EP3380641A1 - Grain boundary cohesion enhanced sulfide stress cracking (ssc)-resistant steel alloys - Google Patents
Grain boundary cohesion enhanced sulfide stress cracking (ssc)-resistant steel alloysInfo
- Publication number
- EP3380641A1 EP3380641A1 EP16869287.9A EP16869287A EP3380641A1 EP 3380641 A1 EP3380641 A1 EP 3380641A1 EP 16869287 A EP16869287 A EP 16869287A EP 3380641 A1 EP3380641 A1 EP 3380641A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- mpa
- nickel
- vanadium
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
- C22C38/54—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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
-
- 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
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- 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
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D18/00—Pressure casting; Vacuum casting
-
- 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
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
- C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/02—Rigid pipes of metal
Definitions
- SSC Sulfide stress cracking
- HSLA high strength low alloy
- yield strength 965-1 100 MPa (140-160 ksi).
- HSLA steels suffer from either a low sulfide stress corrosion cracking toughness or yield strength, or both. Accordingly, there exists a need for an HSLA steel that can be economically manufactured and have good sulfide stress corrosion cracking toughness and good yield strength.
- an alloy comprising, by weight, about 0% to about 8% nickel, about 1% to about 6% tungsten, about 1% to about 4% copper, about 0.1% to about 2% chromium, about 0.01% to about 1% vanadium, about 0.01% to about 0.5% carbon, about 0.01% to about 0.1%) titanium, about 0.001%> to about 0.01%> boron, about 0% to about 1%> silicon, and about 0%) to about 0.1%> calcium, the balance essentially iron and incidental elements and impurities.
- Other aspects of the disclosure include processes for producing the alloy, and manufactured articles comprising the alloy.
- FIG. 1 is an illustration of K1 SCC versus yield strength. The points labeled "Lit.
- HSLA (SSC) in the lower left are literature values for existing HSLA oil and gas SSC-resistant steels. Note that these points are reported values of KISSC (which correlates to KISCC). The bottom curve is a fit to these points. The points labeled “HyTuf ', "4340”, "300M”, and
- FIG. 2 is a CALPHAD equilibrium step diagram of phase fraction vs. temperature for an exemplary embodiment (QT-SSC alloy).
- FIG. 3 is a CALPHAD metastable step diagram of phase fraction vs. temperature for an exemplary embodiment (QT-SSC alloy).
- FIG. 4 is a plot of hardness vs. aging temperature for QT-SSC steel, one embodiment of the disclosed alloys.
- HSLA high strength low alloy
- the disclosed alloys can possess both improved processing and physical properties over existing HSLA steels, such as improved sulfide stress cracking toughness with increased yield strength, making the alloys useful in extreme environments, such as those in oil and gas applications.
- the disclosed alloys have improved sulfide stress cracking (SSC) toughness, reduced hydrogen embrittlement (HE), improved corrosion resistance, and improved yield strength, relative to existing HSLA steels (FIG. 1). These improved properties may be the result of incorporating comparatively greater amounts of tungsten, nickel, and copper in the alloys, which was discovered, in part, due to the development of predictive models.
- the alloy was designed to implement a variety of strategies, including-in conjunction with improved grain boundary cohesion-surface scale formation, improved hydrogen trapping, slow bulk/grain boundary hydrogen diffusion, and promotion of surface H 2 formation.
- Intergranular fracture may be a primary
- E ° is the embrittling potency of element i and ⁇ is the grain boundary composition of element i.
- ⁇ is the grain boundary composition of element i.
- Lower (more negative) values of ⁇ 2 ⁇ indicate a stronger cohesion between grains and a greater resistance to intergranular cracking by SSC.
- the grain boundary composition is predicted by the McLean Gibbs isotherm (McLean, D. Grain boundaries in metals, London: Oxford University Press; 1957
- Grain boundary cohesion was accomplished in the disclosed alloys by specific alloying additions that both segregate to the matrix grain boundary ⁇ E G l B ⁇ 0) and improve cohesion (Ef ot ⁇ 0).
- Tungsten was found to be a particularly potent cohesion enhancing element, and the tungsten content of the disclosed alloys is unique compared to existing alloys.
- Boron was also found to be a potent cohesion enhancing element, and a significant amount of boron can be incorporated to be present at the grain boundaries of the disclosed alloys.
- Scales may be made from oxides, sulfides, or other p-block elements.
- the addition of copper in the disclosed alloys may provide BCC copper precipitates and copper in the grain boundary, which can strengthen the alloy, alter scale formation, and promote H 2 recombination at the surface.
- SSC may occur when hydrogen collects at grain boundaries. Therefore, impeding hydrogen diffusion by trapping hydrogen at precipitate interfaces may reduce intergranular SSC. Modification of the alloy chemistry to promote carbide and other precipitate formation with particular morphology (e.g., fine homogenously dispersed globular carbides) may decrease SSC in the alloys. Accordingly, the disclosed alloys may possess a large volume fraction of M 2 C carbide, and heat treatment can ensure a fine, homogeneous carbide dispersion.
- Promotion of surface H 2 formation Sulfides may poison the steel surface hydrogen recombination reaction, greatly increasing the steel-absorbed H content. Therefore, modification of surface chemistry may promote the recombination of the adsorbed H into H 2 gas that evolves away from the surface. Introduction of alloying elements that lower the hydrogen overvoltage (acting as effective cathodic sites) may enhance the hydrogen recombination process.
- a representative composition of the disclosed alloys is summarized in Table 1.
- the table describes the nominal composition of elements in weight and atomic percentages.
- the matrix and grain boundary compositions are calculated to have the values listed in Table 1 at 500°C (an example temperature).
- the alloy is calculated to have a ⁇ 2 ⁇ value of -2.64 J/m 2 , an M 2 C phase fraction of 0.0129, and a BCC copper phase fraction of 0.0295.
- a CALPHAD equilibrium step diagram of phase fraction vs. temperature (FIG. 2), and a CALPHAD metastable step diagram of phase fraction vs. temperature (FIG. 3) of the disclosed alloy were generated.
- QT-SSC has a significantly lower calculated ⁇ 2 ⁇ value compared to prior art alloys, indicating superior predicted SSC resistance.
- solvus may refer to a line (binary system) or surface
- phase diagram which separates a homogeneous solid solution from a field of several phases which may form by exsolution or incongruent melting.
- solidus may refer to the temperature below which a mixture is completely solid.
- liquidus may refer to the temperature above which a material is completely liquid, and the maximum temperature at which crystals can co-exist with the melt in thermodynamic equilibrium.
- the conjunctive term "or" includes any and all combinations of one or more listed elements associated by the conjunctive term.
- the phrase "an apparatus comprising A or B” may refer to an apparatus including A where B is not present, an apparatus including B where A is not present, or an apparatus where both A and B are present.
- the phrases "at least one of A, B, . . . and N" or "at least one of A, B, . . . N, or combinations thereof are defined in the broadest sense to mean one or more elements selected from the group comprising A, B, . . . and N, that is to say, any combination of one or more of the elements A, B, . . . or N including any one element alone or in combination with one or more of the other elements which may also include, in combination, additional elements not listed.
- the modifier "about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity).
- the modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4" also discloses the range “from 2 to 4.”
- the term “about” may refer to plus or minus 10% of the indicated number. For example, “about 10%” may indicate a range of 9% to 11%, and “about 1" may mean from 0.9-1.1. Other meanings of "about” may be apparent from the context, such as rounding off, so, for example "about 1” may also mean from 0.5 to 1.4.
- the disclosed alloys may comprise nickel, tungsten, copper, chromium, vanadium, carbon, titanium, boron, silicon, calcium, and iron, along with incidental elements and impurities.
- the alloys may comprise, by weight, about 0% to about 8% nickel, about 1% to about 6%) tungsten, about 1% to about 4% copper, about 0.1% to about 2% chromium, about 0.01% to about 1% vanadium, about 0.01% to about 0.5% carbon, about 0.01% to about 0.1% titanium, about 0.001%> to about 0.01% boron, about 0% to about 1% silicon, and about 0% to about 0.1%) calcium, the balance essentially iron and incidental elements and impurities. It is understood that the alloys described herein may consist only of the above-mentioned constituents or may consist essentially of such constituents, or in other embodiments, may include additional constituents.
- the alloys may comprise, by weight, about 0.5% to about 7.5% nickel, about 2% to about 5%) tungsten, about 1.5% to about 3.5% copper, about 0.1% to about 1.5% chromium, about 0.01% to about 0.5% vanadium, about 0.01% to about 0.3% carbon, about 0.01% to about 0.075% titanium, about 0.001%> to about 0.005% boron, about 0% to about 0.5% silicon, and about 0% to about 0.075%) calcium, the balance essentially iron and incidental elements and impurities. It is understood that the alloys described herein may consist only of the above-mentioned constituents or may consist essentially of such constituents, or in other embodiments, may include additional constituents.
- the alloys may comprise, by weight, about 1% to about 7% nickel, about 2.5% to about 4.5%) tungsten, about 2% to about 3% copper, about 0.1% to about 1% chromium, about 0.01% to about 0.2% vanadium, about 0.01% to about 0.2% carbon, about 0.01% to about 0.05% titanium, about 0.001%> to about 0.002% boron, about 0% to about 0.2% silicon, and about 0% to about 0.05%) calcium, the balance essentially iron and incidental elements and impurities. It is understood that the alloys described herein may consist only of the above-mentioned constituents or may consist essentially of such constituents, or in other embodiments, may include additional constituents.
- the alloys may comprise, by weight, about 6.3% to about 6.7% nickel, about 3.8% to about 4.2% tungsten, about 2.3% to about 2.7% copper, about 0.3% to about 0.7% chromium, about 0.08% to about 0.12% vanadium, about 0.08% to about 0.12% carbon, about 0.01% to about 0.03% titanium, about 0.0013% to about 0.0017% boron, about 0% to about 0.02% silicon, and about 0%) to about 0.02% calcium, the balance essentially iron and incidental elements and impurities. It is understood that the alloys described herein may consist only of the
- constituents may consist essentially of such constituents, or in other embodiments, may include additional constituents.
- the alloys may comprise, by weight, about 0% to about 8% nickel, about 0% to about 7%) nickel, about 0% to about 6% nickel, about 0% to about 5% nickel, about 0% to about 4%) nickel, about 0% to about 3% nickel, about 0% to about 2% nickel, about 0% to about 1% nickel, about 0% to about 0.5% nickel, about 0.5% to about 8% nickel, about 0.5% to about 7% nickel, about 0.5% to about 6% nickel, about 0.5% to about 5% nickel, about 0.5% to about 4% nickel, about 0.5% to about 3% nickel, about 0.5% to about 2% nickel, about 0.5% to about 1% nickel, about 1% to about 8% nickel, about 1% to about 7% nickel, about 1% to about 6% nickel, about 1%) to about 5% nickel, about 1% to about 4% nickel, about 1% to about 3% nickel, about 1%) to about 5% nickel, about 1% to about 4% nickel, about 1% to about 3% nickel, about 1%) to about 5% nickel, about
- the alloys may comprise, by weight, 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, or 8%o nickel.
- the alloys may comprise, by weight, about 0% nickel, about 0.5% nickel, about 1%) nickel, about 1.5% nickel, about 2% nickel, about 2.5% nickel, about 3% nickel, about 3.5%) nickel, about 4% nickel, about 4.5% nickel, about 5% nickel, about 5.5% nickel, about 6% nickel, about 6.5% nickel, about 7% nickel, about 7.5% nickel, or about 8% nickel.
- the alloys may comprise, by weight, about 1% to about 6% tungsten, about 1% to about 5%) tungsten, about 1% to about 4% tungsten, about 1% to about 3% tungsten, about 1% to about 2%) tungsten, about 1% to about 1.5% tungsten, about 1.5% to about 6% tungsten, about 1.5% to about 5%) tungsten, about 1.5% to about 4% tungsten, about 1.5% to about 3% tungsten, about 1.5% to about 2% tungsten, about 2% to about 6% tungsten, about 2% to about 5% tungsten, about 2%) to about 4% tungsten, about 2% to about 3% tungsten, about 3% to about 6% tungsten, about 3%) to about 5% tungsten, about 3% to about 4% tungsten, about 4% to about 6% tungsten, about 4%) to about 5% tungsten, or about 5% to about 6% tungsten.
- the alloys may comprise, by weight, 1%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6% tungsten.
- the alloys may comprise, by weight, about 1% tungsten, about 1.5% tungsten, about 1.6% tungsten, about 1.7% tungsten, about 1.8% tungsten, about 1.9% tungsten, about 2% tungsten, about 2.5% tungsten, about 3% tungsten, about 3.5% tungsten, about 4% tungsten, about 4.5%) tungsten, about 5% tungsten, about 5.5% tungsten, or about 6% tungsten.
- the alloys may comprise, by weight, about 1% to about 4% copper, about 1% to about 3%) copper, about 1% to about 2% copper, about 2% to about 4% copper, about 2% to about 3%) copper, or about 3% to about 4% copper.
- the alloys may comprise, by weight, 1%, 1.5%, 2%, 2.5%), 3%), 3.5%), or 4% copper.
- the alloys may comprise, by weight, about 1% copper, about 1.5% copper, about 2% copper, about 2.5% copper, about 3% copper, about 3.5% copper, or about 4% copper.
- the alloys may comprise, by weight, about 0.1% to about 2% chromium, about
- the alloys may comprise, by weight, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%) chromium.
- the alloys may comprise, by weight, about 0.1% chromium, about 0.2% chromium, about 0.3% chromium, about 0.4% chromium, about 0.5% chromium, about 0.6%> chromium, about 0.7% chromium, about 0.8%> chromium, about 0.9% chromium, about 1% chromium, about 1.1% chromium, about 1.2% chromium, about 1.3% chromium, about 1.4% chromium, about 1.5% chromium, about 1.6% chromium, about 1.7% chromium, about 1.8% chromium, about 1.9% chromium, or about 2% chromium.
- the alloys may comprise, by weight, about 0.01% to about 1% vanadium, about
- vanadium 0.01% to about 0.8% vanadium, about 0.01% to about 0.6% vanadium, about 0.01% to about 0.4% vanadium, about 0.01% to about 0.2% vanadium, about 0.01% to about 0.1% vanadium, about 0.01%) to about 0.05%) vanadium, about 0.05% to about 1% vanadium, about 0.05% to about 0.8% vanadium, about 0.05% to about 0.6% vanadium, about 0.05% to about 0.4% vanadium, about 0.05%) to about 0.2% vanadium, about 0.05% to about 0.1% vanadium, about 0.1% to about 1% vanadium, about 0.1% to about 0.8% vanadium, about 0.1% to about 0.6% vanadium, about 0.1% to about 0.4%) vanadium, about 0.1% to about 0.2% vanadium, about 0.2% to about 1% vanadium, about 0.2%) to about 0.8% vanadium, about 0.2% to about 0.6% vanadium, about 0.2% to about 0.4%) vanadium, about 0.4% to
- the alloys may comprise, by weight, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5%), 0.6%), 0.7%), 0.8%), 0.9%), or 1% vanadium.
- the alloys may comprise, by weight, about 0.01%) vanadium, about 0.02% vanadium, about 0.03% vanadium, about 0.04% vanadium, about 0.05%) vanadium, about 0.1% vanadium, about 0.2% vanadium, about 0.3% vanadium, about 0.4% vanadium, about 0.5% vanadium, about 0.6% vanadium, about 0.7% vanadium, about 0.8% vanadium, about 0.9% vanadium, or about 1% vanadium.
- the alloys may comprise, by weight, about 0.01% to about 0.5% carbon, about
- the alloys may comprise, by weight, 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%), 0.45%), or 0.5% carbon.
- the alloys may comprise, by weight, about 0.01%> carbon, about 0.05%) carbon, about 0.1 % carbon, about 0.15% carbon, about 0.2% carbon, about 0.25% carbon, about 0.3% carbon, about 0.35 % carbon, about 0.4% carbon, about 0.45% carbon, or about 0.5%) carbon.
- the alloys may comprise, by weight, about 0.01% to about 0.1% titanium, about
- the alloys may comprise, by weight, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1% titanium.
- the alloys may comprise, by weight, about 0.01% titanium, about 0.02% titanium, about 0.03%) titanium, about 0.04% titanium, about 0.05% titanium, about 0.06% titanium, about 0.07% titanium, about 0.08% titanium, about 0.09% titanium, or about 0.1% titanium.
- the alloys may comprise, by weight, about 0.001%> to about 0.01% boron, about
- the alloys may comprise, by weight, 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, or 0.01% boron.
- the alloys may comprise, by weight, about 0.001%) boron, about 0.002%) boron, about 0.003% boron, about 0.004% boron, about 0.005% boron, about 0.006% boron, about 0.007% boron, about 0.008% boron, about 0.009%) boron, or about 0.01% boron.
- the alloys may comprise, by weight, about 0% to about 1% silicon, about 0% to about 0.75%) silicon, about 0% to about 0.5% silicon, about 0% to about 0.25% silicon, about 0.25% to about 1% silicon, about 0.25% to about 0.75% silicon, about 0.25% to about 0.5% silicon, about 0.5% to about 1% silicon, about 0.5% to about 0.75% silicon, or about 0.75% to about 1% silicon.
- the alloys may comprise, by weight, 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%), 0.8%), 0.9%), or 1% silicon.
- the alloys may comprise, by weight, about 0% silicon, about 0.1%) silicon, about 0.2% silicon, about 0.3% silicon, about 0.4% silicon, about 0.5% silicon, about 0.6%) silicon, about 0.7% silicon, about 0.8% silicon, about 0.9% silicon, or about 1% silicon.
- the alloys may comprise, by weight, about 0% to about 0.1% calcium, about 0% to about 0.075% calcium, about 0%> to about 0.05%> calcium, about 0%> to about 0.025%> calcium, about 0.025% to about 0.1% calcium, about 0.025% to about 0.075% calcium, about 0.025% to about 0.05%) calcium, about 0.05%> to about 0.1%> calcium, about 0.05%> to about 0.075%> calcium, or about 0.075%> to about 0.1%> calcium.
- the alloys may comprise, by weight, 0%>, 0.01%>, 0.02%>, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1% calcium.
- the alloys may comprise, by weight, about 0%> calcium, about 0.01%> calcium, about 0.02%> calcium, about 0.03%> calcium, about 0.04%) calcium, about 0.05%> calcium, about 0.06%> calcium, about 0.07%> calcium, about 0.08%) calcium, about 0.09%> calcium, or about 0.1%> calcium.
- the alloys comprise, by weight, about 6.5%> nickel, about 4.5%> tungsten, about 2.5%> copper, about 0.5%> chromium, about 0.1%> vanadium, about 0.1%> carbon, about 0.02%) titanium, about 0.0015%> boron, about 0%> silicon, and about 0%> calcium, the balance essentially iron and incidental elements and impurities.
- the alloys may comprise, by weight, a balance of iron and incidental elements and impurities.
- incident elements and impurities may include one or more of niobium, ruthenium, lanthanum, zirconium, manganese, cerium, magnesium, and nitrogen.
- the incidental elements and impurities may include one or more of niobium (e.g., maximum 2%>), ruthenium (e.g., maximum 2%>), lanthanum (e.g., maximum 2%>), zirconium (e.g., maximum 2%>), manganese (e.g., maximum 2%>), cerium (e.g., maximum 2%>), magnesium (e.g., maximum 2%>), and nitrogen (e.g., maximum 0.02%>).
- niobium e.g., maximum 2%>
- ruthenium e.g., maximum 2%>
- lanthanum e.g., maximum 2%>
- zirconium e.g., maximum 2%>
- manganese e.g., maximum 2%>
- cerium e.g., maximum 2%>
- magnesium e.g., maximum 2%>
- nitrogen e.g., maximum 0.02%>
- the alloys may comprise, by weight, 6.5%> nickel, 4.5%> tungsten, 2.5%> copper,
- the incidental elements and impurities may include one or more of niobium (e.g., maximum 2%>), ruthenium (e.g., maximum 2%>), lanthanum (e.g., maximum 2%>), zirconium (e.g., maximum 2%>), manganese (e.g., maximum 2%>), copper (e.g., maximum 2%>), vanadium (e.g., maximum 2%>), cerium (e.g., maximum 2%>), magnesium (e.g., maximum 2%>), and nitrogen (e.g., maximum 0.02%>).
- niobium e.g., maximum 2%>
- ruthenium e.g., maximum 2%>
- lanthanum e.g., maximum 2%>
- zirconium e.g., maximum 2%>
- manganese e.g., maximum 2%>
- copper e.g., maximum 2%>
- vanadium e
- the alloys may consist of, by weight, 6.5%> nickel, 4.5%> tungsten, 2.5%> copper,
- the incidental elements and impurities may include one or more of niobium (e.g., maximum 2%), ruthenium (e.g., maximum 2%), lanthanum (e.g., maximum 2%), zirconium (e.g., maximum 2%), manganese (e.g., maximum 2%), copper (e.g., maximum 2%), vanadium (e.g., maximum 2%), cerium (e.g., maximum 2%), magnesium (e.g., maximum 2%), and nitrogen (e.g., maximum 0.02%).
- niobium e.g., maximum 2%
- ruthenium e.g., maximum 2%
- lanthanum e.g., maximum 2%
- zirconium e.g., maximum 2%
- manganese e.g., maximum 2%
- copper e.g., maximum 2%
- vanadium e.g., maximum 2%
- cerium e.g.
- the alloys may have a ⁇ 2 ⁇ value of about -4 J/m 2 to about 0 J/m 2 , about -4 J/m 2 to
- the alloys may have a ⁇ 2 ⁇ value of less than or equal to 0 J/m 2 , less than or equal to -0.5 J/m 2 , less than or equal to -1 J/m 2 , less than or equal to -1.5 J/m 2 , less than or equal to -2 J/m 2 , less than or equal to -2.1 J/m 2 , less than or equal to -2.2 J/m 2 , less than or equal to -2.3 J/m 2 , less than or equal to -2.4 J/m 2 , less than or equal to -2.5 J/m 2 , less than or equal to -2.6 J/m 2 , less than or equal to -2.7 J/m 2 , less than or equal to -2.8 J/m 2 , less than or equal to -2.9 J/m 2 , or less than or equal to -3 J
- the alloys may have a ⁇ 2 ⁇ value of 0 J/m 2 , -0.5 J/m 2 , -1 J/m 2 , -1.5 J/m 2 , -2 J/m 2 , -2.1 J/m 2 , -2.2 J/m 2 , -2.3 J/m 2 , -2.4 J/m 2 , -2.5 J/m 2 , -2.6 J/m 2 , -2.64 J/m 2 , -2.7 J/m 2 , -2.8 J/m 2 , -2.9 J/m 2 , -3 J/m 2 , -3.1 J/m 2 , -3.2
- the alloys may have a ⁇ 2 ⁇ value of about 0 J/m 2 , about -0.5 J/m 2 , about -1 J/m 2 , about -1.5 J/m 2 , about -2 J/m 2 , about -2.5 J/m 2 , about -2.64 J/m 2 , about -3 J/m 2 , about -3.5 J/m 2 , or about -4 J/m 2 .
- the alloys may have a yield strength of about 800 MPa to about 1300 MPa, about
- the alloys may have a yield strength of greater than or equal to 800 MPa, greater than or equal to 825 MPa, greater than or equal to 850 MPa, greater than or equal to 875 MPa, greater than or equal to 900 MPa, greater than or equal to 925 MPa, greater than or equal to 950 MPa, greater than or equal to 975 MPa, greater than or equal to 1000 MPa, greater than or equal to 1025 MPa, greater than or equal to 1050 MPa, greater than or equal to 1075 MPa, greater than or equal to 1100 MPa, greater than or equal to 1150 MPa, greater than or equal to 1200 MPa, greater than or equal to 1250 MPa, or greater than or equal to 1300 MPa.
- the alloys may have a yield strength of 800 MPa, 810 MPa, 820 MPa, 830 MPa, 840 MPa, 850 MPa, 860 MPa, 870 MPa, 880 MPa, 890 MPa, 900 MPa, 910 MPa, 920 MPa, 930 MPa, 940 MPa, 950 MPa, 960 MPa, 965 MPa, 970 MPa, 980 MPa, 990 MPa, 1000 MPa, 1010 MPa, 1020 MPa, 1030 MPa, 1040 MPa, 1050 MPa, 1060 MPa, 1070 MPa, 1080 MPa, 1090 MPa, 1100 MPa, 1150 MPa, 1200 MPa, 1250 MPa, or 1300 MPa.
- the alloys may have a yield strength of about 800 MPa, about 900 MPa, about 1000 MPa, about 1100 MPa, about 1200 MPa, or about 1300 MPa. The yield strength may be measured according to ASTM E8 or ASTM E21.
- the alloys may have a sulfide stress corrosion cracking toughness (K1 SSC) value of about 30 MPa*m 1/2 to about 60 MPa*m 1/2 , about 40 MPa*m 1/2 to about 60 MPa*m 1/2 , about 50 MPa*m 1/2 to about 60 MPa*m 1/2 , about 40 MPa*m 1/2 to about 50 MPa*m 1/2 , or about 40 MPa*m 1/2
- K1 SSC sulfide stress corrosion cracking toughness
- the alloys may have a sulfide stress corrosion cracking toughness (Kl SSC) value of greater than or equal to 30 MPa*m 1/2 , greater than or equal to 33 MPa*m 1/2 , greater than or equal to 35 MPa*m 1/2 , greater than or equal to 38 MPa*m 1/2 , greater than or equal to 40
- Kl SSC sulfide stress corrosion cracking toughness
- MPa*m greater than or equal to 43 MPa*m , greater than or equal to 45 MPa*m , greater than or equal to 48 MPa*m 1/2 , greater than or equal to 50 MPa*m 1/2 , greater than or equal to 55 MPa*m 1/2 , greater than or equal to 58 MPa*m 1/2 , or greater than or equal to 60 MPa*m 1/2 .
- 1 /7 alloys may have a sulfide stress corrosion cracking toughness (Kl SSC) value of 30 MPa*m , 31 MPa*m 1/2 , 32 MPa*m 1/2 , 33 MPa*m 1/2 , 34 MPa*m 1/2 , 35 MPa*m 1/2 , 36 MPa*m 1/2 , 37 MPa*m 1/2 , 38 MPa*m 1/2 , 39 MPa*m 1/2 , 40 MPa*m 1/2 , 41 MPa*m 1/2 , 42 MPa*m 1/2 , 43 MPa*m 1/2 , 44
- Kl SSC sulfide stress corrosion cracking toughness
- the alloys may have a sulfide stress corrosion cracking toughness (K1 SSC) value of about 30 MPa*m 1/2 , about 35 MPa*m 1/2 , about 40 MPa*m 1/2 , about 45 MPa*m 1/2 , about 50 MPa*m 1/2 , about 55 MPa*m 1/2 , or about 60 MPa*m 1/2 .
- K1 SSC sulfide stress corrosion cracking toughness
- the alloys may have an M 2 C phase fraction of about 0.01 to about 0.015, about
- the alloys may have an M 2 C phase fraction of 0.01, 0.011, 0.012, 0.0125, 0.0126, 0.0127, 0.0128, 0.0129, 0.013, 0.0131, 0.0132, 0.0133, 0.0134, 0.0135, 0.014, or 0.015.
- the alloys may have an M 2 C phase fraction of about 0.01, about 0.011, about 0.012, about 0.0129, about 0.013, about 0.014, or about 0.015.
- M is selected from the group consisting of Fe, Cr, Cu, Ni,
- M is selected from the group consisting of Cr, W, V, and Ti, or any combination thereof. In certain embodiments, M is selected from the group consisting of Cr, W, and V, or any combination thereof.
- the alloys may have a BCC copper phase fraction of about 0.025 to about 0.035, about 0.025 to about 0.033, about 0.025 to about 0.03, about 0.027 to about 0.033, or about 0.027 to about 0.03.
- the alloys may have a body centered cubic copper phase fraction of 0.025, 0.026, 0.027, 0.028, 0.029, 0.0295, 0.03, 0.031, 0.032, 0.033, 0.034, or 0.035.
- the alloys may have a body centered cubic copper phase fraction of about 0.025, about 0.026, about 0.027, about 0.028, about 0.029, about 0.0295, about 0.03, about 0.031, about 0.032, about 0.033, about 0.034, or about 0.035.
- the alloys may be produced by vacuum melt practices or air melt practices. Calcium or silicon may be added to the melt for the purpose of decreasing impurities such as sulfur, phosphorous, or nitrogen. Calcium or silicon may be added in minute quantities. Additional titanium may be added to the melt for the purpose of converting nitrogen to TiN.
- the alloys may be produced by methods including, but not limited to, single melting, double melting, casting, centrifugal casting, additive manufacturing, or powder production.
- a method for producing the disclosed alloys may include, but are not limited to, steps such as preparing a melt, melting, casting, homogenization, hot rolling, hot working, cold rolling, cold working, solutionizing, quenching, quenching with oil, cooling, subzero cooling, warming, aging, hardening, or softening. These steps may be performed in a different order. These steps may be performed more than once, in a cycle. Not all steps are required. Other common preparation techniques and variations upon the methods disclosed herein will be apparent to one of ordinary skill in the art.
- manufactured articles including the disclosed alloys.
- Exemplary manufactured articles include, but are not limited to, steel pipes or tubes.
- the steel pipes or tubes may be used in oil or gas drilling, extraction, transport, or other services.
- the steel pipes or tubes may be formed by various methods, including piercing followed by hot rolling, extruding, forging, and other techniques, including those that form a tube or a pipe with no seam.
- a melt was prepared with the nominal composition of 6.5 Ni, 4 W, 2.5 Cu, 0.5 Cr,
- the QT-SSC alloy was prepared. Steel was melted and cast by vacuum induction melting at a weight of about 50 pounds. The steel was subjected to homogenization at 1204°C for 8 hours, and hot rolled from an initial 4 inch round cross section to 0.75 inch by 2.75 inch plate. Test samples of the QT-SSC alloy were excised from the hot rolled plate and solutionized at 950°C for 1 hour, quenched with oil, subzero cooled at -73 °C for about 1 hour, and warmed in air to room temperature.
- the hardness of the QT-SSC steel was measured at about 38 on the Rockwell C scale. Samples were then subjected to isochronal aging heat treatments at secondary hardening temperatures in the range of 450 and 625°C for 5 hours. As shown in FIG. 4, hardness was increased by aging in the range of 450 to 550°C, followed by softening by over-aging at above 550°C. Additional testing of room temperature mechanical properties indicated a range of achievable strength-toughness combinations with different aging conditions, as shown in Table 4.
- An alloy comprising, by weight, about 0% to about 8%> nickel, about 1%> to about 6%o tungsten, about 1%> to about 4% copper, about 0.1% to about 2% chromium, about 0.01% to about 1% vanadium, about 0.01% to about 0.5% carbon, about 0.01% to about 0.1% titanium, about 0.001%> to about 0.01% boron, about 0% to about 1% silicon, and about 0% to about 0.1%) calcium, the balance essentially iron and incidental elements and impurities.
- Clause 2 The alloy of clause 1 comprising, by weight, about 6% to about 7% nickel, about 3.5% to about 4.5% tungsten, about 2% to about 3% copper, about 0.1% to about 1% chromium, about 0.01% to about 0.2% vanadium, about 0.01% to about 0.2% carbon, about 0.01% to about 0.05%) titanium, and about 0.001% to about 0.002%> boron, the balance essentially iron and incidental elements and impurities.
- Clause 4 The alloy of any one of clauses 1-3, wherein the alloy has a yield strength of greater than or equal to 965 MPa (140 ksi), measured according to ASTM E8.
- Kl SSC corrosion cracking toughness
- Clause 6 The alloy of any one of clauses 1-5, wherein the alloy has an M 2 C phase fraction of 0.01 to 0.015, wherein M is selected from the group consisting of W, Cr, V, and Ti, or any combination thereof.
- Clause 7 The alloy of any one of clauses 1-6, wherein the alloy has a body centered cubic copper phase fraction of 0.025 to 0.035.
- Clause 8 The alloy of any one of clauses 1-7, comprising about 6.5% nickel.
- Clause 9 The alloy of any one of clauses 1-8, comprising about 4% tungsten.
- Clause 10 The alloy of any one of clauses 1-9, comprising about 2.5% copper.
- Clause 11 The alloy of any one of clauses 1-10, comprising about 0.5% chromium.
- Clause 12 The alloy of any one of clauses 1-11, comprising about 0.1% vanadium.
- Clause 13 The alloy of any one of clauses 1-12, comprising about 0.1% carbon.
- Clause 14 The alloy of any one of clauses 1-13, comprising about 0.02% titanium.
- Clause 15 The alloy of any one of clauses 1-14, comprising about 0.0015%) boron.
- Clause 16 The alloy of any one of clauses 1-15, comprising, by weight, about 6.5% nickel, about 4.5% tungsten, about 2.5% copper, about 0.5% chromium, about 0.1% vanadium, about 0.1%) carbon, about 0.02% titanium, and about 0.0015% boron, the balance essentially iron and incidental elements and impurities.
- a method for producing an alloy comprising:
- preparing a melt that comprises, by weight, about 0% to about 8% nickel, about 1% to about 6% tungsten, about 1% to about 4% copper, about 0.1% to about 2% chromium, about 0.01% to about 1%) vanadium, about 0.01% to about 0.5% carbon, about 0.01% to about 0.1% titanium, about 0.001%) to about 0.01% boron, about 0% to about 1% silicon, and about 0% to about 0.1% calcium, the balance essentially iron and incidental elements and impurities.
- chromium about 0.01% to about 0.2% vanadium, about 0.01% to about 0.2% carbon, about 0.01% to about 0.05%> titanium, and about 0.001%> to about 0.002%> boron, the balance essentially iron and incidental elements and impurities.
- Clause 19 The method of clause 17 or clause 18, wherein the melt comprises, by weight, about 6.5% nickel, about 4.5% tungsten, about 2.5% copper, about 0.5% chromium, about 0.1%) vanadium, about 0.1%> carbon, about 0.02% titanium, and about 0.0015% boron, the balance essentially iron and incidental elements and impurities.
- Clause 20 The method of any one of clauses 17-19, wherein the alloy has a calculated ⁇ 2 ⁇ value of less than or equal to -2 J/m 2 .
- Clause 21 The method of any one of clauses 17-20, wherein the alloy has a yield strength of greater than or equal to 965 MPa (140 ksi), measured according to ASTM E8.
- Clause 22 The method of any one of clauses 17-21, wherein the alloy has a sulfide
- Kl SSC stress corrosion cracking toughness
- Clause 23 The method of any one of clauses 17-22, wherein the alloy has an M 2 C phase fraction of 0.01 to 0.015, wherein M is selected from the group consisting of W, Cr, V, and Ti, or any combination thereof.
- Clause 24 The method of any one of clauses 17-23, wherein the alloy has a body centered cubic copper phase fraction of 0.025 to 0.035.
- Clause 25 The method of any one of clauses 17-24, wherein the alloy is produced by vacuum melt or air melt practices.
- a manufactured article comprising an alloy that comprises, by weight, about 0%) to about 8% nickel, about 1% to about 6% tungsten, about 1% to about 4% copper, about 0.1%) to about 2% chromium, about 0.01% to about 1% vanadium, about 0.01% to about 0.5% carbon, about 0.01% to about 0.1% titanium, about 0.001% to about 0.01% boron, about 0% to about 1%) silicon, and about 0% to about 0.1% calcium, the balance essentially iron and incidental elements and impurities.
- chromium about 0.01% to about 0.2% vanadium, about 0.01% to about 0.2% carbon, about 0.01% to about 0.05% titanium, and about 0.001% to about 0.002% boron, the balance essentially iron and incidental elements and impurities.
- Clause 28 The article of clause 26 or clause 27, wherein the alloy comprises, by weight, about 6.5% nickel, about 4.5% tungsten, about 2.5% copper, about 0.5% chromium, about 0.1%) vanadium, about 0.1%> carbon, about 0.02% titanium, and about 0.0015% boron, the balance essentially iron and incidental elements and impurities.
- Clause 29 The article of any one of clauses 26-28, wherein the alloy has a calculated ⁇ 2 ⁇ value of less than or equal to -2 J/m 2 .
- Clause 30 The article of any one of clauses 26-29, wherein the alloy has a yield strength of greater than or equal to 965 MPa (140 ksi), measured according to ASTM E8.
- Kl SSC stress corrosion cracking toughness
- Clause 32 The article of any one of clauses 26-31, wherein the alloy has an M 2 C phase fraction of 0.01 to 0.015, wherein M is selected from the group consisting of W, Cr, V, and Ti, or any combination thereof.
- Clause 33 The article of any one of clauses 26-32, wherein the alloy has a body centered cubic copper phase fraction of 0.025 to 0.035.
- Clause 34 The article of any one of clauses 26-33, wherein the article is a steel pipe or steel tube.
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Abstract
Description
Claims
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US201562259835P | 2015-11-25 | 2015-11-25 | |
PCT/US2016/063622 WO2017091743A1 (en) | 2015-11-25 | 2016-11-23 | Grain boundary cohesion enhanced sulfide stress cracking (ssc)-resistant steel alloys |
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US (1) | US20170145547A1 (en) |
EP (1) | EP3380641A4 (en) |
BR (1) | BR112018010493A8 (en) |
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WO (1) | WO2017091743A1 (en) |
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JP2022505878A (en) | 2018-10-26 | 2022-01-14 | エリコン メテコ(ユーエス)インコーポレイテッド | Corrosion-resistant and wear-resistant nickel-based alloy |
WO2022150241A1 (en) | 2021-01-07 | 2022-07-14 | Exxonmobil Upstream Research Company | Process for protecting carbon steel pipe from sulfide stress cracking in severe sour service environments |
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US2895861A (en) * | 1957-05-28 | 1959-07-21 | Creusot Forges Ateliers | Process for improving stress corrosion cracking resistance of alloyed steel in hydrogen sulphide atmosphere |
US3692514A (en) * | 1968-12-13 | 1972-09-19 | Int Nickel Co | Alloy steel containing copper and nickel adapted for production of line pipe |
US3655465A (en) * | 1969-03-10 | 1972-04-11 | Int Nickel Co | Heat treatment for alloys particularly steels to be used in sour well service |
US7235212B2 (en) * | 2001-02-09 | 2007-06-26 | Ques Tek Innovations, Llc | Nanocarbide precipitation strengthened ultrahigh strength, corrosion resistant, structural steels and method of making said steels |
US5352304A (en) * | 1992-11-16 | 1994-10-04 | Allegheny Ludlum Corporation | High strength low alloy steel |
JPH08120399A (en) * | 1994-10-25 | 1996-05-14 | Sumitomo Metal Ind Ltd | Steel for machine structure excellent in delayed fracture resistance |
US20040047758A1 (en) * | 2000-01-05 | 2004-03-11 | Northwestern University | Method for enhancement of grain boundary cohesion in crystalline materials and compositions of matter therefor |
KR100460346B1 (en) * | 2002-03-25 | 2004-12-08 | 이인성 | Super duplex stainless steel with a suppressed formation of intermetallic phases and having an excellent corrosion resistance, embrittlement resistance, castability and hot workability |
US6723182B1 (en) * | 2002-11-14 | 2004-04-20 | Arthur J. Bahmiller | Martensitic alloy steels having intermetallic compounds and precipitates as a substitute for cobalt |
CA2594719C (en) * | 2005-01-25 | 2014-04-01 | Questek Innovations Llc | Martensitic stainless steel strengthened by ni3ti eta-phase precipitation |
JP4978073B2 (en) * | 2006-06-16 | 2012-07-18 | Jfeスチール株式会社 | High toughness ultra-high strength stainless steel pipe for oil wells with excellent corrosion resistance and method for producing the same |
US7658883B2 (en) * | 2006-12-18 | 2010-02-09 | Schlumberger Technology Corporation | Interstitially strengthened high carbon and high nitrogen austenitic alloys, oilfield apparatus comprising same, and methods of making and using same |
IT1403688B1 (en) * | 2011-02-07 | 2013-10-31 | Dalmine Spa | STEEL TUBES WITH THICK WALLS WITH EXCELLENT LOW TEMPERATURE HARDNESS AND RESISTANCE TO CORROSION UNDER TENSIONING FROM SULFUR. |
JP2013129879A (en) * | 2011-12-22 | 2013-07-04 | Jfe Steel Corp | High-strength seamless steel tube for oil well with superior sulfide stress cracking resistance, and method for producing the same |
-
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- 2016-11-23 WO PCT/US2016/063622 patent/WO2017091743A1/en active Application Filing
- 2016-11-23 BR BR112018010493A patent/BR112018010493A8/en not_active Application Discontinuation
- 2016-11-23 US US15/360,655 patent/US20170145547A1/en not_active Abandoned
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