Interfacial chemistry and adhesive durability

The improved understanding of adsorption chemistry which has arisen from the development of new surface analytical techniques during the last twenty years has had a major effect on the understanding of catalytic reaction mechanisms. However, there are many other areas of technology where Interfacial chemistry has a determining role but where the understanding is much less developed. In this paper examples are presented of the role of interfacial chemistry in adhesion. In particular, It Is shown that modification of a surface to the extent of just a few atomic layers in depth can have dramatic effects on the performance of adhesive bonds, particularly when exposed to hostile environmental conditions. These examples will be used to highlight a need for greater fundamental understanding of the interfacial chemistry of adhesion and also other technologies where interface effects are dominant.     

The adsorption/impregnation of catalytic precursors on pure and composite oxides

Three intrinsically connected phenomena occur during adsorption/impregnation of aqueous electrolytes onto oxide carriers. They are: pH-dependent development of surface charge carriers on the oxide; pH-dependent aqueous speciation of catalytic precursors; surface adsorption by complexation and coordination. Modeling of these processes yields basic thermodynamic properties of the adsorbed phase, which could provide useful information of the catalytic properties of the metal, support, and reveal metal-support interactions, thus contributing to design criteria for supported-metal catalysts.

The spectrum of catalytic systems that can be studied using the above approach is greatly extended when both pure and composite oxide carriers are considered. This presentation will focus on three metal/support systems, each of which provides results of both practical and fundamental importance.     

Nitrogen plasma source ion implantation of AISI S1 tool steel

Significant economic savings can be achieved by improving the wear lifetime of precision manufacturing tools through nitrogen-ion implantation. This near-ambient temperature, surface modification process preserves dimensional integrity and surface finish while eliminating delamination problems that are often associated with overlay coatings. Conventional ion implantation is a line-of-sight process which requires elaborate manipulation and masking to uniformly implant components of complex shapes. A recently developed process, plasma source ion implantation (PSII), circumvents this line-of-sight restriction and makes ion implantation more attractive economically. In this article, the effects of PSII of nitrogen at a target bias of 50 kV, to a dose of 0.3 × 10¹⁸ atoms/cm² on the surface microstructure and mechanicalproperties of AISI S1 tool steel are presented.     

Absorption spectra of solid rare earth complexes obtained from the inner filter effect on luminescence

The inner filter effect is observed in luminescence whenever a second substance is present that has absorptions which overlap the luminescence. This results in a diminution of the luminescence at those wavelengths and is generally observed in solution. In the present communication we show that this effect can be observed when a solid rare earth complex is physically mixed with a solid luminescent organic matrix with which it does not interact. The resulting luminescence is reduced in emission intensity at those wavelengths corresponding to the absorptions of the rare earth ion. This is illustrated with a mixture of Na₃[Ho(ODA)₃] ·2NaClO₄·6H₂O and pyrene at 77 K, and it is shown that the absorption spectrum of the holmium complex can be extracted from the luminescence spectrum of pyrene. This absorption spectrum is in good agreement with that obtained by conventional spectroscopy with a single crystal.     

Catalytic behaviour and surface properties of supported lanthana

This paper deals with the role of dispersed lanthana as an active phase in several catalytic reactions: CO hydrogenation, CO oxidation, and oxidative dimerization of methane.

Characterization of the prepared catalysts indicates that lanthana can be effectively dispersed on silica and on ceria. While in the case of silica-supported catalysts lanthana appears at the surface, leading to an almost full coverage for loadings higher than 40%, in the case of ceria-based systems, lanthana forms a solid solution with the support.

In all the reactions studied, the presence of lanthana can be related to significant changes in the catalytic properties of the bare supports. Thus, the selectivity towards the total oxidation products observed on pure ceria is decreased, and the low activity shown by silica is enhanced. For the CO+H₂ reaction, the addition of lanthana also generates upgraded products.     

Autoklaven-Untersuchungen der Spannungsrißkorrosion von Fe-Cr-Ni-Legierungen in NaCl/Co2/H2S-Medien

Autoclave investigation of stress corrosion cracking behaviour of Fe-Cr-Ni alloys in NaCl/CO₂/H₂S-environment In oil and gas production, the corrosion problems increase as the depth of the reservoirs increases. The oil and gas products contain chloride-rich waters and mixtures of H₂S and CO₂ at high pressures and temperatures. Materials that can be used under these conditions are only high strength high alloy steels and nickel base alloys. These materials must be assessed for corrosion resistance under these conditions. The environment contain chloride ions and hydrogen sulphide, which are known to be critical components for SCC. With the aid of autoclave experiments, the fields of corrosion resistance for the materials no. 1.4462, 1.4563 and 2.4618 were determined as a function of temperature and hydrogen sulphide pressure. The base environment was a 5 Molar sodium chloride solution at 20 bar carbon dioxide. While the corrosion resistance of the duplex steel, material no. 1.4462, decreases markedly as the strength of the material and the hydrogen sulphide pressure increase, the two austenitic materials are completely resistant up to 300 °C and hydrogen sulphide pressure of 15 bar. Only at 300 °C and high partial pressures of hydrogen sulphide the material no. 1.4563 did fail, when stressed to stress levels higher than the YS. The crack path was predominantly transgranular with minute fractions of intergranular cracking. The microstructure appears to have no effect. All results indicate that a mixed mechanism of hydrogen- and chloride induced SCC is operting, while a corrosion enhancement due to interaction of both critical components takes place.     

Occurrence of the mycotoxins ochratoxin A, zearalenone and deoxynivalenol in feed components.

The mycotoxin contamination of feed components used by the Dutch cooperative feed industry was surveyed to estimate the risk for animal production losses. Of 89 randomly and 6 selectively taken samples of raw materials harvested in 1988 and 1989 27% were contaminated with ochratoxin A (OCHRA), 31% with zearalenone (ZEA) and 20% with deoxynivalenol (DON). The mean content (microgram/kg) of all positive randomly taken samples was 18 (OCHRA), 62 (ZEA) and 630 (DON). The highest level (microgram/kg) for all samples was 120 (OCHRA) in barley, 3100 (ZEA) in corn cob mix and 1900 (DON) in maizegluten feed. The results of this survey show that feed components are often contaminated with mycotoxins. However, the contamination level could only sporadically cause production losses in animal husbandry.