A standard three-step surface pretreatment employed in the aerospace sector for Al alloys have been investigated prior to the generation of cerium conversion coatings (CeCC) on aluminium-copper alloy 2024. Two pretreatments were analysed, one without final acid etching (Pretreatment 1) and another with this step (Pretreatment 2). Both pretreatments affect the alloy intermetallic phases, playing a key role in the development of the CeCC, and also in the susceptibility to localised corrosion in NaCl medium. Scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDX) revealed that after Pretreatment 2, Al(Cu,Mg) phases were partially or totally removed through dealloying with their subsequent copper enrichment. Conversely, none of these intermetallic phases were affected when the final acid step was not employed (Pretreatment 1). Meanwhile, Al-Cu-Fe-Mn-(Si) phases, the other major Al–Cu alloys intermetallics, suffers minor changes through the whole pretreatments chain. The protective efficiency of CeCC was evaluated using electrochemical techniques based on linear polarisation (LP) and electrochemical impedance spectroscopy (EIS). Samples with CeCC deposited after the Pretreatment 1 gave higher polarisation resistance and impedance module than CeCC deposited after Pretreatment 2. SEM-EDX and X-ray photoelectron spectroscopy analysis (XPS) indicate that the main factors explaining the corrosion resistance of the coatings is the existence of Al(Cu,Mg) intermetallics in the surface of the alloy, which promote the deposition of a cerium-based coating rich in Ce4+ compounds. These Al(Cu,Mg) intermetallics were kept in the 2024 alloy when acid etching was not employed (Pretreatment 1).
The selection of appropriate surface pretreatments is one of the pending issues for the industrial application of cerium-based chemical conversion coatings (CeCC) as an alternative for toxic chromate conversion coating (CrCC). A two-step surface pretreatment based on commercial products has been successfully used here to obtain CeCC on AA2024-T3 and AA7075-T6. Specimens processed for 1 to 15 min in solutions containing CeCl3 and H2O2 have been studied by scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDX), glow discharge optical emission spectroscopy (GDOES), potentiodynamic linear polarization (LP), electrochemical impedance spectroscopy (EIS), and neutral salt spray (NSS) tests. SEM-EDX showed that CeCC was firstly observed as deposits, followed by a general coverage of the surface with the formation of cracks where the coating was getting thicker. GDOES confirmed an increase of the CeCC thickness as the deposition proceed, the formation of CeCC over 7075 being faster than over 2024. There was a Ce-rich layer in both alloys and an aluminum oxide/hydroxide layer on 7075 between the upper Ce-rich layer and the aluminum matrix. According to LP and EIS, CeCC in all samples offered cathodic protection and comparable degradation in chloride-containing media. Finally, the NSS test corroborated the anti-corrosion properties of the CeCC obtained after the commercial pretreatments employed.
Se han investigado los efectos de un pretratamiento superficial empleado en el sector aeroespacial sobre la aleación 2024-T3 Al-Cu antes de la generación de recubrimientos por conversión química. Estos pretratamientos influyen en las fases metálicas, que desempeñan un papel clave en el desarrollo de nuevos recubrimientos de conversión sin cromo y en la susceptibilidad a la corrosión localizada en medios que contienen cloruros. El pretratamiento estudiado consta de dos etapas alcalinas y una ácida. La microscopía electrónica de barrido reveló que después del proceso completo, las fases Al(Cu,Mg) se eliminaban parcial o totalmente mediante desaleación y su posterior enriquecimiento de cobre, mientras que solo se atacó la matriz de aluminio que rodeaba las fases Al(Cu,Fe,Mn,Si). El análisis electroquímico reveló el viraje a catódico de las fases Al(Cu,Mg) que aún permanecen en la superficie mientras que la fases Al(Cu,Fe,Mn,Si) presentaron un mayor potencial de corrosión que la matriz de aluminio. Por el contrario, ninguna de estas fases se vio afectada cuando se emplearon únicamente las dos etapas alcalinas. Identificados los procesos que tienen lugar cuando la aleación es sometida a un pretratamiento superficial, es posible diseñar sistemas de protección alternativos a los cromatos.
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