiance. Beside we have studied the variation of number density as a function of laser irradiance as well as its variation with distance from the target surface. It is observed that electron temperature and electron number density increases as laser irradiance is increased.     

Examination of temperature distribution and the thermal effects on Si3N4 engineering ceramics during fibre laser surface treatment

The thermal effects of fibre laser surface treatment on a Si₃N₄ engineering ceramic were studied using a computational finite element analysis (FEA). Temperature increases on the surface of the Si₃N₄ during fibre laser processing were measured using an infra-red thermometer; temperature distributions in the bulk were measured with specifically located thermocouples. A computational model by using FEA was then developed to model the flow and the distribution of the radiated heat resulting from the fibre laser treatment of the Si₃N₄ ceramic. By utilising data obtained from a TG-DSC analysis the FEA model predictions of the temperature distribution were used to map phase transformations and significant events occurring during the fibre laser surface treatment of the Si₃N₄. The TG-DSC analysis also indicated that the fibre laser surface treatment generally resulted in a phase transformation of the Si₃N₄ from α-phase to β-phase modification as elongated rod-like grains were found.     

Investigation into the photo-induced change in wettability of hydrophobized TiO2 films

The photo-induced change in wettability of hydrophobized TiO₂ films has been investigated for steel coated with acidic TiO₂ nanosols containing varying concentrations of dispersed nanocrystalline titania, such as Degussa P25. The photo-induced change in wettability was evaluated by measuring the time-dependent drop of water contact angle (WCA) after samples had been soaked in either n-octyltriethoxysilane (OTS) or decanoic acid (DA). TiO₂ films treated in this way exhibit superhydrophobic behaviour, with WCA greater than 160°. After radiation with UV (black light), the superhydrophobic properties are transformed into superhydrophilic properties, with WCA of almost 0°. As P25 content and layer thickness increase, high rates of photo-induced change are found, but a moderate calcination regime is required. On the other hand, hardness and E modulus pass through a maximum at 25 wt% P25, so that a P25 content between 25 and 50 wt% is the optimum for practical uses. With such stable coatings, wettability can be controlled over a wide range, and the switch between hydrophobic and hydrophilic states can be carried out repeatedly when DA is used as the hydrophobizing agent. Use of a low calcination temperature (450 °C) for the intermediate annealing of the single layers in multilayer coatings and a short final sintering step at a relatively high temperature (e.g. 630 °C for 10 min) allow the preparation of relatively thin TiO₂ films on steel with a high photoactivity.     

Investigation on femtosecond laser irradiation energy in inducing hydrophobic polymer surfaces

This study investigates the use of ultrashort femtosecond laser pulses to induce hydrophobic properties on PMMA surfaces. The modification of surface wetting property exhibits a strong dependence on the amount of energy deposited on the PMMA surface. A simple equation has been deduced from the laser parameters to express the energy deposition. It was revealed that water contact angle (WCA) of more than 120°, with a maximum of around 125°, could be achieved when the total energy deposited per unit area on the PMMA surface ranged from 600 J/cm² to 900 J/cm² at an energy deposition rate of around 50 J/cm²/s. Beyond this range, WCA reduced with increasing amount of energy deposition. Furthermore, with higher energy deposition rate or higher laser fluence, total energy required to induce hydrophobic surfaces was reduced. Under different energy deposition, the quantity of polar groups or non-polar groups induced was responsible for the changes in WCA and thus the different surface hydrophobicity.     

Controlled growth of superhydrophobic films by sol-gel method on aluminum substrate

Superhydrophobic surface was prepared by sol-gel method on aluminum substrate via immersing the clean pure aluminum substrate into the solution of zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and hexamethylenetetraamine (C₆H₁₂N₄) at different molar ratios and unchanged 0.04 mol/L total concentration, then heated at 95 °C in water bath for 1.5 h, subsequently modified with 18 alkanethiols or stearic acid. When the molar ratios of Zn(NO₃)₂·6H₂O and C₆H₁₂N₄ were changed from 10:1 to 1:1 the contact angle was higher than 150°. The best prepared surface had a high water contact angle of about 154.8°, as well as low angle hysteresis of about 3°. The surface of prepared films using Zn(NO₃)₂·6H₂O and C₆H₁₂N₄ composed of ZnO and Zn-Al LDH, and Al. SEM images of the film showed that the resulting surface exhibits different flower-shaped wurtzite zinc oxide microstructure and porous Zn-Al LDH. The special flowerlike and porous architecture, along with the low surface energy leads to the surface superhydrophobicity.     

Secondary-ion emission from clean and oxygen-covered beryllium surfaces: II. Energy dependence

The secondary-ion energy distribution obtained by sputtering clean and oxygen-covered Be has been analyzed in terms of competing processes in secondary ion emission. The ion energy distribution N⁺(E) has been separated into an ionization coefficient R⁺(E) and a total energy distribution, N(E), i.e. N⁺(E) = R⁺(E) N(E). Experimentally, the dependence of R⁺(E) on both energy and oxygen coverage indicated a linear superposition of adiabatic tunneling and resonanance ionization processes from clean and oxygen-covered portions of the surface with no contributions to the secondary-ion yield from regions of intermediate coverage. Total energy distributions of sputtered Be atoms have been deduced and the principal features agree with the predictions of the collision cascade sputtering model. Variations of the energy distributions with oxygen coverage are in accord with small changes expected in the surface binding energy as a result of surface oxidation.     

Synthesis, structure and luminescence properties of zinc (II) complexes with terpyridine derivatives as ligands

Five zinc (II) complexes (1-5) with 4′-phenyl-2,2′:6′,2″-terpyridine (ptpy) derivatives as ligands have been synthesized and fully characterized. The para-position of phenyl in ptpy is substituted by the group (R), i.e. tert-butyl (t-Bu), hexyloxy (OHex), carbazole-9-yl (Cz), naphthalen-1-yl-phenyl-amine-N-yl (NPA) and diphenyl amine-N-yl (DPA), with different electron-donating ability. With increasing donor ability of the R, the emission color of the complexes in film was modulated from violet (392 nm) to reddish orange (604 nm). The photoexcited luminescence exhibits significant solvatochromism because the emission of the complexes involves the intra-ligand charge transfer (ILCT) excited state. The electrochemical investigations show that the complexes with stronger electro-donating substituent have lower oxidation potential and then higher HOMO level. The electroluminescence (EL) properties of these zinc (II) complexes were studied with the device structure of ITO/PEDOT/Zn (II) complex: PBD:PMMA/BCP/AlQ/LiF/Al. Complexes 3, 4 and 5 exhibit EL wavelength at 552, 600 and 609 nm with maximum current efficiency of 5.28, 2.83 and 2.00 cd/A, respectively.     

Inhibition of copper corrosion by self-assembled films of new Schiff bases and their modification with alkanethiols in aqueous medium

The inhibitive action of self-assembled films derived from two ligands Schiff bases, including N,N′-ethylen-bis (salicylidenimine) and N,N′-ortho-phenylen-bis (salicylidenimine) on copper surface has been studied by electrochemical techniques in chloride and acidic solutions. It was found that when the concentration of the inhibitors was increased the inhibition efficiency was increased, too. The results of the electrochemical studies have illustrated that the inhibition efficiency of S-o-ph-S is higher than S-E-S. Both the Schiff bases obeyed the Langmuir isotherm and thermodynamics calculations revealed that S-o-ph-S had larger adsorption constant and more negative free energy of adsorption with respect to S-E-S. When the films were modified by propanethiol and 1-dodecanethiol, the corrosion resistance of mixed films was significantly increased.