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No 3-1989
AVESTA CORROSION MANAGMENT

All rights reserved. Comments and correspondence can be directed to Sten von Matrn, Technical Editor, Avesta AB, S-77480 Avesta, Sweden. Tel. +46(0)226-818 00. Telex 40976 AVESTA S, telefax +46(0)226-545 07.

Corrosion Problems in the Oil Industry

by Roy Johnsen R&D Manager, Materials Technology, Statoil, Postuttak, N-7004 TRONDHEIM, Norway

Abstract
This paper describes some examples of corrosion failures in the oil industry from the Norwegian sector of the North Sea. The reported problems are mainly concentrated on seawater applications, however, some examples from water injection systems and production systems are included.

Introduction
Failures of structures and equipment on an offshore installation can be very costly due to loss of production. More important failures may present a hazard to platform personnel, as was the case with the Alexander Kielland accident in the Norwegian sector of the North Sea in 1980. If a failure leads to ignition of oil or gas on the installation, the consequences may be catastrophic with a total loss of the installation and loss of human lives, as in the Piper Alpha oil platform disaster last year in the British sector. By investigating the causes of failure, further hazards and lost production may be avoided. In the Norwegian sector there has not been reported any systematic evaluation of damages on offshore installations caused by metallurgical failures. On the British sector, however, Britoil has published a paper describing their experience over the last ten years from five offshore installations and one onshore production terminal linked directly by a pipeline to an offshore unit. According to the results of the investigation which is presented in Table 1 and 2, the most frequently recorded failure mechanism is corrosion. Table 3 details the various corrosion mechanisms experienced (1).

Seawater systems
The seawater systems which include the water injection system, the ballast water system, the firewater system, parts of the fresh water making system and the cooling water system are among the most important auxiliary systems on an offshore installation. However, experience has shown that seawater saturated with oxygen is one of the most corrosive environments to which metallic materials can be exposed. As a result of this experience from offshore installations under operation, the material philosophy for seawater systems has been changed during the last ten to fifteen years (2).

Cement lined pipe

In the project phase for the Statfjord A platform which started in 1975, cement-lined carbon steel was selected for general seawater service. This choice was mainly based on experience from onshore installations in the USA. The Statfjord B and C platforms were also designed with high percentage of seawater piping systems made from cement-lined carbon steel. Soon after system start-up leaks in the piping systems were experienced. The leaks were frequently repaired with patches or large pipe sections were replaced. After failure in a 3" nipple in the ballast water system on Statfjord A in 1982, a review of inspection routines and methods was performed. In addition several studies were started to review materials and ways of improving reliability of the ballast water system. A material review on the use of cement-lined piping, performed by Mobil (the operator of the field until 31.12.86), showed that cement lined pipes corroded most frequently in field joints, in sections with turbulence or high velocity, in sections with cracks or defects, in the cement lining and in areas where metallic couplings to more noble alloys could initiate galvanic corrosion. Based on material and piping design reviews it was decided to replace parts of the ballast water system on Statfjord A with titanium grade 2 using 6 Mo type valves (UNS S31254). The titanium parts should be internally coated with polyurethane to reduce the cathode/anode surface area and by that avoid galvanic corrosion in unreplaced cement lined carbon steel piping material. The titanium installation was performed in 1986. Although inspections have shown large areas with cement lined pipes in good condition after more than nine years in service, Statoil will not recommend this material for new offshore projects.

Table 1: Types of failure on offshore-/onshore installations from a review performed by Britoil (1).
Type of failure Corrosion (all types) Fatigue Mechanical damage/overload Brittle fracture Fabrication defects (excluding welding) Welding defects No defect (ie analysis and quality testing) % 33 18 14 9 9 7 10

Table 2: Main items involved in the failures investigated by Britoil (1).

Item Production pipework and vessels Pumps and compressors Downhole production equipment Drilling and wireline equipment Conductors and casing Cranes and lifting equipment Water injection, equipment and pipework % 18 14 12 12 10 9 6

Cupro-nickel pipes
Piping systems made from 90/10 CuNi or 70/30 CuNi alloys have been used on several installations in the North Sea. According to information from the suppliers these alloys have good properties in chlorinated seawater. However, although practical experience shows that CuNi-alloys do not suffer from corrosion under certain service conditions, a lot of failures have been reported. These failures have often been caused by erosion, polluted seawater, low iron content (< 1.3 wt%) or residues of carbon inside the pipe. Parts of the seawater system on Statfjord B and C were originally designed with 90/10 CuNi. After six to twelve months of service a number of leaks were discovered in this system on Statfjord B. The leaks were mainly located close to elbows and tees or near reducers.

Table 3: Types of corrosion related failures in the review performed by Britoil (1).
Type of corrosion CO2 related H2S related Preferential weld corrosion Pitting (unclassified) Erosion Galvanic Crevice Impingement Stress corrosion % of total failures 9 6 6 4 3 2 1 1 1

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3 A laboratory investigation showed presence of an iron rich second phase in grain boundaries with an increase in magnetic permeability. To overcome this problem, 90/10 CuNi should be purchased in solution annealed condition. If welding is needed it should be performed as rapidly as possible to reduce exposure time in the temperature range 500-550C. Another example is taken from a production platform at the Ekofisk field with parts of the seawater system made from 90/10 CuNi. These include cooling system, oil coolers for the diesel engines and oil water treatment system. According to the design specifications, the water velocity should be lower than 3 m/s and the temperature below 11C. After eight months in service, leakage in a pipewall with thickness 2 mm was discovered. Later on several other leakages were discovered. The reason for these failures were deposit corrosion caused by low water velocity (3). Another failure was reported from the flotel "Kosmos" owned by Jahre Offshore A/S. After less than one year in operation corrosion damages were discovered on a seawater system made from 90/10 CuNi, operating with a velocity of 1.8 m/s and max. temperature 30-40C. The wall thickness was 3.5 mm. The reason for this failure was galvanic corrosion caused by galvanic coupling between valves made from stainless steel and the pipings made from 90/10 CuNi. In this couple, the piping material will act as an anode compared to the passive stainless steel. In earlier literature, CuNi-alloys and stainless steels have been presented with approximately equally free potentials in seawater. As can be seen from Table 4, this is not the case. Depending on the relative area difference between the two metals such couplings can cause severe corrosion damages on the CuNi-alloy. At the Krst terminal, which is an onshore plant operated by Statoil, the cooling water is chlorinated seawater with max. temperature 20C. The piping system and the tubings in the heat exchangers are made from 90/10 CuNi and 70/30 CuNi. After less than one year in operation corrosion failures occured in both the tubings and the piping system. This failure was caused by a combined effect between corrosion and erosion. On the basis of the reported failures and on the fact that cost and weight of these alloys exceed that of other relevant alloys (stainless steel with 6%Mo and glass fibre reinforced plastic (GRP)), Statoil does not recommend CuNi alloys for seawater piping systems.

Stainless steel pipes

Stainless steel pipes have been used for seawater systems even before the offshore activity started in the North Sea. However, the experience from the use of the socalled "stainless steel" which in most cases was AISI 316L, varied. The alloy frequently suffered from localized corrosion. The reason for the positive result in some cases, was often caused by the not intended cathodic protection form less noble alloys coupled to AISI 316L. The selection of stainless steel Avesta 254 SMO (UNS S31254) for the whole seawater piping system on the Gullfaks A platform, was a step into a new world for the oil industry. The order included approximately 40000 m with pipes from 1/2-36" in diameter, 5000 flanges and 23000 fittings. The total weight of the order was approximately 700000 kilos. In addition, several of the valves for the seawater system are made from 254 SMO. Later, 254 SMO has been selected for the seawater system on the Gullfaks B and C, Oseberg and Snorre platforms. After four to five years in service at the Gullfaks field the experience from the use of 254 SMO in seawater system, is very good. Some failures have been reported. Examinations have shown that exchange of alloys very often has been the reason for the failures. On several occasions AISI 316L has been used instead of 254 SMO. In these cases the quality control system has not worked properly. Corrosion failures in welds have been caused by the use of not recommended filler metal. This exchange of alloys has been the most serious problem when using 254 SMO. In some cases, however, 254 SMO has suffered from corrosion. Plate type seawater evaporators for fresh water production made with titanium plates and 254 SMO type shell are installed on one of the Statfjord platforms. After one year in service some corrosion problems were identified in this unit. Crevice corrosion was observed in the fresh water maker vessel door flange seal face where it comes into contact with a nitrite rubber door gasket. Corrosion was also observed on 254 SMO surface of a back plate in line with the titanium plates in the evaporator section. The reason for the corrosion attack on 254 SMO was that the critical crevice corrosion temperature had been exceeded since the service temperature was 48C. Another corrosion failure at the same temperature level has been reported by Norsk Hydro (4). During the last ten years several research projects have been performed to examine the behaviour of stainless steel alloys in seawater with and without chlorination. Critical crevice corrosion temperature of UNS S31254 depends on a lot of parameters like chlorination level, crevice geometry, alloy composition, welding condition, etc.

Table 4: Potential development (mV SCE) of different alloys in natural seawater flowing with velocity 1 m/s and temperature 10C.
Alloy 90/10 CuNi 254 SMO AISI 316L Titanium Hastelloy C Inconel 625 * localized corrosion 1 -215 -100 -100 - 50 -150 -150 7 -215 -180 70 30 200 210 13 -210 220 100* 180 275 270 Exposure period (days) 32 -210 280 120* 250 300 300 50 -210 300 140* 290 310 305 80 -210 310 140* 305 310 310 90 -210 312 140* 310 313 312

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Table 5 shows results from tests in chlorinated seawater at 8C and 30C with flanged connections made from 254 SMO and duplex stainless steel SAF 2205 (4). According to own experience Statoil does not recommend the use of 254 SMO in chlorinated seawater at temperatures exceeding 30-35C. Table 5: Crevice corrosion of flanged connection of SAF 2205 and 254 SMO in chlorinated seawater (4).
Test No. 1 2 3 4 5 Chlorine level, ppm 0.2 0.5 0.2 0.5 1.0 Seawater temp., C 8 8 30 30 30 Number of attacks SAF 2205: 4 254 SMO: 0 SAF 2205: 4 254 SMO: 0 SAF 2205: 5 254 SMO: 0 SAF 2205: 6 254 SMO: 1 SAF 2205: 6 254 SMO: 4

Subsea production systems

During the last five to ten years the use of subsea production systems have increased around the world. Such systems can produce oil and gas from one well or from a cluster of wells, and are connected to a platform or to shore by a flowline. According to results from an investigation published in 1988, more than 250 production wells in the North Sea will be subsea completed within the next ten years. In the Norwegian sector of the North Sea, at the North East Frigg field which is a gas field operated by Elf Aquitaine Norge A/S, the first field development was based on a subsea production concept. The field came on stream in 1983 (6). Later, Statoil has started production from subsea completed wells at the Gullfaks field (satellite wells) and at the Tommeliten field (template sturcture).

Localized corrosion on stainless steel

Pump materials
The most commonly used pump materials for seawater handling on offshore installations are NiAl-bronze and duplex stainless steel (SAF 2205). So far only one prototype pump made from 254 SMO has been corrosion tested in seawater. This test has been performed by Frank Mohn A/S during the last three years. The test results so far are acceptable with only minor corrosion attacks reported. The experience from the use of pumps made from NiAlbronze which can be used with velocities up to 20 m/s without erosion problems, is in most cases acceptable. The reason for the high resistance against erosion is the development of an aluminium rich oxide film on the metal surface. If the pH in the seawater is reduced, the stability of the oxide film will be reduced. This can be the result if the seawater contains traces of sulphide pollutions. In such cases selective corrosion can occur. This means that iron and aluminium are corroded, while copper rich phases are left in the surface. On the Statfjord A platform the impeller on one of the seawater pumps in the ballast water system corroded very fast due to sulphide pollutin in the water. Duplex stainless steel suffers from localized corrosion in seawater under certain conditions even at temperatures in the range of 10-20C. To prevent corrosion attacks a duplex stainless steel pump should be equipped with sacrificial anodes both for the external and internal parts of the pump in contact with seawater. Frank Mohn A/S has during the last five to ten years delivered several pumps to the offshore industry made from duplex stainless steel and equipped with sacrificial anodes. According to their experience, the pumps behave well with intact anodes, while corrosion attacks have been reported on parts without cathodic protection (5).

On subsea completed wells the main equipment like XMAS-tree, pipings, hydraulic cables, etc., are submerged in seawater. The corrosivity of the seawater has not always been taken into consideration. In some cases this has caused corrosion attacks. Localized corrosion on equipment made from stainless steel has been the most frequently occuring corrosion mechanism (7). At the North East Frigg field the hydraulic lines, used for operating valves on the XMAS-trees, consisted of flexible hoses and hard piping. By quick couplings the flexible hoses were connected to the manifold distribution valve and to the hard piping. The hard piping was made from AISI 316L stainless steel and was clamped to the template structure by means of rubber clamps. This isolated the stainless steel pipes and its couplings from the cathodic protection system. The first evidence of problems with the hydraulic lines were discovered in 1985 when blisters were found on several of the nitrile rubber hoses during inspection. All the hoses and its couplings were subsequently replaced by a synflex type the same year. Some of the new couplings were made from AISI 304 stainless steel instead of AISI 316L. During 1985 and 1986 several corroded connections were discovered. Later in 1986 all the original hydraulic piping were bypassed using flexible synflex hoses connected at each end to the structure which was cathodically protected. The main reason for the corrosion damages was localized corrosion on not seawater resistant stainless steel and the fact that the hydraulic piping system was isolated from the cathodic protection system of the structure. On some occasions the corrosion rate was increased by galvanic contact between AISI 304 and AISI 316L. The same type of corrosion has been reported from other subsea installations. To prevent corrosion good electrical contact must be provided between the different alloys in order to protect all parts by means of the cathodic protection system.

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Hydrogen embrittlement of highly alloyed materials

For applications in seawater which require high strength and corrosion resistance, highly alloyed materials have been used extensively during the last years. The most common application is bolting materials. In addition alloys are also used for valve stems, bodies, bonnets, etc. submerged in seawater. Some highly alloyed materials are succeptible to hydrogen embrittlement under certain conditions. The most important parameters are the stress level of the component, the protection level from the cathodic protection system and the microstructure of the component/alloy. Table 6 shows the relative resistance to hydrogen embrittlement of some highly alloyed materials tested in hydrogen and helium (8). Table 6: Relative resistance ment (9).
Alloy INCOLOY 903 AISI 316 OFHC COPPER 6061-T6 INCOLOY 802 7075-T73 A-286 RA330 Be-Cu (ALLOY 25) AISI 310 AISI 347 ASTROLOY HASTELLOY X FM INCONEL 718 AISI 1020 Ti-6Al-4V (ann.) INCONEL 625 AISI 1042 (norm.) HY 100 MONEL 400 MP35N INCONEL 718 AISI 4140 RENE 41 INCONEL X-750 17-7 PH (H 1050) AISI 410 250 MARAGING

Table 7: Results of slow strain rate tests of high alloyed materials (9). Strain Rate = 5 x 10 secAlloy
6 1

Yield Tensile Elonga Reduc- Time to (MPa) (MPa) tion tion failure (% in of area (hours) 2 in.) (%) 579 600 586 565 759 793 745 793 634 710 655 648 655 648 627 655 931 979 917 889 965 993 662 634 896 903 862 876 1034 1103 1062 1034 1041 1048 1027 972 1027 1076 1034 1041 25 27 4.2 3.5 26 24 10 7 22 8 27 27 27 15 10 11 10 9 36 42 8 7 76 65 21 22 45 50 14 12 43 46 36 13 32 45 47 47 36.3 39.8 6.1 4.1 32.8 28.0 11.2 19.1 33.4 32.2 16.3 14.4 32.9 32.3 33.9 19.0 15.7*** 22.7 16.4 22.0

Monel K-500 Air Seawater CP* CP 8 days** Ferralium 255 Air Seawater CP* CP 8 days** Inconel X-750 Air Seawater CP* CP 8 days** Inconel 718 Air Seawater CP* CP 8 days** Beryllium Air Seawater CP* CP 8 days**

to

hydrogen

embrittle-

H2 Pressure (MPa) 35 69 69 69 48 69 69 48 69 69 35 35 35 48 69 69 35 69 69 48 69 69 69 69 48 69 69 69

Strength Ratio* 1.00 1.00 1.00 1.00 0.99 0.98 0.97 0.95 0.93 0.93 0.91 0.90 0.87 0.86 0.79 0.79 0.76 0.75 0.73 0.65 0.50 0.46 0.40 0.27 0.26 0.23 0.22 0.12

A-286 Air 903 1158 17 44 20.6 Seawater 910 1165 15 50 19.3 CP* 924 1158 16 44 21.3*** CP 8 days** 889 1158 17 37 21.4 * Cathodically protected with aluminium anodes. ** Coupled to aluminium anode for 8 days prior to testing coupled to aluminium. *** One specimen.

Corrosion failures in other systems

CO2-corrosion
Corrosion problems related to carbon dioxide in the produced fluids have been a source of failure in production equipment. Damages have been observed in downhole equipment, tubings, flowlines between the wellhead and the process unit and in the process unit itself. The problems are caused by the corrosive effect of carbonic acid produced by the dissolution of carbon dioxide gas in water phases. The corrosion rate is affected by temperature, pressure, pH, water composition and the velocity of the fluid. Even if the iron carbonate corrosion product formed may give some protection to the steel, this is often removed at regions with high turbulence or velocity, forming the "mesa-type" corrosion. This type of corrosion has often been observed on the sides of production tubings or downstream of obstacles, bends etc. causing turbulent flow. Up to now the DeWard & Milliams nomogram, shown in figure 1 (page 6), has been the most widely used to predict the corrosion rate of carbon steel in CO2-environment.

* Notched strength ratio (H2/He) at room temperature

Bolts made from Monel K-500-a precipitation hardening copper-nickel alloy-have been widely used for subsea application in the North Sea. However, during the last years some failures caused by hydrogen embrittlement have been reported. Failures of Inconel 625 bolts have been reported during the last year. The main reason for this failure was a not acceptable microstructure caused by the heat treatment, which was not performed according to specifications combined with a certain stress level and cathodic protection. Conoco Inc. has performed a research project to look at the succeptibility to hydrogen embrittlement of cathodically protected bolt materials. As can be seen from the results in Table 7, Ferralium 255, Inconel X-750, Inconel 718 and Monel K-500 are embrittled, while copperberyllium and A-286 do not suffer from hydrogen embrittlement (9).

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6 Since this nomogram does not take into consideration the development of a protective layer under certain conditions, it gives a conservative estimate of the corrosion rate. During the last ten years several million dollars have been spent trying to develop a more accurate prediction tool. However, the DeWard & Milliams nomogram is still in use.

Conclusions
Corrosion is the most common cause of failure of materials on offshore structures. Severe corrosion failures have been reported on both cement-lined carbon steel piping and CuNipiping for seawater systems. No severe corrosion problems have been reported from the use of austenitic stainless steel Avesta 254 SMO in seawater systems after four to five years in service at the Gullfaks A platform. The main problem with the use of 254 SMO in seawater systems is the mix-up of alloys and consumables for the welds. Submerged parts of seawater pumps made from duplex stainless steel have to be protected by sacrificial anodes to prevent localized corrosion. Pumps made from NiAl-bronze suffer from corrosion in polluted seawater. All parts of a subsea production system (including the hydraulic lines) have to be cathodically protected to prevent corrosion. High strength, high alloyed materials suffer from hydrogen embrittlement under certain conditions including cathodic protection in seawater. Severe corrosion attack on carbon steel tubings/ equipment in seawater injection system caused by galvanic corrosion in welds or too high level of dissolved oxygen, has been reported.

Figure 1 DeWard & Milliams nomogram for calculations of corrosion rates (mm/year) as a function of partial CO2 pressure (bar) and temperature (C). Example: Corrosion rate 0.1 mm/year with 0.1 bar CO2 at 7C.

Water injection systems

Another source of failure has been associated with preferential corrosion of carbon manganese weld metal in seawater injection systems when used to weld typical carbon steel pipework. In pipework made from ASTM A106 Grade B material (0.25% C, 0.29-1.06% Mn) and ASTM A105 fittings (0.25% C, 0.6-1.06% Mn), corrosion attack has been concentrated in the weld metal with the wastage following the fusion boundaries. Corrosion rates up to 4 mm/ year have been reported. No obvious damage to the adjacent parent metal has been observed. Laboratory investigations with welded samples have shown the occurrence of galvanic cells with the parent plate acting as a cathode and the HAZ and weld metal acting as an anode. This explains the selective attack of the weld zone. A series of corrosion trials have been carried out in an attempt to optimise welding parameters using a number of alternative consumables with various percentages of the elements Mn, Ni, Mo, Cr and Cu. The trials indicate that the consumable containing 0.5 %Ni and 0.4%Cu (ANS E 8018 G) appears to give the most satisfactory performance from the welding and corrosion resistance point of view. Further work has been performed by the Welding Institute/CAPSIS in an industry sponsored research project. The amount of dissolved oxygen is another source for corrosion attack in seawater injection systems. According to the specification the oxygen content should not exceed 10-20 ppb in the injection water. However, due to failure in the deaeration equipment and/or increase in the injection rate during certain periods, this critical value can be exceeded. Combined with a water velocity in the range 3-5 m/s this can cause severe corrosion problems in injection tubings and downhole equipment made from carbon steel.

References
1. P. Nelson, J. R. Still: Metallurgical failures on offshore oil production installations. Metals and Materials. September 1988. 2. . Strandmyr: Operational experience from the Statfjord platforms. Presented at Holmenkollen Park Hotel, Oslo. 26-27.10.1988. 3. L. Lunde, R. Johnsen: Seawater resistant alloys (in Norwegian). Ing. Nytt nr 18-20, 1986. 4. R.E. Lye, R.S.Hansen: Seawater corrosion views and experience. Presented at Holmenkollen Park Hotel, Oslo, 26-27.10.1988. 5. N. Nilsen, V. Dagestad: High alloyed materials in seawater pumps (in Norwegian). 6. P. Tobiassen, N. Gil: Practical experience from North East Frigg after four years in production. Presented at the subsea seminar at Royal Garden Hotel, Trondheim, 26-27.01.88. 7. E. A. Molinari: Subsea production systems-corrosion prevention. As above. 8. M. Jooston et al.: Material considerations for critical service subsea XMAS-trees and tubing hangers. As above. 9. LH. Wolfe, M. Jooston: Failures of Nickel/Copper bolts in subsea application. SPE Production Engineering. August 1988.

This paper was published at the 11th Scandinavian Corrosion Congress, Stavanger 1989. It is reprinted here with the kind permission of the Author.

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