This present study employs aluminum substrates to investigate the formation of Cr(VI) species during a trivalent chromium conversion coating process. The study had a particular focus on understanding the influences of copper in the substrate and O 2 , ZrF 6 2− and F − in the bath on the formation of Cr(VI) species, which were detected by Raman spectroscopy. Comparison of electropolished aluminum and sputtering-deposited aluminum substrates revealed greatly increased rates of coating growth associated with an enrichment of copper impurity in the electropolished substrate that was revealed by transmission electron microscopy. With respect to chromium chemistry in a developed coating, the presence of dissolved oxygen and long conversion treatment times promoted the formation of Cr(VI) species that are generated by oxidation of Cr(III) species. The Cr(III) species are oxidized by H 2 O 2 , which was produced by oxygen reduction reaction. The generation of H 2 O 2 was demonstrated by analysis of the treatment bath using UV spectrophotometry. Conversion coating processes are employed as surface pretreatments of aluminum and aluminum alloys to improve the adhesion with organic primers and increase corrosion protection. Chromate conversion coating (CCC) has been widely used as a conventional and effective process in the aerospace and automotive industries.1-3 However, the toxicity of chromates to human beings and the detrimental impact of chromates on the environment are giving rise to greater regulation of their use. 4,5 In contrast, trivalent chromium species are relatively eco-friendly and, hence, trivalent chromium conversion (TCC) coating processes are being investigated as promising alternatives to CCC processes. 6The TCC coating bath generally contains hexafluorozirconate, sodium fluoride and trivalent chromium sulfate, which results in coatings formed on aluminum that contain Zr-/Cr-rich oxides, hydroxides and fluorides.6-8 Interestingly, a freshly-formed TCC coating after a conversion treatment for 1200 s in a naturally-aerated bath displayed chromate presence by a Raman shift at 866 cm −1 , but the peak intensity was negligible in a coating formed in a deoxygenated bath. 8 Notably, the oxidation of Cr 3+ to Cr 6+ in the aqueous electrolyte is not due solely to the presence of dissolved oxygen. This conclusion is supported by experiments in which no significant chromate species were found in the solution bubbled with only air for more than 300 h. 9 In contrast, the Cr 3+ /Cr 6+ reaction has been reported to occur in atmospheric oxygen at high temperature during a bush fire 10 and also with the presence of MnO 2 oxidant in the natural sea water. 11,12 In the case of TCC coatings, chromate formation has been attributed to the transient formation of hydrogen peroxide generated by oxygen reduction. The influence of H 2 O 2 has been explored by Li et al.,13 who immersed TCC coated AA2024 alloy in 0.5 M Na 2 SO 4 solutions with addition of 0.01, 0.1 and 1 v/v % H 2 O 2 for 1 h. A small level (0.01% v/v) of H 2 O 2 ca...

In the present work, modified copper-containing trivalent chromium conversion (TCC) coating processes for aluminum were investigated. The copper addition to the TCC bath was made for the purposes of reducing the generation of hydrogen peroxide and chromium (VI) species during the coating growth. The morphologies and compositions of the coatings were examined using highresolution electron microscopy, energy-dispersive X-ray spectroscopy and Raman spectroscopy. UV photometric measurements were employed to determine the amount of hydrogen peroxide in the TCC solution. The resultant coatings contained zirconium oxides, chromium hydroxide and fluorides and sulfate constituents, as well as copper oxides and copper-rich deposits that were preferred cathodic sites for oxygen reduction. Of most significance, no chromium (VI) species were detected in the coatings by Raman spectra. It is suggested that this results from reduced generation of hydrogen peroxide, as disclosed by photometric measurements, at the cathodic copper-rich particles, due to favoring of the four electron oxygen reduction reaction. Trivalent chromium conversion (TCC) coatings are promising ecofriendly alternatives to chromate conversion coatings due to the lower toxicity of trivalent chromium species compared with hexavalent chromium.1 The TCC coating solution can be regarded as a modified Zr-based conversion coating solution with addition of small amounts of trivalent chromium salts.2,3 Our previous work used scanning electron microscopy and atomic force microscopy to reveal cracking and spalling of the coating formed on superpure aluminum, especially after a prolonged conversion treatment. 4 This was associated with the fast kinetics of aluminum dissolution due to the attack by fluorine ions in the reaction solution and the stress in the coating. 5 In contrast, the TCC coating formed on AA2024 alloy suppressed the oxygen reduction reaction, due to the physical barrier created by the Zr-/Cr-rich coatings, 1,6,7 and the coating displayed improved adhesion, although the coating was significantly thinner than that formed on superpure aluminum.With respect to the effect of copper alloying, George et al. 8 investigated binary alloys containing 1, 5, and 25 at.% Cu prepared by magnetron sputtering and revealed a decrease in the coating growth rate of zirconium-based coatings with increase of the Cu/Al ratio. This was suggested to be due to the copper species present in the coating impeding the cation transport to the coating base. Furthermore, a layer of corrosion products formed at the coating base. Cerezo et al.9-11 modified the Zr-based conversion coating solution by adding a small amount of copper salts (30-50 ppm). The copper components, which had a high deposition tendency, formed copper and/or copper oxide agglomerates on the substrate, which created local alkalinity that supported the coating formation. As a consequence, the coating thickness on the multi-metal substrate (AA6014, cold rolled steel and hot dip galvanized steel) was increased.One conc...

Ni and V deactivate catalysts and promote coking during heavy oil upgrading. Distribution of metals and metalloporphyrins, and its variation in thermal process, would benefit the more efficient upgrading. Majority of metals concentrate in resins and asphaltenes. To thoroughly study the metals distribution in these fractions, both were subdivided. It is indicated that the interactions between metalloporphyrins and asphaltenes play a significant role in metals distribution. Variation of metals distribution showed that the trend metals concentrated into heavier subfractions and was enhanced by thermal treatment and inhibited by hydrogen sources. Synergism was observed between hydrogen and hydrogen donor for the inhibition.

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To predict oil compatibility is crucial because incompatibility could cause severe deposition and fouling problems. Therefore, compatibility of heavy oils and blends in different ratios were evaluated by fouling at heat transfer conditions. Thermal resistance and fouling rates were obtained on a fouling loop. Effect of colloidal stability based on asphaltene precipitation and SARA composition on fouling was also discussed. Results showed that different variations of fouling rate versus blending ratio were observed for these blending systems. For oils whose viscosities approach at heat conditions, the lower colloidal stability of blends is the higher fouling rate is. However, for oils with greatly different viscosities, inconsistency was observed between compatibility by the two indicators, which is attributed to remarkable change of flow condition. This indicates that both colloidal stability and flow condition play key roles in fouling. Oil compatibility at heat transfer condition is favored being predicted by fouling instead of correlating with the colloidal stability.