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Title: Elucidating sweet corrosion scales
Author: Joshi, Gaurav Ravindra
ISNI:       0000 0004 5369 3875
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2015
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The objective of this thesis is to improve understanding of the development of corrosion products (scales) that form on the inner walls of carbon steel pipelines in CO2-rich (sweet) oilfield environments. If well adherent to the carbon steel surface, such scales can significantly reduce the metal’s rate of corrosion. Typically, the open literature labels sweet corrosion scale as ferrous (II) carbonate (FeCO3) or siderite, although this may not always be the case. For example, Fe2(OH)2CO3 (chukanovite) and Fe3O4 (magnetite) are known to modify the protective character of a sweet corrosion product scale. Practical electrochemical methods for the assessment of substrate corrosion, and electron/photon-based characterisation techniques for investigating scale structure and composition, have revealed interesting aspects of the nature of sweet corrosion scale development on model high purity Fe and real-world pipeline steel surfaces. Concerning scale development on model Fe substrates immersed in CO2-saturated deionised water (buffered to pH = 6.8, T = 80°C, Ptotal = 1 bar), electrochemical data supplemented by grazing incidence x-ray diffraction (GIXRD) and scanning electron microscopy (SEM) show that a semi-protective mixed corrosion scale comprising siderite and chukanovite becomes a highly protective siderite scale with longer exposure time. The introduction of sodium chloride to the CO2-saturated solution (T = 80°C, pH = 6.8, Ptotal = 1 bar) impedes the rate of scale formation. Increasing [NaCl] from the start of experiment is suspected to limit the precipitation kinetics of sweet corrosion scale crystals, since chukanovite is no longer observed, and siderite formation is somewhat slowed as well. SEM imaging, using an electronic workfunction-sensitive detector (in lens), reveals nanoscale deposits on the corroded Fe surface in regions that are devoid of µm-scale crystals. With the Raman spectra from these regions considered, it is interpreted that the nanoscale deposits are likely amorphous iron carbonate, albeit oxidised to a significant extent. Moving to real-world carbon steel immersion in sweet solutions, a scale comprising predominantly chukanovite is observed (using GIXRD and SEM) on the 1% Ni weld zone (WZ) surface of a pipeline weld-joint, but not on adjacent, distinct regions (heat affected zones (HAZ) and base metal (BM)). This selective scaling is suggested to be due to some initial corrosion of the weld-joint, which generates sufficient [Fe2+(aq)], and a macro-galvanic effect across the weld, i.e. WZ is cathodic to HAZ and BM. Further, to gain mechanistic insight into compositional changes during sweet corrosion scale growth, an electrochemical cell for in situ GIXRD (named E-cell) has been developed and commissioned. Diffraction patterns acquired using synchrotron radiation, from a pipeline steel surface, reveal the formation and temporal evolution of a multicomponent corrosion scale. Accompanying electrochemical data suggest that the scale is quite protective.
Supervisor: Not available Sponsor: Engineering and Physical Sciences Research Council ; BP plc
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Corrosion scale ; Iron/carbon steel ; Carbon dioxide corrosion ; Iron carbonate (siderite) ; Iron hydroxycarbonate (chukanovite) ; Electrochemistry ; Grazing incidence x-ray diffraction ; Synchrotron source x-ray diffraction ; SEM ; Metallurgy/corrosion