Hydrogen embrittlement of cathodically protected high strength steel in sea water and seabed sediment

C. BATT J. DODSON M. J. ROBINSON

Hydrogen embrittlement tests were carried out using double cantilever beam and slow strain rate tensile specimens to measure the susceptibility of a 900 M Pa yield strength steel in diVerent marine environments, ranging from sterile sea water and ltered natural sea water to open sea water and seabed sediment. T he cathodic protection potential and the presence of biologically generated sulphides in seabed sediment were shown to be important factors that controlled the ex tent of hydrogen uptake and embrittlement. T hreshold stress intensities K were measured for each condition and the optimum cathodic protection potential to th control corrosion with the minimum risk of embrittlement was established. BCJ /1954 A t the time this work was carried out the authors were in the School of Industrial and Manufacturing Science, Cran eld University, Cran eld, Bedfordshire M K 43 0K L , UK ( m.robinson@cran eld.ac.uk) . Dr Batt is now with QCL International, A berdeen, UK and Mr Dodson is now with H alliburton Sperry Sun, A berdeen, UK . Manuscript received 16 A pril 2002; accepted 24 J uly 2002.
2002 IoM Communications Ltd. Published by Maney for the Institute of M aterials, M inerals and M ining.

INTRODUCTION
Cathodic protection (CP) is widely used to control the corrosion of steel in sea water but particular care is required in protecting the newer high strength alloys that are being considered for marine applications. If the steel were to be underprotected some corrosion would occur, whereas overprotection would increase the generation and absorption of cathodic hydrogen, which could cause cracking in susceptible high strength steels. Therefore, it is important to achieve the correct balance between obtaining a low level of corrosion and an acceptable risk of hydrogen embrittlement. In the marine environment it is not only CP that increases the hydrogen content of steels. Sulphate reducing bacteria (SRB), which are usually present in seabed sediment or a bio lm on the metal surface, increase the amount of hydrogen absorbed by the metal substantially.1 For example, the hydrogen concentration has been shown to increase by a factor between 5 and 10 compared to that for steel in sterile sea water at the same potential and this can result in an appreciable increase in hydrogen damage.2 , 3 The eVects of potential and sulphide concentration on the concentration of hydrogen absorbed by steel C o are reviewed in Fig. 1.4 , 5 The C o values increase fairly systematically with both the degree of protection and the sulphide concentration. Tests in sea water saturated with H2 S gas (~3000 ppm), which are used widely to test for hydrogen susceptibility in sour conditions,6 give very high C o values, considerably in excess of those that occur naturally in the marine environment. The C o values measured in seabed sediments have been shown to exceed those for natural sea water, except under free corrosion conditions and at low levels of protection. However, seabed sediments show considerable variability in terms of both their biological activity and sulphide levels and, to a lesser extent, local variations in chemical composition and diversity of marine organisms occur in sea water also. The eVects of CP potentials on the corrosion rate of steel in sea water and seabed sediment have been described previously.7 The aim of the research described in the present paper was to investigate the extent of hydrogen embrittlement of a high strength steel at various CP potentials in diVerent marine environments, ranging from sterile sea water and ltered natural sea water to open sea water and seabed sediment.
194 British Corrosion Journal 2002 Vol. 37 No. 3

EXPERIMENTAL Materials
The tests were carried out on specimens of Steel 900, which is a quenched and tempered high strength steel used in marine applications, having a minimum speci ed yield strength of 900 MPa and a composition of Fe011C 021Si 066Mn 0006P 0005S 05Cr 051Mo 502Ni <0001B01Cu005V (wt-%). The yield strength, tensile strength, and hardness of the steel were 103810 MN m 2 , 1080 10 MN m 2 , and 3726 HV1, respectively

Double cantilever beam tests

Double cantilever beam (DCB) tests were carried out to measure the threshold stress intensity for hydrogen embrittlement in Steel 900. Bolt loaded DCB specimens were machined in the SL orientation from the midsection of 50 mm thick plate. The specimens were 250 mm long with both height and width of 20 mm. The slot was 3 mm wide with a tip radius of 01 mm and length from the load line of 30 mm. Side grooves were machined to a depth of 16% of the beam thickness to control the crack path. The SL orientation was chosen as this was considered to be the most susceptible to embrittlement due to the elongation of microstructural inclusions during fabrication. Each specimen was prefatigued to give a short microscopically sharp precrack. The crack tip stress intensity K I was calculated from the following relationship,8 which includes a factor for the eVect of the side grooves.9
K =
I

dEh [ 3h(a + 06h)2 + h 3 ]1 /2 (B / B n )1 / 4 [(a + 06h)3 + h 2 a]

(1)

where d is the displacement at the load line, E is Youngs modulus of the material, a is the crack length measured from the load line, h is the specimen half height and B n and B are the grooved and ungrooved specimen thicknesses, respectively. The specimen thickness B was designed to be as small as practicable, to minimise the time taken for a uniform hydrogen concentration to be established, while satisfying the plane strain criterion9 for the range of crack tip stress intensities of interest
B 25 (K I / sy )2

(2)

DOI 10.1179/000705902225006606

Batt et al.

Cathodically protected high strength steel in sea water and seabed sediment 195

1 Effect of potential and sulphide concentration on hydrogen uptake by cathodically protected steel

where sy is the yield stress of the material. The majority of the specimens were loaded to give an initial stress intensity close to 75 MN m 3 / 2 . In the case of specimens tested in conditions that cause low levels of hydrogen uptake, it was thought that blunting of the prefatigue crack might prevent initiation of hydrogen embrittlement and a lower initial value of ~50 MN m 3 /2 was used. If cracking was not observed in these conditions the stress intensity was raised to 75 MN m 3 /2 and the test was continued. Where practical, the specimens were loaded just before exposure, except for specimens tested at the coastal site, which were loaded in the laboratory.

800 mV(SCE) in order to reduce the risk of hydrogen embrittlement in high strength steels.1 0 These specimens were retrieved after 190 days.

Crack length measurements

Optical measurements of the crack lengths were made using a travelling microscope. Those exposed to sterile, arti cial sea water in the laboratory were measured weekly at rst and then later at monthly intervals. Those suspended beneath the raft were measured several times during the exposure period while those that had been buried in the mud were removed only at the end of the test. In each case, the DCB specimens were washed in distilled water, followed by propanol-1-ol and left to dry. The notch region was cleaned of calcareous deposits using 1200 grit silicon carbide paper. The crack length was measured on both sides of the specimen and the mean length was calculated. The nal crack length measurements were the most important as they were used to determine K t h , the threshold stress intensity required to cause hydrogen embrittlement. The nal crack lengths were also measured by an ultrasonic NDT technique, which overcame diYculties in accurately detecting the crack tip and enabled an average length to be calculated across the crack front. As the crack fronts were slightly bowed the lengths measured by ultrasonics were slightly longer and these values were used in subsequent calculations. A graph was plotted of crack length against time and a PC based programme was used to t a 36 order polynomial to the data and calculate the crack velocities from the gradients to the curve. The crack tip stress intensity K I was calculated for each crack length value using equation (1) and a graph of crack velocity versus K I was plotted. The K t h value was established from the diagram at the point where the velocity fell below 10 1 0 m s 1 . The maximum errors in K t h arising from the crack length measurements and from setting the specimen displacement were estimated to be 15 and 1 MN m 3 /2 respectively.

Test environments Sterile arti cial sea water

Four DCB specimens were immersed in 120 litres of sterile, arti cial sea water in a tank in the laboratory for 376 days. Their potentials were controlled at 800, 900, 1000 or 1100 mV(SCE) using four separate potentiostats. Distilled water was added to the tank as required to make up for evaporation and at intervals some of the solution was replaced. The pH was checked and found to be unchanged during the experiment.

Filtered natural sea water

Four further DCB specimens were cathodically protected at the same potentials of 800, 900, 1000, or 1100 mV(SCE) and exposed for 217 days to ltered, natural sea water. These tests were carried out at the DERA marine exposure site at Portland Harbour. Sea water was pumped directly from the sea, ltered and passed through test tanks situated outside the laboratory.

Natural sea water

Two DCB specimens were connected to zinc anodes (Zincoline, mass 025 kg) and suspended beneath a raft in the harbour for 303 days. The anodes maintained the potentials of the specimens close to 1020 mV(SCE).

Seabed sediment
A total of six DCB specimens were buried in heavy sulphide containing sediment on the seabed beneath the raft. Four of these were connected to zinc anodes and exposed in pairs for either 190 or 303 days. The two remaining specimens were attached to Al01 wt-%Ga low voltage anodes, which were designed to limit their potential to

Slow strain rate tests

Slow strain rate (SSR) tests were performed on Steel 900 in the laboratory to measure the extent of hydrogen embrittlement caused by active populations of SRB grown in an anaerobic fermenter. This method was complementary to the DCB method and had the advantage of giving an embrittlement index (EI) after a relatively short test,
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Cathodically protected high strength steel in sea water and seabed sediment

without the need to maintain stable microbial numbers and sulphide levels for long periods. Tensile specimens were machined from the plate in the longitudinal direction to give a gauge length 225 mm in diameter and 25 mm long. The fermenter was established from a sample of marine sediment collected from Fleetwood harbour on the North West coast.1 1 A 10 L vessel was half lled with horticultural pearlite, 5 L of marine sediment and sea water were added and the head space was purged with nitrogen. 500 ml of liquor were drawn oV twice a week for use in the SSR tests and this quantity was replaced with a deaerated lactate medium based on Postgates medium B.1 2 The tests were carried out in air and in arti cial sea water, with and without biologically produced sulphides, at the free corrosion potential (approximately 650 mV) and at 600, 800, 900, 1000, 1100, and 1200 mV (SCE). In each case, the strain rate was 12 10 6 s 1 . For the tests in biologically active sea water, the total sulphide level in the cell was sampled at intervals of 4 h using a Chemetrics Vacuette Sulphide Kit K9510D and, if necessary, sodium sulphide was added to maintain a concentration between 100 and 125 ppm. At the end of the test the time to failure (TTF) was recorded and the EI was calculated by comparing it with the time to failure in air (TTFa i r ) as follows EI =1 (TTF/TTFa i r ) . . . . . . . . (3)

RESULTS Double cantilever beam specimens

Graphs of crack velocity plotted against crack tip stress intensity are shown in Fig. 2. The graphs display a range of velocities in the plateau region, with the more protected specimens having the highest crack velocities. As expected, the K t h values decreased at more protective potentials. Neither of the specimens tested at 800 mV(SCE) in arti cial sea water displayed any crack growth and it was assumed that at this potential the K t h was above the initial stress intensity of 52 MNm 3 / 2 . The K t h values are summarised in Table 1. Of the DCB specimens buried in the seabed sediment, four protected at 1020 mV(SCE) and the two protected at 800 mV(SCE), all displayed crack branching and in some cases one or both of the cantilever loading beams had failed. In contrast, the specimens protected at 1020 mV(SCE) in the open sea water beneath the raft did not show any sign of crack branching, although it was noticeable that the one that gave the K t h value of 248 MN m 3 /2 was more heavily fouled than the other. Clearly, the incidence of crack branching in the seabed sediment indicates a much greater susceptibility to embrittlement and demonstrates the eVect of sulphides in promoting hydrogen uptake.

2 Crack velocity as function of stress intensity for Steel 900 in sterile and natural sea water

iodimetric titration.1 3 In each case, the analysis was carried out by rst suspending a known mass of sediment or corrosion product in 25 mL of sea water. For the corrosion product, 3 gm suspended in 25 mL of sea water gave a total sulphide concentration of 50 ppm, whereas 4 g of seabed sediment gave a value in the range 250500 ppm. Sulphide levels of 100125 ppm, which were maintained in the SSR tests, were considered to be close to the concentration present beneath a layer of marine fouling.1 4

Slow strain rate tests

The loadtime graph in Fig. 3 shows the reduction in the time to failure for freely corroding specimens tested in arti cial sea water, with and without biologically generated sulphide, compared to that for a specimen tested in air. More severe reductions in failure times occurred when specimens were cathodically protected and in some cases failure occurred before the stress had reached the yield stress of the steel. The times to failure at each potential are summarised in Fig. 4 and the corresponding embrittlement indices are shown in Fig. 5. There was a systematic reduction in time to failure with more protection and the minimum embrittlement occurred at 600 mV(SCE). Exposure to biologically active sea

Sulphide levels
Sulphide levels in the seabed sediment and in corrosion products on freely corroding surfaces were compared by Table 1 Values of K th (MN m
3/2 )

for Steel 900 measured in different environments at different potentials*

Potential(SCE) Environment Artificial sea water Filtered natural sea water Open sea water Seabed sediment 1100 mV 168 204 . .. . .. 1020 mV . .. . .. 248, 211 CB 1000 mV 221 279 ... ... 900 mV 328, 361 331 ... ... 800 mV NC .. . .. . CB

* NC no crack growth; CB crack branching. Zinc anode. Low voltage anode. British Corrosion Journal 2002 Vol. 37 No. 3

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Cathodically protected high strength steel in sea water and seabed sediment 197

3 Slow strain rate results showing effect of sulphide additions to sterile sea water at corrosion potential

5 Embrittlement indices measured in slow strain rate tests

6 Embrittlement indices measured in slow strain rate tests

4 Times to failure in slow strain rate tests

Effect of fouling and scale formation

At the potential of a zinc sacri cial anode, close to 1000 mV(SCE), the various environments caused a diVerence in K t h of ~10 MN m 3 /2 . The embrittlement susceptibility increased in the order ltered natural sea water< open sea water (heavy fouling)< sterile arti cial sea water< open sea water (light fouling). It is known that the extent of hydrogen uptake by steel is aVected by marine fouling3 and by the formation of calcareous deposits,1 5 both being partially protective. It is signi cant, therefore, that of the DCB specimens exposed to open sea water the more heavily fouled specimen had the higher value of K t h , indicating a lower level of hydrogen absorption. Similarly, the ltered natural sea water, which promoted light fouling of the surface, caused less embrittlement than sterile arti cial sea water in which no fouling occurred. Calcareous scale formation is promoted by a high pH that develops on cathodically protected surfaces1 6 and these conditions are favoured by low ow rates. It follows that a thicker and more protective scale is expected to form in the stationary conditions of the laboratory tests rather than the turbulence of open sea water and this is supported by the open sea water specimen with little fouling having the highest embrittlement susceptibility. Figure 6 includes results for the high strength, low alloy steel DSE690 that had been heat treated to simulate the microstructure in the heat aVected zone of a weld.3 Hardness measurements indicated that its yield strength was ~1023 MPa, close to the measured value of 1038 MPa for Steel 900. Of the two steels, DSE690 was the less susceptible to embrittlement and in sterile sea water it had higher K t h values at all potentials. In sea water containing active SRB and 400 ppm of sulphide, DSE690 was severely embrittled with K t h values below 20 MN m 3 /2 over the full range of potentials but Steel 900 displayed even more embrittlement as evidenced by extensive crack branching.
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water containing 100125 ppm of sulphide at potentials of 800 and 900 mV(Ag/AgCl ) caused failure by hydrogen embrittlement well below the yield stress due to the increased rate of hydrogen uptake.

DISCUSSION
Previous research has shown that CP promotes the absorption of hydrogen by steel and the hydrogen concentration is inversely related to the applied potential.3 , 4 Hydrogen uptake is also in uenced by environment, with the rate of absorption being signi cantly higher in the presence of active populations of SRB and biologically generated sulphides.4

Influence of potential
The results reported in this paper clearly demonstrate that the embrittlement of Steel 900 was directly related to the quantity of hydrogen absorbed during CP. The crack velocity in the plateau region is controlled by the transport rate of hydrogen to the crack tip and it was shown in Fig. 2 that the plateau velocities increased systematically as the potential became more cathodic; the values being 3 10 9 , 5 10 9 , and 2 10 8 m s 1 at potentials of 900, 1000, and 1100 mV(SCE), respectively. The relationships between the threshold stress intensity K t h and the CP potential for Steel 900 in sterile sea water, ltered natural sea water and open sea water are shown in Fig. 6 and it is clear that CP had an important eVect on K t h in each environment. As the potential became more negative, more hydrogen was absorbed and hence K t h was lowered.

198 Batt et al.

Cathodically protected high strength steel in sea water and seabed sediment

Hydrogen embrittlement in sea water containing sulphide

As K t h values were not obtained for DCB specimens of Steel 900 in the seabed sediment due to crack branching, the eVects of a sulphide containing environment can be seen from the results of the SSR tests. Whereas the embrittlement indices measured in sterile sea water increased systematically with the level of protection, with the more negative potentials promoting more hydrogen uptake, the values with sulphide present were relatively constant. An EI greater than 06 is generally considered to indicate severe embrittlement and the EI with sulphide was in the range 0708 for all potentials between 800 and 1200 mV(SCE). While it is known that the more protective potentials would have caused higher levels of hydrogen uptake, as shown in Fig. 1, it appears that the EI had reached a maximum level. With sulphide present the SSR test specimens failed before reaching the yield stress and therefore it would be diYcult for this EI to be exceeded, as time is required during the test for the stress to reach a value high enough to cause failure. In addition, time is also required for suYcient hydrogen generated at the surface to diVuse into the specimen to the most signi cant aws at which incipient cracks will develop. The least hydrogen embrittlement occurred at a potential of 600 mV(SCE) and this level was very similar to that under free corrosion conditions ( 650 mV(SCE)). This trend is comparable to that reported for fatigue of BS4360: Grade 50D steel in sea water, where the minimum fatigue crack growth rate in hydrogen assisted corrosion fatigue occurred at a potential of 700 mV(Ag/AgCl ).1 7

CONCLUSIONS
1. The research has demonstrated that the plateau crack velocity and the K t h values for hydrogen embrittlement in a 900 MPa yield strength steel (Steel 900) are strongly in uenced by the applied cathodic protection potential. 2. The extent of hydrogen embrittlement was aVected by the formation of marine fouling and calcareous deposits as these are both partially protective and limit hydrogen uptake. 3. A potential in the range 770 to 790 mV(SCE) is considered to achieve the dual aims of providing adequate corrosion protection in sea water and a low risk of hydrogen embrittlement. 4. However, this steel would be unsuitable for applications involving exposure to seabed sediments with high levels of microbial activity and total sulphide as these conditions lead to increased hydrogen uptake and promote severe embrittlement. 5. Signi cant diVerences exist between the K t h values of each high strength steel. It is recommended that the risk of embrittlement of a particular grade of steel should be assessed individually and, where appropriate, the composition and activity of the marine sediment should be considered.

ACKNOWLEDGEMENTS
The research described in this paper was supported by the EPSRC. The authors gratefully acknowledge DERA for provision of test facilities at the coastal exposure site.

REFERENCES
1. m. j. robinson, c. h. j. parker, and k. j. seal: Proc. Conf. UK Corrosion 87, Brighton, UK, October 1987, Institute of Corrosion, 279290. 2. m. j. eobinson, r. j. newby, and p. j. kilgallon: Proc. Conf. UK Corrosion 91, Manchester, UK, October 1991, Institute of Corrosion. 3. m. j. robinson and p. j. kilgallon: Corrosion, 1994, 50, 626635. 4. m. j. robinson and p. j. kilgallon: A review of the eVects of sulphate reducing bacteria in the marine environment on corrosion fatigue and hydrogen embrittlement of high strength steels; 1998, Sudbury, HSE Books. 5. c. l. batt and m. j. robinson: Corros. Manage., 1999, 31, 1318. 6. Laboratory testing of metals for resistance to sul de stress cracking and stress corrosion cracking in H2 S environments, Test Method TM017790, NACE, Houston, TX, USA, 1990. 7. c. batt and m. j. robinson: Br. Corros. J., 2002, 37, (1), 3136. 8. m. o. speidel and m. v. hyatt: Advances in corrosion science and technology, (ed. M. Fontana and R. Staehle), Vol. 2, 139144; 1972, New York, NY, Plenum. 9. r. b. heady: Corrosion, 1977, 33, 98. 10. j. p. pautasso, h. le guyader, and v. debout: Proc. Conf. Corrosion 98, San Diego, CA, USA, March 1998, NACE, Paper 725. 11. j. doodson: MSc thesis, Cran eld University, UK, 2001. 12. j. r. postgate: The sulphate reducing bacteria, 2nd edn; 1984, Cambridge University Press. 13. c. batt: Optimising cathodic protection requirements for high strength steels in the marine environment, PhD thesis, Cran eld University, UK, 2000. 14. c. j. thomas, r. g. j. edyvean, and r. brook: Biofouling, 1988, 1, 6578. 15. k. a. lucas and m. j. robinson: Corros. Sci., 1986, 26, 705717. 16. w. h. hartt, c. h. culberson, and s. w. smith: Corrosion, 1984, 40, 609818. 17. p. m. scott and d. r. silvester: J. Mater., 1979, 14, 17731799.

Recommended cathodic protection potentials

Potentiostatic weight loss measurements performed on high strength steel specimens exposed to the same test conditions as described in this paper showed that the corrosion rate was lowered to an acceptable level of 0001 mm year 1 by controlling the potential at 770 and 790 mV(SCE) in natural and sterile sea water, respectively.7 As no cracking was observed at these levels of protection, it is recommended that this potential range is appropriate to give adequate corrosion protection of high strength steel in sea water with a low risk of hydrogen embrittlement. In the seabed sediment, however, severe cracking occurred at 800 mV(SCE) and it is clear that even potentials in the range 770 to 790 mV(SCE) would be too cathodic to avoid the risks of hydrogen embrittlement in Steel 900. It is probable that the high strength of this steel would have led to embrittlement in the sediment even under freely corroding conditions, in which case it could not be recommended for this environment. The sediment at the test site was particularly rich in sulphides, due to the eVects of pollution, and this is thought to have had the eVect of promoting anaerobic conditions, which favour the growth of SRB. However, in making realistic recommendations for the use of steel on the seabed, it must be recognised that sediments vary from site to site. Ideally, each case should be considered individually. The embrittlement susceptibility of a particular grade of steel should be measured and, where possible, the conditions on the seabed should be assessed.

British Corrosion Journal

2002 Vol. 37

No. 3