Super-hydrophobic surface on pure magnesium substrate by wet chemical method

A layer of flower-like super-hydrophobic film was fabricated on pure Mg surface by chemical etching in H₂SO₄, H₂O₂ and subsequent immersion in stearic acid (CH₃(CH₂)₁₆COOH) ethanol solution. The super-hydrophobic surface showed a static water contact angle of 154° with the sliding angle of about 3°. With scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and Fourier-transform infrared (FT-IR) spectrometer, the microstructure and composition of the sample were analyzed. Results showed that the flower-like structure and the bonding of the CH₃(CH₂)₁₆COO⁻ on Mg surface can be responsible for the superior water-repellent property. Electrochemical impedance spectroscopy revealed that the transfer resistance of super-hydrophobic surface was increased about four times than bare Mg after one-hour immersion in 0.1 mol/L NaCl solution.     

Characterization and corrosion studies of titania-coated NiTi prepared by sol-gel technique and steam crystallization

Nickel titanium (NiTi) was dip-coated with titania via the sol-gel route using titanium butoxide (Ti(OC₄H₉)₄) as precursor. The as-coated titania film was crystallized to form anatase by treatment in steam at 105 °C. The crystallized film was relatively thick (about 750 nm) and even. Atomic force microscopy (AFM) revealed that the film was dense with a surface roughness of about 3 nm, and was composed of particles of about 100 nm. X-ray diffractometry (XRD) showed that these particles were composed of nanocrystallites of a few nanometers. Nanoindentation tests of the titania film indicated that the film was tough, possibly due to the nano-size of the crystallites. The mean hardness H and elastic modulus E of the coating were about 1.5 and 70 GPa, respectively. Direct pull-off test recorded a mean coating-substrate bonding strength larger than 17 MPa. Electrochemical impedance spectroscopic (EIS) study and cyclic polarization tests showed that the corrosion resistance of the coated NiTi samples in Hanks’ solution was increased by about two orders of magnitude compared with the substrate. Taken together, the present study showed that steam crystallization is a feasible low-temperature treatment method for sol-gel derived titania coating on NiTi in biomedical applications.     

Hydrogen peroxide treatment on Ti-6Al-4V alloy: A promising surface modification technique for orthopaedic application

Ti-6Al-4V alloy was treated with various concentrations (5 wt.%, 15 wt.% and 25 wt.%) of hydrogen peroxide (H₂O₂) and then heat treated to produce an anatase titania layer. The surface modified substrates were immersed in simulated body fluid (SBF) solution for the growth of an apatite layer on the surface and the formed apatite layer was characterized using various surface characterization techniques. The results revealed that titania layer with anatase nature was observed for all H₂O₂ treated Ti-6Al-4V alloy, irrespective of the H₂O₂ concentrations. Ti-6Al-4V alloy treated with 15 wt.% and 25 wt.% of H₂O₂ induced apatite formation, however 5 wt.% of H₂O₂ treated Ti-6Al-4V failed to form apatite layer on the surface. The electrochemical behaviour of H₂O₂ treated specimens in SBF solution was studied using potentiodynamic polarization and electrochemical impedance spectroscopy. Ti-6Al-4V alloy treated with 25 wt.% of H₂O₂ solution exhibited low current density and high charge transfer resistance values compared to specimens treated with other concentrations of H₂O₂ and untreated Ti-6Al-4V alloy.     

Surface reaction characteristics at low temperature synthesis BaTiO3 particles by barium hydroxide aqueous solution and titanium tetraisopropoxide

Well-crystallized cubic phase BaTiO₃ particles were prepared by heating the mixture of barium hydroxide aqueous solution and titania derived from the hydrolysis of titanium isopropoxide (TTIP) at 328 K, 348 K or 368 K for 24 h. The morphology and size of obtained particles depended on the reaction temperature and the Ba(OH)₂/TTIP molar ratio. By the direct hydrolytic reaction of titanium tetraisopropoxide, the high surface area titania (TiO₂) was obtained. The surface adsorption characteristics of the titania particles had been studied with different electric charges OH⁻ ions or H⁺ ions. The formation mechanism and kinetics of BaTiO₃ were examined by measuring the concentration of [Ba²⁺] ions in the solution during the heating process. The experimental results showed that the heterogeneous nucleation of BaTiO₃ occurred on the titania surface, according to the Avrami's equation.     

Characterization of native and anodic oxide films formed on commercial pure titanium using electrochemical properties and morphology techniques

Potentiostatically anodized oxide films on the surface of commercial pure titanium (cp-Ti) formed in sulfuric (0.5 M H₂SO₄) and in phosphoric (1.4 M H₃PO₄) acid solutions under variables anodizing voltages were investigated and compared with the native oxide film. Potentiodynamic polarization and electrochemical impedance spectroscopy, EIS, were used to predicate the different in corrosion behavior of the oxide film samples. Scanning electron microscope, SEM, and electron diffraction X-ray analysis, EDX, were used to investigate the difference in the morphology between different types of oxide films. The electrochemical characteristics were examined in phosphate saline buffer solution, PSB (pH 7.4) at 25 °C. Results have been shown that the nature of the native oxide film is thin and amorphous, while the process of anodization of Ti in both acid solutions plays an important role in changing the properties of passive oxide films. Significant increase in the corrosion resistance of the anodized surface film was recorded after 3 h of electrode immersion in PSB. On the other side, the coverage (θ) of film formed on cp-Ti was differed by changing the anodized acid solution. Impedance results showed that both the native film and anodized film formed on cp-Ti consist of two layers. The resistance of the anodized film has reached to the highest value by anodization of cp-Ti in H₃PO₄ and the inner layer in the anodized film formed in both acid solutions is also porous.     

Influence of crystallization on the spectral features of nano-sized ferroelectric barium strontium titanate (Ba0.7Sr0.3Tio3) thin films

Ferroelectric barium strontium titanate (Ba_0.7Sr_0.3TiO₃)(BST) thin films have been prepared from barium 2-ethylhexanoate [Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂]_, strontium 2-ethylhexanoate [Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂] and titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄ precursors using a modified sol-gel technique. The precursor except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on pre-cleaned quartz substrates by spin coating. The structural and optical properties of films annealed at different temperatures have been investigated. The as-fired films were found to be amorphous that crystallized to the tetragonal phase after annealing at 550 °C for 1 h in air. The lattice constants “a” and “c” were found to be 3.974 A and 3.990 A, respectively. The grain sizes of the films annealed at 450, 500 and 550 °C were found to be 30.8, 36.0 and 39.8 nm respectively. The amorphous film showed very high transparency (∼95%), which decreases slightly after crystallization (∼90%). The band gap and refractive index of the amorphous and crystalline films were estimated. The optical dispersion data are also analyzed in the light of the single oscillator model and are discussed.     

One-step electrodeposition process to fabricate cathodic superhydrophobic surface

In this work, a rapid one-step process is developed to fabricate superhydrophobic cathodic surface by electrodepositing copper plate in an electrolyte solution containing manganese chloride (MnCl₂·4H₂O), myristic acid (CH₃(CH₂)₁₂COOH) and ethanol. The superhydrophobic surfaces were characterized by means of scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The shortest electrolysis time for fabricating a superhydrophobic surface is about 1 min, the measured maximum contact angle is 163° and rolling angle is less than 3°. Furthermore, this method can be easily extended to other conductive materials. The approach is time-saving and cheap, and it is supposed to have a promising future in industrial fields.     

Effect of Al on the electrochemical corrosion behaviour of Pb free Sn-8.5 Zn-0.5 Ag-XAl-0.5 Ga solder in 3.5% NaCl solution

The effect of Al on the electrochemical corrosion behaviour of Pb-free Sn-8.5 Zn-0.5 Ag-XAl-0.5 Ga solder in 3.5% NaCl solution was investigated by using potentiodynamic polarization techniques. The X content in the solder varied from 0.1 to 3 wt.%. Polarization studies revealed that an increase in Al content upto 1.5 wt.% decreased the corrosion current density (I_corr), corrosion rate of the solder and shifted the corrosion potential (E_corr) towards more noble values. However, higher content of Al, i.e. 3 (wt.%) in the five-element solder enhanced the corrosion rate and resulted in a significant increase in the E_corr towards more negative values. Passivation behaviour was noticed in all the solders having varying Al content, but the passive film formed at 1.5 wt.% Al was most stable due to its low passivation current density (i_p) and low critical current density (i_cc) value in comparison to the other solders. XPS and Auger depth profile results revealed that the passive film consisted of oxides/hydroxides of Al and Zn formed on the surface of the solder with Sn being formed in the subsequent layer. Considerable aluminium segregation occurred towards the surface principally as Al₂O₃/Al(OH)₃ with increase in Al content to 1.5 wt.% in the five element solder. The formation of Al₂O₃ seemed to prevent the oxidation of zinc on the surface of the solder.     

Site-blocking effects of preadsorbed H on Pt(1 1 1) probed by 1,3-butadiene adsorption and reaction

The influence of hydrogen coadsorption on hydrocarbon chemistry on transition metal surfaces is a key aspect to an improved understanding of catalytic selective hydrogenation. We have investigated the effects of H preadsorption on adsorption and reaction of 1,3-butadiene (H₂CCHCHCH₂, C₄H₆) on Pt(1 1 1) surfaces by using temperature-programmed desorption (TPD) and Auger electron spectroscopy (AES). Preadsorbed hydrogen adatoms decrease the amount of 1,3-butadiene chemisorbed on the surface and chemisorption is completely blocked by the hydrogen monolayer (saturation) coverage (θ_H = 0.92 ML). No hydrogenation products of reactions between coadsorbed H adatoms and 1,3-butadiene were observed to desorb in TPD experiments over the range of θ_H investigated (θ_H = 0.6-0.9 ML). This is in strong contrast to the copious evolution of ethane (CH₃CH₃, C₂H₆) from coadsorbed hydrogen and ethylene (CH₂CH₂, C₂H₄) on Pt(1 1 1). Hydrogen adatoms effectively (in a 1:1 stoichiometry) remove sites from interaction with chemisorbed 1,3-butadiene, but do not affect adjacent sites. The adsorption energy of coadsorbed 1,3-butadiene is not affected by the presence of hydrogen on Pt(1 1 1). The chemisorbed 1,3-butadiene on hydrogen preadsorbed Pt(1 1 1) completely dehydrogenates to H₂ and surface carbon upon heating without any molecular desorption detected, which is identical to that observed on clean Pt(1 1 1). In addition to revealing aspects of site blocking that should have broad implications for hydrogen coadsorption with hydrocarbon molecules on transition metal surfaces in general, these results also provide additional basic information on the surface science of selective catalytic hydrogenation of butadiene in butadiene-butene mixtures.     

Electrochemical behaviors of the magnesium alloy substrates in various pretreatment solutions

Interface reactions and film features of AZ91D magnesium alloy in pickling, activation and zinc immersion solutions have been investigated. The surface morphologies of the specimens were observed with scanning electron microscope (SEM). Electrochemical behaviors of AZ91D magnesium alloy in the baths of pickling, activation and zinc immersion were analyzed based on the open circuit potential (OCP) - time curves in various solutions. The results show that the corrosive rate in HNO₃ + CrO₃ or HNO₃ + H₃PO₄ pickling solution was more rapid than in KMnO₄ pickling-activation solution. Both α phase and β phase of the substrates were uniformly corroded in HNO₃ + CrO₃ or HNO₃ + H₃PO₄ pickling solution, the coarse surface can augment the mechanical occlusive force between the subsequent coatings and the substrates, so coatings with good adhesion can be obtained. In HF activation solution, the chromic compound formed via HNO₃ + CrO₃ pickling was removed and a compact MgF₂ film was formed on the substrate surface. In K₄P₂O₇ activation solution, the corrosion products formed via HNO₃ + H₃PO₄ pickling were removed, a new thin film of oxides and hydroxides was formed on the substrate surface. In KMnO₄ pickling-activation solution, a film of manganic oxides and phosphates was adhered on the substrate surface. Zinc film was symmetrically produced via K₄P₂O₇ activation or KMnO₄ pickling-activation, so it was good interlayer for Ni or Cu electroplating. Asymmetrical zinc film was produced because the MgF₂ film obtained in the HF activation solution had strong adhesive attraction and it was not suitable for interlayer for electroplating. However, the substrate containing compact MgF₂ film without zinc immersion was fit for direct electroless Ni-P plating.     

Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH

Kinetics and mechanisms for reactions of OH with methanol and ethanol have been investigated at the CCSD(T)/6-311 + G(3df, 2p)//MP2/6-311 + G(3df, 2p) level of theory. The total and individual rate constants, and product branching ratios for the reactions have been computed in the temperature range 200-3000 K with variational transition state theory by including the effects of multiple reflections above the wells of their pre-reaction complexes, quantum-mechanical tunneling and hindered internal rotations. The predicted results can be represented by the expressions k₁ = 4.65 × 10⁻²⁰ × T^2.68 exp(414/T) and k₂ = 9.11 × 10⁻²⁰ × T^2.58 exp(748/T) cm³ molecule⁻¹ s⁻¹ for the CH₃OH and C₂H₅OH reactions, respectively. These results are in reasonable agreements with available experimental data except that of OH + C₂H₅OH in the high temperature range. The former reaction produces 96-89% of the H₂O + CH₂OH products, whereas the latter process produces 98-70% of H₂O + CH₃CHOH and 2-21% of the H₂O + CH₂CH₂OH products in the temperature range computed (200-3000 K).     

Adsorption and thermal reaction of short-chain alkanethiols on GaAs(1 0 0)

By means of temperature-programmed desorption (TPD) and X-ray photoemission spectroscopy (XPS) with synchrotron radiation, we investigated the adsorption and thermal decomposition of alkanethiols (RSH, R = CH₃, C₂H₅, and C₄H₉) on a GaAs(1 0 0) surface. All chemisorbed alkanethiols can deprotonate to form thiolates below 300 K via dissociation of the sulfhydryl hydrogen (-SH). Two types of thiolates species are observed on GaAs(1 0 0), according to adsorption on surface Ga and As sites. The thiolates adsorbed on a Ga site preferentially recombine with surface hydrogen to desorb as a molecular thiol at 350-385 K. The thiolate on the As site exhibits greater thermal stability and undergoes mainly dissociation of the C-S bond at ∼520 K, independent of the alkyl chain length. The decomposition of CH₃S either directly desorbs CH₃ or transfers the CH₃ moiety onto the surface. The surface CH₃ further evolves directly from the surface at 665 K. The dissociations of C₂H₅S and C₄H₉S yield surface C₂H₅ and C₄H₉, which further decompose to desorb C₂H₄ and C₄H₈, respectively, via β-hydride elimination. The complete decomposition of alkanethiol leads to the formation of surface S without deposition of carbon. Adsorption of CH₃SSCH₃ results in the formation of surface CH₃S at initial exposures via scission of the S−S bond. Compared with the adsorption of CH₃SH, the CH₃S on the Ga site exhibits greater thermal stability because surface hydrogen is absent. At a high exposure, CH₃SSCH₃ can absorb molecularly on the surface and decompose to desorb CH₃SCH₃ via formation of a CH₃SS intermediate.     

Super-hydrophobicity and oleophobicity of silicone rubber modified by CF4 radio frequency plasma

Owing to excellent electric properties, silicone rubber (SIR) has been widely employed in outdoor insulator. For further improving its hydrophobicity and service life, the SIR samples are treated by CF₄ radio frequency (RF) capacitively coupled plasma. The hydrophobic and oleophobic properties are characterized by static contact angle method. The surface morphology of modified SIR is observed by atom force microscope (AFM). X-ray photoelectron spectroscopy (XPS) is used to test the variation of the functional groups on the SIR surface due to the treatment by CF₄ plasma. The results indicate that the static contact angle of SIR surface is improved from 100.7° to 150.2° via the CF₄ plasma modification, and the super-hydrophobic surface of modified SIR, which the corresponding static contact angle is 150.2°, appears at RF power of 200 W for a 5 min treatment time. It is found that the super-hydrophobic surface ascribes to the coaction of the increase of roughness created by the ablation action and the formation of [-SiF_x(CH₃)_2−x-O-]_n (x = 1, 2) structure produced by F atoms replacement methyl groups reaction, more importantly, the formation of [-SiF₂-O-]_n structure is the major factor for super-hydrophobic surface, and it is different from the previous studies, which proposed the fluorocarbon species such as C-F, C-F₂, C-F₃, CF-CF_n, and C-CF_n, were largely introduced to the polymer surface and responsible for the formation of low surface energy.     

Binding of rare earth metal complexes with an ofloxacin derivative to bovine serum albumin and its effect on the conformation of protein

The water-soluble Pr (Ⅲ) and Nd (Ⅲ) complexes with an ofloxacin derivative have been prepared and characterized. The single-crystal X-ray diffraction showed that the Pr (III) and Nd (III) complexes have the similar molecular structure. Under physiological pH condition, the effects of [PrL(NO₃)₂(CH₃OH)](NO₃) and [NdL(NO₃)₂(CH₃OH)](NO₃) on bovine serum albumin (BSA) were examined using fluorescence spectroscopy in combination with UV-vis absorbance and circular dichroism (CD) spectra. The result reveals that the quenching mechanism of fluorescence of BSA by two complexes is a static quenching process and the number of binding sites is about 1 for both. The thermodynamic parameters (ΔH=−14.52 kJ mol⁻¹, ΔS=56.54 J mol⁻¹ K⁻¹ for [PrL(NO₃)₂(CH₃OH)](NO₃) and ΔH=−24.63 kJ mol⁻¹, ΔS=22.07 J mol⁻¹ K⁻¹ for [NdL(NO₃)₂(CH₃OH)](NO₃)) indicate that hydrophobic and electrostatic interactions are the main binding force in the complexes-BSA system. The binding average distance between complexes and BSA was obtained on the basis of Förster's theory. In addition, it was proved by the CD spectra that the BSA secondary structure was changed in the presence of complexes in an aqueous solution.     

The corrosion behavior of intermetallic compounds Ni3(Si,Ti) and Ni3(Si,Ti) + 2Mo in acidic solutions

The corrosion behavior of the intermetallic compounds homogenized, Ni₃(Si,Ti) (L1₂: single phase) and Ni₃(Si,Ti) + 2Mo (L1₂ and (L1₂ + Ni_ss) mixture region), has been investigated using an immersion test, electrochemical method and surface analytical method (SEM; scanning electron microscope and EPMA: electron probe microanalysis) in 0.5 kmol/m³ H₂SO₄ and 0.5 kmol/m³ HCl solutions at 303 K. In addition, the corrosion behavior of a solution annealed austenitic stainless steel type 304 was studied under the same experimental conditions as a reference. It was found that the intergranular attack was observed for Ni₃(Si,Ti) at an initial stage of the immersion test, but not Ni₃(Si,Ti) + 2Mo, while Ni₃(Si,Ti) + 2Mo had the preferential dissolution of L1₂ with a lower Mo concentration compared to (L1₂ + Ni_ss) mixture region. From the immersion test and polarization curves, Ni₃(Si,Ti) + 2Mo showed the lowest corrosion resistance in both solutions and Ni₃(Si,Ti) had the highest corrosion resistance in the HCl solution, but not in the H₂SO₄ solution. For instance, it was found that unlike type 304 stainless steel, these intermetallic compounds were difficult to form a stable passive film in the H₂SO₄ solution. The results obtained were explained in terms of boron segregation at grain boundaries, Mo enrichment and film stability (or strength).     

Thermal decomposition of toluene: Overall rate and branching ratio

The two-channel thermal decomposition of toluene, C₆H₅CH₃ → C₆H₅CH₂ + H (1) and C₆H₅CH₃ → C₆H₅ + CH₃ (2), was investigated in shock tube experiments over the temperature range of 1400-1780 K at a pressure of 1.5 (±0.1) bar. Rate coefficients for reactions (1) and (2) were determined by monitoring benzyl radical (C₆H₅CH₂) absorption at 266 nm during the decomposition of toluene diluted in argon and modeling the temporal behavior of the benzyl concentration with a kinetic model. The first-order rate coefficients determined at a pressure of 1.5 bar are expressed by k₁(T) = 2.09 × 10¹⁵ exp (−87510 [cal/mol]/RT) [s⁻¹] and k₂(T) = 2.66 × 10¹⁶ exp (−97880 [cal/mol]/RT) [s⁻¹]. The resulting branching ratio, k₁/(k₁ + k₂), ranges from 0.8 at 1350 K to 0.6 at 1800 K.     

Carbon molecular sieves from carbon cloth: Influence of the chemical impregnant on gas separation properties

Carbon materials with molecular sieve properties (CMS) were prepared by pyrolysis of cotton fabrics by chemical activation procedures. To evaluate the changes in the chemical and textural properties, the impregnants AlCl₃, ZnCl₂ and H₃PO₄ were used at 1123 K. The materials were characterized using adsorption of nitrogen and carbon dioxide, TPD, and immersion calorimetry in C₆H₆. Adsorption kinetics of O₂, N₂, CO₂, CH₄, C₃H₈ and C₃H₆ were measured in all the prepared materials to determine their behaviour as molecular sieves. The results confirm that the chemical used as impregnant has a significant effect on the resulting CMS separation properties. All materials exhibit microporosity and low oxygen surface group contents; however, the sample impregnated with zinc chloride, with an immersion enthalpy value of 66.4 J g⁻¹ in benzene, exhibits the best performance in the separation of CH₄-CO₂ and C₃H₈-C₃H₆ at 273 K.     

Crystallinity effect in the textural properties of titania-TPA catalysts

Catalysts based in titania mixed with tungstophosphoric acid (TPA), H₃PW₁₂O₄₀, in various proportions (1, 15, 25 and 50 wt%) were obtained by the sol-gel method. The gels were prepared by hydrolysis and gellation of titanium n-butoxide with a TPA solution, using HNO₃ as a catalyst to obtain a pH 3. Fresh samples were thermally treated from 100 to 800 °C, in a stepwise increment of 100 °C during 20 h per step. Specific surface areas were calculated by the BET method from the nitrogen adsorption isotherms; it was found that the surface area increased with TPA content. The crystallization behavior was followed by powder X-ray diffraction. Crystallite size measurements showed that anatase remains nanocrystalline in the studied temperature range. From the X-ray data, it was clear that below 700 °C TPA is highly dispersed in an amorphous state.     

Study of surface interactions of ionic liquids with aluminium alloys in corrosion and erosion-corrosion processes

Surface interactions of alkylimidazolium ionic liquids (ILs) with aluminium alloy Al 2011 have been studied by immersion tests in seven neat ILs [1-n-alkyl-3-methylimidazolium X⁻ (X = BF₄; n = 2 (IL1), 6 (IL2), 8 (IL3). X = CF₃SO₃; n = 2 (IL4). X = (4-CH₃C₆H₄SO₃); n = 2 (IL5). X = PF₆; n = 6 (IL6)] and 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide (IL7)]. Immersion tests for Al 2011 have also been carried out in 1 wt.% and 5 wt.% solutions of 1-ethyl,3-methylimidazolium tetrafluoroborate (IL1) in water. No corrosion of Al 2011 by neat ILs is observed. The highest corrosion rate for Al 2011 in water is observed in the presence of a 5 wt.% IL1 due to hydrolysis of the anion with hydrogen evolution and formation of aluminium fluoride. Erosion-corrosion processes have been studied for three aluminium alloys (Al 2011, Al 6061 and Al 7075) in a 90 wt.% IL1 solution in water in the presence of α-alumina particles. The erosion-corrosion rates are around 0.2 mm/year or lower, and increase with increasing copper content to give a corrosion resistance order of Al 6061 > Al 7075 > Al 2011. Results are discussed on the basis of scanning electron microscopy (SEM) observations, energy dispersive spectroscopy (EDS) analysis, X-ray diffraction (XRD) patterns and X-ray photoelectron spectroscopy (XPS) determinations.