CN113930683A - 一种核电站耐高温压力容器用钢及其制造方法 - Google Patents
一种核电站耐高温压力容器用钢及其制造方法 Download PDFInfo
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Abstract
本发明提供了一种核电站耐高温压力容器用钢及其制造方法,该钢的成分按重量百分比计如下:C:<0.1%;Si≤0.30%;Mn:1.01%~2.00%;P≤0.010%;S≤0.005%;Ni≤0.49%;Cr:0.50%~0.80%;Mo≤0.40%;Nb:0.041%~0.055%;Als≤0.012%;B:0.0011%~0.0029%;ZrO2:0.001%~0.005%,余量为Fe和不可避免的杂质。制造方法,包括冶炼、连铸、轧制、调质;应用本发明生产的钢板调质处理和模拟焊后热处理后‑20℃冲击吸收能量保持在111J以上,压力容器用钢钢板调质处理态和模拟焊后热处理后钢板常温下抗拉强度≥620MPa,350℃高温下抗拉强度≥550MPa,450℃高温下抗拉强度≥450MPa。
Description
技术领域
本发明属于金属材料领域,尤其涉及一种核电站耐高温压力容器用钢及其制造方法。
背景技术
目前国内运行的核电站主要为压水堆核电站,压水堆核电站主要由蒸汽供应***(一回路***)、汽轮发电***(二回路***)及其他辅助***组成,核电站压力容器用钢属于核一级产品,该类材料由于其应用环境的特殊性其服役过程中要承受到堆芯中子轰击而引起的辐照脆化,由于一回路的蒸汽热量的原因钢板还需要耐高温的要求,还需要良好的强韧匹配,同时均需焊接组成所以钢板也需要满足一定的模拟焊后热处理性能。
因此,核电站耐高温压力容器用钢的机械性能要求较多和非常严格。随着华龙一号和CAP1400示范项目的开展,核电技术的全面国有化已经实现,同时对核岛设备用钢的要求逐渐明确,我们也需对该类材料进行细致的研究。
本发明通过设计单位对核电压力容器用钢性能的需求,进而在合金元素方面进行了设计,再配合适宜的轧制和热处理工艺,从而保证钢板在不同状态下的性能满足要求。
目前生产的核反应堆安全壳用钢的相关专利如下:
专利文献《抗拉强度大于690MPa级的核容器用钢及生产方法》(申请号:201110117614.4)公开了一种核容器用钢板的生产方法,其化学元素质量百分含量为:C≤0.08%、Si:0.15~0.50%、Mn:1.30~1.60%、Alt:0.01~0.05%、Ni:0.42~0.70%、Mo:0.32~0.60%、Cr:0.10~0.30%、Ti:0.01~0.04%,控制元素:P≤0.008%,S≤0.005%,N≤0.005%,Cu≤0.03%,V≤0.007%,Sn≤0.005%,Sb≤0.005%,As≤0.010%,Pb≤0.005%其余为Fe及不可避免的杂质。该发明的钢板屈服强度≥570MPa,抗拉强度:690~860MPa,-20℃冲击≥100J。但该发明的化学成分与本发明存在区别,并且该发明的化学成分要求较为严格,会增加冶炼控制难度和成本,同时该发明中并没有考虑钢板的长时间模拟焊后热处理后力学性能,并不能确保核容器用钢的需求。
专利文献《一种压力容器用厚规格钢板的调制处理方法》(申请号:201010154420.7)为山西太钢不锈钢股份有限公司发明的一种压力容器用厚规格钢板调质处理方法,它包括下述依次的步骤:Ι淬火将钢板加热到920℃~930℃,保温45~55分钟,再进行淬火处理;Ⅱ回火处理将淬火后的钢板加热到630℃~650℃保温40~50分钟,取出钢板冷却到室温;Ⅲ二次淬火将加热钢板加热到920℃~930℃,保温50~60分钟,将钢板进行淬火处理;Ⅳ二次回火将二次淬火后的钢板在室状炉内,要求温度控制波动不大于±5℃,加热到615℃~625℃保温40~50分钟,取出自然冷却到室温。该对比文件与本发明存在本质区别,该发明中采用两次调质处理将钢板的抗拉强度Rm提高到630MPa,延伸率A提高到20~23%,而本发明采用一次调质处理即可达到甚至超过其强度,并且能够大幅降低成本。
专利文献《核电站安全壳用厚钢板及其制造方法》(申请号:201210269122.1)公开的钢板合金成分为:C:0.06-0.15%,Si:0.10-0.40%,Mn:1.0-1.5%,Mo:0.10-0.30%,P≤0.012%,S≤0.003%,Alt:0.015-0.050%,Ni:0.20-0.50%;以及V≤0.050%,Ti≤0.030%,Cr≤0.25%,Nb≤0.030%,Ca:0.0005-0.0050%中的至少一种;余量为Fe和不可避免杂质。该发明的方法所述的核电站安全壳用厚钢板具有高强度,高韧性度,并且在低温情况下母材及热影响区都具有良好的冲击韧性,适合应用于核电站安全壳制造领域。但是该对比文件权利要求书中钢板的最大厚度为60mm,说明书中没有提供150℃或200℃高温拉伸指标。
发明内容
本发明的目的在于克服上述问题和不足而提供一种核电站耐高温压力容器用钢及其制造方法,通过成分设计以及与之相配合的加热、轧制、热处理工艺,生产的钢板不仅具有良好的力学性能,而且在长时间模拟焊后热处理后,室温拉伸、高温拉伸和低温冲击等关键指标依然保持良好,完全可以满足一种核电站耐高温压力容器用钢的使用要求。
本发明目的是这样实现的:
一种核电站耐高温压力容器用钢,该钢的成分按重量百分比计如下:C:<0.1%;Si≤0.30%;Mn:1.01%~2.00%;P≤0.010%;S≤0.005%;Ni≤0.49%;Cr:0.50%~0.80%;Mo≤0.40%;Nb:0.041%~0.055%;Als≤0.012%;B:0.0011%~0.0029%;ZrO2:0.001%~0.005%,余量为Fe和不可避免的杂质。
所述钢板调质处理和模拟焊后热处理后-20℃冲击吸收能量保持在111J以上,常温下所述钢板抗拉强度≥620MPa,模拟焊后热处理后钢板抗拉强度≥620MPa,350℃高温下钢板抗拉强度≥550MPa,450℃高温下抗拉强度≥450MPa,钢板厚度10-150mm。
本发明成分设计理由如下:
(1)C:C是强化结构钢最有效的元素,它直接影响钢材的强度、塑性、韧性和焊接性能等。因此本发明钢在设计成分时要求钢中C<0.1%。
(2)Si:Si是钢中五大元素之一,能够起到脱氧和固溶强化的作用,硅能促使铸钢中的柱状晶生长,同时也能减小晶体的各向异性,本发明要求Si≤0.30%。
(3)Mn:Mn是良好的脱氧剂和脱硫剂,钢中含有一定量的锰能消除或减弱由于硫所引起的钢的热脆性,同时Mn是钢中最主要的合金元素,对钢的综合性能有着较大的影响。因此实际生产中Mn含量控制在1.01%-2.00%。
(4)P:P溶于铁素体,增加钢的回火脆性,显著降低钢的塑性和韧性,对焊接也有不良影响,因此磷的含量越低越好,但P能提高钢的强度和耐大气腐蚀性能,本发明要求控制钢中的P≤0.010%。
(5)S:在钢中易形成硫化物夹杂,降低钢的冲击韧性,损害焊接性能,同时加重中心偏析、疏松等缺陷,并会增加辐照脆化,因此本发明要求S≤0.005%。
(6)Ni:一定含量的Ni元素能够降低钢中位错运动阻力,随着位错运动阻力的降低,钢中的应力会松弛,本专利正式利用Ni元素来改基体组织位错和亚结构的方式,从而提高钢的韧性,本发明控制钢中Ni≤0.49%。
(7)Cr:Cr在钢中能显著改善钢的抗氧化作用,由于本发明用钢属于核电站安全壳模块用钢,核电站用钢要求钢板具有一定的耐蚀性,铬能够增加抗腐蚀能力,并且一定量的铬有也能够提高钢的硬度,因此本发明要求钢中Cr:0.50%-0.80%。
(8)Mo:Cr-Mo合金***利于调制钢的生产,同时钼是强碳化物形成元素,当含量较低时,形成复合的渗碳体,并可以提高耐热性和减少回火脆性。因此本发明要求Mo≤0.40%。
(9)Nb:Nb能提高钢的屈服强度,降低脆性转变温度,对钢的焊接性能有益,同时Nb对辐照比较敏感性差,因此本发明要求钢Nb含量控制为0.041%-0.055%。
(10)Als:铝在炼钢中起到一定的脱氧作用,还有利于细化晶粒。通过适当的控制产生细小的Al2O3第二相能够作为形核质点,有利于整体性能。所以本发明要求Als含量≤0.012%。
(11)B:B是唯一的一个晶间强化元素,微量B还可提高其高温强度,并且B吸收中子能力强,但略有促进回火脆性的倾向。因此本发明要求钢B含量控制为0.0011%-0.0029%。
(13)ZrO2:细化晶粒作用,有利于钢的低温韧性,因此钢中加入的ZrO2含量控制在0.001%-0.005%
本发明技术方案之二是提供一种核电站耐高温压力容器用钢的制造方法,包括冶炼、连铸、轧制、调质;
(1)冶炼、连铸:原料经KR铁水预处理,出钢时吹氩气25~45min;进行LF精炼和RH真空脱气处理,RH真空保持25min以上;
板坯连铸时,连铸过热度为15℃~30℃,二冷阶段加强电磁搅拌,搅拌方式为正反转交替搅拌,其中单向搅拌时间12~15s,电流1100~1700A,频率为3~19Hz,使钢液经过连铸获得连铸坯,且连铸坯中等轴晶比例不低于80%,连铸拉坯速率为1.2~1.7m/min;在水平段,即凝固末端投入重压下,连铸坯压下量为15~20mm;
(2)轧制:开轧前利用高压水对出炉后的铸坯进行除鳞32~59s,除鳞机压力为41~59MPa;分两阶段轧制:第一阶段为再结晶轧制即粗轧,粗轧开轧温度为1150~1250℃,粗轧终轧温度为1100~1200℃,粗轧道次数≤7;第二阶段为精轧,精轧开轧温度为1000~1150℃,精轧终轧温度为970~1100℃,精轧道次数≥6;
(2)调质处理工艺为:
淬火温度850℃~950℃保温时间1~6min/mm;
回火温度620℃~680℃保温时间1~10min/mm。
钢板轧后采用调质处理工艺,得到细致、均匀的回火索氏体组织,并使钢板具有良好的综合力学性能。
本发明的有益效果在于:
(1)本发明工艺技术生产的钢板,通过化学成分优化和工艺参数的合理设计,具有优良的低温韧性指标。钢板调质处理和模拟焊后热处理后-20℃冲击吸收能量保持在111J以上。
(2)本发明钢种经调质和模拟焊后热处理(保温温度600℃,保温时间长达15小时)后,不同状态下均具有良好的强韧性。调质热处理和模拟焊后热处理后的钢板常温拉伸的抗拉强度≥620MPa,350℃高温拉伸的抗拉强度≥550MPa,400℃高温拉伸的抗拉强度≥450MPa。
附图说明
图1为本发明实施例1显微组织金相图。
具体实施方式
下面通过实施例对本发明作进一步的说明。
本发明实施例根据技术方案的组分配比,进行冶炼、连铸、轧制、调质。
冶炼、连铸:原料经KR铁水预处理,出钢时吹氩气25~45min;进行LF精炼和RH真空脱气处理,RH真空保持25min以上;板坯连铸时,连铸过热度为15℃~30℃,二冷阶段加强电磁搅拌,搅拌方式为正反转交替搅拌,其中单向搅拌时间12~15s,电流1100~1700A,频率为3~19Hz,使钢液经过连铸获得连铸坯,且连铸坯等轴晶比例不低于80%,连铸拉坯速率为1.2~1.7m/min;在水平段,即凝固末端投入压下,连铸坯压下量为15~20mm;
轧制:轧制前利用高压水对出炉后的铸坯进行除鳞32~59s,除鳞机压力为41~59MPa;分两阶段轧制:第一阶段为再结晶轧制即粗轧,粗轧开轧温度为1150~1250℃,粗轧终轧温度为1100~1200℃;第二阶段为精轧,精轧开轧温度为1000~1150℃,精轧终轧温度为970~1100℃;所述粗轧轧制道次数≤7,所述精轧道次数≥6;
调质处理工艺为:
淬火温度850℃~950℃保温时间1~6min/mm;
回火温度620℃~680℃保温时间1~10min/mm。
本发明实施例钢的成分见表1。本发明实施例钢的主要冶炼、连铸工艺参数见表2。本发明实施例钢的主要轧制工艺参数见表3。本发明实施例钢的主要调质工艺参数见表4。本发明实施例钢的性能见表5。
表1本发明实施例钢的成分(wt%)
表2本发明实施例钢的主要冶炼、连铸工艺参数
表3本发明实施例钢的主要轧制工艺参数
表4本发明实施例钢的主要调质工艺参数
表5本发明实施例钢的性能
为了表述本发明,在上述中通过实施例对本发明恰当且充分地进行了说明,以上实施方式仅用于说明本发明,而并非对本发明的限制,有关技术领域的普通技术人员,在不脱离本发明的精神和范围的情况下,还可以做出各种变化和变型,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内,本发明的专利保护范围应由权利要求限定。
Claims (6)
1.一种核电站耐高温压力容器用钢,其特征在于,该钢的成分按重量百分比计如下:C:<0.1%;Si≤0.30%;Mn:1.01%~2.00%;P≤0.010%;S≤0.005%;Ni≤0.49%;Cr:0.50%~0.80%;Mo≤0.40%;Nb:0.041%~0.055%;Als≤0.012%;B:0.0011%~0.0029%;ZrO2:0.001%~0.005%,余量为Fe和不可避免的杂质。
2.根据权利要求1所述的一种核电站耐高温压力容器用钢,其特征在于,所述钢板调质处理和模拟焊后热处理后-20℃冲击吸收能量保持在111J以上,压力容器用钢钢板调质处理态和模拟焊后热处理后钢板常温下抗拉强度≥620MPa,350℃高温下抗拉强度≥550MPa,450℃高温下抗拉强度≥450MPa。
3.一种权利要求1或2所述的一种核电站耐高温压力容器用钢的制造方法,包括冶炼、连铸、轧制、调质;其特征在于:
(1)轧制:分两阶段轧制:第一阶段为再结晶轧制即粗轧,粗轧开轧温度为1150~1250℃,粗轧终轧温度为1100~1200℃;第二阶段为精轧,精轧开轧温度为1000~1150℃,精轧终轧温度为970~1100℃;
(2)调质处理工艺为:
淬火温度850℃~950℃保温时间1~6min/mm;
回火温度620℃~680℃保温时间1~10min/mm。
4.根据权利要求3所述的一种核电站耐高温压力容器用钢的制造方法,其特征在于:冶炼、连铸:原料经KR铁水预处理,出钢时吹氩气25~45min;进行LF精炼和RH真空脱气处理,RH真空保持25min以上;板坯连铸时,连铸过热度为15℃~30℃,二冷阶段加强电磁搅拌,搅拌方式为正反转交替搅拌,其中单向搅拌时间12~15s,电流1100~1700A,频率为3~19Hz,使钢液经过连铸获得连铸坯,且连铸坯等轴晶比例不低于80%,连铸拉坯速率为1.2~1.7m/min;在凝固末端投入压下,连铸坯压下量为15~20mm。
5.根据权利要求3所述的一种权利要求1或2所述的一种核电站耐高温压力容器用钢的制造方法,其特征在于:步骤(1)轧制前利用高压水对出炉后的铸坯进行除鳞32~59s,除鳞机压力为41~59MPa。
6.根据权利要求3所述的一种核电站耐高温压力容器用钢的制造方法,其特征在于:所述粗轧轧制道次数≤7,所述精轧道次数≥6。
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