CN115011878A - 一种高耐硫酸露点腐蚀圆钢及其制备方法 - Google Patents

一种高耐硫酸露点腐蚀圆钢及其制备方法 Download PDF

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CN115011878A
CN115011878A CN202210699003.3A CN202210699003A CN115011878A CN 115011878 A CN115011878 A CN 115011878A CN 202210699003 A CN202210699003 A CN 202210699003A CN 115011878 A CN115011878 A CN 115011878A
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steel
ferrite
temperature
sulfuric acid
dew point
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郑健
张成元
刘静
杨建华
周文浩
彭志贤
迟云广
罗雄志
黄振华
袁渊
周光杰
徐瑞军
花含平
宋美微
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Wuhan University of Science and Engineering WUSE
Hunan Valin Xiangtan Iron and Steel Co Ltd
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Hunan Valin Xiangtan Iron and Steel Co Ltd
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Abstract

一种高耐硫酸露点腐蚀圆钢及其制备方法，钢中元素质量百分比为C=0.03%～0.08%，Si=0.20%～0.35%，Mn=0.45～0.60%，P≤0.015%，S≤0.008%，Al=0.015%～0.050%，Ti=0.030%～0.060%，Cr=0.90%～1.05%，Mo=0.22%～0.30%，Cu=0.45%～0.55%，W=0.18％～0.20%，Ni=0.25%～0.50%，Sn=0.15%～0.20%，Sb=0.20%～0.25%，其余为Fe和不可避免的杂质。生产的圆钢热轧态耐70℃、50%质量分数硫酸腐蚀速率＜1.8mg/cm2·h，正火态耐70℃、50%质量分数硫酸腐蚀速率＜0.18mg/cm2·h；热轧态组织为88~92%铁素体（F）+8~12%珠光体（P），其中铁素体平均晶粒尺寸为15~19μm；正火热处理后组织为98%以上铁素体（F），夹杂物总量A+B+C+D+Ds≤2.0级。

Description

一种高耐硫酸露点腐蚀圆钢及其制备方法
技术领域
本发明属于耐腐蚀钢技术领域，涉及一种高耐硫酸露点腐蚀圆钢及其制备方法。
背景技术
09CrCuSb(ND钢)钢是一种被广泛应用于预热器和热交换器合金钢管的高钢铁材料，具有较佳的抗硫酸露点腐蚀性能，同时具备良好的塑性及强度，符合当前对绿色、低碳能源发展的需求，被广泛应用于省煤器、空气预热器、高压锅炉换热器和蒸发器等领域。
中华人民共和国能源行业标准于2021年7月1日实施的《锅炉、热交换器用钢管订货技术条件-NB/T47019-2021》，对09CrCuSb钢的成分相较NB/T47019-2011做了较大的调整，特别是大幅增加了钢中的Cu、Sb、Sn、Mo、W等元素。而耐蚀合金元素的增加一方面造成了铸坯及型材质量的波动，另一方面新标准中合金元素含量与当前冶炼、成型工艺失配导致的微观组织结构变化，也会影响09CrCuSb钢耐露点腐蚀性能，对相关钢厂及制管行业带来了新的技术挑战。然而，09CrCuSb此类低碳耐蚀合金钢的性能不仅取决于合金元素含量，还在于工艺参数对合金元素扩散聚集行为对最终组织结构的影响。
CN201610499180.1分开了一种改进型09CrCuSb耐硫酸露点腐蚀用钢，对化学成分及钢板和圆管坯轧制工艺进行了限定保护；CN202111240509.X公开了一种耐硫酸低温露点腐蚀钢09CrCuSb的生产方法，对150mm连铸坯规格的圆管坯连铸及轧制工艺进行了限定保护。
但新国标NB/T47019-2021要求的提高钢中易扩散偏聚的低熔点元素Sn、Sb、Cu、W等含量，势必会严重影响铸坯及管坯表明质量，更高的合金元素含量在温度控制不当时还会造成异常相析出，影响材料的最终耐露点腐蚀性能，因此对材料成形温度的控制的要求也愈发重要。
发明内容
本发明所要解决的技术问题是提供一种高耐硫酸露点腐蚀圆钢及其制备方法。
本发明是通过以下技术方案来实现的：
一种高耐硫酸露点腐蚀圆钢，钢中元素质量百分比为C= 0.03%～0.08%，Si=0.20%～0.35%，Mn= 0.45%～0.60%，P≤ 0.015%，S≤ 0.008%，Al= 0.015%～0.050%，Ti=0.030%～0.060%，Cr= 0.90%～1.05%，Mo= 0.22%-0.30%，Cu= 0.45%～0.55%，W=0.18％～0.20%，Ni= 0.25%~0.50%，Sn= 0.15%～0.20%，Sb= 0.20%～0.25%，其余为Fe和不可避免的杂质；其热轧态组织为88%~92%铁素体（F）+8%~12%珠光体（P），其中铁素体平均晶粒尺寸为15~19μm；正火热处理后组织为98%以上铁素体（F）；夹杂物总量A+B+C+D+Ds≤ 2.0级。
一种高耐硫酸露点腐蚀圆钢的制备方法，关键工艺步骤包括：
（1）炼钢：采用顶底复吹转炉炼钢，出钢过程中加入脱氧剂、合金和部分顶渣进行脱氧合金化；LF炉根据成分要求精确调整化学成分、脱氧去夹杂、控制钢水温度和钙处理；VD炉进行真空脱气并进一步去除夹杂和深度脱硫；
（2）连铸：中间包过热度25～30℃，结晶器液面波动控制在±5mm，采用电磁搅拌和动态轻压下技术，拉速1~1.15m/min，二冷水配比为0.16~0.28L/kg；连铸方坯尺寸规格范围350～430mm；
（3）轧制：预热段温度580～700℃，均热段温度T:1020～1070℃，均热在炉时间270~350min；开轧温度960～1050℃，终轧温度850～900℃；轧后冷床密排冷却至280～400℃后成捆收集入保温坑缓冷≥24h。
发明原理：
溶质原子的非平衡偏聚存在临界峰值时间t c ，在某温度下保温时间小于此临界时间t c 时，元素会逐渐发生晶界偏聚；而当保温时间大于临界时间t c 时，元素偏聚量达到峰值，之后会逐渐发生偏聚的解聚。09CrCuSb钢中含有较高含量的易偏聚元素，如Cu、Sb、Sn等，因此，严格控制过热度和加热保温时间的匹配关系是降低元素偏聚对铸坯质量不利影响的关键环节。本发明中均热温度为1020～1070℃，均热温度T与保温时间t之间的对应关系为t=1.5×(T-840)±5min。
另外，09CrCuSb钢中含有较高含量的Cr元素，同时新国标中还添加了Mo、Nb、V、W这类典型的铁素体稳定化元素，显著增加了钢中Cr当量（Creq）,会造成钢中高温δ-铁素体相在液相线温度附近的析出。钢中δ-铁素体会造成材料疲劳性能及冲击韧性的降低，同时高温δ-铁素体相并不会因后期的正火工艺消失，还会进一步影响09CrCuSb钢的耐硫酸露点腐蚀性能。本发明中连铸中间包过热度为25～30℃。
本发明中高耐硫酸露点腐蚀圆钢及其制备方法，通过合理配比合金元素，提高铸坯表面质量的同时，有效抑制了钢中δ-铁素体析出。使钢在腐蚀过程中生成含Cu、Cr、Sb的致密腐蚀产物，抑制阳极反应和阴极的电化学反应，热轧态耐70℃、50%质量分数硫酸腐蚀速率＜1.8mg/cm2·h，正火态耐70℃、50%质量分数硫酸腐蚀速率＜0.18mg/cm2·h。本发明中的新型耐硫酸露点腐蚀用钢，其热轧态组织为88~92%铁素体（F）+8~12%珠光体（P），其中铁素体平均晶粒尺寸为15~19μm；正火热处理后组织为98%以上铁素体（F），夹杂物总量A+B+C+D+Ds≤2.0级。综合以上因素，该材料具有较好的耐硫酸露点腐蚀性能，并且夹杂物总量水平低、金相组织均匀。
与现有技术相比，本发明的优点在于：（1）提出了一种在新国标成分框架下的高耐露点腐蚀09CrCuSb圆钢及制备方法，克服了高Cu、Sb、Sn等低熔点易偏聚合金元素对铸坯表面质量的不利影响，明显改善了铸坯表面因沿原奥氏体晶界形成的薄膜状铁素体对起裂的不良作用；（2）通过优化连铸和轧制成型工艺，显著降低了新国标成分框架下的钢中高温δ-铁素体含量，提高了09CrCuSb圆钢耐硫酸露点腐蚀能力，本发明制造的09CrCuSb圆钢耐露点腐蚀能力明显高于传统工艺制备的材料。
附图说明
图1为实施例1金相组织图。
图2 为实施例2金相组织图。
图3为实施例1浸泡后的试样表面腐蚀产物形貌图。
图4 为实施例2浸泡后的试样表面腐蚀产物形貌图。
具体实施方式
以下结合本发明的较佳实施例对本发明的技术方案作更详细的描述。
实施例1
一种高耐硫酸露点腐蚀圆钢及其生产方法，钢中元素质量百分比为C= 0.045%，Si= 0.28，Mn= 0.48%，P≤ 0.008%，S≤ 0.006%，Al= 0.012%，Ti= 0.036%，Cr= 0.95%，Mo=0.25%，Cu= 0.50%，W=0.18％，Ni= 0.25%，Sn= 0.18%，Sb= 0.18%，其余为Fe和不可避免的杂质；
关键工艺步骤包括：
（1）炼钢：采用顶底复吹转炉炼钢，出钢过程中加入脱氧剂、合金和部分顶渣进行脱氧合金化；LF炉根据成分要求精确调整化学成分、脱氧去夹杂、控制钢水温度和钙处理；VD炉进行真空脱气并进一步去除夹杂和深度脱硫；
（2）连铸：中间包过热度28℃，结晶器液面波动控制在±5mm，采用电磁搅拌和动态轻压下技术，拉速1.13m/min，二冷水配比为0.18/kg。连铸方坯尺寸规格范围350mm；
（3）轧制：预热段温度650℃，均热段温度T=1050℃，均热在炉时间为t=320min；开轧温度990℃，终轧温度880℃；轧后冷床密排冷却至350℃后成捆收集入保温坑缓冷≥24h；
得到热轧态组织为90%铁素体（F）+10%珠光体（P），其中铁素体平均晶粒尺寸为~17μm，正火热处理后组织中铁素体（F）体积分数为~98%；夹杂物总量A+B+C+D+Ds≤ 2.0级。
经由上述工艺方法制备的耐硫酸露点腐蚀圆钢铸坯表面裂纹深度约为0.8mm，经酸洗处理后的圆钢表面无明显裂纹。经70℃质量分数50%的硫酸溶液浸泡后的腐蚀速率为1.32 mg/cm2·h，腐蚀后的浸泡试样宏观观察表面可见黑色致密坚硬的腐蚀产物膜。经880℃正火处理后，圆钢经70℃质量分数50%的硫酸溶液浸泡后的腐蚀速率为0.16 mg/cm2·h。
实施例2
一种高耐硫酸露点腐蚀圆钢用项生产方法，钢中元素质量百分比为C= 0.05%，Si=0.32%，Mn= 0.45%，P≤ 0.008%，S≤ 0.008%，Al= 0.018%，Ti= 0.050%，Cr= 0.96%，Mo=0.28%，Cu= 0.50%，W=0.20%，Ni= 0.42%，Sn= 0.18%，Sb= 0.18%，其余为Fe和不可避免的杂质；
关键工艺步骤包括：
（1）炼钢：采用顶底复吹转炉炼钢，出钢过程中加入脱氧剂、合金和部分顶渣进行脱氧合金化；LF炉根据成分要求精确调整化学成分、脱氧去夹杂、控制钢水温度和钙处理；VD炉进行真空脱气并进一步去除夹杂和深度脱硫；
（2）连铸：中间包过热度38℃，结晶器液面波动控制在±5mm，采用电磁搅拌和动态轻压下技术，拉速1.16m/min，二冷水配比为0.26/kg。连铸方坯尺寸规格范围400mm；
（3）轧制：预热段温度650℃，均热段温度T=1070℃，均热在炉时间为t=340min；开轧温度970℃，终轧温度850℃；轧后冷床密排冷却至350℃后成捆收集入保温坑缓冷≥24h；
得到的钢其热轧态组织为90%铁素体（F）+7%珠光体（P）+3% δ-铁素体（F）（图2中箭头所示），其中铁素体平均晶粒尺寸为~20μm；正火热处理后组织为97%以上铁素体（F）+3%δ-铁素体（F）；夹杂物总量A+B+C+D+Ds≤ 2.0级。
经由上述工艺方法制备的耐硫酸露点腐蚀圆钢铸坯表面裂纹深度约为2.1mm，经酸洗处理后的圆钢表面无明显裂纹。经70℃质量分数50%的硫酸溶液浸泡后的腐蚀速率为2.04 mg/cm2·h，腐蚀后的浸泡试样宏观观察表面呈红褐色且腐蚀产物膜较疏松。经880℃正火处理后，圆钢经70℃质量分数50%的硫酸溶液浸泡后的腐蚀速率为0.28 mg/cm2·h。
可见，在采用本发明专利所要求的工艺参数时，铸坯质量和圆钢耐蚀性都取得了较好的效果，而采用本发明专利所要求的工艺参数限定的指标范围外时，如实施例2，铸坯质量和圆钢耐蚀性相对较差。

Claims (2)

1.一种高耐硫酸露点腐蚀圆钢，其特征在于：钢中元素质量百分比为C= 0.03%～0.08%，Si= 0.20%～0.35%，Mn= 0.45～0.60%，P≤ 0.015%，S≤ 0.008%，Al= 0.015%～0.050%，Ti= 0.030%～0.060%，Cr= 0.90%～1.05%，Mo= 0.22%~0.30%，Cu= 0.45%～0.55%，W=0.18％～0.20%，Ni= 0.25%-0.50%，Sn= 0.15%～0.20%，Sb= 0.20%～0.25%，其余为Fe和不可避免的杂质；其热轧态组织为88%~92%铁素体（F）+8~12%珠光体（P），其中铁素体平均晶粒尺寸为15~19μm；正火热处理后组织为98%以上铁素体（F）；夹杂物总量A+B+C+D+Ds≤ 2.0级。
2.根据权利要求1所述的一种高耐硫酸露点腐蚀圆钢的制备方法，其特征在于关键工艺步骤包括：
（1）炼钢：采用顶底复吹转炉炼钢，出钢过程中加入脱氧剂、合金和部分顶渣进行脱氧合金化；LF炉根据成分要求精确调整化学成分、脱氧去夹杂、控制钢水温度和钙处理；VD炉进行真空脱气并进一步去除夹杂和深度脱硫；
（2）连铸：中间包过热度25～30℃，结晶器液面波动控制在±5mm，采用电磁搅拌和动态轻压下技术，拉速1~1.15m/min，二冷水配比为0.16~0.28L/kg，连铸方坯尺寸规格范围350～430mm；
（3）轧制：预热段温度580～700℃，均热段温度T:1020～1070℃，均热在炉时间270~350min；开轧温度960～1050℃，终轧温度850～900℃；轧后冷床密排冷却至280～400℃后成捆收集入保温坑缓冷≥24h。
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