US 20190226068A1

( 19) United States

(12) BONNEFOIS
Patent Application
et al.
Publication (10) Pub. No.: US 2019/0226068 A1
(43 ) Pub . Date : Jul. 25 , 2019
(54 ) PROCESS FOR MANUFACTURING C22C 38 /56 (2013.01); B21B 1/26 (2013.01);
HOT-ROLLED PLATE , STRIP OR COIL C21D 6 / 004 (2013 .01); C21D 6 /005
MADE OF DUPLEX STAINLESS STEEL ( 2013 .01); C211 6 / 007 (2013 .01); C21D
6 / 008 ( 2013 .01) ; C211 8 / 021 ( 2013 . 01 ) ;
(71) Applicants : INDUSTEEL CREUSOT, La Plaine C211 8 /0263 ( 2013 . 01 ); C210 9 / 0081
Saint Denis (FR ); UGITECH , Jgine ( 2013 .01) ; C210 9 /46 ( 2013 .01) ; C210 9/52
(FR ) ( 2013 .01 ); C210 9 /525 ( 2013 .01); C22C
38 /002 ( 2013 .01 ) ; C22C 38 /06 (2013 .01) ;
(72 ) Inventors : Bernard BONNEFOIS , Le Breuil C22C 38 / 46 ( 2013 .01); C22C 38 / 44 ( 2013.01) ;
(FR ); Jérôme PEULTIER , Magnien C22C 38 / 42 ( 2013.01); C22C 38 /04 ( 2013 . 01) ;
( FR ); Mickael SERRIERE , Saint C22C 38/ 02 ( 2013 .01) ; C22C 38 / 004
Sernin du Bois (FR ); Jean -Michel ( 2013 .01) ; C22C 38/001 ( 2013 . 01 ); C21D
HAUSER , Ugine (FR ); Eric 2211 /005 (2013 .01); C22C 38 /005 (2013 .01)
CHAUVEAU , Albertville (FR )
(57) ABSTRACT
(21 ) Appl . No.: 16 /371,563 The invention relates to a duplex stainless steel composition ,
(22 ) Filed : Apr. 1, 2019 the composition of which consists of, in % by weight:
Cs0 .05 %
Related U .S. Application Data 21 % sCr < 25 %
1 % sNis2 . 95 %
(60 ) Division of application No . 14 /622 ,402, filed on Feb . 0 . 16 % sN50 .28 %
13 , 2015 , which is a continuation of application No . Mns2 . 0 %
12 / 305,014 , filed on May 11 , 2009 , now abandoned , Mo + W / 230 .50 %
filed as application No. PCT/FR2007/ 000994 on Jun . Mos0 .45 %
15 , 2007 . W s0 . 15 %
Foreign Application Priority Data Sis1. 4 %
(30) Als0 .05 %
Jun . 16 , 2006 ( EP ) ............. 06290991.6 0 .11 % sCus0.50 %
S < 0 .010 %
Publication Classification P < 0 .040 %
Cos0 . 5 %
(51) Int. Ci. REMs0 . 1 %
C22C 38 /60 ( 2006 .01) V 50 . 5 %
C22C 38 /00 ( 2006 .01 ) Tis0 . 1 %
C22C 38 /48 (2006 .01) Nbs0 . 3 %
C210 8 /02 ( 2006 .01 ) Mgs0 . 1 %
C22C 38 /50 ( 2006 .01 ) the balance being iron and impurities resulting from the
C22C 38 /52 ( 2006 .01) smelting, and the microstructure consisting of austenite
C22C 38 /54 (2006 .01) and 35 to 65 % ferrite by volume, the composition fur
C22C 38 /56 ( 2006 .01) thermore satisfying the following relationships:
B21B 1/ 26 ( 2006 .01 )
C21D 6 /00 (2006 .01) 40s1 70
C210 9 /00 ( 2006 .01) where
C210 9 / 46 ( 2006 .01 )
C21D 9 /52 (2006 .01) If =6x ( % Cr + 1. 32x % Mo+ 1.27x % Si) - 10x ( %
Ni+ 24x % C + 16 .15x % N + 0 .5x % Cu + 0 .4x %
C22C 38 /06 (2006 .01) Mn) - 6 . 17
C22C 38 /46 (2006 .01)
C22C 38 /44 ( 2006 .01) and
C22C 38 /42 ( 2006 .01 ) ILCR230 .5
C22C 38 /04 ( 2006 .01) where
C22C 38 /02 (2006 . 01)
(52 ) U .S . CI. ILOR = % Cr + 3 . 3x % Mo + 16x % N + 2 .6x % Ni - 0 .7x %
CPC .............. C22C 38/60 (2013 .01); C21D 6 /002 Mn,
(2013 .01 ); C22C 38 /48 (2013.01); C210 and also to a process formanufacturing plate , strip , coil, bar,
8 /0226 (2013 .01) ; C22C 38 /50 ( 2013 .01 ) ; rod , wire , sections, forgings and castings made of this
C22C 38 /52 ( 2013 .01 ); C22C 38 /54 (2013.01 ); steel.
Patent Application Publication Jul. 25, 2019 Sheet 1 of 3 US 2019/0226068 A1

Figure 1

XI .

at1tamfre0strumie°nrCdt

20 30 40 50 60 70 80 90 100
Figure 2
AO

. : heat 14383
A : heat 14441
. : heat 14382
- - - - - - - - - - - - - -- --- --- --- -

900 950 1000 1050 1100 1150 1200 1250 1300

Deformation temperature in °C
Patent Application Publication Jul. 25, 2019 Sheet 2 of 3 US 2019/0226068 A1

Figure 3

30 g " Cl" at 50°C

A 250 ppm Crat 25°C
)(VpPoitEenCtinSagl

27 29 31 33 35 37
LCR = Cr % + 3 , 3M0 % + 16N96 + 2 ,6Ni% - 0 , 7M0 %
Figure 4

1400 ; V (mV/ECS )
1200
140301

1000

800

600
517077 14382
400
14441 304L
200
14383
25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49
ILOR
Patent Application Publication Jul. 25, 2019 Sheet 3 of 3 US 2019/0226068 A1

Figure 5

Criticaltemperature (°C )
• Crevice - 30 g /1 CC
Pitting - 6 % FeCl3

27 29 31 LOR
33 35 37
US 2019 /0226068 A1 Jul. 25 , 2019

PROCESS FOR MANUFACTURING microstructural stability and good toughness of welded

HOT-ROLLED PLATE , STRIP OR COIL zones , without adding expensive addition elements, and also
MADE OF DUPLEX STAINLESS STEEL providing a process for manufacturing plate , strip , bar, rod ,
[0001] This is a Divisional of U .S . patent application Ser. wire or sections from this steel which is simpler to imple
ment.
No . 14 /622,402, filed Feb . 13 , 2015 , which is a Continuation [0009 ] For this purpose, the first subject of the invention
of U .S . patent application Ser. No . 12 /305 ,014 , filed May 11 , is a duplex stainless steel, the composition ofwhich consists
2009 which is a National Stage Application of International of, in % by weight:
Patent Application PCT/FR2007 /000994, filed Jun . 15 , 2007 [0010] Cs0.05 %
and claims the benefit of European Patent Application EP
06290991.6 , filed Jun . 16 , 2006 , all of which are hereby [0011 21 % s?rs25 %
incorporated by reference herein . [0012 ] 1 % sNis2 . 95 %
[ 0002] The present invention relates to a duplex stainless 10013 ] 0 . 16 % sNs0 .28 %
steel more particularly intended for the manufacture of [ 0014 ] Mn < 2 .0 %
structural components for material production installations 10015 ]. Mo + W /250 .50 %
( chemical, petrochemical, paper and offshore industries ) or 10016 ] Mos0 .45 %
energy production installations, without in any way being [ 0017 ) Ws0 . 15 %
limited thereto , and also to the process for manufacturing [0018 ] Sis1. 4 %
10019 ) Als0 .05 %
plate , strip , bar, rod , wire or sections from this steel . [0020 ] 0 . 11 % sCus0 .50 %
BACKGROUND 10021] S = 0 .010 %
[ 0022 ] P < 0 .040 %
[0003 ] More generally, this steel may be used as a substi [0023] Cos0 . 5 %
tute for a 304L type stainless steel in many applications, for [0024 ] REM < 0 . 1 %
example in the above industries or in the agri- foodstuff [ 0025 ] Vs0 .5 %
industry, including parts produced from formed rod or wire [0026 ] Tis0 . 1 %
(welded grids, etc .), sections ( strainers , etc . ), shafts , etc . It is [0027 ] Nb < 0 . 3 %
also possible to produce castings and forgings . [0028 ] Mg 0 . 1 %
[0004 ] For this purpose, stainless steel grades of 304 type the balance being iron and impurities resulting from the
and 304L type are known which , in the annealed state , have smelting, and the microstructure consisting of austenite and
an essentially austenitic microstructure . In the cold -worked
state they may furthermore contain a variable proportion of 35 to 65 % ferrite by volume, the composition furthermore
martensite . However, these steels include large additions of
satisfying the following relationships:
nickel, the cost of which is generally prohibitive. Further 40s1,570, preferably 4051 560
more , these grades may pose problems from a technical where
standpoint in certain applications, as they have poor tensile
properties in the annealed state, especially as regards the IF = 6x ( % Cr + 1. 32x % Mo + 1.27x % Si) – 10x ( %
yield strength , and a rather low stress corrosion resistance . Ni+ 24x % C + 16.15x % N +0.5x % Cu +0.4x %
Mn) - 6 .17
[0005 ] Austenitic - ferritic stainless steels are also known,
which are composed mainly of a mixture of ferrite and [0029 ] and
austenite , such as the steels 1.4362 , 1 . 4655 , 1 .4477 , 1 .4462 , ILCR230 .5, preferablyz32
1.4507, 1.4410 , 1.4501 and 1.4424 according to the where
EP10088 standard , which all contain more than 3 . 5 % nickel.
These steels are particularly resistant to corrosion and to = % Cr + 3 . 3x % Mo + 16x % N + 2 .6x % Ni - 0 .7x %
stress corrosion . Mn.
[0006 ] Ferritic or ferritic -martensitic stainless steel grades [0030 ] The steel according to the invention may also
are also known, the microstructure of which , for a defined include the following optional features , taken individually or
range ofheat treatments , is composed of two constituents — in combination :
ferrite and martensite preferably in a 50 /50 ratio , such as [0031 ] the proportion of ferrite is between 35 and 55 % by
the 1 .4017 grade according to the EN10088 standard . These volume;
grades, with a chromium content generally less than 20 % , [0032 ] the chromium content is between 22 and 24 % by
have high tensile mechanical properties but do not have weight;
satisfactory corrosion resistance. 0033 ] the manganese content is less than 1 . 5 % by weight;
[0007 ] Moreover, it is also desirable to simplify the pro [0034 ] the calcium content is less than 0 .03 % by weight;
cess for manufacturing steel plate, strip , bar, rod , wire or and
sections. [0035 ] the molybdenum content is greater than 0 . 1 % by
weight .
BRIEF SUMMARY [0036 ] A second subject of the invention consists of a
[0008 ] The objectof the present invention is to remedy the process for hot- rolled plate , strip or coil made of steel
drawbacks of the steels and manufacturing processes of the according to the invention , in which :
prior art by providing a stainless steel exhibiting good [0037 ] an ingotor slab of a steel of composition accord
mechanical properties and in particular a tensile yield ing to the invention is provided ; and
strength greater than 400 or even 450 MPa in the annealed (0038 ] said ingot or slab is hot- rolled at a temperature
or solution -treated state , a high corrosion resistance, in between 1150 and 1280º C . in order to obtain plate ,
particular the same or better than that of 304L , good strip or coil.
US 2019 /0226068 A1
[0039 ] In one particular method of implementation , said
ingot or slab is hot-rolled at a temperature between 1150 and
1280º C . in order to obtain what is called quarto plate ; a heat
treatment is then carried out at a temperature between 900
and 1100° C .; and said plate is cooled by an air quench .
[0040 ] A third subject of the invention consists of a
process for manufacturing hot-rolled bar or rod made of
steel according to the invention, in which :
[0041 ] a continuously cast ingot or bloom of steel of
composition the invention is provided ;
[0042 ] said ingot or bloom is hot-rolled from a tem
perature between 1150 and 1280º C . in order to obtain
bar, which is air- cooled , or a coil of wire stock which
is water -cooled ; and then , optionally:
[0043 ] a heat treatment is carried out at a temperature
between 900 and 1100° C .; and
[0044 ] said bar or a coil of wire stock is quench -cooled .
[ 0045 ] In one particular method of implementation , a
cold - drawing operation is carried out on said bar or a
die -drawing operation is carried out on said rod , after being
cooled .
[0046 ] The invention also covers a process for manufac
turing a steel section , in which a cold - forming operation is
carried out on a hot- rolled bar obtained according to the
invention , and also a process for manufacturing a steel
forging, in which a hot-rolled bar obtained according to the
invention is cut up into slugs and then a forging operation is
carried out on said slugs between 1100° C . and 1280º C .
100471. The invention furthermore covers various products
that can be obtained by the processes according to the
invention and also their uses, such as :
[0048 ] hot-rolled steel quarto plate, having a thickness
between 5 and 100 mm , and strip and coil , which may
be used for the manufacture of structural components
for material production or energy production installa
tions , in particular for material and energy production
installations operating between - 100 and 300° C .,
preferably between – 50 and 300° C .;
[0049 ] cold - rolled steel strip that can be obtained by
cold -rolling a hot-rolled coil;
[0050] hot-rolled bar having a diameter of 18 mm to
250 mm and cold -drawn bar having a diameter of 4 mm
to 60 mm , which products may be used for the manu
facture of mechanical parts such as pumps, valve
shafts , motor and engine shafts and couplings operating
in corrosive media ;
[0051] hot - rolled rod having a diameter of 4 to 30 mm
and die - drawn rod or wire having a diameter of 0 .010
mm to 20 mm , which products can be used for the
manufacture of cold - formed assemblies, for the agri
foodstuff industry , for oil and ore extraction , or for the
manufacture of woven or knitted metal fabrics for the
filtration of chemicals , ores or foodstuffs;
[0052] sections;
[0053 ] forgings that can be used for the manufacture of
brackets or couplings ; and
[0054 ] castings that can be obtained by casting a steel
according to the invention .
[0055 ] Other features and advantages of the invention will
become apparent on reading the following description , given
solely by way of example .
[0056 ] The duplex stainless steel according to the inven
tion comprises the contents defined below .
Jul. 25 , 2019
[0057 ] The carbon content of the grade is equal to or less
than 0 .05 % , preferably less than 0 . 03 % , by weight. This is
because too high a content of this element degrades the
localized corrosion resistance by increasing the risk of
chromium carbides precipitating in the heat-affected zones
of welds.
10058 ] The chromium content of the grade is between 21
and 25 % by weight, preferably between 22 and 24 % by
weight, so as to obtain good corrosion resistance, which is
at least equivalent to that obtained with type 304 or 304L
grades.
10059 ]. The nickel content of the grade is between 1 and
2 .95 % , preferably equal to or less than 2 .7 % , or even 2. 5 % ,
by weight. This austenite - forming element is added so as to
obtain good crevice corrosion resistance . At contents of
greater than 1 % and preferably greater than 1 .2 % by weight,
it has a favourable effect in combating the initiation of
pitting corrosions. However, its content is limited since
above 2 . 95 % by weight a degradation in the resistance to
pitting propagation is observed . Addition of nickel also
makes it possible to obtain a good toughness /ductility com
promise since it has the benefit of translating the toughness
transition curve towards low temperatures, this being par
ticularly advantageous for the manufacture of thick quarto
plate , for which the toughness properties are important.
[0060] Since the nickel content in the steel according to
the invention is limited, it has been found to be necessary , in
order to obtain an appropriate austenite content after heat
treatment between 900° C . and 1100° C ., to add other
austenite - forming elements in unusually high amounts and
to limit the contents of ferrite -forming elements.
[0061 ] The nitrogen content of the grade is between 0. 16
and 0 .28 % by weight, which generally means that the
nitrogen is added to the steel during smelting . This austenite
forming element firstly makes it possible to obtain ferrite
austenite two -phase duplex steel containing an appropriate
proportion of austenite exhibiting good stress corrosion
resistance, and also to obtain metal with high mechanical
properties. It also makes it possible to have good micro
structural stability in the heat-affected zones of welds. Its
maximum content is limited since , above 0 .28 % , a solubility
problem may be observed : formation of blisters during
solidification of slabs, blooms, ingots , castings or welds .
[0062] The content of manganese, which is also an aus
tenite - forming element below 1150° C ., is kept below 2 .0 %
by weight, and preferably below 1. 5 % by weight,because of
the deleterious effects of this element on many counts . Thus ,
it poses problems during smelting and refining of the grade
since it attacks certain refractories used for the ladles . This
requires these expensive elements to be replaced more
frequently , and therefore causes the process to be interrupted
more frequently.
[0063 ] Additions of ferro -manganese normally used to
bring the grade to composition also contain appreciable
amounts of phosphorus and also selenium , which elements
it is not desirable to introduce into the steel and are difficult
to remove when refining the grade .Manganese also disturbs
this refining, by limiting the possibility of decarburation . It
also poses a problem further downstream in the process , as
it impairs the corrosion resistance of the grade because ofthe
formation of manganese sulphides (MnS ) and of oxidized
inclusions . This element is conventionally added to grades
that it is desired to enrich with nitrogen , so as to increase the
solubility of that element in the grade . Without a sufficient
US 2019 /0226068 A1
manganese content, it was therefore not possible to achieve
such a nitrogen level in the steel. However, the inventors
have found that it is possible to limit the addition of
manganese in the steel according to the invention , while still
adding sufficient nitrogen in order to obtain the desired effect
on the ferrite -austenite balance of the base metal and to
stabilize the heat-affected zones of welds.
[ 0064 ] Molybdenum , a ferrite - forming element, is main
tained with a content of less than 0 .45 % by weight, while
tungsten is maintained with a content of less than 0 . 15 % by
weight. Moreover , the contents of these two elements are
such that the sum Mo + W / 2 is less than 0 . 50 % by weight ,
preferably less than 0 .4 % by weight and even more prefer
ably less than 0 .3 % by weight. This is because the present
inventors have found that, by maintaining these two ele
ments, and with the sum of their contents below the values
indicated , no precipitation of embrittling intermetallics is
observed , thereby making it possible in particular to relax
the process for manufacturing steel plate or strip by permit
ting said plate or strip to be air -cooled after heat treatment
or hot processing . Furthermore, they have observed that, by
controlling these elements within the claimed limits , the
weldability of the grade is improved . However, it is pre
ferred to maintain a minimum molybdenum content of 0 . 1 %
so as to improve the hot forgeability of the grade . Further
more , smelting a grade having less than 0 .1 % molybdenum
would imply greatly limiting the use of recycling scrap for
this grade , thereby posing processing problems, in particular
requiring a charge consisting 100 % of pure ferro -alloys to be
used .
[ 0065 ] Copper, an austenite -forming element, is present in
an amount of between 0 .11 and 0 .50 % by weight, and
preferably between 0 . 15 and 0 .40 % by weight. This element
improves the corrosion resistance in a reducing acid
medium . However, its content is limited to 0 .50 % by weight
in order to prevent the formation of epsilon - phases , which it
is desirable to avoid , since these result in hardening of the
ferritic phase and embrittlement of the duplex alloy .
[0066 ] The oxygen content is preferably limited to 0 .010 %
by weight, so as to improve its forgeability.
[ 0067 ] Boron is an optional element thatmay be added to
the grade according to the invention in an amount of
between 0 .0005 % and 0 .01 % by weight, preferably between
0 .0005 % and 0 .005 % and even more preferably between
0 .0005 % and 0 .003 % by weight , so as to improve its hot
conversion . However, in another embodiment, it is preferred
to limit the boron content to less than 0 .0005 % by weight so
as to limit the risk of cracking during welding and continu
ous casting.
[0068 ] Silicon , a ferrite - forming element, is present with a
content of less than 1 .4 % by weight. Aluminium , a ferrite
forming element, is present with a content of less than 0 .05 %
by weight and preferably between 0.005 % and 0 .040 % by
weight, so as to obtain low -melting -point calcium aluminate
inclusions . The maximum aluminium content is also limited ,
so as to avoid excessive formation of aluminium nitrides .
The action of these two elements — silicon and aluminium
is essentially to ensure correct deoxidation of the steel bath
during smelting .
[ 00691 Cobalt, an austenite - forming element, is main
tained with a content of less than 0 .5 % by weight, preferably
less than 0 . 3 % by weight. This element is a residual element
provided by the raw materials. In particular, it is limited
Jul. 25 , 2019
because ofhandling problems that it may pose after irradia
tion of components in nuclear power plants .
[0070 ] Rare earth metals (denoted by REM ) may be added
to the composition in an amount of 0 . 1 % by weight, pref
erably less than 0 .06 % by weight.Mention may in particular
be made of cerium and lanthanum . The contents of these two
elements are limited , as they are liable to form undesirable
intermetallics.
10071 ] Vanadium , a ferrite - forming element, may be
added to the grade in an amount of 0 . 5 % by weight and
preferably less than 0 .2 % , so as to improve the crevice
corrosion resistance of the steel.
[0072 ] Niobium , a ferrite - forming element,may be added
to the grade in an amount of 0 .3 % by weight and preferably
less than 0 .050 % by weight. It helps to improve the tensile
strength of the grade, thanks to the formation of fine niobium
nitrides . Its content is limited , so as to limit the formation of
coarse niobium nitrides .
[0073] Titanium , a ferrite - forming element,may be added
to the grade in an amount of 0 . 1 % by weight and preferably
less than 0 .02 % by weight, in order to limit the formation of
titanium nitrides formed in particular in the liquid steel .
[0074 ] It is also possible to add calcium to the grade
according to the invention , in order to obtain a calcium
content of less than 0 .03 % by weight and preferably greater
than 0 . 0002 % or even greater than 0 .0005 % by weight, so as
to control the nature of the oxide inclusions and improve
machinability . The content of this element is limited , as it is
liable to form , with sulphur, calcium sulphides which
degrade the corrosion resistance properties. In a preferred
embodiment, the calcium content is limited to less than
0 .0005 % , preferably less than 0.0002% , by weight.
[0075 ] Sulphur is maintained with a content of less than
0 .010 % by weight and preferably with a content of less than
0 .003 % by weight. Asmentioned above, this element forms
sulphides with manganese or calcium , the presence of sul
phides being deleterious to the corrosion resistance. Sulphur
is considered as an impurity .
[0076 ] An addition of magnesium in an amount with a
final content of 0 . 1 % may bemade so as to modify the nature
of the sulphides and the oxides.
[0077 ] Selenium is preferably maintained at less than
0 .005 % by weight because of its deleterious effect on the
corrosion resistance . This element is in general introduced
into the grade as impurities of ferrite and manganese ingots .
[0078 ] Phosphorus is maintained with a content of less
than 0 . 040 % by weight, and is considered as an impurity .
[0079 ] The balance of the composition consists of iron and
impurities . Other than those already mentioned above, these
impurities may also be zirconium , tin , arsenic , lead or
bismuth . Tin may be present with a content of less than
0 .100 % by weight and preferably less than 0 .030 % by
weight in order to prevent welding problems. Arsenic may
be present with a content of less than 0 .030 % by weight and
preferably less than 0 .020 % by weight. Lead may be present
with a content of less than 0 . 002 % by weight and preferably
less than 0 . 0010 % by weight. Bismuth may be present with
a content of less than 0 . 0002 % by weight and preferably less
than 0 .00005 % by weight. Zirconium may be present in an
amount of 0 .02 % .
[0080] Moreover, the present inventors have found that ,
when the percentages by weight of chromium , molybdenum ,
nitrogen , nickel and manganese satisfy the relationship
US 2019 /0226068 A1
below , the grades in question exhibit good localized corro
sion resistance , that is to say resistance to the formation of
pits or crevices:
p = % Cr+ 3 .3x % Mo + 16x % N + 2 .6x % Ni - 0 .7x %
Mn30 . 5 .
[0081 ] The microstructure of the steel according to the
invention , in the annealed state , is composed of austenite
and ferrite, which phases are preferably, after treatment for
1 h at 1000° C ., present with a ferrite proportion of 35 to
65 % by volume and more particularly preferably 35 to 55 %
by volume.
[ 0082] The present inventors have also found that the
following formula suitably describes the ferrite content at
1100° C .:
18 =6x ( % Cr + 1.32x % Mo+ 1.27x % Si)- 10x %
Ni+ 24x % C + 16 . 15x % N + 0 .5x % Cu + 0 .4x %
Mn ) - 6 . 17 .
[0083] Thus, to obtain a ferrite proportion between 35 and
65 % at 1100° C ., the ferrite index Ip mustbe between 40 and
70.
10084 ] In the annealed state , the microstructure does not
contain other phases that would be deleterious to its
mechanical properties, especially such as the sigma- phase
and other intermetallic phases. In the cold -worked state , part
of the austenite may have been converted to martensite ,
depending on the actual temperature of deformation and the
amount of cold deformation applied .
[0085 ] In general, the steel according to the invention may
be smelted and manufactured in the form ofhot -rolled plate ,
again called quarto plate , but also in the form of hot -rolled
strip , from slabs or ingots, and also in the form of cold -rolled
strip from hot- rolled strip . It may also be hot-rolled in the
form of bar or rod stock or sections or forgings . These
products may then be hot- converted by forging or cold
converted into bar or drawn sections or die - drawn wire. The
steel according to the invention may also be processed by
casting , whether followed by heat treatment or not.
[0086 ] To obtain the best possible performance character
istic, it will be preferential to use the process according to
the invention that firstly includes the provision of a steel
ingot, slab or bloom having a composition according to the
invention .
[0087] This ingot, slab or bloom is generally obtained by
melting the raw materials in an electric furnace followed by
vacuum remelting of the AOD or VOD type with decarbur
ization . The grade can then be cast in the form of ingots, or
in the form of slabs or blooms by continuous casting in a
bottomless mould . It is also conceivable to cast the grade
directly in the form of thin slabs, in particular by continuous
casting between counter -rotating rolls .
[0088 ] After having provided the ingot, slab orbloom , this
may optionally be reheated so as to reach a temperature
between 1150 and 1280º C ., but it is also possible to work
directly on the slab immediately on being continuously cast,
while still hot.
10089] In the case of plate manufacture , the slab or ingot
is then hot-rolled in order to obtain a quarto plate generally
having a thickness between 5 and 100 mm . The reduction
ratios generally employed at this stage vary between 3 and
30 % . This plate then undergoes a heat treatment to put the
precipitates, formed at this stage , back into solution by
reheating to a temperature between 900 and 1100° C ., and is
then cooled.
Jul. 25 , 2019
[0090 ] The process according to the invention provides for
air- quench cooling, which is easier to implement than the
conventionally used cooling for this type of grade, which is
more rapid cooling , using water. However, it remains pos
sible to carry out a water-cooling operation , if so desired .
10091 ] This slow air cooling is particular made possible
thanks to the limited nickel and molybdenum content of the
composition according to the invention , which is not subject
to the precipitation of intermetallic phases detrimental to its
usage properties . This cooling may in particular be carried
out at a rate ranging from 0 .1 to 2.7° C ./s.
[0092] After being hot-rolled , the quarto plate may be
levelled , cut and pickled if it is desired to deliver it in this
state .
[0093] It is also possible to roll this bare steel on a strip
rolling mill down to thicknesses of between 3 and 10 mm .
10094 ]. In the case of manufacturing long products from
ingots or blooms, it is possible to hot- roll in a single hot pass
on a multi - stand rolling mill, between fluted rolls , at a
temperature between 1150 and 1280º C . in order to obtain a
bar or coil of wire stock , or rolled . The cross - section ratio
between the initial bloom and the final product is preferably
greater than 3 , so as to ensure the internal soundness of the
rolled product.
[0095 ] When a bar has been manufactured , this is cooled
on leaving the rolling mill, by simple air spreading .
100961. When rolled rod with a diameter of greater than 13
mm is manufactured , this may be cooled , on leaving the
rolling mill, by quenching it in coil form in a water tank .
[0097] When rod with a diameter of 13 mm or less is
manufactured , it may be cooled by a water quench in the
form of turns spread out on a conveyor after said turns have
passed along a conveyor for 2 to 5 minutes through a
solution treatment furnace at a temperature between 850° C .
and 1100° C .
[0098 ] A subsequent furnace heat treatment between 900°
C . and 1100° C . may optionally be carried out on this bar or
coil, already treated after the hot- rolling , if it is desired to
complete the recrystallization of the structure and slightly
reduce the tensile properties.
[0099] After this bar or coil of rod has cooled , various
hot - forming or cold - forming treatments may be carried out,
depending on the final usage of the product. The bar may
undergo a cold - drawing operation or the rod may undergo a
die -drawing operation , after being cooled .
0100 ] The hot - rolled bar may also be cold - formed or
parts may bemanufactured after the bar has been cut up into
slugs and then forged .
BRIEF DESCRIPTION OF THE DRAWINGS
[0101] To illustrate the invention , trials were made and
these will be described in particular with reference to FIGS .
1 to 5 which show :
10102 ] FIG . 1 : A correlation between % ferrite after treat
ment at 1100° C . and I, for as - processed products ;
[0103 ] FIG . 2: A relative diametral change AØ as a func
tion of the deformation temperature;
[0104 ] FIG . 3: Pitting potentials El and E2 , determined on
forged bars , as a function of the index ILCR;
[0105] FIG . 4 : The uniform corrosion rate V , determined
on forged bars , as a function of the index IlcR ; and
[0106 ] FIG . 5 : Critical temperatures Tcc and Tcp , deter
mined on forged bars , as a function of the index IlcR :
US 2019 /0226068 A1 Jul. 25 , 2019

DETAILED DESCRIPTION suring 220x1700 mm in cross section before being hot

rolled , after reheating to 1200° C ., into quarto plates with
Examples thicknesses of 7 , 12 and 20 mm . The plates thus obtained
[ 0107] 25 kg laboratory ingots were produced by vacuum then underwent a heat treatment at around 1000° so as to put
induction melting pure ferro -alloy raw materials , followed the various precipitates present at this stage back into
by introducing nitrogen by addition of ferro - alloys nitrided solution . After the heat treatment, the plates were water
under a nitrogen partial pressure and cast into a metalmould cooled , then levelled , cut and pickled .
under an external nitrogen pressure of 0 . 8 bar. Among these, [0109] The compositions in percentages by weight of the
only trials 14441 and 14604 were according to the invention . various grades smelted on a laboratory scale or an industrial
[ 0108 ] An industrial heat according to the invention of 150 scale are given in Table 1, together with the compositions of
tonnes referenced 8768 was produced . This grade was the various industrial products or semi-finished products
smelted by melting in an electric furnace then vacuum smelted in an electric furnace , followed by AOD refining
refined with decarburization in order to achieve the intended and cast into ingots or continuously cast, these being men
carbon level. It was then continuously cast into slabs mea tioned for comparison .
TABLE 1
Heat No.
14441 14604 8768 14382 14383 14439 14426 14422 14425 14424 14660
Product 25 kg 25 kg 150 t 25 kg 25 kg 25 kg 25 kg 25 kg 25 kg 25 kg 25 kg
Al 0 .014 0 .012 0 .0042 0 .010 0 .015 0 .014 < 0 .002 < 0 .002 0 .024
0 .016 0 .028 0 .020 0 .020 0 .020 0 .017 0 .021 0 .022 0 .019 0 .020 0 .024
23.07 22 .80 22.83 23 .03 23.01 23.05 26 .67 26 .56 26 .68 26 .61 22.79
Cu 0 . 301 0 . 3000 . 15 0 . 304 0 .297 0 .299 0 .279 0 . 280 0 . 280 0 .208 0 .284
Mn 1 .282 1 . 284 1 .25 1.288 1 . 277 1. 309 0 .724 0 .706 0 .723 0 .705 4 .780
?? 0 . 249 0 .249 0 . 35 0 .251 0 . 250 0 .251 1 .322 1. 337 1.327 1 .328 0 .296
N 0 .212 0 . 239 0 .21 0 . 110 0 .110 0 . 290 0 . 119 0 .117 0 . 300 0 .237 0 . 199
2.539 1.692 2.50 4 . 249 1 .5521 .485 4 .532 1.419 1.541 2 .549 2.470
0 .0049 0 .0038 0 .0042 0 .0031 0 .0039 0 . 0052 0 .0316 0 .0284 0 .0205 0 .0221 0 .0033
0 .023 0 .023 0 .024 0 .024 0 .024 0 .022 0 .025 0 .022 0 .025 0 .022 0 .025
0 .0009 0 .0010 0 .0005 0 .0008 0 .0008 0 .0009 0 .0209 0 .0203 0 .0210 0 .0203 0 .0014
ZBOAEN 0 .430
0 . 121
< 0 .010
0 .358
0 .061
< 0 .010
0 . 44
0 .064
0 .019
0 .399
0 . 123
< 0 .010
0 .455
0 .122
< 0 .010
0 . 403
0 . 120
< 0 .010
0 .424
0 . 106
< 0 .010
0 . 391
0 . 102
< 0 .010
0 .407
0 . 109
< 0 .010
0 . 408
0 . 107
< 0 .010
0 . 494
0 .013
< 0 .010
0 .0048 0 .0017 0 .007 0 .0027 0. 0039 0 .0027 0 .0041 0 .0059 0 .0047 0 .0050 0 .0011
0.0048 0 .0052 0 .0042 0 .0049 0 .0055 0 .0064 0 .0055 0. 0060 0 .0058 0.0072 0. 0083
< 0 .002 < 0 .002 0 .041 < 0 .002 < 0 .002 < 0 .002 < 0 .002 < 0 . 002 < 0 .002 < 0 .002 < 0 .002
Ca < 0 . 0005 < 0 .0005 0.0003 < 0 . 0005 < 0 .0005 < 0 . 005 < 0 .0005 < 0 . 005 < 0 .0005 < 0 .0005 < 0 .0002
Nb < 0 .002 < 0 .002 0 .0009 < 0 .002 < 0 .002 < 0 .002 <0 .002 < 0 .002 < 0 .002 < 0 .002 < 0 .002
Se < 0. 002 < 0 .002 < 0 .002 < 0 .002 < 0 .002 < 0 .002 <0 .002 < 0 .002 < 0 .002 < 0 .002 < 0. 002
As < 0 .002 < 0 .002 < 0 . 002 < 0 .002 < 0 .002 < 0 . 002 < 0 . 002 0 .002 < 0 .002 < 0 .002 < 0 .002
Ce + La < 0 .0002 < 0 .0002 < 0 .0002 < 0 .0002 < 0 .0002 < 0 .0002 < 0 .0002 < 0 .0002 < 0 .0002 < 0 .0002 < 0 .0002
Mg < 0 .0005 < 0 .0005 0 .0004 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005 < 0 . 0005 < 0 . 0005
< 0 .0005 < 0 .0005 0 .0024 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005
Heat No.
304 304L 316L UNS32101 UNS32304 140301 436002 517077 533054 150091
Product
Al 0 .026 0 .006
0 .020 0 .018 0 .022 0 .018 0 .015 0 .021 0 .026 0 .029 0 .011
18. 23 18 . 4 16 . 5 21. 6 22 . 9 23 .01 22 . 30 22 . 14 22.32 23.02
Cu 0 .15 0 . 11 0 .31 0 . 24 0 . 163 0 . 303 0 . 260 0 .284 0 .083
Mn 0 . 79 1 . 20 1 .66 5 .2 1 . 26 1. 563 1 .097 1. 082 1.054 1.584
?? 0 .37 0 . 16 2.08 0 .3 0 . 24 2 .802 0 .277 0 . 285 0 . 275 3 . 118
N 0 .044 0 .074 0 .067 0 .224 0 . 12 0 .164 0 . 143 0 .119 0 . 106 0 .150
8 .96 10 .2 10 . 24 1 .5 4 . 20 5 .500 4 .022 3. 995 4 . 364 8 .672
0 . 0037
0 .023 0 .020 0 .019 0 .027 0 .028 0 .022 0 .022 0 .023 0.019
0 .0013 0 .0011 0 .0004 0 .0008 0 .0006 0 .0004 0.0004 0 .0006 0 .0009
0 . 37 0 .50 0 .71 0 .40 0 . 206 0 .414 0 .464 0 .400 0 . 390
0 . 103 0 . 114 0 .058 0 .126
0 .028 0. 017 0 .013 0 .022
0 .0065 0 .0040 0 .0030 0 . 0033
?? 0 .063 0 . 129 0 .056 0. 035
1

?? 0 .0007 0 .0026 0 .0028 0 .0007

Nb 0 .0046 0.009 0 .012 0. 0063
Se < 0 .0020 < 0 . 0020 < 0 . 0020 < 0 . 0020 < 0 . 0020
Ce + La
US 2019 /0226068 A1 Jul. 25 , 2019

TABLE 1- continued
Mg 0 .0014 < 0 .0005 < 0 .0005 < 0 .0005 < 0 .0005
0 .0008 < 0 .0005 <0 .0005 0 .0022 < 0 .0005
* Rolled plate or billet or bar.

[0110] 1. Ferrite Contents TABLE 3

[0111 ] 1. 1 Ferrite Contents on As- Processed Products Ferrite contents
[0112 ] Specimens ranging from 1 to 8 cm » in volume were
cut from these laboratory heats in the as -cast state or from ABM CHAZ
industrial products in the as - cast state , and heat treatments Reference Product (% )
for 30 minutes at various temperatures were carried out on 14441 * forged rod
these specimens, in a salt bath , followed by an end -of 14604 * forged rod
treatment water quench , in order to determine the proportion 14382 forged rod
of ferrite at high temperature . Since ferrite is magnetic , 14383 forged rod
14660 forged rod
unlike austenite, carbides and nitrides possibly present, an UNS S32101 HR plate
assaying method was used in which the saturation magne UNS S32304 HR plate
tization was measured . The ferrite contents thus determined
are given in Table 2 and plotted in FIG . 1. * according to the invention ;
HR : hot-rolled ;
[0113 ] FIG . 1 shows that there is a good correlation OBM ( % ) : ferrite content measured on the base metal;
between the index lp and the ferrite contents measured on araz: ferrite content measured in the heat - affected zone.
the base metal after treatments at 1100° C .
[0114 ] It has also been shown thatheat 14441 according to [0117 ] 2 . Castability
the invention has, below 1300° C ., a ferrite content appro [0118 ] Ingot 14439 exhibited blisters and was unusable.
priate to hot transformation to a duplex structure . Further To avoid this phenomenon during casting in air at atmo
more, after heat treatment in the 950° C . to 1100° C . range , spheric pressure , it proved necessary to limit the nitrogen
it has a ferrite content appropriate for stress corrosion content of the heats according to the invention to less than
resistance . 0 .28 % by weight.
TABLE 2
Heat 14382 14383 14441 14426 14422 14425 14424 140301 436002 517077 533054 150091
Product Ingot Ingot Ingot Ingot Ingot Ingot Ingot CCB C CB CCB CCB CCB
AS 55 .6 50 .5 52 .6 50 .3 25 .4
processed
state
+ 900° C . 45 . 6 89 . 5 54 . 4 71. 2 98 . 7 100 91 . 9 45 51. 0 47 .2 20 . 5
+ 950° C . 48 . 7 87. 1 51. 7 71 . 1 98 . 8 99 .6 94 .6 42 . 8 48. 9 46 . 1 25 . 4
+ 1000° C . 50 . 9 90 . 0 54. 5 71. 8 99 . 4 99 . 4 93.4 50 . 8 42 . 1 50 . 7 46 .0 28 . 8
+ 1050° C . 55. 7 81 . 0 53. 0 77 . 8 98 . 6 99 . 1 78 .8 54 44 . 2 54 . 6 48. 3 33 . 7
+ 1100° C . 60 . 8 84 .6 55 . 5 82 . 0 99 .0 87. 4 75 . 4 58 .6 47.6 59 . 4 51. 3 36 . 1
+ 1150° C . 65 . 2 88 .6 59 . 0 88. 1 98. 9 75 .6 78 . 1 64.6 52. 7 66 . 7 57. 9 41 . 1
+ 12000 76 . 6 94 . 2 64. 0 95 .4 98. 8 78 . 4 71.6 59.3 75. 5 64. 8 46 . 7
+ 1250° C . 92. 3 98. 1 67. 7 100 99 . 2 81. 0 86 . 2 81. 5 67 .4 86 . 0 73. 2 55 . 1
+ 1300° C . 95 .2 97. 7 72 .6 99.4 98 .7 859 . 935 . 100 78. 3 99 .0 85 .0 66 .4
CCB = continuously cast bloom .

[0115 ] 1.2 . Ferrite Contents On End -Products [0119 ] 3. Hot-Transformation Capability

[0116 ] The ferrite content was also measured by the grid
method ( according to ASTME 562 standard ) on forged bars
after heat treatmentat 1030° C . and in heat -affected zones of
weld beads deposited by a coated electrode with a constant
energy resulting in cooling rates at 700° C . of 20° C ./s. The
results (ferrite contents of the base metal and of the heat
affected zone) are given in Table 3 . This shows that heats
14441 and 14604 according to the invention have a ferrite
content in the base metal and in the heat- affected zone that
is favourable to localized corrosion resistance and to stress
corrosion resistance , and also favourable to toughness (cf.
Table 5 ) .
[0120 ] The hot-deformability was evaluated using hot
tensile tests carried out on test specimens, the calibrated part
of which , having a diameter of 8 mm and a length of 5 mm ,
was heated by Joule heating for 80 seconds at 1280º C . and
then cooled at 2° C . per second down to the test temperature ,
which varied between 900 and 1280º C . When this tem
perature was reached , the rapid tensile test was immediately
started , at the rate of 73 mm /s; after fracture, the necking
diameter at the break was measured .
[0121 ] The relative diametral change ( Table 4 ), as defined
below , reflects the hot-deformability :
[0122 ] A0 = 100x (1 - ( final diameter /initial diameter)).
US 2019 /0226068 A1 Jul. 25 , 2019

TABLE 4 [0128 ] 5 . Corrosion Resistance

Relative diametral changes (hot tensile test ) [0129 ] Corrosion resistance tests were carried out both on
the forged bars from laboratory heats and on coupons
Test removed from hot-rolled plates coming from the industrial
temperature AØ ( in % ) heats .
Heat 14382 Heat 14383 Heat 14441 * [0130] 5 .1 Localized Corrosion Resistance
1280 85 .0 100 .0 96 . 7
[0131] The pitting corrosion resistance was evaluated by
1250 98 . 3 86 .7 plotting the current -potential curves and determining the
1200 75 .0 98 .3 76 . 7 pitting potential for i= 100 UA /cm². This parameter was
1150 70 . 0 95.0
93 .3
61. 7 measured in a neutralmedium (pH = 6 .4 ) with a high chloride
1100 63.3 56 . 7 concentration ([C1" ] = 30 g /l) at 50° C . (E1), representative of
1050 51 . 7 75 .0 44 . 2
1010 45.0 the brine encountered in seawater desalination plants, and in
1000 65 .0 40 .0 a slightly acid (pH = 5 .5 ) medium with a low chloride con
980 36 . 7 centration ([C1- 1 = 250 ppm ) at room temperature (EU) rep
960 58.3 resentative of drinking water. The critical pitting tempera
950 35 . 8
900 35 .0 51. 7 36 . 7 ture in a ferric chloride medium (6 % FeCl3 ) was also
determined according to the ASTM G48 - 00 standard ,
* according to the invention . method C .
[0123] On examining Table 4 and FIG . 2, which represents [0132 ] In another series of trials, the pitting corrosion
resistance was determined in a deaerated neutral medium
the data in the form of curves, it may be seen that heat 14441 containing 0 . 86 mol/ litre of NaCl, corresponding to 5 %
according to the invention has a hot-deformability compa NaClby weight, at 35° C . A floating potentialmeasurement
rable to that of comparative reference heat 14382. for 900 seconds was carried out. Next, a potentiodynamic
[0124 ] 4 . Mechanical Properties curve was plotted at a rate of 100 mV /min of the floating
[0125 ] The tensile properties Re0 .2 and Rm were deter potential up to the pitting potential . The pitting potential (E3 )
mined according to the NFEN 10002 - 1 standard . The tough was determined for i= 100 UA /cm². Under these conditions ,
ness K , was determined at various temperatures according to specimens according to the invention and reference speci
the NF EN 10045 standard . mens of 304L grade and austenitic -ferritic duplex grades of
1 .4362 type and others were tested .
TABLE 5 [0133 ] The crevice corrosion resistance was studied by
Mechanical properties measuring the critical crevice temperature in the neutral
medium (pH = 6 .4 ) with a high chloride concentration ( C1- 1
Ky ?? = 30 g /l) . The arrangement favouring floating crevice corro
Reo.2 Rm 20°C . - 50° C . sion was in accordance with the recommendations given in
Reference Product (MPa ) (MPa ) (J) the ASTM G78 - 99 standard . The critical crevice tempera
14441* forged bar 477 716 334 51 ture is the minimum temperature for which crevices with a
14604 * forged bar 477 691 288 18 depth of greater than 25 um are observed .
14382 forged bar 436 664 > 339 339
14383 forged bar 458 604 79 9 [0134 ] The values obtained are given in Table 6 . Com
14660 forged bar
HR plate
493 701 293 31 parison between the results obtained on the plate made of
304L 218 523 312 301
UNS S32304 and the bar obtained from heat 14382 , these
316L HR plate 232 537 307 298
UNS S32101 HR plate 466 720 101 60 two being of similar chemical composition , indicates that
UNS S32304 HR plate 438 663 268 153 the corrosion resistance of a bar is lower than that of a
8768 * HR plate 519 743 hot-rolled plate of the same composition .
* according to the invention ; [0135 ] The present inventors have found that the localized
HR : hot-rolled ; corrosion resistance index , that is to say resistance to the
Re0.2: at yield strength 0. 2 % strain ; formation of pits or crevices , abbreviated to I, cpand defined
Ryi tensile strength .
by:
[0126 ] The results of the laboratory heats 14441 and = Cr+ 3 .3xMo + 16xN + 2 .6xNi - 0 .7xMn
14604 and of the industrial heat 8768 , all three according to
the invention , show that a yield strength of greater than 450 [0136 ] (contents in Cr,Mo, N , Niand Mn in % by weight)
MPa, i. e. twice that obtained for austenitic steels of AISI [0137 ] accounts for the classification of all the composi
304L type , may be obtained . tions containing less than 6 % nickel as regards localized
[ 0127 ] The toughness values determined at 20° C . for the corrosion resistance (see FIGS. 3 , 4 and 5 ).
laboratory heats 14441 and 14604 and for the industrial heat [0138 ] Heats 14383 and 14660 not according to the inven
8768, all three according to the invention , are all greater than tion , having Icr indices equal to 28 .7 and 29 . 8 , exhibit an
200 J, this being satisfactory taking into account the yield inferior corrosion behaviour than a steel of AISI 304L type .
strength level of these grades . For heat 14383 not according Heats 14604 and 14441 according to the invention , having
to the invention , having a low nitrogen content and a high an Ilcr of 30 . 9 and 33 , behave at least as well as 304L type
ferrite content in the annealed state , the toughness values at steel. To obtain a corrosion resistance at least equal to that
20° C . are below 100 J. This confirms the need for a of AISI 304L grade, it has been found that the steels
sufficient addition of nitrogen in order to obtain a satisfac according to the invention must preferably have an Ilcr of
tory toughness level. greater than 30 .5 and preferably greater than 32 .
US 2019 /0226068 A1 Jul. 25 , 2019

[0139 ] 5 .2 Uniform Corrosion Resistance What is claimed is :

[ 0140 ] Uniform corrosion was characterized by evaluating 1 . A process for manufacturing a hot-rolled plate, strip or
the corrosion rate by loss of weight after 72 hours ' immer coil made of steel comprising :
sion in a 2 % dilute sulphuric acid solution heated to 40° C . providing an ingot or slab of a steel of composition
[0141 ] Comparing the corrosion rates for the experimental comprising in % by weight:
heats containing 2. 5 % Ni and 0 .2 % N ( 14441 according to Cs0 .05 %
the invention and 14660 not according to the invention ) 21 % sCrs25 %
clearly shows the negative effect of a high Mn content on the 1 % sNis2 . 95 %
uniform corrosion resistance in a sulphuric medium . 0 . 16 % sNs0 .28 %
TABLE 6
Localized and uniform corrosion resistance data

E. E, E, TCP Tcc V
Ref. Product ILCR (V /ECS) (V /ECS ) (V /ECS) (°C.) (°C.) (mm /y )
14441 * forged rod 33 .0 0 . 165 1 .058 0 . 320 7 .5 50 0 .73
14604 * forged bar 30 . 9 0 .159 0 . 802 5 45 1. 8
14382 forged bar 35.8 0 . 302 1 .323 0 .420 15 60 0 . 24
14383 forged bar 28 . 7 0 .049 0 .595 0 .050 0 4 .95
14660
304L
316L
forged bar
HR plate
HR plate
UNS S32101 HR plate
29 . 8
NA
NA
26 .4
0 .094
0 .188
0 .266
0 .163
0 .707
0 .834
0 . 865
0 .855
0 .210
7.5
5
7 .5
12 . 5
aa
45
75
1 . 11

UNS S32304 HR plate 35 . 7 0 .413 1 .3301 17 .5 95

517077 rolled bar 34 .6 0 . 415
140301 rolled bar 47 . 1 1 . 2001
8768* HR plate 33. 1 0.227 1.2731
* according to the invention ;
' odixation potential of the solvent, no pitting observed ;
HR : hot-rolled ; NA : not applicable ;
Ej: pitting potential in neutralmedium (pH = 6 .4 ) having a high chloride concentration (30 g/l of Cl ) at 50° C .;
Ez: pitting potential in slightly acid environment (pH = 5 . 5 ) having a low chloride concentration (250 ppm of C1 )
at 25° C .;
Ez: pitting potential in neutral chloride medium ( 5 % NaCl) at 35° C .;
Tcp critical pitting temperature in a ferric chloride medium ;
Tcd critical crevice temperature in neutralmedium (pH = 6 . 4 ) with a high chloride concentration ( 30 g / l of C1 )
V : uniform corrosion rate in 2 % sulphuric acid medium at 40° C .

[0142] 5 .3 Repassivation Potential Mns2.0 %

[ 0143] The steel specimens were polished under water Mo+ W /230 .50 %
using SiC paper up to 1200 and then aged for 24 hours in air . Mos0 .45 %
[0144 ] The cyclic polarization test in a chloride medium W s0 .15 %
was carried out by starting with measurement of the floating Sis1. 4 %
potential for 15 min , followed by cyclic dynamic polariza Als0 .05 %
tion at 100 mV/min starting from the floating potential up to 0 .11 % sCus0.50 %
the potential for which the current reached an intensity of Ss0 .010 %
300 uA / cm², followed by return to the potential for which P < 0 .040 %
the current is zero . Cos0 . 5 %
[0145 ] Thus, the pitting potential (Ppit) and the repassiva REMS0 . 1 %
tion potentials ( Prepassivation ) of the previously formed pits Vs0 .5 %
were determined . The results obtained are given in Table 7 . Tis0. 1 %
Nbs0 . 3 %
TABLE 7 Mgs0 . 1 %
Repassivation as a function of the nickel content the balance being iron and impurities resulting from the
smelting, and the
Heat % Ni Vpii-Vrepassivation (mV/ECS) microstructure consisting of austenite and 35 to 65 %
14382 4 .5 460 ferrite by volume, the composition furthermore satis
14441 361 fying the following relationships :
14383 1.5 227 40512570
where
[0146 ] From the repassivation potential tests in NaCl IR = 6x ( % Cr+ 1 .32x % Mo+ 1. 27x % Si) - 10 % ( %
medium , the higher the nickel content the greater the dif Ni+ 24x % C + 16 . 15x % N + 0 .5x % Cu + 0 .4x %
ference between the pitting potential and the repassivation Mn) - 6 .17
potential. This shows that nickel is not beneficial to the
repassivation of a grade according to the invention that has and
previously undergone pitting corrosion . ILCR230 .5
US 2019 /0226068 A1 Jul. 25 , 2019

where providing a hot- rolled bar of claim 3 ;

IlcR = % Cr+ 3. 3 % Mo+ 16x % N + 2 .6x % Ni - 0 .7 - %
Mn; and
hot rolling the ingot or slab at a temperature between 1150
and 1280º C . in order to obtain plate , strip or coil.
2 . The process for manufacturing hot-rolled plate made of
steel according to claim 1 , in which :
hot-rolling the ingot or slab at a temperature between
1150 and 1280º C . to obtain a quarto plate ;
performing a heat treatment at a temperature between 900
and 1100° C .; and
cooling the plate by air quench .
3. The process for manufacturing hot-rolled bar or rod
made of steel comprising the steps of:
providing a continuously cast ingot or bloom of steel of
composition comprising in % by weight:
Cs0 .05 %
21 % sCrs25 %
1 % sNis2 . 95 %
0 . 16 % sNs0 .28 %
Mns2. 0 %
Mo+ W /250 .50 %
Mos0 .45 %
W s0 .15 %
Sis1. 4 %
Als0 .05 %
0 . 11 % sCus0 . 50 %
Ss0 .010 %
P < 0 .040 %
Cos0 . 5 %
REMs0 . 1 %
V 50 . 5 %
Tis0 . 1 %
Nbs0 . 3 %
Mgs0 . 1 %
a balance being iron and impurities resulting from the
smelting ;
hot-rolling the ingot or bloom from a temperature
between 1150 and 1280º C . in order to obtain a bar,
which is air- cooled , or a coil of wire stock which is
water-cooled ; and then , optionally :
performing a heat treatment at a temperature between 900
and 1100° C .; and
quench cooling the bar or coil of wire stock .
4 . The process for manufacturing according to claim 3 ,
further comprising the step of:
performing a cold - drawing operation carried out on the
bar or a die -drawing operation on the rod, after being
cooled .
5 . The process for manufacturing a steel section according
to claim 3 , further comprising the step of :
performing a cold -forming operation on the hot-rolled
bar.
6 . The process for manufacturing a steel forging compris
ing the steps of:
cutting the hot-rolled bar into slugs ; and
performing a forging operation on the slugs between
1100° C . and 1280º C .
7 . The process for manufacturing according to claim 1,
wherein 30 .5sILOR $ 38 .6 .
8 . The process for manufacturing according to claim 3 ,
wherein 40s1; 570 — where
1A = 6x ( % Cr + 1.32x % Mo+ 1.27x % Si)- 10x (%
Ni+ 24x % C + 16 .15x % N + 0.5x % Cu + 0.4x %
Mn) - 6 .17
and
where
Ilor = % Cr + 3. 3x % Mo + 16x % N + 2 .6x % Ni- 0 .7 - %
Mn.
9 . The process for manufacturing according to claim 8 ,
wherein 30 .5sIcRs38 .6 .
10 . A hot- rolled steel quarto plate , obtained by the process
according to claim 2 and having a thickness between 5 and
100 mm .
11 . Use of hot- rolled coil obtained by the process accord
ing to claim 1, for the manufacture of structural components
for material production or energy production installations.
12 . Use according to claim 11 , in which said material and
energy production installations operate between - 100 and
300° C ., preferably between - 50 and 300° C .
13 . A cold -rolled steel strip that can be obtained by
cold -rolling a hot-rolled coil obtained by the process accord
ing to claim 1 .
14 . A hot- rolled bar obtained by the process according to
claim 3 and having a diameter of 18 mm to 250 mm or a
hot- rolled rod that can be obtained by the process according
to claim 3 and having a diameter of 4 to 30 mm .
15 . A cold -drawn bar that can be obtained by the process
according to claim 4 , having a diameter of 4 mm to 60 mm ,
or die -drawn rod or wire that can be obtained by the process
according to claim 3 , having a diameter of 0 .010 mm to 20
mm .
16 . A mechanical part such as pumps , valve shafts, motor
and engine shafts and couplings operating in corrosive
media comprising:
a bar according to claim 14 .
17 . Use of a rod or wire according to claim 14 for the
manufacture of cold - formed assemblies , for the agri- food
stuff industry , for oil and ore extraction , or for the manu
facture of woven or knitted metal fabrics for the filtration of
chemicals , ores or foodstuffs.
18 . A steel section obtained by the process according to
claim 5 .
19 . A steel forging obtained by the process according to
claim 6 .
20 . Brackets or couplings comprising :
a steel forging according to claim 19 .