CN115720595A - 强劲、坚韧和坚硬的不锈钢及其制成的制品 - Google Patents
强劲、坚韧和坚硬的不锈钢及其制成的制品 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及一种铁基、细粒的马氏体不锈钢,其使用热机械处理(TMT)来沉淀细小、抗粗化的MX型沉淀物的相对均匀的分散体,且然后通过向钢中扩散碳而硬化来制成。
背景技术
在航空、国防、能源、医疗、运输、消费和工业市场中,存在着对强劲、坚韧和坚硬的不锈钢的需求。可以从这种合金中受益的具体应用包括(尤其是)轴承、齿轮、驱动器、餐具、泵组件、轴、枪管、螺栓、螺栓架、阀和模具。传统的可渗碳不锈钢(比如PYROWEAR® 675和CX13VDW)提供高硬度,但在热处理后没有表现出良好的耐腐蚀性,这可能是很麻烦的。传统的穿透硬化不锈钢(比如AISI 440C型和BG42合金)也能提供高硬度,但在热处理后不能提供良好的耐腐蚀性。此外,它们提供相对较低的冲击韧性。CRONIDUR®30合金具有良好的耐腐蚀性,但不能实现大于60洛氏C硬度(Rc)的硬度。合金还存在冲击韧性很低的问题。鉴于前述,没有现有的提供以下的性能组合的空气熔炼或真空熔炼钢材料:(i)高表面(壳)硬度(即大于58-60 Rc),(ii)深有效壳深度(即大于0.040英寸(1.02毫米)),(iii)在暴露于侵蚀性腐蚀环境比如ASTM B117(盐雾腐蚀测试)后良好的耐腐蚀性,(iv)高屈服强度(即大于135 ksi (930.8 MPa)),(v)高极限拉伸强度(即大于170 ksi (1172.1 MPa)),(vi)良好的拉伸伸长率(即大于8%),(vii)高夏比V型缺口冲击韧性(即大于30 ft-lb (40.7 J)),和(viii)高断裂韧性(即大于80 ksi√in(87.9 MPa√m))。次要目标是合金材料在至少约300℉的温度下回火后提供前述性能,这对于某些航空应用是重要的。
众所周知,在钢铁冶金学中,为了提高硬度通常需要增加钢合金的碳含量。相似地,为了提高耐腐蚀性,通常需要增加钢合金中的铬含量。然而,当期望在同一种钢合金中提高硬度和耐腐蚀性二者时,问题就出现了。穿透硬化不锈钢(比如AISI 440C型和BG42合金)试图通过添加大量的碳和铬二者(例如440C中标称约1%的碳和17%的铬,以及BG42合金中约1.15%的碳和14.5%的铬)来实现高硬度和良好的耐腐蚀性。440C合金可被硬化至约59Rc的峰值硬度,而BG42合金在热处理后可被硬化至约61 Rc。然而,在制造这种合金时,大体积分数的富铬颗粒(例如M7X3和/或M23X6)在合金中沉淀,从而损耗合金基体中的铬,而这是耐腐蚀性所必需的。本领域技术人员将理解,MaXb中的“M”是指一个或多个金属原子,比如铁和/或铬,而“X”通常指碳,但也可以指氮。当穿透硬化不锈钢暴露在通常用于热加工的温度下以及在随后的热处理期间,会出现有害的富铬碳化物、氮化物和/或碳氮化物颗粒的沉淀。这导致围绕富铬碳化物/氮化物沉淀物形成铬损耗区,进而导致折损合金基体材料的耐腐蚀性。如果铬损耗区域的局部铬含量低于约10.5%的Cr,则该钢不再被认为是“不锈的”,而在暴露于正常大气条件(且特别是暴露于侵蚀性条件(例如盐雾))后可能会出现生锈。重要的是要注意,上述现象并不限于上述穿透硬化不锈钢。它也不同程度地影响穿透硬化不锈钢家族,包括但不限于其他已知的马氏体不锈钢,比如AISI 440A、440B和420级。注意,这些其他马氏体不锈钢通常不能被硬化到许多应用和行业所需的高硬度水平(即大于58-60Rc)。
有一类不锈钢被称为渗碳不锈钢(例如PYROWEAR® 675合金和CX13VDW合金),其通常含有约12-13%的铬和相对低的碳(<0.15%)。当这种钢被渗碳时(通常在1600℉至1750℉),扩散到钢中的碳量超过了扩散温度下各自合金中碳的溶解度极限。该过程导致大量大的晶间和晶内的、富铬碳化物的沉淀,从而损耗周围铁基体中的铬。由于富铬颗粒的硬度非常高,而渗碳过程导致大体积分数的这种颗粒,所以渗碳壳的整体硬度可以高,例如61 Rc至63 Rc或者更高。然而,即使在随后的常规热处理后,高硬度所需的富铬碳化物仍保留在壳微观结构中,从而导致周围基体的铬损耗。如前文所提到的,当基体铬含量下降到小于约10.5%的铬的水平时,该钢就不再被认为是“不锈的”,且更容易受到腐蚀侵袭。无论渗碳后的热处理如何,在渗碳期间形成的壳中的大体积分数的富铬沉淀物并没有从微观结构中根除。因此,“不锈的”渗碳钢与传统穿透硬化不锈钢遭受基本相同的影响,即与其他表面硬度值低得多的不锈钢相比,热处理后的耐腐蚀性相对较差。
氮增强型不锈钢(比如CRONIDUR® 30合金)与穿透硬化不锈钢(比如440C型)和渗碳不锈钢(比如PYROWEAR® 675合金)二者相比,可以提供更好的耐腐蚀性,这主要是因为氮代替了碳,有利于耐腐蚀性能。然而,氮增强型不锈钢通常不能被硬化到大于约59 Rc的水平。此外,它们可能具有相对较低的夏比V型缺口冲击韧性。例如,CRONIDUR 30合金易碎,且展现仅为约1.5ft.-lb. (2.0 J)的冲击韧性。
鉴于前述对现有技术的讨论,需要提供非常高硬度而不牺牲良好耐腐蚀性的钢合金。此外,还需要提供这种硬度和耐腐蚀性水平并组合良好韧性的材料。
发明内容
根据本发明的一个方面,提供一种铁基、细粒的马氏体不锈钢,其基本上不含δ铁素体且提供非常高的硬度和良好的耐腐蚀性。合金基本上由以下重量百分比的成分组成。
合金的其余部分是铁和旨在用于类似应用的马氏体不锈钢合金中发现的寻常杂质。合金任选地含有Zr、Ta和Hf,只要1.17×%Ti + 0.62×%Zr + 0.31×%Ta + 0.31×%Hf总和为约0.135%至约1%。
根据本发明的另一个方面,提供一种制造复合制品,其包含基本由上述马氏体不锈钢合金组成的硬壳或表面层,以及由硬壳包裹的坚韧核心。核心材料基本上由具有以下重量百分比成分的合金组成。
核心合金的其余部分是铁和寻常杂质。如上所述,坚韧核心任选地含有Zr、Ta和Hf。根据本发明的这一方面,“坚韧核心”制品的特征在于具有高硬度的坚硬耐腐蚀钢壳,其全部或部分围绕核心,所述核心的特征在于良好的强度以及比壳材料更好的韧性和延展性。
根据本发明进一步的方面,提供由上述第一种合金制成的穿透硬化的薄规格制品。在根据这一方面的穿透硬化制品中,硬化区域在整个制品的长度和横截面上或基本上在整个制品的长度和横截面上延伸。对于穿透硬化部件,钢在整个厚度上表现出高硬度和高强度,但与“坚韧核心”实施方案的核心部分相比,该部件的冲击韧性较低。
在此和整个说明书中,除非另有说明,否则术语“百分比”和符号“%”是指重量百分比或质量百分比。出于本申请的目的,术语“薄规格”是指横截面厚度至多约0.125英寸(3.175毫米)。术语“高硬度”是指硬度至少约58 Rc。术语“有效壳深度”是指钢合金表面层的硬度低于50 Rc的深度。根据本发明,合金的基本和新性能包括至少约50 Rc的硬度组合耐腐蚀性,耐腐蚀性的特征在于当按照ASTM标准测试程序B117测试合金时,没有出现腐蚀。
附图说明
图1是根据本发明的复合制品样品的显微照片;
图2是根据本发明的合金样品按照ASTM标准测试程序B117测试后的照片;
图3是比较实施例A的样品按照ASTM标准测试程序B117测试后的照片;
图4是比较实施例B的样品按照ASTM标准测试程序B117测试后的照片;
图5是比较实施例C的样品按照ASTM标准测试程序B117测试后的照片;而
图6是比较实施例D的样品按照ASTM标准测试程序B117测试后的照片。
具体实施方式
根据本发明的合金和制品由美国专利号6,890,393和6,899,773中描述的基础合金生产,其全部公开内容通过引用而并入本文。如参考专利所述,已知的合金通过使用热机械处理来细化晶粒,并沉淀细小、抗粗化的MX型沉淀物的相对均匀的分散体来生产。本发明的钢合金结合了先前公开的钢的冶金属性,并包括另外的碳以实现相对于已知钢的非常高的硬度和强度。另外的碳通过在渗碳过程中向钢中扩散碳来提供。渗碳过程后,所得合金在扩散区域含有比基础合金显著更多的碳。
根据本发明的合金含有至少约0.20%的碳,以利于合金提供较高硬度,这样可以提供至少约50 Rc的硬度值,而不会显著损失耐腐蚀性。进一步注意到的是,当合金含有至少约0.30%的碳时,合金可提供大于约56 Rc的硬度值。当合金含有约0.35%的碳至约0.63%的碳时,可以提供非常高的硬度,即大于约60 Rc。随着碳水平从约0.63%增加到约0.70%,硬度分别从约60 Rc下降到约50 Rc。 随着碳水平继续从约0.70%增加到约0.83%,硬度继续分别从约50 Rc下降到约32 Rc。随着碳水平从约0.63%增加到约0.83%而硬度下降的原因是,碳水平的增加使钢中更多量相对软的残余奥氏体稳定,即使淬火后的渗碳合金经受低温处理后,其也不会转变为硬马氏体。在碳水平大于约0.83%的情况下,合金中坚硬的富铬颗粒的体积分数增加,这使得钢的整体硬度从约32 Rc逐渐增加到约59 Rc。然而,当合金中存在大于约0.83%的碳时,合金提供的耐腐蚀性会受到不利影响,因为富铬颗粒的形成增加会损耗来自基体材料中的铬。优选地,合金含有不多于约0.70%的碳,而为了硬度和耐腐蚀性的最佳组合,合金含有不多于约0.63%的碳。
根据本发明的合金的碳含量不能以常规方式获得,例如通过在熔炼期间添加碳,因为这样的合金添加会导致相对较大体积分数的颗粒间间距大的初生MC颗粒,在随后的热机械处理或热加工期间不能有效地钉扎晶粒以产生或保持细晶粒微观结构。对于本发明要生产出具有这样高碳水平的钢,优选的方法是在基础合金经过热机械处理后将碳扩散到钢中。
根据本发明的合金通过先熔炼再铸造上述基础合金而生产。熔炼和铸造合金不需要特殊技术。合金可使用传统的空气熔炼工艺(比如电弧熔炼)熔炼,或者可以真空熔炼合金(比如通过真空感应熔炼)。当合金被空气熔炼时,优选控制合金的化学组成,使合金含有至少约0.01%的铝和硅组合作为熔炼期间脱氧添加的残留元素。基础合金被铸造成锭,或者可以使用连续铸造技术进行铸造。
合金锭或坯随后使用前述专利中所述的热机械处理进行加工。热机械处理的目的是在热加工期间使微观结构再结晶,并沉淀出细MX颗粒的均匀分散体,以钉扎新的再结晶晶粒的边界,使得在合金冷却到室温后获得细粒、等轴的微观结构。
碳通过渗碳过程扩散到热加工的合金形式中。在选择以提供期望的碳含量和渗碳层的深度的温度、时间和碳气氛的条件下进行渗碳过程。在期望的碳量扩散到热加工钢中后,对钢进行低温处理,将碳扩散过程期间可能形成的残余奥氏体转化为马氏体。低温处理通过使合金在约-321℉至约-100℉(-196.1℃至-73.3℃)的温度下冷却一段时间而进行,选择所述时间以使任何残余奥氏体基本上完全转化为马氏体。然后使合金在空气中变热至室温。然后当根据本发明的制品被实施为具有非常坚硬、耐腐蚀的壳或表面层以及壳内强劲、坚韧的核心的复合制品时,对钢进行回火,以增加核心和壳的韧性和延展性。根据本发明的合金或制品的回火温度是约200℉至约600℉(93.3℃至315.6℃)。在较高温度下回火会降低耐腐蚀性,而在较低温度下回火会降低韧性和延展性。优选地,本发明的钢或由其制成的复合制品的回火温度为约300℉至约400℉(148.9℃至204.4℃)。对于本领域的技术人员来说,显然可以在前述温度范围之外对合金材料进行回火,并且仍然获得特定应用的期望性能。当如上所述加工时,根据本发明的复合钢制品可具有约38.5 Rc至约41 Rc的核心硬度和约40至约49 ft-lbs (54.2至66.4 J)的夏比V型缺口冲击能量,并组合约59 Rc至约61 Rc的渗碳壳硬度。
本发明的钢合金可用作复合制品的部件,其在碳扩散到较低碳不锈钢“基”合金之前由其形成。复合制品的较高碳表面层可以延伸到约0.025英寸至约0.100英寸(0.635毫米至2.54毫米)的深度。边界可以定义为材料的硬度下降到低于约50 Rc的点。图1示出根据本实施方案的棒10的部分横截面形式的复合制品的一部分。棒10包括内部核心部分20,其特征在于高强度和良好韧性。棒10还具有外部壳部分30,其特征在于具有非常高的强度和硬度。核心部分20和壳部分30的特征还在于具有良好的耐腐蚀性。
尽管有应用要求复合制品具有高表面硬度、良好的耐腐蚀性和良好的核心韧性和延展性的组合(例如轴承和齿轮),但还有其他应用(比如刀和餐具)可以从在整个部件中(即穿过制品的横截面)具有高硬度和良好的耐腐蚀性组合的钢中受益。对于这样的应用,本发明的钢的另一个实施方案是由基础合金制成的薄规格制品,且其中的碳已经扩散到整个部件或基本上扩散到整个部件,从而使其整个变硬,同时保持优异的耐腐蚀性。例如,利用本文所述的技术和方法的穿透硬化的刀刃,可以反复打磨而不产生不良后果。本发明的这一方面已经成功实现,其厚度约为0.09英寸至约0.1英寸(2.29毫米至2.54毫米)。然而,据信本发明可以延伸到厚度高达约0.125英寸(3.175毫米)或更大。
实施例
为了证明根据本发明的合金所提供的硬度和耐腐蚀性的新组合,对合金的实施例进行比较测试。更具体地说,本发明的合金所提供的硬度和耐腐蚀性与四种已知的马氏体耐腐蚀合金样品进行比较,即PYROWEAR 675合金(Ex. A)、BG42合金(Ex. B)、AISI 440C型合金(Ex. C)和CPM S90V合金(Ex. D) (CPM和S90V是注册商标)。测试合金的重量百分比成分在下表展示。
元素 | 本发明 | Ex. A | Ex. B | Ex. C | Ex. D |
C | 0.103<sup>*</sup> | 0.07<sup>*</sup> | 1.15 | 1 | 2.30 |
Mn | 0.43 | 0.65 | 0.5 | 0.5 | |
Si | 0.42 | 0.3 | 0.3 | ||
P | 0.014 | ||||
S | 0.0005 | ||||
Cr | 10.86 | 13 | 14.5 | 17 | 14.0 |
Ni | 2.95 | 2.6 | |||
Mo | 0.49 | 1.8 | 4 | 0.5 | |
Co | 0.03 | 5.4 | |||
Cu | 0.14 | ||||
Ti | 0.29 | ||||
Al | 0.015 | ||||
Nb | 0.06 | ||||
V | 0.10 | 0.60 | 1.2 | 9.0 | |
N | 0.01 | ||||
B | 0.002 | ||||
Sn | 0.004 |
*渗碳前的碳浓度。
每种合金的其余部分基本上是铁。
根据本发明的合金样品如上所述经渗碳、淬火、低温处理,并然后回火。渗碳壳深度约为0.055英寸(1.4毫米)。实施例A的样品经过渗碳,且然后用该合金的已知工艺进行热处理。渗碳壳深度约为0.040英寸(1.02毫米)。实施例B、C和D的样品按照这些合金的已知热处理进行热处理。然后对每种合金的样品进行表面硬度和耐腐蚀性测试。
本发明的合金样品的测量硬度为61 Rc。实施例A的样品的测量硬度为63 Rc。实施例B的样品的测量硬度为61 Rc。实施例C的样品的测量硬度为59 Rc,而实施例D的样品的测量硬度为58 Rc。
根据ASTM标准测试程序B117(盐雾测试)对每种合金的样品进行腐蚀测试。图2-6示出每种合金的样品在暴露于盐雾200小时后的照片。图2示出根据本发明的合金样品。图3示出比较实施例A的样品。图4示出比较实施例B的样品。图5是比较实施例C的样品而图6示出比较实施例D的样品。
本说明书中使用的术语和表达方式是作为描述的术语而非限制的术语使用的。在使用这些术语和表达方式时,并不旨在排除所示和所述特征的任何等同物或其部分。认识到在本文描述和要求保护的发明中,各种修改是可能的。
Claims (11)
2.如权利要求1所述的合金,其含有至少约0.30%的碳。
3.如权利要求1所述的合金,其含有至少约10.5%的铬。
4.如权利要求3所述的合金,其含有不多于约13%的铬。
6.如权利要求5所述的制品,其中所述壳合金含有至少约0.30%的碳。
7.如权利要求5所述的制品,其中所述壳合金含有至少约10.5%的铬。
8.如权利要求7所述的制品,其中所述壳合金含有不多于约13%的铬。
9.如权利要求5所述的制品,其中所述制品为棒,而所述壳部分围绕所述核心部分。
10.如权利要求9所述的制品,其中所述壳的有效壳深度为约0.025英寸至约0.100英寸(0.635毫米至2.54毫米)。
11.如权利要求5所述的制造制品,其中所述制品为薄规格制品。
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