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Super austenitic
M AT E R I A L S
stainless steel B66
By Hervé Le Guyader, Valérie Debout , Anne-Marie Grolleau and Nicolas Dolignon, CETEC DCN Cherbourg.
Franck Demulder, DCN Engineering Cherbourg
INTRODUCTION
The use of corrosion resistant stain-
less steels and alloys increases in
marine technologies (offshore , des-
alinisation, marines civil and milita-
ry applications). This is due to the
increasing severity of corrosive envi-
ronments and to the increased relia-
bility requirements for the equip-
ments. Natural sea water appears
particularly corrosive for stainless
steels and only highly alloyed stain-
less steels can give satisfaction. DCN
has an important feedback on 2507
superduplex UNS S32550, S32750,
and on NiCrMo alloys, especially al-
loy 625 (UNS N06625) and alloy
A59 (UNS N06059). These NiCrMo
alloys and 2507 superduplex were
Figure 1. Sampling locations in forgings
18 S T A I N L E S S S T E E L
used for sea water piping after va-
rious studies of corrosion resistance
in sea water (ref 1 and 2). A new
stainless steel B66 (UNS S31266),
seems to present very interesting
performances for marine applica-
tions. DCN performed a first evalu-
ation of this alloy (on forgings) for
application in sea water piping, on
the basis of its knowledges of study
and use of 2507 superduplex, alloy
625 and alloy A59 (ref 1 and 2).
MATERIALS AND SPECIMENS
Mechanical and metallurgical tests
were carried out on two solution an-
nealed B66 forgings, heavy and me-
dium section (Figure 1). Test speci-
mens sampling was performed in 3
W O R L D M A R C H 2 0 0 6
different orientations: radial, tan-
gential, longitudinal; as well under
skin and in the centre of the for-
gings, in order to check the products
homogeneity. The mechanical tests
consisted of tensile tests and impact
tests. The micrographic examina-
tions were carried out on radial cut.
The inclusion cleanliness according
to ref 4, the structure, the grain size
according to ref 5, and the possible
precipitation of intermetallic phases
(), were characterized. Samples we-
re taken in the broken impact test
specimens and were examined with
the STEM to investigate the phases
morphology, and to analyse them
semi-quantitatively with an X-EDS
analyser. The fine structure was exa-
mined using a TEM on thin blades
or after extraction.
The crevice corrosion tests were car-
ried out on:
• alloy 625 seamless tube, diameter
141.3 mm, thickness 9.5 mm, (re-
melted ESR )
• superaustenitic B66 seamless tube,
diameter 144 mm, thickness 20
mm, (remelted ESR)
• The corrosion testing devices are
described Figure 11. The crevice
corrosion tests carried out are the
same ones as those presented in
the article ref 1 and 2. These tests
are regularly used by DCN becau-
se they gave satisfaction to rank
the sensitivity to crevice corrosion
of stainless alloys in the conside-
red environment i.e. for sea water
piping:
• a temperature over 4 to 35°C, with
temperature peaks up to 55°C,
• a flow rate of aerated seawater
over 1 to 3 ms-1, and quasi per-
manent circulation,
• 100 months without disassem-
bling.
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00_SuperAustenitic 01-03-2006 12:16
Figure 2. Crevice corrosion on alloy 625
flange 1 – under gasket
Figure 3. Crevice corrosion on alloy 625
flange 2 – under gasket
Figure 4. Crevice corrosion on alloy 625
flange 3 – under gasket
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Pagina 19
P RESENTED FEEDBACK
The types of assemblies, and crevice
corrosions met in operating condi-
tions on alloy 625 are presented Fi-
gure 2, Figure 3, Figure 4, Figure 5.
A detail macrographic view of cor-
rosion is presented Figure 6. The Figure 5. Crevice corrosion on alloy 625
crevice corrosions encountered on annulus internal part – metal/metal intrface
the superduplex 2507 are presented
Figure 7 and Figure 8.
D ESCRIPTION OF CORROSION
TESTS
These tests were potentiostatic tests
with a potential fixed at + 300
mV/ECS, representative value of the
natural potential measured on
stainless after colonization by the
biofilm (ref 1 or 2). All specimen
surfaces were wet polished to a 600-
grit finish, degreased in methanol,
and rinsed in deionised water. The
samples were put in sea water baths
at a temperature ranging from 15 to
90°C.
Initiation tests
Three types of assembly are used.
Two assemblies simulate metal/gas-
ket interfaces. The gaskets are made Figure 6. Crevice aspect
either of Glass Reinforced Plastic
(GRP) or, synthetic and mineral fi-
bres bonded with an acrylonitrile
elastomer mix (FAE mix). The GRP
gaskets are not used in the sea water
piping, but they are used as a refe-
rence by DCN because they promo-
te the crevice initiation. The FAE
mix gaskets are those used on sea
water piping. The third type of as-
sembly simulates a metal/metal in-
terface like existing interfaces in sea
water piping, like the flanges assem-
blies and the piled up metallic an- Figure 7. Crevice corrosion on superdu-
nulus that exist in many sea water plex 2507 – internal annulus part 1
piping equipments (cf Figure 5, Fi-
gure 7, Figure 8). The interfaces cle-
anliness is also a parameter which
can influence the crevice initiation.
It is probable that in the works-
hops, metal dust settles on the parts
before assembly. It seemed thus, ju-
dicious to evaluate the influence of
the iron particles in the crevice. So
initiation test were carried out on
identical devices to those presented
Figure 11, including iron particles.
The purpose of these tests is to de- Figure 8. Superduplex 2507 - internal
termine the critical crevice tempera- annulus part 2
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ture of the various crevice corrosion

M AT E R I A L S
devices with uncertainty of 10°C,
and also especially to determine if
the insertion of iron particles is a
propitious factor to crevice initia-
tion. These tests were carried out at
constant temperature. They begin
at 40°C, if an initiation is observed
(increase of the measured current
and corroded aspect of the sample)
the following test is carried out at a
10°C inferior temperature, in the
opposite case, the test temperature Figure 10. Crevice devices for crevice corrosion test
is increased by 10°C until obtaining
the minimal temperature of initia-
tion which is the CCT (Critical Cre-
vice Temperature).

All the assemblies were tightened to

25 N/m.

Environment: natural sea water

Test duration: from 100 to 1200

hours according to obtained results.

Metal/gasket devices:
A ring test specimen, of external
diameter 30 mm and internal 10
mm and thickness 5 mm, is tighte-
ned between GRP or FAE mix gas-
kets with titanium plates, nuts and
bolts.
Metal/metal devices:
Two rings test specimens of the sa-
me dimensions than the ring test
specimens used for the metal/gasket
devices are squeezed together. They
are isolated from the tightening sys-
tem constituted of reinforcing plate
and titanium bolt, by lubricated
gaskets.
For the polluted devices, a small
Figure 11. Impact test results
quantity of iron (0,5 mg or 1 mg) is
introduced into the interface gas-
ket/metal or into the interface me-
tal/metal.
Propagation tests
The purpose of these tests is to
compare the various kinetics of pro-
pagation according to the variation
of temperature, once the crevice
corrosions are initiated; and to de-
termine if the interfaces can be pas-
sivated by decreasing the tempera-
ture. The test devices are the same
ones as for the initiation tests. The
crevice corrosion initiation is car-
ried out either by drops of hydroch-
loric acid, or by ferrous pollution.
These tests begin at a sufficiently
high temperature to ensure the cre-
vice corrosion initiation, then the
temperature is decreased by stage in
order to highlight the corrosion ki-
netic for each temperature.

R ESULTS AND DISCUSSION

Experience feedback on the

sensitivity to sea water corrosion of
alloy 625 and the superduplex 2507.
The experience feedback showed an
important sensitivity of alloy 625 to
crevice corrosion in sea water. Crevi-
ce corrosions were observed under
gaskets of the flanges (Figure 2, Figu-
re 3, Figure 4), into the metal/metal
interfaces of piled up metallic annu-
lus (Figure 5, Figure 7), often near the
Figure 9. Circuit crevice corrosion assemblies O rings, and under bolts (Figure 8).

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M AT E R I A L S

Al C Cb Mn P S Si Ti Cu Ni Fe Cr Mo N W PRENW
min
max
UNS N06625 - - 3,15 - - - - - - 64 20 8 - - - 46,4
0,4 0,1 4,15 0,5 0,015 0,015 0,5 0,4 - - 23 10 - - 0,4 56,0
UNS S31266 - - - 2 - - - - 1 21 23 5,2 0,35 1,5 - 48,2
- 0,03 - 4 0,035 0,02 1 - 2,5 24 25 6,2 0,6 2,5 59,2

Table 1. Chemical composition of B66 SST and alloy 625 PRENW = %Cr + 3,3(%Mo + 0,5 %W) + 16%N

Superaustenitic B66 mechanical
and metallurgical characteristics
The mechanical characteristics (cf
Table 1) are very high for superaus-
tenitic, equivalent to those of alloy
625 grade 1, and only inferior by
100 MPa than that of the superdu-
plex 2507. The results show a good
homogeneity of the mechanical
characteristics in heavy section
thickness in any locations and
orientations of the samplings. The
elongation (50%) is particularly im-
portant. The impact test energy is
very high and not very sensitive to
the low temperatures (Figure 11).
The metallurgical structure, illustra-
ted on the figure 12, is austenitic
with twinned grain of AFNOR index
2, under skin and in the centre. The
alloy is not very sensitive to inter-
metallic precipitations in heavy sec-
Figure 12. Micrographic examination
tions. Precipitations of phases chi
and sigma are observed in the cent-
re of the forgings (Figure 12 and Fi-
gure 13), without effects on the me-
chanical characteristics. These re-
sults confirm the good metallurgi-
cal stability of the B66 stainless
steel, described in article ref 5,
which ensure good mechanical pro-
perties and corrosion resistance
even in the centre of heavy section
forgings. The metallurgical stability
of this alloy is, according to DCN,
equivalent with that of alloy 625
and much superior to that of the
superduplex 2507.
Sea water crevice corrosion
resistance of the superaustenitic B66
Two criteria are discussed
• The initiation conditions - The
results are gathered in table 3
• The crevice corrosion propaga-
tion kinetics – The interpretation
is based on the intensity curve
obtained at different temperatu-
res and on the corrosion aspect
after cleaning.
For the initiation phase, the me-
tal/metal interfaces are more critical
than the metal/FEA mix gaskets on-
es. The severity of these metal/me-
tal crevices is close to the severity
of the metal/GRP crevices. Ferrous
pollution under the sealing gaskets
is a very critical factor for initiation
of crevice corrosion of stainless al-
loys in sea water. Under these seve-
re conditions, alloy 625 initiate cre-
vice very quickly even at low tem-
peratures (< 15°C). The B66 supe-
raustenitic alloy shows a resistance
to crevice corrosion initiation supe-
rior to alloy 625. Without ferrous
pollution, its resistance is over 40°C
and approximately 30°C in the
severest conditions (cf table3).
The results obtained on the curves
figures 14 and 15 confirm that no
difference of corrosion kinetic
could be highlighted according to
sampling locations and orienta-
tions.
After initiation of crevice corrosion,
the corrosion kinetics depends on
the types of interfaces and highly
on the temperatures. (cf figures 16,
17, 18, 19). The corrosions obser-
ved on the metal/metal test speci-
men are extended on all the inter-
face area whereas the corrosions
under gaskets present more locali-
sed attacks. The curves show that
when the temperature decreases be-
low 40°C, the kinetic of corrosion
of B66 decreases notably. The tran-
sition is more obvious on the re-
sults of the metal/gasket device.
The alloy 625 conserves an impor-
tant corrosion rate for temperature

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alloys, in particular on alloy 625.

M AT E R I A L S
These alloys present a significant
sensitivity to sea water corrosion.
DCN developed specific crevice cor-
rosion tests to simulate the sensiti-
vity to corrosion of various alloys
under representative conditions of
the operating conditions (cf ref 1
and ref 2). The results of tests were
correlated with the experience
feedback and are very satisfactory.
In a costs optimization search pur-
pose, DCN performed a first evalu-
ation of a new superaustenitic
stainless steel UNS S31266 (B66).
The mechanical and metallurgical
characteristics on heavy section
and medium section forgings are
homogeneous. The tensile charac-
teristics are quite high for this type
of alloy (yield strength > 420 MPa),
equivalent to alloy 625 grade 1. Its
corrosion resistance in sea water
was tested in comparison to the al-
loy 625 for which the behaviour is
known in operating conditions. Su-
peraustenitic B66 heavy section for-
gings have a very good crevice cor-
rosion resistance in sea water, at
ambient temperature, higher than
the alloy 625. The price of B66 be-
ing potentially notably lower (ap-
proximately 30%) than alloy 625
because of the composition (less
nickel and molybdene), comple-
mentary studies will be undertaken
to assess the stability and the corro-
Figure 13. X-EDS analysis of ␴ phase sion resistance of B66 welding in
sea water. TIG welding with highly
of 30 or 20°C. At the temperatures (cooling sea water piping for boiler alloyed filling wire, type UNS
lower than 40°C, the B66 alloy has or auxiliary). DCN has a broad ex- N10276 or N06059 is recommen-
corrosion rate significantly lower perience feedback on the stainless ded by the manufacturer and
than alloy 625, of a factor 500 for steels superduplex and the NiCrMo should give satisfaction.
metal/gasket devices and 10 for the
Forged part tube ASTM A182
metal/metal devices, and tends cle-
Skin Core Requirements
arly to repassivate. (Figure 17 and C 0.027 0.025 0.025 < 0.03
19). It should be noticed that, at S < 0.001 0.001 < 0.005 < 0.02
the temperatures higher than 40°C, P 0.020 0.020 0.021 < 0.035
the imposed potential of +300 Si 0.18 0.20 0.14 < 1.0
mV/ECS is not justified any more Mn 3.17 3.25 3.00 [2 : 4]
Cu 1.52 1.53 1.62 [1 : 2.5]
in practice, because the natural bio-
Ni 21.0 20.9 21.53 [21 : 24]
film of sea water declines. Under
Cr 24.0 23.8 24.25 [23 : 25]
these conditions, rates of crevices Mo 5.50 5.50 5.50 [5.2 : 6.2]
corrosion strongly decrease (cf ref. Co 0.076 0.077 0.060 -
1) Fe 42.5 42.7 Bal. Bal.
W 1.93 1.91 1.90 [1.5 : 2.5]
CONCLUSION N 0.0449 0.0449 0.45 [0.35 : 0.6]
O 0.0052 0.0054 -
DCN uses stainless steels and alloys
for its applications in sea water Table 2. B66 parts - Chemical compositions

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M AT E R I A L S

Figure 14. B66 Propagation on B66 - test at 25°C – metal/gasket assembly – different locations

Figure 15. B66 Propagation on B66 - test at 50°C – metal/gasket assembly – different locations

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M AT E R I A L S
Figure 16. Propagation test with ferrous pollution on A625 – metal/gasket assembly

Figure 17. Propagation test with ferrous pollution on B66 – metal/gasket assembly

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M AT E R I A L S

Figure 18. Propagation test with ferrous pollution on B66 – metal/metal assembly

Figure 19. Propagation test with ferrous pollution on B66 – metal/metal assembly

Part Localisation Test specimen Tensile strength Yield strength Elongation

orientation (MPa) (MPa) (%)
Radial 817 484 66
Skin 822 488 63
Tangential 813 459 64
813 463 65
Forging Longitudinal 799 461 65
804 470 65
Radial 808 459 64
Centre 813 463 65
Tangential 808 466 66
804 459 63
Tube Longitudinal 853 465 63

Table 3. Tensile test results

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Crevice device
Alloy Metal/GRP Métal/gasket Metal/joint Metal/metal Metal/metal
with ferrous with ferrous
pollution pollution
625 alloy  20°C  70°C  15°C  30°C  25°C
Super-austenitic B66 > 35°C  80°C > 30°C > 40°C > 40°C

Table 4. Critical crevice temperature

ACKNOWLEDGMENTS 2. H. Leguyader, V. Debout, A.M. Grolleau,

This work was funded by the Fren-
ch ministry of Defense. Mr Heuzé
(DGA/SPN) is acknowledged for his
support of this project. The authors
would acknowledge, Aubert & Du-
val Company for the alloy B66
technical data provided. DCN/CES-
MAN laboratory (Mr Corrieu) for its
contribution to the metallurgical
examinations, and also express
their appreciation to the DCN/CE-
TEC laboratory (Nicolas Dolignon,
Emilie François, Béatrice Avaulée)
for their efforts in conducting the
corrosion tests.
REFERENCES
1. H. Leguyader, V. Debout, A.M. Grolleau,
Crevice corrosion of Ni base alloys and
highly alloyed stainless steels in sea water,
Eurrocorr 1999, Event 227 in European
Federation
Crevice corrosion properties of weld over-
lays of alloy 59 for alloy 625 flanges repair,
Eurrocorr 2001, Event ??? in European
Federation …
3. B Mayonobe, F. Roch, R. Cozar , NICRIM-
PHY B66 A 0,5% N Superaustenitic stain-
less steel optimized or heavy section forg-
ings presented at stainless steel 1999
-Science and market - Chia Laguna Sar-
dinia - Italy
4. NF A 04-106 Iron and Steel - Methods of
determination of content of non metallic
inclusions in wrought steel – Part II :
Micrographic method using standards dia-
grams
5. NF EN ISO 643 Micrographic determina-
tion of the apparent grain size
About the author
Franck Demulder has a Masters
of Science in physico-chemistry
analysis of material interfaces
from the University of Marne la
Vallée (France 77). Mr Demulder
spent 3 years at the Schlumberg-
er Riboud Product centre
(France), in charge of procure-
ment and quality of metallic
alloys for wireline tools. (Tools for
characterisation of oil production
wells). After that he spent 5
years at DCN (industrial prime
contractor for integrated war-
ships) in the engineering depart-
ment as material
specialist for war-
ship sub-systems
and seawater pip-
ing.