钢研究总院1209钒在钢中应用进展

钒在钢中应用新进展

,钢铁研究总院

2020年12月10日概况钒微合金化技术钒在钢筋中的应用含钒非调质钢钒在合金钢中应用钒技术推广目录中国含钒钢的生产中国钒的消费：2019年表观消费:6.2万吨金属钒在钢筋中消耗：5.2万吨，>80%特钢中钒消耗：～7600吨V钒钢生产：～1.5亿吨，15%粗钢钒在钢中用途广泛1900年，英国谢菲尔德大学Arnold钢领域，包括了从高速钢到冷作、热作模具钢及耐热钢1910年，福特汽车关键部件1960’s,钒微合金化技术的发展，广泛用于各种结构钢生产，包括：建筑、桥梁、汽车、铁路、船舶、电力、航空、各种军工用钢等。钒在特殊钢中应用工具、模具钢耐热钢、高合金结构钢中国含钒钢标准分布汽车发动机用含钒钢钒钢在国防工业中的应用钒钢在建筑工程中的应用钒钢在石油天然气工业中应用铁路用钢机械工程中的应用钒钢在电力工程中的应用钒钢的冶金学特性（技术优势）良好的工艺性EasytoUseDuringSteelmaking高收得率HighRecoveryInAlloyAdditionsGoodCastability加热过程高溶解度HighSolubilityinReheatOperationsNoAdditionalRollForceRequirements广泛的适应性EffectiveStrengtheningatallCarbonLevels可控的强化效果PredictableStrengtheningoverLargeVAlloyingRange(upto0.15%)钒微合金化的冶金特征V在铁素体中析出0.005%N0.025%N氮对V)

析出的影响钒的析出强化作用5010015020025030035000.050.10.150.20.250.3wt%CRp,MPa0.12V-0.023N0.12V-0.013N0.06V-0.025N0.12V-0.005NIsothermaltransformation650°C/500s(b)5010015020025030035000.0050.010.0150.020.0250.03wt%NRp,MPa0.22C-0.12V0.15C-0.12V0.10C-0.12V0.04C-0.12VIsothermalTransformation

650°C/500s(a)V-N复合微合金化技术利用廉价的氮，提高V析出效率，细化钢的晶粒尺寸，实现低成本、高性能、高效率钒氮微合金化理论体系N在钒钢中的作用析出理论模型V-N钢析出强化定量关系钒氮钢晶粒细化技术钒氮钢生产工艺技术低成本钒氮钢品种技术-PCRP工艺技术系列V-N钢品种钒氮微合金化技术创新与应用奥氏体中析出控制及晶内铁素体形核技术V-N强化作用－高效率、低成本、可预测△YS/0.01%V低氮钢5-10MPa高氮钢25MPaV-N强化定量关系曲线含钒钢晶粒细化新技术途径V-N合金设计

奥氏体中析出VN颗粒

晶内铁素体形核

促进相变

细化晶粒V-N钢晶粒细化原理示意图1200℃870℃t,(s)T钒氮钢中晶内铁素体(IGF)形核steelCSiMnVN(ppm)V-N0.110.411.320.11140V0.090.421.300.1036C-Mn0.100.411.40―32600-700℃钒氮钢晶粒细化效果FerriteGrainRefinementSteel

γ,μmα,μmV-N

37.96.1V46.811.2C-Mn51.412.52026/1/3VN在MnS夹杂上析出0.11%C-0.41%Si-1.32%Mn-0.11%V-140ppm[N],finishingrolledat870℃,thenquenching.sampleetchedbySPEEDmethod(SelectivePotentiostaticEtchingbyElectrolyticDissolution)MnSVNMnSVN2026/1/3奥氏体中析出颗粒MnSV)V)HShapeBeam:30*30*305mm0.15%C-1.5%Mn-0.3%Si-0.12%V-0.02%NParticlesize:60-120nmV)钒钢和钒氮钢中铁素体形核

V-Nsteel,650℃,2sVsteel,650℃,2s钒钢和钒氮钢组织演变

VsteelV-Nsteel650℃2s4s8s12s0.10%C-0.12%V-0.025%N(with0.009%S)晶内铁素体形核“碳氮化钒控制析出轧制工艺技术”

(-PCRP)MnSVNV)Particlesize:60-120nm奥氏体析出控制技术晶内铁素体形核控制技术“-PCRP”技术为常规热轧工艺条件下生产低成本、高性能钒氮钢奠定了工艺基础概况钒微合金化技术钒在钢筋中的应用含钒非调质钢钒在合金钢中应用钒技术推广目录中国钢筋产量最大钒应用--中国钢筋产量及品种结构钒在钢筋中的消耗中国钢筋产量Totalrebarproduction170.89MTinJan.-Aug.2020,Y-O-Y5.25%钒在钢某省市场潜力与风险高强度钢筋的生产技术组织强化PMicrostructureStrengthening:

中碳钢，焊接性差mediumCcontent（0.30-0.40%C）,lowweldability冷加工ColdForming:

高成本，低塑性

highcost,lowductility（El<2%）穿水TEMPORE（Q&T）细晶粒RefineFerriteGrainSize微合金化Microalloying：V/V-N、Nb、Ti中国钢筋标准StandardNo.GradeMechanicalPropertiesV%(V-N)GB1499.1-2017热轧光园钢筋(Hot-rolledPlainBars)HPB235235MPaHPB300300MPaGB1499.2-2018热轧带肋钢筋(Hot-rolledRibbedbars)HRB335335MPaHRB400/EReL≥400MPa;A≥16%0.025-0.05%HRB500/EReL≥500MPa;A≥15%0.06-0.09%HRB600ReL≥600MPa;A≥14%0.10-0.15%GB13014-2013穿水钢筋(QuenchingandSelf-TemperingRibbedBars)RRB400ReL≥400MPa;A≥14%RRB500ReL≥500MPa;A≥13%0.05-0.07%微合金化高强度钢筋

Nb、V、Ti

MicroalloyedRebars钢种CSiMnVNbTi20MnSiV0.17-0.250.20-0.801.20-1.600.04-0.1220MnSiNb0.17-0.250.40-0.801.20-1.600.02-0.0420MnTi0.17-0.250.17-0.371.20-1.600.02-0.05中国曾经研究开发Si-V,Si-Ti,Si-Nb,Mn-Si-V,Mn-Si-Nb,Mn-Ti等系列20多个高强度钢筋品种。过去列入国家标准的III级钢筋：Morethan20HSrebarproductsdesignedwithdifferentalloyingsystemduring1970’s-1990’sinChina:Si-V,Si-Ti,Si-Nb,Mn-Si-V,Mn-Si-Nb,Mn-Ti,etc.Threemicroalloyedgrade3rebarshadbeenlistedinoldversionNationalStandard(GB1499.2-1984)含Nb三级钢筋SteelCSiMnVNbRm/MPaRel/MPaA/%Agt/%V-steel0.230.441.380.029-6204432814Nb-steel0.230.541.38-0.03262445028.514.8V-steel7.7μmNb-steel6.7μmAC含Nb钢筋的技术问题CSiMnVNbPSNbSteel0.270.131.43/0.040.040.03VSteel0.290.101.410.02/0.040.03microstucture：5%WidmannstattenstructureinNbrebars,hardnessHV239,higherthanthehardnessofFerrite(HV198)Nb

rebar:noyeildpointTi微合金化钢筋系列含Ti钢均已淘汰（Ti-containingHSLASteels：15MnTi、20MnTi、14MnVTi、10Ti、06Ti）主要问题Problem:性能波动大StabilityintheProductionofTimicroalloyingsteels连铸困难Con-Castingforbillet细晶粒钢筋PlainCGrade3Rebars20MnSiGrade4RebarsHRBF400/400E,500/500ELowRatioofTS/YS,probleminAnti-SeismicPerformanceandweldabilityV/V-N微合金化钢筋含钒钢的优点高溶解度，加热溶解良好铸造性能，变形抗力小，制生产钒的强化效果可预测钢筋生产：孔型轧制，不控轧V在钢筋中强化系数RegressionequationonVstrengtheningeffect:V-Steel：σs＝σs(20MnSi)＋1056×[V]V-NSteel：σs＝σs(20MnSi)＋1994×[V]氮在钒钢中的作用机理

氮的强化作用StengtheningEffectofN：△YS10MPa/10ppm[N]氮对钢中钒分布的影响EffectofNonVdistributioninSteelV

Steel：56%Vinsolution，35%VinprecipitationV-N

Steel：22%Vinsolution,

70%Vinprecipitation氮对析出相的影响EffectofNonparticlessizeSignificantlyincreasethevolumeoffineparticleswiththesizelessthan10nmV-N微合金化高强度钢筋技术经济性Cost-Effective、HighPerformanceHighStrengthwithGoodElGoodAnti-SeismicPerformance△σs<65MPaTS/YS>1.40，Agt>14%GoodWeldabilityGradeAlloyCSiMnP,SVNGauge,mmHRB400V-N0.20-0.240.45-0.601.25-1.45<0.0350.025-0.030.008-0.012Φ6-Φ160.03-0.04Φ16-Φ40V-Fe0.20-0.240.45-0.601.25-1.45<0.0350.05-0.070.003-0.006Φ10-Φ160.07-0.09Φ16-Φ40HRB500V-N0.20-0.240.45-0.601.40-1.55<0.0350.05~0.070.010-0.015Φ16-Φ320.07-0.090.012-0.018Φ32-Φ40V-Fe0.20-0.240.45-0.601.40-1.55<0.0350.07~0.120.003-0.006Φ16-Φ322019年7月-2020年5月,从某省市市63家钢筋企业取样:25家有不合格产品,~40%HRB400Rebar(Grade3):钢筋尺寸Φ16/Φ20/Φ25VSteel（V＞0.02wt%）：50%Low-VSteel：25%20MnSisteel（V＜0.01wt%）:25%III级钢筋的替代工艺NbMicroalloyingLowV+AcceleratedCoolingSi-Mn+TMCPHRB400(III级)钢筋某省市场调查结果HRB400/400ECSiMnVNstandard≤0.25≤0.80≤0.1.6

--

VSteel0.20~0.270.26~0.621.11~1.520.021~0.0710.006~0.015Low-VSteel0.22~0.260.26~0.701.05~1.50.011~0.020.005~0.01420MnSisteel0.18~0.270.21~0.700.48~1.5＜0.010.002~0.013HRB400钢筋金相组织判断困难HRB400钢筋金相组织判断困难0.23C-0.34Si-1.51Mn-0.016V(Φ25)(不闭合的硬化层)HRB400钢筋金相组织判断困难(a)B+F+P(a1)B+F+P(a2)B+F+P0.23C-0.51Si-1.48Mn（Φ10）HRB400(III级)钢筋与钒含量关系平均钒含量：0.03%VHRB500高强度钢筋No.CSiMnPSVNbNV/N10.240.561.540.0050.0040.047-0.00657.2320.240.581.580.0050.0040.070-0.01007.0030.230.561.530.0050.0050.090-0.01207.5040.230.571.560.0070.0060.112-0.01408.0050.240.581.570.0060.0040.0920.0310.0110V-N钢V-Nb-N钢规格成分RmRelR▫m/R▫eLAgt，%Φ320.09V7205081.4211.060.092V0.03Nb7325211.4012.48Φ250.09V7045081.3910.980.092V0.03Nb7375161.4210.41HRB500钢筋应用性能评估钢种CSiMnPSVNbNV-N0.230.441.390.0250.0200.092/0.018V-N-Nb0.230.311.310.0330.0230.1210.0110.015钢种Rm/MPaRel/MPaR▫m/R▫eLA/%Agt/%V-N7055451.291813V-N-Nb7005421.2923.511.5钢种单向拉伸高应力反复拉伸大变形反复拉压判定指标μ,%Ⅰ

Ⅱ

Ⅲ

V-N0.0350.0460.0650.12112.96ⅠV-N-Nb0.1080.3390.4860.52813.76Ⅲ600MPa级V-N高强度钢筋编号规格/mm化学成分CSiMnSPVCrN1#180.230.441.460.0170.0240.104≥0.250.02072#220.250.471.480.0140.0200.108≥0.250.0211RebarSizeReL/MPaRm/MPaR°m/R°eLR°eL/ReLAgt/%A/%18mm6277921.261.0512.021.522mm6368021.261.0611.520.5技术问题:Technicalchallengeslowyieldtensileratiofor10~16mmsmallsizerebarsLow600MParebarproduction:＜1%标准规范CodefordesignofconcretestructureProductionstandard:HRB600,noHRB600EIndustrystandard:takeeffectinMay5,2020Localstandards:Shandong,Shanhai,Jiangsu,Hubei,Hebei推动600MPa钢筋升级SizeReL/MPaRm/MPaR°m/R°eLR°eL/ReLA%10mm6988531.221.161912mm6658101.221.1117概况钒微合金化技术钒在钢筋中的应用含钒非调质钢钒在合金钢中应用钒技术推广目录非调质钢的优点、分类非调质钢按用途分热锻用非调质钢直接切削用非调质钢冷作强化非调质钢按显微组织分铁素体+珠光体型贝氏体型型SG4102SG4201SG4203SG4204汽车用非调质钢汽车发动机及传动系统非调质钢的国内外应用非调质钢的国内外应用注塑机上的应用棒材直径：φ90-φ120,；长度为2.5m-4.5m顶出油缸拉杆非调质钢经济效益示意图显示调质钢和非调质钢的生产过程

SchematicShowingThermalHistoryQTvMA调质钢非调质钢锻造锻造回火应力消除矫直控制冷却时间淬火非调质钢经济效益生产成本比较

ThroughProcessCostparisons机械加工性能硬度

Hardness(BHN)=245在相同硬度等级时，钒微合金非调质钢的机械加工性能优于QT钢参考文献：EbrahimiA.andMoshksarM.M.,“EvaluationofMachinabilityinTurningofMicroalloyedandQuenched-TemperedSteels:ToolWear,StatisticalAnalysis,ChipMorphology”,JournalofMaterialsProcessingTechnology,Vol.209,2009,pp.910-921.含V非调质钢1980’s,VmicroalloyedForgingSteelsYF35V，YF40V，YF45V，YF35MnV，YF40MnV，YF45MnV，F45V，F35MnVN，F40MnV1990’s,N80(33Mn2V)SeamlessTubeforoilwellN含量的影响（38MnVS6）SurfaceD/4Centre0.0036%N

0.0098N

0.0190%N

Process-I0.0036%N0.0098%N0.0260N0.0190%NProcess-ⅡReheatingtemperature1220℃×1h

Startforgingtemperature1150℃

DeformationΦ90mm→Φ42mm→Φ36mm

Finishforgingtemperature915℃CoolingrateAir-cooled

IncreasingnitrogencontentpromotesgrainboundaryferriteandintragranularferriteN含量的影响（38MnVS6）贝氏体含钒高强度曲轴用钢微合金曲轴钢的演变从铁素体-珠光体型钢到新的高强度贝氏体型钢C(%)Si(%)Mn(%)V(%)N(ppm)YS(MPa)UTS(MPa)FL(%)38MnSiV6

Conv.F-P0.380.601.400.1015055083010035MnV737MnCrV5Bainitic0.350.370.201.801.300.100.088059088011025MnCrSiVB6NewBainitic0.250.751.500.19150690103014042CrMo4Q+T900100011030MnCrSiMoVB5(MetascoD1200®)-贝氏体级钢

30MnCrSiMoVB5(MetascoD1200®)–NewBainiticGradeCSiMnSPNiCrMoCuAlVTiNb0.250.701.001.000.100.500.0150.10--0.301.001.400.100.0150.251.400.301.200.0300.250.0500.030优点：Advantages:热锻造后就可获得所需的机械性能（不需要后部热处理）Mechanicalpropertiesobtaineddirectlyinthehotforgingprocess(nosubsequentheattreatmentneeded.)优势：Benefits:提高生产力

Productivitygains简化生产工艺

Simplermanufacturingprocesses

稳定的机械性能

Regularityofmechanicalproperties应用：Applications:曲轴，喷油器，悬架臂/三角形悬架，轮轴Crankshaft,injectionrail,suspensionarm/triangle,wheelshaftAetal贝氏体（MetascoD1200®）钢化学成分，wt％ChemicalpositionforAetal’sbainiticgradeMetascoD1200®,wt%高强度断裂分离型连杆勒梅特等(2006)介绍了连杆钢发展方面的信息，特别着重于具有改善的耐疲劳强度和车削加工性能的断裂分离型钢C(%)Si(%)Mn(%)S(%)P(%)V(%)YS(MPa)TS(MPa)YS/TSFL(MPa)KCV(J/cm2)C70S60.700.600.550.07N/S05459500.583105.550MnS6+P0.500.651.60>0.150.0705759540.60330438MnSiVS5+P0.380.651.200.0750.0850.0856709330.723505.436MnSiV4*0.380.651.000.075N/S0.3075010100.744297*EuropeanpatentEP1051531B1概况钒微合金化技术钒在钢筋中的应用含钒非调质钢钒在合金钢中应用钒技术推广目录高铁车轴用钢韧化技术新型（微）合金体系的韧脆转变低到-95℃以下，显著低于EA4T

-35℃水平。大颗粒夹杂物尺寸:13.8μm大颗粒夹杂物尺寸:18.9μm107转疲劳强度比EA4T车轴钢提高57MPa以上一次淬火两次淬火在欧洲EA4T高速车轴合金体系(25CrMo)基础上，开发新型Ni、V、Nb（微）合金化体系及其两次淬火细晶热处理工艺技术。690MPa819MPa796MPa856MPa抗回火软化

/二次硬化ElementRetardationintemperingper1%additionC-40Cr0Co8Mn8Ni8W10Mo17Si20V30含钒合金结构钢钢种V%SteelGradeV%20MnV0.07-0.1215MnVB0.07-0.1220SiMn2V0.05-0.1220MnVB0.07-0.1225SiMn2V0.05-0.1240MnVB0.07-0.1237SiMn2V0.05-0.1220CrV0.10-0.2012CrMoV0.15-0.3040CrV0.10-0.2035CrMoV0.15-0.3050CrV0.10-0.2012Cr1MoV0.15-0.3055SiMnVB0.08-0.1525Cr2MoV0.15-0.3060Si2CrVA0.10-0.2025Cr2Mo1VA0.30-0.5030W4Cr2VA0.50-0.8020Cr3MoWVA0.70-0.90抗延迟断裂钢CSiMnSPCrMoVNb0.430.140.300.0010.0031.100.520.330.04抗延迟断裂钢含钒高速钢/工模具钢SteelGradeV%SteelGrade