CN101713046B - 纳米析出相强化及控制的超细晶粒马氏体钢的制备方法 - Google Patents
纳米析出相强化及控制的超细晶粒马氏体钢的制备方法 Download PDFInfo
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- CN101713046B CN101713046B CN 200910242371 CN200910242371A CN101713046B CN 101713046 B CN101713046 B CN 101713046B CN 200910242371 CN200910242371 CN 200910242371 CN 200910242371 A CN200910242371 A CN 200910242371A CN 101713046 B CN101713046 B CN 101713046B
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- Prior art keywords
- rolling
- steel
- temperature
- hot
- insulation
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 134
- 239000010959 steel Substances 0.000 title claims abstract description 134
- 229910000734 martensite Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation methods Methods 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000005096 rolling process Methods 0.000 claims description 62
- 229910034327 TiC Inorganic materials 0.000 claims description 30
- 238000000034 methods Methods 0.000 claims description 27
- 238000009413 insulation Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000005098 hot rolling Methods 0.000 claims description 13
- 239000006104 solid solutions Substances 0.000 claims description 13
- 238000005097 cold rolling Methods 0.000 claims description 12
- 238000007669 thermal treatment Methods 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- 239000003570 air Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
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- 239000000126 substances Substances 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000010960 cold rolled steel Substances 0.000 claims description 5
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- 230000000694 effects Effects 0.000 abstract description 26
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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- 238000006011 modification reactions Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound 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[Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
一种纳米析出相强化及控制的超细晶粒马氏体钢的制备方法，属于马氏体钢制造技术领域。通过纳米尺寸的析出相产生强化和细化的效应，获得抗拉强度范围为1000-2200MPa的具有优异的冲击韧性和焊接性能的超细晶粒马氏体组织为主要组织的合金钢。实现高强度和超高强度马氏体钢的高韧性、优良的氢滞延迟断裂性能和工艺性能，并生产成本低。
Description
纳米析出相强化及控制的超细晶粒马氏体钢的制备方法
技术领域
[0001] 本发明属于马氏体钢制造技术领域，特别是提供了一种纳米析出相强化及控制的超细晶粒马氏体钢的制备方法。通过合金成分设计+控制轧制和冷却及热处理工艺共同控制技术实现。
背景技术
[0002] 获得高强度高韧性，以及低成本化和具有优良的工艺性能的马氏体钢是钢铁工作者持之以恒的追求目标。除珠光体组织的冷拔钢丝外，奥氏体、铁素体和珠光体组织的钢强度通常在IOOOMPa以下。传统IOOOMPa级以上的高强度和超高强度马氏体钢主要分为三类，即主要依靠碳强化的低合金马氏体钢；通过合金碳化物析出强化的中高合金的二次硬化钢，以及通过合金相析出的高合金系马氏体时效钢。后两者通常含有Mo、Cr、V或Ni和Co等贵金属元素，成本较高，一般在关键部件上使用。由于，低合金马氏体钢经济性良好，得到广泛使用。如前所述，传统低合金高强度和超高强度马氏体钢，其强化依靠碳的固溶强化和铁基碳化物的析出强化。钢的强度与碳含量呈线性关系，获得强化的同时将对钢的韧性和焊接性能产生较大危害。另外，高强度和超高强度马氏体钢的韧性和工艺性能提高是材料研究者追求的目标。
[0003] 本发明通过合理的成分设计，结合合理轧制工艺和冷却工艺获得纳米级的TiC等细小弥散析出相，利用合理的热处理工艺使纳米析出相在钢板的重新奥氏体过程中钉轧新形核的奥氏体晶粒，并阻止其长大。通过该技术可获得2-10 μ m的原奥氏晶粒，大幅度提高钢的冲击韧性。纳米析出相产生了析出强化，将钢的强度提高100-300MPa。晶粒细化不仅产生了韧化作用，同时产生了细晶强化，使钢的强度提高50-100MPa。通过上述两种强化方式可有效降低钢中的碳含量，进一步提高钢的工艺性能。另外，钢中析出的细小的TiC相，在焊接过程中阻止了晶粒的·长大，可进一步提高钢的焊接性能。TiC作为氢陷阱可进一步提高钢的氢滞延迟断裂性能。
发明内容
[0004] 本发明目的在于提供一种纳米析出相强化及控制的超细晶粒马氏体钢的制备方法，通过纳米尺寸的析出相产生强化和细化的效应，获得抗拉强度范围为1000-2200MPa的具有优异的冲击韧性和焊接性能的超细晶粒马氏体组织为主要组织的合金钢。实现高强度和超高强度马氏体钢的高韧性、优良的氢滞延迟断裂性能和工艺性能，并生产成本低。
[0005] 本发明基于合理化学成分设计和轧制、冷却及热处理工艺相结合的方法。关键在于控制小于20nm的TiC等的析出相的数量及析出时间。在钢板奥氏体过程中，采用合理的奥氏体化温度和时间，防止TiC长大，利于TiC的钉轧作用获得细小晶粒尺寸。
[0006] 众所周知，Ti元素在现有钢板轧制工艺有四种析出形态，即液态和高温区析出的TiN，其颗粒尺寸较大，对强化和细化原奥氏体晶粒作用不大，若含量较高还将进一步恶化钢的性能，故需控制[N]的含量。在板坯加热的高温区还形成粗大的Ti4C2S2，其对性能有害无益。轧制过程中将有部分Ti析出形成TiC，此时TiC的尺寸范围在20-50nm，对钢材性能的改善作用有限。在700°C以下析出的TiC将可获得20nm以下的析出相尺寸，对钢的强度提高和获得细小尺寸原奥氏体晶粒作用显著，但需要有一定的保温时间。另外，析出的TiC还可能在重新钢材奥氏体过程中长大，影响其作用效果。
[0007] 其针对钢种为Ti含量为，满足钢板的淬透性，从经济性角度出发，本发明以C-Mn-T1-B钢为基础钢。但可以通过其它合金元素的添加获得相同性能或对性能有所提高。钢的化学成分、合金元素配分工艺和生产工艺等是本发明的关键。
[0008] 本发明的制造工艺及条件为:
[0009] 试验过程模拟钢板的热轧、热连轧和冷连轧工艺，以及淬火热处理。
[0010] 热连轧的流程为:冶炼+铸造+热连轧+卷取及冷却(纳米TiC析出)+淬火(获得马氏体+控制TiC析出相不长大)
[0011] 冷连轧的流程为:冶炼+铸造+热轧轧+卷取冷却(保留固溶Ti，TiC不析出)+酸洗+冷轧+退火(纳米TiC析出)+淬火(获得马氏体+控制TiC析出相不长大)
[0012] 热轧的流程:冶炼+铸造+热轧+冷却(保留固溶Ti，TiC不析出)+退火(纳米TiC析出)+淬火(获得马氏体+控制TiC析出相不长大)
[0013] (I)钢的冶炼与凝固:适用于转炉、电炉和感应炉冶炼，采用连铸生产铸坯或模铸
生产铸锭。
[0014] (2)铸坯或铸锭的轧制:根据最终产品的需求不同，主要涉及到三种轧制工艺，即热连轧、热连轧+冷轧和中厚板热轧；本发明以板材生产为代表进行说明，对于棒、线和型材的生产与上述热连轧工艺相近，在此不做详述。
[0015] 热连轧板卷:将连铸坯或铸坯加热到1150_1350°C，保温l_5h，以保证80%以上的Ti实现固溶。随后通过5-15道次粗轧，将上述板坯轧制到30-60mm厚，并1000-1100°C以上完成粗轧，以减少较大尺寸的TiC在轧制过程中析出的数量。随后，钢板进行7道次热连车L，终轧温度为700°C _950°C。轧后层流冷却，在700-600°C之间完成卷取温度，以保证小于20nm的TiC在卷取的缓冷过程中析出。
[0016] 热连轧+冷连轧:冷连轧需要热连轧板提供坯料，由于国内冷连轧机组的轧制能力要求，提供给冷轧的热连轧板的抗拉强度不得超过900MPa，故其生产工艺存在新的特点。
[0017] 将连铸坯或铸坯加热到1150_1350°C，保温l_5h，以保证大部分Ti元素实现固溶。随后通过5-15道次粗轧，将上述板坯轧制到30-60mm厚，并1000-1100°C以上完成粗轧，以减少较大尺寸的TiC在轧制过程中析出的数`量。随后，钢板进行7道次热连轧，终轧温度为T«sa-9500C (注=Twss为奥氏体不发生再结晶的最高温度)，轧后层次冷却，550°C以下完成卷取温度。连轧工艺需保证使钢板的抗拉强度低于900MPa，以便于冷轧。故如上所述提高热连轧的终轧温度，以及降低热轧卷取温度，阻止钢中固溶的Ti析出，避免TiC析出带来的钢板强度提高。随后，将上述热轧钢卷进行酸洗处理后，在冷轧连轧机组进行轧制，得到冷轧钢板。再将冷轧钢板放入罩式退火炉进行550-650°C保温0.3-4h退火处理。其目的有二:一、消除冷轧内应力和改善组织结构。二、使钢中固溶的Ti形成3-20nm的TiC析出相。
[0018] 中厚板热轧:将连铸坯或铸坯加热到1150_1350°C，保温l_5h，以保证80%以上的Ti元素实现固溶；随后通过5-15道次粗轧，轧制到设定厚度规格；终轧温度控制在750-950°C;若将终轧温度控制在Twss以下50-150°C之间，并且在Twss以下温度的轧制变形量在10-25%，可进一步提高钢的性能。轧后钢板以5°C /s〜100°C /s的冷却至500°C以下，随后空冷至室温；轧后的钢板再进行退火炉550-650°C保温l_4h退火处理。
[0019] (3)钢板或零件热处理工艺:
[0020] TiC析出相的长大和奥氏体晶粒尺寸与加热温度和保温时间有较大关系。
[0021 ] 小于、等于8mm的薄规格的钢板和热成形零件:加热温度850-980 °C，保温2-10min。当温度小于880°C时，保温时间对晶粒长大作用不明显。当温度达到930°C以上时，要尽可能减少保温度时间，通常不超过5min。然后进行淬火处理。
[0022] 对于大于8mm厚的钢板:加热温度为850_930°C，保温5_30min，然后进行淬火处理。
[0023] 本发明所述钢的主要化学成分范围为:C:0.08-0.45wt%、P彡0.020wt%,S^0.02wt %, Ti:0.06-0.25wt %, [N]彡0.008wt %，在此基础上可以另加以下一种或多种元素，主要目的是保证钢的淬透性要求:Mn:0.3-2.8wt%, B:0.0005-0.005wt%, Ni:0.1-3.0wt%、Cr:0.2-3.0wt%、Mo:0.1-0.8wt%,S1:0.3-2.3wt%，余量为 Fe 和不可避免的杂质元素。在上述成分基础上还可以添加以下一种或多种元素，以及进一步改善性能:Nb:0.02-0.1Owt%、[N]:0.002-0.25wt%,V:0.02-0.25wt%,Al:0.015-0.060wt%、RE(稀土 ):0.002-0.005wt%,Ca:0.005-0.03wt%。作为经济性能的考虑采用 C-Mn-T1-B 系最为合理。
[0024] 本发明各元素的作用及配比依据如下:
[0025] C:作为主要的间隙固溶强化元素，对淬火马氏体钢的强度起决定作用。另外，碳与Ti结合形成了 TiC。
[0026] Mn:Mn是扩大奥氏体区元素，具有提高钢的淬透性的作用。但过高的Mn含量将降低钢的塑性和韧性，以及焊接性能，Mn含量应控制在0.8-2.3%范围内。
[0027] Ti:Ti是一种强碳氮化物形成元素，可以形成细小弥散分布的碳或氮化物，起到细化奥氏体晶粒的作用。IOnm以下的TiC析出相还可以起到明显的析出强化作用。
[0028] P:在钢液凝固时形成微观偏析，随后在奥氏体后温度加热时偏聚到晶界，使钢的脆性显著增大，从而使氢致延迟断裂敏感性升高。因此，P含量应控制在0.020%以下。
[0029] S:不可避免的不纯物，形成MnS夹杂物和在晶界偏析会恶化钢的韧性，从而降低钢的韧塑性。因此，S含量应控制在0.015%以下。
[0030] B:能够显著提高钢的淬透性和净化晶界。含量低于0.0005%时以上作用不明显，高于0.0050%时作用增加不明显。因此，如添加，B含量应控制在0.0005-0.0050«〖％范围内。
[0031] [N]:与Ti等结合形成化合物，但Ti析出尺寸较大，从而恶化钢的性能。[N]含量应控制在小于0.008wt %范围内。
[0032] Ni =Ni是奥氏体化稳定元素，可以有效降低Ms点，同时可以提高材料塑性和低温韧性，但Ni价格高，其含量应控制在4.0%以下。
[0033] Mo:有效地提高钢的淬透性，还能够强化晶界。含量小于0.20%难以起到上述作用，但含量超过0.80 %则上述作用效果饱和，且成本较高，应控制在0.2-0.8wt %范围内。
[0034] Cr:能够有效提高钢的淬透性和防止高温表面氧化，Cr含量应控制在
0.2-3.0wt % ο[0035] S1:抑制碳化物析出，提高C的配分效果。Si含量在0.30%以下时，不能起到以上作用；Si含量高于2.30%时，以上作用饱和，并可能影响韧性。因此，Si含量应控制在0.50-2.30界七％范围内。
[0036] Nb:形成碳氮化物能够细化晶粒，同时固溶铌可以提高未再结晶区温度，易于通过控制轧制实现奥氏体的扁平化。低于0.02%时上述作用不明显，高于0.10%时作用增加不明显，达到饱和。Nb含量应控制在0.02-0.1Owt%范围内。
[0037] V:以细小的碳氮化物形成存在时，能够细化晶粒；以固溶形式存在时，能够提高淬透性，从而提高强度。适量加入可以改善性能，高于0.15%时易形成大颗粒碳氮化物，反而使韧塑性下降。另外，V还具有析出强化作用，可进一步提高钢的强度。V含量应控制在
0.02-0.50界七％范围内。
[0038] Al:能有效脱氧和细化晶粒，提高韧性。含量低于0.015%时以上作用不明显，高于0.060%时作用增加不明显，且可能形成粗大的氧化铝夹杂物，恶化钢的韧性。因此，Al含量应控制在0.015-0.060wt %范围内。
[0039] RE:起到脱氧和脱硫作用，并且使夹杂物变性，从而能够提高钢的韧塑性。低于
0.001%时以上作用不明显，高于0.050%时作用增加不明显，达到饱和。因此，如添加，RE含量应控制在0.001-0.050wt %范围内。
[0040] Ca:脱氧和脱硫，并且使夹杂物变形，从而能够提高钢的韧塑性。Ca的添加量与钢水中的S含量为3: I。因此，Ca含量应控制在0.005-0.030«七％范围内。
附图说明·
[0041 ] 图1为本发明钢4RLZ的晶粒尺寸图。
[0042] 图2为本发明钢ILLZ的晶粒尺寸图。
具体实施方式
[0043] 实施例:
[0044] 钢的冶炼:
[0045] 本发明钢由试验室真空感应炉冶炼，浇铸锭型为150kg圆锭。共冶炼9炉钢，采用150kg锭型，化学成分见表I。选择采用同样冶炼工艺生产的不同碳含量的MnB系列的钢进行对比。对比钢为:采用试验室模拟常规生产工艺，获得12mm厚的热轧板，成分见表I。
[0046] 表I发明钢的化学成分
[0047]
[0048] 钢的锻造
[0049] 1-9#钢的钢锭经过1100-1250°C加热，保温2_5h，进行锻造开坯。锻造温度范围为800-1150°C，锻后空冷。最终锻造成尺寸 100 X 150mmX 200mm 和 30mmX IOOmmX 150mm 的两种坯料坯料，前者用于模拟热轧板工艺，后者用于模拟热连轧和冷连轧工艺。
[0050] 钢的轧制
[0051] •模拟热连轧
[0052]将 3#-7# 钢的 30mmX IOOmmX 150mm 的锻造坯料经 1150_1350°C加热，保温 2_5h后，由试验热轧机通过7道次轧制，终轧温度为700°C -950°C。平均分配道次压下量，为保证板形，最后一道次压下量为15%，轧后最终钢板成品厚度为3mm。轧制过程模拟热连轧工业生产过程。轧制后钢板空冷到550-650°C时，立即放入550-650°C的箱式加热炉中，钢板在炉内以20-30°C /h的冷却速度，冷却到400°C以下，出炉空冷。本过程主要模拟热连轧轧后冷却和模拟卷取和热轧钢卷的冷却过程。具体工艺参数见表2。
[0053] 表2钢的热连轧工艺
[0054]
[0055] •模拟冷连轧
[0056]将 l#-4# 钢的 30mmX IOOmmX 150mm 的锻造坯料经 1150_1350°C加热，保温 2_5h后，由试验热轧机通过7道次轧制，终轧温度为TffgS-95(TC。平均分配道次压下量，为保证板形，最后一道次压下量为15%，轧后最终钢板成品厚度为3mm。轧制过程模拟热连轧工业生产过程。轧制后钢板空冷到550°C时，立即放入550°C以下的箱式加热炉中，钢板在炉内以20-30°C /h的冷却速度，冷却到400°C以下，出炉空冷。本过程主要模拟热连轧轧后冷却和模拟卷取和热轧钢卷的冷却过程。将上述热轧钢板进行酸洗处理。，由3mm经5道次冷轧到1.5mm厚，平均分配各道次形变量。再将冷轧钢板放入箱式加热火炉进行550-650°C保温0.3-4h退火处理。具体工艺参数见表3。
[0057] 表3钢的冷连轧工艺(含其热连轧准备)
[0058]
[0059] •模拟热轧工艺
[0060]将 3#-9# 钢的 IOOmmX 150mmX 200mm 的锻造坯料加热到 1150_1350°C，保温 2_5h后，由试验热轧机通过6道次轧制，终轧温度控制在950°C以下。平均分配道次压下量，为保证板形，最后一道次压下量为15%，轧后最终钢板成品厚度为12mm。轧后钢板快速冷却至500°C以下，随后空冷至室温。轧后的钢板再进行退火炉550-650°C保温l_4h退火处理。具体工艺见表4。
[0061] 表4钢的热轧工艺
[0062]
[0063] 钢的热处理工艺:
[0064].3mm和1.5mm钢板的热处理工艺
[0065] 加热温度850-980°C，保温2_10min。然后进行油冷淬火处理，或低温回火处理，详见表5和表6。
[0066] 表5 3mm模拟热连乳钢板的热处理工艺
[0067]
[0068] 表6 1.5mm模拟冷连乳钢板的热处理工艺
[0069]
[0070].12mm钢板的热处理工艺
[0071] 加热温度为850-930°C，由于钢板厚度为12mm，故保温10_20min，随后进行淬火处理或低温回火处理。详见表7。
[0072] 表7 12mm模拟热乳钢板的热处理工艺
[0073]
[0074] •对比钢的热处理
[0075] 所有对比钢采用950°C保温lOmin，油冷，12-15#钢还进行200°C保温120min回火处理，其余不回火。
[0076] 钢的力学性能
[0077] 钢的力学性能对比见表7。从数据表征可以看出本发明钢在碳含量相当的情况下，其强度可提高200MPa以上，冲击韧性可提高一倍以上。
[0078] 表7力学性能对比
[0079]
Claims (2)
1.一种纳米析出相强化及控制的超细晶粒马氏体钢的制备方法，其特征在于，制造工艺及条件为: (1)钢的冶炼与凝固:适用于转炉、电炉或感应炉冶炼，采用连铸生产铸坯或模铸生产铸锭； (2)铸坯或铸锭的轧制:采用热连轧、热连轧+冷轧或中厚板热轧； 热连轧板卷:将连铸坯或铸坯加热到1150-1350°C，保温l_5h，以保证80% Ti实现固溶；随后通过5-15道次粗轧，将上述板坯轧制到30-60mm厚，并1000-1100°C完成粗轧，以减少较大尺寸的TiC在轧制过程中析出的数量；随后，钢板进行7道次热连轧，终轧温度为.7000C -9500C ;轧后层流冷却，在700-600°C之间完成卷取温度，以保证小于20nm的TiC在卷取的缓冷过程中析出； 热连轧+冷轧:将连铸坯或铸坯加热到1150-1350°C，保温l_5h，以保证大部分Ti元素实现固溶。随后通过5-15道次粗轧，将上述板坯轧制到30-60mm厚，并1000-1100°C以上完成粗轧，以减少较大尺寸的TiC在轧制过程中析出的数量；随后，钢板进行7道次热连轧，终轧温度为TffgS-950°C，轧后层流冷却，550°C以下完成卷取温度；连轧工艺需保证使钢板的抗拉强度低于800MPa，以便于冷轧；随后，将上述热轧钢卷进行酸洗处理后，在冷轧连轧机组进行轧制，得到冷轧钢板；再将冷轧钢板放入罩式退火炉进行550-650°C保温0.3-4h退火处理；消除冷轧内应力和改善组织结构，使钢中固溶的Ti形成3-20nm的TiC析出相； 中厚板热轧:将连铸坯或铸坯加热到1150-1350°C，保温l_5h，以保证80%以上Ti元素实现固溶；随后通过5-15道次粗轧，轧制到设定厚度规格；终轧温度控制在750-950°C ；若将终轧温度控制在Tffss以下50-150°C之间，并且在Tffss以下温度的轧制变形量.10-25%，可进一步提高钢的性能；轧后钢板5°C /s〜100°C /s的冷却至500°C以下，随后空冷至室温；轧后的钢板再进行退火炉550-650°C保温l_4h退火处理； (3)钢板或零件热处理工艺: 小于、等于8mm的薄规格的钢板和热成形零件:加热温度850-980°C,保温2_10min ;然后进行淬火处理； 对于大于8mm厚的钢板:加热温度为850-930°C，保温5_30min，然后进行淬火处理； 所述的马氏体钢化学成分范围为:C:0.08-0.45wt%,P彡0.020wt%,S ^ 0.015wt%,Ti:0.06-0.25wt%, [N] ^ 0.008wt%，Mn:0.8-2.3wt% ； 在此基础上添加以下一种或多种元素:B:0.0005-0.005wt%, N1:0.1-3.0wt %、Cr:.0.2-3.0wt%、Mo:0.2-0.8wt%, S1:0.3-2.3wt%，余量为 Fe 和不可避免的杂质元素。
2.根据权利要求1所述的方法，其特征在于，在上述基础上再添加以下一种或多种元素:Nb:0.02-0.1Owt V:0.02-0.25wt %、Al:0.015-0.060wt %、RE:0.002-0.005wt %、Ca:0.005-0.03wt %。
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