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The growth of iron carbonate (FeCO3) on the internal walls of carbon steel pipelines used for oil and gas transportation can reduce internal corrosion significantly. Solution pH can be considered as one of the most influential factors with regards to the kinetics, morphology and protection afforded by FeCO3 films. This paper presents results from a recently developed in situ Synchrotron Radiation-X-ray Diffraction (SR-XRD) flow cell integrated with electrochemistry for corrosion measurements. The cell was used to follow the nucleation and growth kinetics of corrosion products on X65 carbon steel surfaces in a carbon dioxide (CO2)saturated 3.5 wt.% NaCl brine at 80 º C and a flow rate of 0.1 m/s over a range of solution pH values (6.3, 6.8 and 7). In all conditions, FeCO3 was identified as the only crystalline phase to form. Electrochemical results coupled with post-test surface analysis indicate that at higher pH, larger portions of the surface become covered faster with thinner, more protective films consisting of smaller, denser and more compact crystals. The comparison between XRD main peak area intensities and FeCO3 surface coverage, mass and volume indicates a qualitative relationship between these parameters at each pH, providing valuable information on the kinetics of film growth.

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An electrochemically integrated Synchrotron Radiation-Grazing Incidence X-Ray Diffraction (SR-GIXRD) flow cell for studying corrosion product formation on carbon steel in carbon dioxide (CO2)-containing brines typical of oil and gas production has been developed. The system is capable of generating flow velocities of up to 2 m/s at temperatures in excess of 80 °C during SR-GIXRD measurements of the steel surface, enabling flow to be maintained over the course of the experiment while diffraction patterns are being collected. The design of the flow cell is presented, along with electrochemical and diffraction pattern transients collected from an initial experiment which examined the precipitation of FeCO3 onto X65 carbon steel in a CO2-saturated 3.5 wt. % NaCl brine at 80 °C and 0.1 m/s. The flow cell is used to follow the nucleation and growth kinetics of FeCO3 using SR-GIXRD linked to the simultaneous electrochemical response of the steel surface which were collected in the form of linear polarisation resistance measurements to decipher in situ corrosion rates. The results show that FeCO3 nucleation could be detected consistently and well before its inhibitive effect on the general corrosion rate of the system. In situ measurements are compared with ex situ scanning electron microscopy (SEM) observations showing the development of an FeCO3 layer on the corroding steel surface over time confirming the in situ interpretations. The results presented demonstrate that under the specific conditions evaluated, FeCO3 was the only crystalline phase to form in the system, with no crystalline precursors being apparent. The numerous capabilities of the flow cell are highlighted and presented in this paper.

This work investigates the Corrosion Layer Accumulation Rate (CLAR) of iron carbonate (FeCO3 onto X65 carbon steel in carbon dioxide containing environments using the direct method of corrosion layer mass gain measur ement. Glass cell experiments wer e per formed at 80 o C and pH 6.3 or 6.8 over a range of bulk FeCO3 saturation ratios using both actively corroding carbon steel and steel pre-filmed with FeCO3 The CLARs obtained from experiments using actively corroding samples displayed strong agreement with the most recently developed precipitation model by Sun and Nesic at high supersaturation for pH 6.3 and 6.8, but a disparity at low supersaturation for the solution at pH 6.8. The observed discrepancy was attributed to the significant difference in surface saturation ratio between the two conditions when the steel is actively corroding. CLARs determined for pre-FeCO3 filmed carbon steel show that the kinetics of FeC O3 formation reduce significantly once the film establishes a protective barr ier at lower values of supersaturation. The results highlight the contrast between surface layer accumulation kinetics in the early stages of growth and those encountered in the long-term after the development of a protective film.