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金属学报  2020, Vol. 56 Issue (4): 558-582    DOI: 10.11900/0412.1961.2020.00058
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钢的高性能化理论与技术进展
董瀚1,2(),廉心桐1,胡春东1,陆恒昌1,彭伟1,赵洪山1,徐德祥1
1.上海大学材料科学与工程学院 上海 200444
2.钢铁研究总院 北京 100081
High Performance Steels: the Scenario of Theoryand Technology
DONG Han1,2(),LIAN Xintong1,HU Chundong1,LU Hengchang1,PENG Wei1,ZHAO Hongshan1,XU Dexiang1
1.School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2.Central Iron and Steel Research Institute, Beijing 100081, China
引用本文:

董瀚,廉心桐,胡春东,陆恒昌,彭伟,赵洪山,徐德祥. 钢的高性能化理论与技术进展[J]. 金属学报, 2020, 56(4): 558-582.
Han DONG, Xintong LIAN, Chundong HU, Hengchang LU, Wei PENG, Hongshan ZHAO, Dexiang XU. High Performance Steels: the Scenario of Theoryand Technology[J]. Acta Metall Sin, 2020, 56(4): 558-582.

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摘要: 

高强度化始终是钢的发展主题，同时还需要解决高强度化后导致的韧塑性降低、疲劳破坏和延迟断裂敏感性增加等问题。在获得高的力学性能之后，实际应用时还需要材料具有良好的工艺适应性与服役性能，达到合适的材料生产-零件制造-服役评价的技术匹配。本文以耐候钢、合金结构钢、紧固件用钢、高氮奥氏体不锈钢、马氏体不锈钢为案例，回顾并展望了与耐腐蚀、高强度、高品质等相关的材料发展动向。近年来的实践充分证明了技术基础研究是创新的源泉，从全产业链流程的组织与性能调控进一步转向合金化的再认识与利用，可能是今后一段时间应该考虑的问题。
关键词 ： 钢,  高性能,  理论,  技术    
Abstract：

Strengthening and toughening are the main topics of steels, and accompanied fatigue failure and delayed fracture requiring to be solved simultaneously. Not just more than that, better performances in fabrication and service are quite important for an intentional steel to be used eventually. It is worth to pay close attention to match up three main courses: steel processing, component fabrication and service evaluation. Over past two decades, ferrite grains can be refined to micron scale in both plain low carbon steel products and microalloyed steel products and lead to remarkable increase of strength. The reason to define the limitation of ferrite grain refinement to microns is ductility decrease, low processing efficiency and heat affected zone (HAZ) coarsening. Ten years ago, a novel microstructure M3 (multiphase, metastable and multiscale) was proposed to overcome the problems stated above, and led to ductility and/or toughness improvement. It based on the idea of crack initiation and propagation retardment. It led to prevalence of the 3rd generation advanced high strength steel (AHSS) and the 3rd generation high strength low alloy (HSLA) steel, presenting higher ductility and/or toughness at high strength level. In the near future, it is imaginable that polymorphic alloying will be taken into consideration instead of recent hot issue on microstructure control during whole processing. From the view point of classic alloying theory, solution and precipitation of alloying elements play an important role on processing and then final microstructure. The distribution and occurrence of small atom radius elements (e.g. C and N) and comparable atom radius elements (e.g. Cr, Mn, Ni, Co) in iron seem quite clear. The ambiguous situation still remains for B and P, and even larger atom radius elements such as rare earth (RE) elements. Segregation of small amount of them to defects and boundaries maybe lead to decrease of energy and result in remarkable change of microstructure characterization. Thanks to the advancement in processing and instrumentation technologies, the distribution and occurrence of alloying elements in steel and the advantages of different alloying elements in steel matrix and surface can be taken, so called the polymorphic alloying. The practices of polymorphic alloying in steel development are engaged to improve corrosion resistance, strengthening and toughening. The performance enhancements are discussed in cases of weathering steel microalloyed with RE, ultrahigh strength steel strengthening by carbide and intermetallic precipitates, bolt steel with C and microalloying elements, austenitic stainless steel alloyed with N, and martensitic stainless steel alloyed with C and Ag.
Key words： steel    high performance    theory    technology
收稿日期: 2020-02-21     
ZTFLH:  TG142  
基金资助:国家重点研发计划项目(2017YFB0304401);国家重点研发计划项目(2017YFB-0304701);中国博士后科学基金项目(2019M651465);上海市教育委员会科研创新计划项目(2019-01-07-00-09-E00024)
作者简介: 董 瀚，男，1962年生，教授
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https://www.ams.org.cn/CN/10.11900/0412.1961.2020.00058      或      https://www.ams.org.cn/CN/Y2020/V56/I4/558

YearDevelopment
1900US started to develop Cu-bearing steels
1916ASTM started research of weathering steels
1933Cor-Ten steel was developed by US Steel
1941First standard for weathering steels (ASTM A-242) was proposed
1955Japan started to develop weathering steels
196509CuPTiRE sheet steel was developed by China
1965~1980Japan, Germany, Britain and other European countries began to use exposed weathering steels
1984China formulated national standard of high weathering steels

1990

First bridge using exposed weathering steels was built in China,

weathering steels was fully used in railway vehicle manufacture

1992

High performance steels (HPS) was developed by US Federal Highway Administration (FHWA) for

bridge building

1999High weathering steels for JT towers were developed in China
表1  20世纪耐候钢的发展历程
图1  耐候钢锈层转变示意图
图2  稀土元素在钢中赋存示意图
图3  添加稀土前后的Q235和09CuPCrNi钢周期浸润腐蚀144 h后的样品形貌及腐蚀速率
图4  09CuPCrNiRE钢中Ce元素的AES谱
图5  钢铁材料强度的发展
图6  合金结构钢强度和塑韧性[17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35]
Toughening mechanismToughening theoryToughening natureRef.
CleaningδIC~X0RVRI|R0Increase crack nucleation energy[42]
Refinement of precipitationKIC=nE2πλIncrease crack nucleation energy[43]
Refinement of microstructureσfc=2Gγksd-12Increase crack propagation energy[43]
Retained austeniteKId=-3Gb21-ν2πrsinθcos(θ2)Increase crack propagation energy[43]
表2  钢铁材料常见韧化机制[42,43]
图7  0.15C5Mn3Al钢中裂纹在马氏体和铁素体中扩展[45]
图8  耐延迟断裂性能和抗疲劳性能随强度的提高而降低
图9  30Cr3Mo2V和25Cr2MoV钢中的碳化物形貌
Type of trapTrapMaterialEaHeating rate
kJ·mol-1℃·min-1
Reversible hydrogen trapDislocationPure iron26.93
Grain boundaryPure iron17.23
F/Fe3C phase boundaryMedium carbon steel18.42.6
TiC (coherent)Low carbon steel46~591.7
NbC (coherent)Tempered martensite steel281.7
NbC (coherent)C080 low carbon steel39~483.33~20
MicrovoidPure iron35.23
Irreversible hydrogen trapGrain boundaryDeformed iron59.93
Retained austeniteDouble phase (DP) steel554
AlN-64-
NbC (incoherent)C080 low carbon steel63~683.33~20
TiC (incoherent)Medium carbon steel863
MnSLow alloy steel72.33
Fe3CMedium carbon steel844
TiC (incoherent)0.025C-0.09Ti138~1493.33~20
表3  钢中不同氢陷阱的结合能(Ea)[51,54]
图10  A286样品显微组织及A286样品与进口产品在650 ℃持久实验后的性能对比
Marterial codeDescriptionTmax / ℃
1.4534.4Precipitation-hardening stainless steel315
1.4534.5(13-8Mo, 0.04C-13Cr-8Ni-2.2Mo-1Al)
1.4534.6
1.4534.7Precipitation-hardening stainless steel850
1.4534.9(0.05C-18Cr-10Ni-0.4Ti)
1.4545.4Precipitation-hardening stainless steel300
1.4545.5(15-5PH, 0.05C-15Cr-5Ni-4Cu)
1.4548.4Austenitic stainless steel300
1.4548.5(17-4PH, 0.05C-16Cr-4Ni-4Cu)
1.4548.6
1.4939.5Tempered martensitic steel550
1.4939.6(0.10C-12Cr-1.8Mo-2.5Ni-0.3V)
1.4944.4Precipitation-hardening stainless steel725
1.4944.6(A286, 0.06-25Ni-15Cr-2.1Ti-1.2Mo)
1.7734.4Tempered martensitic steel500
1.7734.5(0.15C-1.4Cr-0.90Mo-0.25V)
1.7734.6
1.7784.5Tempered martensitic steel500
1.7784.6(0.4C-5Cr-1.3Mo-0.5V)
2.4631.7Precipitation hardened nickel alloy815
(Nimonic 80A, 0Cr-2.3Ti-1.4Al-0.1C)
2.4668.7Precipitation hardened nickel alloy700
2.4668.9(Inconel 718, 19Cr-18Fe-5Nb-3Mo-0.05C)
表4  航空航天用耐热紧固件用典型材料
CountryCodeCSiMnVNbCrOthers
ChinaMFT80.16~0.26≤0.301.20~1.60≤0.08≤0.10--
MFT90.18~0.26≤0.301.20~1.60≤0.08≤0.10--
MFT100.08~0.140.20~0.351.90~2.30≤0.10≤0.20--
JapanKNCH70.19~0.250.15~0.301.35~1.65----
(KOBELCO)KNCH7s0.19~0.25≤0.101.20~1.50----
KNCH80.27~0.330.15~0.301.35~1.65----
KNCH8s0.27~0.33≤0.101.35~1.65----
KNCH8P0.12~0.18≤0.101.35~1.65AdditionAddition--
KNCH9P0.19~0.25≤0.101.35~1.65Addition-0.20~0.40-
KNCH100.37~0.430.15~0.351.00~1.30Addition---
KNCH12P0.15~0.200.40~0.501.00~1.30Addition-1.20~1.40Ti, B, Mo
表5  我国与日本非调质钢主要成分对比 (mass fraction / %)
图11  关键紧固件强度统计分布情况
图12  ZT35K-M钢在线退火组织
图13  一些氮合金化奥氏体不锈钢固溶后的室温力学性能[64,65,66,67,68,69,70]
图14  冷轧和固溶处理05Cr21Mn16Ni2N钢的工程应力-应变曲线
图15  奥氏体不锈钢耐点蚀当量(PREN)随N含量的变化
图16  不同N含量高氮奥氏体不锈钢和钛合金细胞毒性检验结果
GroupIn general populationIn dermatitis patient
Adult8%~19%12%~25%
Adolescent and child8%~10%5%~30%
表6  人群对Ni过敏的比例统计
TimeTechnical innovation

1940s

1) heat treatment instrumentation: improve temperature controls and recorders

2) neutral atmosphere furnace: eliminate surface decarburization

3) large electric furnace melting: produce larger size billets+billets forging to refine the steel grain and carbide size and reduce the size of material's inclusions and segregates

1950s

1) immersion thermocouples: permit better control of steel melting

2) shoe grinding: improve race surface quality and tolerance

3) vacuum degassing and vacuum melting: alter the type of inclusions and trace element

1960s

1) ultrasonic and eddy current inspection: ensure product quality

2) elastohydrodynamic principles: improve lubrication

3) argon atmosphere: improve cleanliness and macro and micro structure unity

4) controlled fiber and hardiness: improve bearing life

1970svaccum-induction melted+vacuum-arc remelted (VIM+VAR)

1990s

1) powder metallurgy: Pyrowear 675 steel; plasma nitriding: nitrides M50 &M50NiL steel2) pressure electroslag remelting: Cronidur30 steel
表7  航发轴承钢的技术创新[89]
图17  6Cr16MoNiV钢和6Cr16MoVAgRE[93]钢夹杂物EDS
图18  不同高碳马氏体不锈钢的点蚀阻抗谱和腐蚀速率。
图19  6Cr16MoVAgRE钢EPMA分析
图20  6Cr16MoMA马氏体不锈钢SEM像和不同高碳马氏体不锈钢不同奥氏体化温度处理后试样冲击功
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