International Journal of Applied Engineering Research ISSN 0973-4562 Volume 10, Number 1 (2015) pp. 325-344 © Research India Publications http://www.ripublication.com Investigation of The Failure of A Drive Rod on an Offshore Platform Due To Microbial Induced Corrosion (MIC) Frank Byron The University of Trinidad and Tobago, Point Lisas Industrial Estate, Point Lisas, Trinidad & Tobago, W. I. E-mail: fdbyron54_@hotmail.com Tel.: 1 868 642 8888 Nazim Mohamed* The University of Trinidad and Tobago, Point Lisas Industrial Estate, Point Lisas, Trinidad & Tobago, W. I. E-mail: nazim.mohamed@utt.edu.tt Tel.: 1 868 642 8888 Clément Imbert The University of the West Indies, Faculty of Engineering, St. Augustine Campus, Trinidad & Tobago, W.I. E-mail: csimbert@tstt.net.tt Tel: 1 868 662 6267 Abstract This paper investigates the premature failure of a drive rod on an offshore platform. Pitting occurred along the length of the three sections of the rod at localized points and at regions where the rod was coupled to other components including the extension supports. Several analysis were undertaken to find the root cause of this failure. Based on the investigation conducted and the results obtained it was concluded that the failure of the drive rod was initiated from the pitting process of microbial induced corrosion (MIC). The microorganisms included the aerobic manganese and iron oxidizing bacteria; the anaerobic sulphur reducing bacteria (SRB) and the facultative aerobic acid producing bacteria. Key words: Drive rod, pitting process, microbial induced corrosion (MIC), aerobic manganese and iron oxidizing bacteria, the anaerobic sulphur reducing bacteria (SRB) and the facultative aerobic acid producing bacteria. Introduction The drive rod (comprising three rods) for a fire pump on an offshore platform failed prematurely two years after installation. Failure occurred while performing a routine maintenance operation and occurred at a region that showed severe pitting close to the coupled area. The type of fire pump is a vertical shaft turbine type having multiple 326 Frank Byron, Nazim Mohamed and Clément Imbert impellers that are submerged in the sea water. It is suspended from a discharge head by sections of column pipes which also support and guide the pump’s vertical drive shaft and bearing. The pump is driven by a diesel engine. A schematic diagram of the pump is shown in Appendix 1. Material and Method The investigation undertaken comprised the following [1]: 1. Visual Inspection. The sample was visually inspected and photographs were taken. 2. Dimensional Measurements. Dimensional measurements were taken using a Mitutoyo Digital Caliper Model CD-6” C. 3. Macrography A macroscope with digital imaging capability, model Omano OMVV-GX4 (T), was used to observe the sample at macro level and to record features of interest. 4. Micrography and Microprobe Analysis. A JEOL Scanning Electron Microscope (SEM) Model JSM-6490LV, with an attached Energy Dispersive Spectrometer (EDS), Model Oxford 7574 was used in the analysis. 5. Microstructure Analysis. A Nikon Optical Microscope Model Epiphot 200 was used in the analysis and photomicrographs were taken at points of interest. 6. Elemental Analysis. The analysis was carried out using a JEOL scanning electron microscope (SEM), Model JSM-35CF, with an attached wavelength dispersive spectrometer (WDS) Model JSM-35FCS. The carbon and sulphur contents were determined using an ELTRA carbon/sulphur determinator Model CS2000. 7. Compound Analysis. The analysis was carried out using a Bruker-Axs X-Ray Diffractometer (XRD) Model D8 Advance. 8. Hardness Testing. An Indentec Vickers Macro and Micro Hardness Tester Model ZHV30 was used to determine the hardness profile. Testing was carried out using guidelines given in ASTM E384 Standard Test Method for knoop and Vickers Hardness of Materials. A hardness scale HV 10 was selected. 9. Electrochemical Test Methods. Studies were carried out using GAMRY Instruments Potentiostat/Galvanostat/ZRA Reference 600. 10. Microbiologically influenced corrosion testing. Samples of seawater within the steel casing of the failed drive rod were sent to the microbiology lab for a total count of microbiological activities. Results obtained from items (6) and (8) above were compared with the specifications of wrought martensitic stainless steel type AISI 416. Results and Discussion Visual Inspection The visual inspection of the rod revealed the following: Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 327 Three rods were coupled by means of threading to form one rod, and were all severely pitted and corroded especially at the joints where final failure occurred. (Figure 1) Figure 1: The drive rod comprised three rods that were coupled together and were all severely pitted and corroded (red arrows). Also note reduction in diameter at failed ends (white arrows). The mode of corrosion showed extensive localized pitting along the length of the rod and uniform corrosion with minute pits that gave a sponge like appearance at areas that were covered by coupled components. (Figure 2) Figure 2: The surface of the rod showed severe localized pitting corrosion (red arrows) and an adjacent area showed severe uniform corrosion with minute pits giving a sponge like appearance (white arrows). The corrosion product in the pits and crevices appeared black in colour while the corrosion product on the exposed surface appeared reddish brown in colour. (Figure 3) 328 Frank Byron, Nazim Mohamed and Clément Imbert Figure 3: Corrosion product in the pits and crevices appeared black in colour (red arrows) while the product on the exposed surface appeared reddish brown in colour (white arrows). Dimensional Measurements Table 1: shows the physical dimensions of the drive rod Table 1: Dimensional Measurements Rod Dimensions (mm) 3,000.00 Total length of rod 60.00 Diameter of rod 30.00 Diameter of rod at failure 8.80 Average depth of irregular pits Average diameter of irregular 10.00 pits 0.52 Average depth of minute pits Average diameter of minute pits 0.77 Macrograph Macrograph of the rod revealed the following: Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 329 The localized pits were irregular in shape and comprised clusters of minute pits closely spaced on the surface. (Figure 4) Figure 4: The localized pits are irregular in shape and they comprise a cluster of minute pits closely spaced on the surface (red arrows). Minute tubercle deposits are shown close to the threaded section of the rod; this region showed the greatest metal lost because of the pitting. (Figure 5) Figure 5: Minute tubercles are shown close to the threaded section of the rod that had the greatest metal lost due to pitting corrosion (red arrows). 330 Frank Byron, Nazim Mohamed and Clément Imbert A cross-section of the rod showed the morphology of the surface pits as elliptical in shape and they appear as a collection of sharp-edged pits. Also note the circular pit below the surface pits. (Figure 6) Figure 6: A cross-section of the rod showed the pits as elliptical in shape and they appear as a collection of sharp-edged pits (red arrows). Also note the circular pit below the surface (white arrows). The transverse section of an elliptical pit was polished and showed a subsurface pit approximately 3 mm below the surface pit. (Figure 7) Figure 7: The cross-section of an elliptical pit was polished and showed a subsurface pit approximately 3mm below the surface pit. Mag. 30X. Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 331 Microstructure Sections of the drive rod were ground, polished and etched and revealed the following: The structure showed a typical quenched and tempered martensitic stainless steel, with a fine martensite structure. (Figure 8) Figure 8: Typical quenched and tempered martensitic stainless steel. Also noted is the fine martensite structure (red arrows) Mag. 500X. A typical cross-sectional profile of one type of pit showed the pit opening being much smaller in diameter at the surface than below the surface; the pit also formed an undercut. (Figure 9) Figure 9: A cross-sectional profile of one type of pit showed the pit opening being much smaller in diameter at the surface than below the surface; the pit also formed an undercut (white arrows) Mag. 500X. 332 Frank Byron, Nazim Mohamed and Clément Imbert A typical cross-sectional profile of another type of pit showed the elliptical shape with the depth and width dimensions. (Figure 10) Figure 10: A typical cross-section of a pit showed the elliptical shape with the depth and width dimensions (red arrows) Mag.100X. Micrograph and Microprobe Analysis SEM micrograph and microprobe analysis of the sample revealed the following: Typical deposit products in the tubercle on the surface of the rod. (Figure 11) Figure 11: SEM micrograph of the tubercle deposit material on surface of rod. Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 333 Microprobe analysis of the tubercle deposit on the surface of the rod revealed the elements present (Figure 12). Figure 12a: Microprobe analysis of the tubercle deposit on the surface of the rod. Element O Mg Al Si Cl K Ca Cr Mn Fe Ni S Zn Totals Weight % 30.12 3.95 2.00 2.09 0.36 0.15 8.21 4.20 22.78 20.56 0.70 3.14 1.73 100.00 Figure 12b: Analysis of Spectrum Microprobe analysis of the corrosion product at the upper layer of the surface pit revealed the elements present (Figure 13). 334 Frank Byron, Nazim Mohamed and Clément Imbert Figure 13a: Microprobe analysis of the corrosion product at the upper surface of the pit. Element O Mg Al Si Cl Ca Cr Mn Fe Ni S Zn Totals Weight % 39.83 1.96 1.11 0.86 0.58 6.75 11.32 12.60 20.93 0.20 3.41 0.53 100.00 Figure 13b: Analysis of Spectrum. Microprobe analysis of the corrosion product at the lower layer of the subsurface pit revealed the elements present. (Figure 14) Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 335 Figure 14a: Microprobe analysis of the corrosion product at the lower surface of the pit. Element O Na Mg Al Si S Cl Ca V Cr Mn Fe Ni Totals Weight % 39.12 0.51 0.61 0.65 0.74 8.35 0.11 20.86 0.14 16.18 0.95 10.92 0.86 100.00 Figure 14b: Analysis of Spectrum. Elemental Analysis A Quantitative analysis of the drive rod is compared with AISI 416 specifications and is presented in Table 2. 336 Frank Byron, Nazim Mohamed and Clément Imbert Table 2: Quantitative Analysis of Drive Rod. Elements Carbon Percentage composition by weight % Rod AISI 416 0.129 0.150 max Sulphur 0.329 0.150 min Phosphorus 0.020 0.060 max Manganese 1.06 1.25 max Silicon 0.56 1.00 max Chromium 12.45 12.00-14.00 Nickel 0.21 0.15-0.25 Molybdenum 0.04 0.60 max Iron Remainder Remainder The sample satisfied the chemical requirements of an AISI 416 martensitic stainless steel [2]. Compound Analysis X-Ray diffraction analysis was performed on the two coloured corrosion deposits observed on the sample. The black deposit was extracted from the pits and crevices of the corroded surface of the rod and the reddish brown deposit was extracted from the exposed corroded surface of the rod. The results are presented in Table 3. Table 3: Compound Analysis Result of Two Coloured Corrosion Deposit. Corrosion Compound Name deposits Reddish Pyrrhotite Black brown Calcium Iron Oxide Hematite Lepidocrocite Goethite Chromium Iron Carbide Iron Manganese Carbide Northupite Groutite Formula Fe0.95S1.05 CaFe3O5/CaO.Fe.Fe2O3 Fe2O3 Fe3+O(OH) Fe2O3.H2O Cr15.58Fe7.42C6 FeO.4Mn3.6C Na3Mg(CO3)2Cl Mn3+O(OH) Similar compounds were identified in both coloured deposits. The difference in colour is as a result of a predominant compound in the iron oxide phase when exposed to the atmosphere. The transformation from lepidocrocite to goethite gives a reddish Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 337 brown colour and is usually formed in the early stages of atmospheric corrosion. The black colour is influenced by the manganese oxide, and iron sulphide compounds. The X-Ray Diffractograms are presented in Charts 1 and 2 below. Chart 1: X-Ray Diffraction pattern of black corrosion products. 338 Frank Byron, Nazim Mohamed and Clément Imbert Chart 2: X-Ray Diffraction pattern of reddish brown corrosion products. Hardness Testing A Vickers hardness profile (HV10) on a polished section of the rod reveals hardness reading shown in Table 4. An equivalent Rockwell Hardness C (HRC) number is also recorded. Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 339 Table 4: Vickers Hardness Test (HV10). Test No Reading # 1 Reading # 2 Reading # 3 Average HRC T121933 248 243 250 247 23 The sample satisfies the hardness requirements as a tempered AISI 416 martensitic stainless steel. Electrochemical Test Methods The corrosion rate of the drive rod was determined from the Potentiostat by using a linear polarization technique in the simulated environment. The applied potential is plotted versus the current within ±20mv which is often linear. The slope produced is proportional to the corrosion rate of the metal in the environment so the corrosion rate is then calculated. The corrosion potential of the drive rod was also measured using the polarization resistance method. The results are shown in Table 5 and the polarization Chart 3 is shown below. Table 5: Polarization Test. Item Environment Temperature pH °C 416 Stainless Steel Sea water 23.6 7.69 Corrosion Rate (mm/y) 0.07 Corrosion Potential (mV) -519 Following the guidelines given in the comparative chart described by M.G. Fontana, the uniform corrosion rate determined can be considered excellent under the simulated conditions. 340 Frank Byron, Nazim Mohamed and Clément Imbert Chart 3: Polarization resistance chart showing corrosion rate of drive rod in sea water. Microbiologically Influenced Corrosion Testing One litre of seawater was sampled from the ocean at the offshore platform in the steel casing that contained the failed drive rod; it was then submitted to the microbiology lab for a total count of microbiological activities. The sample was taken two months after the failure. The results are presented in Table 6. Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 341 Table 6: Microbiological Count. Laboratory Sample No. Sample Label 1 Platform water pump Heterotrophic Plate count (CFU/ml) 1.16 x 102 Heterotrophic Plate Count (HPC) measured in colony forming units per millilitre (CFU/ml) is a non-specific term for the growth of viable, naturally occurring bacteria in water. The plate counts showed that there was a presence of the bacteria in the water; however the type of bacteria could not be determined with this method. Discussion Visual examination of drive rod showed that the drive rod failed as a result of a reduction in diameter due to the pitting corrosion process. Pitting occurred along the length of the three sections of the rod at localized points and at regions where the rod was coupled to other components including the extension supports (see Figures 1, 2, 3, and 5). Uniform corrosion features were also observed at areas on the rod that were enclosed by the appropriate bearings and bushings. (Figure 2) Macrographs of the pits revealed that the localized pits were irregular in shape as they comprised a cluster of minute pits closely spaced to form larger pits on the surface. (Figure 4) The minute pits were formed under deposits that appear as tubercles. (Figure 5) A cross-section of the rod that contained the pits showed the morphology of the pits as trough pits that were elliptical in shape and having sharp edges. (Figures 6 and 10) Some pits were also observed below the surface (subsurface pits) with deep undercuts that can be classified as sideways pits. (Figures 6, 7 and 9) The microstructure showed a typical quenched and tempered martensitic stainless steel structure with fine martensite. (Figure 8) SEM microprobe analysis of the tubercle deposits on the rod surface identified the deposit to be by-products of the metabolism of the micro-organisms that include trapped detrital materials, and corrosion products. (Figures 12, 13 and 14) Analysis of the product in the pit close to the surface showed a large concentration of manganese and a lesser amount of sulphur whereas analysis of the pit below the surface plane showed a larger concentration of sulphur with lesser manganese. (Figures 13 and 14) X-Ray diffraction analysis of both black and reddish brown corrosion products showed similar compounds. The iron oxide phases were present together with other compounds including iron sulphide and manganese oxide which were predominant in the corrosion products. The electrochemical polarization test using the polarization resistance technique showed a uniform corrosion rate of 0.07mm/y and a corrosion potential of the material in the seawater as -519 mV. The stainless steel can be considered active as it will corrode by pitting. The bacterial count at the time of collection can be considered acceptable (<500 CFU/ml) as the sample was taken two months after the removal of the drive rod from the sea water. 342 Frank Byron, Nazim Mohamed and Clément Imbert Microbiological influenced corrosion (MIC) is defined as corrosion that is influenced by the presence and activities of micro organisms, including bacteria and fungi. The by-products from the organisms promote several forms of corrosion including pitting, crevice corrosion and under deposit corrosion, they initiate and accelerate the corrosion process by providing oxidation or reduction reactions [3]. The bacteria are broadly classified under three categories; (a) aerobic, that is one that survives in the presence of oxygen and are metal-oxidizing bacteria which include manganese oxidizing and iron oxidizing bacteria; (b) anaerobic, that is one that do not survive in oxygen and these include the sulphur reducing bacteria (SRB); (c) facultative aerobic, that is one that can live under both conditions and these include the acid-producing bacteria. Aggressive corrosion takes place when all three types are colonized together. The anaerobic bacteria can thrive in aerobic environments when they are present beneath biofilms/ deposits in which aerobic bacteria consume the oxygen [4]. For metabolism of the anaerobic SRB, oxygen is extracted from the sulphate ions, and this reaction converts the soluble sulphates to hydrogen sulphide which attacks the metal surface forming pits that are larger in diameter below the surface than at the surface, the pits can be described as sideways pits with deep undercuts. The corrosion product produced includes iron sulphide. The formed sulphides also lower the repassivation and pitting potential, which increases the metal susceptibility to pitting. The aerobic bacteria biofilms are able to accumulate ions such as the heavy metals manganese and iron in large concentrations from the surrounding water where they reoxidizes manganese species; they deposit the manganese oxide and tubercles of iron oxide on the surface of metals that alter the electrochemical properties on the surface to induce corrosion. Whenever microbial sulphur reduction and manganese deposition occurs simultaneously within biofilms, a differential potential cell is likely to form on the metal surface. The area under the sulphide species becomes anodic while the area under the manganese species become cathodic and localized corrosion occurs. Crevice and galvanic corrosion is also accelerated when copper alloys and steel is coupled on to stainless steel4 as seen the Figures 1, 2, 3, and 5. Crevice corrosion is a major problem in marine environment because of the low resistivity and high salinity of seawater. Threats always exist at threaded joints; crevice corrosion is exacerbated in warm natural sea water where biofilms form rapidly, and pits form in crevices where there is slowly flowing seawater. The salinity recorded in the sea water was 25.43 parts per thousand (ppt) that is total dissolved salts that attacks the stainless steel under certain conditions. The current required for protecting the stainless steel requires a couple of mA/m2, and needs approximately 100 mV to keep the potential below the pitting potential in the safe passive region [5]. The nature of failure occurred as the AISI 416 martensitic stainless steel was used as the material of choice for the drive rod. The rod remained submerged in the almost stagnant water for a long period. During stagnation naturally occurring microorganisms formed biofilms, and aerobic microorganisms used the dissolved oxygen during their metabolism. A heterogeneous colonization of micro organisms occurred; pits developed rapidly especially at the crevices of the coupled material. Investigation of The Failure of A Drive Rod on an Offshore Platform Due To… 343 Uniform corrosion developed on the rod that was covered by the bearing and bushing material when there was an overall breakdown of the passive film. The rubbing against the rod removed the protective oxide layer and the heat generated increased the corrosion rate. The corrosion under the tubercle deposits supported the micro organisms including manganese and iron oxidizing bacteria with their corrosion products predominately identified at the surface of the pit and the SRB and their iron sulphide corrosion products predominately identified at the lower surfaces. The pitting process continued and reduced the rod’s diameter at the coupled areas to approximately half the original diameter. The rod could no longer withstand the strength required for the drive torque and subsequently failed. Conclusion Based on the investigation conducted and the results obtained the following conclusions are drawn. Failure of drive rod initiated from the pitting process of microbial induced corrosion (MIC). The microorganisms included the aerobic manganese and iron oxidizing bacteria; the anaerobic sulphur reducing bacteria (SRB) and the facultative aerobic acid producing bacteria. The organisms formed colonies embedded in a matrix of heterogeneous biofilm and induced pits in an environment of high salinity. The type of corrosion includes uniform corrosion, crevice corrosion and pitting corrosion. Uniform corrosion occurred under the bearings and bushings of the rod while pitting corrosion occurred along the length of the rod and intensified at the crevices of the coupled joints. The morphology of the pits included trough elliptical pits and sideways subsurface pits that initiated from microbial activities and intensified with the salinity of the sea water. The drive rod was made from AISI 416 martensitic stainless steel. Final failure occurred when the rod became so pitted that it could no longer accept the drive torque required to push the pump. Recommendations Martensitic stainless steels are typically not suitable for continuous immersion in slowly flowing seawater. In slowly flowing or stagnant seawater, cathodic protection must be used to prevent pitting and crevice corrosion. Austenitic stainless steel and duplex steels have a greater resistance for salt water environment and MIC corrosion. The fire water pump should be allowed to operate more frequently to minimize the chance of microbial colonization on the rod. Sea water chlorination is the most effective way of controlling biological colonization on steel members; when chlorine is dissolved in water it hydrolyzes rapidly and creates a hostile environment for living organisms3. 344 Frank Byron, Nazim Mohamed and Clément Imbert Bibliography [1] ASM Handbook, Failure analysis and prevention, Vol. 6 and Vol. 13. [2] SAE HS-1086/2004, ASTM DS-561 Metals & Alloys in the Unified Numbering System 10th Edition. [3] Thomas R. Jack, NOVA Chemicals Ltd. Biological Corrosion Failures. ASM Handbook Volume 11: Failure Analysis and Prevention (#06072G). [4] Dillon. C. P. (Ed.), (1982). Forms of Corrosion – Recognition and Prevention: (NACE International Handbook 1, Vol. 1) Houston. [5] Leena Carpén. (2008). Corrosion of Stainless Steel in Fire Protection Systems: Technical Research Centre of Finland (VTT). Appendix 1: Schematic diagram of vertical turbine fire pump with drive rod assemble Drive rod in casing