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Preferential weld corrosion (PWC) remains a major operational challenge that jeopardizes the integrity of oil and gas production facilities. It is the selective dissolution of metal associated with welds, such that the weld metal (WM) and / or the adjacent heat-affected zone (HAZ) corrode rather than the parent metal (PM). Corrosion inhibition is conventionally used to mitigate this problem however several indications suggest that some corrosion inhibitors may increase PWC. Furthermore, it is not possible to detect systems that are susceptible to PWC and or to understand the apparent ineffectiveness of some corrosion inhibitors at high flow rates. Consequently, the aim of this research is to assess the suitability of submerged jet impingement method to study flow accelerated preferential weld corrosion, which is critical to safe and economic operations of offshore oil and gas facilities. In this research, a submerged jet-impingement flow loop was used to investigate corrosion control of X65 steel weldment in flowing brine, saturated with carbon dioxide at 1 bar, and containing a typical oilfield corrosion inhibitor. A novel jet-impingement target was constructed from samples of parent material, heat affected zone and weld metal, and subjected to flowing brine at velocities up to 10 ms- 1 , to give a range of hydrodynamic conditions from stagnation to high turbulence. The galvanic currents between the electrodes in each hydrodynamic zone were recorded using zero-resistance ammeters and their self-corrosion rates were measured using the linear polarisation technique. At low flow rates, the galvanic currents were small and in some cases the weld metal and heat affected zone were partially protected by the sacrificial corrosion of the parent material. However, at higher flow rates the galvanic currents increased but some current reversals were observed, leading to accelerated corrosion of the weld region. The most severe corrosion occurred when oxygen was deliberately admitted into the flow loop to simulate typical oilfield conditions. The results are explained in terms of the selective removal of the inhibitor film from different regions of the weldment at high flow rates and the corrosion mechanism in the presence of oxygen is discussed.

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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.

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