OTH 91 351

HYDROGEN CRACKING OF LEGS AND SPUDCANS ON JACK-UP DRILLING RIGS - A Summary of Results of an Investigation
Authors K Abernethy British Steel Technical Research Organisation C M Fowler CAPCIS, University of Manchester Institute of Science and Technology R Jacob Global Corrosion Consultants Ltd V S Davey Offshore Safety Division Health and Safety Executive With the assistance of Techword Services 153-155 London Road Hemel Hempstead Herts HP3 9SQ
HSE BOOKS Health and Safety Executive - Offshore Technology Report

 Crown copyright 1993 Applications for reproduction should be made to HMSO First published 1993 ISBN 0 7176 0614 7 This report is published by the Health and Safety Executive as part of a series of reports of work which has been supported by funds formerly provided by the Department of Energy and lately by the Executive. Neither the Executive, the Department nor the contractors concerned assume any liability for the reports nor do they necessarily reflect the views or policy of the Executive or the Department. Results, including detailed evaluation and, where relevant, recommendations stemming from their research projects are published in the OTH series of reports. Background information and data arising from these research projects are published in the OTI series of reports.

FOREWORD
This study was initiated by the Department of Energy when the responsibility for offshore safety was with its Petroleum Engineering Division. In April 1991 this responsibility was transferred to the Offshore Safety Division of the Health and Safety Executive, which is now publishing this report. The Fourth Edition Guidance referred to in this report was issued by the Department of Energy in 1990 and is now the responsibility of HSE. Guidance on matters discussed in this report will be included in Amendment No 2 to the Fourth Edition to be published in 1993.

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CONTENTS
vi 1 1 3 3 4 4 5 9 10 21 21 21 25 26 38 38 39 39 41 46 73 73 73 70 78 79 79 80 83 85

Summary 1. Introduction 1.1 History of the problem 1.2 The research programme 1.3 Layout of this report Metallurgical characterisation of Type A steel 2.1 Introduction 2.2 Examinations 2.3 Discussion 2.4 Conclusions Metallurgical characterisation of Type B steel 3.1 Introduction 3.2 Examinations 3.3 Discussion 3.4 Conclusions The hydrogen susceptibility of Type A and Type B steels 4.1 Introduction 4.2 Test technique 4.3 Test programme 4.4 Results and discussion 4.5 Conclusions and recommendations Cathodic protection at limited potentials 5.1 Introduction 5.2 The need for limited CP potentials 5.3 Methods of limiting CP potentials 5.4 Possible risks of limiting potentials 5.5 Conclusions General conclusions 6.1 Draft interim guidance References

2.

3.

4.

5.

6.

7.

Appendix: Comments on interim guidance document

SUMMARY
Hydrogen-assisted cracking is known to be a problem with some high strength steels used in the fabrication of jack-up offshore drilling rigs, particularly in areas adjacent to welds. Following the discovery of such cracks in a number of rigs during routine surveys in the late 1980s, the Department of Energy commissioned a series of research investigations into different aspects of the problem. This report contains the results of the investigations and makes recommendations to minimise the problem in the future. The investigation covered: detailed characterisation of samples of two high strength steels known to have suffered hydrogen-assisted cracking experiments to establish the limiting level of cathodic protection potential beyond which these steels are susceptible to hydrogen cracking (slow strain rate testing was used for this purpose) an assessment of different ways of ensuring that CP potentials in practice do not exceed the limiting level established by the experimental results.

Results of the characterisation tests showed the materials to be of variable strengths and hardnesses. The slow strain rate tests established that hydrogen damage to the steels was small provided CP potentials did not become more negative than -825 mV (with respect to a saturated calomel electrode). The only practical way of ensuring this limit is not exceeded on site is by use of Schottky barrier diodes to separate the CP anodes from the structure being protected. This report also includes a copy of interim guidance drafted by the Department of Energy on the subject of 'Hydrogen-assisted cracking in high strength steels immersed in seawater'. The document was discussed at the end of 1990 at a meeting attended by representatives of interested parties. Important points from this discussion are included in this report.

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1. INTRODUCTION
1.1 HISTORY OF THE PROBLEM

It has been known for some time that hydrogen may attack high strength steels, particularly at areas adjacent to welds where increased hardness and residual stress may exist. Some information on this phenomenon is contained in Offshore Installations: Guidance on Design, Construction and Certification(1) and in other codes of practice associated with the construction and operation of equipment using high strength steels. Salient points in the history of the problem as it has affected jack-up drilling rigs are: The problem was first noticed in February 1988 during surveys of two rigs operating on the UK continental shelf. Centrifugally cast steel had been used for their main leg chords. Cracking was found at the intersection between the leg chords and the spud can top plate and at some internal connections between bulkhead members and the abutting leg chords. All cracking had occurred in the heat affected zone of the high strength material. Boat samples were taken for metallurgical examination but the full implications of what they showed were not immediately recognised. In March 1988 a rig which had been operating in Argentina was found to have extensive cracking inside the spud cans. It required immediate repair on return to the UK but no metallurgical examination was carried out. In June 1988 a further rig was found to have serious cracking within the spud cans. This was associated with hydrogen sulphide (H2S) found to be present in the spud can residues. As the damage appeared to be confined to the spud cans, this led to the assumption that hydrogen-assisted cracking was occurring due to the presence of H2S. Further examination by metallurgists showed that the cracking was of a form induced by hydrogen and that it could also occur in the absence of H2S. In August 1988 a fifth rig was found to have severe cracking within the spud cans (all the rigs so far affected had been of the same type). The cracking extended to the external welds between the leg chords and the spud can top plates. At this point the Department of Energy asked the owners of all remaining units of this type to have them subjected to dry-dock survey as quickly as possible, but no later than 31 October 1988. In the case of this fifth unit a dry-dock survey in early October showed that extensive cracking within the spud cans was complemented externally by severe cracking at brace-to-chord connections up to the third horizontal level. This latter cracking had occurred mainly where the paint coating had been removed to allow underwater inspection. The internal spud can cracking, however, had occurred where the pain coating had deteriorated. All cracking was in the heat affected zone of welds in the high strength material. Boat samples confirmed that in each case hydrogen-induced stress corrosion cracking was the only form of damage present. No cracking due to fatigue was found. From mid October to early December 1988, three further units were subjected to dry-dock survey. In each case the installations were found to be cracked to some degree but, more seriously, one unit which had been repaired in April 1988 showed signs of further cracking within six months. The last four rigs surveyed were also subjected to an investigation by the Department of Energy with a view to understanding what influences may

have caused the cracking. This included measuring cathodic protection (CP) potentials within spud cans and an examination of the spud can contents for the presence or absence of H2S. (On only one rig had CP potentials been measured in service.) The tests showed that CP potentials were excessive for application to high strength steel. The absence of oxygen in the spud can contents and the intermittent presence of H2S in small quantities could have exacerbated the conditions already created by the CP. (The H2S was normally retained in the sediment on the bottom of spud cans and therefore was not necessarily available to cause chemical attack.) Several other types of rigs coming up for survey were examined for this form of cracking. Two of one type showed hydrogen attack to a greater or lesser extent and a further type showed confirmed hydrogen attack at welds on the exterior of spud cans where the high strength steel chords were exposed. Two other rigs suffered from cracking which was confirmed on one as due to hydrogen attack. In the period to the end of February 1989, twelve rigs of five types had been shown to be affected by spud can and leg cracking. Of the five types inspected, all showed damage confirmed as being due to hydrogen attack of the heat affected zone in the high strength steel adjacent to welds. Some cracking due to faulty fabrication was also found. During the 1990 inspection period, one Certifying Authority reported no further problems on two rigs that had suffered from the problem initially. However, serious cracking was discovered on the inside of spud cans adjacent to high strength steel chords on a third rig that had been affected earlier. Some minor cracking had also occurred at similar positions on the outside of the spud cans. Another Certifying Authority reported that they had not had problems revealed in 1990 on any rigs other than those of the type that started the concern in 1988. Four rigs of this type were subjected to full survey and the findings could be summarised as: Where CP anodes had been removed from spud cans and the spud can water was treated with corrosion inhibitor and biocide, minor damage was observed but some of this may have been historic and residual from previous repairs. Where CP systems had not been modified immediately after the previous survey, recurrent damage had been found although some appeared to be due to the previous repairs causing excessive local residual stresses. Some minor cracking had been observed on leg members outside spud cans, but was not as serious as that found in 1988. In summary, there had been improvements overall in the performance of the material in these rigs but not all problems had been overcome. Further efforts would be made to improve this situation using the Certifying Authority's own research. A third Certifying Authority reported that suspected hydrogen attack on two rigs had not been confirmed; it was a different form of cracking not related in any way to hydrogen or CP systems.

1.2

THE RESEARCH PROGRAMME

As soon as it became clear that there was a common problem here affecting a number of jack-up drilling rigs, the Department of Energy convened a meeting of the owners of the affected rigs, the relevant Certifying Authorities and the offshore concession owners currently chartering the rigs. The meeting was held on 11 January 1989 and the subject was discussed extensively. Subsequently, the Department of Energy sponsored further research to investigate the problem and possible solutions. This stage of the work was carried out in three parts: A detailed characterisation of two commercially available high strength steels used in jack-up chords. Carried out by British Steel Technical Research Organisation. Reported in this document in Chapters 2 and 3. An experimental investigation of the susceptibility of these two high strength steels to hydrogen embrittlement at different applied CP potentials. Carried out by Corrosion and Protection Centre Industrial Services at the University of Manchester Institute of Science and Technology. Reported in this document in Chapter 4. A consultancy opinion on the feasibility of prevent corrosion of the steels without exceeding the apparent CP threshold for significant hydrogen embrittlement. Carried out by Global Corrosion Consultants Ltd. Reported in this document in Chapter 5. LAYOUT OF THIS REPORT

1.3

After this introduction (Chapter 1), the report gives a full account of the research programme described in Section 1.2 above (Chapters 2-5). Chapter 6 draws conclusions from the research and contains a draft version of interim guidance on the subject to be published by the Health and Safety Executive (the successor to the Department of Energy on matters concerning the safety of offshore installations). An appendix summarises a discussion that took place on 4 December 1990 when the draft interim guidance was discussed by representatives of offshore owners, contractors, Certifying Authorities and the government bodies concerned.

2. METALLURGICAL CHARACTERISATION OF TYPE A STEEL

2.1 INTRODUCTION

An examination of material from six tubular sections has been carried out in order to characterise the material from which the tubulars were made. The tubulars were stated to be of high strength steel manufactured to the chemical and mechanical property specifications shown in Tables 1 and 2. The steel is referred to in this report as 'Type A'. It is used in a number of jack-up rigs operating on the United Kingdom continental shelf, and the particular tubular supplied for detailed examination had been damaged in a collision. After initial telephone discussions with the client, a programme of work was agreed for the detailed examination of one tubular in order to characterise the microstructural, mechanical and chemical properties of the steel. The following tests were made on the major length of tubular material, Sample 1: on each quadrant of the tubular (ie at Specimen positions 1-4), longitudinal tensile tests for yield stress, ultimate tensile stress, elongation and reduction in area (all in accordance with BS 18:1987 Tensile testing of metals. Charpy impact tests on each quadrant, in longitudinal orientation and undertaken at -40oC for sets of three 10 mm x 10 mm specimens, one set taken at each of the inner and outer surfaces and the mid-wall position hardness traverses across the tube wall for each quadrant chemical composition check via spectrographic analysis for specimens from both the inner and outer tube surfaces microstructural characterisation across the wall thickness including estimation of both the levels of porosity present and the extent of segregation determination of through-thickness tensile properties on specimens produced by welding stub pieces to both inner and outer surfaces (these test were on one quadrant only).

Having completed the detailed examination of material from this tubular, a more limited examination was requested of material from five further tubulars. This was necessary because the first tubular examined apparently consisted of three layers, whilst material being used for sulphide stress corrosion cracking (SSCC) tests by other people was apparently mono-layer. Three of the further tubulars (Samples 2, 3 and 4) came from the same source as the first, Sample 5 came from another rig and Sample 6 was some of the material examined for SSCC. Samples 2-6 were subjected to microscopical examination and hardness testing only. Table 1 Chemical specification of Type A steel
C Si S
<0.012

P
<0.020

Mn

Mo

Nb

Ni

A1total

N
<0.020

0.05-0.10 0.10-0.40

1.70-2.30 0.20-0.40 0.05-0.08 2.50-3.50 0.01-0.05

Table 2 Mechanical specification of Type A steel

Yield stress 700 N/mm2 min UTS 780 N/mm2 min Elongation 14% Impact (KCV) 40 J at -40oC (average of three) 27 J (minimum individual)

2.2 2.2.1

EXAMINATIONS Visual examination

Sample 1 as supplied was a tubular section of approximately 0.8m diameter and 2.8m long, with a wall thickness of 30 mm. One end of the section had been gas cut whilst the other end showed some original, badly rusted, fracture surfaces and further gas cut regions. There was evidence of accident damage close to this fractured region in that the tubular had been dented to a depth of approximately 160 mm. The wall thickness at this point was 28 mm and the mastic around this area had spalled off revealing a machined outer pipe surface. The wall of the pipe gave the appearance of having been stretched in the accident. Figures 1 and 2 are photographs of the tubular. 2.2.2 Tensile properties

As requested, on each quadrant of Sample 1 (ie at Specimen positions 1-4), tensile specimens were machined from longitudinal blanks cut from the outside third, central third and inside third of the wall thickness (referred to as 'top', 'middle' and 'bottom' in Tables 3, 4 and 5). Duplicate specimens were taken at each position. The specimens were tested in accordance with BS 18 and the results are given in Table 3. The stress-strain curves did not exhibit a discontinuous yield, hence 0.2% proof stress values are reported. All of the values observed are in excess of the 700 N/mm2 minimum required in Table 2, being in the range 704-746 N/mm2. The lower values were associated with specimens taken from the central position (average 715 N/mm2) compared with an average of 734 N/mm2 for specimens from the outer third and 731 N/mm2 for specimens from the inner third of the wall thickness. Table 3 Measured longitudinal tensile properties - Sample 1
Specimen position(1) 1 Tensile properties Depth position(1) Top 1 Top 2 Middle 1 Middle 2 Bottom 1 Bottom 2 Top 1 Top 2 Middle 1 Middle 2 Bottom 1 Bottom 2 0.2% proof stress (N/mm2) 738 724 712 704 733 737 732 737 708 719 727 733 Ultimate tensile stress (N/mm2) 793 793 783 764 796 805 799 806 774 783 797 798 Elongation (%) 16 17 16 12 17 17 19 19 18 14 19 15 Reduction of area (%) 63(2) 52/56 45/50 30/40 45 (2) 50/55 55/60 56/62 55/60 40/50 47/52 35/45

(cont'd)
3 Top 1 Top 2 728 733 799 796 18 16 50/55 56/62

Specimen position(1)

Tensile properties Depth position(1) Middle 1 Middle 2 Bottom 1 Bottom 2 0.2% proof stress (N/mm2) 710 711 730 746 739 738 734 721 722 722 700 Ultimate tensile stress (N/mm2) 781 774 792 807 809 807 795 790 788 790 780 Elongation (%) 16 15 15 17 21 13 15 15 17 16 14 Reduction of area (%) 53/58 48/52 50/55 45/50 54/57 47/55 55/60 46/55 55/60 54/60 -

Top 1 Top 2 Middle 1 Middle 2 Bottom 1 Bottom 2

Specification minimum

1 See Section 2.2.2 of the text for positions of specimens 2 All specimens oval except those that are marked (2)

2.2.3

Impact properties

Longitudinal Charpy impact specimens were prepared from material taken from the outer third, central third and inner third of the wall thickness from each specimen position of Sample 1. Sets of three 10 mm x 10 mm specimens were taken at each position and testing performed at -40oC. The results obtained are shown in Table 4. The distributions of absorbed energy from the different positions through the wall thickness are shown in Figure 3, where it can be seen that the incidence of lower energy values increases from the outside to the inside of the tubular. The average values are in excess of the 40 J requirement and individual values are all in excess of the 27 J individual minimum requirement. Table 4 Longitudinal Charpy results at -40oC - Sample 1
Specimen position 1 Depth position Top Middle Bottom Top Middle Bottom Top Middle Bottom Top Middle Bottom Energy absorbed (J at -40oC) 1 65 35 46 76 54 42 62 40 40
60

2 44 68 40 70 58 48 50 42 40 52 54 41

3 58 56 41 49 41 44 53 48 56 56 60 42

Average 56 53 42 65 51 45 55 43 45 56 56 42

53 44

Specification minimum

40 J min at -40oC (average of three) 27 J (minimum individual)

2.2.4

Hardness results

Vickers hardness traverses were carried out using a 30 kg load at 1 mm intervals across the wall thickness on polished specimens from each quadrant of Sample 1, ie on Specimen positions 1-4. The results obtained are shown in Figure 4. It is clear from the figure that hardness variations exist with up to 30 HV difference in hardness being recorded for any one quadrant. A further hardness traverse was carried out at Specimen position 2, using a 5 kg load in order to determine the maximum hardness at segregated positions more accurately. The results are shown in Figure 5, where it can be seen that although individual hardness values are more erratic the general shape of the hardness profile is similar to that obtained at the same position using a 30 kg load. The maximum hardness recorded using the 5 kg load was 325 HV5, compared with 298 HV30 at the same position and 304 HV30 at any position. Arrows are used in both Figures 4 and 5 to mark the positions of the apparent interfaces between the different layers. It can be seen that the hardness values are lower towards the inside of each layer. 2.2.5 Chemical composition

The chemical composition of the steel was determined by spectrographic analysis on specimens from each specimen position (quadrant) of Sample 1. Analyses were performed on ground portions of the outer and inner surfaces. The results obtained are shown in Table 5, where it can be seen that whilst the compositions satisfy the chemical specification in Table 1 the analyses performed on the outer surfaces are consistently richer in most elements, particularly Mn and Ni. Table 5 Measured chemical composition - Sample 1
Specimen Depth position position 1 Top C Si Mn P S Cr 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Ni+Cu 15

Mo 0.26 0.24 0.26 0.24 0.26 0.24 0.26 0.24 0.2/ 0.4

Ni

A1total

Cu

Nb

CEV

0.087 0.35

2.21 0.009 0.010 2.05 0.006 0.006 2.22 0.009 0.010 2.04 0.007 0.006 2.25 0.010 0.010 2.02 0.006 0.006 2.25 0.011 0.005 2.04 0.008 0.006 1.7/ <0.02 <0.01 2.3 2

3.05 0.044 0.11 0.015 0.079 0.726 2.83 0.034 0.10 0.011 0.058 0.671 3.06 0.045 0.11 0.014 0.080 0.721 2.81 0.039 0.10 0.011 0.058 0.655 3.10 0.044 0.11 0.014 0.080 0.739 2.78 0.039 0.10 0.011 0.055 0.652 3.09 0.044 0.11 0.011 0.085 0.719 2.80 0.039 0.10 0.011 0.058 0.660 2.5/ 3.5 0.01/ 0.05 <0.02 0.05/ 0.08 -

Bottom 0.078 0.31 2 Top 0.080 0.34

Bottom 0.065 0.31 3 Top 0.090 0.34

Bottom 0.067 0.30 4 Top 0.071 0.33

Bottom 0.071 0.31 Specification 0.05/ 0.10/ 0.10 0.40

CEV = C +
2.2.6 Microstructure

Mn 6

+V + Cr+Mo 5

Macrographs of transverse sections at all four specimen positions examined from Sample 1 are shown in Figure 6. It is apparent that Sample 1 consists of three layers, each showing varying macrostructure, with more cored dendrites being present towards the outside of each layer. Examples of typical microstructures at various depths from the outer surface for Specimen 2 are shown in Figure 7. The

general microstructure consists of a mixture of tempered martensite and bainite, with some areas more enriched by segregation. Porosity measurements were carried out at various depths on specimens from each of the four specimen positions around Sample 1. Results generated by automatic image analysis are shown for the mean area of individual pores (Figure 8) and the area percentage of all pores (Figure 9) with 95% confidence limits. Some inclusions were detected and included in the porosity data. Specimens from Specimen positions 1 and 2 contained most porosity and it is considered that the inclusions would not significantly affect the results but at Specimen positions 3 and 4, with lower porosity levels, the results may be affected by the inclusions. However, it is clear that some porosity exists and that its extent is variable. Compositional profiles were generated across a specimen from Specimen position 1 using energy dispersive X-ray spectrometry in a scanning electron microscope. Analyses were carried out at 50 m intervals along a line from OD to ID of the sample. At each analysis position the electron beam was scanned over an area of about 18 x 15 m during spectrum accumulation to give an average composition at each small area. The resultant profiles for Mn, Ni, Si, Mo, Cu and Nb are shown in Figure 10. For the first three elements, it is clear that the average concentration increases at positions corresponding to the more cored regions of the microstructure. The profiles for Mo, Cu and Nb are not as obvious in demonstrating segregation because of their lower concentrations (and hence larger relative errors in the analyses) and because of the possibility in the Mo results of some additional scatter due to small MnS inclusions (Mo and S energy peaks overlaps). However, the Mo, Cu and Nb results show highly significant correlations with the Mn and Ni results, indicating that segregation of these elements follows a similar pattern. 2.2.7 Through-thickness tensile properties

Through-thickness tensile specimens were produced in accordance with BS 6780: 1986 by friction welding stubs onto specimens cut from one specimen position of Sample 1. The outer and inner surfaces of the specimens were ground to remove rust prior to friction welding. The specimens were machined to give a gauge length which only included material from the tubular. Results for UTS and percentage reduction of area are shown in Table 6. No proof stress data were generated. The results obtained are in good agreement with those obtained on the longitudinal tensile specimens for the same quadrant (Specimen position 1). Table 6 Through-thickness tensile properties - Sample 1
Specimen 1 2 3 4 Ultimate tensile stress (N/mm2) 787 763 795 785
*Specimen oval

Reduction of area (%) 64 50 63 40/47*

2.2.8

Through-thickness impact properties

Having observed that the Charpy properties of longitudinal specimens only just met specification requirements, it was considered important to determine whether the apparent triple-layer nature of the casting was detrimental to impact resistance. Hence through-the-thickness Charpy specimens were produced by friction welding stubs onto specimens cut from one quadrant (Specimen position 2) of Sample 1. After machine to 10 x 10 mm sections, the specimens were etched in nital. Notches were then located in three specimens from each of three positions - at the top apparent interface line and 2 mm above and 2 mm below the top apparent interface line. The specimens were broken at -40oC and the results obtained are shown in Table 7. The results are all in excess of the average 40 J required at -40oC. Table 7 Through-thickness Charpy results - Sample 1
Specimen position 2 Notch location Top interface line 2 mm above top interface line 2 mm below top interface line Absorbed energy (J at -40oC) 1 64 76 70 2 60 82 76 3 57 48 76 Average 60 69 74

2.2.9

Examinations of material from Samples 2-6

Macrographs of sections prepared from Samples 2-6 are shown in Figure 11. Vickers hardness profiles across the wall thickness of each of the samples are shown in Figure 12. They were generated using a 5 kg load at 1 mm intervals. As with Sample 1, arrows are used to mark apparent interfaces between layers. These profiles too are variable through the thickness, with hardness peaks corresponding to the outside of the different layers. The samples showing the most uniform appearance macroscopically, ie Samples 4, 5 and 6, show the least fluctuation in hardness. 2.3 DISCUSSION

Examination has shown that the Sample 1 material possesses a structure consistent with it having been centrifugally cast and built up in three main layers. The tubular appears to have been heat treated to produce a microstructure consisting of tempered martensite and bainite. The structure provides evidence of significant segregation with cored dendrites being present, particularly at the outside of each layer. Compositional and hardness variations exist across the wall thickness. Some porosity is also evident. It is clear from examination of Samples 2, 3 and 4 material and comparisons with Sample 1 results that the macrostructure of this material, which all came from the same platform, is extremely variable. Sample 3 appears to contain four layers whilst Sample 4 is mono-layer and Sample 2 may also contain more than one layer (it shows evidence of a chill zone at the outer tubular surface). Sample 5 (from another

platform) also appears to consist of more than one layer whilst Sample 6, although apparently mono-layer, shows much coarser grain size than any other section. The mechanical properties of Sample 1 are variable across the wall thickness, with tensile results generally being poorest at the mid-thickness position, whilst Charpy absorbed energies are generally lowest towards the inside of the tubular. Whilst the chemical compositions measures at the outside and inside of the tubular Sample 1 are within specified limits, large differences in composition are apparent and these are also revealed by the analysis profiles generated by X-ray spectroscopy. Generally, the higher compositions appear to be associated with the outer positions of each of the three layers. These compositional variations are responsible for the fluctuations observed in the hardness profiles and are the result of segregation. The hardness profiles generated on all six samples show variation in hardness across the wall thickness, this variation being most evident in the samples showing a multi-layer appearance. Generally, the examinations have shown that the tubulars are of good quality, with only slight apparent deficiencies in ultimate tensile strength at the centre. It should be noted, however, that most the tensile tests in this examination were longitudinal and were taken at three positions through the wall thickness whilst the manufacturer was required to make a tangential test on a ring removed from one end of the tubular after quenching and tempering. Such testing would not necessarily give results similar to those in the present examination but there is reason to believe that the steel would meet the specification requirements. 2.4 CONCLUSIONS

Examination of material from a tubular section of Type A high strength steel has shown: The material did not exhibit a discontinuous yield point, but its 0.2% proof stress exceed the specified minimum. The UTS results showed three values less than the required minimum of 780 N/mm2. All of these were from specimens from the central third of the tubular wall thickness. Charpy properties were satisfactory, with no individual absorbed energy result less than the specified minimum at 27 J at -40oC. The absorbed energy values appeared to be lower towards the inner surface of the original tubulars. Hardness testing showed variable results with the highest hardnesses being observed towards the outside of each of the microstructural bands. Chemical analysis and X-ray spectrometry showed variable compositions with higher element levels being measured towards the outside of each band. Overall, the chemical compositions were within specified limits. Metallographic examination showed the general microstructure to be tempered martensite and bainite. Macrosegregation in the form of cored dendrites and porosity was observed. Through-thickness tensile properties, UTS and percentage reduction of area were similar to corresponding longitudinal properties.

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3. METALLURGICAL CHARACTERISATION OF TYPE B STEEL

3.1 INTRODUCTION

Following the examination of Samples 1-6 material as described in Chapter 2 here, a somewhat similar examination was carried out on another high strength steel, rolled plate, which has also been used in the jack-up chords of the rig from which Samples 1-4 had been obtained. This steel is referred to in this report as 'Type B' steel. A section was extracted from each of four samples (Samples 7-10) and prepared for metallographic examination. A hardness traverse through the wall thickness was also made. This examination was much more limited than that carried out on Samples 1-6 to characterise the Type A material. Later, after the initial results had been obtained on Samples 7-10, some tensile and Charpy tests were requested. Finally, some of the tests were repeated on specimens subjected to further tempering. 3.2 3.2.1 EXAMINATIONS Visual examination

Samples 7-10 each consisted of part of a tubular which had been gas cut from the leg of the rig. Each sample had at least one tubular brace attached. The material was, therefore, a curved section approximately 770 mm wide in each case with the lengths varying between about 900 and 1070 mm. The metallographic samples were taken as far as possible remote from any gas-cut edges and away from welds associated with the braces. 3.2.2 Macroscopic examination

The metallographic specimens were extracted by sawing and were prepared for examination. Figure 13 shows macrographs from each sample etched in 4% nital and in ammonium persulphate. It is apparent that Samples 7 and 8, which are of 31 mm wall thickness, show more segregation than Samples 9 and 10, which have 28 mm wall thickness. The thicker plates also show slightly less working of the cast strucutre. 3.2.3 Microscopic examination

Micrographs were taken from each sample at specific positions through the wall thickness, as shown in Figures 14a-d. The microstructures are all similar, showing a fine-grained tempered martensite. Some evidence of segregation is again apparent, particularly on Sample 8. Examination of the inclusion morphology shows the majority are globular and relatively dark in appearance. These were probably oxides or oxysulphides. A few paler elongated inclusions were observed, particularly in the centrally segregated regions. These were probably unmodified manganese sulphides and suggest that no effective inclusion shape treatments were carried out during steelmaking.

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3.2.4

Hardness tests

Vickers hardness tests were carried out at 1mm intervals through the thickness of each sample using a 5kg load. The results obtained are shown graphically in Figure 15. It is clear that Samples 7 and 8 show reduced hardness at the centre-line, whilst Samples 9 and 10 are slightly harder towards the quarter-depth and three-quarter-depth positions, with lower hardness at the surface and centre-line. Figure 16 shows the frequency distribution of the hardness values obtained and shows that the lowest values obtained on the thinner sections (Samples 9 and 10) are higher than the highest values obtained on the thicker sections, Samples 7 and 8. In view of these marked differences in hardness it was agreed that chemical analysis should be carried out on all four samples and that Charpy and tensile properties should be determined on one of the 31 mm thick samples and one of the 28 mm thick samples. 3.2.5 Chemical analysis

The chemical composition of each of the four samples is shown in Table 8. It can be seen that the two 31 mm thick samples, Samples 7 and 8, are very similar compositions. The two thinner samples, Samples 9 and 10, are also very similar in composition to each other, but generally have a higher alloy content (Si, Mn, Cr, Ni and Cu) than the thicker samples. This is reflected in the higher carbon equivalent value. The sulphur and phosphorous contents of all four samples are low, indicative of good steelmaking practice. Table 8 Chemical analysis - Samples 7-10
Sample C 7 8 9 10 0.16 0.17 0.17 0.17 Si 0.37 0.37 0.40 0.40 Mn 1.08 1.08 1.14 1.14 P 0.004 0.004 0.006 0.006 S 0.001 0.001 0.003 0.004 Cr 1.05 1.05 1.19 1.19 Mo 0.35 0.35 0.33 0.33 Ni 0.96 0.97 1.00 1.00 B <0.0005 <0.0005 <0.0005 <0.0005 Cu Nb Ti V CEV (%) 0.693 0.703 0.742 0.742

0.13 <0.005 0.005 <0.005 0.13 <0.005 0.005 <0.005 0.17 <0.005 0.004 <0.005 0.17 <0.005 0.004 <0.005

Specification <0.19 0.15/0.5 0.8/1.5 <0.03 <0.025 <1.25 <0.45 <1.2 requirement

CEV = C +
3.2.6 Tensile properties

Mn 6

+Cu +V + Cr+Mo + Ni15 5

Longitudinal tensile specimens were machined from the central portion of one sample of each thickness (Samples 7 and 9). The specimens were of round cross-section with a cross-sectional area of approximately 150mm2. Duplicate specimens were tested for each thickness and the results obtained are shown in Table 9. As is common on quenched and tempered steels the specimens did not exhibit a yield point, hence 0.2% proof stresses are quoted. It is apparent that Sample 7 meets the tensile requirements of the Type B steel specification in all respects, whilst Sample 9 has higher UTS and lower percentage elongation than permitted.

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Table 9 Longitudinal tensile properties - Samples 7 and 9

Tensile properties Sample 0.2% proof stress (N/mm2) 778 787 912 882 685 minimum Ultimate tensile stress (N/mm2) 873 883 1036 1010 785-930 Elongation (%) (5.65A) 19 17 14 16 16 minimum Reduction of area (%) 68 70 63 64

7 9 Specification requirement

3.2.7

Charpy properties

Three 10 mm x 10 mm Charpy Vee-notch specimens were machined longitudinally from the outer subsurface and central regions of Samples 7 and 9. As required by the Type B material specification, the specimens were tested at -40oC. The impact energies obtained are reported in Table 10. It can be seen that the specimens from Sample 7 gave good impact performance at both subsurface and central positions although the central position results are lower, reflecting the segregation observed at this position. The results from specimens from Sample 9 are unsatisfactory, with both subsurface and central positions showing average energies lower than the 40 J required at -40oC. The subsurface results are marginally worse than those from the centre-line, indicating that, in the absence of segregation, the harder tempered martensite observed has poorer toughness. Table 10 Longitudinal Charpy results - Samples 7 and 9
Sample Position 1 7 9 Subsurface Centre Subsurface Centre 172 140 38 40 Energy absorbed (J at -40oC) 2 180 174 36 37 28 individual 3 178 120 23 40 Average 177 145 32 39 40

Specification minimum

3.2.8

Additional testing

In view of the high hardness, high tensile strength and low Charpy result on Sample 9, it was agreed that further tensile and Charpy testing, in addition to hardness surveys, should be carried out on specimens subjected to further tempering. The specification for the Type B steel allows for the quenched steel to be tempered between 550 and 650oC. Because of availability of specimen material, coupons were extracted from Sample 10. They were tempered for one hour at 550oC, 600oC and 650oC before tensile and Charpy specimens were cut and machined. Similar specimens were also prepared from the as-received Sample 10 for comparison.

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Metallographic samples were also prepared in each condition and these were subjected to optical examination and hardness testing. Micrographic examinations Representative micrographs in each tempered condition are shown in Figure 17. There are no marked differences in microstructure. Hardness tests The results of through-thickness hardness testing for specimens in each tempered condition are shown in Figure 18. It is apparent that an additional temper of 1 h at 550oC has little effect on hardness, whilst tempering for 1 h at 600oC substantially reduces the hardness. This is further indicated in Figure 19 which shows the distribution of hardness values obtained in each condition. Tensile properties The tensile results obtained are shown in Table 11. In the as-received condition, the 0.2% proof stress values are similar to those obtained on Sample 9 material, whilst the UTS values are slightly lower (in line with the slightly lower hardness values). As with Sample 9. Table 11 Longitudinal tensile properties of Sample 10 material, as-received and after retempering for one hour
Tensile properties Retempering temperature (oC) 0.2% proof stress (N/mm2) 925 891 893 923 600 650 767 753 688* 687* 685 minimum 785-930 *Yield point Ultimate tensile stress (N/mm2) 963 1012 976 994 859 850 793 789 Elongation (%) (5.65A) 14 14 17 21 19 19 20 20 16 minimum Reduction of area (%) 61 61 63 65 68 68 71 70

As received 550

Specification requirement

the UTS results are still, however, higher than the 930 N/mm2 maximum required by the specification whilst the percentage elongation values are below the minimum requirement. Tempering for 1 h at 550oC appears to have improved the ductility slightly (resulting in higher percentage elongation and reduction of area values) but the effect on proof stress and UTS are negligible. Tempering at 600oC produces a marked reduction in proof stress and UTS as well as further improvement in ductility whilst tempering at 650oC causes further reduction in strength and improvement in ductility. At this tempering temperature, the tensile specimens exhibited a yield plateau, with some Lders extension rather than the proof stress values shown by all

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other specimens. The results at this temperature are close to the minimum required for both yield and ultimate tensile stress. Charpy properties The Charpy results obtained on specimens prepared from Sample 10 in the as-received condition and after retempering at 550oC, 600oC and 650oC are shown in Table 12. In the as-received condition, the results are similar to those obtained on specimens from Sample 9 and fail to meet the requirements of the specification for the Type B steel. At the subsurface position, two of the three samples failed to meet the individual requirement of 27 J and the average of the three results were less than the 40 J at -40oC required. The samples from the centre-line also failed in this latter respect, though all three values met the individual requirement. In line with the changes produced on hardness and tensile properties with retempering, the Charpy results show a slight improvement after 1 h at 550oC, with subsurface results averaging 55 J at -40oC being obtained. The tempering effect was slightly less at the centre but the impact values averaged 40 J and just satisfied the specification requirement. Tempering at 600oC caused a marked improvement in absorbed energy values, giving results similar to those previously obtained on Sample 7 material, with the subsurface results being higher than the centre-line though both easily satisfy the specification requirements. At 650oC, the results are more uniform throughout the thickness. The effects of increased tempering are illustrated in Figure 20. Table 12 Longitudinal Charpy properties of Sample 10 material, as-received and after retempering for one hour
Specimen position Subsurface Centre Subsurface Centre Subsurface Centre Subsurface Centre Specification minimum Retemperting temperature (oC) As-received 550 600 650 1 19 30 60 40 186 133 153 153 Energy absorbed (J at -40oC) 2 3 Average 39 36 45 42 181 115 145 147 28 individuals 24 35 61 39 185 130 156 141 27 34 55 40 184 126 151 147 40

3.3

DISCUSSION

The examinations of Samples 7-10 clearly demonstrated differences in properties between the two thicker tubulars (Samples 7 and 8) and the two thinner tubulars (Samples 9 and 10). The two thicker ones are slightly leaner in composition and their measured properties in terms of tensile strength and Charpy absorbed energy are satisfactory when compared to the Type B steel specification requirements. As well as leaner composition they also contain more macrosegregation. The extent of segregation is partly related to the casting conditions and may be worse in the lower alloyed steels due to different casting conditions.

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The two thinner plates (Samples 9 and 10) have been shown to fail to meet the specification tensile strength requirements, being too strong, and to have lower than the minimum required Charpy properties. It has been shown that retempering can improve both tensile and Charpy properties to bring them in line with the specification. Such changes in mechanical properties produced by tempering differences would not produce marked changes in microstructure. At the temperatures used, the redistribution of the carbides would be relatively slow. It is therefore suggested that the abnormal properties displayed in the as-received condition are a result of incorrect tempering. The chemical analyses and mechanical properties of the two thicker tubulars are similar enough to suggest that they probably came from the same case and heat treatment batch. Similarly, the analyses and properties of the thinner plates suggest that they also came from one case and heat treatment batch, but a different one from the thicker plates. Hence the available evidence suggests that the product of one heat treatment batch has been incorrectly tempered. 3.4 CONCLUSIONS

Examinations of material from four samples of Type B high strength steel have shown: Of the four tubulars examined, the two thicker ones appeared to be very similar in terms of chemistry and hardness and the mechanical properties of the only one tested were satisfactory. The two thinner tubulars also appeared to be very similar to each other in terms of chemistry, hardness and mechanical properties, but they were slightly more alloyed than the thicker tubulars. The mechanical properties of the thinner tubulars were unsatisfactory, being excessively strong and sub-standard in toughness. The incorrect properties probably resulted from inadequate tempering.

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4. THE HYDROGEN SUSCEPTIBILITY OF TYPE A AND TYPE B STEELS

4.1 INTRODUCTION

This chapter describes an investigatory programme to characterise the hydrogen susceptibility of the Type A material described in Chapter 2 and the Type B material described in Chapter 3. The brittle cracking behaviour observed in jack-up rigs was thought to have been caused by exposure to hydrogen sulphide or by over-protection from the rig's cathodic protection system. Prior to the test programme described in this chapter, the on-site conditions were examined to ascertain the presence of hydrogen sulphide and the actual cathodic protection levels on the rigs. This work has been reported (3) and the data may be summarised as follows: H2S was detected but was considered to be locked up in a sludge at the bottom of the spud cans - the water phase in the spud cans contains little, if any, free H2S the level of cathodic protection was measured as -981 mV to -1013 mV against an Ag/AgC1 reference electrode.

Materials were tested in two batches: the first in an initial test programme and the second in a 'focused' test programme to assess the effect of applying various levels of cathodic protection: Batch 1 - initial test programme Two pieces were received from a chord of the same rig that Sample 5 had come from (see Chapter 2). Each piece measured approximately 300 mm x 100 mm and they are referred to here as Sample 11. The material was supplied to the specifications detailed in Tables 1 and 2 of Chapter 2. It was understood that one piece of the material was below specification. Later examination revealed casting defects in both pieces of material, with more in one than the other. Batch 2 - focused test programme The specimens for the focused test programme were taken from Samples 12-16 (the correlations of these samples with earlier samples is explained in Table 13). Their metallographic characteristics are described in Chapters 2 and 3. Materials exhibiting a multi-layer microstructure were specifically selected so that the effect of any interfaces could be assessed during the test programme.

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Table 13 Material samples selected for 'focused' test programme

Sample No for Corresponding Sample No Steel Microstructure Chapter 4 from Chapters 2 and 3 type 12 4 Type A Single layer containing weld 13 1 Type A Single layer 14 4 Type A Single layer containing weld 15 5 Type A Two layers 16 9 Type B Homogeneous strucutre These samples were obtained from different rigs from those referred to in Chapter 2

4.2

TEST TECHNIQUE

It was considered that slow strain rate testing was the most suitable method to produce the required results within a short period. The technique comprises loading a round tensile specimen slowly under conditions of constant strain rate, with the gauge area exposed to the test environment. There are four parameters to assess using this test method: time to failure reduction in cross-sectional area sample elongation fracture surface examination.

For this investigation, the time to failure and fracture surface examination were considered to be the more important parameters. The reduction in area was not used since the variable porosity and large grain size of the material would have rendered the data of little value. The slow strain rate technique has the ability to differentiate between brittle and ductile behaviour. In all test programmes of this type an air control sample is run to provide reference information. A typical load versus time plot is illustrated in Figure 21. For the materials under consideration this represents the behaviour of a ductile material as typified by the fracture morphology shown in Figure 22. It a material behaves in a brittle manner, the plot illustrated in Figure 23 would be typical and the fracture morphology shown in Figure 24 would be characteristic of such a failure. Essentially, brittle behaviour is characterised by a reduction in time to failure and a change in fracture morphology from ductile dimples to planar cleavage. The equipment used to conduct slow strain rate tests is shown in Figure 25. A very important consideration is the rate of strain; it must be slow enough for the environment to act. A strain rate of =1.6 x 10-7 S-1 was used as experience has shown this rate provides satisfactory results. 4.3 TEST PROGRAMME

Initially, a series of electrochemical tests was conducted on Sample 11 material (Type A) in order to generate a set of polarisation curves. These data indicate the free corrosion potential of the steel under different test conditions and allow predictions of possible hydrogen evolution to be made. Potentiometric curves were obtained on Sample 11 material for the following conditions:

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aerated seawater, pH 8.26 deaerated seawater, N2 purged, pH 8.8 collected spud can water, N2 blanket, pH 7.5.

In total, 48 slow strain rate tests were conducted. The first tests were conducted on Sample 11 material in varying environments. The remaining 36 tests were conducted on material from Samples 12-16 in order to focus on the lowest cathodic protection level which caused little or no hydrogen damage to the material under the imposed test conditions. The full catalogue of test environmental conditions is listed in Tables 14 and 15. Table 14 Test environmental conditions for Type A material - Sample 11
Test No 1 2 3 4 5 6 7 8 9 10 11 12 Air control Aerated seawater Deaerated seawater Spud can seawater and nitrogen blanket Seawater and hydrogen sulphide at saturation level (approximately 3000 ppm) Seawater control (spud can seawater under nitrogen blanket) Seawater with dilute hydrogen sulphide (approximately 500 ppm) Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Environmental conditions Cathodic protection level (mV vs SCE) -1050 -1050 -980 No CP No CP No CP -800 -890 -945 -920 -945

Table 15 Test environmental conditions for the 'focused' series of tests Samples 12-16
Test No Sample 12 13 14 15 16 17 18 19 20 Sample 13 21 22 23 24 25 26 27 28 Air control Air control Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Air control Air control Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Environmental conditions Cathodic protection level (mV vs SCE)

-850 -850 -825 -825 -837 -837 -850 -850 -825 -825 -837 -837

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Table 15 (Cont)
Test No Sample 14 29 30 31 32 33 34 Sample 15 35 36 37 38 39 40 41 42 Sample 16 43 44 45 46 47 48 Air control Air control Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Air control Air control Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Air control Air control Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket Spud can seawater under nitrogen blanket -850 -850 -825 -825 -850 -850 -825 -825 -837 -837 -980 -980 -850 -850 Environmental conditions Cathodic protection level (mV vs SCE)

4.4 4.4.1

RESULTS AND DISCUSSION Electrochemical potential tests on Sample 11 material

The three potential curves for different environmental conditions are illustrated in Figure 26. It can be seen that for all three conditions H2 or Habsorbed can be produced below -700 mV (versus a saturated calomel electrode (SCE), which is = 9 mV away from Ag/AgC1). The effect of the oxygen level in both aerated and deaerated seawater environments can be seen in the change in slope in the cathodic sweep in the region -750 mV to -950 mV (v SCE) where a distinct limiting current density of about 100 A/cm2 can be seen for the aerated seawater. This is not as pronounced in the dearated environment and may even be due to oxide reduction from the previously imposed anodic polarisation. At any potential more negative than -700 mV, some hydrogen will be produced as part of the cathodic reaction sustaining Fe Fe2+ + 2e-. However, at neutral pH, the oxygen reduction reaction will predominate until the potential is below the intersect of the oxygen line with the H2 line as shown in Figure 26. It should be noted that the cathodic reaction will be mixed hydrogen evolution and oxygen reduction but that, as the potential falls (becomes more negative), the proportion of OH-/H2 in the overall cathodic reaction will change to produce more hydrogen. The tests indicate that significant hydrogen could be produced at cathodic protection levels of -800 mV or at more negative values. 4.4.2 Slow strain rate tests on Sample 11 material

The load v time plots for Tests 1-12 are illustrated in Figure 27. The data are summarised in Table 16. All specimens had a reduction in time to failure when compared with the air control test, although it should be noted that some specimens

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exhibited casting defects which would have contributed to premature failure (especially Tests 3, 8, 10 and 11). Scanning electron microscopy was undertaken on the fracture surfaces and typical micrographs of salient features are included in Figure 28. Table 17 summarises the features illustrated. As expected, the air control test exhibited typical ductile behaviour. Table 16 Summary of slow strain rate testing - Sample 11
Test No Environmental conditions Cathodic protection level (mV vs SCE) -1050 -1050 -980 -800 -890 -945 -920 -945 Time to failure (hours) 260 154 109 108 80 190 66 140 203 87 93 102 Reduction in area (%) 37 13 5.5 7.0 0 0 0 Reduction in area normalised to air control 0.35 0.148 0.189 0 0 0

1 2 3 4 5 6 7 8 9 10 11 12

Air control Aerated seawater Deaerated seawater Spud can seawater under N2 blanket Seawater and H2S (3000 ppm) Spud can seawater under N2 blanket (solution control) Spud can seawater and dilute H2S (500 ppm) Spud can seawater under N2 blanket Spud can seawater under N2 blanket Spud can seawater under N2 blanket Spud can seawater under N2 blanket Spud can seawater under N2 blanket

Table 17 Failure modes of Sample 11 material subjected to slow strain rate testing
Cathodic protection level Failure mode (mV vs SCE) 1 Air control Ductile 2 Aerated seawater -1050 Brittle* 3 Deaerated seawater -1050 Brittle** 4 Spud can seawater under N2 blanket -980 Brittle* 5 H2S level 3000 ppm Brittle 6 Seawater control Ductile 7 H2S level 500 ppm Brittle** 8 Spud can seawater under N2 blanket -800 Ductile** 9 Spud can seawater under N2 blanket -890 Ductile 10 Spud can seawater under N2 blanket -945 -** 11 Spud can seawater under N2 blanket -920 -** 12 Spud can seawater under N2 blanket -945 Ductile/brittle *Brittle areas evident around edge of specimen: ductile areas due to specimen overload caused by reduction in area also observed. **Casting defects observed which probably contributed to the failure, however the environment still caused significant embrittlement. Test No Environmental conditions

Two tests were conducted in H2S - containing environments at levels of 3000 ppm (the accepted saturation level) and 500 ppm (the maximum level attainable under the action of sulphate-reducing bacteria). They showed that significant hydrogen damage would occur to material exposed to such an environment. However, the site inspections of drilling rigs had reported very little, if any, presence of H2S in the regions of cracking and therefore more emphasis was placed on the cathodic protection system investigation. The environment in the spud cans was simulated for the remaining tests in this programme (and in the focused programme - see Section 4.4.3) using collected spud can under a nitrogen blanket. This produced a partially deaerated condition similar to that observed on site.

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A control was run in seawater with no cathodic protection to verify that the seawater itself was not causing the problem. The results were acceptable and the remaining eight tests were all run under applied cathodic protection conditions ranging from -1050 mV to -800 mV vs SCE. All these tests conducted under cathodic protection exhibited an overall loss of ductility, a reduction in time to failure and, fractographically, some degree of cleavage. The material under investigation did contain casting pores and the data are subject to a degree of variability. In particular, the test conducted at -800 mV, although having a reduced time to failure, exhibited very little evidence of brittle cleavage. 4.4.3 Focused cathodic protection tests on Samples 12-16 material

Combining the cathodic protection levels measured on site and the slow strain rate testing data from Tests 1-12, it was evident that a level of cathodic protection should be focused upon where hydrogen damage was minimised and protection afforded. Therefore a further 36 tests (Tests 13-48) were conducted to ascertain: if other materials being used exhibited similar characteristics the optimum cathodic protection level to use in practice.

Four Type A materials (Samples 12-15) were tested and one Type B material (Sample 16) was tested for comparison purposes. Each test at each chosen level of cathodic protection was duplicated to limit experimental variations. The load v time plots are illustrated in Figures 29-33 and summarised in Table 18. Scanning electron fractography was undertaken on typical specimens and the features observed are illustrated in Figures 34-38. Table 19 summarises the fractographic examinations. Sample 12 material - Type A (Tests 13-20) The two air control test samples showed normal ductile failure. The two -850 mV cathodic protection tests exhibited a significant reduction in time to failure and some cleavage on the fracture surface. Two tests were run at -825 mV, one produced a result nearing the air control condition but the second exhibited a defective fracture surface (casting porosity). Two further tests were conducted at -837 mV and again one sample had a defective area. The other exhibited signs of hydrogen damage but not as severe as the -850 mV test. Sample 13 material - Type A (Tests 21-28) Tests 21-28 followed the pattern of Tests 13-20. The air tests gave typical ductile results and the -850 mV tests showed a reduction in time to failure but not as significant as that of Sample 12. The remaining four tests, at -825 mV and -837 mV, also exhibited a small reduction in time to failure with some evidence of cleavage.

Sample 14 material - Type A (Tests 29-34) This material had the same parent metal as Sample 12 but contained a circumferential weld and the specimens were machined so that the weld portion was

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in the centre of the gauge lengths. The two air tests produced ductile failures as expected. However, the time to failure was lower than that for the parent metal and showed a reduced elongation of the specimens. Four tests under cathodic protection conditions were conducted, two each at -850 mV and -825 mV. The 850 mV and -825 mV. The -850 mV specimens had a reduced time to failure and showed brittle fracture characteristics but the -825 mV test specimens had the same time to failure as the air control tests and exhibited a ductile fracture mode. Table 18 Summary of slow strain rate testing of focused cathodic protection programme Samples 12-16
Test No Cathodic protection level (mV vs SCE) Time to failure (hours) Reduction in area (%) Reduction in area normalised to air control 0.07 0.156 0.175 0.25 0.175 0.375 0.41 0.55 0.569 0.85 0.5 0.63 0.186 0.352 0.395 0.49 0.594 0.853 0.594 1.16 0.838 0.909 0.29 0.22 0.403 0.476

Sample 12

13 14
15 16 17 18 19 20 Sample 13 21 22 23 24 25 26 27 28 Sample 14 29 30 31 32 33 34 Sample 15 35 36 37 38 39 40 41 42 Sample 16 43 44 45 46 47 48

Air control Air control -850 -850 -825 -825 -837 -837 Air control Air control -850 -850 -825 -825 -837 -837 Air control Air control -850 -850 -825 -825 Air control Air control -850 -850 -825 -825 -837 -837 Air control Air control -980 -980 -850 -850

340 380 205 225 315 175* 225 165* 325 315 240 265 265 280 265 290 245 260 190 210 245 280 290 235 265 230 250 305 265 305 240 255 180 215 170 240

57 48 4 7.5 10 12 10 16 58 60 24 33 33 51 29 38 43 51 8 18 17 25 37* 24* 22 14 22 28 31 20 62 63 18 14 25 30

*High levels of porosity observed (casting defects) Note: In all cases the final gauge diameter away from the fracture was reduced by approximately 3.5%, therefore figures are comparative and not definitive.

Sample 15 material - Type A (Tests 35/42) A high level of porosity was noted in this material. The -850 mV tests exhibited some brittle behaviour but a comparison with the air control specimens is difficult as the high level of porosity masked the embrittling

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effect. Overall, some brittle behaviour was evident, the quantity reducing as the cathodic protection level approached -825 mV. Sample 16 - Type B (Tests 43-48) Six tests were conducted, two as air controls, two at -980 mV and two at -850 mV for general comparison with the earlier work. The strength of the material was significantly higher than that of the Type A steel samples, 1120 MPa compared with 850 MPa. The air controls exhibited typical ductile failure. The cathodic protection test specimens all exhibited a degree of brittle failure with associated reduction in time to failure. Table 19 Fractography summary from focused cathodic protection testing programme Samples 12-16
Test No Sample 12 13 13 16 16 18 18 18 19 19 Sample 13 21 21 24 24 24 27 27 Sample 14 30 30 30 32 32 32 33 34 34 34 Sample 15 35 35 37 37 39 39 41 41 Sample 16 43 43 44 45 45 46 46 47 47 48 48 Feature Ductile necking Ductile dimples Low magnification fracture Secondary cracking Low magnification fracture Ductile dimples Casting porosity Ductile Secondary cracking Low magnification fracture Ductile dimples Low magnification fracture Ductile areas Brittle/cleavage area Low magnification fracture Cleavage Low magnification fracture Ductile dimples Casting porosity Low magnification fracture Brittle features Cleavage planes Ductile failure Low magnification fracture Ductile failure Intergranular attack Low magnification fracture Ductile dimples Casting porosity Brittle area Low magnification fracture Ductile features Casting porosity Cleavage facets Low magnification fracture Ductile dimples Low magnification necking Low magnification failure Brittle failure Low magnification failure Cleavage with secondary cracking Low magnification fracture Brittle with secondary cracking Low magnification fracture Brittle facets

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4.4.4

Results summary

The Sample 11 material (Type A steel) did not tolerate H2S at levels of 500 ppm or above when loaded under conditions approaching yield. The application of cathodic protection of the order of -900 mV (v SCE) produced hydrogen damage. The material neared its UTS level as measured in the air control test before the effect was evident. Hydrogen severely reduced the capacity of the material for plastic flow and hence induced embrittlement. Overall, the tests conducted at -850 mV on Samples 12-15 materials (Type A) all showed a reduction in time to failure when compared with the air control specimens. The effect of testing at less negative cathodic protection levels was to reduce the effect of hydrogen. In most cases, the material approached its UTS under the test conditions and the effect of the cathodic protection hydrogen was again to lower the capacity of the material for plastic flow. The Sample 16 material (Type B) performed similarly to the Type A material. Overall, even in the air tests, its plastic flow capacity was lower than that of the Type A material, making the embrittling effect of cathodic protection less marked. 4.5 4.5.1 CONCLUSIONS AND RECOMMENDATIONS Conclusions

Slow strain rate tests have shown that: All the materials under investigation suffered hydrogen-induced stress corrosion cracking under the application of cathodic protection at loading levels approaching the measured UTS. The level of damage was reduced with decreasing cathodic protection levels (ie less negative potentials). At a CP level of -825 mV, the hydrogen damage appeared to be small and the performance of the materials in slow strain tests was generally less affected. Exposure of Type A material to wet H2S caused severe damage, failure occurring well before the 0.2% proof stress. Recommendations

4.5.2

The following recommendations can be made: Exposure of the materials examined to wet H2S should be avoided. It would be useful to clarify the effects of very dilute H2S concentrations (ie less than 500 ppm) to ascertain if the biocide packages commonly used in the industry to control sulphate-reducing bacteria activity are necessary. The applied cathodic protection level should be limited to -825 mV. If such control is not practicable, a coating system (together with regular inspections) should be considered. The load at which failure occurred was approaching the measured UTS. Any tensional loading should be limited to below the 0.2% proof stress.

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5. CATHODIC PROTECTION AT LIMITED POTENTIALS

5.1 INTRODUCTION

It has been demonstrated in Chapter 4 that some high strength steels used in jack-up rigs suffer from hydrogen embrittlement in the potential range conventionally used for cathodic protection (CP). One option for overcoming this problem is to limit the potential produced on steel by the CP system to a value more positive than that at which embrittlement has been shown to become significant, ie no more negative than -830 mV v Ag/Ag CI (for -825 mV v SCE). This chapter provides advice on the feasibility of this approach and discusses the inherent problems associated with it. What corrosion risks could be inherent in limiting the potential to this limit? Is there any practical experience of operating offshore CP systems at such potentials? 5.2 THE NEED FOR LIMITED CP POTENTIALS

Uncoated carbon steel in seawater is protected from corrosion in seawater at potentials more negative then -800 mV (v Ag/Ag CI) and any properly designed CP system will meet this criterion. In systems designed to comply with published recommendations and codes of practice (4-6) produce more negative potentials. Thus a bare steel strucutre should achieve -800 mV at launch and the potential will drift more negative as protective calcareous deposits are formed by the CP process. For a system using sacrificial anodes, the most negative potential possible will be that of the anodes (-1050 or -1100 mV dependent on anode type). This potential could well be achieved close to anodes on a bare steel strucutre. The situation is reversed for a well coated offshore strucutre or pipeline. Here, the initial potential will be close to the anode potential at all points, and will move less negative with time as the coating deteriorates. The result is that for either coated or bare steel structures protected by sacrificial CP, potentials at some point during the operating life are likely to be substantially more negative than the -830 mV limit apparently necessary to avoid hydrogen embrittlement in high strength steels. This situation will be exacerbated if impressed current is used for CP since there is then no 'natural' negative limit and each anode will usually have a higher current output than a sacrificial anode, giving more negative local potentials. Clearly, a non-conventional approach to CP design is required if potentials are to be limited to no more negative than -830 mV. There are a variety of possible approaches to this problems. 5.3 5.3.1 METHODS OF LIMITING CP POTENTIALS Control of anode distribution

A conventional CP design balances the current required to provide protection to the steel against the current output (IA) available from the sacrificial anodes. The latter is calculated using Ohm's Law:

IA =

V RA

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where V

is the anode driving voltage, ie the difference between the anode potential and the local steel potential

RA

is the anode resistance and is dependent on the anode size and shape.

For a bare steel strucutre, the current required to polarise the steel initially is substantially higher than the maintenance current needed for protection once polarised. Sufficient anodes are provided in a conventional CP design to supply the initial, higher, current at the target protected steel potential of -800 mV. For, say, zinc anodes this is at a driving voltage, V, of 250 mV. Since RA is essentially constant, once the initial current requirement falls to the maintenance level, Ohm's Law requires that V also falls. Polarisation current densities are typically three times higher than maintenance levels, and hence V will fall from 250 mV to about 80 mV, giving a steel potential (the maintenance level) of -970 mV - much more negative than the target level of -830 mV. In order to guarantee that steel potentials never become more negative than -830 mV it would be necessary to limit the number of anodes to that capable of providing only the maintenance current density at (for zinc) a driving voltage of 220 mV. A similar effect could be achieved by limiting anode sizes and hence increasing the value of RA. There are major problems with attempting to control potential by this method: It cannot be applied to a coated structure, where the current demanded from the anodes increased with time. By definition, there will be insufficient anodes to provide the initial polarisation current on a bare strucutre, ie the steel would never become protected. This could be overcome by the additional use of a small number of short life, high output, anodes to provide for polarisation. Such anodes would need to be in the form of ribbon. This technique has been used by Aramco to reduce the weight requirements on small platforms in the Arabian Gulf. There, magnesium ribbon with a life of 1-2 months was used for initial polarisation, with a limited number of very large aluminium anodes catering for maintenance current needs. Magnesium anodes could not be used with the high strength steels under consideration here since their very negative potentials could exacerbate the embrittlement that the design seeks to avoid. However, a design using aluminium alloy ribbon anodes could, in principle, be developed. It would be necessary to know accurately the maintenance current requirement at the design stage. This is a more serious obstacle. Jack-up rigs are used in a variety of locations and maintenance current density depends, inter-alia, on seawater temperature, oxygen content and flow rate, as well as the previous polarisation history of the steel. It is highly unlikely that a 'correct' value could be defined.

It is the last point in this list, rather than any practical design problems, that makes this approach unviable. 5.3.2 Use of dielectric shields

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Dielectric shields are used in impressed current CP systems to limit steel potentials close to high current output anodes. In principle they could be used for the same purpose with sacrificial anodes but the size of shield required is, to a first approximation, inversely proportional to the difference between the general protection level required and the most negative acceptable potential. For the problem under consideration, this difference (30 mV) is much smaller than that for a typical impressed current installation (500 mV) and very large sizes (several metres across) would be needed. This approach can, therefore, also be ruled out. 5.3.3 Low driving voltage anodes

In principle, the CP potential limit of -830 mV could be met by using a sacrificial anode material with an operating potential of about -850 mV. There appears to be no basic theoretical impediment to the production of such an alloy but the authors know of no such material having been developed commercially - despite its attraction for the protection of steels susceptible to hydrogen embrittlement. 5.3.4 Sacrificial coatings

Flame sprayed aluminium (FSA) coatings have been used for the protection of steel offshore over a number of years. They have been in use on a steel tower off the Durhan coast since 1958 and on steel pilling in both Norway and the USA(7). Both sealed and unsealed aluminium coatings have been subjected to considerable testing and are reported as giving good protection in seawater for periods up to 18 years. Probably the best reported case of FSA coatings offshore is their use on the Conoco 'Hutton' TLP. They have been used to protect tension leg components after Conoco USA had conducted a series of investigations on the metallurgical effects of the flame spraying process on the substrate(7) and its effect on corrosion fatigue. The electrochemical properties have also been investigated(8) and a recent paper(9) reviews the performance of these coatings on the TLP after two years service. It is understood that tension leg elements removed for examination in 1990, after 6 years exposure, were found to be in excellent condition with no significant change in appearance since the two year study(10). FSA has also been used on the 'Hutton', which operate at 80oC. FSA coatings are useful for the protection of high tensile steels (eg the 'Hutton' tension legs) because they maintain potentials in the range -850 mV to -900 mV over long periods. They can also be applied at sufficient thickness to ensure a 20 year operating life(8). Although these potentials are somewhat more negative than the -830 mV target of this investigation, FSA coatings may be worth further study for the jack-up leg application. 5.3.5 Voltage-limiting devices

Schottky barrier diodes have been successfully used by Boeing to prevent overprotection of ferritic stainless steel struts and hydrofoils on marine hydrofoil vessels with aluminium hulls(11). The stainless steel components are electrically isolated from the hull but connected to the aluminium sacrificial anode system on the vessels using low-voltage-drop diodes. The diodes only allow the passage of current when the potential difference between the aluminium anodes and the stainless steel is

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greater than 300 mV. Thus the steel cannot reach potentials more negative than -800 mV when using AI-Zn-In alloy anodes, or -750 mV when using zinc. This arrangement has recently been used for the protection of duplex stainless steel flowlines installed as part of the Marathon Central Brae development in the North Sea. AI-Zn-In bracelet anodes have been installed over the neoprene pipe coating thus isolating them from the pipeline steel. Connection was then made to the latter through Schottky barrier diodes. See Figure 39. Data obtained from the fixed monitoring system on the flowlines show clearly that the system is working well, giving protection potentials in the range -840 to -790 mV. The overprotection at PMU 411 shown in Figure 40 has been attributed to faulty electronics. The

fluctuations in potentials between -840 and -790 mV can presumably be attributed to the diodes 'switching'.

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It would appear that this approach is capable of achieving the -830 mV limit and is worthy of further study. Detailed design attention would need to be paid to the engineering of anode mountings and electrical connections, but the installed system has the advantage of being passive in the sense that it would require no regular maintenance attention after installation. It represents by far the best option for the protection of high strength steels in jack-up rigs. 5.3.6 Potentiostatic impressed current

It is possible to control an impressed current system potentiostatically. However, with such a narrow range of control potentials required, a large number of relatively low output anodes would be needed. Although possible, this would lead to engineering and control difficulties and is not considered worth pursuing. 5.4 POSSIBLE RISKS OF LIMITING POTENTIALS

The free corrosion potential of steel in seawater is approximately -640 mV. Application of CP current moves the potential in a negative direction, the relationship between the (anodic) current applied and potential being given by the Tafel equation(12).

(E E o ) = a + b log I
where E Eo I a and b is the potential reached is the free corrosion potential is the current are the constants.

It is not necessary to pursue the theory of corrosion and CP further here, but it follows from the application of the theory that: If the potential of carbon steel is lowered, by the application of a cathodic current, to a value more negative than a certain value of E then corrosion will cease. Experience shows that the relevant potential value is -800 mV for carbon steel in seawater. Lowering the potential of carbon steel to a value between the free corrosion potential (-640 mV) and -800 mV produces a reduction in corrosion rate without preventing corrosion completely. This requires less current than full protection. Due to the logarithmic nature of the current potential relationship, the first increment of potential shift produces a greater effect than later increments. Lowering the potential below -800 mV does not confer any additional corrosion protection and is wasteful in terms of additional current.

It follows from the foregoing that protection of carbon steel in the range - 830 to 800 mV, as required to present hydrogen embrittlement, represents the most efficient mode of cathodic protection and has no adverse protection consequences. If the technique used to limit the CP potential allows potentials less negative than -800 mV, say down to -760 mV, then the effect will not be disastrous due to the logarithmic

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relationship discussed above. At potentials around -760 mV, the corrosion rate of steel will be some two orders of magnitude less than the free corrosion rate - not a serious consequence. 5.5 CONCLUSIONS

From the investigation reported here it can be concluded that: The most appropriate technique for limiting CP potentials to -830 mV appears to be the use of Schottky barrier as voltage-limiting devices. This should be capable of providing potentials in the range -830 to -770 mV if properly engineered. Flame sprayed aluminium coatings will also restrict the potential, but only to the range -900 to -850 mV. No other method is available at present for achieving the -830 mV limit. There appear to be no significant corrosion risks in operating CP in a limited potential range.

6. GENERAL CONCLUSIONS
Some high strength steel types used for the construction of jack-up drilling rigs are susceptible to hydrogen embrittlement, causing cracking in highly stressed areas. This has been shown to take place in both aerobic and anaerobic conditions, but is most likely to occur where hydrogen is generated by the cathodic protection system and where there is insufficient oxygen available at the site to remove the hydrogen. To avoid these conditions: CP levels should be arranged so that generation of hydrogen is avoided or at least minimised particular care should be taken where anaerobic conditions exist (ie either within spud cans or where spud cans and lower leg sections are buried in mud) to ensure that CP potentials are within the safe range for the steel being used care should be taken during repair welding, by using agreed procedures, to minimise residual stresses in the areas adjacent to the weld the weld procedures set up for new building at the design and construction stages should ensure that the combined residual stress plus applied stresses met in service do not exceed the yield stress or the 0.2% proof stress. Weld and fabrication procedures (including the sequence of fabrication) should be arranged to minimise residual stresses, for example by avoiding major welds in high strength steel which is highly restrained.

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6.1

DRAFT INTERIM GUIDANCE

As a result of the research described in earlier chapters of this report and discussions held with interested parties, draft interim guidance has been prepared to control and prevent hydrogen-assisted cracking in high strength steels. The guidance is reproduced here, and comments made on it at a discussion meeting held on 4 December 1990 are summarised in the appendix to this report. Interim Guidance Document

HYDROGEN ASSISTED CRACKING OF HIGH STRENGTH STEELS IMMERSED IN SEAWATER

INTRODUCTION Since early 1988, the Department of Energy has been investigating a widespread problem of hydrogen assisted cracking of high strength steels, particularly those used in the leg chords and spud cans of many self-elevating offshore installations. The findings of the investigations and of several meetings with owners, operators, Certifying Authorities and relevant industry associations are set out below as conclusions and interim guidance so that all may be aware of the problem and of how it may be dealt with. This information should be read in conjunction with Sections 4, 12, 21 and 33 of the Department's Guidance on design, construction and certification 4th Edition 1990. It will be included in an amendment to the 4th Edition, issued by the Health and Safety Executive. CONCLUSIONS 1. Some high strength steels can be susceptible to embrittlement by hydrogen which can arise from the CP system, particularly in the absence of oxygen, or from the generation of hydrogen sulphide in anaerobic conditions (eg in spud cans). 2. The susceptibility of the steel to hydrogen assisted cracking is influenced by residual stresses which can be high in the case of high strength steels with no post-weld heat treatment. 3. tests. The susceptibility of steels to hydrogen embrittlement can be established by

4. Commonly used CP systems are likely to give excessive negative voltages which will render high strength steels susceptible to hydrogen embrittlement. However, CP systems are available which can offer controlled voltages with a predetermined limit to the negative value. 5. The potential susceptibility of high strength steels to hydrogen embrittlement should be taken into account at the design stage as part of the material selection process, as should the design of the CP system. Internal volumes which can be sealed, such as the interior of spud cans, may be protected by a corrosion inhibitor with an approved biocide.

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6. Surveys need to take account of the possibility of the occurrence of hydrogen assisted cracking. 7. The finding and characterisation of hydrogen assisted cracks requires high quality NDT. Where paint coatings are removed (eg in dry dock) to facilitate inspection of areas which would normally be submerged and thus protected by CP, the coatings must be fully reinstated. If underwater inspections are necessary, paint coatings should not be removed, but NDT methods which can give adequate levels of detection through paint coatings should be used. 8. Consideration should be given to special surveys of legs which have been submerged in mud or slit. FUTURE ACTIONS 9. Jack-ups known to be vulnerable. a) A further review of in-service experience and trend analysis is required on completion of the latest round of structural surveys. b) Requirements for future surveys must be defined. It is suggested that detailed NDT surveys of vulnerable areas on legs and within spud cans be undertaken at intervals not exceeding 2 years. c) CP systems should be modified as soon as possible to maintain close control of the CP voltage at all times, within the limits determined by the susceptibility of the steels in the strucutre. d) The above should apply also when the jack-up unit is working alongside or over a fixed installation to which it may be connected electrically, either directly or fortuitously. e) CP surveys should be undertaken on a routine basis (at least annually) to check the functioning of the CP systems. f) There should be consideration of special surveys to check on weld repairs which involve high strength material. g) Consideration should be given to special surveys of legs which have been submerged in mud or silt. To assist with these surveys the owner should maintain records which include the depth of penetration, the type of soil, the duration, the state of the CP system and any modifications made to it to accommodate the changed circumstances. 10. Other existing jack-ups a) Surveys should include a methodical search for evidence of hydrogen assisted cracking. Survey schedules should be amended accordingly and Surveyors properly trained in what to look for. b) All cracks in high strength material found during survey should be investigated. Cracks should not be dismissed as arising due to previously undetected fabrication defects. c) Tests should be undertaken to determine the susceptibility, of the materials used, to hydrogen embrittlement/cracking at the existing CP levels. (The simplest method available is slow strain rate testing). d) CP measurements should be taken routinely to ensure that CP levels are not such as to give rise to hydrogen embrittlement/cracking.

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e) Consideration should be given to special surveys of legs which have been submerged in mud or silt. To assist with these surveys the owner should maintain records which include the depth of penetration, the type of soil, the duration, the state of the CP system and any modifications made to it to accommodate the changed circumstances. 11. New construction a) Materials should be selected having regard to their susceptibility to hydrogen embrittlement. b) Proposed materials should be tested to determine their susceptibility at appropriate CP levels (refer to 9c above). c) CP system design should be compatible with 10c. d) Welding procedures, pre- and post-weld heat treatment and NDT should take due account of potential delayed cracking problems. Final NDT should take place a sufficient time after welding to identify delayed cracking (typically 48 hours or more for high strength steels). e) Assembly methods should be arranged so that the residual stress and hardness levels in the heat affected zones of welds in high strength steel are kept to values shown to be acceptable in the tests described in 10c above. f) Quality assurance programmes should take account of all of the above and include schedules for ensuring that specification details (eg the processing and heat treatment of high strength steels) are met. A R McIntosh 30/9/91 REFERENCES Department of Energy (now Health and Safety Executive). Offshore installations: Guidance on design, construction and certification. Fourth edition, 1990, [ISBN 0 11 412961 4] and amendments [ISBN 0 11 886389 4], HMSO London. Marine Technology Directorate Ltd. Design and operational guidance on cathodic protection of offshore structures, subsea installations and pipelines. 1990, MTD Publication 90/102, London.

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7. REFERENCES
1 DEPARTMENT OF ENERGY Offshore Installations: Guidance on Design, Construction and Certification Department of Energy, fourth edition, 1990, available from HMSO. BRITISH STANDARDS INSTITUTION Tensile Testing of Metals (Including Aerospace Materials) BSI, BS 18: 1987. DAVEY, V S Hydrogen Assisted Cracking of High Strength Steels in the Legs of Jack-Up Rigs International Jack-Up Conference, City University, London, September 1991. DET NORSKE VERITAS Cathodic Protection Design DnV Recommended Practice RP B401, March 1986. NATIONAL ASSOCIATION OF CORROSION ENGINEERS Corrosion Control of Steel Fixed Offshore Platforms Associated with Petroleum Production NACE Standard RP 0176-83. BRITISH STANDARDS INSTITUTION Code of Practice for Cathodic Protection BSI Code of Practice CP 1021: 1973. COOPER, M T, THOMASON, W H AND VARDON, J D C Flame Sprayed Aluminium Coatings for Corrosion Control for the Hutton Tension Leg Components Proceedings of Conference 'UK Corrosion 83', I Corr ST, Birmingham, 1983 pp 23-17. THOMASON, W H Materials Performance, Vol 24 No 3, 1984, pp 20-28. ROSEBROOK, T, THOMASON, W H AND BYRD, J D A Review of the Performance of Flame Sprayed Aluminium Coatings Used on Subsea Components Proceedings of Conference 'Corrosion 89', NACE, Paper No 624, Houston, 1989. ROSBROOK, T Private Communication DEES, D D Combined Cathodic Protection of 5000 Series Aluminium Alloys and 15-5 PM Stainless Steel in Seawater Proceedings of Conference 'Corrosion 87' NACE, Paper No 73, Houston, 1987.

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11

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12

TAFEL, J Physik. Chem. 50A 641, 1905.

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APPENDIX: COMMENTS ON INTERIM GUIDANCE DOCUMENT

The draft interim guidance document Hydrogen Assisted Cracking of High Strength Steels Immersed in Seawater (see Section 6.1) was presented for discussion at a meeting attended by owners, contractors, Certifying Authorities and government bodies on 4 December 1990. The chairman of the meeting stated that it was intended to circulate the document to the industry in the near future, subject to modification by comments from the meeting. He also referred to the guidance already provided by the Department of Energy in Part 12 of the 4th edition of Offshore Installations: Guidance on Design, Construction and Certification. In addition, the publication Design and Operational Guidance on Cathodic Protection of Offshore Structures, Subsea Installations and Pipelines published by the Marine Technology Directorate Limited dealt in some detail with the protection of high strength steels. During the discussion the following points were raised: What was meant by high quality NDT? The NDT method used should be reliable in identifying cases of very fine cracking typical of that associated with hydrogen embrittlement. Although magnetic particle inspection had been used exclusively to date, other methods based on the detection of electromagnetic fields were able to detect and characterise defects through paint coatings without the need to clean down to bare metal. The reliability of these techniques for use underwater had not been fully evaluated yet. Operators of this equipment needed to be specially trained and briefed when examining for hydrogen-related cracking. A request was made to establish a standard format for tests, which should be carried out at the design stage or as a result of inspections and surveys, to determine the quality and resistance of materials to hydrogen attack. One Certifying Authority had prepared a note on the operation of one type of jack-up rig where the legs may penetrate into mud so that the cathodic protection system can be modified to cope with anaerobic conditions. Surveys (for hydrogen attack and other reasons) would need to include brace levels 0-4 immediately above the spud cans. A strenuous effort must be made by all concerned to reduce the activity of CP systems to acceptable limits, ie to ensure the voltage applied to the steel does not go more negative than -850 mV of -825 mV should tests indicate that this is necessary. Owners were reminded that it is their obligation to ensure that adequate CP voltage readings are undertaken for survey purposes. This may mean that the owners would have to commission studies on how to measure the CP voltages (including inside spud cans), how to reduce them to adequate levels and how to avoid interference with the rig CP system from an adjacent fixed platform when the rig was performing a tender operation alongside another installation. Owners and Certifying Authorities were reminded that CP voltage measurements should be carried out on all rigs, not just on those believed to be susceptible to hydrogen cracking. Serious consideration should be given to replacing conventional anodes with diode-controlled CP systems at least at the bottom of the legs and within spud cans, ie in those areas where anaerobic conditions may exist for more

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than short periods. Parameters indicating correct operation of these systems or their failure are quite definite and can easily be measured by conventional techniques, eg: open circuit at anode: -700 mV correct operation: -825 mV short circuit of diode or contact with another system: 950 mV or more negative.

Special surveys may be required from time to time and attention should be given during these surveys to previous weld repairs in order to detect incipient cracking caused by the process of repair. Surveys need good reporting methods to record and identify cracking. Owners and Certifying Authorities were reminded that proper inspections must be carried out to identify this form of damage. Special surveys may not be necessary for existing jack-ups which are not believed to be susceptible to this problem. Where new designs of jack-up rig were intended for construction it was the duty of Certifying Authorities and owners to ensure that the steels to be used and the weld-induced heat affected zones were examined for strength, hardness and toughness levels as indicators of their susceptibility to hydrogen attack. Previously this had been carried out using hydrogen sulphide testing but this is very difficult to control. Testing using a slow strain rate with a range of CP voltages is more easily controlled and large numbers of tests can be carried out in a relatively short time. The Department of Energy believed that all steels in the high strength range (ie actual yield stress greater than 650 MPa) should be examined for the possibility of hydrogen damage in service, both for the parent material and weldments. Where spud cans were protected by biocide and corrosion inhibitor, annual inspection programmes should include tests to ensure adequate performance of the protection system.

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