Material Recommendations for Production

of Wellhead and Christmas Tree

Components
Abstract:
Presented herein is the review of material requirements a production well. This review
includes evaluation of guidelines for wellhead and Christmas tree components which will be
in contact with produced fluids under the following conditions: Partial Pressure CO2: 2.30
bar maximum Partial Pressure H2S: 0.015 bar maximum Water: 0-60 vol. Percent Chlorides
in Water: 2 wt. Percent Reservoir Temperature: 94 C
Introduction

Presented herein is the review of material requirements a production well. This review includes
evaluation of guidelines for wellhead and Christmas tree components which will be in contact with
produced fluids under the following conditions:
Partial Pressure CO2: 2.30 bar maximum
Partial Pressure H2S: 0.015 bar maximum
Water: 0-60 vol. Percent
Chlorides in Water: 2 wt. Percent
Reservoir Temperature: 94 C
This review has been separated into three tasks:
Task 1 - Evaluation of Materials Guidelines and Specification
Task 2 - Verification of Corrosion Performance of Materials
Task 3 - Review of Special Parameters for Corrosion Resistance, Fabrication and Inspection
Each task will be presented separately in the following sections.
Task 1 - Evaluation of Materials
Guidelines and Specifications

Section 1. Introduction

1. This section describes the production environment. By the information provided, it is readily
evident that the effects of both hydrogen sulfide and carbon dioxide must be taken into
account. The hydrogen sulfide partial pressure of 0.015 bar (0.22 psia) is above the 0.05 psia
level cited by NACE Standard MR-01-75 [1] where sulfide stress cracking (SSC) can occur
and where SSC resistant materials should be used.
2. The carbon dioxide partial pressure of 2.30 bar (34.5 psia) is above the level cited by the
American Petroleum Institute where corrosive conditions can exist [2] apart form the low
concentration of hydrogen sulfide, the conditions are similar to those described for gas
condensate wells in the United States. [3] As shown in Figure 1, severe corrosion of steels
can result from exposure to such environments. It is also shown, however, that chromium is
an effective alloy element for the mitigation of carbon dioxide corrosion. At a chromium
concentration of 12 approximately percent, carbon dioxide corrosion is essentially mitigated
in steels.
3. The chloride concentration of the production environment is 2 wt. Percent (20,000 ;ppm). This
should be considered moderate However, the chloride concentration is significant from the
standpoint of stress corrosion cracking (SCC) at elevated temperatures (>65 C). From the
 standpoint of corrosion of materials with 11.5 percent chromium and higher, problems are not
expected in deaerated production environments.

Section 2. Materials

2.1 General

1. Reference to stainless steels with more than 12 percent chromium should more appropriately
reference materials with more than 11.5 percent chromium. This statement should be
changed because AISI 410 CA-15, F6-NM and CA6-NM, which may be acceptable for
service, have ranges for chromium that are 11.5 - 13.0 percent. AISI 420 has ranges for
chromium of 12.0 to 14.0 percent. AISI 420 is common for tubular grades; however, AISI 410
and other materials such as CA-15 and CA-6NM (F-6 NM) are more common for wellhead
components. All of these materials should be considered for service.
2. Copper base alloys have exceptional resistance to corrosion in production environments
containing carbon dioxide. It has also been shown that these materials can perform in an
acceptable manner in environments containing carbon dioxide with minor amounts of
hydrogen sulfide at moderate temperatures.
3. In selecting materials, reference should be made to using only those materials found in
NACE Standard MR-0175 unless exception has been specifically approved.
4. Where testing for SSC is required, a minimum performance requirement should be specified.
5. In qualifying welding procedures, a maximum hardness restriction should be given.

2.2 Materials for Wellhead and X-mas Trees.

1. Casing hangers and casing heads may be made from low alloy steels provided that they can
be manufactured per NACE MR-0175.
2. Candidate materials for seal surfaces should include Alloy 718 and 625.
3. Tubing head and hanger materials should be manufactured of corrosion resistant material
and per NACE MR-0175.
4. Precipitation hardened materials for valve components: Alloy 718 should be limited to HRC
40 per NACE MR-0175.

Task 2 - Verification of Corrosion Performance of Materials

Three main material alternatives are being considered for well head materials: (1) ASTM F6-NM, (2)
22-25 Cr Duplex Stainless Steel, and (3) Alloy 625 clad steel.

Evaluation of SCC and SSC Performance

Both the F6-NM and duplex stainless steels have a slight susceptibility to SCC in elevated
temperature brine environments arising from their nickel content. Both materials should give
acceptable SSC performance in service if manufactured according to NACE MR-0175. Susceptibility
to SSC is further reduced by the extremely low level of hydrogen sulfide to be present in the
production environment. Alloy 625 clad steel should give acceptable performance from the standpoint
of both SSC and SCC.
There is limited documented service experience and valid laboratory simulated field environment test
data from which to predict the SCC behavior of F6-NM and 22-25 Cr duplex stainless steels. Several
operators limit the service temperature of F6-NM to <65 ;C to prevent SCC. However, this limit was
obtained from general experience with SC of stainless steels and not specified performance data on
this alloy. Some data exists for duplex stainless steels which indicates cracking can occur in carbon
dioxide/brine environments containing more than 0.007-0.07 bar (0.1 - 1.0 psia) hydrogen sulfide.
This level of hydrogen sulfide is in the range of that being considered for this project.
Further studies are recommended to evaluate both F6-NM and duplex stainless steels.
Evaluation of Weight-Loss, Pitting and Crevice Corrosion

From both laboratory and field data it can be shown that materials with at least 11.5 percent
chromium will effectively mitigate weight-loss corrosion in carbon dioxide/brine systems
which exclude oxygen. [3] In contrast, very little practical engineering data exists from which
to predict the localized corrosion performance of these materials. Such determinations must
be made based on electrochemical measurements made in simulated field environments
specific to the particular situation at hand. Studies such as these are also recommended to be
conducted on F6-NM and duplex stainless steels.

Experimental Program for the Evaluation of Wellhead Materials

A program of study is proposed which will evaluate the cracking and localized corrosion
behavior of F6-NM, 22 and 25 Cr duplex stainless steels in the specific environment to be
encountered in the Oseberg Project. It will be based on the methods given in Reference 6
which include slow strain rate tests for determination of SCC susceptibility and
electrochemical tests for determination of susceptibility to localized corrosion. Furthermore,
the effect of the hydrogen sulfide can be specifically isolated thereby showing the differences
in performance which can be expected at the beginning and end of production.

Task 3 - Review of Special Parameters for Corrosion Resistance, Fabrication and Inspection

Based on the previous discussion, it is recommended that all of the candidate materials
should be considered for use in the Oseberg project until adequate data can be generated. This
data will allow the optimum cost-effective selection to be made. The Alloy 625 clad steel if
manufactured properly will give the most superior performance of the three candidate
materials; however, it will involve the most complicated manufacturing process, require the
most detailed quality assurance program and be the most expensive solution. If either the F6-
NM, 22Cr or 25Cr duplex stainless steels prove to give acceptable performance in corrosion
tests they can be used to manufactured wellhead equipment with a minimum of cost and
special processing controls.

A preliminary review of the special parameters for control of corrosion resistance, fabrication
and inspection are given below.

F6-NM
 If F6-NM successfully passes the proposed qualification tests, the only special processing
parameters required will be the heat treatment and maximum hardness as specified by NACE
MR-0175. I requires that this material be austentitized at 1010 C minimum, followed by air
cooling or oil quenching to room temperature, followed by double tempering at 675 C and
600 C minimum. It is also noted that a maximum carbon content of 0.03 percent is normally
required to meet the HRC 23 maximum hardness specified for service in hydrogen sulfide
environments.

22 and 25 Cr Duplex Stainless Steel

These materials should be processed in the solution annealed condition for optimum
resistance to SCC. They should have a microstructure containing approximately a 50/50 mix
of austenite and ferrite. Typically, 22Cr duplex stainless steel (DIN 1.4462) has been
qualified at hardness up to HRC 28 for sour service.

Repair welding can produce microstructural conditions in duplex stainless steels which can
be extremely susceptible to localized corrosion. [7] It is recommended that all welded
components be solution annealed after welding, where possible, at a sufficiently high
temperature to produce a uniform austenite/ferrite structure.

Alloy 625 Clad Steel

All steel used for clad components should be manufactured in accordance with NACE
MR-0175 to have a maximum hardness of HRC 22.

Both Hot-Isostatic-Pressing (HIP) and weld cladding techniques are acceptable provided
that they meet the requirements of NACE MR-0175. This will require that the maximum
hardness in the base material not exceed HRC 22.

The minimum cladding thickness of 2mm should be maintained. Furthermore, the process
should be evaluated metallographically prior to manufacturing for evidence of carbon
diffusion from the base material into the alloy cladding. Such diffusion zones characterized
by heavy carbide precipitation should be minimized and should not approach the surface of
the alloy to be in contact with the production environment.

Evaluation of the exposed surface for susceptibility to localized corrosion can be

conducted with a ferric chloride solution (5% ferric chloride and 10% sodium chloride) at 23
C for 3 days. No evidence of localized corrosion should be visible.
 Evaluation of the metallurgical bond between the Alloy 625 and the steel can be obtained
sing a hydrogen charging test. In this test, hydrogen is electrolytically charge from the outside
of a cylindrical, prototype cladded component. The hydrogen produced on the steel surface
can diffuse into the material and will accumulate at the interface between the Alloy 625 and
the steel. If defects (i.e., cracks, non-bond regions or anomolous microstructures) exist at the
interface the hydrogen pressure will separate the cladding from the base material. This
disbonding can be determined at the conclusion of the test by measuring dimensional
changes, dye penetrant and metallographic inspection of the sectioned component. For
acceptable performance the following results should be obtained:

I.D. dimensions before and after testing to be within 0.13 mm (0.005 inch),

No dye penetrant indication at interface

No evidence of disbonding at interface when observed at 200X.

References

"Sulfide Stress Cracking Resistant Metallic Materials for Oil Field Equipment", NACE
Standard MR-0175 (1984 edition).

Corrosion of Oil- and Gas-Well Equipment, American Petroleum Institute, 1975 p. 8.

The Field Testing of 32 Alloys in the Flow Streams of Seven Condensate Wells,
Publication No. 50-3, NACE 1950 (July), p. 130.

"Corrosion Behavior of Berryllium Copper and Other Nonmagnetic Alloys in Simulated

Drilling Environments", J. Booker, W. R. Cribb, J. C. Turn and R. D. Kane, NACE
Corrosion/84, Paper No. 220, 1984 (September) p. 429.

"Corrosion of Stainless Alloys in Oilfield Production Environments", R.D. Kane, Stainless

Steel '84, The Institute of Metals, 1984 (September) p. 429.
 "Application of Corrosion Resistant Alloys in Oilfield Production Environment", U.K.
Corrosion/85, R. D. Kane, S.M. Wilhelm and D. R. McIntyre, Institute of Corrosion Science
and Technology, 1985 (November), p.313.

"Effects of Welding Parameters on Localized Corrosion of a Duplex Stainless Steel", N.

Sridar, L.H. Flasche and J. Kolts, Materials Performance, 1984 (December), p. 52.

"Slow Strain Rate Testing for Materials Evaluation in High Pressure H2S Environments",
D. R. McIntyre, R. D. Kane and S. M. Wilhelm, NACE Corrosion/86, (1986) March.

Figure 1 - Effect of Chromium content or CO2 corrosion of steels in gas condensate well
service