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CN113278890A - 高铬耐热钢 - Google Patents

高铬耐热钢 Download PDF

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CN113278890A
CN113278890A CN202110565231.7A CN202110565231A CN113278890A CN 113278890 A CN113278890 A CN 113278890A CN 202110565231 A CN202110565231 A CN 202110565231A CN 113278890 A CN113278890 A CN 113278890A
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resistant steel
chromium heat
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南雄介
小野达雄
G·库米诺
P·马里亚尼
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Tenaris Connections BV
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Abstract

本发明提供一种高铬耐热钢。该钢含有以质量%计,C:0.08%‑0.13%、Si:0.15%‑0.45%、Mn:0.1%‑1.0%、Ni:0.01%‑0.5%、Cr:10.0%‑11.5%、Mo:0.3%‑0.6%、V:0.15%‑0.25%、Nb:0.01%‑0.06%、N:0.015%‑0.07%、B:0‑0.005%和Al:0‑0.04%。余量由Fe和不可避免的杂质元素组成。该钢示出马氏体微结构。

Description

高铬耐热钢
本申请是向中国知识产权局提交的申请日为2014年6月24日的标题为“高铬耐热钢”的第201480035461.0号申请的分案申请。
技术领域
本发明涉及高铬耐热钢。
发明背景
迄今为止,己提出含有δ铁素体的几种9%Cr耐热钢作为高铬钢以改善可焊接性,且其一些己被用于热电厂中的蒸汽接触组件。然而,由于9%Cr耐热钢的长期蠕变强度和冲击性能极大受损,因而现在主要使用具有不含有δ铁素体的马氏体微结构的9%Cr-1%Mo钢。近年来,己大大增加蒸汽条件的温度和压力以改善热电厂中的热效率。因此,电厂的运行条件从超临界压力变至超超临界压力。另外,设计了在更苛刻蒸汽条件下可运行的工厂。随着蒸汽条件中这种逐渐增加的苛刻性,目前使用的9%Cr-1%Mo钢(91级钢)由于其有限的抗氧化性和高温强度不能适应未来工厂中的锅炉管。同时,奥氏体耐热不锈钢可以是待用于未来工厂的候选材料,但其应用受到经济效率的限制。因此,希望研发用在具有甚至更高温度的蒸汽条件中的耐热钢。
在这种情况下,如JP-A-1993-311342、JP-A-1993-311345和JP-A-1997-291308中所公开的,己研发了主要改善了蠕变强度的新型高铬钢。这些钢己通过加入W作为固溶硬化元素以及进一步地通过加入合金元素诸如Co、Ni和Cu改善了蠕变断裂强度和韧性。另外,JP-A-1988-89644公开了具有最优化的W和Nb含量以及改善的蠕变强度的钢。US-4564392描述了其中优化了C/N比的含Cr钢。后一个US专利文献中举例的钢含有相对大量的Mo和N。含有12%Cr的钢被认为特别适用于在高温下和在高应力下使用。所有这些已知钢据称具有己通过向常规耐热钢中加入合金元素诸如W和Co经固溶硬化改善了蠕变强度。然而,由于W和Co是昂贵的元素,导致材料价格增加,从经济效应的角度,这些元素的使用受到限制。
而且,抗蒸汽氧化性的改善是对抗高温蒸汽不可缺少的。另外,增加常规9%Cr钢的Cr含量有效地改善了现有条件中的抗蒸汽氧化性。然而,由于增加Cr含量导致δ铁素体的形成,需要增加奥氏体形成元素诸如C和Ni以获得回火马氏体结构。然而,这些元素的含量受限制,因为C和Ni含量的增加分别降低了可焊接性和长期蠕变强度。虽然存在加入Co等来抑制δ铁素体的形成的情况,但这种元素昂贵,因此导致经济效率降低。
发明内容
鉴于上述情况,本发明的一个目的是提供改良的高铬耐热钢,其以质量%计由以下组成:C:0.08%-0.13%、Si:0.15%-0.45%、Mn:0.1%-1.0%、Ni:0.01%-0.5%、Cr:10.0%-11.5%、Mo:0.3%-0.6%、V:0.10%-0.25%、Nb:0.01%-0.06%、N:0.015%-0.07%、B:≤0.005%和Al:≤0.04%,其中余量为Fe和不可避免的杂质元素。另一个目的是提供能用于超超临界压力锅炉的钢。另一个目的是在不加入昂贵元素如W和Co的情况下,基于经济的钢提供用于高温蒸汽的蠕变断裂强度和蒸汽氧化性质改善的钢。
本发明的钢成分包含低碳(C)、锰(Mn)、硅(Si)、铬(Cr)、镍(Ni)、钼(Mo)、钒(V)、铌(Nb)和氮(N)。
在一个实施方案中,可以加入一种或多种以下元素:铝(Al)和硼(B)。
该成分的剩余部分包含铁(Fe)和不可避免的杂质。
本发明涉及高铬耐热钢。下表1中示出其实施方案(成分以质量%表示),其中余量为Fe和不可避免的杂质元素:
表1
Figure BDA0003080707950000031
Figure BDA0003080707950000041
说明:M=必有的;O=可有的;I=可能存在的不可避免的杂质元素
在高铬耐热钢的一个实施方案中,B在以质量计0.001%至0.005%的范围内。
在高铬耐热钢的一个实施方案中,不可避免的杂质元素的质量%小于0.4%。
在高铬耐热钢的一个实施方案中,不可避免的杂质元素包含除C、Si、Mn、Ni、Cr、Mo、V、Nb、N、Fe之外的元素。
在高铬耐热钢的一个实施方案中,不可避免的杂质元素可包含磷(P)、硫(S)、钴(Co)、铜(Cu)、锑(Sb)、砷(As)、锡(Sn)和铅(Pb)中的一种或多种。
在高铬耐热钢的一个实施方案中,P+S+Co+Cu+Sb+As+Sn+Pb≤0.40%(以质量%计)。
在高铬耐热钢的一个实施方案中,P+S+Co+Cu+Sb+As+Sn+Pb≤0.35%(以质量%计)。
不可避免的杂质元素涉及由钢生产导致的正常污染物。
本发明己提供了具有迄今为止一直在常规9Cr-1Mo钢中难以实现的在蠕变断裂强度和抗蒸汽氧化性方面的性质都改善了的高铬耐热钢。另外,本发明的主要成分不含有昂贵元素诸如W和Co,和含有较少量的Mo,因而在经济效率方面有利。因此,本发明可以满足具有较高温度和压力作为蒸汽条件的未来热电厂的使用。
本发明还涉及由本发明的高铬耐热钢制造的蒸汽接触组件例如管。该管可以是无缝或焊接管。
本发明还涉及包括由本发明的高铬耐热钢制造的一种或多种蒸汽接触组件例如锅炉汽包(boiler drum)和/或管的压力锅炉。
本发明还涉及包括本发明的蒸汽接触组件的热电厂。
本发明还涉及包括本发明的压力锅炉的热电厂。
发明详述
下面将讨论单种元素的限制的原因。
C:0.08%-0.13%;
C是抑制铁素体形成的奥氏体形成元素。因此,由铁素体形成元素诸如Cr确定C的适合量,以获得回火马氏体结构。另外,C沉淀作为MC型(M代表合金元素(同样适用于下文))和M23C6型碳化物,其大大影响了高温强度和特别是蠕变断裂强度。C含量小于0.08%时,沉淀的量不足以用于沉淀强化,而且δ铁素体相的抑制不完全。由于该原因,其下限设为0.08%。加入多于0.13%的C时,可焊接性受损和韧性降低。而且,碳化物的团聚粗化(agglomerated coarsening)加速,导致高温长期侧的蠕变断裂强度降低。由于该原因,其范围设为0.08%-0.13%,优选在0.08%-0.11%(质量百分比)的范围内。
Si:0.15%-0.45%;
加入Si作为脱氧剂和用于抗氧化性。然而,Si是强铁素体形成元素,且韧性通过铁素体相而受损。由于该原因,其范围设为0.15%-0.45%以平衡抗氧化性和回火马氏体结构;优选在0.15%-0.35%(质量百分比)的范围内。
Mn:0.1%-1.0%;
加入Mn作为脱氧剂和脱硫剂。另外,其也是抑制δ铁素体相的奥氏体形成元素,但其过度加入会削弱蠕变强度。由于该原因,其范围设为0.1%-1%;优选在0.40%-0.60%(质量百分比)的范围内。
Ni:0.01%-0.5%;
Ni是抑制铁素体形成的强奥氏体形成元素。然而,其过度加入会削弱长期蠕变断裂强度。由于该原因,所建议范围设为0.01%-0.5%,优选在0.01%-0.20%(质量百分比)的范围内。
Cr:10.0%-11.5%;
Cr是保护抗蒸汽氧化性的重要元素。从用于高温蒸汽的抗蒸汽氧化性考虑,Cr含量为10.0%或更高是有必要的。然而,Cr以及Si的过度加入引起铁素体形成,也引起长期蠕变中脆性相的形成,从而削弱了断裂强度。由于该原因,其上限设为11.5%,优选在10.45%-11%(质量百分比)的范围内。
Mo:0.3%-0.6%;
Mo是铁素体形成元素,同时由于固溶硬化的影响,其提高了蠕变强度。然而,其过度加入导致对蠕变断裂强度没有贡献的δ铁素体的形成和粗金属间化合物的沉淀。由于该原因,其范围设为0.3%-0.6%,优选在0.45%-0.55%(质量百分比)的范围内。
V:0.10%-0.25%;
V沉淀为细碳氮化物,并因此改善高温强度以及蠕变断裂强度。含量小于0.1%时,沉淀的量不足以提高蠕变强度。相反,其过度加入导致对蠕变断裂强度没有贡献的大体积V(C,N)沉淀的形成。由于该原因,其范围设为0.1%-0.25%,优选在0.15%-0.25%(质量百分比)的范围内。
Nb:0.01%-0.06%;
Nb也沉淀为细碳氮化物,且是改善蠕变断裂强度的重要元素。要获得该效果,0.01%或更大的含量是必要的。然而,与V相似,Nb的过度加入导致大体积碳氮化物的形成,以降低蠕变断裂强度。因此,其范围设为0.01%-0.06%,优选在0.035%-0.06%(质量百分比)的范围内。
N:0.015%-0.07%;
N沉淀为氮化物或细碳氮化物,从而改善蠕变断裂强度。其也是抑制δ铁素体相的奥氏体形成元素。然而,其过度加入削弱韧性。由于该原因,其范围设为0.015%-0.070%,优选在0.040%-0.070%(质量百分比)的范围内。
Al:≤0.04%;以及
Al可以用作脱氧剂,但过度加入时,其削弱长期蠕变断裂强度。由于该原因,当可选地使用时,其上限设为0.04%,优选小于0.025%(质量百分比)。
B:0.001%-0.005%。
B是强化晶界且也具有沉淀硬化为M23(C,B)6的作用的元素,因此对改善蠕变断裂强度有效。然而,其过度加入削弱高温下的可加工性,导致引起破裂,且也削弱蠕变断裂延展性。由于该原因,当可选地使用时,其范围设为0.001%-0.005%,优选0.002%-0.004%(质量百分比)。
P:≤0.03%;
P是熔融原材料中含有的且钢制造过程中不容易降低的不可避免的杂质元素。其削弱室温和高温下的韧性以及热可加工性。若存在的话,上限设为0.03%,优选少于0.018%(质量百分比)。
S:≤0.01%;
S也是不可避免的杂质元素,且其削弱热加工性。其也是裂纹、划痕等的原因。若存在的话,上限设为0.01%,优选少于0.005%(质量百分比)。
在本发明中,制造条件没有特定限制。回火马氏体结构可以通过在范围为950-1150摄氏度的温度下加热的常规正火处理,接着空气冷却和在范围为700-800摄氏度的温度下加热的回火处理而获得。
实施例
使用真空感应熔炼炉熔化具有表2中示出的化学成分的本发明的钢(A至C号)和对比钢(D至F号),铸成50kg或70kg铸坯,然后热轧成厚度为12mm至15mm的钢板。然后,通过正火,然后回火对钢板进行热处理。正火温度在1050℃至1100℃的范围内,和回火温度在770℃至780℃的范围内。获得的微结构是不含δ铁素体的回火马氏体结构。在对比钢中,钢D具有目前广泛使用的称为91级钢的9Cr-1Mo钢的成分系统。钢D用作代表现有材料的钢。
表2
类别(division) C Si Mn P S Ni Cr Mo V Nb Al N B
发明的钢 A 0.09 0.21 0.25 0.012 0.002 0.20 10.6 0.51 0.22 0.04 0.012 0.044 -
发明的钢 B 0.12 0.42 0.75 0.009 0.003 0.15 10.3 0.55 0.18 0.05 0.008 0.028 -
发明的钢 C 0.11 0.18 0.48 0.013 0.001 0.41 11.3 0.34 0.20 0.03 0.015 0.040 0.0025
对比钢91级 D 0.10 0.32 0.47 0.011 0.003 0.20 <u>8.5</u> <u>0.98</u> 0.25 <u>0.07</u> 0.013 0.045 -
对比钢 E 0.13 0.29 0.53 0.015 0.004 0.17 <u>12.2</u> 0.48 0.21 0.03 0.007 0.048 -
对比钢 F 0.09 0.36 0.38 0.009 0.002 0.31 <u>9.2</u> 0.38 0.16 0.04 0.019 0.035 -
(质量%)标下划线的数字表示超出本发明范围的值。
测试样品取自热处理板,并进行蠕变断裂测试和蒸汽氧化测试。使用6mm直径的样品在650℃的测试温度以及110MPa和70MPa的应力下进行蠕变断裂测试。对于该种类的钢,测试需要数以万计的小时来弄清600℃的测试温度,即实际热电厂的实际温度下的优势或劣势。因此,测试温度升高至650℃,随约1000小时和约10000小时的估计断裂时间段应用两种应力条件。因为对于使用110MPa测试条件的约1000小时的短期侧测试(short-time sidetesting),钢中断裂时间的差异被假设很小,所以应用70MPa测试条件作为约10000小时的长期测试,以区分钢中的断裂强度。
对于蒸汽氧化测试,温度设为650℃,其与用于蠕变断裂测试的温度相同。在测试中,使用光学显微镜测量进行1000小时蒸汽氧化测试的样品的表面上氧化层(scale)的平均厚度。以这种方式,评估抗蒸汽氧化性。样品是取自热处理板材的15mm×20mm×10mm的小样品。
表3中示出蠕变断裂测试和蒸汽氧化测试的结果。
表3
Figure BDA0003080707950000091
与相当于现有91级钢的钢D相比,本发明的钢展现优异的高温性质。例如,使用70MPa的应力的长期测试中,断裂时间是三倍或更多,以及蒸汽氧化中形成的氧化层的平均厚度不超过一半。因此,在蠕变断裂强度和抗蒸汽氧化性方面示出显著的改善。
具有12.2%的较高Cr含量的对比钢E显著改善了抗蒸汽氧化性,然而其降低了长期蠕变断裂强度。虽然钢E的微结构是不含δ铁素体的回火马氏体,但认为降低的蠕变断裂强度是由于Cr含量增加。具有与现有91级钢相等的Cr含量的对比钢F不能改善蒸汽氧化性质,且相较于本发明的钢具有相当厚的氧化层。
工业实用性
根据本发明,可提供即使不含昂贵元素如W和Co并含较少Mo时,仍增强蠕变断裂强度以及抗蒸汽氧化性的高铬耐热钢。因此,本发明提供了优异的经济效率。发明的钢可以有利地用于蒸汽接触组件,例如用于压力锅炉和/或锅炉汽包的管。

Claims (26)

1.一种高铬耐热钢,其以质量%计由以下组成:
C:0.08%-0.13%;
Si:0.15%-0.45%;
Mn:0.1%-1.0%;
Ni:0.01%-0.5%;
Cr:10.0%-11.5%;
Mo:0.3%-0.6%;
V:0.15%-0.25%;
Nb:0.01%-0.06%;
N:0.015%-0.07%;
B:0-0.005%;和
Al:0-0.04%;
其中,余量为Fe和不可避免的杂质元素。
2.根据权利要求1所述的高铬耐热钢,其中,B在以质量计0.001%至0.005%的范围内。
3.根据权利要求1所述的高铬耐热钢,其中,所述不可避免的杂质元素的质量%小于0.4%。
4.根据权利要求1所述的高铬耐热钢,其以质量%计由以下组成:
C:0.08%-0.11%;
Si:0.15%-0.35%;
Mn:0.40%-0.60%;
Ni:0.01%-0.2%;
Cr:10.45%-11.0%;
Mo:0.45%-0.55%;
V:0.15%-0.25%;
Nb:0.035%-0.06%;
N:0.040%-0.070%;
B:0-0.005%;和
Al:0-0.04%;
其中,余量为Fe和不可避免的杂质元素。
5.根据权利要求4所述的高铬耐热钢,其中,B在0.002%至0.004%的范围内。
6.根据权利要求4所述的高铬耐热钢,其中,Al以质量计为:0-0.025%。
7.根据权利要求1所述的高铬耐热钢,其中,所述所述高铬耐热钢具有马氏体微结构。
8.根据权利要求7所述的高铬耐热钢,其中,所述高铬耐热钢不含δ铁素体。
9.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的温度在70MPa的应力下具有至少21,985小时的蠕变断裂时间。
10.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的温度在70MPa的应力下具有至少23,801小时的蠕变断裂时间。
11.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的温度在70MPa的应力下具有至少25,451小时的蠕变断裂时间。
12.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的温度在70MPa的应力下具有在21,985小时和25,451小时之间的蠕变断裂时间。
13.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的蒸汽氧化温度下1000小时形成至多33μm的氧化层平均厚度。
14.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的蒸汽氧化温度下1000小时形成至多39μm的氧化层平均厚度。
15.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的蒸汽氧化温度下1000小时形成至多40μm的氧化层平均厚度。
16.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的蒸汽氧化温度下1000小时形成在33μm到40μm之间的氧化层平均厚度。
17.根据权利要求1所述的高铬耐热钢,其中,所述高铬耐热钢在650℃的温度在70MPa的应力下具有在21,985小时和25,451小时之间的蠕变断裂时间,并且其中,所述高铬耐热钢在650℃的蒸汽氧化温度下1000小时形成在33μm到40μm之间的氧化层平均厚度。
18.根据权利要求1所述的高铬耐热钢,其中,Ni以质量计在0.01%至0.2%的范围内。
19.根据权利要求1所述的高铬耐热钢,其中,Mo以质量计在0.45%至0.6%的范围内。
20.一种蒸汽接触组件,其由权利要求1所述的高铬耐热钢制造。
21.根据权利要求20所述的蒸汽接触组件,其中,所述蒸汽接触组件是管。
22.一种压力锅炉,其包括根据权利要求1所述的高铬耐热钢制造的一个或多个蒸汽接触组件。
23.根据权利要求22所述的压力锅炉,其中,所述一个或多个蒸汽接触组件是锅炉汽包。
24.根据权利要求22所述的压力锅炉,其中,所述一个或多个蒸汽接触组件是管。
25.一种热电厂,其包括根据权利要求20所述的蒸汽接触组件。
26.一种热电厂,其包括根据权利要求22所述的压力锅炉。
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