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    valle online at wr scencedirectcom scree Goineer: CORROSION FLSEVIER Corrvon tence (205 2836-386 SCIENCE www clever com/locateleorch The corrosion of nickel-aluminium bronze in seawater J.A. Wharton **, R.C. Barik *, G. Kear °, R.LK. Wood *, K.R. Stokes **, F.C. Walsh * * Serfuce and Electrochemical Engineering Groups, Uniery of Southampton School of Engineering Science, Highfield. Southampton SO1? 1d, United Kingdom BRANZ Lid, Science and Bngmering Secces, Private Bag 50 908, Pris Ciy, Wellington 6220, New Zealand «Physical Sciences Department, stl, Porton Down, Salisbury Wishire SP4 010, United Kingdom Avilable online 26 September 2005, Abstract \Nickel-aluminium bronze (NAB) alloys show good corrosion resistance under marine con- ditions. The corrosion behaviour of cast and wrought NAB alloys is illustrated in this work through a range of electrochemical techniques including open-circuit potentiometry with time oxygen reduction voltammetry, NAB dissolution voltammetry, potential step (oF flow step) current transieals and Linear polatisation resistance. The galvanic coupling of NAB to stainless steel or copper is examined by zero resistance atsmetery. The importance of using controlled flow working electrodes i illustrated by the use ofa rotating dise electrode, a rotating cylinder electrode and a bimelallic (NAB/copper-nickel) rolating cylinder electrode. In addition to controlling the hydrodynamics, such electrodes allow charge transfer data to separate from, those of mass transport control under mixed kinetic control, Longer term seawater immersion trials on planar coupons coupled to titanium or cupronickel are also reported. The relative contributions of erosion and corrosion altack are considered using a wallet electrode and the corrosion characteristics of NAB are compared to those of copper and copper-nickel chloride media. (© 2008 Elsevier Lid, All rights reserve. * Coresponding author. Tel: 4-44 23 8059 2890; fax: =44 28 £059 3016 Email address jaw6@soton.acuk (1A. Wharton) 0010-988X/5 - see front matter © 2008 Blevier Lid. All rights reserve. oi 10-1016 consi 2005 05.088, JA. Wharton etal | Corrosion Science 47 (2008) 3886-8367 a7 Keywords: NAB; RDE; RCE, Brosion; Wallet electrode; Galvanic coupling: ZRA; LPR; Charge traae ser kinetic: Mass raneport 1. Introduction Aluminium bronzes are copper-based alloys in which aluminium (<14 wt.%) is the ‘main alloying element. In addition, some of the alloys contain iron, nickel, manga nese or silicon, Both cast and wrought aluminium bronzes offer a good combination ‘of mechanical properties and corrosion resistance. Consequently, aluminium bronzes have been widely used for decades in a variety of marine applications, including valves and fittings, ship propellers, pump castings, pump shafts, valve stems and heat exchanger waterboxes [1] Nickelaluminium bronze (NAB) alloys containing 9-12 wi.% aluminium with additions of up to 6 wi.% each of iron and nickel represent one of the most impor tant groups of commercial aluminium bronzes. Increasing aluminium content results in higher strength, which is attributable to a hard face-centred cubic (fec) phase which enbances the properties of castings as well as hot working in wrought alloys 2], The other alloying elements also improve properties and alter microstructure, ‘Nickel improves corrosion resistance, while iron acts as a grain refiner and increases tensile strength. Nicke! also improves yield strength, and both nickel and manganese act as microstructure stabilisers [2], Table 1 shows the composition of the main com- mercial alloys: CuAILOFeSNiS, CuAIONiSFe4, CuAIIINi6Fe6 and CuAI9NiS- FeéMn, NAB alloys are metallurgically complex alloys with several intermetallic phases in which small variations in composition can result in the development of markedly different microstructures [2-4], which can result in wide variations in sea- water corrosion resistance. The microstructures that result in optimum corrosion resistance can be obtained by controlling the composition and heat treatment (5) For example, castings of CuAISNiSFe4Mn used for naval applications are given ‘an annealing treatment at 675 °C for 2 to 6h (2] ‘The microstructure of a sand cast NAB (Fig. 1a) consists of light etched areas of aephase, which is a fec copper-rich solid solution and dark etched martensitic regions (ephase or retained f'-a high temperature phase), surrounded by lamellar eutectoid phases and a series of intermetallic x-phases. The xj-phase is globular or rosette shaped and is reported to be iron-rich (based on Fe Al). The xurphase also takes the form of dendritic rosettes which are unevenly distributed at the a/B boundary and are smaller than the ky rosette, The xirphase can appear in cither a lamellar ‘or sometimes a coagulated or globular (degraded lamellar) form. It grows normal to the o/ boundary, as well as forming at the boundary of the large xr-phase, and is described as being nickel-rich (NiAl). The kry-phase is a fine precipitate within the a-phase and is considered to be iron-rich, The microstructure perpendicular to the extrusion direction for the wrought NAB bar is shown in Fig. 1b). The micro- structure has been influenced by the extrusion with little evidence of the i and kurphases. The heat treatment specified for the NES747 Part 2 British Naval me JA. Wharton et ab Corrosion Science 47 (2008) 4336-8867 Nomenclature B — Stern-Geary constant, V bulk concentration of reactant, mol_m volume fraction of sand mean diameter of sand, ma. equilibrium potential, V potential corresponding to limiting current conditions, V Kinetic energy for erosion, J corrosion potential, V critical potential, V Faraday constant, C mol? exchange current density, Am limiting current density, A my standard rate constant constant in Eq. (5) constant in Eq. (6) constant in Eq. (8) kinetic energy exponent in Eq. (10) mass loss, kg mean erodent mass, ke peripheral velocity exponent in Eq. (6) peripheral velocity exponent in Eq, (8) partial pressure of oxygen molar gas constant, JK‘ molt polarisation resistance, Q om? slurry volume flow rate, m? =~ ' time, 8 y temperature, K U peripheral velocity of electrode, ms v mean erodent velocity, ms" AV, volume loss per impact, m? = number of electrons in electrode process Greek symbols % cathodic transfer coefficient Be anodic Tafel slope, V B cathodic Tafel slope. V p density of sand, kg m=" @ —_totation speed of electrode, rad s Abbreviations BRCE_ bimetallic rotating cylinder electrode EPS extracellular polymeric substances JA. Wharton etal | Corrosion Science 47 (2008) 3886-8367 sa39 LPR linear polarisation resistance LSV linear sweep voltammetry OCP open-circuit potential PSCT potential step current transient RDE rotating disc electrode RCE rotating cylinder electrode WIDE wallet disc electrode ZRA zero resistance ammetry standard results in the minimising or elimination of the more corrodible Pephase and ‘an increased density of fine x-phase precipitates in the auphase, see Fig. Le The corrosion resistance of NAB has been attributed to a protective layer, per= hhaps 900 to 1000 nm thick, containing both aluminium and copper oxides [6,7] The oxide layer is aluminiumerich adjacent to the base metal and richer in copper in the outer regions. There are also oxides of nickel and iron, together with trace amounts of copper salts and copper hydroxychlorides, ¢., CuyOMsC1 and ‘CuOHDCI, which form after longer exposure times to seawater. The oxide layer ad- Iheres firmly to the base metal and consequently provides corrosion protection redue- ing the corrosion rate by a factor of 20-30 [7]. This protection has been attributed to both a decrease of the anodic dissolution reaction which hampers the ionic transport across the oxide layer, as well asa decrease in the rate of the cathodic reaction on the oxide layer (6) In quiet, tidal or flowing seawater, provided the low velocity does not exceed a certain limit, the protective film corrosion resistance continues to improve ‘until it achieves a long-term steady-state of 0.015-0.05 mm y~! (0,6-2.0 yA cma) 1,2) NAB is the most resistant of the readily available coppes-based alloys to flow-induced corrosion, However, under conditions of service involving exposure to seawater flowing at high speed, or with a high degree of tuzbulence, damage cean occur to the protective oxide layer, locally exposing the unprotected bare metal NAB is vulnerable to such attack in unpolluted seawater at flow speeds in excess of 4.3m s7! and the degree of attack is reported to vary logarithmically with velocity: from 0.5mm y' (20uAcm™’) at 7.6ms"' to 0.76mmy! (31 pAcm*) at 30.5ms"', and even at 7.6m" corrosion rates could rise locally to 2mm y~" [8] Tn contrast to the many studies ofthe corrosion of copper [9) and its alloys [10] in chloride media, there have been few studies devoted to electrochemical kinetics at NAB surfaces, Schissler and Exner [6,11] studied the dissolution of cast NAB in sca- water but they considered a fxed velocity of electrolyte and performed a limited kinetic analysis, Kear etal, have considered both cathodic [12] and anodie [13] polar isation during NAB corrosion, In aerated seawater, the anodic dissolution of NAB shows many featured in common with the dissolution of copper, a simplified anodic reaction being the formation of the dichlorocuprous anion: cu +2CP — CuCl, a) Designation Componioalvi Meehan ropes ISOICEN saad Ba ASM Gy A “OR Me Hardee, Tene (eunbes) seclication ——_oquivakat Veeess sents can CuLOR SNC sido ABZ COSIO0 BAL, ASUS AOE ASS Rom SHE eamESO CUAIIONSFe# (WHT) AIO coo Bal ASI 4oeO SOSO = hoa so min CUAILIFeANG (WHOS) - Bu losi2s S070 sono > rooass 150-830 * Brish Naval spieaton ar 7 anoeied a 675°C Tora 6h ad cole in for superior eorrdon ean. ose LBt6-95E (S00) ib DUDS HowoUND | oH MOLINA VE JA. Wharton etal | Corrosion Science 47 (2005) 3838-8367 saat Fig. 1. Optical micrographs of ncketaluminium bronze (a) sand east NAB, (b) wrought bar NAB (as ‘wed in RDE and RCE studies) c) British Naval specification, cast then annealed (NES 747 Par 2 as ‘used in ersion-conresionWIDE and pontoon im The predominant cathodic reaction is the four electron reduction of dissolved oxygen: san JA. Wharton etal! Coresion Sconce 7 (2008) $336-8867 0,+2H,0+4e 40H @ Al the mixed potential, the anodic kinetics are influenced by charge transfer and mass transport contributions, Consequently, the rate and mechanism of corrosion (which are dependent on film formation) are very flow sensitive [12,13] as is the bime- tallic corrosion of NAB when coupled to copper-nickel or copper (14) ‘The aim of this paper is to illustrate the corrosion characteristics of NAB in sea- water using both electrochemical and traditional exposure techniques. The short term potentiometric and voltammetric techniques are complemented by bimetallic coupling, erosioncorrosion studies and the monitoring of corrosion rates over ex- tended periods of up to twelve months. It is important to consider flow conditions during corrosion studies of NAB as mass transport is an essential component of the anodic kinetics; the protective films formed are also flow sensitive. Rotating disc electrode (RDE), rotating cylinder electrode (RCE), walhjet dist electrode (WIDE) and bimetallic rotating cylinder electrode (BRCE) geometries have been used as complementary, hydrodynamic working electrodes (Fig. 2). The smooth RDE and RCE provide well-defined surfaces for laminar and turbulent flow studies, respec tively, while a twin electrode, bimetallic RCE allows galvanic studies under well-con- trolled turbulent flow conditions. The WIDE facilitates a comparison of NAB (a) (b) Inutng rooms a me Nebede ns See ig 2. Types of hydrodynamic workin electrode used inthis study: (a) rotating dsc electrode (RDE), (6) rotating cinder electrode (RCE), (c) bimetallic rotating cylinder eeetrode (BRCE), (@) wallet dise leetrode (WIDE) JA. Wharton etal | Corrosion Science 47 (2008) 3886-8367 ss dissolution rates under corrosion, erosion and combined erosion-corrosion condi- tions using the jet impingement geometry. The longer-term corrosion rates of NAB (including galvanic effects) have also been considered using planar coupons un- der tidal conditions. A range of experimental time scales, electrode geometry, flow conditions and NAB alloys have been used to quantify the corrosion characteristics of NAB over a broad range of operational conditions. 2, Experimental details 2.1. Electrochemical measurements at RDE and RCE electrodes Rotating electrode studies were carried out using discs or cylinders machined from wrought NAB, supplied by Stone Manganese Marine Ltd. in rod form to BS. 2874; 1986: CA 104 and having the composition Cu balance, Fe 4.43, Si 0.05, Mn 0.14, Pb 0.02, AL 9.31, Ni 4.65, Mg 0.01 max, Zn 0.11 wt.%. Copper (09.9% wt ‘wt,) and 90-10 Cu-Ni (BS 2874: 1986; CN 102) were also used for comparison pur- poses, A Pine Instruments Company, model AFMSRX analytical rotator was used to control the rotation speed to within 1%. The dimensions of the active RDE were 0.40 cm diameter and 0.13 em? area while those of the RCE were diameter 1.99 cm, length 1.60 cm and area 10.05 em? High-density polyethylene rod was used as the inert sheathing material. The range of rotation speed was 200-9500 rpm (29- 995 rads") for the RDE and 100-4000 rpm (10-398 rad s"!) for the RCE. The working electrode surfaces were mechanically polished on micropolishing cloth ‘and degreased in ethanol prior to each individual polarisation and corrosion poten tial measurement. The polishing procedure consisted of a double, 3 min polish with a 0.3 um sealumina slurry. Natural seawater was collected from a short-term holding tank in Langstone Harbour, Hampshire, UK. The seawater was subsequently vac ‘uum filtered down to a 0.2 um pore size membrane to remove suspended solids microorganisms and the majority of biological spores. Artificial seawater to BS 3900: Part F4:1968 (supplied by BDH) was used as a standard solution for compar ison with the filtered seawater. Typical mean values of pI, conductivity, chloride ion concentration, salinity and dissolved oxygen (DO) concentration were pI 8.0, 50.8 m$ em”, 0.550:mol dm-*, 33.4%, (eke ') and 7.0 ppm, The clectrolyte was aerated for 10:min prior to measurements. When necessary, de-oxygenation was achieved by purging with 99.99% nitrogen (British Oxygen Company) for 10 min fol lowed by a continuous N; blanket to prevent air ingress. Electrochemical measure- ments were made at 25.£0.2°C with a PC-controlled, Eco Chemie Autolab potentiostat (PGSTAT20) using the General Purpose, Electrochemical Software (GPES) version 4.5. The electrochemical cel incorporated a thermostatically con- ‘rolled, glass water jacket, a platinum gauze counter electrode and a (Radiometer Analytical A/S, Ref 401) saturated calomel electrode (SCE) used in conjunction with ‘a Luggin-Haber capillary. LPR measurements were made by polarising the NAB 10mV each side of the steady corrosion potential and monitoring the current ZRA data was obtained using a proprietary instrument (ACM), ay JA. Wharton et ab Corrosion Science 47 (2008) 4336-8867 2.2. Extended seawater immersion tests using planar coupons NAB (NES 747 Part 2) supplied by Meighs Ltd, (chemical composition: Cu bal- ance, Al 9,32, Fe 5.00, Ni 5.38 Mn 1,10, Si 0.05 wt.%), Cu-ISNi alloy (chemical composition: Cu balance, Ni 15.4, Mn 4.36, AL 61, Fe 0.94 wt.%) and commercially pure titanium (Ti 99 wt.%) were used for galvanic coupling tests. The specimens were wot polished with 600-grade SiC paper, degreased in acetone, rinsed in distilled water then air-dried, The galvanic couple specimens had dimensions of 5.0 x 4.0 x 0.7 cm for NAB/Ti, 5.0 x 4.0x0.4 om for NAB/CulSNi and 5.0/5.1 x 0.4 em for NAB/ NAB. The anode to cathode area ratio was 1:1. The galvanic couples (x2 replicates) ‘were connected via electrical leads, with a separation of 5 cm and were mounted in a planar orientation on two non-metallic boards. The boards were immersed in seawa- {er (below the splash zone) from a pontoon located at the National Oceanographic Centre, University of Southampton. Boards 1 and 2 were retrieved after 6-months and 12-months, respectively. The galvanic current and couple potential were men- sured using a zero resistance ammeter (ACM Instruments Galvogill), The reference electrode used was a Ag/AgCl with seawater electrolyte. The salinity of the seawater was approximately 31%, reflecting its brackish nature and the pH was 7.9, which is within the range normally cited for seawater (ie. 7.7-8.3 for surface waters). The sea- water temperature and DO were monitored using a Hanna Instruments 119145 probe, the DO level ranged between 6 and 10 ppm, being dependent on seawater temperature and salinity 2.3. Jet impingement testing The tests were carried out using a slurry jet impingement rig, which has been pre- viously described (15,16), for kinetic energies ranging from 0.02 to 0.41 wJ (calculated from experimental parameters) and a working electrode of 4 x 4 cm. Modifications ‘were made to accommodate an Ag/AgCl reference electrode and a platinum counter electrode. The ejector assembly, used for sand particle intake, was located down- stream fo prevent erosion damage on the counter and reference electrodes. A valve situated near the ejector allowed the sand intake to be completely isolated under flow corrosion conditions. The flow corrosion test electrolyte consisted of a 3.5% NaCl solution, while the slurry was a 3.5% NaCl solution with 3% wt/wt, silica sand, Pure corrosion (Jetcoroxios) experiments Were carried out in the absence of slurry, whilst the erosion-cotrosion (Jetyesomsonosion) eXpetiments were cartied out with sand, A Gamzy Instruments PC4750 potentiostat and ESA400 software were used to monitor the potential, For pure erosion (Jetson @ —0.200 V cathodic protection, was applied, based on the potentials observed from erosion-corrosion conditions. The test duration was 5h. The NAB (NES 747 Part 2) and high strength structural steel BS 4360 (chemical composition: Fe balance, Mn 1.6, Si 0.5, C 0.25 wt.%) spec» imens used in the erosion and erosion-corrosion experiments were wet-polished (up to grade 1200 SiC paper) and lapped (up to 3 ym diamond suspension) to a surface finish of R, NAB, Ia comparison to the other analysis used, this method. ‘would lead to a significant decrease in precision due to the large overpotentials range over which the extrapolation to the equilibrium potential was performed, Using measured (experimentally derived) B and k., exchange current densities can also be determined by @ JA. Wharton etal | Corrosion Science 47 (2008) 3886-8367 ss Table 2 “Esumated values ofthe equilibrium potential and exchange current desity for oxygen reduction at copper sand wrought NAB in both the filered and artical eawatere Parameter Filtered seawater TBS 3900 arial eawater & NAB & NAB Tull extrapolation ues? 3107 9x10 2x10) x 1 Eq, (4) fywAem® 410 1x10 1 oxi kfens* Delo Sx TIO? Eve SCEIV 10.502 0.508 In general, a reasonable correlation is observed between the two methods of js determination, In the case of the NAB in the filtered seawater, similar values were pro duced with Eq, (4) relative to the direct Tafel extrapolation measurement (Table 2). Further analysis allowed the standard rate constant, k, for oxygen reduction to be calculated using, = 2Fhycy (3) The resulting rates of k,, derived from j, values taken from Eq. (4), are also given in Table 2. The Tafel slope, rate constant and exchange current density data confirm that the rate of oxygen reduction at the copper is generally higher than that of the nickel-aluminium bronze. For the copper, oxygen reduction was faster within the artificial seawater. This was not the case for the NAB where all data indicate very similar rates of oxygen reduction in both electrolytes. 3.3. Anodic kineties (metal dissolution) ‘The anodic voltammetry of NAB in Fig. 5a [13] shows a rotation rate dependence Between rotation rates of 800 and 1800 rpm, a transition from the typical quasi-pas- sivation behaviour (also commonly observed for copper [9] and 90-10 eoppernickel 10). For the NAB RDE above 1800 rpm, the rate of reaction i effectively inhibited from the OCP until a critical potential is reached (By * 10.025 V vs, SCE), At potentials more positive than Ey, the current density steps ditectly to a con’ tive-dffusion controlled value of j,. Iti clear from Fig. Sa that there is a definite change in the mechanism of polarisation (and protective formation) above a critical range of rotation rates. This change in mechanism can possibly be explained by con- sidering the limiting mole fractions for aluminium oxide formation ('4,0,) (30), as considered in detail elsewhere (13). ‘The passivation of Cu-Al alloys is based upon the common system of oxidation resistant materials, where solute Al has a greater affinity for oxygen than solute Cu ‘Under standard conditions, Al,O, is almost eleven times more stable than Cu,0 rele ative to their metals in the zero oxidation state. For Cu-L0%4AI alloys, thermal oxi- dation is based on a rapid intial production of Cuz0 from which Nao, is achieved at the alloy/oxide interface due to the depletion of Cu, Alumina subsequently forms 3350 JA Wharton etal! Coram Scene 47 (205) 3886-8867 25 198 sol N89 10004 5} Stmmeosone fof arebon os 0 lo ox as az BT 00a a0 ® Poti vs SCE = 20m. 2 200m ¥ Modqm & Ospm, * toga, 8 tip Y 2pm 1400 a1 Eo # ad ss ‘ha 0a m0 aes 0219 as (o) ‘Potential vs, SCE! WV Fig. 5. Anoie dissolution of wrought NAB. (a) Anodic linear sweep voltammetry st the nickel~ aluminium bronze RDE as « finetion of electrode rolaton rate (exchiding 4800 spr) in aerated, filtered Seawater at a sean fate of 10mVs"" (Q) Apparent Tafel slopes (corrected Tor oxygen seduction) desenbing the anodic estolution of nicke-auminium bronze in the filtered seawater at funtion of RCE as a protective oxide which is highly impermeable to the passage of cuprous cations ‘which can no longer enter what is the outermost layer of cuprous oxide. The higher the aluminium content of the alloy, therefore, the greater the corrosion resistance due to the protective Al;O, film since the limiting mole fraction is achieved over a shorter exposure time and is maintained at lower copper dissolution rates. The anodic kinetics have also been examined at a smooth RCE surface. Within the mixed control region (at polarisations of approximately +300 mV) for each of the copper-based alloys, anodic currents were plotted as a series of ‘apparent’ Tafel slopes (Fig, 5b). These are similar to those similar to those measured at copper in chloride media [14], Each apparent Tafel slope was plotted at a specific electrode rotation rate between 200 and 1400 rpm (21-146 om s-?). In all cases, the magnitude of current density measured at these curves increased in a predictable and reproduc- JA. Wharton etal | Corrosion Science 47 (2008) 3886-8367 sist ible manner. It is clear from the plots that the current has both charge transfer and ‘mass transport controlling component (mixed control), This behaviour is attribut- able to a shift of the equilibrium potential of the anodic reaction to mote negative values as the electrode rotation rate is increased [13 3.4. The mixed{openscireuit corrosion) potential Using the Tafel extrapolation technique and assuming uniform corrosion, the influence of mass transport conditions on the overall corrosion mechanism for these metals can be related dircctly to the angular velocity of the electrode. It can be as sumed here that the polarisation behaviour close to the OCP is representative of that ‘ccurring at the mixed potential and extrapolation of the cathodic and anodic Tafel slopes to the point of equal current density (atthe mixed potential) wil yield the cor- rosion current density. It can also be assumed that the dominant cathodic reaction (oxygen reduction) is slow enough to be taken as reversible at the mixed potential ‘The anodic reaction in these cases is generally assumed to be under mixed charge transfer and mass transport control where the apparent Tafel slope dominates at these potentials. ‘The pure charge transfer controlled current density produced from the Koutecky~ Levich equation for oxygen reduction was used to produce cathodic Tafel slopes completely fiee of the influence of mass transport of oxygen. Tafel slopes were also zmeasured within a large potential window from which the extrapolation of currents to the mixed potential will be more accurate. Evans diagrams, therefore, can be pro= duced which deseribe the polatisation behaviour of all three copper-based alloys at ‘the mixed potential for both filtered and artificial seawater. A typical example is pre= sented in Fig. 6a for the NAB RDE in filtered seawater. The extrapolated Tafel slope for pure oxygen reduction is also shown as a solid line. The anodic half-cell reaction is represented by the apparent Tafel slopes (not corrected for oxygen reduction) for the electro-dissolution reaction. The anodic polarisation curves are shown as a func tion of electrode rotation rate. As the rate of rotation is increased, the effective inter cepts between the cathodic Tafel slope and the anodic slopes increases in terms of the corrosion current and becomes more negative in terms of the mixed potential, This is due to an inerease in anodic current density with rotation rate Fig, 6a can be used to demonstrate the corrosion mechanism of the copper, NAB and 90-10 copper-nickel. At constant oxygen concentration, temperature and chlo- ride based electrolyte, itis the rate of the dichlorocuprous anion, which is corrosion rate controlling for each metal. I is clear from the preceding discussion that the zixed potential can be derived from either LSV derived data, PSCT data or a com- bination of both techniques. In order to establish the optimum combination of polarisation data, the mixed potential for copper in the filtered seawater was derived from three possible combinations of polarisation data: (a) LSV derived cathodic and anodic data, (b) PSCT derived cathodic and anodic data and (c) LSV derived catho~ dic data and PSCT derived anodic data. The best ft between the directly measured and derived values was observed for case (b), where only pure PSCT data was used to reproduce the mixed potential, The percentage deviation from the means of ne JA. Wharton et ab. Corresion Science 47 (2005) 4336-8867 a, aol —— Stamnes Tarot 245 Eso ¢ «| Naa «s| Potential vs, SCE/V 12.0, 9010-Datved & dcty mesure 191.5 NAB- Derived & dey mead # be ct = a Angular Velocity rad s* Fig. 5. Mixed potential plots at wrought NAB RCE, (a) The mised potential forthe nickelaluminium bronze im the filtered seawater derived via Tafel extrapolation of curves derived from steady-state, potential step, and eutent ransens with bydeodyaanie steps (9) Compaiton ofthe derived Irom PSCT data) and the directly measured openiteit potentials for copper, the 90-10 copper-nickel and NAB in the Altered seater, the derived data from the directly measured ones over the whole range of angular velocities, were averaged as 1.57 + 0.01%. The deviations measured for cases (a) and (c) were much greater at 5.04 0.01% and 4.51 + 0.01% for the LSVeun, and LSVanoa and the LSVexq, and PSCTooq, curves, respectively. This trend was also observed in both the filtered and artificial electrolytes for all of the metals examined im this section. It was assumed from these results, therefore, that the most accurate method for the replication of the mixed potential conditions was Tafel extrapolation using only the PSCT polarisation data. The directly measured and derived mixed potentials for cach of the copper-based metals are compared in Fig. 6b using the filtered seawater as an example. Generally, the fit between the two derivations is excellent where the deviation of the means is within the standard deviation of each technique, Diagnostic plots of logarithmic JA. Wharton etal | Corrosion Science 47 (2008) 3886-8367 353 (nixed potential) vs, logarithmic (angular velocity) were produced in order to deter~ rine the dependence of the mixed potential on fluid velocity. Analysis of the open circuit corrosion potential vs. rotation speed data may be used to give the velocity dependence of the mixed potential via the relationship: Eons = hyo? 6 (Overall, the results given here strongly indicate that the OCP of copper, the 90-10 copper-nickel and the NAB can be modelled using the assumption that at the mixed potential: (a) the cathodic reaction is essentially pure oxygen reduction which is under pure charge transfer control and (b) both charge transfer and the mass trans- port of dichlorocuprous anion from the electrode surface to the bulk solution con- trols the rate of the anodic reaction, 3.8, Linear polarisation resistance ‘The Sterm-Geary relationship: Pap ___B Jon S3R (BTR) Bp can be used to directly caloulate the corrosion current density as can Tafel data “Tafel extrapolation detived corrosion current densities for copper, 90-10 copper nickel and NAB in the filtered seawater have been studied as a function of RCE peripheral velocity. A clear dependence on fuid velocity was seen forall the cop= per-based metals where the current densities incteased in a very reproducible mane her. The general rates of corrosion of the metals can be given in the order NAB > 90-10 Cu-Ni> Cu, Corrosion current densities measured at 1000 rpm for the copper, the 90+10 copper-nickel, and the NAB were 3.706, 56:04 and 7.8+0.5 nA cm™, respectively. ‘The LPR derived zelative corrosion rates in Fig. 7 show that the order of suscep- tibilty to corrosion i 90-10 Cu-Ni = NAB > Cu. All the copper-based metals exhi- bited a rotation rate dependence on corrosion current density. The corrosion rate increased with electrode peripheral velocity, At 4800 rpm, the corrosion rate mea sured for the 90-10 copper-nickel was 9yAcm * while for the NAB it was 10 wA cm *, The equivalent corrosion current density measured at the copper was 6 WA cm. Diagnostic plots of logarithmic (corrosion current density) vs. logarith- tic (peripheral velocity) were used to determine the dependence of corrosion rate on flow velocity, The linar regression data taken from these plots, where B is derived from pure charge transfer controlled anodic Tafel slopes, are given in Table 3 for the RCE, This table also gives B values derived from mixed controlled anodic current (the appatent Tafel slopes). For both eases, the general relationship: kw ®) may be used to give an estimate of how the corrosion current density changes with peripheral velocity. From the largely similar values of q given in Table 3 for the RCE, it is clear that the corrosion rates derived for the copper-based materials are o owt ast JA. Wharton et ab Corrosion Sconce 7 (200 sssei67 160 80 ao] : % or 0 Pergherl Velocity ems! Fig. 7, Linear polarisation resistance measurements of corrosion current density vs. RCE peripheral ‘velocity at wrought NAB and other copper-based RCEs in tered seawater. Table 3 Linear regression data describing plots of logarithmic corrosion current density vs. logai potpheral velocity ie RCE Mew “Slope Gog, mA em "Vlosiem =D Tnvereept dogma em") (value of ¢) (value of ky Ge 0276 007 2802 = 0080 (O02 OUD) (0304+ 00168) (-2914 = 0.029 0.001 = 0.001) 90-10 CON: 0.219 4 0.005, 2.487 4 0010 (0.008 1 0.001) (038s 0.048) (2938 + 0.080 0.001 0.001) ‘Wrought NAB ‘0228 + 0033 2.491 £0,642 (0.003 + 0001) (0257 0.010) (2.597 = 0.018 (0.008 = 0.001) Corrosion current density data are shown derived from A values produced from pure charge transfer controlled Tafel slopes and with mixed controlled anodic Tafel slopes (the latter being in parentheses) similarly dependent on fluid velocity hence on the rate of mass transport. This was also the case for the RDE and laminar flow. Table 4 provides a summary of the B values found for NAB, Cu and Cu-Ni in chloride media in this work and in other studies. Although a relatively wide range of values is apparent, the wrought NAB gives broadly similar values to copper and the 90-10 copper-nickel 3.6. Zero resistance ammetry at a BRCE BRCE measurements are useful in the study of galvanic coupling under well defined turbulent flow conditions and have been used by a number of workers [14,31-33}. Fig, 8a shows the mean free corrosion and bimetallic corrosion potential transients (measured at the same electrode at different times) of the 90-10 Cu-Ni/ NAB couple [14]. The uncoupled metal potentials were recorded until 900 s, after Table + Experimental and Iterature values ofthe proportionality constant, Bin the Stern-Geaty equation aN Metal o 90410 CN NAB JA. Wharton etal | Corrosion Science 47 (2008) 3886-8367 age transfer controlled and pi, values) “Actcial seawater (charge tanster controled f. and pi, values) Filtered seawater (mixed contcolied values) Artifcal seawater (mined controlled values) [Natural seawater We NaCl [Natural seawater 3.455% NaCl and natural seawater [Natoral snd artical seawater Filtered seawater (cuarge transfer controled fl and p, values) ‘Artifical seawater (coarge transfer controled fl and f, value) Filtered seawater (ited conteolled fi values) Artifical seawater (mixed controlled values) ‘Natural seawater Artifical seawater ‘Natural seawater [Natoral seawater ‘Natural seawater [Nataral seawater ‘Natural seawater 523.5% NaCl and seawater ‘Natural seawater [Natural seawater [Natural and artical sawatere Filtered seawater (charge transfer controled and fi valuet) ‘Acbfcal seawater (cuarge transfer controled fi, and f, values) Filtered seawater (mixed controled, values) Artifical seawater (mined controlled values) 3% NaCl 545% NaCl 0026 0.019 + 0.001, (0.021 40.001 0.006 0.031 £0901 0.014 and 0.020 ons ox 0.021 + 0.001, 0.019 + 0.001, 0.089 oars 0.089 oars e070 0.040-0.107 ool 0.018 and 0016 0.021 ose 0.014 and 0.019 ons 021 0.018 + 0.001 0.030 = 0.001, 0012 as ass Re Bl 53] 655) ie) 57 6) (0) (ss 5) [591 (oo) [a (2) us) (5) [63 (sa) bs) 213) (55) (6s) ‘Values icomporating mixed control Tail slopes and mean valuce of Bare given for RDE rotation rates from 200 to 9500 xp, which the metals were galvanically coupled. The uncoupled potential of the NAB is very similar to that shown in Fig. 3a. At 200rpm, the steady potentials were =0.296 V vs. SCE (Cu), -0.263 V vs. SCE (90-10 Cu-Ni) and ~0.301 V vs. SCE (NAB), ‘The potential of the couple and the galvanic current were then measured while rotation speed steps were applied to the BRCE. Following a 100 s settling period, the individual potential of copper alloys becomes more negative as the rotation speed. as6 JA. Wharton et ab! Corrosion Science 47 (2005) 3336-8967 0210 : NO = 020 \__ AGE 9300 20pm HOE 0 a 720 7300 ® Time Post Iniiason of Rotation /s = oMOy, © 04m, ao: 10 ¥sssv, @ assay Gasp onan < ts 17 Ts a Be » og (Peripheral Veloiy ems") Fig. §. Galvanic coupling wing a twin electrode, bimtale RCE (BRCE), (a) Mean single metal and bimetallic potential transients of the 90-10 eopper-nikel and the wrought NAB ia the aerated, filtered seawater as a function of BRCE rotation rate (14) (6) Logarithmic plots describing the dependence of reas applied eutreut density on the coppes/iweought NAB BRCE peripheral velocity in th filtered feamater as a function of applied potential, increases due to mass transport aflects on the anodic process. At 1400 rpm, for exam= ple, the potentials become —0.315 V, -0.284 V and ~0.321 V, respectively Over a wide range of rotation speeds, the uncoupled NAB is base with respect to both the uncoupled copper and copper-nickel clectrodes. When coupled, the mean bimetallic potentials ranged from —0,294 to ~0,303 V vs, SCE (copper/NAB) and =0.282 to —0.295 V vs. SCE (90-10 Cu-Ni/NAB) over the rotation speed range of 200-1400 rpm. The directly measured and derived (from RCE PSCT polarisation data for the single metals) current densities resulting from the impressed current cathodic protection of the Cu/NAB bimetallic couple are given in Fig. 8b and show good correlation, This behaviour shown is consistent with a system showing mixed control kinetics [14) JA. Wharton etal | Corrosion Science 47 (2008) 3888-8367 387 3.7. Galvanic effects in seawater over an extended time (pontoon studies) 3.7.1. NABINAB couple (NES 747 Part 2) ‘On immersion, the couple potential for the NAB/NAB couple, see Fig. 9a, was 0.260, similar to the reported corrosion potential of NAB in seawater and is con- sidered to indicate the formation of a CuO film [34-36]. The couple potential ine creased to between ~0,070 and ~0.080V after 3 months which has been attributed to the transformation of CuO to CuO [34,35], The most significant change in couple potential occurred at the start of the biofouling season when sea- water temperatures reach about 10°C (from a minimum of approximately 6°C in February). The galvanic current density for this same period was relatively low at 0.1 to 0.5 uA em * (Fig. 9b). After approximately $ months immersion, however, the decoupled potentials (Fig. 9a) show that the couple had become polarised, with @ subsequent increase in galvanic current density (1.0- 2.5 yA em *). While initially Tie enh » — [ud wt i Z 7” Bu — E 0: 8a S a ig. 9, Extended seawater exposute test involving NES 747 Bart 2 NAB (pontoon studies: February 2008 to Tanuaty 2005). (a) Coupled and decoupled potential measurements for NAB/NAB. (b) Seawater temperature and galvanic current density forthe NAB/NAB. nist JA. Wharton et ab Corrosion Science 47 (2008) 4336-8867 immune from biofouling due to the toxicity copper-ion release within the protective oxide film, this immunity diminishes over time. For copper-based alloys, it has been previously reported that after exposure to natural seawater for several months, a multilayer structure of microorganisms and extracellular polymeric substances (EPS) were found entrapped between layers of different copper corrosion products [37]. In the presence of a biofilm, the subsequent corrosion behaviour will vary according to the extent of the interactions between cortosion products layers and the various components in the biofilm. Even when the biofouling season comes to an end, the presence of a patchy biofilm can create chemical conditions very different from those expected from the ambient environ ‘ment [38]. The biofilm can act as a diffusion barrier as well as a source or sink for chemical species that are important (o corrosion processes. Factors such as pH, dis solved oxygen and peroxides can vary greatly at the metal/biofilm interface, Patchy biofilms on copper-nickel have been reported to produce complex corrosion beha- viours resulting in physical heterogeneities on the metal surface, thus leading to the formation of differential aeration cells [39], Another aspect related to biofilm-cor- rosion product interactions is spalling or sloughing of corrosion products associated with EPS in the biofilms and this has been observed for copper-based alloys exposed to seawater [40]. 3.7.2. NABICu-ISNi couples Coupled and decoupled potential measurements for the NAB/Cu-15Ni couple can be seen in Fig. 10a. On immersion the couple potential was approximately 0.230 V. A sharp shift in the noble direction to about —0.070 V occurred in the fole lowing 2 months. During this time there was a low net current galvanic current den= sity (0.1-0.5 wA em™), see Fig. 10b. Here, both couple components are undergoing film formation and growth processes. After 3-months, with mature protective oxide layers, the couple components become increasingly polarised as evident from the decoupled potentials. The Cu-15Ni is depolarised by 0.040-0.050 V in the noble direction while the NAB depolarises in the active direction by 0.020 V and suggests Cu-15Niis cathodic to NAB, Increased corrosion resistance and the cathodic nature of the copper-nickel alloys have been attributed to enrichment in iron and nickel within the protective oxide film [10]. Once the couple became polarised, the galvanic current density increased significantly reaching a maximum of approximately 30 A cm * between 3 and 6 months. This behaviour also coincided with the sea~ sonal increase in seawater temperature and its associated biofouling activity. When there is an established biofilm, modification of the oxygen reduction kineties can occur simply by the presence of the bacteria and bacterial metabolites/enzymes, which act as electrocatalysts [41-43]. This bacterial influence appears to be respon- sible for the increased galvanic currents observed during this period. At the end of the summer (after 10 months exposure) the biofouling activity diminishes and the depolarisation of the couple components is seen to reduce with a corresponding decrease in the galvanic current density. It has been suggested that enzymes (such as catalase) entrapped in the EPS could be responsible for a possible increase in cathodic currents observed here [44]. Catax JA. Wharton etal | Corrosion Science 47 (2008) $888-8367 359 & Poti: ABAECY Fig. 10, Galvanic efbcts on NES 747 Part? NAB, in seawater, over en extended time (pontoon studies Tanuary 2008 to December 2003), (a) Coupled and decoupled potential messuremens for the NAB/C = 1SNi couple immersed. (b Seawater temperature and galvanic Curent density for the NAB/Cu-ISNi and [NABIT couples. c) Coupled and decoupled potentials measurement for the NAB/T; coupe insmersed Jase is an integral component of bacterial cells’ response to oxidative stress and is be~ lieved to limit the accumulation of reactive oxygen species in the cell [45]. The mech anism requires the electrochemical production of hydrogen peroxide during the ‘oxygen reduction process, and involves electron recycling during the enzymatic decomposition of the peroxide to water and oxygen by catalase, The oxygen gener ated by the enzyme can be electrochemically reduced, reaching the surface by diff- sion. Thus, higher cathodic currents can result. It has been established that oxides forming the protective films on copper and copper-based alloys play a Key role in both the hydrogen peroxide and oxygen reduction reactions [9,10,43,46}. Hydrogen peroxide reduction proceeds through the chemical oxidation of Cu,O, to yield CuO. Cupric oxide is then electrochemically reduced to regenerate CuO [46]. CuzO acts as a redox mediator allowing fast electroreduction of H;0;. However, on a CuO sur- face the reduction of peroxide is inhibited and H,O; accumulates at the interface to finally desorb into the solution. The catalytic reduction of oxygen and hydrogen peroxide on copper-nickel alloys appears to emulate that which occurs on copper ne JA. Wharton et ab Corrosion Science 47 (2008) 4336-8867 [47], This has been verified in a comparison of oxygen reduction on 90-10 copper nickel, copper and nickel-aluminium bronze in artificial and filtered seawater (26) It was found that susface corrosion products in each case influenced the reaction rate where cuprous and cupric species acted to catalyse and slow the kinetics of oxygen reduction, respectively. Similarly, differences in the reduction kinetics of oxygen and hydrogen peroxide on 70-30 and 90-10 copper-nickels have been attributed to the nickel content within the protective oxide film [43], since HO, reduction is inhibited on nickel oxide. 4.7.3, NABIT couples The NAB/Ti couple-potential was approximately —0.230V om immersion (ig. 106) and reveals ite polarisation ofthe NAB by the titanium, ic. the titanium is readily polarised, During the frst month, the galvanic current density increased from 0.1 to 10 wAcm * (Fig. 10b), This is possibly related to the Cu,0 to CuO tcansformation when the protective oxide film thickens, as indicated by the rapid shift in couple potential to ~0,050 V. As titanium does not display any toxicity to- wards marine organisms, biofouling can ocour quickly on exposed surfaces, Initially the decoupled potential for the titanium was about +-0.075 to +0,090 V more noble than the potential of the couple, whercas the NAB was depolarised in the active direction by between 0.020 and 0.030 V. Titanium has been reported to undergo slow ennoblement in both fresh and brackish water [48], Once the biofouling season started, in the third mouth of exposure, a significant ennoblement of the titanium occurred with the decoupled potentials increasing to approximately +0.150 to 0.180 V. However, the decoupled NAB potentials remained close to that of the couple potential with litle further depolarisation occuring. The galvanic current densities after 6 months are significantly lower than the NAB/Cu-1SNi couple at approximately 7 uA cm”, The influence ofthe biofouling season appeated tobe less dramatic for the NAB/Ti couples compared with the NAB/Cu-15Ni, probably due to the poor catalytic activity of titanium for oxygen reduction even in the presence of a biofilm, 3.8. Jet impingement and erosion-corrosion Mass loss measurements for flow corrosion, pure erosion and erosion-corrosion of NAB (NES 747 Part 2) and 4360 steel (as a reference material) are shown in Table 5. Thus, direct comparisons can be made between the different test conditions, assuming that Jet.orroson: Jetgovion Bd Tely.sdion-corovon effects occurred uniformly over the specimen surface. The flow corrosion rates for the NAB and steel are rela- tively constant, whereas for the Jeteoson» ad Jeterosi-

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