An XPS study of passive films on Nickel and alloy 600 in acids

Compositions of surface films formed on nickel and Alloy 600 in I M HCI, 0.5 M H₂SO₄ and I/3 M H₃PO₁ solutions were investigated as a function of polarization potential. The main constituent of surface films formed on Ni in 0.5 M H₂SO₄ or 1/3 M H₃PO₄ solution was hydrated nickel oxyhydroxide, in which the ratio of O₂ to OH⁻ increased when passivation occurred. The surface films formed on Ni and Alloy 600 at lower potentials in 0.5 M H₂SO₄ solution contain S² ions other than SOP_4²⁻ ions, whereas S²⁻ ions were not incorporated in the passive film. Passivation of Alloy 600 took place by the formation of hydrated chromium oxyhydroxide. Pitting led to no substantial change in the average composition of the film.     

Importance of initial surface film in the degradation of stainless steels by atmospheric exposure

The surface compositions of stainless steels types 304, 316, 430, and 444 combined with four types of surface finishes, 2B finish, hairline polishing, mirror polishing, and bright annealing, were measured by ICP-AES, EPMA, and XPS before exposure. The surface finish that most enriched the chromic species in the surface film was mirror polishing, followed by bright annealing, 2B finish, and hairline polishing. The order of corrosion-resistance was type 444, type 316, type 304, and type 430. The surface compositions were correlated with the rating number and pitting depth after exposure to atmospheric environments. The rating number had a high positive correlation with the concentration of Cr in the surface film, and had a slight correlation with the near-surface composition measured by EPMA at 12 kV, but did not show any correlation with bulk composition within the composition range covered in the present work. This same trend was observed for pitting depth. It was concluded that the cationic concentration of Cr in the surface film before atmospheric exposure is the prime factor in controlling the resistance of stainless steels to atmospheric corrosion.     

Orientation in uniaxially drawn polystyrene plasticized by CO2 sorption

Uniaxial drawing experiments of the polystyrene films plasticized by a sorption of compressed CO₂ gas at pressures up to about 18 MPa were carried out with strain rates ε of 0.0290 and 0.0079 s^?1. The drawing was performed successfully with draw ratio λ up to 4 at the temperatures of 308.15, 318.15, 328.15, and 338.15 K. The Hermans orientation function f of the drawn samples was determined from the dichroic ratio measured by an infrared spectrophotmeter. While f value increases with increasing ε or λ, it decreases with increasing CO₂ pressure or temperature. © 1995 John Wiley & Sons, Inc.     

Studies on the nuclear magnetic resonance spectra of olefinic protons of conjugated fatty acid methyl esters

The NMR spectra of olefinic protons in the four representative conjugated fatty acid methyl esters, methylcis-9,trans-11-octadecadienoate, methyltrans-9,trans-11-octadecadienoate, methyl α eleostearate, and methyl β eleostearate, were studied. The chemical shift of each olefinic proton in these compounds was determined by considering their intramolecular environment. Coupling constants were also obtained as the results of spectral analysis.     

Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification

The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO₂ gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O₂-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O₂/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char.     

The surface film formed on amorphous Pd-Ti-P alloy by anodic polarization in 2 m NaCl solution

X-ray photoelectron spectroscopy was used to investigate the effect of the composition and thickness of surface film on the electrocatalytic properties for chlorine gas evolution on amorphous Pd-Ti-P alloy in NaCl solution. The amount of charge for gas evolution exhibited a wavy change with an increase in polarization potential. The gas evolution became active with an increase in palladium content of the surface film and slowed down with increases of titanium and phosphorus contents of the film. However, despite the fact that the formation of surface film consisting mainly of titanium as a cation in the potential region higher than 1.6 V (sce), the catalytic activity for gas evolution increased, suggesting the change in the gas evolution mechanism in the higher potential region.     

Anodic characteristics of amorphorous palladium-base alloys in sodium chloride solutions

The anodic characteristics of a variety of amorphous palladium-base alloys were examined with a view to their use for the production of sodium hypochlorite by electrolysis of dilute sodium chloride solutions at ambient temperature. The corrosion resistance of palladium-metalloid alloys was obtained by alloying with platinum group metals and/or valve metals. Among these alloys, rhodium-containing alloys showed high electrocatalytic activities for chlorine evolution. Surface activation treatment was, however, necessary to obtain sufficiently high activities for chlorine evolution at low overpotentials. Surface-activated amorphous alloys possessed considerably higher current efficiency for chlorine evolution in comparison with currently used anodes.     

Interaction of cation-exchange membrane with polycation I. Poly(N-methyl-4-vinylpyridinium chloride)

We elucidated the effect of the molecular weight of poly(N-methyl-4-vinylpyridinium chloride) (PMVP) on its adsorbed or ion-exchanged amount on the cation-exchange membrane and the preferntial permselectivity of the membrane for sodium ion to calcium ion. The amount of the adsorbed or ion-exchanged PMVP increases with time and then attains to a definite value at a definite concentration. Also, the ultimate value increases with increasing the concentration of PMVP. When the molecular weight of PMVP is 3090, the ratio of the pyridinium groups of PMVP ion-exchanged with the sulfonic acid groups on the membrane surface to the total pyridinium groups of the cohered PMVP is in the range of 70–80%. The relative transport number of calcium ions to sodium ions(P_Na^Ca) decreases with increasing the amount of adsorbed or ion-exchanged PMVP and the numbe rof non-ion-exchanged pyridinium groups of PMVP and the number of non-ion-exchanged pyridinium groups of PMVP on the membrane surface. The smaller the molecular weight of PMVP, the more the adsorbed or ion-exchanged amount and the more preferable the permselectivity for sodium ion.     

An X-ray photoelectron spectroscopic study of electrocatalytic activity of platinum group metals for chlorine evolution

A correlation of the catalytic activity for anodic chlorine evolution of platinum group metals to the nature of the surface film formed during chlorine evolution in a sodium chloride solution was studied by X-ray photoelectron spectroscopy. The change in the surface film with increasing potential was found on platinum, including an increase in the cationic valence. This seemed responsible for the decrease in the activity for chlorine evolution on platinum in the high potential region. Increasing potential did not result in the appreciable increase in the cationic valence in the surface film on the other platinum group metals. Replacement of hydroxyl ions in the surface film by chloride ions became easier in the order of rhodium, iridium and palladium, and the activity for anodic chlorine evolution increased in this order due possibly to an increase in the amount of chloride ions in the film which seemed to be one of the reactants in the rate determining electrochemical desorption of adsorbed chlorine atom. Chlorine molecules adsorbed on the surface film were also found. It was assumed that the activity for anodic chlorine evolution might be low when the metal surface was covered by a large amount of molecular chlorine which was the reaction product.     

Ni-Mo alloying of nickel surface by alternating pulsed electrolysis using molybdenum(VI) baths

Electrochemical Ni-Mo alloying of the surface of a nickel substrate was investigated using alternating pulsed electrolysis in an aqueous solution containing only molybdate ions (MoO₄²⁻) as a metal ion component. In this electrochemical process, the nickel substrate was slightly dissolved during the anodic pulses, providing nickel ions into the solution in the vicinity of the substrate, while Ni and Mo were both electrodeposited on the substrate surface during the subsequent cathodic pulses. Through the optimization of anodic and cathodic conditions independently based on a set of direct-current electrolysis data, amorphous Ni-Mo alloy layers were found to be formed at the surface of the nickel substrate by the alternating pulsed electrolysis using the MoO₄²⁻ solution of pH 3.0-5.0. The conditions for Ni-Mo alloy formation were discussed in terms of the dissolving regime of ionic species in the electrolytes determined by an equilibrium calculation.