BACKGROUND OF THE INVENTION
[0001] This invention relates to martensitic stainless steels used in seamless steel pipe
such as oil-well pipe and pipeline tubing. Martensitic stainless steels, two representative
grades of which are SUS 410 and SUS 420 (Japan Industrial Standard [JIS) designations),
have excellent corrosion resistance in highly corrosive environments containing C0
2. These materials are thus regarded as excellent candidates for use in oil-well pipe,
geothermal well pipe, and pipeline tubing.
[0002] The strength of oil-well pipe is normally required to be .least equivalent to that
of American Petroleum Institute (API) standard L80 grade steel (yield strength > 80
ksi). Pipeline tubing should generally have a strength at least equal to that of API
standard X60 grade steel (yield strength > 60 ksi).
[0003] Martensitic stainless steels having a variety of strengths can be obtained by the
application of specific types of heat treatment, such as quench-tempering, normalizing-tempering,
or just tempering. However, it is known that the resistance to stress-corrosion cracking
of martensitic stainless steels in C0
2- containing environments falls when tempering is performed at a temperature of less
than 600°C. We tempered the martensitic stainless steels in Table 1 at various temperatures
and cut out test pieces 120 mm long by 20 mm wide by 3 mm thick. These pieces were
subjected to U-bend tests at a bending radius of 15 mm in a 3.5% aqueous solution
of NaCl heated to 80°C and having a carbon dioxide partial pressure of 1 atmosphere.
As shown in Table 1, each of these steels developed stress-corrosion cracking when
tempered at less than 600°C, but none demonstrated stress-corrosion cracking when
tempered at 600°C or more (a cross "X" in Table 2 indicates the presence of stress-corrosion
cracking; an open circle "0" indicates the absence of stress-corrosion cracking).
Hence, to achieve good resistance to stress-corrosion cracking in C0
2-containing environments, an important property of martensitic stainless steels, it
is clear that the steel must be tempered at a temperature of at least 600°C.

[0004] As is well known, the strength of martensitic stainless steels decreases as the ferrite
content of the steel structure increases. When the ferrite content at 1200°C exceeds
40%, the ferrite content in the normal quenching or normalizing temperature range
of 900-1000°C rises to 20% or more, making it difficult to achieve the high strength
required in linepipe tubing and oil-well pipe by tempering at 600°C or more. Accordingly,
to allow tempering to be performed at the temperatures of 600°C or more necessary
to impart good resistance to stress-corrosion cracking, and at the same time satisfy
the high-strength requirements for use in pipeline tubing and oil-well pipe, martensitic
stainless steels must be composed of not more than 40% ferrite at 1200°C.
[0005] Compositions in which the austenite phase (which becomes martensite at room temperature)
exists in combination with a ferrite phase comprising 20-30% of the composition have
the worst hot workability. When the amount of ferrite is about 40%, the hot workability
is about the same as that of austenitic single-phase steels (which become martensitic
single-phase steels at room temperature or below the Ms point). The hot workability
rises sharply with increasing ferrite content above this point. Thus, because martensitic
stainless steels with a ferrite content of 40% or less at 1200°C have inferior hot
workability, their use in the production of high-strength seamless steel pipe by the
processes described below tends to result in defects, complicating pipe manufacture.
[0006] Seamless stainless steel pipe is generally produced either by an inclined rolling
method such as the plug mill or mandrel mill process, or by a hot extrusion method,
of which the Ugine- Sejournet and Erhart pushbench processes are typical. However,
certain types of martensitic stainless steels (namely, those with a ferrite content
of 40% or less at 1200°C), have poor hot workability. When seamless steel pipe is
manufactured from these steels by a cross rolling process such as the plug mill process
or the mandrel mill process, defects arise on both the outside and inside walls of
the pipe during piercing of the billet on a piercing mill. For this reason, seamless
pipe made of this type of steel is generally produced by a hot extrusion process,
such as the Ugine-Sejournet process.
[0007] However, when a hot extrusion process is employed and the billet directly pierced
(a process known as direct piercing), a billet length 5-7 times the diameter results
in a greater eccentricity in the wall thickness of the pipe. This makes it difficult
to produce long pipe. A partial solution to this problem is provided by a process
for producing long pipe that makes use of what is known as the expansion method. This
method consists of mechanically opening a guide hole in the center of the billet,
then extending the hole. However, even with the use of this expansion method the billet
length is still limited to only about 15 billet diameters. Another problem concerns
the glass lubricant used in the Ugine-Sejournet hot extrusion process. This must be
peeled off following rolling, a process that is both time-consuming and costly.
[0008] The limits on billet length inherent in the Ugine-Sejournet and other hot extrusion
processes make it impossible to raise productivity above a certain level. Moreover,
the use of short billets inevitably results in a low yield and is therefore also disadvantageous
in terms of cost. In contrast, both the plug mill and mandrel mill processes involve
piercing the billet on a piercing mill that utilizes the Mannesmann effect. These
processes permit the manufacture of longer pipe than is possible by the Ugine-Sejournet
and other hot extrusion processes. These processes are thus known to be advantageous
in terms of productivity and cost. However, as indicated above, certain types of martensitic
stainless steels are not suitable for use in the production of seamless pipe on account
of the formation of defects during pipe manufacture.
[0009] The present invention was arrived at following careful consideration of the problems
described above. The object of this invention is to enable the practical application
of the plug mill and mandrel mill processes in martensitic stainless steels, particularly
those having a ferrite content of 40% or less at 1200
0C, for which the manufacture of seamless steel pipe by the plug mill and mandrel mill
processes has hitherto been complicated by the formation of defects during pipe fabrication,
and by making it possible to use these processes, to enable the manufacture of seamless
steel pipe from this type of martensitic stainless steel at high productivity and
low cost.
[0010] To recapitulate, it has hitherto been possible to manufacture seamless steel pipe
made of martensitic stainless steel by the plug mill process or the mandrel mill process
without the formation of defects during fabrication when the ferrite content is greater
than 40% at 1200
oC. However, when steels having a ferrite content of 40% or less at 1200
0C are used, numerous defects arise on the inside and outside walls of the pipe during
manufacture, and cracking at the ends of the pipe is also common. This has made it
difficult to use these processes in the production of seamless steel pipe. After carefully
investigating the causes of such defects in steels with a ferrite content of 40% or
less, we discovered that impurities such as P and S in the steel exert a large influence
on the formation of these defects. Further examination revealed that by holding the
level of S to 0.003% or less and the level of P to 0.020 or less, seamless steel pipe
can be produced on a practical basis by both the plug mill process and the mandrel
mill process. This discovery led ultimately to the present invention.
SUMMARY OF THE INVENTION
[0011] The invention contemplates martensitic stainless steels for use in seamless steel
pipe containing not more than 0.30% by weight of C, not more than 1.0% by weight of
Si, not more than 2.0% by weight of Mn, 11-14% by weight of Cr, 0.005-0.10% by weight
of Al, and not more than 0.10% by weight of N, the remainder being Fe and unavoidable
impurities, of which the impurities P and S are held respectively to levels of not
more than 0.02% and 0.003% by weight, the ferrite content of these steels being no
more than 40% by weight at 1200°C.
[0012] This invention also contemplates martensitic stainless steels for use in seamless
steel pipe having the contents of C, Si, Mn, Cr, Al, and N noted above, and containing
one or more elements selected from the group consisting of up to 3.5% by weight of
Ni, up to 2% by weight of Cu, up to 2.5% by weight of Mo, up to 0.10% by weight of
Nb, and up to 0.10% by weight of V, the remainder being Fe and unavoidable impurities,
of which the impurities P and S are held at the levels cited above, the ferrite content
of these steels being no more than 40% by weight at 1200°C.
[0013] The present invention furthermore contemplates martensitic stainless steels for use
in seamless steel pipe having the above- stated levels of C, Si, Mn, Cr, Al, and N,
and containing one or more elements selected from the group consisting of the rare
earth elements, Ca, and B, the amount of the rare earth elements ranging from 4x(%
of S) to 20x(% of S), that of Ca from 1x(% of S) to 10x(% of S), and that of B from
0.001 to 0.008% by weight, the remainder being Fe and unavoidable impurities, of which
the impurities P and S are held at the levels cited above, the ferrite content of
these steels being no more than 40% by weight at 1200°C.
[0014] Lastly, the invention also contemplates martensitic stainless steels for use in seamless
steel pipe having the above- stated levels of C, Si, Mn, Cr, Al, and N, and also containing
one or more elements selected from the group consisting of Ni, Cu, Mo, Nb, and V,
as well as one or more elements selected from the group consisting of the rare earth
elements, Ca, and B, these all being present in the ranges indicated above, the remainder
being Fe and unavoidable impurities, of which the impurities P and S are held at the
levels cited above, the ferrite content of these steels being no more than 40% by
weight at 1200°C.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The martensitic stainless steels of the present invention shall now be described
in detail. We shall begin by explaining the reasons for each of the limits placed
on the contents of the basic constituents in the steels of the invention.
[0016] Carbon is necessary for strength. However, because corrosion resistance declines
at a carbon content in excess of 0.30%, the upper limit on carbon content has been
set at O.30%.
[0017] Chromium markedly increases corrosion resistance in C0
2- containing environments. The addition of at least 11% is intended to prevent pitting
and crevice corrosion. However, this element also is ferrite-forming. The addition
of more than 14% therefore increases the amount of ferrite, making it difficult to
achieve the desired strength under the heat conditions (tempering temperature) necessary
to preserve resistance of the steel to stress-corrosion cracking. The range in the
chromium content was thus set at 11-14%.
[0018] Silicon is effective as a deoxidizer and should preferably be included at a level
of at least 0.2%. A content of more than 1.0% reduces toughness, so we set an upper
limit of 1.0%.
[0019] Manganese acts to strengthen the steel and improve toughness. Therefore a content
of not less than 0.5% is desirable. However, no further improvement in strength and
toughness can be gained from the addition of more than 2.0%. Hence, the Mn content
was set at not more than 2.0%.
[0020] Aluminum acts as a deoxidizer, reducing the level of oxygen in the steel by oxygen
fixation, enhancing the hot workability. The stabilizing effects of Al addition are
not observed at less than 0.005%; these effects reach a saturation level at 0.10%.
The content of Al was thus limited to a range of from 0.005% to 0.10%.
[0021] Nitrogen increases the strength and corrosion resistance of the steel up to a concentration
of 0.10%, beyond which additional improvement is not observed. For this reason, the
N content was set at not more than 0.10%.
[0022] Sulfur is present in the steel as an undesirable impurity that severely reduces the
hot workability of the steels in the present invention. This adverse effect is particularly
large during piercing of the billet on a piercing mill when the seamless pipe is fabricated
by the plug mill process or the mandrel mill process. A sulfur level in excess of
0.003% makes it difficult to produce scratch-free seamless pipe, which is why the
S content must be held to no more than 0.003%.
[0023] P is another impurity unavoidably present in steels. It produces a marked deterioration
in the hot workability of the steel at high temperatures of 1200°C and above. This
element causes scratch formation on the inside wall of the tube during piercing of
the billet on a piercing mill. Piercing without scratch formation is difficult at
a P level above 0.02%, and so this must be held to 0.02% or less.
[0024] In addition to the above basic constituents, the martensitic stainless steels of
the present invention may also contain one or more elements selected from the group
consisting of Ni, Cu, Mo, Nb, and V, and one or more elements chosen from the group
consisting of rare earth metals, Ca, and B. The reasons for the ' limits set to the
contents for each of these are given below. Nickel: Ni increases corrosion resistance.
The addition of more than 3.5%, however, produces no further improvement in corrosion
resistance. Because Ni is expensive, the upper limit of addition was set at 3.5%.
[0025] Molybdenum: Mo enhances the strength and corrosion resistance of the steel. At levels
of under 0.01%, this effect is not fully exhibited, while the addition of more than
2.5% produces no corresponding increase in effect. Because Mo too is a high- priced
metal, Mo addition was limited to a range of from 0.01% to 2.5%.
[0026] Niobium: Nb increases steel strength, but is ineffective at levels of under 0.01%.
The addition of over 0.10% fails to produce additional improvement. The range of Nb
addition was thus set at 0.01-0.10%.
[0027] Vanadium: V increases the strength of the steel, but is not effective at levels below
0.1%. Further improvement does not result from the addition of more than 0.10%. The
range in the content of V was thus set at 0.01-0.10%.
[0028] Copper: Copper improves the strength and corrosion resistance of the steel. However,
because the addition of more than 2.0% reduces hot workability, the upper limit on
copper addition was set at 2.0%.
[0029] Rare earth metals (REM), calcium: The rare earth metals and calcium are powerful
sulfide-forming elements. The formation of the sulfides of rare earth metals or calcium
reduces the amount of sulfur in solid solution within the steel, thereby improving
the hot workability of the steel. However when the amount of rare earth elements is
four times as great as the sulfur content (wt%) or the amount of calcium less than
equivalent to the amount of sulfur, this effect is minor. On the other hand, when
the level of rare earth elements is greater than 20 times, or the level of calcium
greater than 10 times, the amount of sulfur, this effect reaches a saturation point
and the oxides and sulfides of these elements may even have the opposite effect of
increasing surface defects. For these reasons, we limited the amount of rare earth
metals to a range of from 4x(%S) to 20x(%S), and the amount of calcium to a range
of from 1x(%S) to 10x(%S). Boron: The addition of a trace amount of boron improves
the hot workability of the steel. This effect does not arise at a level of less than
0.001%. However, the addition of more than 0.0O8% of boron has the opposite effect
of reducing the hot workability at temperatures of 1200°C and over. We therefore limited
boron addition to a range of 0.001-0.008%.
[0030] We have also set a ferrite content for the steels of the present invention of 40%
or less at 1200°c. This is because, as we have seen above, even the plug mill and
mandrel mill processes can be used to manufacture seamless pipe without hindrance
or defects from steels having a ferrite content of more than 40% at 1200°c. The ferrite
content (%) at 1200°C is defined by Eq. (1) below:

[0031] We shall now describe a method for fabricating seamless steel pipe using the martensitic
stainless steels of the present invention.
[0032] First, a bloom obtained by continuous casting or blooming.is rolled into a round
billet. This billet is then heated to a given temperature, preferably from 1200 to
1250
0c, and pierced and rolled by means of the Mannesmann plug mill process or the Mannesmann
mandrel mill process. When the Mannesmann plug mill process is employed, the billet
is first pierced on a piercer, then rolled by an elongator, a plug mill, a reeler
and a sizer, in that order. When the Mannesmann mandrel mill process is used, the
billet is first pierced on a piercer then rolled respectively on a mandrel mill and
hot-stretch reducer. Following this, the pipe is heat-treated either in a batch-type
furnace or by induction heating. This heat treatment may consist of quench-tempering,
normalize-tempering, or simply tempering. This gives steel pipe of the desired strength.
In the case of oil-well pipe, it is more common to first increase the wall thickness
at the tube ends by upsetting, then heat-treat.
[0033] Table 2 shows the chemical constituents and whether or not defects were formed for
a number of examples illustrating the present invention and several comparative examples.
In each case, a billet having a diameter of 175 mm was heatea to 1230°C and pierced
on a piercer to form a tube with an outside diameter of 185mm and a wall thickness
of 19.76mm. The inside and outside walls of the tube were examined. An "X" in the
table denotes that defects such as scratches or cracks were found on the tube wall.
An open circle ○ indicates that no defects were observed, or only minor faults of
no practical consequence noted. Theferrite(%) shown in Table lshowstheferrite contents(%)
at 1200° which were calculated using Eq. (1). If the computed value was negative,
this was indicated in the table as 0. The rare earth metals used in the examples shown
in Table 2 consisted primarily of cesium (approx. 50%).
[0034] The P and S levels of specimens 21-26 (comparative examplés) in Table 2 all exceed
the upper limits of the ranges set in the present invention. Defects were observed
in each of these specimens. Similarly, the levels of the rare earth metals, B, and
Ca in specimens 27-29 (comparative examples) all exceeded the upper limits defined
above. Defects were again noted in each of these.
[0035] As we have indicated in the preceding explanation, the martensitic stainless steels
for use in seamless steel tube of the present invention raises the hot workability,
and especially the hot piercability, of steels having ferrite contents of 40% or less
at 1200
oC, despite the difficulty previously encountered in manufacturing seamless pipe from
such steels by a plug mill or a mandrel mill process. This is achieved by holding
down the P and the S contents of the steel. As a result, seamless steel pipe need
no longer be manufactured by a hot extrusion process, and can now be manufactured
free of defects by a plug mill or a mandrel mill process. Because this permits the
use of plug mill and mandrel mill processes in the production of seamless pipe from
this type of steel, higher productivity can be achieved, along with increased yield
and reduced costs.
[0036] This invention also provides martensitic stainless steels for use in seamless steel
pipe wherein, in addition to restricting the levels of P and S, one or more elements
selected from the rare earth metals, calcium, and boron are added, further increasing
the hot piercability of the steel. This permits the manufacture of defect-free seamless
steel pipe by means of a mandrel mill or plug mill process.

1. Martensitic stainless steels for use in seamless steel pipe containing not more
than 0.30% by weight of C, not more than 1.0% by weight of Si, not more than 2.0%
by weight of Mn, 11-14% by weight of Cr, 0.005-0.10% by weight of Al, and not more
than 0.10% by weight of N, wherein the amount of P is held to no more than 0.02% by
weight and the amount of S to no more than 0.003% by weight, the remainder thereof
being substantially Fe, said 'steels having a ferrite content of not more than 40%
by weight at 1200°C.
2. Martensitic stainless steels for use seamless steel pipe containing not more than
0.30% by weight of C, not more than 1.0% .by weight of Si, not more than 2.0% by weight
of Mn, 11-14% by weight of Cr, 0.005-0.10% by weight of Al, and not more than 0.10%
by weight of N, and containing also one or more elements selected from the group consisting
of up to 3.5% by weight of Ni, up to 2% by weight of Cu, up to 2.5% by weight of Mo,
up to 0.10% by weight of Nb, and up 0.10% by weight of V, wherein the amount of P
is held to no more than 0.02% by weight and the amount of S to no more than 0.003%
by weight, the remainder being substantially Fe, said steels having a ferrite content
of not more than 40% by weight at 1200oC.
3. Martensitic stainless steels for use in seamless steel pipe containing not more
than 0.30% by weight of C, not more than 1.0% by weight of Si, not more than 2.0%
by weight of Mn, 11-14% by weight of Cr, 0.005-0.10% by weight of Al, and not more
than 0.10% by weight of N, and containing also one or more elements selected from
the group consisting of the rare earth elements, Ca, and B, the amount of the rare
earth elements ranging from 4x(% of S) to 20x(% of S), that of Ca from 1x(% of S)
to 10x(% of S), and that of B from 0.001 to 0.008% by weight, wherein the amount of
P is held to no more than 0.02% by weight and the amount of S to no more than 0.003%
by weight, the remainder being substantially Fe, said steels having a ferrite content
of not more than 40% by weight at 1200°C.
4. Martensitic stainless steels for use in seamless steel pipe containing not more
than 0.30% by weight of C, not more than 1.01 by weight of Si, not more than 2.0%
by weight of Mn, 11-14% by weight of Cr, 0.005-0.10% by weight of Al, and not more
than 0.10% by weight of N, and containing one or more elements selected from the group
consisting of up to 3.5% by weight of Ni, up to 2% by weight of Cu, up to 2.5% by
weight of Mo, up to 0.10% by weight of Nb, and up to 0.10% by weight or less of V,
as well as one or more elements selected from the group consisting of the rare earth
elements, Ca, and B, the amount of the rare earth elements ranging from 4x(% of S)
to 20x(% of S), that of Ca from 1x(% of S) to 10x(% of S), and that of B from 0.001
to 0.008% by weight, wherein the amount of P is held to no more than 0.02% by weight
and the amount of S to no more than 0.003% by weight, the remainder being substantially
Fe, said steels having a ferrite content of not more than 40% at 1200°C.