WO2019080893A1 - 一种低屈强比超高强度连续油管用钢及其制造方法 - Google Patents

一种低屈强比超高强度连续油管用钢及其制造方法

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Publication number
WO2019080893A1
WO2019080893A1 PCT/CN2018/111845 CN2018111845W WO2019080893A1 WO 2019080893 A1 WO2019080893 A1 WO 2019080893A1 CN 2018111845 W CN2018111845 W CN 2018111845W WO 2019080893 A1 WO2019080893 A1 WO 2019080893A1
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Prior art keywords
strength
steel
coiled tubing
low
ultra
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Ceased
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PCT/CN2018/111845
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English (en)
French (fr)
Inventor
章传国
孙磊磊
郑磊
庞厚君
刘剑
张勇
徐国栋
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to JP2020521899A priority Critical patent/JP7134230B2/ja
Priority to RU2020116360A priority patent/RU2744590C1/ru
Priority to US16/758,528 priority patent/US11396680B2/en
Priority to CA3078406A priority patent/CA3078406C/en
Publication of WO2019080893A1 publication Critical patent/WO2019080893A1/zh
Anticipated expiration legal-status Critical
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    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a steel for low to high strength super high strength coiled tubing and a manufacturing method thereof.
  • Coiled tubing is a continuous pipe, flexible tubing, serpentine or coil, which can be wound on a large diameter reel, and is made of several sections of steel.
  • a jointless continuous tube that is slanted together and welded by rolling.
  • Coiled tubing is mainly used for auxiliary operations such as oilfield logging and completion.
  • Coiled tubing needs to be operated with special equipment, which has many advantages such as strong maneuverability, flexible operation and reusability.
  • the coiled tubing is subjected to repeated bending, clamping, stretching and other deformations during use, and the stress state is complicated and the working conditions are bad. Therefore, the local damage of the coiled tubing is often an important cause of the overall failure.
  • high strength is beneficial to improve the anti-loading and torsional resistance of coiled tubing and improve fatigue strength.
  • Low yield ratio is beneficial to improve its uniform extension performance and work hardening ability, so with the increasing depth of oil drilling and very
  • the exploitation of oil and gas fields requires higher requirements for working depth, operating pressure and torsion resistance.
  • High-end coiled tubing with ultra-high strength, high fatigue and certain corrosion resistance is required to ensure higher load carrying capacity and more. Long service life.
  • Coiled tubing has been developed and applied for more than 50 years, and its material has undergone several stages of development.
  • the coiled tubing of the 1960s and 1970s was mainly made of carbon steel.
  • the carbon steel coiled tubing has low strength, many welds and poor corrosion resistance, and can not resist cyclic bending and tensile force. Therefore, the coiled tubing frequently occurs during use. It has severely restricted the development of coiled tubing technology.
  • low-alloy high-strength steel and diagonal butt welding technology were applied in the field of coiled tubing manufacturing, and the service life and reliability of coiled tubing were greatly improved.
  • coiled tubing products with high strength and long life such as titanium alloys and composite materials were developed, but they were not popularized due to high manufacturing and maintenance costs. Therefore, the current coiled tubing manufacturing is still mainly based on low-alloy high-strength steel.
  • Chinese patent 200710168545.3 discloses a steel for high plasticity coiled tubing and a manufacturing method thereof, and is mainly for the development of steel for coiled tubing of CT70 and higher steel grade.
  • the patent adopts low Mn, low Cr and V-free alloy design.
  • the steel for coiled tubing with moderate toughness and uniform structure is produced.
  • the deformation resistance of the steel during rolling is obtained.
  • Small, the rolling mill loss is small.
  • due to the low strength of the steel strips produced it is unable to meet the manufacturing requirements of the 110ksi grade coiled tubing, and the low cycle fatigue life is also low.
  • Chinese patent CN104046918A discloses a steel strip which can be used for manufacturing continuous tubes with a yield strength of 80 Ksi and above, and the main components are 0.17-0.35% C, 0.30-2.00% Mn, 0.10-0.30% Si and 0.010-0.040% Al, and are controlled.
  • the upper limits of S and P are 100 ppm and 150 ppm, respectively, and the microstructure of tempered martensite and bainite is obtained by reasonable process control, and the continuous tube made thereof comprises more than 90% by volume of tempered martensite. Due to the existence of a large proportion of martensite structure, it is not suitable for the acid resistance of the finished steel pipe.
  • the object of the present invention is to provide a low yield ratio ultra high strength coiled tubing steel and a manufacturing method thereof, the steel yield strength ⁇ 620 MPa, tensile strength ⁇ 750 MPa, elongation ⁇ 11%, yield ratio ⁇ 0.83, For the manufacture of ultra-high strength coiled tubing of 110ksi and above.
  • the invention adopts the material theory of grain refinement, precipitation strengthening, phase transformation control and the like, and adopts the composition design of medium and low C content, V/Nb microalloying and Cu/Ni/Cr/Mo alloying, and combined control Tighten the cold and low temperature coiling process to obtain ultra-high strength coiled tubing steel with MA (Martensite-Austenite constituents) component + bainite + ferrite multiphase microstructure, the steel has a low yield ratio High strength and good heat treatment adaptability.
  • MA Martensite-Austenite constituents
  • a low-strength ratio ultra-high strength coiled tubing steel whose chemical composition mass percentage is: C: 0.05-0.16%, Si: 0.1-0.9%, Mn: 1.25-2.5%, P ⁇ 0.015%, S ⁇ 0.005 %, Cr: 0.51 to 1.30%, Nb: 0.005 to 0.019%, V: 0.010 to 0.079%, Ti: 0.01 to 0.03%, Mo: 0.10 to 0.55%, Cu: 0.31 to 0.60%, and Ni: 0.31 to 0.60% Ca: 0.0010 to 0.0040%, Al: 0.01 to 0.05%, N ⁇ 0.008%, and the balance is Fe and an unavoidable impurity element.
  • microstructure of the low-strength ratio ultra-high strength coiled tubing steel is MA component + bainite + ferrite multiphase structure.
  • the invention adopts a low carbon microalloying component system, and the design basis is as follows:
  • Carbon (C) The most basic strengthening element. C dissolves in steel to form a gap solid solution, acts as a solid solution strengthening, and forms a carbide precipitate with a strong carbide forming element, thereby acting as a precipitation strengthening.
  • C content is controlled to be 0.05 to 0.16%.
  • Silicon (Si) solid solution strengthening element, can effectively improve the tensile strength of steel; it is also a deoxidizing element in steel, but too high Si content will deteriorate the welding performance of steel, and it is not conducive to hot rolling of iron oxide during rolling. It is removed, and therefore, the Si content in the present invention is controlled to be 0.1 to 0.9%.
  • Mn Manganese
  • the strength of steel is enhanced by solid solution strengthening, which is the most important and economical strengthening element for compensating for the loss of strength due to the decrease of C content in steel.
  • Mn is also an element that enlarges the ⁇ phase region, which can lower the ⁇ phase transition temperature of steel, contribute to obtaining fine phase change products, and can improve the toughness of steel. Therefore, the Mn content in the present invention is controlled to be 1.25 to 2.5%.
  • Chromium (Cr) an important element to improve the hardenability of steel, effectively improve the strength of steel; it is also a ferrite forming element that promotes the precipitation of ferrite; and when the Cr content is above 0.51%, it can be on the surface of steel. Forming a dense spinel structure passivation film, significantly improving the corrosion resistance of steel. However, too high chromium and manganese are added to the steel at the same time, which leads to the formation of a low-melting Cr-Mn composite oxide, which forms surface cracks during hot working and seriously deteriorates the welding performance. Therefore, the Cr content in the present invention should be limited to 0.51 to 1.30%.
  • Titanium (Ti) is a strong carbonitride forming element. Ti's undissolved carbonitride prevents the growth of austenite grains during steel heating and precipitates during high-temperature austenite rough rolling. TiN and TiC can effectively inhibit austenite grain growth. In addition, during the welding process, TiN and TiC particles in the steel can significantly prevent grain growth in the heat-affected zone, thereby improving the welding performance of the steel plate and improving the impact toughness of the heat affected zone. Therefore, in the present invention, the Ti content is controlled to be 0.01 to 0.03%.
  • Niobium (Nb) microalloying element, Nb strain induced by solid solution during hot rolling to form Nb(N, C) particles, pinning grain boundaries inhibit deformation of austenite, controlled rolling and controlled cooling
  • the deformed austenite is transformed into a fine product having a high dislocation density; the solid solution Nb is dispersed in the matrix by the second phase particles NbC, and acts as a precipitation strengthening effect.
  • the effect of too low Nb content precipitation is not obvious, and it can not refine the grain and strengthen the matrix; too high Nb content is easy to produce slab cracks, affecting the surface quality, and will seriously deteriorate the welding performance. Therefore, the Nb content in the present invention should be limited to 0.005 to 0.019%.
  • Vanadium (V) a microalloying element.
  • the precipitation phase V of solid solution V during hot rolling can effectively pin the grain boundary to inhibit the growth of deformed austenite.
  • the controlled austenite transformation into a fine product with high dislocation density by controlled rolling and controlled cooling The solid solution V is dispersed in the matrix by the VC particles during the coiling and heat preservation process, and plays a role of precipitation strengthening.
  • the invention mainly utilizes the grain refinement and precipitation strengthening effect of V to control the structural properties of the steel.
  • the effect of too low V content dispersion is not obvious, and it can not refine the grain and strengthen the matrix; too high V content, the precipitated phase particles tend to grow, and the precipitation strengthening effect can not be exerted. Therefore, the V content in the present invention should be limited to 0.010 to 0.079%.
  • Molybdenum (Mo) enlarges the elements in the ⁇ phase region, can reduce the ⁇ phase transition temperature of steel, can effectively promote the bainite transformation to strengthen the matrix, obtain finer microstructure, and promote the formation of MA components. . Mo can also overcome the temper brittleness during heat treatment and improve the heat treatment performance and fatigue performance. In high-strength low-alloy steels, the yield strength increases with increasing Mo content, so too high Mo is detrimental to plasticity. Therefore, in the present invention, the Mo content is controlled to be 0.10 to 0.55%.
  • Copper, nickel (Cu, Ni) can improve the strength of steel by solid solution strengthening, while Cu can also improve the corrosion resistance of steel.
  • the addition of Ni is mainly to improve the hot brittleness of Cu in steel, and toughness. Good.
  • the range of content of Cu and Ni is controlled to be 0.31 to 0.60%.
  • Sulfur and phosphorus (S, P): It is an inevitable impurity element in steel. The lower the hope, the better.
  • the inclusion morphology control of sulfides by ultra-low sulfur (less than 30ppm) and Ca treatment can ensure good impact toughness of the steel sheet.
  • the S and P contents are in the range of P ⁇ 0.015% and S ⁇ 0.005%.
  • N Nitrogen
  • an appropriate nitrogen content can form a high-melting TiN particle, thereby suppressing grain coarsening during reheating of the slab, and improving the toughness of the steel.
  • the N content is too high, the high concentration of free N atom pinning dislocations after aging, the yield strength is significantly improved, and the toughness is impaired. Therefore, in the present invention, N ⁇ 0.008 is controlled.
  • the micro-Ca treatment can control the morphology of long-shaped sulfides and form spherical inclusions of spheroidized calcium aluminates, which is an effective measure to improve the anisotropy of steel sheets and improve low-temperature toughness.
  • the Ca content is too low, the above effect is not obtained; when the Ca content is too high, CaS inclusions having a high melting point are easily formed, resulting in deterioration of castability of steel. Therefore, the present invention controls the Ca content to be 0.0010 to 0.0040%.
  • Al is an element added to steel for deoxidation. Adding an appropriate amount of Al is beneficial to refining crystal grains and improving the toughness of steel.
  • composition design of the present invention is mainly through the addition of 0.05-0.16% medium-low C, 1.25-2.5% medium-high Mn, 0.51 ⁇ 1.30% medium-high Cr and V alloying design, comprehensive application of grain refinement, precipitation strengthening and phase transformation.
  • Strengthening and other means to improve the toughness, and the carbon equivalent is lower, which is beneficial to improve the welding performance; increase the content of Si and Cr and further increase the V microalloying element on the basis of Nb microalloying to meet the high strength after heat treatment of the tube Need; use micro-calcium treatment to spheroidize inclusions to avoid the formation of long-shaped inclusions that affect the use, thereby improving the low temperature toughness and fatigue resistance of steel, improving the service life; precipitation strengthening by microalloying element V, grain Refining and other alloying elements, solid solution strengthening, phase transformation strengthening to increase strength, and adding lower Nb, to avoid casting cracks in continuous casting process under high alloy conditions, thereby improving steel quality and manufacturability; The high Ni content increases the toughness of the steel and avoids thermal cracking problems due to higher Cu.
  • the method for manufacturing low-strength ratio ultra-high strength coiled tubing steel according to the present invention comprises the following steps:
  • the furnace refining is carried out for LF desulfurization + RH vacuum degassing, RH vacuum degassing time ⁇ 5 min, and the superheat degree is controlled during the continuous casting process. 30 ° C, sedation time 8 ⁇ 17min;
  • the winding temperature is ⁇ 70 ° C
  • the pickling temperature is 65-80 ° C
  • the pickling time is 45-100 seconds.
  • microstructure of the low-strength ratio ultra-high strength coiled tubing steel has a MA component + bainite + ferrite multiphase microstructure.
  • the refining outside the furnace comprises LF desulfurization + RH vacuum degassing (degassing time ⁇ 5 min), and the S content in the steel can be reduced by LF smelting, which is beneficial to reduce sulfide inclusions; and degassing by RH vacuum to reduce
  • the content of O, N and H in the steel grade reduces the oxide inclusion during the subsequent treatment and reduces the effect of hydrogen cracking and nitrogen aging on performance.
  • the superheat degree is in the temperature range of 15-30 ° C for a sedation time of 8 to 17 min, which is beneficial to the steel material inclusions to fully float, improve the purity of the steel, and at the same time ensure the segregation of the steel.
  • the heating temperature of the slab is controlled to be 1200 to 1260 ° C in the hot rolling process to ensure sufficient solid solution of the alloy elements, and to perform grain refinement, phase transformation control, precipitation strengthening, etc. in subsequent deformation and phase transformation. effect.
  • the invention controls the finishing rolling temperature in the range of 840-920 ° C, adopts a relatively low finishing rolling temperature, is beneficial to increase the nucleation point, combines the ferrite formation characteristics of Cr to promote the ferrite phase transformation, and refines the crystal grains. And avoid the formation of banded tissue.
  • the invention controls the coiling temperature in the range of 450-550 ° C, combines the reduced phase transition temperature characteristic of Mo and the characteristic of stable austenite, and the coiling heat preservation in this temperature range is beneficial to stabilize the bainite transformation process and promote C is sufficiently diffused into the retained austenite to further stabilize the retained austenite, and finally a microstructure in which bainite is used as a matrix and the MA component is dispersed is formed.
  • the roll-up temperature is controlled to be ⁇ 70° C., if the roll-up temperature is too high, the device is damaged, and the acid solution is easily volatilized.
  • Controlling the pickling temperature is 65-80 ° C, the pickling temperature is too low, the chemical reaction rate is slow, resulting in acid cleaning is not clean; the pickling temperature is too high, causing the acid to volatilize, affecting the pickling effect.
  • the invention adopts the above pickling process, can effectively remove the iron oxide scale on the surface of the steel coil, and improve the fatigue resistance of the steel.
  • the invention adopts the composition design method of medium carbon, Nb/V microalloying and Cu/Ni/Cr/Mo alloying, can be manufactured by suitable controlled rolling and low temperature coiling process, and is subjected to pickling and oiling treatment.
  • Steel for coiled tubing with low yield ratio, high strength and good corrosion resistance, the yield strength of the steel is R p0.2 ⁇ 620MPa, tensile strength Rm ⁇ 750MPa, elongation A 50 ⁇ 11%, yield ratio R p0 .2 / Rm ⁇ 0.83, with good surface quality and thickness uniformity, and easier manufacturability, can be used to manufacture super-strength coiled tubing suitable for deep well and unconventional oil and gas exploration.
  • the invention adopts medium-low C, medium-high Mn and alloying component system, and combines suitable processes to achieve high-strength plasticity and good processability and heat treatment adaptability of steel; adding high Cu and Ni to obtain high strength and high at the same time Corrosion resistance; adding V microalloying elements to achieve grain refinement, precipitation strengthening effect, and adding appropriate amount of Nb to further strengthen grain refinement and precipitation strengthening effect, while avoiding continuous casting crack; adding Cr element to promote Ferrite formation, and is beneficial to improve the corrosion resistance of steel; add appropriate amount of Mo element to promote bainite transformation, and help to stabilize retained austenite, while improving or inhibiting brittleness of subsequent heat treatment; using low sulfur design, and Micro-Ca treatment is carried out to ensure that the developed steel has no long strip inclusions and improves impact toughness and fatigue resistance.
  • the invention adopts a lower temperature finish rolling and a low temperature coiling process, and utilizes a phase change control effect of Cr and Mo alloy elements to obtain a MA component + bainite + ferrite multiphase structure, and achieves low
  • the yield ratio and ultra-high strength have better comprehensive properties such as processability and heat treatment adaptability.
  • the steel produced by the present invention has a yield strength R p0.2 ⁇ 620 MPa, a tensile strength Rm ⁇ 750 MPa, an elongation A 50 ⁇ 11%, a yield ratio R p0.2 / Rm ⁇ 0.83, and has a good surface quality and Uniform thickness and excellent comprehensive mechanical properties, suitable for the manufacture of super strength coiled tubing of 110ksi and above.
  • the steel of the invention has a simple composition and a wide manufacturing process window, and is relatively easy to implement on site.
  • Figure 1 is a typical microstructure of Example 4 of the present invention.
  • Table 1 shows the composition of the steel of the embodiment of the present invention
  • Table 2 shows the main process parameters of the steel of the embodiment of the present invention
  • Table 3 shows the properties of the steel of the example of the present invention.
  • the steel structure produced by the present invention is a MA component + bainite + ferrite multiphase structure.
  • the steel produced by the present invention has a yield strength R p0.2 ⁇ 620 MPa, a tensile strength Rm ⁇ 750 MPa, an elongation A 50 ⁇ 11%, a yield ratio R p0.2 / Rm ⁇ 0.83, and a good surface.
  • Quality and thickness uniformity, as well as manufacturability that is easier to achieve, can be used to make super-strength coiled tubing suitable for deep wells and unconventional oil and gas production.

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Abstract

一种低屈强比超高强度连续油管用钢及其制造方法，该钢化学成分质量百分数为：C：0.05～0.16％，Si：0.1～0.9％，Mn：1.25～2.5％，P≤0.015％，S≤0.005％，Cr：0.51～1.30％，Nb：0.005～0.019％，V：0.010～0.079％，Ti：0.01～0.03％，Mo：0.10～0.55％，Cu：0.31～0.60％，Ni：0.31～0.60％，Ca：0.0010～0.0040％，Al：0.01～0.05％，N≤0.008％，其余为Fe和不可避免的杂质元素。该化学成分结合低温终轧、低温卷取工艺，得到MA组元+贝氏体+铁素体多相组织；该钢具有低屈强比和超高强度，具体性能为：屈服强度≥620MPa，抗拉强度≥750MPa，延伸率≥11％，屈强比≤0.83，适用于制造110ksi及以上级别的超强度连续油管。

Description

一种低屈强比超高强度连续油管用钢及其制造方法 技术领域
本发明涉及一种低屈强比超高强度连续油管用钢及其制造方法。
背景技术
连续油管(Coiled tubing，简称CT)是相对于常规螺纹连接油管而言的，又称为连续管、挠性油管、蛇形管或盘管，可缠绕在大直径卷筒上，由若干段钢带斜接在一起，经轧制成型焊接而成的无接头连续管。连续油管主要用于油田测井、完井等辅助作业，近十多年来，随着连续油管作业装备技术的不断进步，其在钻井领域的应用得到快速发展。
连续油管需采用专用的装备进行作业，具有机动性强、作业灵活、可重复使用等诸多优点。但连续油管在使用过程中要经受重复的弯曲、夹持、拉伸等变形，受力状态复杂、工况恶劣，因此连续油管的局部破坏往往是导致其整体失效的重要诱因。有研究表明，高强度有利于提高连续油管的抗载、抗扭能力和提高疲劳强度，低屈强比有利于提高其均匀延伸性能和加工硬化能力，因此随着石油钻井深度的不断增加以及非常规油气田的开采，对作业深度、作业压力及抗扭性均提出了更高要求，需采用超高强、高疲劳且具有一定耐蚀的高端连续油管，以确保获得更高的抗载能力和更长的使用寿命。
连续油管已有50多年的发展及应用历程，其材质也经历了多个发展阶段。上世纪60～70年代的连续油管主要采用碳钢进行制造，碳钢连续油管强度低、焊缝多且耐蚀性较差，不能抵抗循环弯曲和拉力，因而连续油管在使用过程中事故频发，曾严重制约了连续油管技术的发展。80～90年代，随着冶金技术、焊接技术的不断发展，低合金高强钢和斜对焊技术在连续油管制造领域的得到应用，连续油管的使用寿命和可靠性大大提高。随后，开发了钛合金、复合材料等具有高强度、长寿命的连续油管产品，但由于制造和维修成本过高而未得到推广应用。因此，现阶段连续油管制造仍主要以低合金高强钢为主。
中国专利200710168545.3公开了一种高塑性连续油管用钢及其制造方法，主要针对CT70及更高钢级的连续油管用钢的开发。该专利采用低Mn、低Cr不含V的合金设计，通过炼钢工艺控制及控轧空冷工艺控制，生产出强韧性适中、组织均匀的连续油管用钢，该钢在轧制过程中变形抗力小，对轧机损耗小。但由于其制造的钢带强度较低，无法满足110ksi级别连续油管的制造要求，且低周疲劳寿命也较低。
中国专利CN104046918A公开了一种可用于制造屈服强度80Ksi及以上连续管的钢带，主要成分为0.17-0.35％C，0.30-2.00％Mn，0.10-0.30％Si及0.010-0.040％Al，并控制S、P上限分别为100ppm和150ppm，通过合理的工艺控制得到回火马氏体和贝氏体的显微组织，其制成的连续管中包括多于90％体积的回火马氏体。由于存在较大比例的马氏体组织，不利于成品钢管的抗酸性能。
发明内容
本发明的目的在于提供一种低屈强比超高强度连续油管用钢及其制造方法，该钢屈服强度≥620MPa，抗拉强度≥750MPa，延伸率≥11％，屈强比≤0.83，用于制造110ksi及以上级别的超高强连续油管。
为达到上述目的，本发明的技术方案是：
本发明以晶粒细化、析出强化、相变控制等材料理论为基础，采用了中低C含量、V/Nb微合金化以及Cu/Ni/Cr/Mo合金化的成分设计，并结合控扎控冷及低温卷取工艺，得到具有MA(Martensite-Austenite constituents)组元+贝氏体+铁素体多相显微组织的超高强度连续油管用钢，该钢具有低的屈强比、高的强度和良好热处理适应性特征。
一种低屈强比超高强度连续油管用钢，其化学成分质量百分数为：C：0.05～0.16％，Si：0.1～0.9％，Mn：1.25～2.5％，P≤0.015％，S≤0.005％，Cr：0.51～1.30％，Nb：0.005～0.019％，V：0.010～0.079％，Ti：0.01～0.03％，Mo：0.10～0.55％，Cu：0.31～0.60％，Ni：0.31～0.60％，Ca：0.0010～0.0040％，Al：0.01～0.05％，N≤0.008％，其余为Fe和不可避免的杂质元素。
进一步，所述低屈强比超高强度连续油管用钢的显微组织为MA组元+贝氏体+铁素体多相组织。
所述低屈强比超高强度连续油管用钢的屈服强度R p0.2≥620MPa，抗拉强度Rm≥750MPa，延伸率A 50≥11％，屈强比R p0.2/Rm≤0.83。
本发明采用低碳微合金化的成分体系，设计依据如下：
碳(C)：最基本的强化元素。C溶解在钢中形成间隙固溶体，起固溶强化的作用，与强碳化物形成元素形成碳化物析出，则起到沉淀强化的作用。但太高的C对钢的延性、韧性和焊接性能不利，C太低降低钢的强度。因此，本发明中C含量控制在0.05～0.16％。
硅(Si)：固溶强化元素，可以有效提高钢的抗拉强度；同时也是钢中的脱氧元素，但Si含量过高会恶化钢材的焊接性能，同时不利于轧制过程中热轧氧化铁皮去除，因此，本发明中Si含量控制在0.1～0.9％。
锰(Mn)：通过固溶强化提高钢的强度，是钢中补偿因C含量降低而引起强度损失的最主要且最经济的强化元素。Mn还是扩大γ相区的元素，可降低钢的γ→α相变温度，有助于获得细小的相变产物，可提高钢的韧性。因此，本发明中Mn含量控制在1.25～2.5％。
铬(Cr)：提高钢的淬透性的重要元素，有效提高钢的强度；同时也是铁素体形成元素，促进铁素体的析出；而且Cr含量在0.51％以上时，能在钢的表面形成一种致密的尖晶石结构钝化膜，显著提高钢的耐腐蚀性能。但太高的铬和锰同时加入钢中，会导致低熔点Cr-Mn复合氧化物形成，在热加工过程中形成表面裂纹，同时会严重恶化焊接性能。因此，本发明中Cr含量应限定在0.51～1.30％。
钛(Ti)：是一种强烈的碳氮化物形成元素，Ti的未溶的碳氮化物在钢加热时可以阻止奥氏体晶粒的长大，在高温奥氏体区粗轧时析出的TiN和TiC可有效抑制奥氏体晶粒长大。另外在焊接过程中，钢中的TiN和TiC粒子能显著阻止热影响区晶粒长大，从而改善钢板的焊接性能同时对改善焊接热影响区的冲击韧性有明显作用。因此，本发明中Ti含量控制在0.01～0.03％。
铌(Nb)：微合金化元素，热轧过程中固溶的Nb应变诱导析出形成Nb(N，C)粒子，钉扎晶界抑制形变奥氏体的长大，经控制轧制和控制冷却使形变奥氏体相变为具有高位错密度的细小的产物；固溶的Nb以第二相粒子NbC在基体内弥散析出，起到析出强化作用。但太低的Nb含量弥 散析出效果不明显，起不到细化晶粒、强化基体作用；太高的Nb含量，易产生板坯裂纹，影响表面质量，同时会严重恶化焊接性能。因此，本发明中Nb含量应限定在0.005～0.019％。
钒(V)：微合金化元素。热轧过程中固溶的V的析出相VN可有效钉扎晶界抑制形变奥氏体的长大，经控制轧制和控制冷却使形变奥氏体相变为具有高位错密度的细小的产物；固溶的V在卷取保温过程中以VC颗粒在基体内弥散析出，起到析出强化作用。本发明主要利用V的晶粒细化、析出强化效应来进行钢的组织性能控制。但太低的V含量弥散析出效果不明显，起不到细化晶粒、强化基体作用；太高的V含量，析出相颗粒易长大，同样发挥不了析出强化效果。因此，本发明中V含量应限定在0.010～0.079％。
钼(Mo)：扩大γ相区的元素，可降低钢的γ→α相变温度，能有效促进贝氏体转变起到强化基体的作用，得到更加细小的组织，同时促进MA组元的形成。Mo还能起到克服热处理过程中的回火脆性，改善热处理性能、疲劳性能的作用。在高强度低合金钢中，屈服强度随Mo含量的增加而提高，因此太高的Mo有损塑性。因此，本发明中Mo含量控制在0.10～0.55％。
铜、镍(Cu、Ni)：可通过固溶强化作用提高钢的强度，同时Cu还可改善钢的耐蚀性，Ni的加入主要是改善Cu在钢中易引起的热脆性，且对韧性有益。本发明中Cu、Ni含量范围均控制为0.31～0.60％。
硫、磷(S、P)：是钢中不可避免的杂质元素，希望越低越好。通过超低硫(小于30ppm)及Ca处理对硫化物进行夹杂物形态控制，可保证钢板具有良好的冲击韧性。本发明中S、P含量范围为P≤0.015％、S≤0.005％。
氮(N)：在微合金化钢中，适当的氮含量可以通过形成高熔点的TiN粒子，起到抑制板坯再加热过程中晶粒粗化的作用，改善钢的强韧性。但当N含量过高时，时效后高浓度的自由N原子钉扎位错，使屈服强度明显提高，同时有损韧性。因此，本发明中控制N≤0.008。
钙(Ca)：通过微Ca处理可以控制长条形硫化物的形态，形成球化的钙铝酸盐球状夹杂，是改善钢板的各向异性、提高低温韧性的有效措施。当Ca含量过低时，起不到上述效果；Ca含量过高时，易形成高熔点的 CaS夹杂，导致钢的浇铸性变差。因此，本发明控制Ca含量为0.0010～0.0040％。
铝(Al)：Al是为了脱氧而加入钢中的元素，添加适量的Al有利于细化晶粒，改善钢材的强韧性能。
综上，本发明成分设计方面主要通过添加0.05～0.16％中低C、1.25～2.5％中高Mn、0.51～1.30％中高Cr及V合金化设计，综合运用晶粒细化、析出强化和相变强化等手段来提升强韧性，且碳当量较低，有利于改善焊接性能；提高Si、Cr含量且在Nb微合金化基础上进一步增加了V微合金元素，以满足制管热处理后高强度的需要；采用微钙处理进行夹杂物球化，以避免生成影响使用的长条形夹杂物，从而提升钢的低温韧性及抗疲劳性能，提高使用寿命；通过微合金元素V的析出强化、晶粒细化及其它合金元素的固溶强化、相变强化来提高强度，并添加较低Nb，避免高合金条件下连铸过程中出现铸坯裂纹，从而提升钢的品质及可制造性；采用较高的Ni含量提升钢的韧性，并可避免由于较高Cu带来的热裂问题。
本发明所述低屈强比超高强度连续油管用钢的制造方法，其包括如下步骤：
1)冶炼、铸造
按上述化学成分进行电炉或转炉冶炼+炉外精炼+连铸，所述炉外精炼进行LF脱硫+RH真空脱气，RH真空脱气时间≥5min，所述连铸过程中控制过热度15～30℃，镇静时间8～17min；
2)热轧
加热温度1200～1260℃，终轧温度840～920℃，卷取温度450～550℃；
3)酸洗、涂油
上卷温度≤70℃，酸洗温度65～80℃，酸洗时间45～100秒。
进一步，所述低屈强比超高强度连续油管用钢的显微组织具有MA组元+贝氏体+铁素体多相显微组织。
所述低屈强比超高强度连续油管用钢的屈服强度R p0.2≥620MPa，抗拉强度Rm≥750MPa，延伸率A 50≥11％，屈强比R p0.2/Rm≤0.83。
本发明步骤1)中炉外精炼包括LF脱硫+RH真空脱气(脱气时间≥5min)，通过LF冶炼可降低钢中S含量，有利于减少硫化物夹杂；通过 RH真空脱气，以降低钢种中O、N、H含量，减少后续处理过程中氧化物夹杂，并降低氢裂和氮时效对性能的影响。
本发明步骤1)中，连铸过程中将过热度在15～30℃温度范围内镇静时间8～17min，有利于钢种夹杂物充分上浮，提升钢质纯净度，同时可保证钢的偏析在曼内斯曼标准2级以内。
本发明步骤2)热轧工艺中控制板坯加热温度为1200～1260℃，以保证合金元素充分固溶，在后续变形及相变过程中起到晶粒细化、相变控制、析出强化等效果。
本发明控制终轧温度在840～920℃范围内，采用相对较低的终轧温度，有利于增加形核点，结合Cr的铁素体形成特性促进铁素体相转变进行，细化晶粒，并避免形成带状组织。
本发明控制卷取温度在450～550℃范围内，结合Mo的降低相变温度特性和稳定奥氏体的特性，在此温度范围内卷取保温有利于稳定贝氏体相变进程，并促进C充分扩散至残余奥氏体中进一步稳定残余奥氏体，最终形成以贝氏体为基体并弥散分布MA组元的显微组织。
本发明步骤3)中控制上卷温度≤70℃，上卷温度过高对设备造成损伤，且容易造成酸液挥发。控制酸洗温度为65～80℃，酸洗温度过低化学反应速率慢，导致酸洗不干净；酸洗温度过高，导致酸液挥发，影响酸洗效果。控制酸洗时间45～100秒，酸洗时间过短，会导致酸洗不干净；时间过长，会造成过酸洗，钢的表面泛黄。本发明采用上述酸洗工艺，可以有效去除钢卷表面氧化铁皮，提高钢的抗疲劳性能。
本发明采用中碳、Nb/V微合金化及Cu/Ni/Cr/Mo合金化的成分设计方法，配合合适的控制轧制及低温卷取工艺，并经过酸洗涂油处理，可以制造出具有低屈强比、高强度及良好耐蚀性连续油管用钢，该钢的屈服强度R p0.2≥620MPa，抗拉强度Rm≥750MPa，延伸率A 50≥11％，屈强比R p0.2/Rm≤0.83，同时具有良好表面质量和厚度均匀性，以及更容易实现的可制造性，可用于制造适合深井及非常规油气开采的超强度连续油管。
本发明的有益效果：
(1)本发明采用中低C、中高Mn及合金化成分体系，结合合适工艺，实现钢的高强塑性及良好加工性、热处理适应性；添加较高的Cu、Ni以 获得高强度同时得到高的耐蚀性；添加V微合金化元素以达到细化晶粒、析出强化效果，并添加适量的Nb进一步强化晶粒细化、析出强化效果，同时可避免连铸裂纹；添加Cr元素以促进铁素体形成，并有利于改善钢的耐蚀性能；添加适量Mo元素以促进贝氏体转变，并有利于稳定残余奥氏体，同时改善或抑制后续热处理脆性；采用低硫设计，并需进行微Ca处理，以保证开发钢无长条形夹杂，提升冲击韧性和抗疲劳性能。
(2)本发明在工艺上通过采用较低温终轧、低温卷取工艺，利用Cr、Mo合金元素的相变控制效应，得到MA组元+贝氏体+铁素体多相组织，实现低屈强比和超高强度，具有更优的可加工性能、热处理适应性等综合性能。
(3)本发明制造的钢屈服强度R p0.2≥620MPa，抗拉强度Rm≥750MPa，延伸率A 50≥11％，屈强比R p0.2/Rm≤0.83，并具有良好表面质量和厚度均匀性，综合力学性能优良，适用于制造110ksi及以上级别的超强度连续油管。
(4)本发明钢成分简单，制造工艺窗口较宽，比较容易在现场实施。
附图说明
图1为本发明实施例4的典型显微组织。
具体实施方式
下面结合实施例和附图对本发明做进一步说明。
表1为本发明实施例钢的成分，表2为本发明实施例钢的主要工艺参数，表3为本发明实施例钢的性能。
本发明实施例的工艺路线：冶炼→炉外精炼→连铸→板坯再加热→控制轧制→冷却→卷取→上卷→酸洗→涂油。
由图1可知，本发明制造的钢组织为MA组元+贝氏体+铁素体多相组织。
由表3可知，本发明制造的钢屈服强度R p0.2≥620MPa，抗拉强度Rm≥750MPa，延伸率A 50≥11％，屈强比R p0.2/Rm≤0.83，并具有良好表面质量和厚度均匀性，以及更容易实现的可制造性，可用于制造适合深井及非常规油气开采的超强度连续油管。
Figure PCTCN2018111845-appb-000001
Figure PCTCN2018111845-appb-000002

Claims (6)

  1. 一种低屈强比超高强度连续油管用钢，其化学成分质量百分数为：C：0.05～0.16％，Si：0.1～0.9％，Mn：1.25～2.5％，P≤0.015％，S≤0.005％，Cr：0.51～1.30％，Nb：0.005～0.019％，V：0.010～0.079％，Ti：0.01～0.03％，Mo：0.10～0.55％，Cu：0.31～0.60％，Ni：0.31～0.60％，Ca：0.0010～0.0040％，Al：0.01～0.05％，N≤0.008％，其余为Fe和不可避免的杂质元素。
  2. 根据权利要求1所述的低屈强比超高强度连续油管用钢，其特征在于，所述低屈强比超高强度连续油管用钢的显微组织为MA组元+贝氏体+铁素体多相组织。
  3. 根据权利要求1或2所述的低屈强比超高强度连续油管用钢，其特征在于，所述低屈强比超高强度连续油管用钢的屈服强度R p0.2≥620MPa，抗拉强度Rm≥750MPa，延伸率A 50≥11％，屈强比R p0.2/Rm≤0.83。
  4. 如权利要求1-3任一项所述低屈强比超高强度连续油管用钢的制造方法，包括如下步骤：
    1)冶炼、铸造
    按权利要求1所述的化学成分经电炉或转炉冶炼、炉外精炼、连铸，所述炉外精炼进行LF脱硫+RH真空脱气，RH真空脱气时间≥5min，所述连铸过程中控制过热度15～30℃，镇静时间8～17min；
    2)热轧
    加热温度1200～1260℃，终轧温度840～920℃，卷取温度450～550℃；
    3)酸洗、涂油
    上卷温度≤70℃，酸洗温度65～80℃，酸洗时间45～100s。
  5. 根据权利要求4所述的低屈强比超高强度连续油管用钢的制造方法，其特征在于，所述低屈强比超高强度连续油管用钢的显微组织为MA组元+贝氏体+铁素体多相组织。
  6. 根据权利要求4或5所述的低屈强比超高强度连续油管用钢的制造方法，其特征在于，所述低屈强比超高强度连续油管用钢的屈服强度R p0.2≥620MPa，抗拉强度Rm≥750MPa，延伸率A 50≥11％，屈强比R p0.2/Rm≤0.83。
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