WO2023160613A1 - Acier de chaîne d'amarrage et son procédé de production, et chaîne d'amarrage et son procédé de production - Google Patents

Acier de chaîne d'amarrage et son procédé de production, et chaîne d'amarrage et son procédé de production Download PDF

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WO2023160613A1
WO2023160613A1 PCT/CN2023/077888 CN2023077888W WO2023160613A1 WO 2023160613 A1 WO2023160613 A1 WO 2023160613A1 CN 2023077888 W CN2023077888 W CN 2023077888W WO 2023160613 A1 WO2023160613 A1 WO 2023160613A1
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Prior art keywords
steel
mooring chain
chain
production method
mooring
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PCT/CN2023/077888
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English (en)
Chinese (zh)
Inventor
殷匠
高欣
邱海东
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上海茵矩材料科技有限公司
江阴南工锻造有限公司
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Publication of WO2023160613A1 publication Critical patent/WO2023160613A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B21/00—Tying-up; Shifting, towing, or pushing equipment; Anchoring
    • B63B21/04—Fastening or guiding equipment for chains, ropes, hawsers, or the like
    • B63B21/10—Fairleads
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur

Definitions

  • the invention relates to the technical field of low alloy steel and the field of marine engineering accessories, in particular to a mooring chain steel and its production method, as well as the mooring chain and its production method.
  • Mooring chain steel finger diameter in Between the mooring chains with round steel. Because the mooring chain is immersed in seawater for a long time and the service environment is harsh, the mooring chain steel must have high strength, good toughness, seawater corrosion resistance, hydrogen evolution embrittlement resistance, fatigue resistance, wear resistance and other characteristics. In addition, in practical applications, it is usually bent into a ring, and the mooring chain steel needs to have good hot bending and welding properties.
  • the target composition of R4 grade mooring chain steel with million-ton production is 0.22Mn1.5Cr0.8Ni0.8Mo0.45Nb0.03, provided by Shanghai No. 5 Iron and Steel Works (Liu Yongxin, Xu Yun, Chen Yifeng, Zhao Ronghua, The optimization of the heat treatment process parameters of the four-grade anchor chain steel, "Thermal Processing Technology" 1990No533 ⁇ 35), has been used in China for decades. Due to the large diameter of the offshore mooring chain link, the quenching and cooling conditions are limited. In order to ensure the hardenability of the chain link and obtain stable strength and toughness, the MnCrNiMo composition of the R4 chain steel products of various steel companies has not changed significantly over the years. . Although there were 5 patents on R4 grade chain steel published from 1998 to 2015, among which the Chinese patent application No. 98110160.7 stipulated that the upper limit of Mn was 1.90wt%, in fact, none of these patents had practical records.
  • the object of the present invention is to provide a kind of mooring chain steel, on the basis of improving the cost performance of R3, R4, R4S grade mooring steel, utilize Mn to affect the bay effect of the continuous cooling curve of structural steel, that is, the law of influence is similar to Mo, When the alloy Mn content increases to a certain amount, the continuous cooling curve of the steel begins to appear a river bend.
  • the composition system of increasing the cheap elements Mn and Al and reducing the precious elements Mo and Ni is designed. After the trial production of steel and chain, The effect of reducing the cost of chain products and improving their strength and toughness is obtained.
  • the present invention provides a mooring chain steel, the composition content of which is C 0.18 ⁇ 0.32, Mn 1.95 ⁇ 2.60, Si 0.15 ⁇ 0.50, Cr 0.45 ⁇ 1.20, Mo 0.008 ⁇ 0.250, Ni 0.02 ⁇ 1.20, Cu ⁇ 0.40, S ⁇ 0.005, Al 0.005 ⁇ 0.250, (V+Ti+Nb) ⁇ 0.35, (Sn+As+Sb) ⁇ 0.06, N 0.004 ⁇ 0.024, O ⁇ 0.002, H ⁇ 0.00015, the balance is Fe and unavoidable impurities.
  • the composition of the present invention the amount of Mn is higher than that of the prior art.
  • the amount of Al is higher than that of the prior art, the amount of Mo is lower than that of the prior art, and the amount of Cr and Ni is lower than or equal to the prior art.
  • manganese is lower than 1.95%, the above effects cannot be achieved; if it is higher than 2.60%, the segregation of components will not be easily reduced or eliminated, thus affecting the structure and mechanical properties, the uniformity of process performance and other additional properties, such as hydrogen embrittlement susceptibility.
  • steel and chains contain more than 1.95% manganese, and the content of martensite in the structure does not increase but decreases. Due to the reasonable combination of soft and hard phases, the yield ratio of quenched-high temperature tempered steel is controllable; the steel with composite bainite (BU+BL+M) structure, the edge and center of the cross-section of the chain, the base metal and The strength difference of the weld seam is greatly reduced.
  • the steel of the present invention in which the increased amount of manganese is combined with other elements can also increase and stabilize the phase transformation temperature of austenite during cooling from the austenitizing temperature, Increase the volume fraction of bainite in the matrix of the bainite/martensite quenching structure, expand the cooling rate range for the stable formation of bainite phase, and overcome the high crack sensitivity and heat treatment sensitivity of ultra-high-strength steel, especially for large diameter
  • the difficult problem of poor productivity of chain continuous heat treatment has created conditions for satisfying the controllable low yield ratio of the invented steel after tempering.
  • the reduction of the carbide-forming element chromium and the reduction of the M3C type carbide FeCr3C are beneficial to reduce the micro-battery effect and improve the corrosion performance.
  • Silicon can improve the strength and hardenability of steel, and has the same deoxidation effect as manganese, and can improve the corrosion performance of steel and chains in seawater.
  • the present invention controls its residual content to be 0.15% or above. However, if the silicon content is too high, the toughness will be affected. Therefore, its upper limit is set at 0.50%.
  • Chromium is also the main element to improve the strength and hardenability of chain steel, increase tempering stability and corrosion resistance in seawater.
  • the chromium content should not be lower than 0.45%. Since a large amount of manganese has been added to the steel of the present invention, considering the cost and effect, the upper limit is 1.20%.
  • the nickel content of chain steel above grade 4 shall not be less than 0.20%.
  • Nickel is not easy to burn out during flash welding, which is beneficial to improve the uniformity of the weld. But the content is too high to increase the cost.
  • SCC stress corrosion
  • the steel of the present invention stipulates that the addition amount shall not exceed 1.20%.
  • the carbon equivalent (Ceq) coefficient of nickel is low, and it can be used to balance Ceq if necessary, so as not to make Ceq too high.
  • Nickel improves the hardenability, and ensures good strain-slip ability of the link, including the weld joint, and reduces the brittle transition temperature, which is beneficial to improve the low-temperature toughness of the link weld. Its solid solution strengthening effect is weak.
  • Molybdenum delays the ferrite-pearlite transformation of steel, prevents temper brittleness, and significantly improves the impact toughness of steel. Molybdenum also improves the corrosion resistance of steel, and is an element that is not easily burned during flash welding. Molybdenum, molybdenum and chromium, especially the combination with manganese can stabilize the bainite content, control the bainite/martensite ratio, increase the phase transition temperature, reduce the crack sensitivity, and benefit the stability and buckling of the cross-section of the link. Stronger control. Since molybdenum is classified as a precious element, it increases the cost of steel.
  • the present invention substitutes manganese for molybdenum, reducing the amount of molybdenum by more than half. (V+Ti+Nb) ⁇ 0.35%
  • V, titanium Ti, and niobium Nb have the effects of strengthening, refining, and hydrogen trapping, and they are also commonly used elements in marine chain steel in the past 10 years. Due to factors such as raw materials and furnace lining, titanium is unavoidable.
  • vanadium is used as a strengthening element to form extremely fine VCN of 1 to 4 nm.
  • These VCNs are not only high-energy strong hydrogen traps, which can limit the diffusion of hydrogen embrittlement steel, but also increase the micro-zone yield strength, reduce the local hydrogen accumulation caused by micro-zone strain (micro-yield), and reduce the HE sensitivity on the other hand. sex.
  • niobium can supplement the deficiency of aluminum (AlN) and titanium (TiN) refinement. Considering the cost factor, it is stipulated that the sum of the three shall not exceed 0.35%. Cu ⁇ 0.40%,
  • Aluminum is the main deoxidizing element, and it can form AlN, refine grains, and a small amount of aluminum can improve the comprehensive mechanical properties of the chain base material and weld. When aluminum exceeds 0.2%, it can also improve the corrosion resistance of steel. When niobium is used to refine the grains of alloy structural steel, the role of aluminum can only be deoxidation, and the residual aluminum is allowed to be not less than 0.005% when the steel is lifted.
  • the implementation of the present invention shows the corrosion resistance tendency of aluminum in seawater, and limits it to ⁇ 0.250%, and controls restrain its influence on the phase transition.
  • the premise of applying higher aluminum is that the flash butt welding process is in place, and the size and quantity of oxide inclusions in the weld joint are limited to not exceed the normal level.
  • Nitrogen in steel is unavoidable, and fixed into AlN, TiN, VN, NbN can prevent strain aging, refine grains and/or increase strength. Smelting engineers to reduce the oxygen, hydrogen and nitrogen targets of structural steel. However, the inventors feel that the potential of oxygen in the compound existing as a solid phase transition core and nitrogen as a light element has yet to be brought into play through practical applications. In the process of nitrogen utilization, it is necessary to prevent excessive free nitrogen or solid solution nitrogen from forming pores during the solidification of molten steel, and to prevent the precipitation of microalloy nitrides from increasing crack sensitivity. The invention allows the actual nitrogen content of product steel and chain to be 0.004-0.024wt%.
  • Tramp elements such as antimony, arsenic, and tin also embrittle the grain boundaries of prior austenite, reduce toughness, and may cause hot working cracks when the content is large. Although it is hoped that the lower the better, considering the cost of industrial products, the total amount is allowed to be no more than 0.06%.
  • the second object of the present invention is to provide a kind of production method of above-mentioned mooring chain steel, comprising the following steps,
  • the mass percentage of the tapping composition is: C 0.18 ⁇ 0.32, Mn 1.95 ⁇ 2.60, Si 0.15 ⁇ 0.50, Cr0.45 ⁇ 1.20, Mo 0.008 ⁇ 0.250, Ni 0.02 ⁇ 1.20, Cu ⁇ 0.40, S ⁇ 0.005, Al 0.005 ⁇ 0.250, (V+Ti+Nb) ⁇ 0.35, (Sn+As+Sb) ⁇ 0.06, N 0.004 ⁇ 0.024, O ⁇ 0.002, H ⁇ 0.00015, the balance is Fe and unavoidable impurities;
  • the metal raw material used in the primary smelting process of an electric furnace or a converter is molten iron, One or a mixture of any two or more of pig iron, steel scrap, ferroalloy, sponge iron, metal oxide and ore.
  • step S2 the ratio of the cross-sectional area of the steel ingot to the cross-sectional area of the finished round steel is ⁇ 7.
  • step S3 After step S3, step S4 is also included, after the round steel is straightened and grinded or turned by a grinding wheel, flaw detection, sampling and testing are carried out according to classification society specifications.
  • the third object of the present invention is a mooring chain, which is prepared by using the round steel made of the mooring chain steel mentioned above.
  • ABS American Bureau of Shipping
  • DNVGL Det Norske Veritas
  • Rm tensile strength
  • Rp0.2 conditional yield strength
  • YR yield ratio
  • Aim value target value
  • A elongation
  • Z section Shrinkage
  • CVN Charpy V-notch impact energy
  • B ring back
  • W weld.
  • YR this patent selects a more demanding ABS target value.
  • the fourth object of the present invention is to provide a production method of the above-mentioned mooring chain.
  • the mooring chain adopts the above-mentioned mooring chain steel, which is sequentially cut, heated at 950-850°C, and bent at 900-800°C. °C, temperature measurement, flash butt welding, and finally weaving chains; among them, the braided chains are heat treated in batch or vertical continuous tempering furnaces, and their accessories are heat treated in batch tempering furnaces.
  • the heat treatment steps are: firstly carry out at least one quenching treatment, each time the quenching temperature is >890°C, water cooling, the water temperature is less than 50°C; after the quenching treatment, tempering treatment is carried out, the tempering temperature is 570-650°C, water cooling or air cooling.
  • the braided chain and its accessories are quenched twice in a batch or vertical continuous tempering furnace.
  • the first production covers the diameter range required by the market, which improves performance and reduces costs
  • the steel of the present invention is applied to flash butt welding workpieces for the first time to obtain stable and tough welds.
  • One of the reasons is that, Compared with C0.22MnCrNiMo steel, increasing Mn and reducing Mo, Cr, and Ni reduces the thermal deformation resistance of link flash butt welding by 6-16%, and it is easy to form a well-bonded tight weld, and the decrease rate of weld toughness is greatly reduced.
  • the allowable final close upsetting temperature of the R4 steel of the present invention is about 750 ⁇ 850°C; while the final close upsetting temperature allowed by traditional R4 steel is about 800-850°C;
  • the problem can be solved by adjusting the tempering parameters within the fluctuation range of the high temperature tempering temperature ⁇ 30°C; Mass production management, reducing manufacturing costs, improving efficiency, and realizing the management revolution of chain steel production and chain ring manufacturing;
  • Quenching is relatively uniform in the cross-sectional performance of the present invention in the phase transformation of the bainite region; the present invention has NbCN, AlN, TiN alone or a combination of multiple methods to prevent the growth of austenite grains to choose from, improving the comprehensive performance and reduced EAC sensitivity;
  • Table 1 Steelmaking composition of the embodiment of the present invention and comparative example, wt%
  • the production method of the mooring chain steel in embodiment 1 ⁇ 8 is as follows:
  • the mass percentage of the tapping composition is: C 0.18 ⁇ 0.32, Mn 1.95 ⁇ 2.60, Si 0.15 ⁇ 0.50, Cr0.45 ⁇ 1.20, Mo 0.008 ⁇ 0.250, Ni 0.02 ⁇ 1.20, Cu ⁇ 0.40, S ⁇ 0.005, Al 0.005 ⁇ 0.250, (V+Ti+Nb) ⁇ 0.35, (Sn+As+Sb) ⁇ 0.06, N 0.004 ⁇ 0.024, O ⁇ 0.002, H ⁇ 0.00015, the balance is Fe and unavoidable impurities; electric furnace, primary refining
  • the metal raw materials used in the process are molten iron, pig iron, scrap steel, ferroalloy, ore, etc.
  • the round steel prepared by the above-mentioned production method for the mooring chains of Examples 1 to 8 is sequentially cut, heated at 950-900°C, bent at 850-800°C, temperature measured, flash-butt welded, chain-braided, and bottomed.
  • the heat treatment steps are: heating to 920°C for water-cooling and quenching, and the water temperature is less than 50°C; reheating to 610°C for tempering, and water cooling.
  • Embodiment 1 ⁇ 8 and comparative example 1 ⁇ 6 are now carried out the mechanical performance detection under the same conditions, and the detection results are shown in Table 2
  • Comparative Examples 3, 4, and 5 have been used consistently for decades. Compared with the embodiment, the contents of the precious alloy elements Mo and Ni are increased by about one time respectively, and the cost will increase correspondingly.
  • the yield strength ratio YR of Comparative Examples 1 and 5 exceeds the ABS standard of the American Bureau of Shipping. Comparative examples 2, 3, and 4 are R4 chains whose tensile strength is lower than the standard. Comparative example 6 is an R3 grade chain, and its toughness is unqualified.
  • the weld seam toughness reduction rate of the comparative example is 42-73%, and the Mn content of the comparative example exceeds the upper and lower limits of the scope of the invention respectively. Even with the addition of elements Cr and Ni, the mechanical properties (yield ratio or tensile strength or toughness) are still unqualified.
  • Table 3 is the corrosion rate trend and environmental crack resistance performance table in the seawater of embodiment 5 and 7
  • the internal hydrogen of the steel and the chain is at a very low level; the corrosion rate tends to decrease with the increase of Al and Cu; the corrosion rate in the deep-sea anoxic environment decreases by an order of magnitude; the data of environmental crack sensitivity is provided.
  • Table 4 is the hardness (wt %) of r/3 of embodiment and comparative example cross-section and core portion

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Ocean & Marine Engineering (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

La présente invention concerne un acier de chaîne d'amarrage et son procédé de production. L'acier de chaîne d'amarrage comprend les composants suivants, en pourcentages en masse : C : 0,18-0,32, Mn : 1,95-2,60, Si : 0,15-0,50, Cr : 0,45-1,20, Mo : 0,008-0,250, Ni : 0,02-1,20, Cu ≤ 0,40, S ≤ 0,005, Al : 0,005-0,250, (V+Ti+Nb) ≤ 0,35, (Sn+As+Sb) ≤ 0,06, N : 0,004-0,024, O ≤ 0,002, H ≤ 0,00015 et le reste étant du Fe et des impuretés inévitables. Sur la base d'une amélioration des performances de coût de l'acier d'amarrage de qualité R3, R4 et R4S, en utilisant un effet de baie d'une courbe de refroidissement continue d'acier structural influencé par Mn, à savoir similaire à la règle d'influence de Mo, à mesure que la teneur en alliage de Mn est augmentée jusqu'à une certaine quantité, la courbe de refroidissement continue de l'acier commence à apparaître sous une forme de méandre de rivière, un système de composant permettant d'augmenter les éléments peu chers Mn et Al et de réduire les éléments précieux Mo et Ni est conçu, et au moyen d'une production d'essai de l'acier et d'une chaîne, les effets de réduction du coût d'un produit de chaîne et d'amélioration de la résistance et de la ténacité de celui-ci sont obtenus. La présente invention concerne également une chaîne d'amarrage et son procédé de production.
PCT/CN2023/077888 2022-02-23 2023-02-23 Acier de chaîne d'amarrage et son procédé de production, et chaîne d'amarrage et son procédé de production WO2023160613A1 (fr)

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CN115216697A (zh) * 2022-07-27 2022-10-21 无锡派克新材料科技股份有限公司 一种提高低合金钢模拟焊后热处理性能的制造方法

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