Ballot Item 2006-04 (Revised) Modified Limits for K-500

For NACE TG 299 (ISO 15156 Oversight Committee) review

For information only - No vote required

Proposal for the amendment of ISO 15156-3, Table A.34 —

Environment and materials limits for precipitation-hardened nickel-
based alloys used for wellhead and christmas tree components
(excluding bodies and bonnets), valve and choke components and
downhole equipment internal components

Contents Page
Message to Oversight Committee 2
Summary of voting and comments by the Maintenance Panel 3
Proposed change to ISO 15156-3, Table A.32 6
Original proposal as submitted to Maintenance Panel 17

1
Message to Oversight Committee

Dear Oversight Committee member,

Ballot 2006-04 (Revised) is being tendered to you for your review. The ballot is a
proposal for revision of Table A.34 of ISO 15156-3 to change the limits of UNS N05500.
This proposal received insufficient support from the Maintenance Panel to go forward in
its present form. The reasons the Maintenance Panel members gave are shown on
Page 3.

The proposed revised version of Table A.34 is that shown on Page 6. The earlier
history of the ballot process for this proposal is also included and begins on Page 17.

No further action is needed on your part.

Greg Chitwood

2
Votes and comments of the ISO 15156 Maintenance Panel on
Ballot 2006-04 (Revised) Modified Limits for K-500

Voter Vote Comments

1 Affirmative Any explanation for the change in pH in the 60 day GHSC test?
I think there must be reconciliation between lab test results and field
failures of K-500. The coupling to low alloy steel parts needs to be
investigated. The effects of minor cold working on hydrogen
2 Negative embrittlement need to be investigated. Something is missing here. There
are other CRA's available that are clearly far superior to K-500. I see no
reason to add K-500 for high stressed parts such as stems and hangers
at higher H2S levels than what is currently in the standard.
There are some reporting errors (e.g. H2S pp, duration of test) that need
3 Affirmative correcting.
This ballot meets all technical requirements for inclusion of this material
in the standard. If relevant failures exist, detailed information must be
brought forward to evaluate the merits of limiting use of this material. To
date, these failures have been mentioned anecdotally, but supporting
4 Affirmative details have not been available to fully evaluate. Interestingly, most of the
K500 failures cited for the rewrite of NACE MR0175-2003 have occurred
in internal valve parts, which is an application for which K500 is still
permitted with no restrictions (see Table A.35).
The additional laboratory test results and the revised serviceability limits
5 Affirmative argue for acceptance of the revised ballot proposal.
My negative vote has more formal reasons and is linked to the
chemistries of the UNS N 05500 heats, hardness and pH selected for the
test specimens / test environments. My interpretation of clause 8.3.2 -
Part 1- requires for the selection of the chemistries of the material a
representative range of the UNS range. My concern is that commercial
products may provide a chemistry above the median of the UNS number
element range but the tests indicate that the heats had almost the same
composition and were within the lower half of the UNS range. There is no
explanation why the chemistries were selected and what might be the
anticipated implication for the test result if the chemistry moves up to the
upper end, either way for Ni or Cu including the minor elements. The
6 Negative other reason is the proposed pH of pH 4.6 which is for me for practical
reasons not different than pH 4.5. In addition, the test used material with
a maximum hardness of HRC 33 but there is no reasonable justification
why HRC 35 was proposed for the standard. I feel very uncomfortable to
test a material at HRC 33 and permit the use of a higher hardness.
Because of that I can not vote positive.

Resolution: my vote can be changed if my interpretation of clause 8.3.2 is

not aligned with the general view of how the material is represented for
testing by the required 3 heats and if we found some justification for pH
4.6 vs pH 4.5 and HRC 35 / HRC 33. The hardness issue certainly will be
resolved by testing HCR 35 material.

3
Voter Vote Comments
I think we need to be careful in trying to relate lab data and field
experience within the rules of ISO 15156 - it is acceptable to propose an
alloy on the basis of lab data even if this would appear to contradict some
field experience. However reason for voting negative is that even if
testing was conducted in accordance with ISO 15156, have some
concerns that material under test fully meets the requirements of 8.3.2 of
7 Negative Part 1 - have we sufficient data to say that hardness levels per se do not
influence cracking susceptibility therefore it is acceptable to extrapolate
from 33HRC to 35HRC on basis of testing on lower hardness material
(similar issue with IMP Ballot 2007-04 for Alloy 945)? There is also
question that by only testing for GCSC we are penalizing material when
not subject to CP or coupling to carbon steel - the table makes no
reference to this.
I vote Negative for the following reasons: 1) No test results are presented
for material with 35 HRC. Maximum hardness tested is 33 HRC; 2)
Material was only tested in the hot rolled and aged condition. Material
conditions b) and c) in Table A.34 were not tested; 3) Chemical
compositions of the heats tested are almost identical. Is there evidence to
support that these test samples are representative of commercial product
available; i.e. reference Part 1 para. 8.3.2.
8 Negative Proposed resolution: 1) Test material having 35 HRC maximum or
change proposed ballot hardness to 33 HRC; 2) test material conditions
b) and c) in Table A.34 or justify why the material in the tested condition
has the greatest susceptibility to cracking in H2S service when compared
to the other conditions listed in the table; 3) I think that we, MP, need to
reach a consensus on the interpretation of Part 1 para. 8.3.2 to be able to
make a decision on whether or not the materials tested are
representative of what is commercially available.
I do not see why we have to squeeze this material into the table when the
"field experience" has proven that it has a high failure potential. The
chemistry of this alloy (similar to that of the new 945) has been designed
to perfection and I appreciate the amount of work that this took. However,
there is no re-assurance that this carefully designed metallurgy is
repeatable in the mills.
9 Negative
I also believe that the option for using "field experience" when selecting
materials that are not in the tables is best used for controversial materials
such as this one.

I do appreciate the presence of the pH value though…

4
Voter Vote Comments
Very interesting discussion, sorry for the Monel.
As some other voting members already mentioned, there is an open
thread in the standard about admission of either laboratory tested or field
experienced cases. Particularly when field experience is negative as in
this case.

Support for proposed ballot is an important piece of work and merit

should have to be recognized. The only point against is that is not
covering the total range of chemistries as defined in the UNS number and
industrially available hardness. Also I assume that all material tested was
10 Negative of a single manufacturing route (and even manufacturer). Therefore,
under this basis, only what was successfully tested can be admitted. I
understand this was not the case in the past for many other materials
today within the standard, but this logic rule needs to start to be applied.
The field failures might have had a reason. Failure mechanisms and
unsafe conditions, both in material and environment side, should have to
be investigated as to verify that the proposal ballot is not failing. This
would be the ideal case, but I am not sure if there is documented
evidence to build such verification. In such a case this group should have
to ignore it and stay to what is written in the standard (or propose a
modification to it).
I think that it is necessary to have test results of K-500 with 35 HRC. Or it
11 Negative is necessary to change the proposed ballot maximum hardness to 33
HRC.
The maximum hardness value in the standard can only reflect the value
of the tested material. So 35 HRC cannot replace 33 HRC.
The discussion about the range of chemistries is also important. I believe
not only chemistry must reflect materials used in the field but also
12 Negative microstructure ... I know that this is not asked for in the current ballots but
we should decide if it needs to be in future test ballots.

We all know that when we test materials all metallurgical parameters can
be of importance and that they must be documented as well as possible.
There is no evidence presented to support that the 107 C temperature of
hydrogen charging results in the most severe charging of the material.
13 Negative Yet since this charging mechanism seems to be the basis for inclusion of
the alloy. The maximum allowable temperature should be 107 C unless it
can be demonstrated that peak charging occurs here.
14 Did Not Vote
First Vote Result: Fail
Affirmative 31% (Required 80% of votes cast)

5
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

Ballot 2006-04 (Revised)

FORM 1 – BALLOT ITEM FOR NACE MR0175/ISO 15156 (Latest Edition)

SUBMITTING COMPANY: Honeywell Process Solutions (previously InterCorr) for JIP Group

SUBMITTED BY: Dr. Russell D. Kane

MAILING ADDRESS: 14503 Bammel N. Houston Road, Suite 300; Houston, TX 77014 USA

TELEPHONE NUMBER: +1-281-444-2282 Ext 32.

EMAIL: [email protected]

MATERIAL: Nickel-Based Precipitation Hardened (Nickel – Copper) Alloy

UNS NUMBER: UNS N05500 (Alloy K-500)

SUGGESTED ALTERATION To NACE MR0175/ISO 15156-3 (latest edition)

Modification of Table A.34 to include expanded serviceability limits as given below (in red):

Table A.34 - Environment and materials limits for precipitation-hardened nickel-based alloys used for
wellhead and christmas tree components (excluding bodies and bonnets), valve and choke components
and downhole equipment internal components

Individual Temperature Partial Chloride pH Sulfur Remarks

alloy UNS Pressure Conc. Resistant
Number Max. H2S, pH2S ?
C (F) Max. Max.
kPa (psi) mg/l
N05500 See remarks 3,4 (0,5) See > 4,5 NDSa Any combination of
remarks temperature and chloride
concentration occurring in
production environments
are acceptable
N05500 See remarks 104 (15) 50,000 > 4.6 Not Temperatures occurring in
Tested production environments
are acceptable.
For these applications, this material shall also comply with the following:
Wrought UNS N05500 shall have a maximum hardness of 35 HRC and shall be either:
a) hot-worked and age-hardened,
b) solution annealed, or
c) solution-annealed and age-hardened.
a
No data submitted to ascertain whether these materials are acceptable for service in the presence of
elemental sulfur in the environment.

6
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

MATERIAL DESCRIPTION

UNS N05500 is a nickel-base (nickel-copper), precipitation hardenable, wrought corrosion resistant alloy
intended for use in critical applications and/or severe environments requiring high strength and corrosion
resistance with resistance to environmental cracking in environments containing carbon dioxide, hydrogen
sulfide and chloride. This material is typically supplied to a specified minimum yield strength of 100,000
psi (690 MPa); minimum elongation of 20 percent and hardness in the range of 28-35 HRC.

APPLICATION

The material is suited for any equipment or components intended for sour service in oil and gas
production. Examples of, but not limited to, components that can be manufactured with UNS N05500
(Alloy K-500) are found in equipment such as packers, hangers, valve stems and tubular components
found in downhole, wellhead, Christmas tree components.

SERVICE CONDITIONS

NA – Field experience not used as a basis for balloting.

MECHANISM OF CRACKING

A literature survey was conducted to document the relevant mechanism(s) of cracking found in UNS
N05500 in oilfield service and related laboratory test environments. A summary of this data is found in
Appendix I. It shows that the relevant cracking mechanism is hydrogen embrittlement resulting from
cathodic charging or galvanic coupling (GHSC) with a more active material such as steel. Hydrogen
embrittlement is most prevalent at temperatures around room temperature and in cold worked material.
No cases of stress corrosion cracking (SCC) or sulfide stress cracking (SSC) were identified for this
material except where cold worked or cold worked and aged material was indicated, which is outside the
scope of this ballot.

The test utilized by the original 2006 ballot for N05500 involved use of steel coupled C-rings exposed to a
sour environment at 23 C to generate data on GHSC specifically per the procedures given in the NACE
MR0175 / ISO 15156 document (Type 3 GHSC Test).

Discussions with the Maintenance Panel members since the initial ballot results for this material in 2006
has indicated that there is some concern that the conventional tests given in NACE TM0177 and test
conditions cited in NACE MR0175 / ISO 15156 for the GHSC mechanism may not properly simulate
conditions that may have resulted in a particular series of failures of UNS N05500 components
experienced in the late-1980’s. Alternatively, some panel members felt that these field failures may have
been caused by problems with the composition and/or processing of specific heats of UNS N05500.

To respond to the abovementioned concerns, it was decided to develop a two-step test modified Type 3
GHSC test sequence for additional testing that included:
1. Exposure of stressed specimens to a sour environment at moderately high temperature to
produce a more severe condition of hydrogen charging in the metal.
2. Subsequent exposure of the stressed and hydrogen charged specimens at near ambient
temperature for a prolonged period.
3. Use of notched specimens to localize the effect of hydrogen in the material at a point of stress
concentration.

This multi-step test sequence is predicated on the extremely low diffusivity of hydrogen at the normal
testing temperature (23 C) and that even if substantial hydrogen was generated by galvanic coupling, the
bulk material may not have been exposed to hydrogen charging conditions. It is believed that at a higher

7
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

test temperature (107 C) will promote generation of atomic hydrogen on the steel coupled test specimens
and diffusion of the hydrogen into the metal lattice at the higher temperature. Secondly, the subsequent
exposure of the stressed and hydrogen charged test specimens to the lower temperature condition, is
designed to test the material at a temperature were its susceptibility should be greatest (23 C).

FIELD HISTORY

See summary provided in Appendix I for support of applicable cracking mechanism, not for actual field
data for balloting purposes.

8
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

FORM 1-BALLOT ITEM FOR NACE MR0175/ISO 15156 (latest edition)

LABORATORY DATA SUMMARY

Type 3 GHSC Test with test conditions per Paragraph B 3.5.3 in NACE MR0175 / ISO 15156
(Environments given below) NACE Standard TM0177 Method C (C-ring) with steel couple.

Modified Type 3 GHSC Tests. Same as Type 3 GHSC except two-step exposure sequence using notched
C-ring specimens with steel couple: 30 days at elevated temperature (107 C) followed by 30 days at
ambient temperature (23 C) while exposure to the test environment for the total 60 day duration.

ENVIRONMENTS

Test 1 – (Type 3 GHSC) Autoclave test – 50 psia (345 kPa) H2S, 50,000 ppm chloride, pH 4.5 (final pH
4.7), 23 C, specimens continuously coupled to steel.

2L liters of brine were prepared 165 g of NaCl (50,000 ppm chloride) and 0.36 g NaC2H3O2+3H2O to
1835 ml of DI water; pH 4.5 adjusted with either HCl or NaOH, and saturated at room temperature with
345 kPa H2S.

Test 2 – (Type 3 GHSC) Autoclave test – 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 4.5 (final pH
4.7), 23 C, specimens continuously coupled to steel.

2L liters of brine were prepared by adding 165 g of NaCl (50,000 ppm chloride) and 0.74 g
NaC2H3O2+3H2O to 1834 mL of DI water; pH 4.5 adjusted with either HCl or NaOH, and saturated at
room temperature with 690 kPa H2S.

Test 3 – (Type 3 GHSC) Autoclave test – 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 3.5 (final pH
3.6), 23 C, specimen was continuously coupled to steel.

2L liters of brine were prepared by adding 165 g of NaCl (50,000 ppm chloride), 4.6 g glacial acetic acid,
and 13.3 g NaC2H3O2+3H2O to 1834 ml of DI water (pH was adjusted to 3.5 with addition of HCl or
NaOH, and saturated at room temperature with 690 kPa H2S.

Test 4 – (Modified Type 3 GHSC) Autoclave test – 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 3.5
(final pH 4.6), specimen was continuously coupled to steel. Test ran for 30 days at 107 C followed by 30
days at 23 C with galvanic coupling to steel and stress for entire 60 day duration.

2L liters of brine were prepared by adding 165 g of NaCl (50,000 ppm chloride), 4.6 g glacial acetic acid,
and 13.3 g NaC2H3O2 + 3H2O (trihydrate) to 1834 mL of DI water (pH to 3.5 after adding the HCl and
NaOH, and saturated at room temperature with 104 kPa H2S.

MECHANISM(S) OF CRACKING
Hydrogen embrittlement was identified as the applicable cracking mechanism for UNS N05500 (See
Appendix I). Also note previous discussion of cracking mechanism and the development of test sequence
for Test 4 (Modified Type 3 GHSC Test).

SELECTION, SAMPLING, AND PREPARATION OF TEST SPECIMENS

Specimens were machined into C-rings from bar stock with only 0.0625 inch removed from O.D. Three
specimens were taken from each of three heats selected from approximately 50 candidate heats available
from multiple commercial suppliers at the start of the test program.

Heats were selected to cover the allowable range of available hardness from commercial heats covering
those in the supplied hardness range of HRC 28 to 35. Materials tested were in the hardness range HRC
30 to 33 made by the acceptable processing methods given in NACE MR0175/ISO 15156 (hot-worked

9
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

and age-hardened, solution annealed, or solution-annealed and age-hardened – excluding cold worked
and cold worked and aged).

When the original introduction of N05500 was made into MR0175 it appears that other forms of material
processing (e.g. full solution annealing before aging versus low temperature, mill annealing and aging that
is used most prevalently today, or limited cold working followed by aging) were being used that promoted
generally higher hardness values.

The results from the tests in this ballot are considered representative of materials presently manufactured
according to the acceptable processing methods state in this standard and in the specified hardness
range (HRC 28 to 35).

C-ring specimens were machined per requirements given in Appendix II. NACE TM0177 Method C. The
general requirements for these tests were those found in NACE MR0175/ISO 15156 Annex B.

JUSTIFICATION OF THE TEST ENVIRONMENT AND PHYSICAL TEST CONDITIONS

The environments chosen were based on a review of test data from the literature (See Appendix I). Based
on a relevant cracking mechanism of hydrogen embrittlement, the tests were conducted at room
temperature (23 C) – i.e. acknowledged worst case for hydrogen embrittlement – with the test specimens
continuously coupled to steel. The stress level was chosen to be 100 percent of actual yield stress (AYS)
as required by NACE MR0175/ISO 15156 Annex B.

The actual test environments were based on additions of H2S to attain specific partial pressures of H2S
into a solution of defined chloride concentration (with addition of NaCl). The pH of 4.5 and buffering was
derived using additions of sodium acetate with the pH adjusted to the required value with the addition of
HCl or NaOH. The pH of 3.5 was attained with additions of glacial acetic acid and sodium acetate with
adjustment to the initial pH with additions of HCl or NaOH.

Also, please note previous discussion of cracking mechanism as justification for use of modified Type 3
GHSC procedure.

TEST RESULTS DEMONSTRATING COMPLIANCE WITH NACE MR0175/ISO 15156

No failures were observed based on four sets of tests (three using the standard Type 3 GHSC method
and one using a modified Type 3 GHSC method), each containing three specimens machined from three
heats of UNS N05500 (at maximum available hardness) continuously coupled to steel, thus
demonstrating resistance to GHSC per NACE MR0175/ISO 15156 Annex B and to GHSC resistance in
two step test sequence at high temperature (107 C) and low temperature (23 C). The details of the
material properties, composition and test data are shown in the Tables found in Appendix II.

APPENDIX I

Based on review the references cited below1-12, it was assessed that failure of UNS N05500 was mainly
due to the influence of hydrogen resulting from cathodic protection or galvanic couple to a more active
material such as steel.

Efird1 noted that failures were mostly apparent in materials involving cold working with hardness values
greater than HRC 35. An example of this is, the affect of cold working in thread roots of bolting material.

Work by Chance2 also identified cold working resulting of plastic deformation resulted in higher absorbed
hydrogen levels than normally processed material. The cold worked materials failed at 80 percent of YS
after 11 days under cathodic charging. Elevated hydrogen content levels were also observed which
increased with the degree of plastic deformation. Hydrogen content also increased with applied stress
level.

Harris7 showed that UNS N05500 exhibited loss of ductility in the slow strain rate test under cathodic
charging in seawater which was up to 90 percent after pre-exposure 30 days.

10
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

Pound8 identified that hydrogen embrittlement was a predominant environmental cracking mechanism for
UNS N05500.

The only data found for UNS N055009-11 actually exposed to H2S-containing test environments showed
that in the absence of steel coupling (cathodic charging), no failures were obtained when material
(HRC 32-37) was exposed in the following ranges of test conditions: 0.1 to 30 psia (0.7 to 207 kPa) H2S;
pH 3.5 to 5.0; >20,000 ppm chloride.

Additional data on UNS N05500 was found as a result of a literature and experience survey as part of a
major joint industry sponsored program.12 No failures were found in laboratory tests over the temperature
range from room temperature to 218 C when tested in saturated (100 kPa) H2S solutions brine solutions
(0, 1, 5 and 20 percent NaCl, 0.5% acetic acid) without steel coupling. Field failures in H2S applications in
wellhead and downhole components were all found to occur at low to intermediate temperatures (< 93 C)
which is consistent with a hydrogen embrittlement phenomenon.

References

1. K.D. Efird, “Failure of Monel Ni-Cu-Al Alloy K-500 Bolts in Seawater”, Materials Performance,
April 1985, pp. 676 – 679
2. M. R. Chance, “Hydrogen-Stress Relationships, Hydrogen in Metals in H2S-CO2-CH4-H2O
Environments”, H2S Corrosion in Oil and Gas Production – A Compilation of Papers, pp. 464 –
468
3. L. H. Wolfe, C. C. Burnette, M.W. Joosten, “Hydrogen Embrittlement of Cathodically Protected
Subsea Bolting Alloys, Corrosion 1993, Paper 288
4. P. W. Rice, “Evaluating Nickel Base and Stainless Alloys for Subsurface H2S Service”, H2S
Corrosion in Oil and Gas Production – A Compilation of Papers, pp.416 – 425
5. R. N. Tuttle, “Selection of Materials Designed for Use in a Sour Gas Environment”, H2S
Corrosion in Oil and Gas Production – A Compilation of Papers, pp. 159 – 161
6. G.B. Kohut, W.J. McGuire, “Sulfide Stress Cracking Causes Failure of Compressor Components
in Refinery Service”, H2S Corrosion in Oil and Gas Production – A Compilation of Papers, pp.
102-107.
7. J.A. Harris, E. F. Clatworthy, “Hydrogen Embrittlement of Incoloy Alloy 925, Monel Alloy K-500
and Inconel Alloy 625 by Slow Strain Method”, Corrosion 1986, Paper 150.
8. B. G. Pound, “Comparison of Hydrogen Trapping/Tensile Testing Correlations with Field Service
Results for Alloy K-500, Corrosion 1999, Paper 633.
9. E.L Hibner & C.S. Tassen, “Corrosion Resistance OCTG’S and Matching Age- Hardenable Bar
Products for a Range of Sour Gas Service Conditions “, Paper No 01102, Corrosion/2001.
10. Robert Mack, “Corrosion of Two Nickel-Copper Alloys in Simulated Sour Production
Environments”, Paper No 01098, Corrosion/2001.
11. R. D Kane, M. Kornmann, J.H. Payer, and W.K Boyd, “Guidelines for Selection of Materials for
H2S Services.” Vol 1 – Test Results, December 1981, pp 7-24.
12. R. D Kane, M. Kornmann, J.H. Payer, and W.K Boyd, “Guidelines for Selection of Materials for
H2S Services.” Vol 2 – Experience/Literature Survey, December 1981, pp 968-980.

11
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

APPENDIX II

TABLE 1 - NACE Uniform Material Testing Report Form (Part 1):

Testing in Accordance with NACE Standard TM0177(A)
Method C—NACE Standard C-Ring Test

Submitting Company: Honeywell Process Solutions (for JIP) Submittal Date: April 11, 2006
Submitted by: Dr. Russell D. Kane Telephone No: +1-281-444-2282 Ext 32 Testing Lab: Honeywell
(previously InterCorr)
Alloy Designation: UNS N05500 General Material Type: Precipitation-Hardened Nickel-Based Alloys

Heat Number/Identification

Composition #9640 #9654 #9655

C 0.13 0.12 0.127

Mn 0.65 0.59 0.65
Si 0.06 0.03 0.07
P 0.002 0.002 0.002
S 0.004 0.004 0.004
Ni 66.3 65.8 65.3
Cr -- -- --
Mo -- -- --
V -- -- --
Al 2.99 2.97 2.95
Ti 0.45 0.45 0.44
Nb -- -- --
N -- -- --
Cu 28.49 28.82 29.44
Other (Fe, Co) (0.80; 0.03) (1.06; 0.03) (0.91; 0.04)

Material Hot rolled Hot rolled Hot rolled

Processing History and age and age and age
Melt Practice (e.g., hardened hardened hardened
OH, BOF, EF, AOD)
(B)

Product Form 63.5 mm 50.8 mm 63.5 mm

O.D. Bar O.D. bar O.D. bar

Heat Treatment 595C/8 hrs 595C/8 hrs 595C/8 hrs >

(Specify time, > 12 C/hr to > 14 C/hr to 12 C/hr to
temperature, and 482 C/air 482 C/air 482 C/air
cooling mode for
each cycle in
process.)
Other Mechanical, None None None
Thermal, Chemical,
or Coating
Treatment(C)
(A)
Test method must be fully described if not in accordance with TM0177.
(B)
Melt practice: open-hearth (OH), basic oxygen furnace (BOF), electric furnace (EF), argon-oxygen decarburization
(AOD).
(C)
E.g., cold work, plating, nitriding, prestrain.

12
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

TABLE 2a - NACE Uniform Material Testing Report Form (Part 2):

Testing in Accordance with NACE Standard TM0177
Method C—NACE Standard C-Ring Test (Standard Type 3 GHSC Tests)

Lab Data for Material: UNS N00550_________________________________________________ Tested per NACE Standard TM0177-Method C (A)

Test Specimen Geometry: Outside Diameter #9640/9655: 60.3mm; #9654: 47.6 mm Wall/Thickness #9640/9655: 6.02 mm; #9654: 4.7 mm Width 15.9 mm
Test Equipment: Bolting Material Same as Specimen (C276 with TFE isolation)
Correction for 100% 0.2% Offset Yield Applied Stress Steel Couple (Area Ratio: approximately 1:1)

Chemistry: Test Solution A Test Solution B Test Solution C (define) Other Test Solution Env. #1 See Below(F)

Outlet Trap to Exclude Oxygen Temperature Maintained 24°C ±3°C (75°F ±5°F) Temperature Maintained ±3°C (±5°F)

Test Specimen Properties Applied Stress (% of Yield Strength) Test Solution Applied Remarks
pH(E) Heat (Including
Treatment Surface
Material Finish Condition and
Location(B)

Orientation(C)

( MPa)
Strength(D)

(MPa )
Strength
Tensile
Ultimate

(%)
Elongation

(%)
Area
Reduction In

( HRC)
Hardness
Identification 100 H2S Level)
Yield

Start(F)
-Specimen # AYS

Time-to-Failure (Hours)
NF = No Failure at 720 hours

9640-4 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack

9640-5 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack
9640-6 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack
9654-4 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9654-5 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9654-6 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9655-4 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
9655-5 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
9655-6 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
(A)
Test method must be fully described if not in accordance with NACE Standard TM0177.
(B)
Location of test specimen may be: tubulars—outside diameter (OD), midwall (MW), or inside diameter (ID); solids—surface (S), quarter-thickness (QT), midradius (MR), center (C), or edge (E).
(C)
Orientation may be longitudinal (L) or transverse (T).
(D)
Open parentheses must be filled with metric or English units, as appropriate to the data. Yield strength is assumed to be 0.2% offset unless otherwise noted.
(E)
Enter pH for test conducted on nonfailed C-ring test specimen at highest stress if summarizing data .
(F)
Env. #1: 50 psia (345 kPa) H2S, 50,000 ppm chloride, pH 4.5 (final pH 4.7), 23 C, specimens continuously coupled to steel.

13
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

TABLE 2b - NACE Uniform Material Testing Report Form (Part 2):

Testing in Accordance with NACE Standard TM0177
Method C—NACE Standard C-Ring Test (Standard Type 3 GHSC Tests)

Lab Data for Material: UNS N00550_________________________________________________ Tested per NACE Standard TM0177-Method C (A)

Test Specimen Geometry: Outside Diameter #9640/9655: 60.3mm; #9654: 47.6 mm Wall/Thickness #9640/9655: 6.02 mm; #9654: 4.7 mm Width 15.9 mm
Test Equipment: Bolting Material Same as Specimen (C276 with TFE isolation)
Correction for 100% 0.2% Offset Yield Applied Stress Steel Couple (Area Ratio: approximately 1:1)

Chemistry: Test Solution A Test Solution B Test Solution C (define) Other Test Solution Env.#2 See Below(F)

Outlet Trap to Exclude Oxygen Temperature Maintained 24°C ±3°C (75°F ±5°F) Temperature Maintained ±3°C (±5°F)

Test Specimen Properties Applied Stress (% of Yield Strength) Test Solution Applied Remarks
pH(E) Heat (Including
Treatment Surface
Material Finish Condition and
Location(B)

Orientation(C)

( MPa)
Strength(D)

(MPa )
Strength
Tensile
Ultimate

(%)
Elongation

(%)
Area
Reduction In

( HRC)
Hardness
Identification 100 H2S Level)
Yield

Start(F)
-Specimen # AYS

Time-to-Failure (Hours)
NF = No Failure at 720 hours

9640-7 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack

9640-8 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack
9640-9 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack
9654-7 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9654-8 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9654-9 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9655-7 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
9655-8 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
9655-9 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
(A)
Test method must be fully described if not in accordance with NACE Standard TM0177.
(B)
Location of test specimen may be: tubulars—outside diameter (OD), midwall (MW), or inside diameter (ID); solids—surface (S), quarter-thickness (QT), midradius (MR), center (C), or edge (E).
(C)
Orientation may be longitudinal (L) or transverse (T).
(D)
Open parentheses must be filled with metric or English units, as appropriate to the data. Yield strength is assumed to be 0.2% offset unless otherwise noted.
(E)
Enter pH for test conducted on nonfailed C-ring test specimen at highest stress if summarizing data .
(F)
Env. #2: Test 2 – Autoclave test – 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 4.5 (final pH 4.7), 23 C, specimens continuously coupled to steel.

14
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007

TABLE 2c - NACE Uniform Material Testing Report Form (Part 2):

Testing in Accordance with NACE Standard TM0177
Method C—NACE Standard C-Ring Test (Standard Type 3 GHSC Tests)

Lab Data for Material: UNS N00550_________________________________________________ Tested per NACE Standard TM0177-Method C (A)

Test Specimen Geometry: Outside Diameter #9640/9655: 60.3mm; #9654: 47.6 mm Wall/Thickness #9640/9655: 6.02 mm; #9654: 4.7 mm Width 15.9 mm
Test Equipment: Bolting Material Same as Specimen (C276 with TFE isolation)
Correction for 100% 0.2% Offset Yield Applied Stress Steel Couple (Area Ratio: approximately 1:1)

Chemistry: Test Solution A Test Solution B Test Solution C (define) Other Test Solution Env.#3 See Below(F)

Outlet Trap to Exclude Oxygen Temperature Maintained 24°C ±3°C (75°F ±5°F) Temperature Maintained ±3°C (±5°F)

Test Specimen Properties Applied Stress (% of Yield Strength) Test Solution Applied Remarks
pH(E) Heat (Including
Treatment Surface
Material Finish Condition and
Location(B)

Orientation(C)

( MPa)
Strength(D)

(MPa )
Strength
Tensile
Ultimate

(%)
Elongation

(%)
Area
Reduction In

( HRC)
Hardness
Identification 100 H2S Level)
Yield

Start(F)
-Specimen # AYS

Time-to-Failure (Hours)
NF = No Failure at 720 hours

9640-1 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 3.6 None No Pit / No Crack

9640-2 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 3.6 None No Pit / No Crack
9640-3 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 3.6 None No Pit / No Crack
9654-1 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 3.6 None No Pit / No Crack
9654-2 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 3.6 None No Pit / No Crack
9654-3 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 3.6 None No Pit / No Crack
9655-1 S Trans. 717.6 1097.1 24 41 32 NF 3.5 3.6 None No Pit / No Crack
9655-2 S Trans. 717.6 1097.1 24 41 32 NF 3.5 3.6 None No Pit / No Crack
9655-3 S Trans. 717.6 1097.1 24 41 32 NF 3.5 3.6 None No Pit / No Crack
(A)
Test method must be fully described if not in accordance with NACE Standard TM0177.
(B)
Location of test specimen may be: tubulars—outside diameter (OD), midwall (MW), or inside diameter (ID); solids—surface (S), quarter-thickness (QT), midradius (MR), center (C), or edge (E).
(C)
Orientation may be longitudinal (L) or transverse (T).
(D)
Open parentheses must be filled with metric or English units, as appropriate to the data. Yield strength is assumed to be 0.2% offset unless otherwise noted.
(E)
Enter pH for test conducted on non-failed C-ring test specimen at highest stress if summarizing data .
(F)
Env. #3: 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 3.5 (final pH 3.6), 23 C, specimen was continuously coupled to steel.

15
 Honeywell Process Solutions
Alloy K-500 (UNS N05500) Ballot – June 25, 2007
TABLE 2b - NACE Uniform Material Testing Report Form (Part 2):
Testing in Accordance with NACE Standard TM0177
Method C—NACE Standard C-Ring Test (NOTE: Modified Type 3 GHSC Test using a Notched C-Ring Specimen)

Lab Data for Material: UNS N00550_________________________________________________ Tested per NACE Standard TM0177-Method C (A)

Test Specimen Geometry: Outside Diameter #9640/9655: 60.3mm; #9654: 47.6 mm Wall/Thickness #9640/9655: 6.02 mm; #9654: 4.7 mm Width 15.9 mm
Test Equipment: Bolting Material Same as Specimen (C276 with TFE isolation)
Correction for 100% 0.2% Offset Yield Applied Stress Steel Couple (Area Ratio: approximately 1:1)

Chemistry: Test Solution A Test Solution B Test Solution C (define) Other Test Solution Env.#2 See Below(F)

Outlet Trap to Exclude Oxygen Temperature Maintained 107 ±3°C (225 F ±5°F) for 30 days followed by 24°C ±3°C (75°F ±5°F) for 20 days

Test Specimen Properties Applied Stress (% of Yield Strength) Test Solution Applied Remarks
pH(E) Heat (Including
Treatment Surface
Material Finish Condition and
Location(B)

Orientation(C)

( MPa)
Strength(D)

(MPa )
Strength
Tensile
Ultimate

(%)
Elongation

(%)
Area
Reduction In

( HRC)
Hardness
Identification 100 H2S Level)
Yield

Start(F)
-Specimen # AYS

Time-to-Failure (Hours)
NF = No Failure at 720 hours

9640-10 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 4.6 None No Pit / No Crack

9640-11 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 4.6 None No Pit / No Crack
9640-12 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 4.6 None No Pit / No Crack
9654-10 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 4.6 None No Pit / No Crack
9654-11 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 4.6 None No Pit / No Crack
9654-12 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 4.6 None No Pit / No Crack
9655-10 S Trans. 717.6 1097.1 24 41 32 NF 3.5 4.6 None No Pit / No Crack
9655-11 S Trans. 717.6 1097.1 24 41 32 NF 3.5 4.6 None No Pit / No Crack
9655-12 S Trans. 717.6 1097.1 24 41 32 NF 3.5 4.6 None No Pit / No Crack
(A)
Test method must be fully described if not in accordance with NACE Standard TM0177. NOTE: Included a 5% Charpy V-notch at the location of maximum stress.
(B)
Location of test specimen may be: tubulars—outside diameter (OD), midwall (MW), or inside diameter (ID); solids—surface (S), quarter-thickness (QT), midradius (MR), center (C), or edge (E).
(C)
Orientation may be longitudinal (L) or transverse (T).
(D)
Open parentheses must be filled with metric or English units, as appropriate to the data. Yield strength is assumed to be 0.2% offset unless otherwise noted.
(E)
Enter pH for test conducted on nonfailed C-ring test specimen at highest stress if summarizing data .
(F)
Env. #2: Test 2 – Autoclave test – 15 psia (104 kPa) H2S, 50,000 ppm chloride, pH 3.5 (final pH 4.6), 107 C followed by 23 C, specimens continuously coupled to steel.

16
Earlier ballot history for IMP Ballot 2006-04 (2006-06-26)

Votes and comments of the ISO 15156 Maintenance Panel on original

Ballot 2006-04 and resolution of negatives
Affirmative(Y)/
Voter Negative(N)/ Comments Status/Action
Abstain(A)
I vote negative. I agree that hydrogen embrittlement is the most
likely cause of many past failures of K500. I also think that this
failure mode may occur in some H2S environments (subsea under
C/P for instance). There are many unresolved issues with past K500
failures. I am not comfortable accepting lab data as a true indicator
1 N of field performance for this alloy until these field failures are better
understood. There are now several high strength Ni alloys that have
been thoroughly proven in H2S environments that are superioir
substitutes to K500. I see no overriding need to take a chance with
K500 at the proposed environmental limits.
I vote negative. I have discussed this with Voter 1in detail and
agree with him on this issue Hydrogen embrittlement is the most
likely cause of many past failures of K500. I am also not
comfortable accepting lab data as a true indicator of field
2 N performance for this alloy until these field failures are better
understood. There are now several high strength Ni alloys that have
been thoroughly proven in H2S environments that are superioir
substitutes to K500. I see no overriding need to take a chance with
K500 at the proposed environmental limits.
The vote on the K500 is difficult.
The balloter correctly identifies galvanic coupling as being the
critical cracking parameter. Hydrogen cracking is the mode of
failure.
Cracking requires the following steps:
1. Hydrogen charging from the galvanic current
2. Hydrogen diffusion into the alloy
3. Cracking in the alloy
The first two steps are independent from the last step. Charging will
occur at all temperatures, but diffusion is best at high temperature.
Dislocation transport is also a significant factor.
Cracking occurs at the lower temperature. However, in K500,
cracking is not as temperature sensitive as steel. Cracking still
3 A occurs by hydrogen at quite elevated temperatures.
Thus, charging and cracking at the same temperature may not be
the critical condition.
Why all this rhetoric? It is not clear that the data supplied qualifies
the K500 to all conditions of pH and temperature. The amount of
charging is pH dependent. The corrosion rate of steel is related to
the pH. Charging is related to Current to the 0.5 power.
In other words, the situation for K500 was treated like steel, and it
is quite different from steel.
I choose to abstain from this vote.

PS: The data shows that cracking in the absence of steel coupling is
minimal. Why do we not include K500 into those applications where
galvanic coupling does not occur?
4 N I agree with Voters 1 and 2.

As the ballot author suggested, N05500 has resistance to

environmental cracking containing CO2, H2S and Chlorides.

However, TM0177 was never intended for Hydrogen embrittlement

assessment which was identified as the primary cracking

17
 mechanism for this material. The galvanic couple with iron will
increase SSC in materials exposed to CO2, H2S and Chlorides.
However, the H charging will be depleted by the formation of scale.
(The higher the temperature the faster the scale formation). It is
obvious that the alloy will "pass" this test.

What we need to find is the threshold for H2 embrittlement for this

material.
If the alloy is cathodic then no significant scale should form, in
addition the evolution of hydrogen should disrupt the scale,
therefore I do not entirely agree with Irina.
5 N
However I vote negative as there is not sufficient data included to
include the alloy under the conditions proposed.
I feel there hasn't been sufficient testing data provided to accept
the ballot. However, the ballot author has made a bonafide effort to
comply with the testing requirements currently in the standard.
I feel uncomfortable about taking the position that the data supplied
is insufficient and not providing guidance on what additional testing
6 A or use restrictions would be required for acceptance.
PS: I am aware of a K500 failure downhole where high temperature
corrosion occurred. There was no cracking but high H2S and the
high copper content of K500 were presumed to be major
contributors to the unusually severe corrosion.
Abstain

I think we need to discuss the case of this material. The data are
7 A good but if there are issues that have been missed for the
introduction of this material they should be discussed in the MP
first.
8 A I agree with Voter 7
9 A I think we need to discuss K500 before voting.
Abstain - this is more or less a no-vote, because I think we should
have a discussion regarding K500 and judge the provided data
10 A before we vote on this subject. For the time being I am not
comfortable with any of the voting options.
Well out of time today, but it appears there is not much point in
11 A voting on this one anyway. Look forward to the discussions at the
next meeting.
I am concerned that the ballot claims a hardness limit of HRC 35
12 N when the hardest material tested was HRC 33. I am uncertain of
the importance of hardness over this limited range.
13 N I vote negative. I am concerned by the many issues raised by
abstaining voters, and some of those arguments seemed sufficiently
convincing to support a negative vote.

Voter 3's comments in particular caused me to look back through our

records of past failure investigations. I discovered many more than I
expected, dating from the mid to late 1980s. The majority of these
involve downhole equipment, where the temperature is elevated, and
the fracture mode is intergranular. It was common then as it still is
today that often these CRA pieces of downhole equipment are
galvanically coupled to lower alloyed tubing strings.

Three failure analyses in particular were conducted between 1986

and 1987 and were related by being in the same field. The H2S levels
reported by the end user during these investigations varied from
"none" to "low" to specifically 0.34 psi partial pressure. The CO2
varied from about 10% to 37%. The temperature was 120 C. The K-
500 equipment was coupled to martensitic stainless steels, but in
each case, the K-500 was actively corroding as evident by sulfidic

18
 corrosion scales. Active corrosion of the K-500 raises some doubt as
to the contribution of galvanic charging. But nevertheless these
factors suggest to me that Voter 3's comments about elevated
temperature charging, diffusion, and cracking are founded, and
indeed the susceptibility to cracking may be higher here than at room
temperature.

I cannot propose a reasonable resolution to my negative, other than

to suggest that more tests be done that must also replicate failures in
order to clarify the fracture mechanism. It is not reasonable to limit
the use of this material to room temperature, where the testing has
been conducted.

Result: Fail
Affirmative 0% (Required 80% of votes cast)

19
Proposed amendment to ISO 15156-3 as submitted to ISO 15156 Maintenance
Panel
FORM 1 – BALLOT ITEM FOR NACE MR0175/ISO 15156 (Latest Edition)

SUBMITTING COMPANY: Honeywell Process Solutions (previously InterCorr) for JIP Group

SUBMITTED BY: Dr. Russell D. Kane

MAILING ADDRESS: 14503 Bammel N. Houston Road, Suite 300; Houston, TX 77014 USA

TELEPHONE NUMBER: +1-281-444-2282 Ext 32.

EMAIL: [email protected]

MATERIAL: Nickel-Based Precipitation Hardened (Nickel – Copper) Alloy

UNS NUMBER: UNS N05500 (Alloy K-500)

SUGGESTED ALTERATION To NACE MR0175/ISO 15156-3 (latest edition)

Modification of Table A.34 to include expanded serviceability limits as given below (in red):

Table A.34 - Environment and materials limits for precipitation-hardened nickel-based alloys used for
wellhead and christmas tree components (excluding bodies and bonnets), valve and choke components
and downhole equipment internal components

Individual Temperature Partial Chloride pH Sulfur Remarks

alloy UNS Pressure Conc. Resistant
Number Max. H2S, pH2S ?
C (F) Max. Max.
kPa (psi) mg/l
N05500 See remarks 3,4 (0,5) See > 4,5 NDSa Any combination of
remarks temperature and chloride
concentration occurring in
production environments
are acceptable
N05500 See remarks 690 (100) 50 000 > 3.6 Not Temperatures occurring in
Testeda production environments
are acceptable.
For these applications, this material shall also comply with the following:
Wrought UNS N05500 shall have a maximum hardness of 35 HRC and shall be either:
a) hot-worked and age-hardened,
b) solution annealed, or
c) solution-annealed and age-hardened.
a
No data submitted to ascertain whether these materials are acceptable for service in the presence of
elemental sulfur in the environment.

20
MATERIAL DESCRIPTION

UNS N05500 is a nickel-base (nickel-copper), precipitation hardenable, wrought corrosion resistant alloy
intended for use in critical applications and/or severe environments requiring high strength and corrosion
resistance with resistance to environmental cracking in environments containing carbon dioxide, hydrogen
sulfide and chloride. This material is typically supplied to a specified minimum yield strength of 100,000
psi (690 MPa); minimum elongation of 20 percent and hardness in the range of 28-35 HRC.

APPLICATION

The material is suited for any equipment or components intended for sour service in oil and gas
production. Examples of, but not limited to, components that can be manufactured with UNS N05500
(Alloy K-500) are found in equipment such as packers, hangers, valve stems and tubular components
found in downhole, wellhead, Christmas tree components.

SERVICE CONDITIONS

NA

MECHANISM OF CRACKING

A literature survey was conducted to document the relevant mechanism(s) of cracking found in UNS
N05500 in oilfield service and related laboratory test environments. A summary of this data is found in
Appendix I. It shows that the relevant cracking mechanism is hydrogen embrittlement resulting from
cathodic charging or galvanic coupling (GHSC) with a more active material such as steel. Hydrogen
embrittlement is most prevalent at temperatures around room temperature and in cold worked material.
No cases of stress corrosion cracking (SCC) or sulfide stress cracking (SSC) were identified for this
material except where cold worked or cold worked and aged material was indicated, which is outside the
scope of this ballot.

FIELD HISTORY

See summary provided in Appendix I for support of applicable cracking mechanism, not for actual field
data for balloting purposes.

21
 FORM 1-BALLOT ITEM FOR NACE MR0175/ISO 15156 (latest edition)

LABORATORY DATA SUMMARY

Test Type: Type 3 GHSC Test with test conditions per Paragraph B 3.5.3 (Environments given below)
NACE Standard TM0177 Method C (C-ring) with steel couple.

ENVIRONMENTS

Test 1 – Autoclave test – 50 psia (345 kPa) H2S, 50,000 ppm chloride, pH 4.5 (final pH 4.7), 23 C,
specimens continuously coupled to steel.

2L liters of brine were prepared 165 g of NaCl (50,000 ppm chloride) and 0.36 g NaC2H3O2+3H2O to
1835 ml of DI water; pH 4.5 adjusted with either HCl or NaOH, and saturated at room temperature with
345 kPa H2S.

Test 2 – Autoclave test – 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 4.5 (final pH 4.7), 23 C,
specimens continuously coupled to steel.

2L liters of brine were prepared by adding 165 g of NaCl (50,000 ppm chloride) and 0.74 g
NaC2H3O2+3H2O to 1834 mL of DI water; pH 4.5 adjusted with either HCl or NaOH, and saturated at
room temperature with 690 kPa H2S.

Test 3 – Autoclave test – 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 3.5 (final pH 3.6), 23 C,
specimen was continuously coupled to steel.

2L liters of brine were prepared by adding 165 g of NaCl (50,000 ppm chloride), 4.6 g glacial acetic acid,
and 13.3 g NaC2H3O2+3H2O to 1834 ml of DI water (pH was adjusted to 3.5 with addition of HCl or
NaOH, and saturated at room temperature with 690 kPa H2S.

MECHANISM(S) OF CRACKING
Hydrogen embrittlement was identified as the applicable cracking mechanism for UNS N05500 (See
Appendix I).

SELECTION, SAMPLING, AND PREPARATION OF TEST SPECIMENS

Specimens were machined into C-rings from bar stock with only 0.0625 inch removed from O.D. Three
specimens were taken from each of three heats selected from approximately 50 candidate heats available
from multiple commercial suppliers at the start of the test program.

Heats were selected to cover the allowable range of available hardness from commercial heats covering
those in the supplied hardness range of HRC 28 to 35. Materials tested were in the hardness range HRC
30 to 33 made by the acceptable processing methods given in NACE MR0175/ISO 15156 (hot-worked
and age-hardened, solution annealed, or solution-annealed and age-hardened – excluding cold worked
and cold worked and aged).

When the original introduction of N05500 was made into MR0175 it appears that other forms of material
processing (e.g. full solution annealing before aging versus low temperature, mill annealing and aging that
is used most prevalently today, or limited cold working followed by aging) were being used that promoted
generally higher hardness values.

The results from the tests in this ballot are considered representative of materials presently manufactured
according to the acceptable processing methods state in this standard and in the specified hardness
range (HRC 28 to 35).

C-ring specimens were machined per requirements given in Appendix II. NACE TM0177 Method C. The
general requirements for these tests were those found in NACE MR0175/ISO 15156 Annex B.

22
JUSTIFICATION OF THE TEST ENVIRONMENT AND PHYSICAL TEST CONDITIONS
The environments chosen were based on a review of test data from the literature (See Appendix I). Based
on a relevant cracking mechanism of hydrogen embrittlement, the tests were conducted at room
temperature (23 C) – i.e. acknowledged worst case for hydrogen embrittlement – with the test specimens
continuously coupled to steel. The stress level was chosen to be 100 percent of actual yield stress (AYS)
as required by NACE MR0175/ISO 15156 Annex B.

The actual test environments were based on additions of H2S to attain specific partial pressures of H2S
into a solution of defined chloride concentration (with addition of NaCl). The pH of 4.5 and buffering was
derived using additions of sodium acetate with the pH adjusted to the required value with the addition of
HCl or NaOH. The pH of 3.5 was attained with additions of glacial acetic acid and sodium acetate with
adjustment to the initial pH with additions of HCl or NaOH.

TEST RESULTS DEMONSTRATING COMPLIANCE WITH NACE MR0175/ISO 15156

No failures were observed based on three sets of tests, each containing three specimens machined from
three heats of UNS N05500 (at maximum hardness available) continuously coupled to steel, thus
demonstrating resistance to GHSC per NACE MR0175/ISO 15156 Annex B. The details of the material
properties, composition and test data are shown in the Tables found in Appendix II.

APPENDIX I

Based on review the references cited below1-12, it was assessed that failure of UNS N05500 was mainly
due to the influence of hydrogen resulting from cathodic protection or galvanic couple to a more active
material such as steel.

Efird1 noted that failures were mostly apparent in materials involving cold working with hardness values
greater than HRC 35. An example of this is, the affect of cold working in thread roots of bolting material.

Work by Chance2 also identified cold working resulting of plastic deformation resulted in higher absorbed
hydrogen levels than normally processed material. The cold worked materials failed at 80 percent of YS
after 11 days under cathodic charging. Elevated hydrogen content levels were also observed which
increased with the degree of plastic deformation. Hydrogen content also increased with applied stress
level.

Harris7 showed that UNS N05500 exhibited loss of ductility in the slow strain rate test under cathodic
charging in seawater which was up to 90 percent after pre-exposure 30 days.

Pound8 identified that hydrogen embrittlement was a predominant environmental cracking mechanism for
UNS N05500.

The only data found for UNS N055009-11 actually exposed to H2S-containing test environments showed
that in the absence of steel coupling (cathodic charging), no failures were obtained when material
(HRC 32-37) was exposed in the following ranges of test conditions: 0.1 to 30 psia (0.7 to 207 kPa) H2S;
pH 3.5 to 5.0; >20,000 ppm chloride.

Additional data on UNS N05500 was found as a result of a literature and experience survey as part of a
major joint industry sponsored program.12 No failures were found in laboratory tests over the temperature
range from room temperature to 218 C when tested in saturated (100 kPa) H2S solutions brine solutions
(0, 1, 5 and 20 percent NaCl, 0.5% acetic acid) without steel coupling. Field failures in H2S applications in
wellhead and downhole components were all found to occur at low to intermediate temperatures (< 93 C)
which is consistent with a hydrogen embrittlement phenomenon.

References

23
13. K.D. Efird, “Failure of Monel Ni-Cu-Al Alloy K-500 Bolts in Seawater”, Materials Performance,
April 1985, pp. 676 – 679
14. M. R. Chance, “Hydrogen-Stress Relationships, Hydrogen in Metals in H2S-CO2-CH4-H2O
Environments”, H2S Corrosion in Oil and Gas Production – A Compilation of Papers, pp. 464 –
468
15. L. H. Wolfe, C. C. Burnette, M.W. Joosten, “Hydrogen Embrittlement of Cathodically Protected
Subsea Bolting Alloys, Corrosion 1993, Paper 288
16. P. W. Rice, “Evaluating Nickel Base and Stainless Alloys for Subsurface H2S Service”, H2S
Corrosion in Oil and Gas Production – A Compilation of Papers, pp.416 – 425
17. R. N. Tuttle, “Selection of Materials Designed for Use in a Sour Gas Environment”, H2S
Corrosion in Oil and Gas Production – A Compilation of Papers, pp. 159 – 161
18. G.B. Kohut, W.J. McGuire, “Sulfide Stress Cracking Causes Failure of Compressor Components
in Refinery Service”, H2S Corrosion in Oil and Gas Production – A Compilation of Papers, pp.
102-107.
19. J.A. Harris, E. F. Clatworthy, “Hydrogen Embrittlement of Incoloy Alloy 925, Monel Alloy K-500
and Inconel Alloy 625 by Slow Strain Method”, Corrosion 1986, Paper 150.
20. B. G. Pound, “Comparison of Hydrogen Trapping/Tensile Testing Correlations with Field Service
Results for Alloy K-500, Corrosion 1999, Paper 633.
21. E.L Hibner & C.S. Tassen, “Corrosion Resistance OCTG’S and Matching Age- Hardenable Bar
Products for a Range of Sour Gas Service Conditions “, Paper No 01102, Corrosion/2001.
22. Robert Mack, “Corrosion of Two Nickel-Copper Alloys in Simulated Sour Production
Environments”, Paper No 01098, Corrosion/2001.
23. R. D Kane, M. Kornmann, J.H. Payer, and W.K Boyd, “Guidelines for Selection of Materials for
H2S Services.” Vol 1 – Test Results, December 1981, pp 7-24.
24. R. D Kane, M. Kornmann, J.H. Payer, and W.K Boyd, “Guidelines for Selection of Materials for
H2S Services.” Vol 2 – Experience/Literature Survey, December 1981, pp 968-980.

24
 APPENDIX II

TABLE 1 - NACE Uniform Material Testing Report Form (Part 1):

Testing in Accordance with NACE Standard TM0177(A)
Method C—NACE Standard C-Ring Test

Submitting Company: Honeywell Process Solutions (for JIP) Submittal Date: April 11, 2006
Submitted by: Dr. Russell D. Kane Telephone No: +1-281-444-2282 Ext 32 Testing Lab: Honeywell
(previously InterCorr)
Alloy Designation: UNS N05500 General Material Type: Precipitation-Hardened Nickel-Based Alloys

Heat Number/Identification

Composition #9640 #9654 #9655

C 0.13 0.12 0.127

Mn 0.65 0.59 0.65
Si 0.06 0.03 0.07
P 0.002 0.002 0.002
S 0.004 0.004 0.004
Ni 66.3 65.8 65.3
Cr -- -- --
Mo -- -- --
V -- -- --
Al 2.99 2.97 2.95
Ti 0.45 0.45 0.44
Nb -- -- --
N -- -- --
Cu 28.49 28.82 29.44
Other (Fe, Co) (0.80; 0.03) (1.06; 0.03) (0.91; 0.04)

Material Hot rolled Hot rolled Hot rolled

Processing History and age and age and age
Melt Practice (e.g., hardened hardened hardened
OH, BOF, EF, AOD)
(B)

Product Form 63.5 mm 50.8 mm 63.5 mm

O.D. Bar O.D. bar O.D. bar

Heat Treatment 595C/8 hrs 595C/8 hrs 595C/8 hrs >

(Specify time, > 12 C/hr to > 14 C/hr to 12 C/hr to
temperature, and 482 C/air 482 C/air 482 C/air
cooling mode for
each cycle in
process.)
Other Mechanical, None None None
Thermal, Chemical,
or Coating
Treatment(C)
(A)
Test method must be fully described if not in accordance with TM0177.
(B)
Melt practice: open-hearth (OH), basic oxygen furnace (BOF), electric furnace (EF), argon-oxygen decarburization
(AOD).
(C)
E.g., cold work, plating, nitriding, prestrain.

25
 TABLE 2a - NACE Uniform Material Testing Report Form (Part 2):
Testing in Accordance with NACE Standard TM0177
Method C—NACE Standard C-Ring Test

Lab Data for Material: UNS N00550_________________________________________________ Tested per NACE Standard TM0177-Method C (A)

Test Specimen Geometry: Outside Diameter #9640/9655: 60.3mm; #9654: 47.6 mm Wall/Thickness #9640/9655: 6.02 mm; #9654: 4.7 mm Width 15.9 mm
Test Equipment: Bolting Material Same as Specimen (C276 with TFE isolation)
Correction for 100% 0.2% Offset Yield Applied Stress Steel Couple (Area Ratio: approximately 1:1)

Chemistry: Test Solution A Test Solution B Test Solution C (define) Other Test Solution Env. #1 See Below(F)

Outlet Trap to Exclude Oxygen Temperature Maintained 24°C ±3°C (75°F ±5°F) Temperature Maintained ±3°C (±5°F)

Test Specimen Properties Applied Stress (% of Yield Strength) Test Solution Applied Remarks
pH(E) Heat (Including
Treatment Surface
Material Finish Condition and
Location(B)

Orientation(C)

( MPa)
Strength(D)

(MPa )
Strength
Tensile
Ultimate

(%)
Elongation

(%)
Area
Reduction In

( HRC)
Hardness
Identification 100 H2S Level)
Yield

Start(F)
-Specimen # AYS

Time-to-Failure (Hours)
NF = No Failure at 720 hours

9640-4 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack

9640-5 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack
9640-6 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack
9654-4 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9654-5 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9654-6 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9655-4 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
9655-5 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
9655-6 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
(A)
Test method must be fully described if not in accordance with NACE Standard TM0177.
(B)
Location of test specimen may be: tubulars—outside diameter (OD), midwall (MW), or inside diameter (ID); solids—surface (S), quarter-thickness (QT), midradius (MR), center (C), or edge (E).
(C)
Orientation may be longitudinal (L) or transverse (T).
(D)
Open parentheses must be filled with metric or English units, as appropriate to the data. Yield strength is assumed to be 0.2% offset unless otherwise noted.
(E)
Enter pH for test conducted on nonfailed C-ring test specimen at highest stress if summarizing data .
(F)
Env. #1: 50 psia (345 kPa) H2S, 50,000 ppm chloride, pH 4.5 (final pH 4.7), 23 C, specimens continuously coupled to steel.

26
 TABLE 2b - NACE Uniform Material Testing Report Form (Part 2):
Testing in Accordance with NACE Standard TM0177
Method C—NACE Standard C-Ring Test

Lab Data for Material: UNS N00550_________________________________________________ Tested per NACE Standard TM0177-Method C (A)

Test Specimen Geometry: Outside Diameter #9640/9655: 60.3mm; #9654: 47.6 mm Wall/Thickness #9640/9655: 6.02 mm; #9654: 4.7 mm Width 15.9 mm
Test Equipment: Bolting Material Same as Specimen (C276 with TFE isolation)
Correction for 100% 0.2% Offset Yield Applied Stress Steel Couple (Area Ratio: approximately 1:1)

Chemistry: Test Solution A Test Solution B Test Solution C (define) Other Test Solution Env.#2 See Below(F)

Outlet Trap to Exclude Oxygen Temperature Maintained 24°C ±3°C (75°F ±5°F) Temperature Maintained ±3°C (±5°F)

Test Specimen Properties Applied Stress (% of Yield Strength) Test Solution Applied Remarks
pH(E) Heat (Including
Treatment Surface
Material Finish Condition and
Location(B)

Orientation(C)

( MPa)
Strength(D)

(MPa )
Strength
Tensile
Ultimate

(%)
Elongation

(%)
Area
Reduction In

( HRC)
Hardness
Identification 100 H2S Level)
Yield

Start(F)
-Specimen # AYS

Time-to-Failure (Hours)
NF = No Failure at 720 hours

9640-7 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack

9640-8 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack
9640-9 MR Trans. 776.9 1126.8 24 48 33 NF 4.5 4.7 None No Pit / No Crack
9654-7 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9654-8 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9654-9 MR Trans. 732.8 1084.0 28 51 30 NF 4.5 4.7 None No Pit / No Crack
9655-7 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
9655-8 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
9655-9 S Trans. 717.6 1097.1 24 41 32 NF 4.5 4.7 None No Pit / No Crack
(A)
Test method must be fully described if not in accordance with NACE Standard TM0177.
(B)
Location of test specimen may be: tubulars—outside diameter (OD), midwall (MW), or inside diameter (ID); solids—surface (S), quarter-thickness (QT), midradius (MR), center (C), or edge (E).
(C)
Orientation may be longitudinal (L) or transverse (T).
(D)
Open parentheses must be filled with metric or English units, as appropriate to the data. Yield strength is assumed to be 0.2% offset unless otherwise noted.
(E)
Enter pH for test conducted on nonfailed C-ring test specimen at highest stress if summarizing data .
(F)
Env. #2: Test 2 – Autoclave test – 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 4.5 (final pH 4.7), 23 C, specimens continuously coupled to steel.

27
 TABLE 2c - NACE Uniform Material Testing Report Form (Part 2):
Testing in Accordance with NACE Standard TM0177
Method C—NACE Standard C-Ring Test

Lab Data for Material: UNS N00550_________________________________________________ Tested per NACE Standard TM0177-Method C (A)

Test Specimen Geometry: Outside Diameter #9640/9655: 60.3mm; #9654: 47.6 mm Wall/Thickness #9640/9655: 6.02 mm; #9654: 4.7 mm Width 15.9 mm
Test Equipment: Bolting Material Same as Specimen (C276 with TFE isolation)
Correction for 100% 0.2% Offset Yield Applied Stress Steel Couple (Area Ratio: approximately 1:1)

Chemistry: Test Solution A Test Solution B Test Solution C (define) Other Test Solution Env.#3 See Below(F)

Outlet Trap to Exclude Oxygen Temperature Maintained 24°C ±3°C (75°F ±5°F) Temperature Maintained ±3°C (±5°F)

Test Specimen Properties Applied Stress (% of Yield Strength) Test Solution Applied Remarks
pH(E) Heat (Including
Treatment Surface
Material Finish Condition and
Location(B)

Orientation(C)

( MPa)
Strength(D)

(MPa )
Strength
Tensile
Ultimate

(%)
Elongation

(%)
Area
Reduction In

( HRC)
Hardness
Identification 100 H2S Level)
Yield

Start(F)
-Specimen # AYS

Time-to-Failure (Hours)
NF = No Failure at 720 hours

9640-1 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 3.6 None No Pit / No Crack

9640-2 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 3.6 None No Pit / No Crack
9640-3 MR Trans. 776.9 1126.8 24 48 33 NF 3.5 3.6 None No Pit / No Crack
9654-1 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 3.6 None No Pit / No Crack
9654-2 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 3.6 None No Pit / No Crack
9654-3 MR Trans. 732.8 1084.0 28 51 30 NF 3.5 3.6 None No Pit / No Crack
9655-1 S Trans. 717.6 1097.1 24 41 32 NF 3.5 3.6 None No Pit / No Crack
9655-2 S Trans. 717.6 1097.1 24 41 32 NF 3.5 3.6 None No Pit / No Crack
9655-3 S Trans. 717.6 1097.1 24 41 32 NF 3.5 3.6 None No Pit / No Crack
(A)
Test method must be fully described if not in accordance with NACE Standard TM0177.
(B)
Location of test specimen may be: tubulars—outside diameter (OD), midwall (MW), or inside diameter (ID); solids—surface (S), quarter-thickness (QT), midradius (MR), center (C), or edge (E).
(C)
Orientation may be longitudinal (L) or transverse (T).
(D)
Open parentheses must be filled with metric or English units, as appropriate to the data. Yield strength is assumed to be 0.2% offset unless otherwise noted.
(E)
Enter pH for test conducted on non-failed C-ring test specimen at highest stress if summarizing data .
(F)
Env. #3: 100 psia (690 kPa) H2S, 50,000 ppm chloride, pH 3.5 (final pH 3.6), 23 C, specimen was continuously coupled to steel.

28