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Maria Sawford
Research Engineer II
ATI Powder Metals
6515 Steubenville Pike
Pittsburgh, PA 15205
USA
T: 412-923-2955 x276
E: Maria.Sawford@ATImetals.com
Andrzej Wojcieszynski
Senior Technical Director,
Specialty Products and Alloys
ATI Powder Metals
T: 412-923-2955
E: A.Wojcieszynski@ATImetals.com
Roy T. Carlson
Account Manager
ATI Powder Metals
T: 412-923-2670
E: Roy.Carlson@ATImetals.com
Brian J. McTiernan
General Manager
ATI Powder Metals
T: 412-923-2670
E: Brian.McTiernan@ATImetals.com
Abstract
Various parts and components used in the oil
and gas industry are manufactured from duplex
and super duplex stainless steels and Ni-Cr
alloys due to their combination of high strength
and corrosion resistance. Manufacturing these
alloys with the HIP PM process (i.e., hot isostatic
pressing of gas atomized powder) results
in numerous advantages over conventional
products. This paper reviews the HIP PM
process and examines the microstructure,
corrosion resistance and mechanical
properties of three alloys commonly used in oil
and gas exploration and processing: the super
duplex stainless steel S32760 PM and two
Ni-Cr alloys ATI A625 PM and ATI 625M
PM. The property characteristics of the HIP
PM alloys are compared to the corresponding
alloys made by conventional ingot metallurgy.
The results show that the corrosion resistance
and mechanical properties of the HIP PM alloys
Keywords
PM powder
hot isostatic pressing (HIP)
corrosion resistance
mechanical properties
Introduction
Highly alloyed duplex and super duplex
stainless steels (SDSS) and Ni-Cr alloys
are used in the oil and gas industry when
corrosion and strength are of utmost concern.
Due to the high alloy content, these alloys can
be difficult to manufacture using conventional
methods, e.g., casting, forging and hot rolling.
The high alloy content of conventionally
produced material causes segregation during
cooling which results in these materials having
an inhomogeneous chemical composition,
anisotropic mechanical properties and a
nonuniform microstructure, all of which lead
to hot working difficulties. These issues can
be minimized through the use of the HIP PM
process (i.e., hot isostatic pressing (HIP) of gas
atomized powder) [1,2] . After a review of this HIP
PM process, the microstructure, corrosion
resistance and mechanical properties of three
alloys commonly used in oil and gas exploration
will be discussed. The alloys included in
this study are the super duplex stainless
steel S32760 PM (a HIP PM version of UNS
S32760), ATI A625 PM (argon atomized UNS
N06625) and ATI 625M PM (argon atomized
UNS N07626). The property characteristics
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PAPER 6F
Figure 1. Steps in the HIP PM process which includes a) vacuum induction melting, b) screening, c) blending, d) loading, e) outgassing and f) HIP.
a
HIP PM Processing
Several steps are included in the HIP PM
process: melting of the raw materials, inert
Figure 2. Examples of HIP/clad applications: a) mill rolls and b) compounding segments and barrel for plastics processing.
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PAPER 6F
Cr
Nb
Mo
Fe
Ni
Cu
Al
Ti
PRE1
0.028
0.268
25.40
3.72
Bal.
7.20
0.56
0.62
43.0
Zeron 100
0.023
0.239
25.27
3.60
Bal.
7.06
0.56
0.61
42.0
ATI A625 PM
0.017
0.0079
21.26
3.83
8.83
0.43
Bal.
0.29
0.23
50.5
ATI 625M PM
0.016
0.0063
20.13
5.03
8.66
5.20
Bal.
0.47
48.8
0.049
0.0095
20.87
3.32
8.29
4.09
Bal.
0.25
0.28
48.2
Ni-Cr Alloys
Materials
The S32760 PM powder was nitrogen
atomized in a 23 kg (50 lbs) laboratory
atomizer at ATI Powder Metals. The ATI A625
PM and ATI 625M PM powders were argon
atomized in a 3640 kg (8,000 lbs) furnace
also at ATI Powder Metals. Laboratory sized
compacts were filled with -60 mesh powder,
outgassed and HIPed to full density. The
conventional ATI 625 alloy was supplied as
31.75 mm and 57.2 mm (1.25" and 2.25")
diameter bars from ATI Allvac in the annealed
condition. Plate material of conventional
ZERON 100 measuring 15.9 mm (0.625")
thick was obtained from ATI Allegheny Ludlum.
The chemical compositions of the alloys that
were tested are given in Table 1.
S32760 PM has a higher N and Mo content
than the ZERON 100 plate. Thus the pitting
resistance equivalent number (PRE) of S32760
PM (43.0) is higher than that for the ZERON
100 plate (42.0).
The ATI A625 PM material has a higher Cr
and Mo content than the conventional ATI 625
plate and thus has a higher PRE number (50.5
Experimental Procedure
Corrosion and mechanical test specimens
were prepared from HIPed compacts and the
conventional bar and plate material. The heat
treatments given to the test specimens and
their designations are given in Table 2. These
designations are used throughout this article.
The heat treatments given to ATI A625 PM
and ATI 625M PM alloys are those that are
typically used for components in the oil and
gas industry and do not necessarily result in
the maximum tensile properties.
The microstructure of S32760 PM and
the ZERON 100 plate was examined after
electrolytic etching in a 20% NaOH at 3V dc
for 45 seconds. The austenite spacing was
determined according the procedure given in
the Recommended Practice DNV-RP-F112 [3] .
The mean and standard deviation reported
herein were determined from a total of four
photomicrographs of each alloy. The Ni-Cr
alloys were etched with a waterless Kallings
etchant at 37.8C (100F) for 2 minutes.
Corrosion resistance was evaluated
according to ASTM G48 Methods A, C and D.
Prior to testing, the specimens were pickled
in a solution of 10% HCl + 3% HF at 60C
(140F) for 20 minutes and passivated in air
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PAPER 6F
Results
Super Duplex Stainless Steels
Metallography
The microstructure of S32760 PM in the asHIP condition and after solution annealing is
given in Figure 3. The as-HIP microstructure
Table 2. Heat treatments and resulting hardness results of the tested alloys.
Alloy
Heat Treatment
Designation
Hardness, HRC
S32760 PM
1141C/1hr, WQ
SA
24.0
Zeron 100
1099-1141C/1hr, WQ
22.0
Ni-Cr Alloys
ATI A625 PM
ATI 625M PM
as-HIP
as-HIP
21.5
STA1
29.0
STA2
32.0
as-HIP
as-HIP
26.5
STA3
34.0
DA
39.0
871C/30min, WQ
anneal
20.5
760C/8hrs, OQ
aged
21.0
OQ = oil quench, WQ = water quench, SA = SOlution anneal, STA = Solution Treat & Age, DA = Double Age
Figure 3. Photomicrographs showing the etched microstructure of S32760 PM: a) in the as-HIP condition, b) after solution annealing and c) of the
ZERON 100 plate. Note the different scale for the ZERON 100 plate.
a
sigma
ferrite
ferrite
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Heat Treat
G48 Method A
G48 Method C
G48 Method D
PRE
Wt loss, g/m2
CPT, C (F)
CCT, C (F)
as-HIP
476
SA
0.09
65 (149)
35 (95)
SA
65 (149)
40 (104)
42.0
as-HIP
85 (185)
45 (113)
50.5
STA1
85 (185)
50 (122)
STA2
85 (185)
40 (104)
as-HIP
85 (185)
50 (122)
STA3
85 (185)
45 (113)
DA
85 (185)
40 (104)
anneal
85 (185)
25 (77)
aged
85 (185)
30 (86)
Zeron 100
43.0
Ni-Cr Alloys
ATI A625 PM
ATI 625M PM
48.8
48.2
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PAPER 6F
of 65C (149F). The resistance of S32760
PM to crevice corrosion, CPT = 35C (95F),
is comparable to that of the ZERON 100 alloy,
CPT = 40C (104F).
Mechanical Properties
Tensile Properties
The room temperature tensile properties
of S32760 PM, the ZERON 100 plate
(transverse) and cast S32760 [6] are given in
Figure 4. Solution annealed S32760 PM has
a yield strength (YS) of 570 MPa (82.7 ksi),
an ultimate tensile strength (UTS) of 830
MPa (120 ksi) and an elongation of about
Figure 6. Photomicrographs showing the etched microstructure of the a) as-HIP ATI A625 PM alloy, b) as-HIP ATI 625M PM alloy and c)
conventional ATI 625 bar.
a
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Ni-Cr Alloys
Metallography
The microstructure of the as-HIP ATI A625
PM (21.5 HRC) and ATI 625M PM (26.5
HRC) alloys and the conventional ATI 625
bar (20.5 HRC) are given in Figure 6. The
PM alloys have a fine and uniform austenitic
microstructure. Evidence of microstructural
banding and elongated grains are present in the
microstructure of the conventional ATI 625
bar, Figure 6c. The microstructure of the ATI
A625 PM, ATI 625M PM and conventional
ATI 625 alloys is unaffected by heat treatment
when viewed with an optical microscope.
However, the hardness of the ATI A625 PM
alloy increases to 29 HRC and 32 HRC with the
STA1 and STA2 heat treatments, respectively.
The hardness of the ATI 625M PM alloy
increases to 34 HRC and 39 HRC with the
STA3 and DA heat treatments, respectively.
The effect of heat treatment on the hardness of
these alloys is summarized in Table 2.
Corrosion Resistance
Results of corrosion testing on the Ni-Cr alloys
are given in Table 3. The pitting resistance of
the ATI A625 PM and ATI 625M PM alloys
is the same as the conventional ATI 625 bar
as all materials have a CPT of 85C (185F).
Additionally, Table 3 shows that the pitting
resistance of the PM materials is unaffected by
the heat treatments.
The results in Table 3 show that ATI A625
PM (STA1) and ATI 625M PM (as-HIP)
alloys have the highest resistance to crevice
corrosion as both materials have a CCT of 50C
(122F). The resistance of the ATI A625 PM
and ATI 625M PM alloys to crevice corrosion
does not vary significantly with heat treatment
as the CCT values range from 40-50C (104122F). In most cases, the crevice corrosion
resistance of the ATI A625 PM and ATI 625M
PM materials is higher than the conventional
ATI 625 bar which has a CCT of 25-30C
(77-86F), depending on heat treatment.
Mechanical Testing
Tensile Properties
The room temperature tensile properties of
the HIP PM and conventional 625 alloys are
given in Figure 7. The UTS and YS of the asHIP ATI A625 PM material are 959 MPa
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Discussion
S32760 Alloys
Microstructural evaluations on S32760 PM
showed the presence of sigma in the as-HIP
condition. This phase precipitates during the
slow cool down cycle in the HIP unit. However,
the sigma phase dissolves during solution
annealing. The test results on S32760 PM
shown herein confirm that sigma degrades
corrosion resistance and the tensile properties
as evidenced by the ASTM G48 Method A test
results in Table 3 and the ductility in Figure 4.
Thus, S32760 PM cannot be used in the asHIP condition and must be solution annealed to
produce a sigma-free microstructure.
When properly solution annealed, the
corrosion resistance of S32760 PM is similar
to that of the ZERON 100 alloy. However,
a benefit of the PM processing route is
evidenced in the austenite spacing. The
austenite spacing of S32760 PM is 10.6 m
8.3 m whereas the ZERON 100 plate has
an austenite spacing of 22.9 m 25 m in
the longitudinal direction. The fine and uniform
austenite spacing of S32760 PM is expected
to minimize the risk of HISC as compared to
conventional S32760 [3] .
Conclusion
The HIP PM process can be used to
manufacture conventional mill products,
near net shapes and HIP/clad components.
The results herein show that the corrosion
resistance and mechanical properties of the
HIP PM materials are comparable to and at
times exceeds those of the conventionally
produced counterparts. Specifically:
The corrosion resistance of S32760 PM is
similar to that of the ZERON 100 plate.
The uniform and fine austenite spacing
of S32760 PM should minimize the risk
of HISC as compared to conventionally
produced S32760.
The toughness of S32760 PM is comparable
to the transverse toughness of the ZERON
100 plate with a toughness of 199 J (147
ft-lbs) at -46C(-51F)
The tensile properties of S32760 PM
are similar to those of the ZERON 100
plate with YS of 585 MPa (85 ksi) and an
elongation of 45%.
The crevice corrosion resistance of the
ATI A625 PM and ATI 625M PM alloys
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References
1. John H. Moll, John J. Conway and Brian
J. McTiernan, As-HIP P/M Superalloys:
A Technical and Commercial Success,
Advances in Powder Metallurgy &
Particulate Materials, Vancouver, 1999.
2. John H. Moll, Brian J. McTiernan,
Powder Metallurgy Superalloys,
ASM Handbook. 10th, Vol. 7, ASM
International, 1998.
3. Design of Duplex Stainless Steel
Subsea Equipment Exposed to Cathodic
Protection, Recommended Practice
DNV-RP-F112, Det Norske Veritas,
October 2008.
4. Petroleum and Natural Gas Industries:
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