Marine environments pose an obvious challenge to the lifetime of metals, with multiple forms of corrosion and failure possible. Seawater is an efficient electrolyte that facilities the electrochemical reaction of corrosion. The presence of chloride ions accelerates the reaction, together with the presence of dissolved oxygen. In addition, there can be an influence from the speed of water flow, local pollution and microbiological activity. The different corrosion mechanisms that may occur are briefly explained to gain a better understanding of which corrosion resistant alloys may be better-suited to particular environments.
i) General corrosion
For corrosion resistant alloys, general corrosion is not normally a consideration. The alloy additions made ensure that a very thin, passive layer is formed on the surface during its manufacture and subsequent exposure to the environment. Therefore, corrosion typically only occurs where this passive layer is damaged or removed.
ii) Pitting corrosion
The most immediate risk of corrosion comes from pitting. The passive layer may be physically damaged and then unable to re-passivate if immersed in seawater. Alternatively, steelmaking impurities, known as inclusions, could be present at the metal surface and prevent the formation of an effective passive layer. Or the passive layer can be chemically damaged due to localised conditions. Once pitting has started, it can progress rapidly given the creation of a small anode (within the pit) compared with a large cathode (the remaining metal surface) accelerating the electrochemical reaction.
In general, increasing the chromium, molybdenum and nitrogen content will increase a stainless steel’s resistance to pitting (and crevice) corrosion. This can be simply summarised as the Pitting Resistance Equivalent number (PREN), calculated as:
PREN = % Cr + 3.3 x % Mo + 16 x %N
although alternative formulas also include tungsten (W) as a beneficial alloy addition. From Langley Alloys experience of super duplex stainless steels, increased additions of Cu can also be helpful in limiting the impact of pitting corrosion.
It is also possible to measure the Critical Pitting Temperature (CPT) through controlled experiments, to indicate the effect of temperature on the likelihood of pitting corrosion. The CPT is found by exposing metal samples in an aggressive 6% FeCl3 / 1% HCl solution, typically for up to 72 hours. The temperature is progressively raised until pitting is observed at a specified magnification/incidence. Both the PREN and CPT will give an indication of resistance to pitting, so are useful as a basic reference, but give no information on their actual behaviour in a live environment. Testing in more representative laboratory conditions or the actual application give the best measure if time and budgets allow.
iii) Crevice corrosion
Narrow gaps around a component can lead to different environmental conditions compared with the bulk i.e. more acidic, or typically oxygen-depleted. This can initiate corrosion, which can then proceed at an accelerated rated in a similar manner to pitting corrosion. As with pitting corrosion, it is possible to measure the Critical Crevice Corrosion Temperature (CCCT) by exposing metal samples to the same solution and test duration. However, an artificial crevice feature is created by applying a washer, band, tape or through standardised fittings.
Crevice corrosion can be limited through careful design of components, ensuring there is uniform flow around a component to avoid such conditions occurring.
iv) Erosion corrosion
Here, the impact of high flow rates or abrasive media in the water can lead to the partial removal or damage of the protective passive layer. At this point corrosion can begin. Continued removal of both the passive layer (if it attempts to re-from) or the products of corrosion (which can slow down subsequent corrosion) are removed, leading to more general and continued corrosion occurring.
v) Cavitation corrosion
Cavitation is the formation of vapour cavities within a liquid, usually when it is subject to rapid changes in pressure. The cavities form in areas where the pressure is lowest, and these voids effectively ‘implode’ and can damage the passive layer on the metal surface at this point. Cavitation can commonly occur around propellers, pump vanes and seals and piping and is designed-out by limiting the pressure changes within a system.
Impingement corrosion is a variation on cavitation corrosion, and it is often difficult to distinguish between phenomenon. Air bubbles or suspended solids in the liquid can become entrained in turbulent or impinging flow, impacting the metal and damaging its surface.
vi) Hydrogen embrittlement
Hydrogen embrittlement has been historically associated with the presence of hydrogen in steel from its initial production. However, another source of hydrogen is from poorly controlled cathodic protection systems used in marine applications, hence its consideration here.
Hydrogen diffuses along the grain boundaries and combines with carbon, which is alloyed with the iron, to form methane gas. The methane gas collects in small voids along the grain boundaries where it builds up enormous pressures that initiate cracks. If the metal is under a high tensile stress, brittle failure can occur. At normal room temperatures, the hydrogen atoms are absorbed into the metal lattice and diffused through the grains, tending to gather at inclusions or other lattice defects.
Hydrogen embrittlement is not a permanent condition. If cracking does not occur and the environmental conditions are changed so that no hydrogen is generated on the surface of the metal, the hydrogen can re-diffuse from the steel, so that ductility is restored.
vii) Stress corrosion cracking
As the term suggests, this form of failure depends upon the co-existence of both corrosive conditions and stress (either applied or residual from the fabrication process). Their combined effect results in relatively rapid or gross failure in a discrete part of the component, as cracks can quickly propagate (usually along grain boundaries). The stress experienced by a part can be limited by careful design, avoid sharp corners or other ‘stress concentrators’ using more gentle radii.
viii) Sulphide stress corrosion cracking
This form of failure combines elements of both hydrogen embrittlement and stress corrosion cracking. In environments where hydrogen sulphide (H2S) is present, such as in oil & gas applications, the metals react with H2S to generate hydrogen, which is then absorbed into the metal. For applications in such sour environments, there is a considerable level of materials data available from the NACE MR 0175 specification, allowing the careful specification of metals at different environmental temperatures and concentrations.
ix) Microbiologically induced corrosion
Metals immersed in water may be subject to the colonisation by micro-organisms, resulting initially in a thin biofilm (or slime) before progressing to larger deposits. Ultimately the surface may become colonised by macro-fouling, such as shell-fish and weeds. The composition of the deposit is significantly different from and more corrosive than the bulk water environment as concentration cells and differential aeration occurs. At this point, localised corrosion such as pitting or crevice corrosion with initiate.
In open systems, reducing the likelihood of MIC can be improved through design by trying to prevent sediment from building up on surfaces, altering their shape, location or ensuring faster flow regimes exist around it. In closed systems, the same principles exist, but the opportunity to filter or dose the water is possible, as well as limit the potential for oxygenation. Such closed systems are particularly prone to MIC during stop-start conditions, where they may not be fully drained during an extended maintenance period, allowing build-up to occur in near perfect breeding conditions.
Materials for marine applications are selected to maintain the integrity of the structure (mechanical properties such as strength, hardness and impact) and to be corrosion resistant. Stainless steels are commonly used because they combine resistance to corrosion, are easily fabricated and offer good mechanical properties.
a) Austenitic Stainless Steels
Standard austenitic stainless steel grades i.e. Alloy 316L and its derivatives are suitable for coastal service environments, splash zone applications and intermittent submersion in seawater. Once described as “marine grade” stainless steel, they are no longer recommended for permanent contact with seawater. As such, applications are diverse, but include handrails, housings for equipment, ladders and a plethora of ship deck components like deck eyes, brackets for anchor ropes, housings for equipment, shackles and rails handrails.
Fermonic is a nitrogen-strengthened austenitic stainless steel, providing almost twice the yield strength of standard grades. It is therefore more suited to load bearing applications such as chain plate pins and supports for rigging in yacht applications – the increased strength allowing designers to reduce the section thickness and weight of the components for equivalent or higher performance. Available in Fermonic 50 – Annealed form, its high level of ductility makes it easier to work, thus benefiting from the considerable increase in strength seen by austenitic alloys when work hardened. It is also available as Fermonic 50 – High Strength, achieving even higher levels of strength in bars up to 9” diameter. This also opens up applications such as shafts and masts, as well as marine pumps and valves.
Other features of Fermonic are that it retains good toughness and retention of mechanical properties from cryogenic to elevated temperatures, along with non-magnetic properties, which combine to make it well suited to marine sensors.
Fermonic 60 is a more specialised alloy designed to provide superior galling resistance. Its corrosion resistance is somewhere between that of Alloy 304 and Alloy 316L, so less than Fermonic 50. However, for components where there is sliding or rotating contact it can often be used without addition lubrication – ideal for marine applications. Similarly, the anti-galling properties make it suited for applications where there will be repeated assembly and disassembly i.e. sensors, shackles.
Completing the family of austenitic stainless steels are more highly alloyed products such as Alloy 254, sometimes referred to as a ‘super austenitic’ stainless steel. As it contains high levels of molybdenum, its PREN is ≥42, providing excellent levels of pitting and crevice corrosion resistance. This is particularly relevant for both brackish, polluted and seawater exposure, where it is widely used in marine pumps and valves, as well as tubes and pipes in associated cooling systems. It also finds use in equipment attached to hulls of boats and ships where there is prolonged contact with seawater. The one downside, apart from its relatively high cost because of the alloy content, is lower strength levels.
b) Duplex and super duplex stainless steels
Such alloys provide a competitive alternative to the higher performance austenitic grades, combining high levels of pitting and crevice corrosion resistance and higher strength levels. Standard duplex grades are based upon 22% Cr, and so have a PREN c. 34, which is above that of Alloy 316L (29). However, super duplex stainless steels, based upon 25% Cr such as Ferralium have PREN > 40, making them credible alternatives for more expensive nickel alloys in selected applications. Although the level of chromium addition is higher, providing that superior pitting resistance, it is able to utilise lower additions of the more expensive nickel and molybdenum elements, so can be very cost effective. This is particularly so if the much higher strength is utilised to optimise the design and reduce the weight of material needed. The only downside with duplex grades is the degree of care needed when welding to avoid the creation of undesirable phases. Compared with other duplex grades, Ferralium is less susceptible to the formation of sigma phase. In addition, the inclusion of copper helps retard the creation of pitting. Common marine applications include shipbuilding propellers, shafts, rudders, shaft seals, pumps, bolts, fasteners, valves and instrumentation.
Offshore structures themselves present different requirements of materials depending upon whether their application is topside, splash zone or subsea. Ferralium 255 – SD50 is widely used for bolting and fasteners. Matching B7 carbon steel strengths but with far superior corrosion resistance and a service life equal to the life of the system, contributing to reduced maintenance costs. In the splash zone, it has demonstrated its suitability for sea water resistance with over 15 years’ service on North Sea installations and has been widely employed for riser bolting and components on riser protection system on platforms.
c) Copper-nickel alloys (cupronickels)
Such alloys are widely used for marine applications due to their excellent resistance to seawater corrosion, low macro-fouling rates, and ease of fabrication. The addition of nickel to copper improves strength and corrosion resistance while allowing the alloy to remain ductile. Other elements can be added to copper-nickel to increase strength, corrosion resistance, hardening and weldability. Langley Alloys offers a number of such copper alloys with properties tailored to particular applications.
Hiduron 130 is a high-strength cupronickel, where aluminium additions result in significant precipitation strengthening (it is one of the highest strength copper alloys commercially available). Being a cupronickel, it has excellent resistance to corrosion by seawater and in marine and industrial atmospheres and it is highly resistant to crevice corrosion. The major use of Hiduron 130 is in subsea hydraulic and electrical connectors such as flying lead connectors for stab plates. It is also used in naval winches, seawater valves and marine engineering.
Hiduron 191 is an update on the original Hiduron 130 product. Although the yield strength is somewhat reduced, the ductility and impact resistance are significantly improved. It has been widely used in naval and defence applications (under the UK DTD 900/4805 specification) for fasteners for ships and submarines, control elements of submarines, pump shafts, mechanical seals, winch components, gears, hose couplings, weapons handling equipment, components in sonar devices, propeller shafts and drive bushes.
Hidurel 5 is a copper-nickel-silicon alloy combining high electrical and thermal conductivity with very good notch ductility and high mechanical strength. Resistance to corrosion under marine and industrial conditions is excellent and the alloy has good anti-frictional and bearing properties. With a magnetic permeability of less than 1.001, the alloy is essentially non-magnetic. Previous naval applications have included shafts and bolting for ships & submarines, flanges, swash plate pump components and mine detection equipment.
d) Nickel Alloys
Finally, we can consider nickel alloys for marine applications. There are a larger number of alloy specifications available, but generally they have excellent corrosion resistance including resistance to pitting and sulphide stress corrosion cracking. They also have high strengths and retention of mechanical properties over a wide range of temperatures. However, they are inherently more expensive than other metals, and so are widely used in applications where their specification can be justified. As such, there properties are more considered in greater detail in the Oil & Gas application section.
Ferralium 255-SD50 – Sonardyne P-DORT
Sonardyne ist ein führender Entwickler und Hersteller von Unterwasserakustik, Inertial-, optischer und Sonartechnologie, die in vielen marinen Anwendungen zur Ortung eingesetzt wird. Der P-DORT (Programmable Deep Oceanographic Release Transponder, programmierbarer tiefozeanographischer Auslösetransponder) bietet die Möglichkeiten robuster Akustikauslöser und die Hardware für automatische Auslösung in der Tiefe. Der P-DORT verfügt über zwei Betriebsmodi. Erstens reagiert er wie ein Standard-DORT auf sicher codierte akustische Befehle von der Oberfläche im Niederfrequenzband (9-13 kHz). Zweitens kann er vor dem Einsatz für die automatische Auslösung in einer bestimmten Tiefe programmiert werden. So können schwere Objekte, wie z. B. U-Boot-Kabel, sehr genau auf dem Meeresboden positioniert werden und dann nach automatischer Auslösung der Versenkapparat wieder eingeholt werden. Die Akustiksensoren des P-DORT ermöglichen auch das Wiederauffinden von Ausrüstung, wenn das Versenkkabel reißt.
Ferralium 255-SD50 wird bei der Herstellung dieser Geräte aufgrund seiner hervorragenden Korrosionsbeständigkeit im Meerwasser eingesetzt. Hinzu kommt die höhere Festigkeit, die den Einsatz in größeren Tiefen und das Anhängen größerer Lasten erlaubt und für eine zuverlässige Einsatzfähigkeit sorgt.
Ferralium 255-SD50 – Teledyne Benthos R2K
Teledyne Benthos ist eine Unternehmensgruppe in den Vereinigten Staaten, die sich auf die Herstellung von Produkten für die akustische Kommunikation, Positionierungslösungen, ferngesteuerte Fahrzeuge, autonome Unterwasserfahrzeuge und profilierende Driftkörper spezialisiert hat, die unabhängig oder zusammen als vernetzte Unterwasser-Systeme arbeiten. Das Unternehmen besteht seit mehr als 50 Jahren. Seine FAA Black Box ‚Pinger‘ dienen zur Ortung von Flugzeugwracks und Seefracht.
Akustische Auslöser sind ein verbreitetes Hilfsmittel für das sichere und zuverlässige Aussetzen und Wiederauffinden wichtiger ozeanographischer Instrumente. Von der Wasseroberfläche wird ein sicherer akustischer Befehl an die Unterwassereinheit gesendet, um so bis zu 25 Tonnen Inline-Instrumentierung an die Oberfläche zu holen. Die Akustikauslöser von Teledyne Benthos werden von einer Universaleinheit an der Wasseroberfläche bedient, die ein breites Spektrum an Systemfähigkeiten und Diagnosen bietet, um so eine einfache Bedienung und ein erfolgreiches Wiederauffinden von Instrumenten zu gewährleisten.
Das Modell R2K Acoustic Transponding Release ist ein voll funktionsfähiger Akustikauslöser für den Einsatz in Tiefen bis 2.000 Meter und Lasten bis zu 2.000 kg. Sein Gehäuse besteht aus Ferralium® 255-SD50, das hier wegen seiner Robustheit und hervorragenden Korrosionsbeständigkeit in Meerwasser als langlebiger Schutz für das empfindliche Innenleben gewählt wurde.
TP13 – Evaluation of a Diffusion-Trapping Model for Hydrogen Ingress in High-Strength Alloys – US Navy
Das Paper bietet eine detaillierte Untersuchung einer Reihe von Legierungen, die im Auftrag der US-Marine durchgeführt wurde. Betrachtet wurde die Wahrscheinlichkeit von Wasserstoffeinbrüchen als Vorläufer wasserstoffinduzierter Rissbildung. Die bessere Leistungsfähigkeit von Hiduron® 220 (ehemals Marinel 220) wird im Vergleich mit Alloy K-500 ausführlicher erörtert.
TP14 – The Erosion-Corrosion Behaviour of Copper Nickel Alloys – Vassilou (2001)
Diese Dissertation untersucht das Erosionskorrosions-Verhalten von Hiduron ® 220 (ehemals Marinel 220) und von Kupferlegierungen mit 10 % Nickelanteil bei Auftreffen eines Wasserstrahls. Über die gesamte Bandbreite der untersuchten Bedingungen war die Erosionskorrosions-Beständigkeit von Hiduron® 220 deutlich besser als die von Cu-10% Ni. Dies ist eine Abschlussarbeit. Das Dokument ist daher recht groß (ca. 11 MB) und kann als Volltextversion oder als Zusammenfassung hier eingesehen werden: http://theses.gla.ac.uk/2458/
TP28 – Development of a Cavitation Erosion Resistant Advanced Material System – K.Light, University of Maine
Dieses Paper betrachtet eine Reihe von möglichen Materialien für den Rumpf eines neuartigen Bootsentwurfs. Die Beständigkeit gegen Kavitationskorrosion ist dabei die Hauptsorge. Von allen untersuchten Legierungen hat sich Ferralium® als beste Lösung erwiesen (S. 40), obwohl auch Verbundwerkstoffe und GFK-Materialien getestet und in anderer Hinsicht, etwa bezüglich Gewicht, betrachtet wurden.