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Active anodic zinc content below 90 wt.% does not support sufficient electrical contacts but higher contents cause high porosity of traditional liquid zinc-rich paints (ZRPs). To resolve this problem, our proposal is the application of highly dispersed polypyrrole (PPy) coated alumina inhibitor particles (PCAIPs) in zinc-rich paint compositions. Using these nano-size inhibitor particles at concentrations from 4.55 to 0.85 wt.%, hybrid paints were formulated with zinc contents ranging from 60 to 85 wt.% at the same time. Submicron morphology and nano-scale structure, spectroscopy characteristics and electrochemical properties of the PCAIPs were studied by transmission electron microscopy (TEM) and rheology, Fourier-transform infrared spectroscopy (FT-IR) and cyclic voltammetry (CV) in first part of the work. In the second part, electrolytic corrosion resistivity of two sets of paint coatings were salt-spray chamber and immersion tested with 5 wt.% aqueous solution of sodium chloride. Active corrosion prevention ability of the salt-spray tested coatings was evaluated in compliance with ISO recommendations. Dielectric properties of the coatings during the immersion tests were monitored by electrochemical impedance spectroscopy (EIS). Corrosion tested area of the coatings was investigated by glow-discharge optical emission spectroscopy (GD-OES) to disclose infiltration of corrosive analytes and oxygen enrichment in the cross-section of the primers in comparison with their pristine states. Morphology of the zinc pigments was examined by scanning electron microscopy (SEM), and quality of steel specimens and the interfacial binder residues by X-ray photoelectron spectroscopy (XPS) as well as FT-Raman and Mossbauer spectroscopy. The results of both types of corrosion tests evidenced efficient utilisation of sacrificial anodic current for galvanic protection and improved barrier profile of the hybrid coatings, along with the PCAIP inhibited moderate self-corrosion of zinc. As a result of well balanced active/passive function, the hybrid coating containing zinc at 80 wt.% and PCAIPs at 1.75 wt.% embedding PPy at 0.056 wt.% indicated the most advanced corrosion prevention. Galvanic function of the hybrid paints is interpreted on the basis of size-range effect and spatial distribution of the alumina supported PPy inhibitor particles and basic electrical percolation model considerations.

In part 1 of this work, preparation, structure, spectroscopic, and electrochemical characteristics of the polypyrrole (PPy) deposited alumina/multi-walled carbon nanotubes (MWCNTs) inhibitor particles (PDAMIPs) are presented. TEM observations evidenced uniform deposition of thin PPy film on the functionalized nanotubes, whereas co-deposition of PPy and polystyrene sulfonic acid (PSS) lead to thick polymer coverage on hydrated alumina. Modification with polymer complexes resulted in moderately dispersed PDAMIPs, which is due to the various degrees of aggregation and coalescence. FTIR revealed compact and dense PPy structure on the functionalized MWCNTs while it was not the case on alumina and the PSS modified nanotubes. Closer interaction of PPy with the MWCNTs resulted in enhanced charge mobility, whereas greater electroactivity and reversibility of PPy were noted to samples containing functionalized nanotubes and low amount of PSS. Rheological study verified moderate micron-scale dispersity and the modification caused various degrees of aggregations of the PDAMIPs. These were recognized to be valid in the suspensions at a solid phase concentration with component contents similar to the corrosion tested hybrid coatings. Rheological percolation of the nanotubes (with anisotropic factor of ∼100) was confirmed at volume fractions of 3.30 × 10−3 and 6.0 × 10−4 which were under the dilute/semi-dilute boundary type theoretical and experimental thresholds. This is related to the extensive interconnection of the nanotube-supported filaments. Thus, overlapping of the nanotubes should contribute to the electrical percolation thereby galvanic corrosion prevention function of the zinc-rich hybrid coatings, which is discussed in the 2nd part.

High porosity and intense galvanic function related low electrolytic barrier profile and fast delamination of zinc-rich paints (ZRPs) are addressed by the utilisation of intimately structured, highly dispersed, polypyrrole (PPy) deposited alumina particles (PDAPs) embedded zinc-rich hybrid paints. The more globular but less-packed structure type PPy-contained water-solvent-prepared PDAPs-composited hybrids comprising spherical zinc pigment at 70 wt.%, provided moderate galvanic function with enhanced electrolytic barrier properties. In addition, the less globular structured but well-packed PPy-comprised aqueous ethanol-solvent-prepared PDAPs-composited hybrid coatings indicated highly efficient suppressed galvanic function and improved barrier properties, realising solid performance improvement over conventional ZRPs in immersion and salt-spray chamber tests. Furthermore, the application of highly dispersed PDAPs at a content of 3.2 wt.% while PPy incorporated into zinc-rich hybrids at 0.16 wt.% is proposed to result in emerging additional functionalities increasing long-term anticorrosive performance of ZRPs by inhibiting sacrificial and self-corrosion of zinc and scavenging oxidative radicals thereby hindering oxidative degradation of the organic binder.

A systematic study on anti-corrosion and anti-fouling effect of hydrophobic Langmuir-Blodgett and self-assembled molecular layers deposited on metal surfaces, as well as anti-microbial adhesion properties of coatings with biocide is presented. Both types of efficiencies produced by LB films are enhanced by Fe 3+ ions built in the molecular film. The quaternary ammonium type biocide embedded into the cross-linked gelatin decreased significantly the microbial adhesion, the biofilm formation.

Ordered mesoporous materials (SBA-15 and KIT-6 silica and MFI zeolite) supported nickel phosphide (NixPy) hydrotreating catalysts were prepared by reduction of oxidic precursors with an initial stoichiometric Ni/P ratio of 2 The metal loading (20 and 30 wt.% NixPy) and pretreatment conditions (773 K or 873 K reduction temperature, in situ sulfidation at 723 K) of the precursors were varied. Temperature programmed reduction, in situ XRD, and 31P NMR indicate the formation of metallic nickel then different nickel phosphides (Ni3P, Ni12P5, then Ni2P) in this order upon reduction. The changes in the textural properties of the catalysts compared to their parent supports promote the conclusion that a significant part of the NixPy phases is located inside the mesopores. The catalytic activity (parallel dibenzothiophene hydrodesulfurization and o-methyl aniline hydrodenitrogenation) increases strongly with increasing NixPy loading. The KIT-6 and SBA-15 supported catalysts exhibit higher hydrotreating activities than reference CoMo/Al2O3 and Ni12P5/SiO2 catalysts. In contrast, the catalyst based on a mesoporous MFI support had the lowest hydrotreating activity. This activity trend is explained by the propensity of high-surface area mesoporous silica supports to well disperse metal phosphide particles. The active phase composition of the spent catalysts is in the range of Ni2.0–2.6P1.0S0.4–0.7. This suggests that bulk Ni2P with some sulfur in its surface forms the active phase in the mesopores of SBA-15 and KIT-6.

Investigation on time-dependent layer formation was performed on high purity polycrystalline zinc surface in reaction with aqueous solution of 1, 5-diphosphono-pentane (DPP) at room temperature. Film evolution was characterized by X-ray photoelectron spectroscopy, contact angle, atomic force microscopy, glow discharge optical emission spectroscopy and detailed infrared reflection absorption spectroscopy measurements. Development of a partly crystalline zinc-diphosphono-pentane conversion layer of increasing thickness with time was determined by consistent evaluation of the results. The formed layers turned the hydrophobic zinc surface to hydrophilic. The conversion-type interaction of diphosphonic acid compounds with the oxidized zinc surface resulting in zinc-diphosphonate salt was unambiguously justified by XPS and GD-OES analysis. The corrosion behaviour of the coated zinc substrate was studied using electrochemical impedance spectroscopy (EIS). The formed layers show significant protective effect in sodium-sulphate solutions. It was shown, that under the applied conditions, a 4 h treatment is necessary to obtain 75% protection efficiency after 4 h of immersion into the Na 2 SO 4 .

The objective of our studies was to investigate the layer formation of 1, 5-diphosphonopentane (DPP) on zinc surface from aqueous solution. For surface treatment, water based solutions of 1, 5-diphosphono-pentane was applied with different treatment times. Evidence of the adsorption of the diphosphonic acid on the zinc surface was obtained using the Infrared Reflection Absorption Spectroscopy (IRRAS).

The infrared (IR) spectra of CO adsorbed on 10, 20, and 30 wt % nickel phosphide-containing reduced SBA-15 and KIT-6 mesoporous silica-supported catalysts have been studied at 300-473 K. On the catalysts containing a stoichiometric amount of phosphorus with 20 wt % loading, the most intense IR absorption band was observed at 2097-2099 cm(-1), which was assigned to CO terminally bonded to coordinatively unsaturated Ni(delta+) (0delta1) sites. The frequency of this band was 15 cm(-1), higher than that in the spectrum of a reduced Ni2P/SiO2 catalyst, indicating a modified Ni-P charge distribution. This band shifted to lower wavenumbers, and its intensity decreased, while the relative intensity of another band at 2191-2194 cm(-1) assigned to CO terminally bonded to P increased going to catalytically less active, excess-P-containing SBA-15-supported catalysts. CO also adsorbed as a bridged carbonyl (1910 cm(-1)) and as Ni(CO)4 (2050 cm(-1)) species, and the formation of surface carbonates was also identified. The nature of the surface acidity was studied by temperature-programmed desorption of ammonia (NH3-TPD). Weak and strong acid sites were revealed, and the high excess-P-containing catalyst released the highest amount of ammonia, indicating that a high concentration of strong acidity can be disadvantageous for reaching high hydrotreating catalytic activity. The modified Ni-P charge distribution, the mode of CO adsorption on surface nickel phosphide sites, as well as the acidity can be directly connected to the catalytic activity of these mesoporous silica-supported catalysts.

The infrared emission spectra of CO adsorbed on alumina-supported 1, 3, and 5 wt % Rh, Ir, and Pt metal-containing catalysts were studied at 423 and 473 K. While CO is adsorbed in dicarbonyl (dimer), linearly (on-top) bonded and bridged carbonyl forms on rhodium and platinum, the dimer form is dominant on iridium. The relative intensity of Rh-CO and Ir-CO linear bands decrease with increasing temperature compared to the intensity of the dicarbonyl bands; the corresponding bands on Pt behave the opposite way. Two dicarbonyl and two linear Pt-CO bands were identified in the infrared spectra of Pt/Al 2 O 3 catalysts. The surface structure (kinked or planar Pt atoms), the dispersity of the metal, the temperature, and the quantity of adsorbed CO on the surfaces all have an effect on the fine structure of the Pt-CO stretching bands. The metal-carbon and CO stretching force constants were calculated for surface dicarbonyl, linearly bonded CO, and bridged carbonyl species. The metal-carbon stretching wavenumbers and force constants were predicted and compared between surface species and metal carbonyl complexes. The iridium-carbon bonds were found always stronger than the Rh-C and Pt-C ones in all surface species. The observed stretching wavenumbers and force constants seem to support the idea that CO and metal-carbon bonds are always stronger in metal carbonyl complexes than in adsorbed surface species. The distribution and mode of CO adsorption on surface metal sites can be effectively studied by means of infrared emission spectroscopy.

Refluxing montmorillonite-containing raw bentonite ((Na,Ca)o.33(Al,Mg)2Si 4 O 10 (OH) 2 ) in aq HNO 3 , then neutralizing it with NH 3 produces NH 4 NO 3 -containing NH 4 -bentonite. The NH 4 NO 3 intercalated can be eliminated as a gaseous product (N 2 O and H 2 O) by heating at 400 °C, and the deammoniation and dehydroxylation process of the preactivated bentonite leads to formation of bleaching earth (H x (Al,Mg) 2 -ySi 4 O 10 -(OH) 2 ).