CN116043126A - 一种高强高韧高熵钢及制造方法 - Google Patents
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 71
- 239000010959 steel Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000005096 rolling process Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000009749 continuous casting Methods 0.000 claims abstract description 20
- 238000010583 slow cooling Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000003723 Smelting Methods 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000005266 casting Methods 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 description 16
- 239000000956 alloy Substances 0.000 description 16
- 239000006104 solid solution Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
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- 230000000694 effects Effects 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910000915 Free machining steel Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000005098 hot rolling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种高强高韧高熵钢及制造方法,化学成分按重量百分比计为:C:0.45%~0.80%,Si:4.5%~6.0%,Mn:21.0%~25.0%,Cr:1.0%~3.0%,Al:4.0%~6.0%,S≤0.005%,P≤0.010%,余量为Fe及不可避免的杂质。工艺流程:转炉冶炼、LF、VD、连铸、板坯缓冷、板坯加热、控制轧制、固溶处理,板坯加热:将连铸板坯加热至1230~1270℃;控制轧制:一阶段开轧温度为1050~1100℃,前三个道次的压下率为20%~23%;二阶段开轧温度≥920℃,控制终轧温度850±20℃,轧后空冷。优点是:钢板具有良好的综合性能。
Description
技术领域
本发明属于高熵钢制造领域,尤其涉及一种高强高韧高熵钢及制造方法。
背景技术
目前对于高熵合金的定义主要有两种:基于成分的定义和基于混合熵的定义。基于成分的定义认为高熵合金是包含5种或以上的主要元素,且每种主要元素的摩尔百分比介于5%到35%之间的一类合金。高熵合金主要的合金体系包括以3d过渡族金属元素(Cr,Mn,Fe,Co,Ni等)为主的3d过渡族高熵合金系列、以难熔金属元素(Nb,Mo,Ta,W,V等)为主的难熔高熵合金系列、轻质高熵合金系列、贵金属高熵合金系列和稀土高熵合金系列等。
受到高熵合金的启发,我们研究了以高构型熵为基础的钢的设计思想,以确立一种单相固溶体基体,研究的目标是Fe-Mn-Al-Si-C系。不同于传统的高熵合金那样使用5种或5种以上的等原子比的成分,我们将平面构型熵转化为金属混合物,确定出固溶体体系,即非等原子比体系。在高熵合金当中,没有任何元素是占主导地位的,但是,在我们这里,我们将这样的概念转化为铁基材料,我们称之为高强高韧高熵钢。
为克服现有技术的不足,本发明的目的是提供一种高强高韧高熵钢及制造方法,成分设计简单,以Mn为主,成本较低,抗拉强度≥800MPa,-60℃V型冲击功≥100J,在满足使用性能的条件下显著降低成本。
为实现上述目的,本发明通过以下技术方案实现:
一种高强高韧高熵钢,化学成分按重量百分比计为:C:0.45%~0.80%,Si:4.5%~6.0%,Mn:21.0%~25.0%,Cr:1.0%~3.0%,Al:4.0%~6.0%,S≤0.005%,P≤0.010%,余量为Fe及不可避免的杂质。
一种高强高韧高熵钢的制造方法,工艺流程包括:转炉冶炼—LF—VD—连铸—板坯缓冷—板坯加热—控制轧制—固溶处理,具体包括以下工艺步骤:
1)板坯加热:将连铸板坯加热至1230~1270℃,保温时间4~6h;
2)控制轧制:控制一阶段开轧温度为1050~1100℃,钢板轧制时前三个道次的压下率为20%~23%;二阶段开轧温度≥920℃,控制终轧温度850±20℃,轧后空冷;
3)固溶处理:将室温钢板进加热炉,在1000~1100℃保温3~5min/mm,出炉后立即水冷淬火。
在转炉+LF+VD精炼过程中,LF炉造还原渣脱硫,钢液在VD真空炉内脱气,VD炉的保压时间为20~25min,[H]≤2ppm,[O]≤20ppm。
在连铸过程中全程保护浇注。
所述的板坯缓冷:连铸坯进缓冷坑缓冷。
所述的缓冷的时间≥48小时。
与现有技术相比,本发明的有益效果是:
高熵合金当中很少使用间隙元素,这里,我们却需要重视C在面心立方固溶体相中的作用。高强高韧高熵钢具有优异的机械性能,如:非常好的延展性和低温韧性,强度超过800MPa。通过调整堆垛层错能,可以获得非常好的组织稳定性。考虑到高强高韧高熵钢具有成本低、易加工、力学性能突出以及适用范围广等优点,这种具有高延展性的钢铁结构/功能一体化材料将具有广阔的应用前景。具优点是:
1)采用发明方法制造的高强高韧高熵钢,其屈服强度≥400MPa,抗拉强度≥800MPa,延伸率≥70%,-60℃V型冲击功≥100J;钢板具有良好的综合性能,满足用户的使用要求;
2)本发明成分设计简单,以Mn为主,成本较低,添加少量的Si、Al、Cr元素,产生固溶强化和沉淀强化效果,提高钢的强度,Al的加入降低了钢的密度;
3)采用洁净钢冶炼工艺,降低钢中气体、P、S及非金属夹杂物含量,结合铸坯缓冷工艺,获得了内外部质量优良的连铸坯;
4)采用控制轧制工艺,有效细化轧态组织;
5)本发明方法形成单一的面心立方组织,轧后固溶处理大幅度提高了钢的综合性能。
具体实施方式
下面对本发明进行详细地描述,但是应该指出本发明的实施不限于以下的实施方式。
高强高韧高熵钢,化学成分按重量百分比计为:C:0.45%~0.80%,Si:4.5%~6.0%,Mn:21.0%~25.0%,Cr:1.0%~3.0%,Al:4.0%~6.0%,S≤0.005%,P≤0.010%,余量为Fe及不可避免的杂质。
根据对固溶体价电子浓度VEC的观察结果统计,VEC≥8形成稳定的面心立方相。非等原子比Fe-Mn基高熵钢在只计算置换元素时其价电子浓度为7-8,但是,如果计算时加上间隙元素,如C,高熵钢的价电子浓度将大于8。
高强高韧高熵钢中:
碳:间隙元素C可以提高面心立方固溶体的稳定性,其原理就是其对价电子浓度的影响,同时C直接影响钢的强度,但是,碳含量过高对钢的冷脆性及焊接性能影响不利,综合考察,将碳含量控制在0.45%~0.80%;
硅:硅元素一是对于提高钢的价电子浓度有很大的作用,二是可提高钢的淬透性和基体强度,三是Si会对奥氏体产生固溶强化作用,过冷奥氏体的切变强度增强,引起Ms点降低,本发明添加适量Si元素,一方面避免出现比较严重的偏析情况,另一方面增强奥氏体的稳定性,将其含量控制在4.5%~6.0%;
锰:独立元素的VEC值Mn是7,Mn是形成面心立方相的主导元素,也是高熵钢获得高延展性和低温韧性的主要来源,将锰含量应控制在21.0%~25.0%;
铬:Cr可以提高钢的强度和耐蚀性能,将铬含量控制在1.0%~3.0%;
铝:铝可以产生明显的沉淀强化效果,并降低钢的密度,将铝含量控制在4.0%~6.0%;
硫:硫在钢中易形成FeS和MnS夹杂,MnS在热轧过程中沿着轧制方向伸长,使得硫易切削钢的横向力学性能显著降低,加剧了钢材的各向异性,同时它导致基体内部产生空洞并成为氧化向纵深发展的通道,显著降低钢的韧性,因此,应尽量降低钢中的硫含量;
磷:磷容易在奥氏体晶界发生偏析使基体材料晶界上原子间结合力减弱,破坏基体的连续性,显著降低钢的韧性,使焊接性能变坏,易产生冷脆,应尽量降低钢中的磷含量。
高强高韧高熵钢的生产工艺:转炉冶炼—LF—VD—连铸—板坯缓冷—板坯加热—控制轧制—固溶处理,具体包括以下步骤:
1)转炉+LF+VD精炼:LF炉造还原渣脱硫,减少夹杂,调整成分。然后,钢液在VD真空炉内脱气,保证VD炉的保压时间为20~25min。测定H、O含量,保证[H]≤2ppm,[O]≤20ppm;
2)连铸:全程保护浇注,减少连铸过程的二次氧化,降低钢中的夹杂物含量,提高钢的纯净度;
3)板坯缓冷:连铸坯进缓冷坑缓冷,使铸坯中的气体得到充分的扩散排出,最大程度降低铸坯气体含量,缓冷时间≥48小时;
4)板坯加热:将连铸板坯加热至1230~1270℃,保温时间4~6h,合金含量高通常需要高加热温度、长保温时间使合金元素在基体中充分固溶,改善板坯成分不均匀性,减轻成分偏析;
5)控制轧制:控制一阶段开轧温度为1050~1100℃,钢板轧制时前三个道次的压下率为20%~23%,采用大压下率可以提高变形渗透深度,使粗大的柱状晶得以破碎,形成细小均匀的晶粒,二阶段开轧温度≥920℃,为避免终轧温度过高导致轧态组织粗大,控制终轧温度850±20℃,轧后空冷;
6)固溶处理:将室温钢板进加热炉,在1000~1100℃保温3~5min/mm,出炉后立即水冷淬火,可消除沿晶界分布的未溶碳化物和带状碳化物,细化晶粒,得到组织和成分均匀一致的全奥氏体组织。
高强高韧高熵钢的冶炼采用转炉+LF+VD精炼,保证了对钢成分和钢中气体含量的精确控制;连铸过程全程保护浇注和板坯缓冷,保证了铸坯的内部质量;控制轧制细化热轧态组织;离线固溶处理可以大幅度提高钢的综合性能。
实施例
高强高韧高熵钢及制造方法,表1为高强高韧高熵钢冶炼、连铸、缓冷工艺,表2为高强高韧高熵钢化学成分,表3为高强高韧高熵钢轧制工艺,表4为高强高韧高熵钢固溶工艺,表5为高强高韧高熵钢性能。
钢的冶炼、连铸、缓冷见表1。
表1高强高韧高熵钢冶炼、连铸、缓冷
钢板成分见表2。
表2高强高韧高熵钢化学成分(余量为Fe及杂质)wt%
C | Si | Mn | Cr | Al | P | S | |
实施例1 | 0.52 | 5.03 | 22.5 | 2.60 | 4.50 | 0.0060 | 0.0020 |
实施例2 | 0.65 | 4.68 | 23.6 | 2.05 | 5.50 | 0.0055 | 0.0017 |
实施例3 | 0.78 | 5.56 | 24.6 | 1.55 | 5.80 | 0.0056 | 0.0018 |
实施例4 | 0.45 | 4.50 | 21.0 | 2.78 | 4.30 | 0.0056 | 0.0020 |
实施例5 | 0.49 | 5.72 | 25.0 | 2.22 | 4.90 | 0.0058 | 0.0019 |
实施例6 | 0.66 | 5.16 | 24.5 | 1.85 | 5.65 | 0.0060 | 0.0019 |
轧制工艺见表3。
表3高强高韧高熵钢轧制工艺
钢的固溶工艺见表4。
表4高强高韧高熵钢固溶工艺
钢板性能见表5。
表5高强高韧高熵钢性能
Claims (6)
1.一种高强高韧高熵钢,其特征在于,化学成分按重量百分比计为:C:0.45%~0.80%,Si:4.5%~6.0%,Mn:21.0%~25.0%,Cr:1.0%~3.0%,Al:4.0%~6.0%,S≤0.005%,P≤0.010%,余量为Fe及不可避免的杂质。
2.根据权利要求1所述的一种高强高韧高熵钢的制造方法,其特征在于,工艺流程包括:转炉冶炼—LF—VD—连铸—板坯缓冷—板坯加热—控制轧制—固溶处理,具体包括以下工艺步骤:
1)板坯加热:将连铸板坯加热至1230~1270℃,保温时间4~6h;
2)控制轧制:控制一阶段开轧温度为1050~1100℃,钢板轧制时前三个道次的压下率为20%~23%;二阶段开轧温度≥920℃,控制终轧温度850±20℃,轧后空冷;
3)固溶处理:将室温钢板进加热炉,在1000~1100℃保温3~5min/mm,出炉后立即水冷淬火。
3.根据权利要求2所述的一种高强高韧高熵钢的制造方法,其特征在于,在转炉+LF+VD精炼过程中,LF炉造还原渣脱硫,钢液在VD真空炉内脱气,VD炉的保压时间为20~25min,[H]≤2ppm,[O]≤20ppm。
4.根据权利要求2所述的一种高强高韧高熵钢的制造方法,其特征在于,在连铸过程中全程保护浇注。
5.根据权利要求2所述的一种高强高韧高熵钢的制造方法,其特征在于,所述的板坯缓冷:连铸坯进缓冷坑缓冷。
6.根据权利要求5所述的一种高强高韧高熵钢的制造方法,其特征在于,所述的缓冷的时间≥48小时。
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