ATR characterisation of synergistic corrosion inhibition of mild steel surfaces by cerium salicylate

The nature of deposits on mild steel surfaces formed by exposure to corrosive and inhibiting solutions has been examined by attenuated total reflectance spectroscopy. For cerium-based inhibitors, e.g. CeCl₃ the formation of cerium-containing coatings was detected whilst the cerium carboxylate Ce(sal)₃ (sal=salicylate), which combines the Ce³⁺ with the known organic inhibitor sal⁻, was shown to involve substantial deposition of both cerium and a salicylate species. These results, combined with corrosion inhibition data for the respective inhibitor compounds clearly indicate a synergistic corrosion mechanism for Ce(sal)₃ which underpins the improved performance of this corrosion inhibitor in comparison to the individual components (i.e. Na(sal) or CeCl₃).

New insights into the fundamental chemical nature of ionic liquid film formation on magnesium alloy surfaces

Ionic liquids (ILs) based on trihexyltetradecylphosphonium coupled with either diphenylphosphate or bis(trifluoromethanesulfonyl)amide have been shown to react with magnesium alloy surfaces, leading to the formation a surface film that can improve the corrosion resistance of the alloy. The morphology and microstructure of the magnesium surface seems critical in determining the nature of the interphase, with grain boundary phases and intermetallics within the grain, rich in zirconium and zinc, showing almost no interaction with the IL and thereby resulting in a heterogeneous surface film. This has been explained, on the basis of solid-state NMR evidence, as being due to the extremely low reactivity of the native oxide films on the intermetallics (ZrO₂ and ZnO) with the IL as compared with the magnesium-rich matrix where a magnesium hydroxide and/or carbonate inorganic surface is likely. Solid-state NMR characterization of the ZE41 alloy surface treated with the IL based on (Tf)₂N− indicates that this anion reacts to form a metal fluoride rich surface in addition to an organic component. The diphenylphosphate anion also seems to undergo an additional chemical process on the metal surface, indicating that film formation on the metal is not a simple chemical interaction between the components of the IL and the substrate but may involve electrochemical processes.

Substituted naphthoquinones as novel amino acid sensitive reagents for the detection of latent fingermarks on paper surfaces

In this paper, we present our preliminary studies into naphthoquinones as novel reagents for the detection of latent fingermarks on paper. Latent fingermarks deposited on paper substrates were treated with solutions of selected naphthoquinones in ethyl acetate/HFE-7100, with subsequent heating. The selected compounds were 1,4-dihydroxy-2-naphthoic acid, 1,2-naphthoquinone-4-sulfonate, 2-methoxy-1,4-naphthoquinone and 2-methyl-1,4-naphthoquinone. All of the tested compounds yielded purple-brown visible fingermarks, which also exhibited photoluminescence when illuminated with a high intensity filtered light source at 555nm and viewed through red goggles. Indirect heat using an oven at 150 ◦C for 1 h was found to be superior to direct heat with an iron, which while providing faster development lead to increased levels of background colouration. Luminescence spectrophotometry revealed differences in photoluminescence characteristics for fingermarks developed with the different naphthoquinones, with excitation over the range 530–590 nm. Luminescence spectrophotometry of developed lysine, glycine and serine spots on paper was used to confirm that the naphthoquinones were reacting with amino acids in the latent fingermark.

Surfaces and depths : evaluating the theoretical assumptions of cognitive skills programmes

Cognitive skills programmes for offenders such as Reasoning and Rehabilitation (R & R) have been around now for over 20 years and were developed in part to address their poor reasoning and decision-making skills. In this paper we critically examine the theoretical underpinnings of the R & R programme in light of current theoretical developments and research from cognitive neuroscience, philosophy, biology, and psychology. After considering recent theoretical and empirical research on rationality, emotions, distributed cognition, and embodiment we conclude with some thoughts about how to fine-tune cognitive skills programmes such as R & R in light of this research.

Acetylene plasma polymerized surfaces for covalent immobilization of dense bioactive protein monolayers

Smooth polymerized surfaces, suitable for biochemical and biomedical applications, were deposited using a modified plasma enhanced chemical vapour deposition method with acetylene as a reaction precursor. Horseradish peroxidase (HRP) activity assays showed that the protein immobilized on the plasma polymerized surfaces maintained its biological function for a much longer period of time compared to that on uncoated surfaces. The kinetics of HRP attachment to the plasma polymerized surfaces were analyzed using quartz crystal microbalance with dissipation analysis. Spectroscopic ellipsometry and attenuated total reflection Fourier transform infrared spectroscopy were used to determine the thickness and the quantity of the attached protein. The results showed that the plasma polymerized surfaces provided a high density of attachment sites to covalently immobilize a dense monolayer of proteins.

Stepwise synthesis of Gly−Gly−His on gold surfaces modified with mixed self-assembled monolayers

Peptide-modified electrode surfaces have been shown to have excellent recognition properties for metal ions. An efficient method of screening a potential peptide for its selectivity for a given metal would involve the synthesis of the peptide directly on the electrode surface. This paper outlines a procedure in which the tripeptide Gly−Gly−His was synthesized one amino acid at a time on a gold surface modified with a self-assembled monolayer of the mixed alkanethiolates 3-mercaptopropionic acid (MPA) and 3-mercaptopropane (MP). Electrochemistry and high-resolution mass spectrometry were used to elucidate the structure of the adsorbed species and follow the synthesis. The amino acids can be attached only to MPA, but the presence of a diluting unreactive molecule of MP reduces steric crowding about the reaction center. The maximum coverage of synthesized tripeptide occurs at a ratio of MPA/MP of 1:1.

A digital watermarking scheme for Bezier surfaces

Owners and vendors are increasingly publishing their materials in digital form. Because such materials can be exactly copied, a mechanism is required that will protect the legitimate owners of these works, by providing proof of original ownership. Digital watermarking has now become one accepted method of establishing ownership of digital materials. The owner of a work embeds a pattern, called a digital watermark, in the content. This embedded watermark is normally undetectable, but its presence can be demonstrated by the owner of the work or his agent, thereby proving ownership. Digital watermarking has been used for many types of multimedia content, primarily audio, video and flat images. Recently, interest has been shown in applying digital watermarking schemes to 3D surfaces, in various formats. In this paper, we examine a method whereby a digital watermark can be embedded in a Bezier surface. A prototype watermarking method for such surfaces is presented, with some experimental results, and a discussion of directions for future research.

Graph matching with subdivision surfaces for texture synthesis on surfaces

Existing texture synthesis-from-example strategies for polygon meshes typically make use of three components: a multi-resolution mesh hierarchy that allows the overall nature of the pattern to be reproduced before filling in detail; a matching strategy that extends the synthesized texture using the best fit from a texture sample; and a transfer mechanism that copies the selected portion of the texture sample to the target surface. We introduce novel alternatives for each of these components. Use of p2-subdivision surfaces provides the mesh hierarchy and allows fine control over the surface complexity. Adaptive subdivision is used to create an even vertex distribution over the surface. Use of the graph defined by a surface region for matching, rather than a regular texture neighbourhood, provides for flexible control over the scale of the texture and allows simultaneous matching against multiple levels of an image pyramid created from the texture sample. We use graph cuts for texture transfer, adapting this scheme to the context of surface synthesis. The resulting surface textures are realistic, tolerant of local mesh detail and are comparable to results produced by texture neighbourhood sampling approaches.

The drainage of thin liquid films between solid surfaces

We present measurements of the thickness as a function of time of liquid films as they are squeezed between molecularly smooth mica surfaces. Three Newtonian, nonpolar liquids have been studied: octamethylcyclotetrasiloxane, n-tetradecane, and n-hexadecane. The film thicknesses are determined with an accuracy of 0.2 nm as they drain from ∼1 μm to a few molecular layers. Results are in excellent agreement with the Reynolds theory of lubrication for film thicknesses above 50 nm. For thinner films the drainage is slower than the theoretical prediction, which can be accounted for by assuming that the liquid within about two molecular layers of each solid surface does not undergo shear. In very thin films the continuum Reynolds theory breaks down, as drainage occurs in a series of abrupt steps whose size matches the thickness of molecular layers in the liquid. The presence of trace amounts of water has a dramatic effect on the drainage of a nonpolar liquid between hydrophilic surfaces, causing film rupture which is not observed in the dry liquids.

Structuring in liquid alkanes between solid surfaces : force measurements and mean-field theory

Measurements have been made of the solvation forces between mica surfaces in the even-numbered n-alkanes from hexane to hexadecane. In all cases the force law is qualitatively very similar, characterized by a decaying oscillatory function of distance, as occurs for simple isotropic liquids. The spacing between successive minima in the force does not increase with carbon number, and is comparable to the width of a linear alkane molecule rather than its length or any average diameter. This suggests that the alkanes have some tendency towards a parallel orientation near the mica surfaces. The measurements give no indication of any strong repulsive component expected from mean-field theories of higher alkanes or polymers. The results of one such theory are presented, and the reasons for its failure to match the experimental data are discussed.

Forces between mica surfaces in ethylene glycol

Measurements are presented of the force as a function of separation between two molecularly smooth mica surfaces immersed in ethylene glycol, and in solutions of lithium chloride and sulfuric acid in ethylene glycol. At surface separations greater than 3 nm the measured force is in very good agreement with double-layer theory, but at smaller separations there is an oscillatory solvation force which is superimposed on the double-layer repulsion. In contrast to the case in water, the adsorption of hydrogen ions at the mica surface does not markedly affect the short-range forces.

Measurement of aqueous film thickness between charged mercury and mica surfaces : a direct experimental probe of the Poisson-Boltzmann distribution

A stable aqueous electrolyte film is formed between a mercury drop and a flat mica surface due to electrical double-layer repulsion when a negative potential is applied to the mercury. Film thickness has been measured as a function of applied potential while keeping the film pressure constant. By making measurements in this way, it is possible to map the data directly according to the Poisson-Boltzmann equation. An excellent fit to the data is obtained, providing direct evidence for this classical equation and its use as the basis of the Gouy-Chapman model of the diffuse double layer in electrolyte solutions.