U.S. patent application number 10/472758 was filed with the patent office on 2004-06-10 for steel and steel tube for high- temperature use.
Invention is credited to Arbab, Alireza, Lefebvre, Bruno, Vaillant, Jean-Claude.
Application Number | 20040109784 10/472758 |
Document ID | / |
Family ID | 8861915 |
Filed Date | 2004-06-10 |
United States Patent
Application |
20040109784 |
Kind Code |
A1 |
Arbab, Alireza ; et
al. |
June 10, 2004 |
Steel and steel tube for high- temperature use
Abstract
The invention concerns steel for high temperature use containing
by weight: 0.06 to 0.20% of C, 0.10 to 1.00% of Si, 0.10 to 1.00%
of Mn, not more than 0.010% of S, 10.00 to 13.00% of Cr, not more
than 1.00% of Ni, 1.00 to 1.80% of W, Mo such that (W/2+Mo) is not
more than 1.50%, 0.50 to 2.00% of Co, 0.15 to 0.35% of V, 0.040 to
0.150% of Nb, 0.030 to 0.12% of N, 0.0010 to 0.0100% of B and
optionally up to 0.0100% of Ca, the rest of the chemical
composition consisting of iron and impurities or residues resulting
from or required for preparation processes or steel casting. The
chemical constituent contents preferably verify a relationship such
that the steel after normalizing heat treatment between 1050 and
1080.degree. C. and tempering has a tempered martensite structure
free or practically free of .delta. ferrite.
Inventors: |
Arbab, Alireza;
(Valenciennes, FR) ; Lefebvre, Bruno; (Estreux,
FR) ; Vaillant, Jean-Claude; (Paris, FR) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
8861915 |
Appl. No.: |
10/472758 |
Filed: |
October 3, 2003 |
PCT Filed: |
April 3, 2002 |
PCT NO: |
PCT/FR02/01151 |
Current U.S.
Class: |
420/37 |
Current CPC
Class: |
C22C 38/54 20130101;
C22C 38/48 20130101; C22C 38/46 20130101; Y02P 10/20 20151101; C21D
8/105 20130101; C22C 38/001 20130101; C22C 38/44 20130101; C22C
38/52 20130101 |
Class at
Publication: |
420/037 |
International
Class: |
C22C 038/30 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 4, 2001 |
FR |
0104551 |
Claims
1. A steel for seamless tubular products intended for high
temperature use, characterized in that it contains, by weight:
13 C 0.06% to 0.20% Si 0.10% to 1.00% Mn 0.10% to 1.00% S 0.010% or
less Cr 10.00% to 13.00% Ni 1.00% or less W 1.00% to 1.80% Mo such
that (W/2 + Mo) is 1.50% or less CO 0.50% to 2.00% V 0.15% to 0.35%
Nb 0.030% to 0.150% N 0.030% to 0.120% B 0.0010% to 0.0100%
and optionally, at most 0.050% by weight of al and at most 0.0100%
by weight of Ca; the remainder of the chemical composition being
constituted by iron and impurities or residual elements resulting
from or necessary to steelmaking or casting:
2. A steel according to claim 1, characterized in that the amounts
of the constituents of the chemical composition are linked by a
relationship such that after normalization heat treatment between
1050.degree. C. and 1080.degree. C. and tempering, the steel has a
tempered martensitic structure that is free of or almost free of
.delta. ferrite.
3. A steel according to claim 1 or claim 2, characterized in that
its Cr content is in the range 11.00% to 13%.
4. A steel according to any one of claims 1 to 3, characterized in
that its Si content is in the range 0.20% to 0.60%.
5. A steel according to any one of claims 1 to 4, characterized in
that its C content is in the range 0.10% to 0.15%.
6. A steel according to any one of claims 1 to 5, characterized in
that its Co content is in the range 1.00% to 1.50%.
7. A steel according to any one of claims 1 to 6, characterized in
that its Mo content is 0.50% or less.
8. A steel according to any one of claims 1 to 7, characterized in
that its Mn content is in the range 0.10% to 0.40%.
9. A steel according to any one of claims 1 to 8, characterized in
that its Ni content is 0.50% or less.
10. A steel according to any one of claims 1 to 9, characterized in
that the residual elements are controlled so that the Cu content in
the steel is 0.25% or less and preferably 0.10% or less.
11. A steel according to any one of claims 1 to 10, characterized
in that its S content is 0.005% or less, and preferably 0.003% or
less.
Description
FIELD OF THE INVENTION
[0001] The invention relates to steels for use under stress at high
temperatures of about 600.degree. C. to 650.degree. C., more
particularly steels known as ferritic steels with a high chromium
content with a tempered martensitic structure both at ambient
temperature and at service temperatures.
[0002] The invention is applicable to tubular metal products such
as superheater tubes, reheater tubes, headers or pipings for
superheated or reheated steam for boilers, or tubes for furnaces
for chemistry or petrochemistry.
BACKGROUND TECHNIQUE
[0003] Such products are usually seamless tubes obtained after a
severe hot plastic deformation operation carried out on solid bars
of highly specialized steel.
[0004] Apart from ferritic steels with 2.25% Cr-1% Mo according to
ASTM A213 type T22, austenitic stainless steel tubes according to
ASTM A213 (ASTM=American Society for Testing and Materials) type
TP321H, TP347H have long been known, containing about 0.05% C, 18%
Cr, 11% Ni and stabilized with Ti or Nb respectively.
[0005] Such steels are highly resistant to corrosion by steam
because of their chromium content and have high creep rupture
strengths of up to 700.degree. C. due to their austenitic
structure.
[0006] In contrast, they suffer from major drawbacks due to their
austenitic structure, which renders them incompatible with steels
with a ferritic or martensitic structure, which are of necessity
used in other parts of the boiler that are less exposed to high
temperatures; hence, the search for materials with a ferritic or
martensitic structure is of great importance.
[0007] For high temperature uses, then, tubes of ASTM A213 T91
steel (generally used for small superheater tubes) or ASTM A335 P91
(generally used for the largest pipes for header or superheated
steam piping) are known. These grades contain 0.1% C, 9% Cr, 1% Mo,
0.2% V, 0.08% Nb and 0.05% N and have a creep rupture strength at
10.sup.5 hrs at 600.degree. C.
(.sigma..sub.R10.sup.5.sub.h600.degree. C.) of 98 MPa.
[0008] ASTM A213 T92 steel (or ASTM A335 P92 steel) has a chemical
composition close to T91/P91 except that the Mo content is greatly
reduced and it contains 1.8% W and a tiny amount of boron; the
creep rupture strength at 10.sup.5 hrs at 600.degree. C.
(.sigma..sub.R10.sup.5.sub.h600.degree. C.) for that steel is of
the order of 120 MPa.
[0009] Said steels T91, P91, T92, P92 contain 9% Cr and some of
their users believe that such a Cr content is insufficient to
resist hot oxidation and/or corrosion by steam beyond 600.degree.
C., in particular at 650.degree. C. because of the metal
temperature envisaged for the tubes of the superheaters in future
power stations.
[0010] Certainly, the presence of an oxide layer on the inner
surface of the tubes of superheaters, which layer derives from
corrosion of the steel by the steam moving in the tubes, creates a
thermal resistance which increases with the thickness of said layer
and, at constant thermal flux, entrains an increase in the mean
temperature of the tubes and thus a large reduction in their
service life.
[0011] Further, flaking of said layer when it is too large may lead
to accumulation of debris in the bends in the superheaters,
impeding the movement of steam with a supplemental risk of
overheating the tubes. Flaking can also result in debris being
entrained into the turbine and can thus damage its blades.
[0012] German DIN 17175 X20CrMoV12-1 (abbreviated to X20) steel is
also known, containing 0.20% C, 11% to 12% Cr, 1% Mo and 0.2%
V.
[0013] That steel is claimed to be more resistant to hot oxidation
than T91 or T92 because of its Cr content, but it is far less
resistant to creep rupture than T91/P91 and it is difficult to
weld, in particular when very thick.
[0014] It would thus be of advantage to modify the T92/P92 steel
for which the creep strength is satisfactory but for which the hot
oxidation resistance is insufficient by increasing its Cr content
to 12% Cr, but such an increase would come up against the problem
of the appearance of .delta. ferrite in the structure, which is
deleterious to the transformation of steel (forgeability), for its
toughness and for its creep strength.
[0015] The increase in the Cr content in X20 steel is compensated
for by a higher C content (0.20% as opposed to 0.10%) and by
addition of a moderate amount of Ni (between 0.5% and 1%).
[0016] A C content of 0.20% or more appears to be not much
desirable as regards weldability. Adding a large amount of Ni,
though, has the disadvantage of greatly reducing the Ac1 point and
thus limiting the maximum tempering temperature of the tubes; it
also appears to be deleterious to the creep rupture strength.
[0017] U.S. Pat. No. 5,069,870 discloses the addition of Cu
(austenite forming element) in amounts of 0.4% to 3% to a 12% Cr
steel to compensate for the increase in Cr content. However, adding
Cu causes problems as regards forgeability when fabricating tubes
for superheaters by hot rolling.
[0018] A grade with 11% Cr, 1.8% W, 1% Cu and micro-alloyed with V,
Nb and N with the same disadvantages is defined in ASTM A213 and
A335 and termed T122, P122.
[0019] Japanese patent application JP-A-4 371 551 discloses adding
between 1% and 5% (and generally more than 2%) of Co (also
austenite forming) to a steel containing 0.1% C, 8% to 13% Cr, 1%
to 4% W, 0.5% to 1.5% Mo, less than 0.20% Si (and in fact less than
0.11% Si) and micro-alloyed with V, Nb, N and B to obtain a creep
rupture resistance that is very high and a Charpy V-notch impact
test strength that is sufficient after ageing. Such a steel is
expensive to produce, however.
[0020] The same is true for the steels described in European
patents EP-A-0 759 499, EP-A-0 828 010, JP-A-9 184 048 and JP-A-8
333 657, which contain more than 2% Co and preferably at least
3%.
[0021] European patent application EP-A-0 892 079 also proposes
adding Co in amounts of 0.2% to 5% but in a steel containing less
than 10% Cr, which does not solve the problem described above.
[0022] Japanese patent application JP-A-11 061 342 and European
patent application EP-A-0 867 523 also propose adding Co, but
jointly with the addition of Cu for the first document and at least
1% Ni for the second document. However, we described the
unacceptable disadvantages of such additions above.
[0023] European patent application EP-A-0 758 025 also proposes
adding Co, generally in very large amounts; for that reason, to
prevent the formation of intermetallic precipitates based on Cr,
Mo, Co, W, C and Fe, that document jointly proposes adding (Ti or
Zr) and alkaline-earths (Ca, Mg, Ba) or rare earths (Y, Ce,
La).
[0024] Adding Ti or Zr, however, suffers from the major drawback of
forming coarse nitrides with the nitrogen in the steel and
preventing the formation of ultrafine carbonitrides of V and Nb
responsible for the high creep strength.
[0025] JP-A-8 187 592 also proposes adding Co with a particular
relationship between the (Mo+W) and (Ni+Co+Cu) contents, but said
additions and relationships are proposed for optimizing the
composition of the added materials for welding, and are not
proposed to tolerate forming such as that carried out when
fabricating seamless tubes (forgeability properties).
[0026] JP-A-8 225 833 also proposes adding Co, but concerns a heat
treatment to reduce the amount of residual austenite and not a
chemical composition; the chemical composition ranges are thus
broad and a teaching for the envisaged use cannot be deduced
therefrom.
DISCLOSURE OF THE INVENTION
[0027] The present invention proposes the production of a
steel:
[0028] with a creep strength at 600.degree. C. and 650.degree. C.
at least equivalent to that of T92/P92 steel;
[0029] with a hot oxidation resistance and steam corrosion
resistance that is at least that of X20CrMoV12-1 steel;
[0030] which results in a lower production cost for seamless tubes
compared with the improved grades cited above, the production cost
being affected not only by that of the addition elements but also
by that for transformation into seamless tubes.
[0031] We have also strived to produce a steel of the invention
that allows the fabrication of small or large diameter seamless
tubes using a variety of known hot rolling processes such as the
Stiefel plug mill, MPM, pilger mill, push bench, continuous rolling
mill with stretch reducing-mill, Axel rolling mill or planetary
rolling mill processes.
[0032] In accordance with the invention, the steel under
consideration contains, by weight:
1 C 0.06% to 0.20% Si 0.10% to 1.00% Mn 0.10% to 1.00% S 0.010% or
less Cr 10.00% to 13.00% Ni 1.00% or less W 1.00% to 1.80% Mo such
that (W/2 + Mo) is 1.50% or less Co 0.50% to 2.00% V 0.15% to 0.35%
Nb 0.030% to 0.150% N 0.030% to 0.120% B 0.0010% to 0.0100%
[0033] and optionally, at most 0.050% by weight of Al and at most
0.0100% by weight of Ca.
[0034] The remainder of the chemical composition of said steel is
constituted by iron and impurities or residual elements resulting
from or necessary to steelmaking and casting.
[0035] Preferably, the amounts of the constituents of the chemical
composition are linked so that after normalization heat treatment
between 1050.degree. C. and 1080.degree. C. and tempering, the
steel has a tempered martensitic structure that is free of or
almost free of .delta. ferrite.
[0036] The elements in the chemical composition of the steel have
the following influence on the properties:
[0037] Carbon
[0038] At high temperatures, in particular during the process for
hot fabrication of metal products or during austenitization in the
final heat treatment, said element stabilizes the austenite and as
a result, tends to reduce the formation of .delta. ferrite.
[0039] At ambient temperatures or at service temperatures, the
carbon is in the form of carbides or carbonitrides the initial
distribution and the change in said distribution of which with time
act on the mechanical characteristics at ambient temperature and at
the service temperature.
[0040] A C content of less than 0.06% would render obtaining a
structure free of .delta. ferrite and the production of the desired
creep characteristics difficult.
[0041] A C content of more than 0.20% is deleterious to the
weldability of the steel.
[0042] A content range of 0.10-0.15% is preferred.
[0043] Silicon
[0044] This element is an element that deoxidizes liquid steel and
also limits the kinetics of hot oxidation by air or steam in
particular, according to the inventors, acting in synergy with the
chromium content.
[0045] A content of less than 0.10% of Si is insufficient for
producing said effects.
[0046] In contrast, Si is a ferrite forming element which has to be
limited to avoid the formation of .delta. ferrite and it also tends
to encourage precipitation of embrittling phases in service. For
this reason, its content is limited to 1.00%.
[0047] A content range of 0.20% to 0.60% is preferred.
[0048] Manganese
[0049] This element encourages deoxidation and fixes the sulphur.
It also reduces the formation of .delta. ferrite.
[0050] In an amount of over 1.00%, however, it reduces the
resistance to creep rupture.
[0051] A content range of 0.15% to 0.50% is preferred.
[0052] Sulphur
[0053] This element essentially forms sulphides which reduce the
impact properties in the transverse direction and forgeability.
[0054] An S content limited to 0.010% prevents the formation of
defects when hot piercing billets during the fabrication of
seamless tubes.
[0055] A content that is as low as possible, for example 0.005% or
less, or even 0.003% or less, is preferred.
[0056] Chromium
[0057] This element is found both dissolved in the steel matrix and
precipitated in the form of carbides.
[0058] A minimum Cr content of 10% and preferably 11% is necessary
for the hot oxidation behaviour.
[0059] Because of the ferrite forming nature of chromium, a content
of more than 13% makes avoiding the presence of .delta. ferrite
difficult.
[0060] Nickel
[0061] This encourages impact strength and prevents the formation
of .delta. ferrite, but substantially reduces the Ac1 temperature
and thus reduces the maximum tempering temperature of the
steel.
[0062] Thus, a content of more than 1% is undesirable; moreover,
nickel tends to reduce the creep rupture strength.
[0063] Preferably, the maximum Ni content is limited to 0.50%.
[0064] Tungsten
[0065] This element, which is both dissolved and precipitated in
the form of carbides and intermetallic phases, is findamental to
the creep behaviour at 600.degree. C. and above, hence the minimum
content of 1.00%.
[0066] However, this element is expensive, highly segretative and
ferrite forming, and tends to form embrittling intermetallic
phases.
[0067] The inventors have discovered that it is not advisable to
increase the W content beyond 1.80%.
[0068] Molybdenum
[0069] This element has an effect similar to tungsten even though
it appears to be less effective as regards creep strength.
[0070] Its effects add to that of tungsten and so the (W/2+Mo)
content is advantageously limited to 1.50%.
[0071] The molybdenum content is preferably 0.50% or less.
[0072] Cobalt
[0073] This element stabilizes austenite and thus enables more than
10% Cr to be tolerated; it also improves the creep strength
properties; a minimum content of 0.50% is thus desirable.
[0074] In contrast, this element contributes to forming embrittling
intermetallic compounds that can precipitate at the service
temperature; further, it is very expensive.
[0075] Until now, this element has been used in contents of more
than 2% in materials for use at high temperatures to improve their
creep rupture strength.
[0076] The inventors of the present invention have surprisingly
established that a range of cobalt contents of 0.50% to 2.00% and
preferably 1.00% to 1.50% can satisfy the aims for said steel and
in particular provide an optimum compromise between the various,
possibly contradictory characteristics (for example oxidation
resistance, creep strength and forgeability), using a relatively
simple metallurgy and a limited manufacturing cost for metal
products.
[0077] This is not the case with steels containing more than 2% of
Co, which until now have not been used.
[0078] Vanadium
[0079] This element forms nitrides and carbonitrides that are very
fine and stable and thus very important for the creep rupture
strength.
[0080] A content of less than 0.15% is insufficient for producing
the desired result.
[0081] A content of more than 0.35% is deleterious as regards the
risk of the appearance of .delta. ferrite.
[0082] A preferred range is from 0.20% to 0.30%.
[0083] Niobium
[0084] Like vanadium, this element forms stable carbonitrides and
its addition reinforces the stability of vanadium compounds.
[0085] A Nb content of less than 0.030% is insufficient.
[0086] A Nb content of more than 0.15% is not favorable as the Nb
carbonitrides may become too large and reduce the creep
resistance.
[0087] A preferred range is from 0.050% to 0.100%.
[0088] Nitrogen
[0089] This austenite forming element can reduce the appearance of
.delta. ferrite.
[0090] It can also, and especially, form very fine nitrides and
carbonitrides which are much more stable than the corresponding
carbides.
[0091] A minimum nitrogen content of 0.030% is therefore
stipulated.
[0092] A nitrogen content of more than 0.120% results in blow holes
in ingots, billets or slabs in the steels under consideration and
as a result to defects in the metal products. The same risk exists
on welding when processing said products.
[0093] A nitrogen content range of 0.040% to 0.100% is
preferred.
[0094] Boron
[0095] This element contributes to stabilizing carbides when added
in an amount in excess of 0.0010%.
[0096] A content of more than 0.0100% can, however, substantially
reduces the burning temperature of products, in particular of as
cast products, and thus is detrimental.
[0097] Aluminium
[0098] This element is not necessary per se to produce the desired
metallurgical characteristics and it is considered here as a
residual; its addition is thus optional.
[0099] It is a powerfill metal and slag deoxidant and can thus
allow rapid, effective desulphurization of the steel by metal-slag
exchange.
[0100] This element is also ferrite forming and scavenges nitrogen;
thus, Al contents of more than 0.050% are discouraged.
[0101] Depending on requirements, if necessary, aluminium can be
added to obtain a final content of up to 0.050%.
[0102] Calcium
[0103] A Ca or Mg content of less than 0.0010% results from
exchanges between liquid steel and slag containing lime or magnesia
in a highly deoxidized medium: they are thus inevitable steelmaking
residuals.
[0104] However, calcium can optionally be added in amounts of a
little over 0.0010% to improve castability and/or control the form
of oxides and sulphides.
[0105] A Ca content of more than 0.0100% denotes an oxygen-rich and
therefore dirty steel and is thus discouraged.
[0106] Other Elements
[0107] Apart from iron, which is the base constituent of steel, and
the elements indicated above, the steel of the invention only
contains other elements as impurities; examples are phosphorus and
oxygen, and residuals deriving mainly from the iron added to the
furnace to produce the steel or from exchange with the slag or
refractories or necessary to the steelmaking and casting
processes.
[0108] Ti or Zr contents of less than 0.010% result thus from the
furnaced scrap and not from any deliberate addition; such low
contents actually have no substantial effect on the steel for the
use under consideration.
[0109] Preferably, as regards forgeability care is taken that the
copper content (resulting from furnaced scrap and not from
deliberate addition) remains less than 0.25% and optionally less
than 0.10%. Contents of more than said contents may proscribe
certain hot rolling processes for seamless tube rolling and require
the use of more expensive glass extrusion processes.
[0110] Chemical Composition Relationship and .delta. Ferrite
Content
[0111] Steelmakers know how to equilibrate the chemical composition
of a steel containing about 12% Cr, aiming at an absence or near
absence of .delta. ferrite after heat treatment from a relationship
between the contents of the elements in the chemical composition.
The term "structure almost free of .delta. ferrite" means a
structure containing no more than 2% of .delta. ferrite and
preferably no more than 1% of .delta. ferrite (measured with an
absolute precision of .+-.1%).
[0112] One example of such a relationship is given below, but any
relationship that is in the public domain or otherwise can be used,
providing it has the desired effect.
[0113] An example is the Shaeffler diagram or diagrams derived
therefrom which in particular incorporate the influence of nitrogen
(De Long diagram) and the parameter Md derived from electronic
orbital studies mentioned by Ezaki et al (Tetsu-to-Hagane, 78
(1992), 594).
BRIEF DESCRIPTION OF THE DRAWINGS
[0114] The accompanying drawings illustrate a non-limiting example
of an implementation of the invention.
[0115] FIG. 1 shows a diagram of .delta. ferrite content against
equivalent chromium content for different specimens of heat treated
steels containing 8% to 13% of Cr.
[0116] FIG. 2 shows a diagram of the results of forgeability tests
on steel F in accordance with the invention compared with other
steels.
[0117] FIG. 3 shows, for the same steel F compared with other
steels, a diagram of hot tensile tests, FIG. 3a) relating to the
yield point and FIG. 3b) to the tensile strength.
[0118] FIG. 4 shows, for the same steel F compared with other
steels, a transition curve for the Charpy V-notch impact strength
test.
[0119] FIG. 5 shows, for the same steel F compared with other
steels, a graph of results of creep rupture strength tests under a
constant unit load.
[0120] FIG. 6 shows, for the same steel F compared with other
steels, a master curve for the results of creep rupture strength
tests under different unit loads as a function of the Larson-Miller
parameter.
IMPLEMENTATIONS OF THE INVENTION
1.sup.ST EXAMPLE
Tests on Experimental Heat
[0121] A 100 kg laboratory heat formed from the steel of the
invention was produced under vacuum (F).
[0122] FIG. 1 shows the relationship between an equivalent chromium
parameter (Cr.sub.equ) derived from the chemical composition and
the .delta. ferrite content:
Cr.sub.equ=Cr+6Si+4Mo+1.5W+11V+5Nb+8Ti-40C-30N-2Mn-4Ni-2Co-Cu
[0123] The parameter Cr.sub.equ derives from studies by Patriarca
et al (Nuclear Technology, 28 (1976), p 516).
[0124] In FIG. 1, we show the .delta. ferrite content measured by
image analysis in the optical microscope for a certain number of
heats of T91, P91, T92 and X20 as a function of the parameter
Cr.sub.equ.
[0125] FIG. 1 provides analytical evidence that the amounts of
elements in heat F lie within the ranges given in the chemical
composition defined in claim 1. We aimed to obtain a Cr.sub.equ
content of 10.5% or less and if possible 10.0% or less to seek to
remain substantially free of .delta. ferrite (less than 2% and
preferably less than 1%) after heat treatment.
2TABLE 1 Chemical composition (weight %) steel type grade C Si Mn P
S Cr Ni W Mo invention F 0.12 0.48 0.22 0.013 0.002 11.50 0.23 1.38
0.29 comparative steels P91 0.10 0.30 0.40 0.015 0.002 9.00 0.15 --
1.00 (mean analysis) X20 0.20 0.30 0.45 0.020 0.002 11.50 0.60 --
1.00 P92 0.10 0.30 0.40 0.015 0.002 9.00 0.15 1.50 0.40 P122 0.10
0.20 0.50 0.015 0.002 11.00 0.30 1.90 0.40 steel type grade Co V Nb
N B Al Cu Cr.sub.equ invention F 1.37 0.24 0.060 0.056 0.0030 0.10
9.9 comparative steels P91 -- 0.22 0.080 0.050 -- 0.02 0.20 10.7
X20 -- 0.30 -- 0.020 -- 0.02 0.20 8.7 P92 -- 0.22 0.080 0.050
0.0030 0.02 0.20 10.6 P122 -- 0.22 0.050 0.050 0.0020 0.02 0.80
10.8
[0126] Table 1 shows the chemical composition of this heat F and
the mean chemical composition of known prior art grades (weight %)
as well as the corresponding value of the parameter Cr.sub.equ.
[0127] Said heat F contains no added Ca and its Al content is less
than 0.010% (Al and Ca as residuals).
[0128] The ingots obtained were heated to 1250.degree. C. then hot
rolled to a 20 mm thick sheet which then underwent stress-relieving
tempering.
[0129] The specimens for the tests and examinations described below
were produced from this sheet.
[0130] Firstly, a metallographic specimen taken in the longitudinal
direction from said sheet was examined under the optical microscope
after metallographic attack using Villela's reagent.
[0131] The presence of .delta. ferrite was observed in the form of
short white filaments in zones segregated into ferrite forming
elements (Cr, W, Mo . . . ). Its content was determined using
automatic image analysis as 0.50%, i.e., an amount of almost
zero.
[0132] Specimens were then taken from the transverse direction to
carry out hot tensile forging tests at a mean deformation speed of
1 s.sup.-1.
[0133] The forging tests were carried out comparatively on these
specimens of heat F and on specimens from a rolled 310 mm diameter
bar in P91 steel and from a rolled 230 mm diameter bar in P92
steel.
[0134] FIG. 2 shows the reduction in area results.
[0135] It can be seen that the reduction in area remained over 70%
from 1200.degree. C. to 1320.degree. C. and was comparable to that
of P92.
[0136] Such behaviour was attributed to the low sulphur content of
heat F and a relatively low .delta. ferrite content at said
temperatures.
[0137] The influence of temperature on the .delta. ferrite content
was also verified by metallographic tests: see Table 2.
3TABLE 2 Change in .delta. ferrite content at high temperatures
temperature 1200.degree. 1220.degree. 1240.degree. 1260.degree.
1280.degree. 1300.degree. C. C. C. C. C. C. % .delta. ferrite 5% 6%
9% 14% 16% 22%
[0138] The values for the .delta. ferrite content obtained were
comparable with those measured under the same conditions for
comparative steels P91, P92.
[0139] The .delta. ferrite content was less than 15% up to
1250.degree. C. and less than 20% up to 1280.degree. C.
[0140] The limited .delta. ferrite content in heat F at high
temperature probably resulted from the deliberate absence of
.delta. ferrite at ambient temperatures.
[0141] The burning temperature was over 1320.degree. C.
[0142] Thus, satisfactory behaviour can be expected for material F
during hot piercing of round bars (termed rounds for tubes) between
rolls using the Mannesmann process if heating of the rounds is
limited to less than 1300.degree. C. and if possible to
1250.degree. C.
[0143] Thus, it should be possible to produce seamless tubes by a
number of hot rolling processes and thus it should be possible to
produce them at relatively low cost. This is not the case for
austenitic grades or grades containing 12% Cr and 1% Cu which, at
least for small diameter tubes of the superheater tube type, have
to be produced using the less productive glass extrusion
process.
[0144] Dilatometric specimens were then taken from steel F of the
invention and the steel transformation points on heating (Ac1, Ac3)
and cooling (Ms, Mf) were determined by dilatometry.
[0145] Table 3 shows the results obtained compared with typical
results for known steels.
4TABLE 3 Phase transformation points grade Ac3 (.degree. C.) Ac1
(.degree. C.) Ms (.degree. C.) Mf (.degree. C.) T/P91 915 820 450
190 T/P92 910 830 470 200 T/P122 905 805 350 X20 965 800 320 Steel
F (invention) 940 830 350 130
[0146] Temperature Ac1 of 830.degree. C. for steel F is comparable
with that of P91 and P92 and much higher than that of P122
containing copper which does not allow a tempering temperature of
more than 780.degree. C. In contrast, a tempering temperature of
800.degree. C. is entirely possible with steel F of the
invention.
[0147] Temperatures Ms and Mf at the beginning and end of the
martensitic transformation remained sufficiently high for the
transformation of austenite to martensite to be on cooling to
ambient temperature.
[0148] The microstructure and hardness were measured after a
normalizing heat treatment of 20 minutes at 1060.degree. C.
(treatment N1) or 1080.degree. C. (treatment N2); the results are
shown in Table 4.
5TABLE 4 Results after normalizing heat treatment microstructure
HV10 hardness present invention treatment N1 martensite (<0.5%
.delta. 420 (F) ferrite) treatment N2 martensite (0.5% .delta. 410
ferrite) comparative steel P92 martensite (<0.5% .delta. 425
ferrite)
[0149] The microstructure and hardness were also measured after
normalizing heat treatment N1 and tempering for 1 hour at
780.degree. C. (T1), 30 minutes at 800.degree. C. (T2) or 1 hour at
800.degree. C. (T3): see the results shown in Table 5.
6TABLE 5 Results after normalization and tempering microstructure
(size of .gamma. grains, mm) HV.sub.10 hardness present invention
N1 + T1 100% tempered 255 (F) martensite (.gamma. grain size 0.022
mm) N1 + T2 100% tempered 236 martensite (.gamma. grain size 0.022
mm) N1 + T3 100% tempered 236 martensite (.gamma. grain size 0.022
mm) comparative steel T92 100% tempered 220 martensite (.gamma.
grain size 0.010 mm)
[0150] Note the fine austenitic grain size the dimensions of which
did not exceed 0.030 mm.
[0151] The tensile characteristics were then determined at ambient
temperature and at 500.degree. C. and at 600.degree. C.--see the
results in Table 6 and FIGS. 3a and 3b.
[0152] The Charpy V-notch impact strength characteristics were then
measured in the longitudinal direction at test temperatures of
-60.degree. C. to +40.degree. C. after heat treatments N1+T1, N1+T2
or N1+T3.
[0153] The results obtained and those on a tube with an outer
diameter of 356 mm and wall thickness 40 mm in P92 are illustrated
in FIG. 4. The transition temperature for the Charpy V-notch impact
strength was about 0.degree. C. for heat F, as for tubes P92.
7TABLE 6 Ambient temperature tensile characteristics R.sub.p0.2 Rm
(MPa) (MPa) A5.65{square root}s (%) present invention (F) N1 + T1
790 615 21 N1 + T2 749 559 25 N1 + T3 739 551 24 comparative steel
T92 700 540 23
[0154] The creep rupture strength characteristics were then
determined using different tests at different temperatures under a
constant unit load (140 and 120 MPa) compared with steel F of the
present invention (heat treatments N1+T2 or N2+T2) and on a P92
tube.
[0155] The results of the stress rupture test at 120 MPa are shown
in FIG. 5 as a function of the parameter 1000/T (in .degree.
K.sup.-1), as is conventional for this type of grade. The
temperatures were selected so that the maximum duration of the test
was close to 4000 h. FIG. 5 allows the temperature corresponding to
a test duration of 10.sup.5 h to be extrapolated for a unit load.
It can be seen that for steel F, this temperature at least equals
if not exceeds that of steel P92.
[0156] Other creep rupture strength tests at constant temperature
were also carried out or are still running at 600.degree. C.,
625.degree. C., 650.degree. C.
[0157] The results of these tests (and those under a constant unit
load) are shown in FIG. 6 in the form of a diagram (master curve)
showing log .sigma..sub.R as a function of the Larson-Miller
parameter (LMP) which combines the duration and temperature of the
test: LMP=10.sup.-3.T.(c+log t.sub.R) where c=36 and T and t.sub.R
are respectively expressed in .degree. K and hours. The ruptured
tests reached a duration of 7800 h at 600.degree. C., 10000 h at
610.degree. C., 7800 h at 625.degree. C. and 7200 h at 650.degree.
C.; the arrow on the diagram indicates a test at 600.degree. C.
that had still not been ruptured after 11000 h.
[0158] FIG. 6 shows that the tests are favourable compared with the
mean master curve (solid line) and the lower scatter band (dotted
line) for steels T92 and P92 defined by ASME.
[0159] Hot oxidation tests in steam were undertaken for product F
in the N1+T2 temper at 600.degree. C. and 650.degree. C. for
periods of up to 5000 hours compared with different steels for high
temperature use according to ASTM A213 or DIN 17175:
[0160] T22, T23 at low Cr contents (2.25%);
[0161] T91, T92 at 9% Cr;
[0162] X20, T122 at about 11% Cr;
[0163] TP347H (austenitic grade, 18% Cr-10% Ni--Nb).
[0164] Intermediate weight gain results, measured by weighing after
1344 h (8 weeks), are shown in Table 7.
[0165] The results are coded as follows:
[0166] 1: weight gain of 2 mg/cm.sup.2 or less;
[0167] 2: weight gain in the range 2 to 5 mg/cm.sup.2;
[0168] 3: weight gain in the range 5 to 10 mg/cm.sup.2;
[0169] 4: weight gain in the range 10 to 50 mg/cm.sup.2;
[0170] 5: weight gain over 50 mg/cm.sup.2.
[0171] The X20 specimens could not be used for measurements due to
major exfoliation of the oxide layers when leaving the furnace or
during weighing (results shown in the Table as NA). In contrast,
specimens of heat F and TP347H showed an absence of flaking of
oxide layers. The fine crystallization of the oxidation products on
heat F should also be noted.
[0172] These intermediate results allow it to be predicted, in
particular at 650.degree. C., that the steam oxidation behaviour of
heat F of the invention will satisfy expectations, namely better
than that for P91, P92 and at least equivalent to that of X20, or
even close to that of TP347H.
8TABLE 7 Results of hot oxidation tests after 1344 h weight gain
code steel type grade 600.degree. C. 650.degree. C. present
invention F 2 2 comparative steels T22 (2.25Cr-1Mo) 4 5 T23
(2.25Cr-1.5W-V-Nb-Ti) 4 5 T91 (9Cr-1Mo-V-Nb-N) 3 4 T92
(9Cr-1.8W-V-Nb-N) 3 4 T122 (11Cr-1.8W-1Cu-V-Nb-N) 3 4 X20
(11Cr-1Mo-V) NA NA TP347H (18Cr-10Ni-Nb) 1 2
[0173] The same specimens were removed after 5376 h and the loss of
mass was measured after stripping off the oxides formed; this type
of measurement is more accurate than weight gain measurements
without stripping, but can only be carried out at the end of the
test.
[0174] The table below summarizes the corrosion rates for the steel
in mm/year, deduced from these measurements.
[0175] A test result order similar to that of Table 7 was
found.
[0176] The corrosion rates for X20 and T122 (which contain 11% Cr)
are not substantially different from those for T91 and T92, which
contain only 9%.
[0177] In contrast, highly surprisingly, the corrosion rates for
grade F of the invention were extremely low, lower even than for
the austenitic steel specimen 347H containing 18% Cr and almost as
low as for the 347 GF steel specimen (also austenitic, 18% Cr)
which is a reference for hot oxidation behaviour.
[0178] The steel of the invention allows thus to produce boilers
with a steam temperature of more than 600.degree. C. completely
from ferritic steel, including the hottest parts of the boiler.
9TABLE 8 Corrosion rate corrosion rate (mm/year) steel type grade
600.degree. C. 650.degree. C. present invention F 0.008 0.013
comparative steels T22 0.175 1 T23 0.216 1.43 T91 0.055 0.09 T92
0.070 0.10 T122 0.074 0.114 X20 0.076 0.116 TP347H 0.026 0.077
TP347GF(*) 0.001 0.020 (*)TP347 GF: fine grained variation of
TP347H
[0179] It should also be noted that the corrosion rates obtained
for grade F were extremely low despite the very low sulphur
contents, while certain prior art documents disclose moderate
sulphur contents to combat hot oxidation, of the order of 0.005% or
even 0.010%, and sulphur fixing by adding rare earths and/or
alkaline-earths.
[0180] In contrast, grade F of the invention perfectly fits in with
sulphur contents of 0.005% or less or even 0.003% or less, and does
not necessitate the addition of rare earths and/or alkaline-earths
which are difficult to implement.
2.sup.ND EXAMPLE
Tests on Industrial Heat
[0181] An industrial heat labeled 53059 formed from grade F of the
invention was produced (mass=20 t) and cast into ingots.
[0182] The analysis for the heat was as follows.
10TABLE 9 Chemical composition (% by weight) of heat 53059 formed
from steel of the invention C Si Mn P S Cr Ni W Mo 0.115 0.49 0.35
0.018 0.001 11.5 0.29 1.50 0.29 Co V Nb N B Al Cu Cr.sub.equ 1.62
0.26 0.050 0.066 0.0049 0.008 0.08 9.28
[0183] Ingots were forged into solid bars with a diameter of 180
mm, which were then transformed into seamless tubes with an outer
diameter of 60.3 mm and a thickness of 8.8 mm using continuous
rolling over a retained mandrel with diameter reduction on a
stretch reducing-mill.
[0184] This transformation into tubes was carried out without
problems (no defects resulting from the presence of .delta.
ferrite) and the resulting tubes were of satisfactory quality
according to non-destructive testing using ultrasonic waves.
[0185] Other ingots were transformed into large pipes with an outer
diameter of 406 mm and a wall thickness of 35 mm using the hot
pilger mill rolling process.
[0186] Here again, rolling was carried out without problems and no
defects were observed during the inspection procedure.
[0187] These results confirm the expectations derived from the
forgeability test results on the experimental heat (see FIG. 2 and
Table 2 above).
[0188] Table 10 shows the results of tensile tests at ambient
temperature on tubes treated by normalization at 1060.degree. C.
and tempering for 2 h at 780.degree. C.
[0189] Table 11 shows the results of Charpy V-notch impact strength
tests on tubes that underwent the same heat treatment as that for
the tensile tests.
11TABLE 10 Results of ambient temperature tensile tests on steel
tubes of the invention R.sub.p0.2 (MPa) R.sub.m (MPa) A5.65{square
root}s (%) tube, 60.3 .times. 8.8 mm 564 781 26 tube, 406.4 .times.
35 mm 587 784 23
[0190]
12TABLE 11 Results of Charpy V impact test on a steel tube of the
invention KV (J) at: -60.degree. C. -40.degree. C. -20.degree. C.
0.degree. C. +20.degree. C. tube, 60.3 .times. 39 63 72 72 76 8.8
mm (*) tube, 406.4 .times. 102 35 mm (**) (*) reduced specimens, 5
mm .times. 10 mm - longitudinal tests (**) 10 mm .times. 10 mm
specimens - transverse tests.
[0191] The mechanical traction and resilience characteristics for
the tube were in line with the results for the bars from the
experimental heat.
* * * * *