CN113528953B - 一种耐液态铅/铅铋腐蚀的马氏体耐热钢 - Google Patents
一种耐液态铅/铅铋腐蚀的马氏体耐热钢 Download PDFInfo
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Abstract
本发明公开了一种耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢及其制备方法,属于耐腐蚀耐热合金钢技术领域。该耐热钢化学成分为:C0.08~0.13%,Si 0.70~1.50%,Ni 0.70~1.40%,Cr 7.0~10.0%,Mo 0.50~1.0%,Mn 0.45~0.95%,V 0.10~0.35%,Nb 0.10~0.35%,Fe余量。该耐热钢在液态铅(铅铋)腐蚀时,利用形成的含Si致密氧化层,显著提高合金钢的耐液态铅(铅铋)腐蚀性能;此外通过调整Ni、Mn、Mo等元素,平衡合金钢的铬镍当量从而获得完全的回火马氏体组织,并含有大量的碳化物,保证该合金具有优异的室温、高温力学性能。
Description
技术领域
本发明涉及耐腐蚀耐热合金钢技术领域,具体涉及一种耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢及其制备方法。
背景技术
随着全球经济的高速发展以及人类生活水平的日益提高,人们对电能的需求急剧增长。传统煤、石油和天然气等化石能源不仅存在环境污染问题,而且是不可再生资源。而核能是一种高效、低碳清洁、可以依赖的最有前途的能源。由于铅(铅铋)合金具有良好的中子学性能、优良的导热性能以及液态铅(铅铋)不存在辐照损伤等优点,因此铅(铅铋)快堆被列为未来发展的四代堆型中的一种。在铅(铅铋)冷却快堆运行过程中存在高温、液态铅(铅铋)、高温水蒸气及辐照等服役环境。液态铅(铅铋)对材料具有较强的冲蚀和腐蚀作用,这是由于结构材料中的组分元素会逐渐溶解和质量迁移至液态铅(铅铋)中,同时液态铅(铅铋)也会沿晶界向材料内扩散,使得材料发生腐蚀破坏,因此不可避免地将对结构材料产生腐蚀,从而影响快堆的安全运行。铁素体/马氏体耐热钢因具有优异的力学性能、耐热、低膨胀、耐辐照等特点,在火电和核电领域获得了大量的应用,是铅(铅铋)冷却快堆建设所需的候选关键结构材料,主要用于换热管、堆芯支承等结构部件。但这类铁素体/马氏体耐热钢的耐液态铅(铅铋)腐蚀性能较差,如何提高其耐液态铅(铅铋)腐蚀性能是亟待解决的问题。
发明内容
本发明的目的是提供一种耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢及其制备方法,该耐热钢不仅具有良好耐液态铅(铅铋)腐蚀性能,还具有良好室温、高温力学性能。
为实现上述目的,本发明所采用的技术方案是:
一种耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢,按重量百分比计,其化学成分为:C 0.08~0.13%,Si 0.70~1.50%,Ni 0.70~1.40%,Cr 7.0~10.0%,Mo 0.50~1.0%,Mn 0.45~0.95%,V 0.10~0.35%,Nb 0.10~0.35%,S≤0.010%,P≤0.010%,Fe余量。
按重量百分比计,该耐热钢的优选化学成分为:C 0.08~0.13%,Si 0.90~1.40%,Ni 0.75~1.20%,Cr 8.5~10.0%,Mo 0.60~0.80%,Mn 0.55~0.85%,V 0.15~0.25%,Nb 0.10~0.20%,S≤0.010%,P≤0.010 %,Fe余量。
该耐热钢的铬镍平衡当量(CNB)<15,以降低δ铁素体的析出倾向;其计算公式为:CNB=(Cr+6Si+4Mo+5Nb+11V-40C-2Mn-4Ni-1Cu)*100,公式中各元素符号表示耐热钢中相应元素的重量百分比。
所述耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢的制备方法为:首先按照合金成分进行配料和熔炼,并浇铸成铸锭;然后经过均质化处理、锻造和轧制变形;最后将轧制后的板材进行正火和回火热处理。
所述的均质化工艺为1050~1250℃保温5h以上,也可不采用均质化处理直接进行锻造、轧制。
所述的锻造工艺为在1050~1250℃保温1h以上,然后锻造开坯,终锻温度在900℃以上。
所述的轧制工艺为在1050~1250℃保温1h以上,然后开始轧制变形,终轧温度不低于900℃。
所述的正火工艺为在900~1200℃保温15~240min,然后空冷至室温,也可采用水淬处理。
所述的回火工艺为在700~800℃保温20~240min,然后空冷至室温,也可采用水冷处理。
本发明的设计思想是:
本发明的出发点:一方面通过添加适量的Si,利用Si与氧结合能力强、反应生成均匀、致密、稳定富Si氧化层的特点。该氧化层能有效降低合金元素的扩散速率,具有抑制结构材料发生溶解腐蚀的作用,从而保证了合金钢具有耐液态铅(铅铋)腐蚀的性能。另一方面,因Si是强铁素体形成元素,加入较多的Si会增强δ铁素体析出倾向,而析出δ铁素体后会损害合金钢的韧性和组织稳定性。为了降低δ铁素体的析出倾向,并保证在高温时能够获得完全的奥氏体组织,通过CNB值对奥氏体 /铁素体的稳定元素含量进行了设计,如提高Ni、Mn含量,降低Mo含量,从而经正火、回火处理后获得的是单相回火马氏体组织,同时借助富Cr的M23C6、富Mo的MX等碳化物对位错的钉扎作用,保证了合金钢具有良好的室温和高温力学性能。
本发明的优点在于:
1、本发明的耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢,利用 CNB值对合金成分进行设计,能够获得不含δ铁素体的单一回火马氏体组织,可同时满足耐液态铅(铅铋)腐蚀、耐高温和高强韧性的性能要求。
2、本发明的耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢,具有良好的耐液态铅(铅铋)腐蚀,在550℃液态铅铋中腐蚀1000h后,氧化层厚度约20μm。
3、本发明的耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢,其室温力学性能:拉伸强度大于600MPa,屈服强度大于400MPa,延伸率大于20%,断面收缩率不小于55%,常温夏比V口冲击功不小于100J。合金钢的550℃拉伸性能:拉伸强度大于390MPa,屈服强度大于290MPa,延伸率大于20%,断面收缩率不小于55%。
4、本发明的耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢,其合金体系、加工方法和热处理工艺与传统铁素体/马氏体钢相近。因此,本发明合金钢的工业化生产制备易于实现。
5、本发明的耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢,可推广应用于高性能铸件、锻件和管材的生产。
附图说明
图1为本发明实施例1经1050℃正火处理后的扫描电镜照片。
图2为本发明实施例1经760℃回火处理后的扫描电镜照片。
图3为本发明实施例1在550℃饱和氧浓度液态铅铋中腐蚀1000h 后的腐蚀层断面形貌照片。
具体实施方式
下面的实施例将对本发明给予进一步的说明,但并不因此而限制本发明,在本发明构思的前提下对本发明做出的改进,都属于本发明的保护范围。
本发明提供一种耐液态铅(铅铋)腐蚀的铁素体/马氏体耐热钢及其制备方法,一方面通过添加一定含量的Si,在液态铅(铅铋)环境下形成一层富Si的氧化膜,该氧化膜能有效地阻止元素的向内、向外扩散,从而有效地降低液态铅(铅铋)对耐热钢的腐蚀;另一方面,通过调整 Ni、Mn、Mo等含量,以获得合适的铬镍当量(CNB),避免出现δ铁素体,获得了富含碳化物的单一回火马氏体组织,从而保证该合金具有优良的室温和高温力学性能。
以下各具体实施例中,采用真空感应炉熔炼合金,选用工业纯铁和 99.9wt.%的高纯金属Cr、Si、Ni、Mn、Mo、V、Nb等金属为原材料,一共熔炼了5炉合金钢,其化学成分如表1所示,其中实施例1~4合金钢的CNB均小于15,而实施例5合金钢的CNB>15。铸锭的加工、热处理工艺为:均质化→锻造→热轧→正火→回火,具体的制备工艺步骤如下:
1)均质化:将铸锭加热至1200℃,保温12h,然后空冷至室温,铸锭取出后将表面扒皮处理;
2)锻造:将扒皮后的铸锭加热至1150℃,保温2h,迅速放置在锤锻机上锻造成板坯,然后空冷至室温,终锻温度在900℃以上;
3)轧制:将锻造后的锻坯加热至1150℃,保温1h,在二辊热轧机进行轧制成板材,然后空冷至室温,终轧温度在900℃以上;
4)正火:将轧板加热到1050℃保温30min,然后空冷至室温,其组织如图1所示。
5)回火:将正火处理后的板材加热到760℃保温90min,然后空冷至室温,其组织如图2所示。
由图1可以看出,正火处理后合金钢为单一的马氏体组织;而从图 2可见,回火后在晶界和晶内都析出了大量弥散分布的碳化物。
表1本发明实施例合金钢的化学成分(质量百分比)
采用Charpy V型缺口标准试样进行室温冲击功测量,拉伸性能根据 GB/T 228进行取样、测试,各合金钢的室温力学性能如表2所示。由表可见,本发明合金钢实施例1~4的屈服强度均在600MPa以上,其冲击功均大于150J。不同的是实施例5,其屈服强度略低,达到564MPa,但其冲击功仅14J,这是因为该实施例合金钢的CNB值大,合金钢中析出了δ-Fe,损害了合金钢的力学性能。各合金钢的550℃力学性能如表3 所示。由表可见,本发明合金钢实施例1~4的550℃屈服强度均在300MPa 以上,而实施例5的550℃屈服强度较低,为261MPa。
表2本发明实施例合金钢的室温力学性能
表3本发明实施例合金钢的550℃拉伸性能
在550℃饱和氧浓度液态铅铋中腐蚀1000h后,合金钢的腐蚀层断面形貌如图3所示。可见,本发明合金表面生成了约20μm厚的腐蚀层,具有较好的耐铅铋腐蚀性能。
实施例结果表明,本发明合金钢具有良好的耐液态铅(铅铋)腐蚀性能、室温和高温力学性能,可同时满足对高强韧性、耐高温、耐液态铅铋腐蚀的性能要求,可作为铅(铅铋)冷却快堆的结构材料。
Claims (6)
1.一种耐液态铅/铅铋腐蚀的马氏体耐热钢,其特征在于:按重量百分比计,该耐热钢的化学成分为:C 0.08~0.13%,Si 0.70~1.50%,Ni 0.70~1.40%,Cr 7.0~10%,Mo 0.50~1.0%,Mn 0.45~0.95%,V 0.10~0.35%,Nb 0.10~0.35%,S ≤ 0.010 %,P ≤ 0.010 %,Fe余量;
该耐热钢的铬镍平衡当量<15,其计算公式为:CNB=(Cr+6Si+4Mo+5Nb+11V-40C-2Mn-4Ni-1Cu)*100,公式中各元素符号表示耐热钢中相应元素的重量百分比;
所述耐液态铅/铅铋腐蚀的马氏体耐热钢的制备方法为:首先按照耐热钢化学成分进行配料和熔炼,并浇铸成铸锭;然后进行均质化处理、锻造和轧制变形处理;最后将轧制后所得板材进行正火和回火热处理;所述正火工艺为在900~1200℃保温15~240min,然后空冷至室温,或采用水淬处理;所述回火工艺为在700~800℃保温20~240min,然后空冷至室温,或采用水冷处理。
2.按照权利要求1所述的耐液态铅/铅铋腐蚀的马氏体耐热钢,其特征在于:按重量百分比计,该耐热钢的化学成分为:C 0.08 ~ 0.13 %,Si 0.90 ~ 1.40%,Ni 0.75 ~ 1.20 %,Cr 8.5 ~ 10 %,Mo 0.60 ~ 0.80 %,Mn 0.55 ~ 0.85 %,V 0.15 ~ 0.25 %,Nb 0.10 ~0.20 %,S ≤ 0.010 %,P ≤ 0.010 %,Fe余量。
3.按照权利要求1所述的耐液态铅/铅铋腐蚀的马氏体耐热钢,其特征在于:所述均质化工艺为1050~1250℃保温5h以上,或不采用均质化处理直接进行锻造、轧制。
4.按照权利要求1所述的耐液态铅/铅铋腐蚀的马氏体耐热钢,其特征在于:所述锻造工艺过程为:在1050~1250℃保温1h以上,然后锻造开坯,终锻温度在900℃以上;所述轧制工艺过程为:在1050~1250℃保温1h以上,然后开始轧制变形,终轧温度不低于900℃。
5.按照权利要求1所述的耐液态铅/铅铋腐蚀的马氏体耐热钢,其特征在于:经热处理后,耐热钢的室温力学性能为:拉伸强度大于600 MPa,屈服强度大于400MPa,延伸率大于20%,断面收缩率不小于55%,常温夏比V口冲击功不小于100 J。
6.按照权利要求1所述的耐液态铅/铅铋腐蚀的马氏体耐热钢,其特征在于:经热处理后,耐热钢的550℃拉伸性能为:拉伸强度大于390 MPa,屈服强度大于290MPa,延伸率大于20%,断面收缩率不小于55%。
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