EP1538232B1 - Korrosionsbeständige, austenitische Stahllegierung - Google Patents

Korrosionsbeständige, austenitische Stahllegierung Download PDF

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Publication number
EP1538232B1
EP1538232B1 EP04450211A EP04450211A EP1538232B1 EP 1538232 B1 EP1538232 B1 EP 1538232B1 EP 04450211 A EP04450211 A EP 04450211A EP 04450211 A EP04450211 A EP 04450211A EP 1538232 B1 EP1538232 B1 EP 1538232B1
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EP
European Patent Office
Prior art keywords
weight
steel alloy
alloy according
temperature
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Prior art date
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Expired - Lifetime
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EP04450211A
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German (de)
English (en)
French (fr)
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EP1538232A1 (de
Inventor
Gabriele Dr.-Ing. Saller
Herbert Dipl.-Ing. Aigner
Josef Dipl.Ing. Bernauer
Raimund Huber
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Voestalpine Boehler Edelstahl GmbH
Schoeller Bleckmann Oilfield Technology GmbH and Co KG
Original Assignee
Schoeller Bleckmann Oilfield Technology GmbH and Co KG
Boehler Edelstahl GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2261/00—Machining or cutting being involved
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation

Definitions

  • the invention relates to an austenitic, substantially ferrite-free steel alloy.
  • the invention comprises the use of an austenitic, substantially ferrite-free steel alloy.
  • the invention relates to a process for the production of austenitic, substantially ferrite-free components, in particular boring bars, for oil field technology.
  • Austenitic alloys may be essentially ferrite-free, that is to say with a relative magnetic permeability ⁇ r smaller than 1.01. Thus, austenitic alloys can meet the above requirement and therefore be used principally for drill string components.
  • a selected austenitic material reaches minimum mechanical properties, in particular 0.2% proof strength and tensile strength and has grown during drilling operation dynamically changing loads, so in addition has a high fatigue strength. Otherwise, for example, boring bars of corresponding alloys can not withstand the high tensile and compressive stresses and torsional stresses occurring during use, or only for a short service life; undesirable rapid or premature material failure is the result.
  • Austenitic materials for drill string components are typically high alloyed with nitrogen to achieve high levels of yield strength and tensile strength of components such as drill rods.
  • a requirement to be considered is a lack of pores of the material used, which can be influenced by alloy composition and manufacturing process.
  • alloys are economically favorable alloys which lead to non-porous semi-finished product under solidification under atmospheric pressure.
  • austenitic alloys are rather rare because of the high nitrogen content, and solidification under elevated pressure is required throughout to achieve freedom from pores. Melting and solidification under nitrogen pressure may also be necessary to obtain enough nitrogen in the solidified material if insufficient nitrogen solubility is otherwise present.
  • austenitic alloys intended for use as components of drill strings should have good resistance to various types of corrosion.
  • high resistance to pitting corrosion and stress corrosion cracking is desirable, especially in chloride containing media.
  • austenitic alloys are known, each of which meets some of these requirements, namely extensive freedom from ferrite, good mechanical properties, freedom from pores and high corrosion resistance.
  • An austenitic alloy which leads to objects with low magnetic permeability and good mechanical properties when melted under atmospheric pressure is described in AT 407 882 B.
  • Such an alloy has in particular a high 0.2% proof stress, high tensile strength and a high permanent fatigue strength.
  • Alloys according to AT 407 882 B are expediently thermoformed and at temperatures of 350 ° C. subjected to a second deformation to about 600 ° C.
  • the alloys are suitable for the production of boring bars, which in the context of a drill bit in oilfield technology also satisfactorily meet the high demands with regard to static and dynamic load capacity over long periods of use.
  • the invention of the invention and has set itself the task of specifying an austenitic steel alloy which can be melted at atmospheric pressure and porenrud semi-finished and which with good mechanical properties, especially at high 0.2% proof stress, high tensile strength and high fatigue strength, at the same time a high resistance has both against stress corrosion cracking and pitting corrosion.
  • Another object of the invention is to provide uses for an austenitic, substantially ferrite-free alloy.
  • an austenitic, substantially ferrite-free steel alloy is provided, which has good mechanical properties, in particular high values of 0.2% proof stress and tensile strength and which simultaneously has a high resistance to stress corrosion cracking and also to Pitting corrosion has.
  • an at least largely pore-free block of an alloy according to the invention can thus be produced on melting and solidification under atmospheric pressure.
  • a temperature below the recrystallization temperature preferably below 600 ° C, in particular in the range of 300 ° C to 550 ° C.
  • Carbon (C) may be present in a steel alloy of the invention at levels up to 0.35% by weight. Carbon is an austenite former and has a favorable effect in terms of high mechanical properties. With a view to avoiding carbide precipitations, in particular for larger dimensions, it is preferable to adjust the carbon content to 0.01% by weight to 0.06% by weight.
  • Silicon (Si) is provided in amounts up to 0.75% by weight and serves mainly to deoxidize the steel. Higher contents than 0.75% by weight prove to be disadvantageous in terms of formation of intermetallic phases. Moreover, silicon is a ferrite former and therefore a silicon content should be limited to a maximum of 0.75% by weight. It is favorable, and therefore preferred, to provide silicon in contents of from 0.15% by weight to 0.30% by weight, because in this content range a sufficient deoxidizing effect is given with a small contribution of silicon to ferrite formation.
  • Manganese (Mn) is provided at levels of greater than 19.0% by weight to 30.0% by weight. This element contributes significantly to high nitrogen solubility. Non-porous materials from an inventive Steel alloy can therefore be produced even under solidification under atmospheric pressure. With respect to a nitrogen solubility of an alloy in the molten state and during and after solidification, it is preferred to use manganese in contents of more than 20% by weight. Manganese also stabilizes the austenite structure, especially at high degrees of deformation, against the formation of deformed martensite. With regard to a preferably good corrosion resistance, an upper limit of the manganese content has been found to be 25.5% by weight.
  • Chromium (Cr) proves to be high in corrosion resistance at levels of 17.0% by weight or more.
  • chromium allows Zulegieren large amounts of nitrogen.
  • Higher contents than 24.0 wt .-% can adversely affect a magnetic permeability, because chromium is one of the ferrite-stabilizing elements.
  • Molybdenum (Mo) is an element which contributes substantially to corrosion resistance in general and to pitting corrosion resistance in particular in a steel alloy according to the invention, wherein the effect of molybdenum in a content range of more than 1.90 wt% is enhanced by a presence of nickel ,
  • An optimal and therefore preferred range of molybdenum content in terms of corrosion resistance is defined by a lower limit of 2.05% by weight, a particularly preferred range by a lower limit of 2.5% by weight.
  • molybdenum on the one hand is an expensive element and on the other hand increases the tendency to form intermetallic phases at higher levels, a molybdenum content of 5.5 wt .-%, in preferred variants of the invention with 5.0 wt .-%, in particular 4.5 wt. %, limited.
  • Nickel (Ni) has been found to contribute actively and positively to corrosion resistance in a content range greater than 2.50% to 15.0% by weight and in cooperation with the other alloying elements. In particular, and this is considered to be completely surprising from a professional point of view, in the presence of more than 2.50 wt .-% nickel is given a high stress corrosion cracking resistance. Contrary to the opinion outlined in relevant textbooks, with increasing nickel levels, stress corrosion cracking resistance of chromium-containing austenites in chloride-containing media decreases dramatically and is at a minimum at about 20 wt% (see, eg: AJ Sedriks, Corrosion of Stainless Steels, 2 ed. , John Wiley & Sons Inc., 1996, page 276), a high stress crack corrosion resistance can be achieved in a steel alloy according to the invention even with nickel contents of more than 2.50% to 15.0% by weight in chloride-containing media.
  • Nickel contents of at least 2.65% by weight, preferably at least 3.6% by weight, in particular 3.8% by weight to 9.8% by weight, of nickel are particularly preferred in this connection.
  • Co Co
  • Co may be present at levels up to 5.0% by weight for substitution of nickel. Preferably, however, it is because of the high cost of this element due to keep a cobalt content below 0.2 wt .-%.
  • Nickel as stated above, makes a high contribution to corrosion resistance and is a strong austenite former.
  • molybdenum also makes a significant contribution to corrosion resistance, but is a ferrite former. Therefore, it is favorable if the nickel content is equal to or greater than the molybdenum content. In this context, it is particularly favorable if a nickel content is more than 1.3 times, preferably more than 1.5 times, a molybdenum content.
  • Nitrogen (N) is required in amounts of at least 0.35 wt% to 1.05 wt% to ensure high strength. Further, nitrogen contributes to the corrosion resistance and is a strong austenite former, therefore, higher contents than 0.40 wt .-%, especially higher than 0.60 wt .-%, are favorable. On the other hand, as nitrogen content increases, nitrogen-containing precipitate formation tends to increase, for example, Cr 2 N. In advantageous variants of the invention, nitrogen content is therefore limited to 0.95% by weight, preferably 0.90% by weight.
  • Boron (B) can be provided in amounts of up to 0.005% by weight and, in particular in a range from 0.0005% by weight to 0.004% by weight, promotes hot workability of the material composed according to the invention.
  • Copper (Cu) is tolerable in a steel alloy according to the invention in a content of less than 0.5 wt .-%. At levels of 0.04 wt.% To 0.35 wt.%, Copper proves to be quite advantageous in special drill bit applications, for example when boring bars come in contact with media such as hydrogen sulfide, especially H 2 S. Contents higher than 0.5% by weight promote precipitation formation and are disadvantageous for corrosion resistance.
  • Aluminum (Al) contributes to deoxidation of the steel besides silicon, but is a strong nitride former, which limits this element to less than 0.05% by weight.
  • S Sulfur
  • S is provided at levels up to 0.30% by weight. Greater contents than 0.1% by weight have a very favorable effect on the processing of a steel alloy according to the invention, because machining is facilitated. However, if one considers the highest corrosion resistance of the material, a sulfur content of 0.015 wt .-% is limited.
  • the content of phosphorus (P) is less than 0.035% by weight.
  • a phosphorus content is limited to a maximum of 0.02 wt .-%.
  • Vanadium (V), niobium (Nb), titanium (Ti) act in a complementary manner in the steel and can be present for this purpose individually or in any desired combination, with a maximum concentration of the elements present being at most 0.85% by weight. In view of a grain-refining effect and avoidance of coarse precipitations of these strong carbide formers, it is beneficial if a sum concentration of the elements present is more than 0.08% by weight and less than 0.45% by weight.
  • the elements tungsten, molybdenum, manganese, chromium, vanadium, niobium and titanium contribute positively to the solubility of nitrogen.
  • the further object of the invention to provide uses for an austenitic, substantially ferrite-free alloy is achieved by using a steel alloy according to the invention as a material for components for oil field technology.
  • a steel alloy according to the invention as a material for components for oil field technology.
  • the component is a Bohrstrangteil.
  • the further object of the invention is also achieved by using an alloy according to the invention for tensile and compression stressed components, which come into contact with corrosive media, in particular a corrosive liquid such as saline water.
  • the method of the invention is achieved by a method according to claim 26.
  • the semifinished product is expediently a bar which is deformed in the second deformation step with a degree of deformation of 10% to 20%.
  • Such degrees of deformation provide sufficient strength for use and permit turning or peeling machining with reduced tool wear.
  • Rapid and cost effective component manufacturing is enabled when the machining involves turning and / or peeling.
  • blocks were prepared whose chemical compositions correspond to alloys 1 to 5 and 7 in Table 1.
  • An alloy 6 cast in Table 1 was remelted under nitrogen atmosphere at 16 bar pressure and stitched.
  • the semifinished blocks were quenched with water to ambient temperature and finally subjected to a second deformation step at a temperature of 380 ° C to 420 ° C, with a degree of deformation of 13% to 17%.
  • the objects created in this way were examined or further processed into boring bars.
  • Alloys A, B, C, D and E represent products available on the market.
  • the alloys listed in Table 1 were examined for pitting corrosion resistance and stress corrosion cracking.
  • the determination of the pitting corrosion resistance was carried out by measuring the pitting potential against a standard hydrogen electrode according to ASTM G 61.
  • the stress corrosion cracking (SCC) was determined by determining the value of the SCC limit stress according to ATSM G 36.
  • the value of the SCC cut-off voltage represents the externally applied maximum test voltage which a test sample can withstand for more than 720 hours in 155% boiling 45% MgCl 2 solution.
  • Pitting potential E pit or SCC limit stress can even reach values corresponding to those of high alloyed Cr-Ni-Mo steels and nickel base alloys, with better strength properties as shown in Tables 4 and 5 at the same time. It is particularly favorable with respect to an SCC limit voltage, if a sum of molybdenum and nickel 4.7 wt .-% or more, in particular more than 6 wt .-%, is.
  • articles made of the alloys 1 to 7 according to the invention have a relative magnetic permeability of ⁇ r ⁇ 1,005 and at room temperature permanent fatigue strengths of at least 400 MPa at 10 7 load changes.
  • indexable inserts could be used 12% longer when machining Alloys 3 and 4 than when machining Alloy C rods Boring bars, which have high mechanical characteristics and improved corrosion resistance, are produced with less tool wear.
  • an alloy according to the invention is also optimally suitable as a material for fastening or connecting elements, such as Screws, nails, bolts or similar components, if they are exposed to high mechanical loads and aggressive environmental conditions.
  • alloys according to the invention find advantageous use is in the field of corrosion and wear parts such as baffles or parts that are exposed to high loading speeds.
  • components of alloys of the invention due to their combination of properties lowest material wear and thus achieve maximum life.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Steel (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Earth Drilling (AREA)
EP04450211A 2003-12-03 2004-11-17 Korrosionsbeständige, austenitische Stahllegierung Expired - Lifetime EP1538232B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0193803A AT412727B (de) 2003-12-03 2003-12-03 Korrosionsbeständige, austenitische stahllegierung
AT19382003 2003-12-03

Publications (2)

Publication Number Publication Date
EP1538232A1 EP1538232A1 (de) 2005-06-08
EP1538232B1 true EP1538232B1 (de) 2007-01-03

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Country Status (7)

Country Link
US (3) US7708841B2 (no)
EP (1) EP1538232B1 (no)
AT (2) AT412727B (no)
CA (1) CA2488965C (no)
DE (1) DE502004002524D1 (no)
ES (1) ES2280936T3 (no)
NO (1) NO340359B1 (no)

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US20050145308A1 (en) 2005-07-07
US7708841B2 (en) 2010-05-04
CA2488965C (en) 2013-04-09
ATE350505T1 (de) 2007-01-15
NO20045271L (no) 2005-06-06
AT412727B (de) 2005-06-27
ATA19382003A (de) 2004-11-15
ES2280936T3 (es) 2007-09-16
US20110253262A1 (en) 2011-10-20
EP1538232A1 (de) 2005-06-08
US8454765B2 (en) 2013-06-04
US7947136B2 (en) 2011-05-24
DE502004002524D1 (de) 2007-02-15
NO340359B1 (no) 2017-04-10
US20100170596A1 (en) 2010-07-08

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