PETRONAS TECHNICAL STANDARDS

DESIGN AND ENGINEERING PRACTICE

REPORT (SM)

DEVELOPMENTS IN MATERIALS
& CORROSION ENGINEERING
FOR OIL & GAS PRODUCTION

PTS 20.124
MARCH 1986

PREFACE

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CONTENTS
SUMMARY
1.

INTRODUCTION

2.

SULPHIDE STRESS CORROSION CRACKING (SSCC) IN LOW ALLOY STEELS

3.

CORROSION RESISTANT ALLOYS (CRA'S)

3.1

12Cr 3.5 Ni alloy in sour service

3.2

Duplex stainless steels

3.3

Marine applications

3.4

General CRA's for oil and gas wells

4.

COMPUTERS IN CORROSION CONTROL (Paper 45, 47, 48 )

5.

CATHODIC PROTECTION (Papers 278, 290, 295, 299)

6.

DOWNHOLE MATTERS (Papers 134, 161, 314, 316)

7.

CRACKING IN DEAERATORS (paper 306)

TABLE
Appendix A:

Complete list of papers from the conference

SUMMARY

This report summarises the contents of a selection of papers from the NACE Corrosion '86
conference. It includes new information on the mechanism of stress corrosion cracking, particularly in
duplex stainless steels, recent results on cathodic protection of stainless steels and a few papers
relating to downhole matters.

1.

INTRODUCTION
Over 400 papers were presented with up to 30 simultaneous sessions and meetings. The full
programme with titles and numbers for the papers is given in the Appendix. The following
summarises highlights from a number of papers taken from sessions on 'Environmental
Cracking' ,'The Importance of Metallurgy in Corrosion of Oilfield Equipment', 'Marine
Corrosion', 'Computers in Corrosion', 'Cathodic Protection in Natural Waters' and a few
isolated papers from other sessions.
As usual the conference was accompanied by an extensive materials performance and
corrosion show.
The highlight of this exhibition was the Shell Development Company
booth, selling a joint industry research programme on CO2 corrosion to alleviate the running
costs of their Dynamic Test Facility at Thomasville (estimated at US $1-2 m/a). They were
looking for around 30 sponsors for a 3-4 year programme and seemed to attract quite a lot of
interest.

2.

SULPHIDE STRESS CORROSION CRACKING (SSCC) IN LOW ALLOY STEELS (Papers

167, 168)
Paper 168 studied the stress corrosion cracking behaviour of 8 high strength low alloy (HSLA)
steels, grades N80-C140, and 2 13Cr alloys in H2S + CO2 environments. The results given in
Table 4 confirm that the low strength grades (N80, C90) did not crack even at 0.5 PSi H2S.
The higher strength grades shaved surface fissures in short term tests which developed into
cracks over longer periods. The grades above P110 could be expected to crack even at H2S
levels below the theoretical "threshold" value of 0.05 PSi H2S. No cracks were observed in
the 13Cr alloys.
A mechanism for SSCC at very low H2S concentrations (e.g. 2 ppm) was proposed by
Kawasaki Steel Corporation (167). This required initial transgranular microcracks caused by
active path corrosion. The tips of these microcracks acted as nucleation sites for intergranular
cracks caused by hydrogen embrittlement. At high H2S concentrations it was proposed that
the higher level of general corrosion obscured the surface transgranular microcracks so that
the classic hydrogen embrittlement mechanism seemed to control the cracking process. Four
point bend and slow strain rate tests on a range of HSLA steels with various nickel contents
showed that for the same hardness level (240 Hv),steels with more than 0.5% Ni content
showed microcracking in low H2S environments (50 ppm). Thus the critical hardness to avoid
microcracking in Ni containing steels was around 220 Hv whereas the figure for Ni-free steels
was around 300 Hv.
For ordinary SSCC, at higher H2S concentrations, the critical hardness for Ni-free steels is
around 250 Hv and for Ni containing steels it was again 220 Hv. Thus alloying with Ni seems
to strongly affect microcracking (initiation of SSCC) but does not affect hydrogen
embrittlement (propagation of SSCC).
They reinforced their conclusions by showing that a 1 mm mild steel cladding (220 Hv) was
sufficient to inhibit SSCC (by preventing initiation through microcracking) on underlying base
metal of hardness 320 Hv or even 400 Hv in some solutions. Evidently if this cladding
corroded generally and exposed the underlying metal then problems would arise in practice.

3.

CORROSION RESISTANT ALLOYS (CRA's)

3.1

12Cr 3.5 Ni alloy in sour service (Paper 169)

Results of electrochemical study and slow strain rate (SSR) tests on a martensitic 12Cr 3.5 Ni
alloy (169) indicated that the alloy would perform well in environments which were not too
aggressive e.g. temperature < 52 C, pH >5 with low concentrations of active gasses (CO2,
H2S). Outside these constraints the stable passive film was easily broken down. Active
dissolution initially resulted in surface pitting and cracks initiated from the pits, propagating
predominantly transgranularly as a result of a hydrogen embrittlement mechanism.
This dual mechanism of an initial anodic process followed by cathodic hydrogen
embrittlement was proposed by a number of speakers to explain stress corrosion cracking in
diverse CRA's. The change over point was proposed to occur when the local environment in
an actively corroding pit became sufficiently acidic to prevent repassivation (particularly in the
presence of sulphide) and allow hydrogen entry into the metal.

3.2

Duplex stainless steels (Papers 155, 157, 158, 159, 331, 396)
There was some conflict of opinion and experimental results with these steels.
Pitting corrosion (with-or without a crevice) initiates at the grain boundaries. The mechanism
for this was variously claimed to be due to:(1)

the local cell (galvanic coupling of the ferrite () and austenite () phases);

(2)

twinning of the ferrite phase in the cold worked condition or under an applied
strain producing local strain across the / boundary (Desestret);

(3)

sensitisation of the boundaries by precipitation of chromium nitrides if

incorrectly heat treated (Paper 155).

Thus pitting resistance is improved by using duplex in the solution annealed condition to
prevent the last two effects contributing. Pits were claimed to grow preferentially in the
austenite phase in alloys with <24% Cr (Paper 159) or ferrite phase (Paper 158).
Chloride stress corrosion cracking was believed to initiate from surface pits as described in
Part 2.1 above. At slow strain rates and slow crack growth rates there van time for diffusion in
the local environment resulting in anodic dissolution of one phase preferentially and crack
propagation along the / grain boundaries. At higher strain rates acid conditions could build
up in the crack and the crack tended to take a more transgranular route, showing brittle
fracture across the ferrite grains (Paper 158) propagation along / boundaries and
dissolution of austenite (in <24% Cr alloys) (Paper 157). Brittle fracture across the ferrite
grains was believed to be due to a hydrogen embrittlement mechanism (dislocation pinning?)
and this was enhanced at higher chromium contents. Results of chloride stress corrosion
cracking tests by Sandvik (Paper 331) showed faster crack growth rates in 2205 (22 Cr 5 Ni)
than 3RE60 (19 Cr 5 Ni), both being faster than 316 (18 Cr 8 Ni).
However, the threshold stress below which cracks did not initiate was higher in the order 2205
> 3 RE60 > 316 (similarly the threshold cracking temperatures for 2205 and 3 RE60 were
above 150C compared to 60C for 316). Thus we conclude that the higher chromium alloys
have greater resistance to crack initiation in the aerated chloride environments but that once
initiated, failure may occur more rapidly.
In the presence Of H2S, the hydrogen embrittlement mechanism was enhanced and the
influence of chromium less pronounced. That is because the sulphide ion interferes with
repassivation so that pit (and crack) initiation is easier. Hence the 22 Cr and 25 Cr types of
duplex show similar properties under these conditions (Ikeda, Sumitomo Metals and Paper

157). In the H2S-CO2-Cl-environment duplex stainless stools show increased risk of cracking
at higher chloride levels, lover pH's, higher stresses and higher temperatures. Comparative
tests (Paper 157) of a superaustenitic (28 Cr 31 Ni 4 Mo (Sanicro 28 type)) showed such
lower susceptibility to attack than the 22 Cr and 25 Cr duplex stainless steels; fracture of the
superaustenitic occurring above 1.2 bar H2S and above 160 C at a pH of 2.7, 60 bar CO2
and 50 g/l NaCl.
Welding at optimum heat input conditions produced welds and HAZ's having very similar
properties to the parent metal (Paper 331). Single pass welding carried the risk of chromium
nitride (Cr2 N) precipitation at grain boundaries in the HAZ with attendant risk of sensitisation.
This problem was overcome by solution heat treatment at 1050C or (fortuitously) by
multipass welding as found in line pipe girth welding (Paper 155). Further comments on
welding are given in Paper 396.
Two papers were concerned with the influence of austenite: ferrite ratio on mechanical
properties, corrosion resistance and sulphide stress corrosion cracking. The NKK Paper (159)
indicated that resistance to cracking at ambient temperature was affected by the compositions
of the ferrite and austenite rather than the / ratio. Vallourec showed (158) that at 180C
under similar tests conditions (but cold worked specimens) optimum resistance to SSCC vas
obtained at 50-60% ferrite. Both quoted that the chromium and nitrogen content of the
austenite phase were critical; high nitrogen (0.15%) being beneficial but Cr only 22-24%.
Above this level of Cr the ferrite phase was apparently more susceptible to hydrogen
embrittlement type SSCC in the H2S -Cl-environment. This is in agreement with Sandvik's
results for the sour environment (157).
Thus we can conclude that the high Cr duplex (25Cr, ASTM 31250 type) is very beneficial
relative to the 22Cr for the aerated CO2-Cl-environment but for the H2S containing
environment it does not given any additional benefits for the increased cost.
It is of interest to note that Sandvik have recently brought out duplex alloy 2304 (23 Cr 4 Ni).
This is a "poor mans duplex" intended for environments where it is usual to choose 304 or
316. This alloy has higher strength than 316, comparable corrosion resistance (aerated
conditions) but is available at lower cost (no molybdenum). They also intend to produce an
alloy 2507 (DP3 type) in about 6 months time.

3.3

Marine applications (Papers 117, 219, 221, 228, 230)

Coupling extra low interstitial superferritic stainless steels in chloride environments to less
noble metals (e.g. Zn or Al alloy sacrificial anodes) was found to cause hydrogen induced loss
of ductility. This risk existed even if coupled to Armco iron (mixed potential approx. -0.7 V
sce). Added nickel enhances hydrogen uptake (Paper 117).
Galvanically coupled dissimilar metal crevices in seawater (such as could occur at flanges
between high alloy steels) showed that
a).

if both metals were highly resistant to crevice corrosion with standard inert washer
tests, no accelerated corrosion occurred;

b).

where a difference in resistance to crevice corrosion existed the less resistant alloy
corroded first causing a local drop in pH which then depassivated the more resistant
alloy if it was a ferritic stainless steel. The very highly resistant austenitic alloys (e.g.
Alloy 625) and titanium still remained unaffected (Paper 228).

Seawater testing of welds in alloys 254SMO, SAF2205 and Sanicro 28 showed (not
surprisingly) that the initiation of crevice corrosion and corrosion rate were dependent on alloy
composition and welding conditions. Alloy 254 SMO showed the best resistance (it contains
6% Mo vs 3% Mo in the other 2 alloys). At 30C alloy 2205 and Samicro 28 spontaneously
initiated crevice corrosion.

Initiation could be prevented by holding the specimens at low potentials (-0.2 V sce).
Chlorination caused a rise in potential to +500 to +600 mV sce and reduced crevice corrosion
resistance, although 254SMO was still resistant. Poor welds gave reduced corrosion
resistance in all 3 alloys, 254SMO being the least sensitive (Paper 230).
A general paper on materials for offshore seawater (Paper 221) asked more questions than it
answered but stimulates thought for future research in this field. It also summarises some
comparison of the 6 Mo stainless steels and 90:10 Cu Ni alloys for use in seawater service
(Table 3 Paper 221).
A surprising example of the use of Ti 6 Al 4 V alloy as a riser material was given (219) which
concentrated on methods for improving the corrosion fatigue strength in seawater. Despite
very favourable mechanical and corrosion properties, high cost and difficulties of welding
make this an unlikely materials choice at present.

3.4

General CRA's for oil and gas wells (Papers 322, 323)
Papers 322 and 323 give extensive summaries of existing knowledge. Many CRA's have
limitations on the presence of sulphide and apparently there are still few options for our most
severe environments although guidelines are available from specific laboratory tests or field
experience. The superaustenitic stainless steels seem to show a maximum susceptibility to
Cl-/H2S SSCC at a temperature between 80C and 150C depending on the alloy.
Higher nickel contents (>30%) shift the maxima susceptibility temperature even higher but
these alloys may still not be totally immune at room temperature. For the most aggressive
environments the Hastelloy C276 type is proposed as the best option for resistance to general
corrosion and chloride SCC - but it is very costly.

4.

COMPUTERS IN CORROSION CONTROL (Papers 45, 47, 48)

Almost without exception the papers on uses for computers fell into either the "Expert
Systems" category or numerical modelling of CP systems. The expert systems/data bases
now available are numerous, heavily structured and in most cases cannot be added to or
altered by the user. None of those presented at this conference were specifically designed for
the oil industry although some undoubtedly do contain useful and pertinent data.
Interestingly the NACE guidebook on corrosion control has itself been "computerised" and
may be on its last printed edition.
The main uses of computer modelling in cathodic protection are in design analysis for new
structures or for processing in-situ potential readings on existing structures for troubleshooting
purposes. The techniques mostly used classical equations (45) but some made use of
electronic spreadsheets (48) so that optimisation of anode type, geometry and position could
be achieved - particularly for congested anode arrays (47).

5.

CATHODIC PROTECTION (Papers 278, 290, 295, 299)

A study of the long term current demand of cathodically protected metals in seawater was
carried out over 800 days (295). The range of metals included copper alloys, aluminium,
titanium, mild steel and 316 stainless steel. In general all the samples tested showed the
minimum current demand at a potential of -1.0V (as can be obtained with Zn and Al anodes).
All the alloys were polarised within 50 days to within 20% of their final current demand (which
was 25-40 mA m-2). In designing a CP system for a structure containing several alloys, the
current requirement for practical purposes was therefore regarded as independent of the alloy
composition.

For stainless steels the potential required for cathodic protection may not actually need to be
as low as -1.0V. Electrode potential vs chloride concentration diagrams have been
constructed for 304, 316 and a superaustenitic alloy (TSS 310LMR. 20Cr 25 Ni 4-5 Mo) at
22C, 45C and 64C (278). These show that the 'controlled protection potential' to prevent
localised corrosion (and chloride stress corrosion crack initiation) is fairly independent of the
chloride concentration. For 304 and 316 the potential should be below -400 mV sce and for
the superaustenitic; below -340 mV sce. Current requirements of cathodically protected
-2
samples up to 140 days were around 10 mA m .
A protection system for submerged offshore structures was proposed (299) based on the use
of Al coatings in combination with a small number of sacrificial anodes. Model calculations
showed that even allowing 10% of the coating areas as holidays, the structure could remain
safely polarised with less than 20% of the anodes needed for a bare steel structure because
-2
of the much reduced current demand (5-10 mA m ). Flame sprayed aluminium based
coatings 200 m thick would last 20-30 years whereas zinc coatings would only last 1-2
years.
Bio-fouling of cathodic protection systems was apparently a problem in the United Arab
Emirates (290) which was being tackled by using A.C. impressed current systems, but not
very successfully.

6.

DOWNHOLE MATTERS (Papers 134, 161, 314, 316)

The ANR pipeline company operates 15 gas storage fields in Michigan. They described their
casing corrosion monitoring programme first established in 1970 (134). Pitting type corrosion
was found on the external surface of the production string; most frequently at the annular fluid
level and sometimes opposite the shoe of the surface casing. They use a magnetic flux
leakage casing inspection tool, with base corrosion logs run at the time the well is completed
to prevent erroneous interpretations and facilitate corrosion rate calculations. Shut-in annular
pressure surveys are performed every 6 months for additional leak detection.
Corrective action (liner-installation) is only taken if the log shows 90% wall penetration. This
follows the results of burst tests on corroded casing samples whose burst pressures
exceeded predicted values (based on NG-18 surface flaw equations) by more than 30%, and
in 13 out of 18 tests, exceeded API internal test pressures for new casing.
Paper 161 attempted to show (on very little evidence) that stress corrosion cracking of nonmagnetic Cr-Mn drill collars could be prevented by introducing compressive surface residual
stresses on the ID during manufacturing. Methods of achieving this in practice were not
discussed, nor was any technique proposed for quality control. Despite these drawbacks
there is some appeal in this approach in view of the high cost of NMDC's and it might
therefore warrant further thought.
Tests were conducted to demonstrate the effects of using common oil well service tools in
fibre glass casing. The cup type packer, retrievable packer with slips, and retrievable bridge
plug with slips were all run successfully inside 5" fibre glass casing up to its rated working
pressure (2,000 psi). Drilling out a drillable squeeze packer caused extensive damage to the
fibre glass casing.
A series of polyolefinic thermoplastic rubbers have been found suitable for use in downhole
and subsea environments (316). These EP-TPV's retain their properties up to 150C when
aged in brine solutions, corrosion inhibitors and pressurised natural gas. They are proposed
for a range of oilfield applications such as packers and seals. Tables of properties are given in
the paper.

7.

CRACKING IN DEAERATORS (Paper 306)

The complete 5 hour session on deaerator cracking was best summarised by Exxon's paper
no. 306. Their survey of 6 case histories of deaerator failures showed that crack
characteristics in deaerators are associated with stress induced corrosion and corrosion
fatigue. Thus high localised stresses, particularly residual stresses associated with welds,
play a large role. These results support the NACE T-7H guidelines; to post weld heat treat to
relieve residual stresses and to reduce high localised stresses in design. No evidence of
embrittlement or alkaline stress cracking was found.
Cracking was not associated with any particular vessel designer, fabricator or material
specification. The influence of water chemistry on cracking rate was unclear; nor was it well
established whether corrosion occurred primarily during operation or shutdown, but any
upsets in operation (shutdown, start-up. water hammer, aeration) accelerated corrosion and
cracking.

Table 4.

SUMMARY OF RESULTS OF EXPOSURE OF STEELS TO LOW H2S CONCENTRATIONS.

Table 3.

Comparison for properties for highly alloyed austenitic stainless steels (6%Mo) and
cupronickel 90:10.
Fluid: Seawater

Property

Stainless 6Mo-steel

CuNi 90:10

Resistance to pitting

Excellent

Excellent Somewhat reduced if

deposits

Resistance to crevice corrosion

Excellent up to appr. 40C

Excellent

Resistance to stress corrosion

Excellent up to appr. 80C

Excellent

Resistance to erosion corrosion

Excellent

Very poor above 2.5 m/s

Resistence to polluted
seawater, esp. sulphides

Excellent

Very poor

Corrosion resistance in weld

area

Slightly reduce

Unaffected

Marine Growth

Normal

Very little

Good

Good

Proof stress Rp 0.2 N/mm , min.

300

90

Ductility/impact

Excellent

Excellent

Formability

Good

Excellent

Machinability

Acceptable

Good

Weldability
2

APPENDIX A
COMPLETE LIST OF PAPERS FROM THE CONFERENCE