The effect of corrosion on material

selection-sweet corrosion environments

TESA-AR

La información aquí contenida es CONFIDENCIAL, y no puede ser distribuida ni usada por terceros sin
autorización previa de TENARIS. © 2009 TENARIS. Todos los derechos reservados.
The effect of corrosion on material
selection
Agenda

•Introduction
•Sweet corrosion resistance of C/LA steels and CRAS: two
different worlds
•C/LA steels: no standard for sweet corrosion
•De Waard model and its evolution: attempts to quantify
•Corrosion resistant alloys

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Introduction

Once the first stage of analysis is completed (to avoid cracking in H2S
containing environments), in the case of tubulars that will be
continuously exposed to production fluids, it is necessary to determine if
the candidate materials are adequate or not from the point of view of
corrosion.

CO2 corrosion is the most predominant form of corrosion in oil and gas
production wells.

Cracking
ISO 15156 Corrosion
Additional
Considerations

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Sweet corrosion resistance:
Carbon/low alloy steels vs CRAs
On the sweet corrosion resistance of C/LA alloy steels

•Carbon dioxide in the produced gas or oil can lead to very rapid
deterioration of alloys containing less than 12%Cr (Oilfield Metallurgy and
Corrosion, 3rd edition, 2004, Craig)

•Carbon/low alloy steels present a poor resistance to this type of

corrosion (Kermani and Morshed, Corrosion, Vol 59, No 8, 2003)

•The mechanistic understanding of CO2 corrosion remains incomplete.

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Introduction

The use of CRAs could be unacceptable in terms of CAPEX, particularly

when partial pressure of H2S is too high for the application of martensitic
or even duplex stainless steels. In those cases carbon/low alloys steels
could be the only option.

Other important factors are:

- the simplicity for accessing the well
- the “consequence” of failures.

For instance, the cost of workover in an offshore well is typically much

higher than in onshore wells. Consequently a more conservative approach
in the selection is normally taken in this type of wells even for non-
permanent strings.

The character of the tubular is also a factor. Some companies consider

periodical replacement of non permanent tubulars is acceptable. A more
conservative approach is generally applied for permanent installations than
for tubing.

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Sweet corrosion resistance:
Carbon/low alloy steels vs CRAs

Dramatic effect of Cr addition in corrosion (sweet environment), from NKK

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Carbon/low alloy steels
No standard for sweet corrosion

• An industry standard approach for predicting CO2 corrosion does

not exist.

• There is no agency or association providing standard guidelines,

unlike the case of H2S cracking.

• Over the years relationships appear, trying to relate

environmental variables and tendency to sweet corrosion (or
corrosion rate).

•The simplest ones are “rules of thumb” based on CO2 partial

pressure. Complexity growths up to models level.

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Carbon/low alloy steels
No standard for sweet corrosion
CO2 partial pressure: Rule of thumb for Carbon Steel (API 50’)

PCO2 < 7 psi (0,5 bar) Low corrosion risk

7 psi (0,5 bar)< PCO2 < 30 psi (2 bar) Medium corrosion risk
PCO2 > 30 psi (2 bar) High corrosion risk

It is only a thumb rule and has been widely mentioned in the
bibliography for gas wells but also for oil wells.
It has to be used for a first look of the possible scenarios
It gives an indication of the limited corrosion resistance of Carbon and
low alloyed steels in sweet environments

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Carbon/low alloy steels
No standard for sweet corrosion
The previous rule of thumb has been also mentioned (i.e: Corrosion
of oil and gas well equipment, API) as:

PCO2 < 3 psi Non corrosive condition

3 psi < PCO2 < 30 psi May indicate a corrosive condition
PCO2 > 30 psi (2 bar) Usually indicates a corrosive condition

In this case is explicitly mentioned that due to the composition of water

phase in oil wells, these rule not always apply.

In TPC Publication 5 of NACE International, the rule is also cited with the
value of 3 psi instead of 7 psi.

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Is there a limit of CO2 pressure for C/LA
steel?

Martensitic Steels
1000

Super Duplex

Super Duplex
Duplex Steels

(SAF2507)
Austenitic steels Fe based or Ni
(SAF2205)
CO2 Partial Pressure, psi

based
100 Martensitic Steels
SANICRO 28/29
13Cr , M13Cr, S13Cr

10 TN XX CS + Inh / 3Cr
7 psi 7
0.3 1.5 3

1 T<60=L, C, T

Any Grade T>80=N, P, HC

API Grades
0.1 up to 150 Ksi Tenaris S, SS, HS proprietary grades

0.01

0.001 0.01 0.05 0.1 1 10 100 1000

H2S Partial Pressure, psi

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Is there a limit of CO2 pressure for C/LA
steel?

3 psi

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BP isocorrosion plots
pH=4.5 At 0.1 bar corrosion rates
around 1 mm/yr are predicted

1 bar

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De Waard and Milliams, Lotz (weight loss)
First to quantify. Partly on theoretical, partly on experimental basis.

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The evolution of De Waard nomogram
As said, an industrial standard approach to predict CO2 corrosion
damage does not exist.
The work of Shell (starting with the previously presented nomogram)
has evolved and provided a strong reference.

The current form

De Waard, Milliams and Dugstad model
This semi-empirical model takes into consideration the effect of
flow, CO2 partial pressure, temperature and pH as main variables.
Different protection factors as carbonate protection and steel
composition and microstructure are included.

Correlation with field experience suggest that De Waard approach

generally predicts the worst-case corrosion rate.
More recent work from de Waard has also proposed an oil correction.

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De Waard, Milliams and Dugstad model
The model is based mainly in flow loop experiments

Strict validity limits are:

Temperature up to 120°C
CO2 partial pressure up to 20 bar
Liquid velocity up to 13 m/sec

Most testing carried out at pH 4.5 and 6

Most testing 2-3 days (!)
Turbulent flow conditions

It appear to be less applicable at low flow rate (0.1 m/sec)

Only water in original experiments!

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The structure of the model
A baseline corrosion rate is calculated by considering:
•The kinetics of the surface reaction.
•The mass transfer of the dissolved CO2 from the bulk of the solution to
the surface of the steel.
•The effect of steel Cr and C content, through compositional correction
factors.
Fcr
Vcor 
 1 1 
  
 Vr Fc Vm 

•The rationale behind this combination of two different “rates” is the

concept of limiting step (the slowest process will control global velocity).

•Vr is the highest possible reaction rate (i.e. when mass transfer is
infinitely fast)
•Vm is the highest possible mass transfer rate of the corrosive species

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The equations
For normalized steel
Surface reaction
1119
log(V r )  4.84   0.58 log( p CO 2 )  0.34( pH act  pH CO 2 )
T
Mass transfer U = liquid velocity (m/s)
d = diameter of the tube (m)
U 0.8
Vm  2.8 0.2 pCO 2 pCO2 = CO2 partial pressure (bar)
d T = temperature (K)

For quenched and tempered steel

Surface reaction
1119
log(V r )  5.07   0.58 log( p CO 2 )  0.34( pH act  pH CO 2 )
T
Mass transfer

U 0.8
Vm  2.7 0.2 pCO 2
d
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The equations
Mass transfer

U 0.8
Vm  2.8 0.2 pCO 2 U = liquid velocity (m/s)
d d = diameter of the tube (m)
pCO2 = CO2 partial pressure (bar)
T = temperature (K)

For oil and gas well it is

necessary to have a flow
model for knowing the liquid
velocity in the point where
corrosion rate is estimated.

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The equations

pHCO2 = 3.82 + 0.00384 t - 0.5 log (pCO2)

pHact = Actual pH of brine (can be predicted using Oddo-Tomson correlation)

 HCO 3- 
2 0.5

  8.68  0.00405  t  32   4.58 10 -7  t  32   3.07 10 -5 P 14.5  0.477 

9 9 TDS   TDS 
pH act  log    0.193 
 CO 2 
p  5   5   58500   58500 

HCO3- is the bicarbonate concentration expressed in mol/lt (mg/lt divided by 61000)

pCO2 = CO2 partial pressure (psi)
t = temperature (°C)
P is total pressure (bar)
TDS is “total dissolved solids”, the sum of ion concentrations in mg/lt

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Protection by scales in De Waard
Model
At certain levels of temperature and depending on CO2 pressures, iron
carbonates or oxides can be formed on the surface of the tube.
This products can lower corrosion rates appreciably.

The model takes into account the effect of scaling by means of a

multiplication factor Fscale.
This factor is 1 when temperature is lower than Tscale and takes a value
lower than 1 when Tscale is surpassed.

2400
Tscale 
6.7  0.44 log pCO 2
2400
log Fscale   0.44 log( pco 2 )  6.7 Fscale1
T

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 The effect of temperature (FeCO3)
Increase of Corrosion rate
expected from a purely kinetic
point of view.
Corrosion Rate

Corrosion product films expected

to reduce corrosion rate.

Temperature

“Scaling” temperature depending

on CO2 partial pressure

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Other correction (protection)
factors
Oil protection factor
A work from de Waard, Smith and Craig proposed a model to quantify the influence
of crude oil on the corrosion rate of oil-water mixtures; corrosion data from two oil
fields have been used as the basis for the model.
Take into account that predictions of the model remain speculative due to the
restricted data on which it is based.

W 1.1 10 4  W 
Foil  0.059 U 2
 0.059 U
Wbreak Wbreak 90 Wbreak 90
W = watercut, expressed as fraction (range 0-1)
U = liquid velocity (m/s)
 = angle of deviation of the tubing (°)
Wbreak = maximum fraction of water in oil, that can be calculated as:
Wbreak = -0.0166 API + 0.83
API is gravity of oil in °API
Foil expression can be applied in the range 50>°API>20.
Outside this range we recommend to use:
Foil=1 if API equal to or higher than 50
Foil=Foil (20) if API lower than 20

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Other correction (protection)
factors oil protection factor

Oil protection factor may predict strong reduction in corrosion rates,

particularly at low flow rates, heavy oil and low watercuts.

A rule of thumb indicates that that corrosion greatly reduced for watercuts
below around 30% in crude oils. The transition from water-in-oil to an oil-
in-water emulsion occurs at around 30-40% water in oil but this aspect
cannot be separated from the flow characteristic.

There is a risk in applying this rule of thumb (or oil protective factor) for
design: water separation may occur at lower water cuts and corrosion has
been observed in wells with as low as 1% water cut.

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Other correction (protection) factors
Oil protection factor
Corrosion occurs when water is present in the system and it wets the steel surface.
Consequently, water cut and the notion of water wetting will be important.
Experimentally it has been recognized that oil presence could reduce corrosion rates.

Corrosion rate of steels and stainless steels in

oil/water mixtures vs Cr content.

100
Corrosion Rate [mm/y]

90
80
70
60
50
40
30
20
10
0
0 5 10 15 20 25

Cr [%]

100% Water 20% Water Emulsion

It has been reported that light oils give less protection than heavy ones, and that gas
condensates gives hardly any protection at all. iIn general, the influence of the oil on
corrosion rates has not been quantified.
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Other correction (protection)
factors-sulfide films formation
No accepted models exists to predict when this type of protection take
place or to quantify the extent of it. Recently, De Waard proposed to take
into account the effect of H2S on sweet corrosion rate by means of a
multiplier on Vcor:

1
FH 2 S 
1  100000 [ HS  ]

Take into account:

The factor is highly speculative, no field validation has been shown.
Sulfide film can be susceptible to localized breakdown leading to severe
pitting corrosion under extreme conditions.

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Main lessons from this model
•The model also predicts a poor sweet corrosion resistance for
carbon/low alloy steels.
•It gives a good simplified way to conceptualize the influence of
relevant variables (as CO2 partial pressure, temperature, water
cut, etc.) and also on the effect of its interaction (i.e. what if flow
removes protective products?).
•The model (and recent proposed factors) shows that low or
moderate corrosion rates could be consequence of processes that
protect steel surface. Operations, local conditions or changes in
environment affecting those processes could trigger higher
corrosion rates.
•From the application of the model does not seem possible to
establish a single value of CO2 partial pressure to be used as the
threshold for sweet corrosion.

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 General comments on models

De Waard model is not the only available. Oil companies and research
institutes have developed numerous empirical, semi-empirical and some
mechanistic prediction models for CO2 corrosion of carbon steel.

A program of evaluation of the different corrosion prediction models against

actual corrosion field data has shown that it can vary considerable from case
to case which models are successful in their prediction (Nyborg, paper
10371, NACE Corrosion 2010). In other words: existing quantitative models
are unreliable in predicting the actual long term performance of carbon and
low alloy steels in sweet scenarios.

Prediction could be a useful tool to assist in the selection of materials, but it

should be taken into account that misuse of corrosion models can potentially
cause severe problems. Common misapplications include: accepting model
predictions without applying sound engineering judgment or using corrosion
models to model “real world” situations such as sand deposits, bacteria, etc.
(Franco et al, paper 10370, NACE Corrosion 2010).

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Corrosion resistant alloys in sweet
environments
Introduction

Dramatic effect of Cr addition in corrosion (sweet environment), from NKK

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Corrosion resistant alloys in sweet
environments -Introduction
From this dramatic effect it should not be assumed that CRAs are
immune to general corrosion in CO2-containing environments.

Specifically, it is known that 13%Cr is prone to general corrosion at

elevated temperatures.

Not only uniform but localized corrosion is a risk for corrosion

resistant alloys and several variables could influence the feasibility
of application of the different families.

Prediction models are not common for CRAs (typically, application

domains and even rules of thumb are used during its selection).

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13%Cr steels
Modified and Super 13Cr

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 13%Cr steels/Simplified Domain
150 °F 200 °F 250 °F 300 °F 338 °F

20
NaCl (%)

YIELD STRENGTH
REFERENCE
15
TN Cr13M
TN Cr13S GRADE YS (Ksi)

TN Cr 13 80 & 95
10 TN Cr 13 M or S 95 & 110

This graph can give some

5 TN Cr13 support for usual
temperature limit for 13Cr:
TN Cr13M 150°C and Cl- being not
higher than 50000 mg/lt
0
50 100 150 170
Temperature (°C)

This is a simplified domain for first step selection, it shows that limits for
temperature and chloride content exist for conventional 13Cr and they are
interrelated.
More accurate evaluation can be done by NKK through the use of a model, if
complete information of environment is provided.
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13%Cr steels/Pitting and Cl- content
An example of the influence of Chloride on pitting of martensitic steels
(electrochemical lab testing, conventional L80 Cr13, 1 bar CO2, 60°C)
0.01

1E-3
Current density (A/cm )
2

1E-4

1E-5

1E-6

1E-7 Solution I
Solution II
Solution III
1E-8
-100 0 100 200 300 400 500 600 700
 (Eapp-Ecorr, mV)

Solutions I, II and III differ greatly in Cl- content (75000, 30000 and 5000 mg/lt).
Onset of pitting is highly dependent on this variable.
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 13%Cr steels/Simplified Domain

From a comprehensive work

of Craig (Selection Guidelines
for corrosion resistant alloys
for the oil and gas industry)
the dependence of maximum
service temperature and
chloride content is confirmed.

It is clear that maximum

temperature depends also on
CO2 partial pressure.

Martensitic SS have shown

good performance in
production wells with high
content of CO2 and very low
H2S
It might be emphasized that these domains are determined in the absence of
O2, H2S and elemental sulfur.

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Corrosion resistant alloys in sweet
environments -Beyond the limits of 13%Cr
stainless steels
For conditions beyond those presented for 13Cr martensitic steels, it is
necessary to consider metallurgies with more stable passive film,
presenting improved general and localized corrosion resistance.

Main families used for OCTG are:

•Duplex and superduplex stainless steels

•Highly alloyed austenitic steels
•Nickel alloys

Tenaris provides duplex (22Cr), superduplex (25Cr) and highly alloyed

austenitic steels (Sanicro 28 and 29) and we will focus the analysis on
those families.
These materials are highly resistant to CO2 corrosion and, consequently, this
is not the main consideration in determining its suitability.
Pitting corrosion and/or cracking are the primary concerns: chloride content,
temperature, presence of H2S and pH are the key factors which determine
their acceptability.
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Corrosion resistant alloys in sweet
environments
Duplex and superduplex
Duplex materials combine high pitting resistance and high strength.
A parameter for comparing the resistance to pitting is the PRE number (Pitting
Resistance Equivalent):

PREN = Cr wt% + 3.3 * (Mo wt% + W wt%) + 16 * N wt%

Superduplex also includes more nitrogen and it is possible to reach PREN

numbers higher than 40.

There are several variations of the PREN. All them were developed to
reflect and predict the pitting resistance of Fe/Ni/Cr/Mo CRAs in the
presence of dissolved chlorides and oxygen. e.g. in sea water.

Though useful, these indices are not directly indicative of corrosion

resistance in oil field environments.

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Corrosion resistant alloys in sweet
environments
Duplex and superduplex
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In sweet environments,
duplex stainless steels permit
to go beyond temperature
limits of martensitic stainless
steels.
Typically, a limit of 200°C is
considered for 22%Cr.
Super Duplex is even more
resistant.
They should never be used
over 250°C during prolonged
periods due to metallurgical
reasons.
These products are used in:
-Production wells with high
content of CO2 and low H2S
-Water injection wells (25Cr)
-CO2 injection wells
36
Corrosion resistant alloys in sweet
environments
Highly alloy austenitic steel: Sanicro 28 and 29
High strength, high corrosion (and erosion) resistance and, in contrast to
previously presented martensitiic and duplex stainless steels, it is highly
resistant to environments containing H2S.
Sanicro 28 and 29
Very high resistance to pitting
and crevice corrosion.
Used for high strength downhole
production tubing, casing, and
liners in sour gas wells.

Sanicro 29
Higher pitting resistance
equivalent than Sanicro 28.
Developed for improved localized
corrosion resistance at high Cl-,
CO2 and H2S concentrations at
high temperatures.

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Corrosion resistant alloys in sweet
environments
Nickel alloys
When even highly alloyed
austenitic steels are not
adequate for the
environment (as in the case
of very high temperature,
CO2 and H2S), nickel alloys
are the option because of its
great performance.

The graph from the work of

Craig shows the very high
maximum temperature that
can be reached in the case
of Alloy C276.

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Selection also depends on exposure time,
character of the tubular and accessibility

Surface casing
Tubing and production casing
below packer are continuously
Intermediate & production exposed to production fluids.
casing
Casing is permanent and tubing
is not.

Cost of workover could be

Packer completely different depending
on the character of the well (on
shore of off shore).
Production casing below
packer

Production tubing

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Where are we in the process now?

Cracking
ISO 15156 Corrosion
Additional
Considerations

Additional considerations are also important (sometimes

determinant) to define which of the “possible” materials are the best
alternative for a given scenario:

•Economics and logistic (onshore vs offshore, remote areas vs accesible

areas, workover cost).
•Failure consequences (economics, image, environmental).
•Other damage mechanisms: secondary environments, erosion.
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END OF THE PRESENTATION

Questions

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La información aquí contenida es CONFIDENCIAL, y no puede ser distribuida ni usada por terceros sin
autorización previa de TENARIS. © 2009 TENARIS. Todos los derechos reservados.
TenarisUniversity 42