[0001] The present invention relates to a low interstitial, corrosion resistant, weldable
ferritic stainless steel with improved toughness and to a process for the manufacture
thereof. More specifically, the present invention is directed to a low interstitial,
corrosion resistant, weldable ferritic stainless steel with a small addition of either
columbium or titanium to improve the toughness when the maximum achievable cooling
rate is limited.
[0002] A ferritic stainless steel must have superior pitting and crevice corrosion resistance
in order to be used in certain chemical environments as for example in power plants
exposed to sea water, and pulp and paper process equipment. Stainless steel containing
29% chromium and 4% molybdenum are highly resistant to crevice corrosion. These steels
require a low level of interstitials, for example a total carbon plus nirtogen content
of less than 0.025% by weight, to have good post-welding ductility and intergranular
corrosion resistance.
[0003] The applications mentioned above often require heavy gauge supporting products such
as plate, as well as light gauge welded tubing such as condenser tubing. This equipment
is often assembled through a welding process. The shape and size of the assembled
equipment usually prevents the use of a final heat treatment or, if capable of a final
heat treatment, the shape and size often severely limit the ability of the assembled
equipment to cool rapidly from the heat treating temperature. Moreover, the toughness
of the alloy decreases as the thickness increases and as the cooling rate decreases.
This is illustrated in Figure 12 in a paper by H.E. Deverall entitled "Toughness Properties
of Vacuum Induction Melted High-Chromium Ferritic Stainless Steels", published in
ASTM STP 706, Toughness of Ferritic Stainless Steels, R.A. Lula, Ed., American Society
for Testing and Materials, 198O. The decrease in toughness decreases weldability such
that the plate, which in some instances may be incapable of being water-quenched because
of its size, might exhibit cracking during welding. Or, if the plate is water-quenched,
the cooling rate because of the thickness of the plate may not be rapid enough to
achieve suitable toughness such that the plate may exhibit cracking during welding.
Therefore, better toughness must be achieved by some other means where water-quenching
is impractical or where water-quenching does not achieve suitable toughness to improve
the weldability of the various components comprising the final assembled structure.
[0004] Even if the final product is to be of light gauge, the conventional production methods
require the cooling of thicker slabs and bands during processing. The cooling rates
of these heavier section sizes is slow. Water-quenching would speed up the cooling
process, however water-quenching is often impossible or impractical due to shape and
size.
[0005] As the thickness of the product section increases, the toughness as measured by Charpy
impact transition temperature decreases. Toughness is the ability of a metal to absorb
energy by deforming plastically before fracturing. The transition temperature is the
temperature at which the fracture which occurs from the impact is 50 percent shear
(ductile) and 50 percent cleavage (brittle).
[0006] The toughness of the 29% chromium - 4% molybdenum alloy is low compared to substantially
lower chromium alloys of an equivalent carbon and nitrogen content because of the
high alloy content. The toughness of the 29% chromium - 4% molybdenum alloy is improved
by water-quenching to speed up the cooling process instead of the slower air-cooling.
However, in many cases the water-quenching process is not poss- .ible or practical
to use, so a method is needed to improve the toughness of the steel in those situations
where the maximum cooling rate is limited.
[0007] A 29% chromium - 4% molybdenum ferritic stainless steel with a maximum carbon plus
nitrogen content of 0.025% is disclosed in United States Patent No. 3,929,473. United
-States Patent No. 3,932,174 is a modification to which small amounts of other elements
are added to achieve the same range of corrosion properties as United States Patent
No. 3,929,473. However these patents do not teach the use of columbium or titanium.
[0008] United States Patent No. 3,807,991 teaches the addition of between 13 and 29 times
the amount of nitrogen or between 0.065% and 0.363% columbium to a steel of 1% molybdenum
for improved toughness and intergranular corrosion resistance in the air-cooled condition.
United States Patent 3,957,544 discusses the addition of titanium and columbium according
α to the equation %Ti
/6 + %CB
/8 = (%C + %N). The molybdenum content of the steels in these patents is lower than
that of the present invention.
[0009] The presence of titanium and columbium in the steel reduces the susceptibility of
a steel to intergranular attack, but the weldability of the steel is poor unless the
level of interstitials is low. Molybdenum improves pitting and crevice corrosion resistance,but
according to United States Patent 4,119,765 if molybdenum is present in an amount
of over 3.5% and is combined with chromium, titanium, silicon or columbium, the notch
toughness is reduced, especially in the as-welded condition. United States Patent
4,119,765 adds from 2% - 4.75% nickel to improve the weldability of the steel. The
amount of nickel must be regulated carefully so as to improve notch toughness and
acid corrosion resistance without interfering with other properties.
[0010] A final reference is a paper entitled "Ferritic Stainless Steel Corrosion Resistance
and Economy" by Remus A. Lula. The paper appeared on pages 24-29 of the July 1976
issue of Metal progress. This reference does not disclose the ferritic stainless steel
of the present invention.
[0011] For the reasons noted hereinabove, the present invention is distinguishable from
the references referred to.
[0012] An object of the present invention is to provide a low interstitial, corrosion resistant,
weldable ferritic stainless-steel with a high molybdenum content which exhibits improves
toughness in heavier section thickness when the maximum achievable cooling rate is
limited.
[0013] A further object of the present invention is to provide a low interstitial, corrosion
resistant, weldable ferritic stainless steel with a high molybdenum content which
exhibits improved toughness due to a small addition of either columbium or titanium.
[0014] In particular, this invention provides a low interstitial ferritic stainless steel
which is corrosion resistant and weldable at room temperature. The improvement of
the present invention being an addition of a small critical amount of columbium and/or
titanium to improve the toughness of the steel in situations where water quenching
is impossible or impractical.
[0015] The present invention provides a low interstitial, corrosion resistant, weldable
ferritic stainless steel with improved toughness characterized in that it consists
of, by weight percent: 25.0%-35.0% chromium, 3.6%-5.6% molybdenum, less than 3% nickel,
less than 2% manganese, less than 2.0% silicon, less than 0.5% aluminum, less than
0.50% copper, less than 0.050% phosphorus, less than 0.05% sulfer, less than 0.01%
carbon, less than 0.02% nitrogen, the sum of the carbon and nitrogen being less than
0.025%, 0.05-050% of columbium and/or titanium, and the balance of iron.
[0016] The present invention further provides a process for the manufacture of ferritic
stainless steel of improved toughness wherein said steel is hot rolled, annealed and
cold-rolled to strip thickness, characterized in that the process comprises air-cooling
from the annealing temperature before cold rolling a ferritic stainless steel consisting
essentially of, by weight per cent: 25.0% - 35.0% chromium, 3.6% - 5.6% molybdenum,
less than 3.0% nickel, less than 2.0% manganese, less than 2.0% silicon, less than
0.5% aluminum, less than 0.5% copper, less than 0.5% phosphorus, less than 0.05% sulfer,
less than 0.01% carbon, less than 0.02% nitrogen, the sum of the carbon and nitrogen
being less than 0.025%, 0.05% - 0.50% of columbium and/or titanium, and the balance
iron, so as to produce a steel with a Charpy impact transition temperature of below
-17.8°C (O°F) as cold-rolled to a thickness of 1.575mm(0.062 inches).
[0017] Chromium and molybdenum are preferably present in respective amounts of 28.5% to
30.5% and 3.75% to 4.75%. Columbium and/or titanium is present preferably in the amount
of 0.05% to 0.20%. Manganese and silicon are each usually present in amounts of less
than 1%. Aluminum, copper, phosphorous, and sulfer are present usually in amounts
of less than 0.1%. Carbon and nitrogen are present preferably in amounts of less than
0.008% and 0.016% respectively.
[0018] The advantages of the steel of this invention will be apparent from the following
description which is illustrative of several aspects of the invention. This invention
relates to a low interstitial ferritic stainless steel having a chromium content of
between 25.0% and 35.0% and a molybdenum content of between 3.6% and 5.6%. A small
amount of columbium or titanium of between 0.05% and 0.20% is added to the steel composition
to improve its toughness when the maximum achievable cooling rate is limited.
[0019] Ingots from four heats were vacuum-induction melted to the compositions given in
Table I.
The ingots were conditioned, heated to a temperature of 1121°C(2050°F) and hot rolled
to a strip about 3.556mm (0.140 in.) thick. The hot rolled band was annealed at a
temperature of 1010°C(1850°F), and water-quenched and cold rolled to a thickness of
1.575mm(0.062 in.). The strip was then annealed at a temperature of 1010°C(1850°F),
water-quenched and TIG welded.
[0020] Four sets of transverse Charpy V-notch impact subsize specimens were taken, two from
the hot rolled band and the others from the 1.575mm(0.062 in.) thick strips. After
annealing the specimens at a temperature of 1010°C (1850°F), the specimens were either
water-quenched or air-cooled. The cooled specimens were then tested for toughness
characteristics. The results of the tests are: shown in Table II.
[0021] The transition temperature decreases with increasing columbium content in the air-cooled
condition thus indicating that columbium acts against the detrimental effects on toughness
of slow cooling. Although the impact transition temperatures of the air-cooled specimens
are higher than those of the water-quenched specimens it can be seen from Table II
that the difference in impact transition temperatures of an air-cooled and a water-quenched
1.575mm(0.062 in.) thick steelstrip is less than 38°C (100°F). Whereas the difference
in impact transition temperature for prior art compositions is 115°C(240°F). However,
in situations where water-quenching is impractical or in situations where the cooling
rates achieved by water-quenching of heavy thickness sections approach or are slower
than those of air cooling lighter thickness sections, the addition of columbium improves
the toughness. The impact transition temperature of the 1.575mm (0.062 in.) steel
strip of a composition according to the present invention is below -17.8°C(0°F) whereas
that of prior art composition A is 54°C(130°F). It is essential that the impact transition
temperature of such a steel strip be below room temperature so that the steel strip
will not crack upon welding. Steels of prior art compositions had to be water-quenched
before cold rolling in order to achieve the necessary toughness characteristics. The
composition of this invention enables us to achieve good toughness characteristics
by air-cooling the steel before cold-rolling instead.
[0022] Corrosion tests were also performed on the 1.575mm (0.062 in.) thick strip in the
as welded condition and on the base metal specimens which were heat treated at 1232
0C (225
00F) and air-cooled to simulate the heat affected zone upon welding a heavier thickness.
The specimens 25.4mm x 50.8mm (1 in. x 2 in.) were exposed to a boiling solution of
ferritic sulfate-50% sulfuric acid for 120 hours according to ASTM A262 Practice B
for intergranular corrosion testing. The corrosion rates are given in Table III.
[0023]
[0024] The results of additional tests of the mechanical properties of the steel in the
welded condition are shown in Table IV.
1. A low interstitial, corrosion resistant, weldable ferritic stainless steel with
improved toughness characterized in that it consists of, by weight percent: 25.0%-35.0%
chromium, 3.6%-5.6% molybdenum, less than 3.0% nickel, less than 2.0% manganese, less
than 2.0% silicon, less than 0.5% aluminum, less than 0.50% copper, less than 0.050%
phosphorous, less than 0.05% sulfer, less than 0.01% carbon, less than 0.02% nitrogen,
the sum of the carbon and nitrogen being less than 0.025%, 0.05%-0.50% of columbium
and/or titanium, and the balance of iron.
2. A low interstitial, corrosion resistant, weldable ferritic stainless steel with
improved toughness according to claim 1 with a chromium content of from 28.5% to 30.5%.
3. A low interstitial, corrosion resistant, weldable ferritic stainless steel with
improved toughness according to claim 1 or 2, with a molybdenum content of from 3.75%
to 4.75%
4. A low interstitial, corrosion resistant, weldable ferritic stainless steel with
improved toughness according to claim 1, 2 or 3, with 0.05%-0.20% of columbium and/or
titanium.
5. A low, interstitial, corrosion resistant, weldable ferritic stainless steel with
improved toughness according to any one of the preceding claims with 0.05%-0.20% columbium.
6. A process for the manufacture of ferritic stainless steel of improved toughness
wherein said steel is hot rolled, annealedand cold-rolled to strip thickness, characterized
in that the process comprises air-cooling from the annealing temperature before cold
rolling a ferritic stainless steel consisting essentially of, by weight per cent:
25.0% 35.0% chromium, 3.6%-5.6% molybdenum, less than 3.0% nickel, less than 2.0%
manganese, less than 2.0% silicon, less than 0.5% aluminum, less than 0.5% copper,
less than 0.5% phosphorous, less than 0.05% sulfer, less than 0.01% carbon, less than
0.02% nitrogen, the sum of the carbon and nitrogen being less than 0.025%,0.05% -
0.50% of columbium and/or titanium, and the balance iron, so as to produce a steel
with a Charpy impact transition temperature of below -17.8°C(0°F) as cold-rolled to
a thickness of 1.575mm(0.062 inches).
7. A process for making a low interstitial, corrosion resistant, weldable ferritic
stainless steel with improved toughness according to claim 6, with the additional
step of welding.
8. A low interstitial, corrosion resistant, weldable, ferritic stainless steel with
improved toughness made accord-- ing to the process of claim 6 or 7.