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THE NEW 200-SERIES : AN ALTERNATIVE ANSWER TO NI. SURCHARGE ?

DREAM OR NIGHTMARE?

Dr. Jacques CHARLES.

U&A, ARCELOR. Immeuble PACIFIC-11,13 cours Valmy F-92070 La Defense cedex.


jacques.charles@arcelor.com

Abstract
For more than 50 years manganese additions have been considered to replace nickel in austenitic
stainless steels. As a result, reductions in alloy surcharge particularly when nickel price are jumping
can be expected. This has result in the development of the so-called 200 series. The grades are
know to have complementary nitrogen additions in order to further stabilize the austenitic phase.
Copper additions have also been successfully considered in order to provide a stable austenite. With
copper additions, nitrogen additions can be reduced providing softer manganese austenitic grades.
The grades until end of last century, with a few exceptions like in India, had only very limited
applications and where selected mainly for their combination of high strength and ductility ( possible
strengthening by very high nitrogen additions and / or by cold deformations ) More recently huge
amount of 200 series have been produced in Asia. The grades have modified chemical compositions
– low chromium additions, extra low nickel additions, ... – and high residual elements like sulfur which
are know to have detrimental effects on localized corrosion resistance ( pitting ). The paper will
present a review of the 200 – series grades and point out the specificities of the new developed
grades. Chemical compositions, mechanical properties, corrosion resistance properties and
applications are presented. The lack of international codes , references for those grades are pointed
out. Finally warnings are addressed for improper uses of those grades which might lead on end-
users.

INTRODUCTION nitrides manganese were replaced by blowing


gaseous nitrogen in the molten steel in the AOD
The 200 series of stainless steels was developed vessel. Once again nickel shortage ended and
in the early 1930’s. Although the first chemical with high level of availability Ni price was
analysis investigated where of 205 kind (Ni reduced. For more than 30 years the 304 grade
content close to 1% and austenitic phase started to be the standard of the stainless steel
stabilized due to simultaneously high Mn and family. His well know properties when
Nitrogen additions - see Table I - ), the first considering corrosion resistance, formability
grades which received the AISI label in the mid- and weldability made it possible to achieve a
fifties were the 201 and 202 grades ( Ni content average yearly growth of 6%. 200 series still
around 4 to 6 % and nitrogen additions lower had in the eighties and nineties marginal
than .25 % ).They became more popular during applications where there attractive properties –
the Korean War to conserve the nickel. In that combination of strength (30% higher than 304)
time due to Nickel shortage, nickel uses were and high ductility - are used. Furthermore some
mainly restricted to military applications. The new grades with very high nitrogen levels ( 0.5
Tenelon grade / AISI 214 grade with less than to 1% and more) were developed by a new ESR
2% Ni and about .35%N were produced at the process. The small size ingots are obtained by
end of the fifties. The Mn-austenitic grades melting under high nitrogen pressure. Those
containing Mo to improve the corrosion alloys are considered for marginal applications.
resistance properties appeared in the mid-
sixties both in US and Europe. Simultaneously Indian government, for economical reasons,
Mn + Cu containing grades were developed decided to limit the Ni importations. As a result
which made it possible to produce 4 / 6 %Ni local producers, including Jindal, started to
austenitic grades (AISI 211 and 203) having produce huge quantities of so-called 200 series
relatively low nitrogen content (< 0.06 %). grades for local uses. Specific grades were
Equivalent drawing properties than 304 could be developed. This includes 4 and 1 %Ni grades with
achieved . The grades started to be popular in the and without Copper. Most of the production was
early 70’s due to new Ni shortage phenomenon’s. restricted to local applications. A real knowledge
With the new AOD technology nitrogen additions concerning their in service properties was
in the 200 series were made easier and on a developed so that material selection experience
more cost-effective way. Expensive nitrided was build up. With the new century, a new period
ferrochromium, ferromanganese or eventually of high volatility of nickel price started.

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2 Table I. Chemical analysis of different 200 series grades.

Type Standard Cr Ni Mn N C S OTHERS


201 S20100 16.0 - 18.0 3.5 - 5.5 5.5 - 7.5 0.25MAX 0.15MAX 0.030MAX -
201LN S20153 16.0 - 17.5 4.0 - 5.0 6.4 - 7.5 0.10 - 0.25 0.03MAX 0.015MAX Cu 1.0MAX
202 S20200 17.0 - 19.0 4.0 - 6.0 7.5 - 10.0 0.25MAX 0.15MAX 0.030MAX -
204L S20400 15.0 - 17.0 1.5 - 3.0 7.0 - 9.0 0.15 - 0.3 0.03MAX 0.030MAX
S20430 15.5 - 17.5 1.5 - 3.5 6.5 - 9.0 0.05 - 0.25 0.15MAX 0.030MAX Cu 2.0 - 4.0
205 S20500 15.5 - 17.5 1.5 - 3.5 14.0 - 15.5 0.32 - 40 0.12 - 0.25 0.030MAX
214 S21400 17.0 - 18.5 1.0MAX 14.0 - 16.0 0.35MIN 0.12MAX 0.030MAX
216 S21600 17.5 - 22 5.0 - 7.0 7.5 - 9.0 0.25 - 0.5 0.08MAX 0.030MAX Mo 2.0 - 3.0
S24000 17.0 - 19 2.25 - 3.75 11.5 - 14.5 0.2 - 0.4 0.08MAX 0.030MAX
S32001 19.5 - 21.5 1.0 - 3.0 4.0 - 6.0 0.05 - 0.17 0.03MAX 0.030MAX Cu 1.0MAX

EN 1.4371 16.0 - 17.0 3.5 - 5.5 6.0 - 8.0 0.15 - 0.20 0.03MAX 0.015MAX -
EN 1.4372 16.0 - 18.0 3.5 - 5.5 5.5 - 7.5 0.05 - 0.25 0.15MAX 0.015MAX
EN 1.4373 17.0 - 19.0 4.0 - 6.0 7.5 - 10.5 0.05 - 0.25 0.15MAX 0.030MAX

Simultaneously China became a major consumer phase stability and make it possible to increase
of stainless steel. Part of the tonnage was somewhat the chromium content of the low Ni.
produced locally. The continuous pressure to grades.
obtain low cost grades resulted in the
development of cheaper grades with always less
alloying elements like nickel and even less
chromium. Due to low cost manufacturing routes
or less performing facilities grades with very
high sulfur and carbon containing grades were
sold on the market. Those productions from a
marginal production level moved to hundred of
thousands tons production.

Now about two millions of so-called 200 series


grades are consumed in Asia – mainly China
(Figure 1). Some of the grades are not covered by
international codes or specifications. Some
other are in the international standards or at Figure 1. Stainless Steel Crude Production by
least are manufactured with up to date categories in %.
equipments with a control of the residual
elements like sulfur and carbon which have a The experimental data provided are issued from
clear impact on the in service properties of the tests performed on industrial plates collected in
grades. Several new austenitic manganese different countries. Chemical analysis are
grades were developed recently by major presented Table II. Figure 4 presents the
stainless steel producers . They are designed for different grades plotted versus
specific applications. The purpose of this paper
is to present mechanical properties, corrosion Mn. and Ni. contents. Most of the 200-series
resistance properties and manufacturing grades are plotted on a line joining 10%Ni and
properties of the new developed grades (Table 16%Mn.
II). Their properties are also compared to those
of the more classical 200 series. Almost complete replacement of Nickel is
possible by combined Mn. and Nitrogen + Carbon
additions. Lower nickel addition requires more
PHASE DIADRAMS / MECHANICAL manganese and nitrogen to stabilize the
PROPERTIES austenitic phase. To conclude, austenitic
manganese stainless steels with a nickel content
Figures 2 and 3 provide some data concerning of 1% or less requires about 10 %Mn with and
the austenitic phase stability. It is observed that more than 0.25% N. to stabilize the austenitic
lower nickel, even with high manganese phase. The strength of the grades due to high N.
contents, reduces the solubility limit of contents is about 30% higher than a 304 grade.
chromium in the austenitic phase. Hopefully the Higher draw ability properties may be obtained
manganese additions increase the solubility of with lower nitrogen additions but than chromium
the nitrogen in the austenitic phase which , by content must be reduced down to 14-15% in
the way, has a powerful effect on austenitic order to preserve the austenitic phase.
Table II. Chemical analysis of different 200 series industrial plates and sheets.

Country Cie Usual name UNS Cr Ni Mn Cu C N S (ppm) Rp0.2 Rm Md


Europe U&A 16-4Mn S20100 16,3 4,1 6,5 0,09 0,16 40 400 770 39,99
U&A 16-7Mn † S20400 16 1,6 7,5 2,9 0,05 0,19 < 10 390 710 28,92
KTN H400 18 3,8 6,8 0,035 0,16 7 450 770 48,35
USA Nitronic 30 S20400 16 2,5 8,5 0,02 0,17 390 830 101,82
Nitronic 19D * S32001 20 1,6 5 0,5 0,02 0,13 500 850 105,8
Allegheny 219 S21904? 21 6 9 0,03 0,25 460 780 -113,86
S.Amer. Acesita P201A - 15,2 1,1 9 1,7 0,1 0,1 <10 370 870 95,36
Acesita P202A - 15,1 4 7,2 1,6 0,06 0,05 <10 310 730 71,87
Acesita P300A † S20400 16,1 1,5 7,4 2,9 0,05 0,18 3 370 745 35,89
Asia Jindal J1 - 15 4 7 1,6 0,06 0,05 60 300 700 74,88
Jindal JI - 16,1 4 7,1 1,7 0,06 0,07 31 46,85
Jindal J4 - 15,5 1 10 1,6 0,09 0,14 60 470 820 74,99
Jindal J4 - 15,9 1 9,7 1,6 0,1 0,15 82 62,73
NTK D10 - 17,5 4,8 3,7 2,8 0,06 0,15 10 355 675 -36,51
Posco 204M S20400 16 2,5 8 0,03 0,25 480 840 64,34
Posco 202 2D - 15,5 4,8 7,4 1,2 0,06 0,07 10 43,91
Posco 204 2D - 14,4 1,04 10,3 1,2 0,05 0,16 5 107,28
CHX1 - - 15 1,1 9,6 1,7 0,1 0,14 123 74,7
CHX2 - - 11,3 1,1 12,8 0,08 0,13 0,045 60 176,16

Figure 4. Ni and Mn contents in stainless steels


Figure 2. Effect of Cr and Mn on nitrogen
alloys
solubility.

Figure 3. Austenite stability at 1075 °C (Franks) Figure 5. Mechanical properties of several S.S.

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4 Combining high manganese, high nitrogen and elongation even for the grades having huge
chromium additions, make it possible to design a transformation at room temperature (figure 7).
family of grades having very high mechanical Although several Md formula are available, no
properties ( Figure 5 : yield strength ) . Those one is really designed for such compositions.
grades have limited draw ability properties. Indicative Md temperatures are provided table II
( Nohara kind formula ).
Copper additions have been considered for their
austenite forming properties. Those copper
containing 200 series can be designed for an
equivalent level of nickel, manganese and
chromium with lower nitrogen additions. The
grades are softer and deep drawing properties,
without needing high power equipments, can be
achieved. An alternative solution for the copper
additions, instead of decreasing the nitrogen
additions, is to make a further decrease of the
nickel content – from 4 to 1 % Ni. ( substitution
of nickel by copper, an austenite forming
element ).

DEFORMATION AND PHASE


STABILITY
Figure 7. Volume fraction of martensite alpha
versus % of deformation. Tests performed at
Isothermal tensile tests were performed on an
60°C.
Instron 8082 machine at room temperature and
60°C. The strain rate was 1% per min. Automatic
The very sensitive effect of temperature explain
measuring system of strain ( ASAME) was used.
The sigma-meter was used to quantify the why testing conditions may greatly modify the
magnetism. Figure 6 presents the % of measured martensite level in the grades.
martensite versus the strain %. Testing Heating effects due to deformation in non
temperature is very sensitive since the Md isothermal conditions may reduce significantly
temperature is close to room temperature. J1 the amount of transformed austenite. No epsilon
and J4 grades tested had a more stable martensite was detected by X-ray investigations.
austenite. This can be correlated to their relative
higher content in nitrogen compared to the To conclude 200 series grades are sensitive to
equivalent grades. martensitic transformations particularly when
nitrogen and or carbon contents are reduced in
order to reduce the strength of the grades. As a
result higher draw ability properties are often
correlated to unstable microstructures .

DEEP DRAWING AND DELAYED


CRACKING

Figure 8 presents the risk of delayed cracking


versus deep drawing ratio for several stainless
steels. It is observed that unless the austenitic
304 grade is know to undergo a partial alpha
martensitic transformation during deformation,
the grade in those conditions do not present
cold cracking phenomenon’s. On the opposite, 4
Figure 6. Volume fraction of martensite alpha % Ni 200 series grades and, even more, the
versus % of deformation. Tests performed at 1%Ni grade are sensitive to cold cracking
20°C. phenomenons. To conclude, the 1%Ni grade even
with copper additions is very sensitive to cold
All grades were free of martensite in the as cracking phenomenon’s. When necessary post
received conditions and tested samples at 60°C heat treatment must be considered in order to
exhibited very few martensite after 40% avoid such undesirable phenomenon.
Figure 8. Delayed cracking tests data.
Figure 10. Pitting potential of several stainless
CORROSION RESISTANCE PROPERTIES steels performed in a NaCl 2M solution at 23°C.

Figures 9 presents current density data It is clearly observed that pitting corrosion
recorded on several stainless steels (ferritic, resistance is directly related to the chromium
manganese austenitic and nickel austenitic content of the grades. Higher sulfur contents
grades ) being immersed in sulfuric 2M acid have a negative effect on pitting corrosion
solution at 23°C. Corrosion resistance is directly resistance (Figure 11). This is a well know
linked to the chromium content. The current phenomenon since sulfide inclusions are
density data are plotted on a logarithmic scale. preferential sites to initiate pits. The grades
This underlines the powerful effects of newly manufactured particularly in China have
chromium content on the corrosion resistance of the worst pitting corrosion resistance and in no
stainless steels in acidic conditions. case may perform as an austenitic 304 grade.
Figure 12 presents data performed on a multipit
cell. About 20 samples per plate have been
High corrosion rates
tested. It is confirmed that the new developed
grades of 4 and 1 Ni. families are more sensitive
to pitting than a 304 grade even if the testing
conditions are not severe.

Figure 9. Current density data measured on


ferritic 430, 441 and austenitic grades in a 2M
H2SO4 solution at 23°C.
Figure 11. Pitting potential of 1Ni and 4 Ni manga-
Figures 10 to 12 presents some data concerning nese containing austenitic stainless steels. Tests
the resistance to pitting for several stainless performed in NaCl 2M solution at 23°C.
steels. Data are recorded by polarization curves.
Higher voltage for pit initiation means better When increasing the temperature from room to
resistance to pitting. 50°C we observe that pitting corrosion is as
expected reduced but that the 1% Ni grades are
more affected than the 4%Ni grades (figure 13 ).

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6 spectacular on the edges. Clearly the grades do
not perform equally to 304 austenitic grades.
The grades are not suitable for sea shore
applications.

Figure 12. Pitting corrosion resistance of several


stainless steel grades. ( 20 samples per plate
tested) .

Figure 14. Typical depassivation pH of Stainless


Steel grades. Data obtained by means of polari-
zations curves in 2M NaCl solution at several pH.
Figure 13. Effect of temperature on the pitting
corrosion resistance. Tests performed in NaCl
2M sol.

Crevice corrosion resistance of the different


grades has been also investigated by means of
polarization curves. Tests were performed in a
2M NaCl solution at various Ph in order to
investigate the depassivation pH – pH under
which the grade is no more passive – as well as
the kinetics of corrosion of the different grades
under the depassivation potential. Those data
provide us useful information concerning the
effects of alloying elements and structure on the
crevice corrosion resistance. Data are provided
figures 14 and 15.

It is observed once again that the 4 Ni and 1Ni


grades do not perform like a 304 grade. The 1 Ni Figure 15. Crevice corrosion propagation rate.
particularly with low chromium and high sulfur Tests performed in a 2M NaCl solution at pH of
content are the worth. The grade are really 1.5.
subject to crevice corrosion in relatively non
severe conditions. It is obvious that the use of Inter granular corrosion tests have also been
such grades in acidic conditions like performed on several plates issued from the
encountered In process industry is prohibited. Chinese market. Strauss-test and red. Strauss-
The alloys are also not to be considered for uses test (35°C) testing conditions have been
in sea water or sea shore conditions. selected. TIG welds and spot welds structures
have been considered. It is clearly observed that
Complementary salt spray tests have been in those conditions grades having more than
conducted on 304, 4 Ni, 1 Ni and 439 ferritic 0.09 carbon present in both base and weld
grades. The two austenitic 4 Ni and 1 Ni exhibited deposit areas cracks. When welding such grades
corrosion marks. Corrosion was particularly with high carbon level, at least for thicknesses
higher than 2 mm., PWHT must be considered to hot rolling with a steckel mill or tender mill plus
obtain satisfactory inter granular corrosion cold rolling on ZS – is selected with some
resistance properties. specificities ( capture of the fumes, … more
power needed for rolling, specific conditions for
pickling… ) which explain that some extra
production costs must be considered. Their main
advantage is an increase of the mechanical
properties of nearly 30 % which allows the
designers to cut weight. The grades had more or
less successes taking in to account the nickel
price. Once again the grades are well defined
and used for many years in specific applications
like transport industry.
304 4 Ni 1 Ni 439
India, for many decades, decided to restrict
Figure 16. Salt spray tests performed during 575 sharply the imports of nickel metal to save
Hours on several stainless steels. foreign currency and by the way develop internal
mining resources. This resulted in local
production of Mn austenitic grades for the Indian
market. 304 grades were selected only when in
service applications including safety aspects
requested their use. With time and experiences
several applications could be considered as
potential areas for the use of Mn containing
austenitic grades. ( non critical applications
when considering corrosion resistance, internal
building and architecture stainless steel uses,
household applications..).In the nineties India
started to produce huge quantities of the so
called 4 and 1 Ni grades with copper - another
austenite stabilizing element - which made it
Figure 17. Inter granular corrosion resistance possible to achieve a further decrease of the
test results performed on 1 and 4 Ni grades costly nickel or with the same Ni level, reduce
issued from the Chinese market. the nitrogen content. This latest possibility
made it possible to develop grades with
DISCUSSION improved drawing properties. Some grades were
also developed in order to reduce the costly
The partial or almost total substitution of Ni by alloying elements. Grades with 1 Ni and even less
combined Mn and nitrogen additions in the started to be more and more popular since with
stainless steel grades makes it possible to the new century since nickel price jumped to
produce austenitic grades with lower Ni. new records. The need of low cost austenitic
content. Furthermore, manganese additions grades equivalent to 304 to fill up the growing
have a beneficial effect on the increase of the demand in Asia started to be a strong driving
nitrogen solubility in the austenitic structure. force for new material selection. Deep drawing
This has lead, for now many years, to the properties were requested as well as “ soft “
development of high strength austenitic grades. grades because the manufacturing equipments
Nowadays more than 1 % N is considered. Hot were designed for the 304 grades. The 1 Ni grade
and cold rolling are more difficult due to the with copper additions started to be the best
strengthening effect of nitrogen additions. Most candidate. Unfortunately has earlier presented
of those grades concern a very marginal the chromium content of 18% is not compatible
tonnage and are dedicated to specific with such low nickel grade without forming
applications. ferrite. Chromium content was thus reduced
down to 16 % … 15% and now even for some
Some thousands of tons of grades equivalent to producers 14 %... 13 %! Clearly those grades
201, 202 or 205 grades with lower nitrogen have not equivalent corrosion resistance than
levels ( 0.12/0.25) are produced by big players in 304 grades! The chromium content is the key
the stainless steel business. This concerns US, factor for the corrosion resistance. Furthermore
Europe and Asia. The classical production route manganese and to some respect copper may
– electrical furnace, AOD, continuous casting, have specific detrimental effects. Repassivation

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8 properties are lowered and particularly in - Austenitic stainless steels with lower Ni
acidified conditions which are developing under contents – down to 1Ni max – can be produced
deposit corroded areas or in crevices their rate thanks to combined Mn. and N. additions .
of dissolution is 10 to 100 time higher than that - Several grades were developed for many years,
of the 304 grades. The 1 Ni grades are also know at a marginal scale, with success for their
to be much more sensitive to stress corrosion combined high strength and ductility
cracking. The grades particularly with low properties. This include the “classical” 200-
nitrogen content have an unstable austenite serie grades as well as extra high nitrogen
which transforms in to alpha martensite when containing grades ( 0.5….1,2 %N ). Their uses
deformed. In such conditions the grades are are well controlled and their low tonnage do
very sensitive to cold cracking phenomenons. not affect the scrap recycling business.
Cracks easily develop. And on top of all this - India at a “country scale” has developed a local
detrimental aspects, hundred of thousands of economy were Mn austenitic grades play a
tons are produced in China with poor major role. Grades are specified for specific
equipments. Chemistry is not precisely applications; mainly non critical and non highly
controlled, carbon level exceed the acceptable corrosive applications. With time, learning
ranges, sulfur contents reach 80 .. even more about their restricted uses has growth. The
than 100 ppm. … This affect the corrosion grades are not called “equivalent to 304”.
resistance properties of the grades! Their - With the new century, the booming Asian and
properties are much closer to than of a 409 particularly the Chinese economies combined
grade than a 304!!!! with a jump to new record of Ni prices, has
encouraged the uses of cheaper austenitic
Development takes place at an extraordinary stainless steels. Hundred thousands of tons of
speed and production has rose to more than a mainly 1 Ni but also 4 Ni grades were imported.
million of tons. Most of the grades do not fulfill Local producers started also to produce the
international standards, traceability do not exist grades with low cost driven approach
and grades are provided to distributors with conducting to melt grades with lower alloying
“black” marketing : cheaper and equivalent to elements – including Cr.- and no control of
304 !!! Such development is a real nightmare for residual elements like S, C, O. Grades were
our stainless steel industry since it may ruin the called “ equivalent to 304 and cheaper”!
image of confidence of our products. Some - Corrosion resistance of such grades is
failures have already occurred ( petrochemical drastically lower than a 304 kind material.
plant ) and many outdoor applications presents This concerns the general, pitting, crevice,
an unusual rusty appearance for stainless steel! stress corrosion and inter granular corrosion
More will occurred since part of that production resistance! They are clearly not designed for
will be included in final products for export. Set corrosive conditions encountered in process
of 4 pans issued from China and sold in Europe industry, sea shore applications and even will
presented 4 different chemistries : from 301 to 4 rust if used in water systems!
and 1 Ni grades! More will have to be done in - The products will through exports of final
traceability and international rules! In the products reach all countries around the world.
future, recycling the scraps will be complicated Since they behave not like 304 rusty and
and scrap dealers will have to certify the real Ni corroded products will be observed after few
content of the grades. Copper when used as a months when improperly used. Recycling will
standard alloying element in 4Ni. and 1Ni. grades be more difficult since stainless steel scrap
will pollute the standard 304 chemistry…. may be contaminated. ( Cu, Mn... ).
- Traceability and conformity to standards, codes
Definitively we need to stay professional in our and norms must be a common habit. Material
business and keep on the safety area. Traceability specification must be written taking in to
must be a general goal and teaching all the actors account the real properties of the products and
– producers, suppliers, layers, transformators, end in service conditions. If not , uses should be
users...- concerning the real properties of the prohibited. Poor quality products should be
different stainless steel grades a need. restricted to marginal local applications if not
banished.
CONCLUSION - Education is of first concerns! Scientific data
should be provided to all the actors in order to
The paper has presented the so-called Mn austenitic preserve the image of the stainless steel
stainless steels of which Ni is partially replaced – up industry.
to 90% - by combined Mn and nitrogen additions.
The main following conclusions can be addressed :
ACKNOWLEDGEMENTS

Many thanks to the team of U&A RC for making


many of the data here presented. This includes
P.O. SANTACREU, J.D. DENIS, A. MORIZOT and L.
PEGUET.
Thanks also to TKN R&D and particularly Dr
KRAUTSCHICK for the data provided with
regards to the delayed cracking and inter
granular corrosion.
I would like also to express many tanks’ to Dr
SINGHAL of Jindal for the useful informations
provided concerning the Mn. austenitic grades
produced in India as well as his work on the
history of the Mn austenitic grades.
My acknowledgements are also addressed to
members of the ISSF team and particularly
Staffan Malm for his continuous
encouragements.

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