In-situ identification of iron--zinc intermetallics in galvannealed steel coatings and iron oxides on exposed steel

Identification of all the compounds present in various coatings on steels is particularly difficult. Non-destructive, in-situ analysis is necessary if the fraction of each compound as well as its probable layering within the coating, is to be determined. Mössbauer spectroscopy is one valuable probe capable of uniquely identifying all iron compounds which form as coatings on steel and other iron alloy surfaces. To investigate a complete coating several criteria need to be considered. Removing the coating inevitably leaves a small and perhaps important component intact on the substrate. Therefore investigating the coating as it remains intact on the steel is important if complete identification of the iron compounds is to be made. This also preserves crystalline texture or preferred growth orientation within the coating to which the Mössbauer effect is sensitive. Mössbauer spectroscopy is a non-destructive technique which allows the integrity of the coating to be maintained during analysis. The combined transmission and scattering Mössbauer geometries generally result in accurate analysis of the coating composition. For the scattering geometry added information on compound layering is obtained if separate Mössbauer spectra are recorded using the re-emitted gamma rays as well as the conversion electrons and subsequently emitted X-rays. In-situ scattering Mössbauer spectroscopy has been used to characterize the iron--zinc alloys which form in the coatings of commercially produced corrosion resistant galvannealed sheet steel, a product of great interest to automotive producers. The results show that different amounts of four iron--zinc phases are present depending on the production conditions of the coating. The different phases are also distinctly layered. Mössbauer analyses of corrosion coatings formed on the surface of steels which have been exposed to different environments has also been undertaken. Materials include structural steels exposed for up to 25 years in marine, rural and industrial environments, and the interior surfaces of boiler pipes subjected to adverse chemical and temperature environments.     

Distributions in fuzzy logic

Probability distributions associated with several ‘ply’-operators are discussed. These exact distributions are compared with relevant Gaussian approximations.     

Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule

The photophysics of a covalently linked perylenediimide–diketopyrrolopyrrole–perylenediimide acceptor–donor–acceptor molecule (PDI–DPP–PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in τ = 3.1 ± 0.2 ps, with charge recombination in τ = 340 ± 10 ps, while in unannealed/disordered films of 1, charge separation occurs in τ < 250 fs, while charge recombination displays a multiexponential decay in ∼6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, upon CH₂Cl₂ vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron–hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for ∼4 μs. This result has significant implications for the design of organic solar cells based on covalent donor–acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems.     

Measurements of anisotropic elastic constants of type 308 stainless-steel electroslag welds

In austenitic-stainless-steel weld metal, mechanical anisotropy is caused by preferred local orientation of elongated subgrains and preferred crystallographic orientation. Ultrasonic and static tensile-test methods used to determine elastic stiffness and compliance matrices, respectively, demonstrated that orthotropic symmetry exists. Inversion of this compliance matrix gave a stiffness matrix which showed general agreement between the two methods. It is suggested that the data can be used directly in finite-element analyses of weldments containing Type 308 stainless steel.     

Evaluation of direct analysis in real time mass spectrometry for onsite monitoring of batch slurry reactions

Batch slurry reactions are widely used in the industrial manufacturing of chemicals, pharmaceuticals, petrochemicals and polymers. However, onsite monitoring of batch slurry reactions is still not feasible in production plants due to the challenge in analyzing heterogeneous samples without complicated sample preparation procedures. In this study, direct analysis in real time mass spectrometry (DART-MS) has been evaluated for the onsite monitoring of a model batch slurry reaction. The results suggested that automation of the sampling process of DART-MS is important to achieve quantitative results. With a sampling technique of manual sample deposition on melting point capillaries followed by automatic sample introduction across the helium beam, relative standard deviation (RSD) of the protonated molecule signals from the reaction product of the model batch slurry reaction ranged from 6 to 30%. This RSD range is improved greatly over a sampling technique of manual sample deposition followed by manual sample introduction where the RSDs are up to 110%. Furthermore, with the semi-automated sampling approach, semi-quantitative analysis of slurry samples has been achieved. Better quantification is expected with a fully automated sampling approach.     

Development of a gas diffusion probe for the rapid measurement of pCO2 in aquatic samples

A capillary electrophoresis (CE) procedure with contactless conductivity detection (C(4)D) has been developed for monitoring of neutral mono- and disaccharides in drinks and foodstuffs. The separation of a mixture of seven neutral saccharides (glucose, fructose, galactose, mannose, ribose, sucrose and lactose) employed a quartz capillary, 5 μm i.d., with an effective length of 18.3 cm, and 75 mM NaOH (pH 12.8) as the background electrolyte (BGE). The limit of detection (LOD) values obtained lied within a range from 0.4 μmol L(-1) for lactose to 0.9 μmol L(-1) for ribose, with a separation time shorter than 140 s. The procedure was successfully applied to determinations of saccharides in fruit juices, Coca-Cola, milk, red and white wines, yoghurts, honey and a foodstuff additive.     

Molecular recognition probes of solvation thermodynamics in solvent mixtures

High-throughput UV-Vis experiments using four molecular recognition-based probes, made by the combination of two hydrogen bond acceptors, tri-n-butylphosphine oxide and N,N'-bis(2-ethylhexyl)acetamide, and two hydrogen bond donors, 4-phenylazophenol and 4-nitrophenol, were performed. The association constants for the 1 : 1 H-bond interaction involved in each probe system were measured in mixtures of a polar and non-polar solvent, di-n-hexyl ether and n-octane, respectively. Similar behaviour was observed for all four systems. When the concentration of the polar solvent was low, the association constant was identical to that observed in pure n-octane. However, once the concentration of the polar solvent exceeded a threshold, the association constant decreased linearly with the concentration of di-n-hexyl ether. Selective solvation in mixtures can be understood based on the competition between the multiple competing equilibria in the system. In this case, solvation thermodynamics are dominated by competition of the ether for solvation of H-bond donors. For the more polar solute, 4-nitrophenol, the selective solvation starts at lower concentrations of the polar solvent compared with the less polar solute, 4-phenylazophenol. Thus the speciation and hence the properties of systems containing multiple solutes and multiple solvents can be estimated from the H-bond properties and the concentrations of the individual functional groups.