EP3812479B1 - R6 high toughness offshore mooring chain steel applicable to anchor moored positioning cathodic protection floating body and mooring chain thereof - Google Patents
R6 high toughness offshore mooring chain steel applicable to anchor moored positioning cathodic protection floating body and mooring chain thereof Download PDFInfo
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- EP3812479B1 EP3812479B1 EP19925101.8A EP19925101A EP3812479B1 EP 3812479 B1 EP3812479 B1 EP 3812479B1 EP 19925101 A EP19925101 A EP 19925101A EP 3812479 B1 EP3812479 B1 EP 3812479B1
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- chain
- toughness
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- strength
- mooring
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- 229910000831 Steel Inorganic materials 0.000 title claims description 46
- 239000010959 steel Substances 0.000 title claims description 46
- 238000004210 cathodic protection Methods 0.000 title claims description 20
- 238000007667 floating Methods 0.000 title claims description 20
- 238000012360 testing method Methods 0.000 claims description 29
- 239000013535 sea water Substances 0.000 claims description 26
- 229910001566 austenite Inorganic materials 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005496 tempering Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 19
- 238000010791 quenching Methods 0.000 claims description 18
- 230000000171 quenching effect Effects 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 238000004873 anchoring Methods 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 15
- 238000005260 corrosion Methods 0.000 claims description 15
- 229910001563 bainite Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000009749 continuous casting Methods 0.000 claims description 6
- 229910000734 martensite Inorganic materials 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000003466 welding Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- 229910000746 Structural steel Inorganic materials 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 230000006866 deterioration Effects 0.000 claims description 2
- 238000010583 slow cooling Methods 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 238000009864 tensile test Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 11
- 238000005728 strengthening Methods 0.000 description 11
- 230000009466 transformation Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
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- 230000007423 decrease Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910000851 Alloy steel Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- -1 NbCN Chemical compound 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011692 calcium ascorbate Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/50—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for welded joints
- C21D9/505—Cooling thereof
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- 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")
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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- C21D9/50—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for welded joints
Definitions
- the present application relates to alloy steel and ferrous metallurgical products for offshore engineering, in particular a grade R6 steel and chain for offshore mooring in the steel series for offshore mooring chain and the evaluation of its offshore environmental performance degradation resistance.
- a mooring system is acquired for positioning and mooring with floating bodies in the process of the marine exploration, deep-sea oil and gas extraction, national defense construction and so on.
- the main component of the mooring system is offshore mooring chain by the steel.
- the offshore mooring chain can be classified into six grades called R3, R3S, R4, R4S, R5, and R6 according to its strength grading.
- the tensile strength of the chains at all grades after overall quenching-tempering shall be equal or greater than 690 MPa, 770 MPa, 860 MPa, 960 MPa, 1000 MPa, and 1100 MPa respectively.
- the grade R5 is the highest grade of the mooring chain produced and used at home and abroad by the first half of the year of 2018.
- the long mooring chain for positioning can be divided into two types which are stud and studless for drilling type and production type of the floating bodies respectively.
- the length of a single chain can reach several kilometers. Alloy steel bars of diameter 52-230 mm are used accordingly. All offshore mooring chain steels have an ultrahigh strength, as marine steel with a tensile strength above 690 MPa is ultrahigh-strength steel according to DNVGL.
- the qualified mechanical properties and service performance of the offshore mooring chain are requisite in the offshore environment.
- its toughness especially the toughness of the flash weld area, must be ensured for the safety and reliability for resisting wild winds and huge waves.
- the chain is usually continuously treated in a special vertical furnace, i.e. the final performance of the chain is obtained after continuous quenching and tempering heat treatment.
- the accessories are forged from the steel, and their final properties are obtained through intermittent heat treatment.
- DNVGL has defined grade R6 chain as the extreme technology and performance of the offshore mooring chain since 2013, and the provisional standard was not be terminated until 2018. DNVGL officially announced a standards includeing the grade R6 chain, specifying the performance of the chain and the basic process requirements of the production of the chain steel in July 2018.
- DNVGL also proposed an additional standard named Class programme-DNVGL-CP-0237, Edition July 2018, Offshore mooring chain and accessories which evaluates the EAC (environment assisted cracking) of grade R6 chain under CP (cathodic protection) conditions according to the standards of ASTM G129 and ASTM E1820.
- the specific requirement is to carry out two tests: the one is SSRT with the applied potential of -850 mV, -1200 mV(saturated calomel electrode SCE) and strain rate of ⁇ 10 -5 /s; the other is the K IEAC test (fracture toughness type I in seawater) with CT (conpact tension) specimen, applied potential of -950 mV, -1050mV (SCE) and the test speed of ⁇ 6x10 -9 m/s in seawater. So as to evaluate the degradation resistance of grade R6 chain in the seawater environment.
- the seawater environment is generally considered as the service forbidden zone for ultrahigh-strength steel with yield strength over 1000MPa.
- the main way to lighten the chain is ultrahigh intensification. There is a restraining relationship each other between strength and toughness, and the same is true of the relationship between strength and deterioration resistance of service performance in the seawater environment. Once the strength is improved, there must be a decrease of toughness, plasticity and the degradation resistance in the seawater environment performance. But according to DNVGL, when the strength is increased, the toughness is increased instead of decreasing with its EAC evaluated at the same time.
- DNVGL proposes the above additional requirements for the evaluation of EAC of the chain by impressed cathodic protection potential of the grade R6 chain for the sake of reliability. This is a new challenge in the research and development of the ultrahigh-strength chain.
- Vanadium are the element for refining or strengthening effect in the form of VC in the invention.
- the invention does not cover the technology to balance corrosion potential and cathodic protection potential to prevent embrittlement by hydrogen generation of the chain caused by cathodic overprotection, coping with new standard.
- the content of evaluating the embrittlement by hydrogen generation caused by cathodic protection is added in the latest standards of DNVGL2018 under the premise of ensuring the mechanical properties of the chain. While the reliability of the chain mainly depends on the overall performance given by the steel.
- the toughness of base and weld of the chain are reduced below the qualified line by coarse eutectic niobiumcarbide.
- the air cooling process is impossible to be implemented in the continuous heat treatment production line to avoid the low-temperature phase transformation crack although this patent requires air cooling after heattritment.
- retained austenite will decompose during the high-temperature tempering although austenite is beneficial to toughness and environmental performence.
- the steel with high content of N has a greater driving force for precipitation, higher density of precipitation phase, and greater strengthening effect, than that with the low content of N.
- the technical problem to be solved by the present invention is to propose a new manufacturing scheme of a grade R6 offshore mooring chain as well as its steel for use in anchoring and mooring floating bodies with cathodic protection.
- the precipitation strengthening effect and the toughness and a low corrosion rate of the chain are improved on the premise of ensuring the hardenability and reduces the corrosion potential when the total contents of alloy and microalloy are narrowed, to curb the embrittlement by hydrogen generation due to the chains are received by cathodic overprotection passively.
- the chemical composition by wt% are as follows: C 0.18 ⁇ 0.24, N 0.006 ⁇ 0.024, P 0.005 ⁇ 0.025,S ⁇ 0.005,Si 0.15 ⁇ 0.35, Mn 0.20 ⁇ 0.40, Cr 1.40 ⁇ 2.60, Ni 0.80 ⁇ 3.20, Mo 0.35 ⁇ 0.75, Cu ⁇ 0.50, Al ⁇ 0.02, Ti ⁇ 0.005, V 0.04 ⁇ 0.12, Nb 0.02 ⁇ 0.05, Ca 0.0005 ⁇ 0.004, O ⁇ 0.0015, H ⁇ 0.00015, the rest is Fe and unavoidable impurity elements.
- the content of N in the chemical composition is 0.016-0.024.
- the chain is made of round bars corresponding to the above chain steel.
- the present invention further limits the content of C and N and the range of ⁇ M and ⁇ MM on the basis of the related product composition applied by two the Chinese invention patents whose publication numbers are CN103667953 B and CN106636928A .
- the chain link is transformed into a composite bainite microstructure consisting of BU (upper bainite) with a small amount of BL (lower bainite) and M (martensite) during the cooling process after austenitizing.
- BU upper bainite
- BL lower bainite
- M martensite
- the phase transformation temperature of BU with Bs ⁇ 500°C is higher than that of the martensite with Ms of ⁇ 320°C.
- the cooling crack sensitivity decreases with the increase of the phase transformation temperature.
- the K IC data is obtained, and the EAC here is expressed as KIEACE, KIEAC 0 .
- KQEAC of the weld zone of the chain is also tested for comparing the performance of the weld zone with that of the base.
- the chain of the present invention is made of round bar having the corresponding chemical composition, and the round bar is processed in sequence by chain making, flash butt welding, and heat treatment to obtain the final product, wherein the heat treatment include high-temperature quenching with ⁇ 980°Cand tempering with 600°C to 690°C. Quenching and tempering are cooled with water less than 50°C.
- Round bar is made from continuous casting bloom or ingot having corresponding chemical composition, and in sequence by heating, blooming, rolling and slow cooling, in which the heating temperature is more than 1230°C, so that nitride and carbonitride are all dissolved in austenite; in the cooling process, due to the combination of micro-alloying elements MM and the limit of C+N, the precipitation sequence of nitride and carbonitride is TiN-AlN-NbCN- MCN.
- the nitride and carbonitride are controlled to be precipitated in the sequence of TiN-AlN-NbCN-MCN on the basis of the general technology, that is smelting-bloom continuous casting-blooming with high temperature heating-intermediate billet heating-forging or rolling-chain making-flash butt welding-heat treatment, and so on.
- the solubility product of [Nb][C+N] is smaller, the effect of inhibiting the growth of austenite grain of NbCN is stronger than that of NbC, and the existence of NbCN (and solid solution of Nb) allows the temperature of the chain to increase from ⁇ 920°C to ⁇ 980°C before quenching.
- Carrying out example (invention example) 1-4 and contrast example 3 are about the process wherein continuous casting bloom with the size of 390 ⁇ 510mm are rolled into the round bars with a diameter of 120mm, while contrast example 1, 2 and 4 are about the process that 420kg test ingots are forged into round bars with a diameter of 95mm, and then the round bars are processed in sequence by blanking, heating, bending, flash welding, forming chain and heat treatment (quenching + tempering) to obtain the finished chain.
- the performance data is the average value of the results of three groups of specimens. Numerical treatment of the third place after the decimal point: ⁇ 4 discard and ⁇ 6 into 1.
- Loading test Zwick 50kN testing machine, made by Zwick Co., Germany; prefabricated fatigue crack: MTS 810 (100kN) electro-hydraulic servo testing machine system, made by MTS, Co., America; corrosion test device: seawater corrosion test container, equipped with slow tension and compact tension fixture; potentiostat: CHI660D electrochemical workstation, Shanghai Chenhua Instrument Co., China; pH value of artificial seawater is 8.2 ⁇ 7.0; 25 °C. See Figure 5-8for specimens and tests.
- EAC test is additionally required for the grade R6 chain.
- the SSRT and KIEAC (CT) test is included to evaluate EAC resistance.
- the SSRT test is carried out with no potential, potential of -850 mV, -1200 mV (SCE) and axial cylindrical smooth specimen in dry atmosphere and artificial seawater.
- the CT test is carried out with potential of -950, -1050 mV (SCE) and in artificial seawater.
- Z E /Z 0 and KQEAC 0 / KQEAC E indicate the degradation degree of EAC resistance.
- Z 0 and Z E refer to the results of the reduction of area of SSRT without and with potential respectively.
- the potential is not added or added to -950 mV and -1200 mV (SCE).
- KQEAC 0 and KQEAC E refer to the results of CT test without and with potential respectively.
- the CT specimen was precharged hydrogen for 48 hours.
- Tensile speed ⁇ 6 ⁇ 10 -9 m/s.
- KQEAC 0 /KQEAC E refers to the degradation degree of EAC resistance in the carrying out example and the contrast examples.
- KIC data is obtained, and here KIEAC 0 and KIEAC E refer to the results of the CT test without and with potential respectively.
- chain making and simulated quenching-tempering are carried out first, then EAC test is carried out by sampling.
- KQEAC of the weld zone of the chain is also tested for the comparison of the performance of the weld zone and the base.
- Carrying out example (invention example) 1-4 all conform to the range of the composition limitation of the present invention.
- the limited TiN and AlN combined with a small content of N are first precipitated in the cooling process of continuous casting bloom, according to the solubility product from small to large, which ensures the subsequent precipitation of NbCN and VCN.
- the heat temperature is more than 1230°C, the continuous casting bloom is forged and rolled, AlN, NbCN, VCN, M3C and M2C was first all dissolved in austenite, and then precipitated during cooling.
- TiN, NbCN, and AlN do not dissolve when the chain is quenched at 980°C, which hinders the growth of austenite grain.
- NbCN which is still insoluble at 1150°C, is used as the main precipitate to hinder the growth of austenite grain.
- M3C, M2C, and VCN are fully solid solution with a high-temperature quenching at 980°C, and then precipitated again during a high-temperature tempering.
- the quenching-tempering steel is strengthened by fine and dense VCN, so as to make up for the loss of strengthening effect caused by reducing the total content of alloy in the present invention.
- KIEAC E /KIEAC 0 0.85
- KIEAC E and KIEAC 0 meet the plane strain condition and KIC criterion. This is the first KIEAC data of grade R6 steel obtained in the world.
- the potential measured after immersion in seawater for 80 hours is used as the corrosion potential under laboratory conditions.
- the difference between corrosion potential and applied potential is overprotection potential.
- the overprotection potential to - 850mV(SCE) in In the carrying out example 1 and 3 is about 200 and 232mV (SCE) respectively, which are within the allowable range.
- the overprotection potential to -1200mV (SCE) is about 550 and 580mv (SCE) respectively, which is hard to bear.
- the carrying out example 1, 2 is compared with the contrast example 4, the strength is increased by 62-75 MPa by adopting similar quenching-tempering treatment, which shows that the strengthening effect of VCN is better than that of VC.
- Ms is low, and it is sensitive to cooling crack; N has a low content, N is exhausted by first precipitated NbCN, and is not enough to form AlN.
- the impact value is 61J, which barely conform with the standard, but the tensile strength is as low as 1080 MPa, which is unqualified.
- the total content of alloy exceeds the scope of the invention.
- the difference between -850 mV and its corrosion potential of -520 mV, that is, the overprotection potential is about 330 mV (SCE).
- SCE corrosion potential
- SSRT test show a tendency of embrittlement.
- the content of Nb is as high as 0.07, and NbCN is precipitated before AlN.
- Ms is low, it is sensitive to cooling crack; with the increase of Al and Ti, the total content of micro-alloy elements exceeds the scope of the invention. Due to the consumption of N, N was exhausted when NbCN was precipitated. There are only VC, no VCN. The yield ratio is 0.96 and greater than regulation 0.95. The strengthening and toughening effects are not obvious when the quenching temperature is at 980°C. Impact toughness is unqualified.
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CN201910306407.XA CN110144516B (zh) | 2019-04-16 | 2019-04-16 | 一种适用于锚泊定位阴极保护浮体的r6级高强韧性海洋系泊链钢及其系泊链 |
PCT/CN2019/087168 WO2020211137A1 (zh) | 2019-04-16 | 2019-05-16 | 一种适用于锚泊定位阴极保护浮体的r6级高强韧性海洋系泊链钢及其系泊链 |
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CN113322420A (zh) * | 2020-02-28 | 2021-08-31 | 宝山钢铁股份有限公司 | 一种具有优异低温冲击韧性的控制屈强比钢及其制造方法 |
AR124169A1 (es) * | 2020-11-30 | 2023-02-22 | Dalmine Spa | Composición de acero, artículo forjado y método de fabricación de un recipiente de presión sin costura para gas comprimido |
CN114369759A (zh) * | 2021-12-20 | 2022-04-19 | 江苏亚星锚链股份有限公司 | 一种耐低温锚链 |
CN116179939A (zh) * | 2022-10-31 | 2023-05-30 | 上海茵矩材料科技有限公司 | 一种高环境裂纹抗力的系泊链钢及系泊链 |
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JPS54115618A (en) * | 1978-02-28 | 1979-09-08 | Kawasaki Steel Co | Steel for high tensile large diameter chain |
RU2085610C1 (ru) * | 1994-04-05 | 1997-07-27 | Центральный научно-исследовательский институт конструкционных материалов "Прометей" | Феррито-перлитная литейная сталь |
US6852175B2 (en) * | 2001-11-27 | 2005-02-08 | Exxonmobil Upstream Research Company | High strength marine structures |
CN101161843A (zh) | 2007-11-21 | 2008-04-16 | 广州珠江钢铁有限责任公司 | 一种提高v-n微合金化高强度钢钒合金利用率的方法 |
CN101519751B (zh) * | 2008-02-27 | 2011-06-15 | 宝山钢铁股份有限公司 | 一种高性能海洋系泊链钢及其制造方法 |
CN103667953B (zh) * | 2013-11-28 | 2016-09-28 | 江苏亚星锚链股份有限公司 | 一种低环境裂纹敏感性超高强韧性海洋系泊链钢及其制造方法 |
KR101657421B1 (ko) * | 2015-09-22 | 2016-09-13 | 현대제철 주식회사 | 체인강 및 이의 제조방법 |
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