CN115323142B - 一种耐海洋大气腐蚀钢板的生产方法 - Google Patents

一种耐海洋大气腐蚀钢板的生产方法 Download PDF

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CN115323142B
CN115323142B CN202211028402.3A CN202211028402A CN115323142B CN 115323142 B CN115323142 B CN 115323142B CN 202211028402 A CN202211028402 A CN 202211028402A CN 115323142 B CN115323142 B CN 115323142B
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steel plate
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CN115323142A (zh
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周文浩
杨建华
刘喜锚
张成元
彭宁琦
张勇伟
史术华
程浩轩
罗松云
丁兴艳
陈志斌
葛金婧
范明
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Hunan Valin Xiangtan Iron and Steel Co Ltd
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Abstract

一种耐海洋大气腐蚀钢板的生产方法，钢的重量百分组成为C=0.03%~0.08%、Si=0.15%~0.30%、Mn=0.60%~1.50%、P≤0.025%、S≤0.010%、Al=0.020%~0.050%、Ti=0.007%~0.030%、Nb=0.010%~0.060%、Cu=0.20%~0.50%、Ni=0.50%~3.50%、Cr≤0.50%、Mo≤0.30%，余量为Fe和不可避免的杂质元素；关键工艺步骤包括：加热、轧制、冷却、表面处理和热处理。本发明通过对铸坯和钢板表面氧化铁皮和锈层的控制，使钢板能够快速获得一层附着性很强的磷酸盐、硝酸盐或铬酸盐的保护膜以及一层均匀稳定的含镍、铬、铜或钙的氧化层保护膜，在钢板使用和服役过程中有防止锈液流挂和起到“以锈止锈”的作用。

Description

一种耐海洋大气腐蚀钢板的生产方法
技术领域
本发明属于低合金钢生产技术领域，特别是涉及一种耐海洋大气腐蚀钢板的生产方法。
背景技术
中国是一个海洋大国，拥有漫长的海岸线和丰富的海洋资源。进入21世纪以来，国家加快了在南海海洋资源利用、沿岸以及离岸工程等方面的建设。但是南海海洋环境具有高湿热、强辐射、高盐雾等特点，腐蚀成为桥梁、塔架、罐箱等海洋基础设施建设材料的痛点。
中国专利CN108004488A提出了一种耐海洋气候高韧性桥梁钢板及其生产方法。该钢板的原料化学成分的质量百分比为C：0.041～0.087％、Mn：1.03～2.00％、Si：0.67～1.43％、P≤0.007％、S≤0.003％、Nb：0.047～0.083％，Ti：0.010～0.027％，Mo：0.32～0.73％，Cr：0.50～1.17％，Cu：0.50～1.05％，Ni：2.51～6.70％，Ca：0.0021～0.0073％，Sb：0.08～0.31％，其余为Fe和不可避免的杂质。该发明添加了较多的Ni、Cr、Mo等贵重金属以及钢中易挥发元素Ca、易偏析元素Sb、易产生表面缺陷元素Si等，其合金成本高、冶炼工艺复杂、钢板表面质量差。
中国专利CN112647014A公开了一种适用于海洋大气环境用建筑结构钢，其化学成分及其质量分数如下：碳：0.07％～0.17％，硅：0.6％～0.8％，锰：0.3％～1.0％，磷：0.08％～0.15％，硫：0.005～0.035％，铜：0.15％～0.2％，锑：0.1％～0.2％，铈：0.0025％～0.0045％；并选择性包含：锡：0.01％～0.02％，钒：0.05-0.1％中任意一种或两种，其余为铁以及不可避免的杂质。该钢复合添加较多的P-Sb-Ce等低熔点元素，影响钢的低温韧性、可焊性、冷成形性等。
中国专利CN113621873A提出了一种具有稳定化锈层的耐候结构钢及其制备方法。制备时，先通过冶炼、轧制和冷却工艺制备钢板，然后经抛丸后通过周期性洒水的快锈处理（每8小时1次，每天3次，保持干湿交替，连续洒水≥7天）和喷洒5%～10%的磷酸钾溶液的稳定化处理（7~10天），使钢板表面形成一层稳定化锈层。该发明除了通过合金元素提高钢基体的耐候性能之外，还关注于钢板表面锈层的形成及状态以起到“以锈止锈”的作用，使钢的耐蚀性更佳。但是这种方法需要长时间进行快锈处理和锈层稳定化处理，延长了交货期，增加了库存。
中国专利CN113529152A公开了一种实现钢铁材料快速生锈的表面处理方法，通过电化学阳极氧化的方法将钢板表面的单质铁氧化成化合态（电解氧化处理），然后在其表面涂覆水或盐溶液，促进铁盐水解成铁的氧化物或羟基氧化物的水合物（湿润处理），再通过自然晾干，使得形成的铁氧化物的水合物脱水（脱水处理），从而使钢板表面形成均匀的锈层。这种方法虽然加速了锈层的形成，但电解能耗大，具有静电效应，有触电风险，并且长时间接触电磁波，可能会影响操作工人的身体健康。
发明内容
针对上述现有技术的不足，本发明的目的在于提供一种耐海洋大气腐蚀钢板的生产方法，钢板经加热、轧制、冷却、表面处理及热处理工序后，钢板表面能够快速形成稳定化锈层，从而有效提高耐海洋大气腐蚀钢板的生产效率，使交货期大为缩短。
本发明的技术方案：
一种耐海洋大气腐蚀钢板的生产方法，钢的重量百分组成为C=0.03%~0.08%、Si=0.15%~0.30%、Mn=0.60%~1.50%、P≤0.025%、S≤0.010%、Al=0.020%~0.050%、Ti=0.007%~0.030%、Nb=0.010%~0.060%、Cu=0.20%~0.50%、Ni=0.50%~3.50%、Cr≤0.50%、Mo≤0.30%，余量为Fe和不可避免的杂质元素；关键工艺步骤包括：
（1）加热：加热前对铸坯表面进行机械修磨，修磨深度以去除连铸过程形成的表面氧化铁皮为基准，然后喷涂含SiO2、Al2O3、MgO等的高温抗氧化涂料，涂层厚度为0.1~0.3mm；加热过程不使用焦炉煤气作燃料，并控制炉内残氧量≤2.5%，控制均热温度为1250±20℃、加热时间≤300min；
（2）轧制：铸坯出加热炉后进行初除鳞，然后进行粗轧和精轧的两阶段控制轧制，粗轧轧制的板坯表面温度≥1000℃，精轧轧制的板坯表面温度在900~800℃间或更低且精轧压缩比≥3，每个阶段轧制时间≤180s并至少除鳞3道次；同时控制两个阶段间隔间板坯表面温度在1000~900℃范围内的时间≥60s并确保精轧轧制前除鳞；所有除鳞均使高压水压力不低于22MPa且除鳞喷嘴距钢板表面不大于500mm；
（3）冷却：轧后以≥5℃/s的冷却速度加速冷却至600~400℃，之后继续冷却至钢板表面温度一直到250℃，控制该段区间的冷却时间≥600s；
（4）表面处理：钢板在室温下进行抛丸处理，抛丸除锈等级不低于Sa2.5且钢板表面粗糙度为40~80um；然后在钢板表面上喷洒质量分数为2%～10%的含Ni离子或Cu离子或Cr离子或Ca离子或几种离子混合的水溶液；
（5）热处理：采用明火炉进行回火热处理，控制空气流量与燃气流量比例为9~11,炉膛内压力为-5~0Pa；控制回火温度为400~600℃、保温时间≥45min。
进一步地，步骤（4）中，所述含Ni离子的溶液为Ni(NO3)2溶液、所述含Cu离子的溶液为Cu(NO3)2溶液、所述含Cr离子的溶液为Cr(NO3)2溶液、所述含Ca离子的溶液为Ca(H2PO2)2或CaCrO4溶液。
优选地，步骤（4）中，钢板抛丸后在表面上喷洒质量分数为2%～3%的Ni(NO3)2、0.5%～1.0%的Ca(H2PO2)2，余量为H2O的溶液。
优选地，步骤（4）中，钢板抛丸后在表面上喷洒质量分数为1%～2%的Ni(NO3)2、1%～2%的Cu(NO3)2、1%～2%的Cr(NO3)2、0.5%～1.0%的CaCrO4、余量为H2O的溶液。
本发明所述生产方法的科学原理：本发明所述耐海洋大气腐蚀钢采用低碳、添加合金元素Ni、Cr、Cu等以及微合金化元素Nb和Ti的成分设计，使生产的钢板具有良好的力学性能和焊接性能；同时为获得良好的耐海洋大气腐蚀性能，对铸坯和钢板表面氧化铁皮和锈层的控制采取了一系列措施：（1）加热前对铸坯表面进行修磨和涂层处理，并结合均热温度、加热时间及炉内气氛、初除鳞工艺等的控制，目的是减少一次氧化铁皮的生成，并使其变得疏松，可以通过高压水除鳞完全去除；（2）通过控制轧制板坯表面温度、轧制时间、除鳞压力及道次数等以减小二次氧化铁皮，同时控制在表面氧化铁皮容易起皮的温度区间（900~1000℃）冷却较长时间并随后除鳞，有利于粗轧高温过程形成的二次氧化铁皮的去除，之后保证精轧压缩比使表面氧化铁皮厚度变小；（3）钢板轧制后加速冷却至中温区域，避免生成对耐蚀性不利的珠光体组织，之后控制在FeO的先共析转变和共析转变温度区间有足够时间冷却，使表面氧化铁皮发生相变而使其剥离性得以改善；（4）钢板热处理前对表面进行抛丸和喷洒含Ni、Cr、Cu或Ca离子的涂层处理，然后保证一定的温度、时间及炉内氧化氛围进行回火加热，一方面使钢板表面有更多的Ni、Cr、Cu、Ca等耐海洋大气腐蚀性元素以形成均匀的氧化膜；另一方面形成磷酸盐、硝酸盐、铬酸盐等，使回火过程形成的氧化层粘附性更强。从而使钢板表面形成能够阻碍大气中氧和水向钢基体进一步渗入腐蚀的稳定锈层。
本发明的有益效果：（1）本发明所述耐海洋大气腐蚀钢采用较少的P、Sn等杂质元素，钢板具有良好的强韧性，同时采用较少的Ni、Mo、Cr等贵重金属，合金成本低；（2）本发明通过对铸坯和钢板表面氧化铁皮和锈层的控制，使钢板能够快速获得一层附着性很强的磷酸盐、硝酸盐或铬酸盐的保护膜以及一层均匀稳定的含镍、铬、铜或钙的氧化层保护膜，在钢板使用和服役过程中有防止锈液流挂和起到“以锈止锈”的作用；（3）本发明提出的一种耐海洋大气腐蚀钢板的生产方法，可实现工业化批量生产，且生产效率高、交货期短；（4）本发明提出的钢板表面氧化铁皮的控制工艺对高表面质量钢板的生产有借鉴作用。
附图说明
图1为本发明实施例1的耐海洋大气腐蚀钢板表面氧化铁皮的微观形貌图。
具体实施方式
以下结合实施例及附图对本发明的内容作进一步说明。
实施例1
耐海洋大气腐蚀钢板的生产。钢的重量百分组成为C=0.05%、Si=0.22%、Mn=0.90%、P=0.015%、S=0.003%、Al=0.035%%、Ti=0.015%、Nb=0.025%、Cu=0.30%、Ni=1.00%、Cr=0.02%、Mo=0.10%，余量为Fe和不可避免的杂质元素；关键工艺步骤包括：
（1）加热：加热前对铸坯表面进行机械修磨，修磨深度以去除连铸过程形成的表面氧化铁皮为基准，然后喷涂含SiO2、Al2O3、MgO的高温抗氧化涂料，涂层厚度为0.2mm；加热过程不使用焦炉煤气作燃料，炉内残氧量最大为2.1%，均热温度为1250℃、加热时间为240min；
（2）轧制：铸坯出加热炉后进行初除鳞，然后进行粗轧和精轧的两阶段控制轧制，粗轧轧制的板坯表面温度最低为1020℃，精轧轧制的板坯表面温度在890~780℃间，精轧压缩比为3.2，粗轧轧制时间为140s，除鳞3道次，精轧轧制时间为160s，除鳞3道次，精轧第1道次除鳞；粗轧与精轧间隔间板坯表面温度在1000~900℃范围内的时间为65s；所有除鳞的高压水压力均为22MPa，除鳞喷嘴距钢板表面最大为475mm；
（3）冷却：轧后以约15℃/s的冷却速度加速冷却至520~580℃，之后进入保温罩缓冷，当冷却至钢板表面温度到250℃时的冷却时间为650s；
（4）表面处理：钢板在室温下进行抛丸处理，抛丸除锈等级不低于Sa2.5且钢板表面粗糙度为50~60um；然后在钢板表面上喷洒质量分数2.5%的Ni(NO3)2、0.8%的Ca(H2PO2)2、余量为H2O的溶液；
（5）热处理：采用明火炉进行回火热处理，控制空气流量与燃气流量比例为9.5~10.5,炉膛内压力为-5~0Pa；控制回火温度为550℃、保温时间为65min。
对实施例1钢板的表面氧化铁皮微观形貌进行观察，如图1所示。可见实施例1钢板有一层均匀稳定的氧化层，其与基体间有一层磷酸盐和硝酸盐的保护膜，有力地提高钢板耐海洋大气腐蚀能力。
实施例2
耐海洋大气腐蚀钢板的生产。钢的重量百分组成为C=0.07%、Si=0.18%、Mn=1.36%、P=0.012%、S=0.002%、Al=0.028%%、Ti=0.018%、Nb=0.036%、Cu=0.32%、Ni=3.10%、Cr=0.20%、Mo=0.15%，余量为Fe和不可避免的杂质元素；关键工艺步骤包括：
（1）加热：加热前对铸坯表面进行机械修磨，修磨深度以去除连铸过程形成的表面氧化铁皮为基准，然后喷涂含SiO2、Al2O3、MgO的高温抗氧化涂料，涂层厚度为0.2mm；加热过程不使用焦炉煤气作燃料，炉内残氧量最大为2.2%，均热温度为1260℃、加热时间为280min；
（2）轧制：铸坯出加热炉后进行初除鳞，然后进行粗轧和精轧的两阶段控制轧制，粗轧轧制的板坯表面温度最低为1040℃，精轧轧制的板坯表面温度在880~760℃间，精轧压缩比为4.0，粗轧轧制时间为125s，除鳞4道次，精轧轧制时间为170s，除鳞4道次，精轧第1道次除鳞；粗轧与精轧间隔间板坯表面温度在1000~900℃范围内的时间为80s；所有除鳞的高压水压力均为22MPa，除鳞喷嘴距钢板表面最大为480mm；
（3）冷却：轧后以约12℃/s的冷却速度加速冷却至420~480℃，之后下线堆冷，冷却至钢板表面温度到250℃的冷却时间超过600s；
（4）表面处理：钢板在室温下进行抛丸处理，抛丸除锈等级不低于Sa2.5且钢板表面粗糙度为60~70um；然后在钢板表面上喷洒质量分数为1.5%的Ni(NO3)2、1.5%的Cu(NO3)2、1.5%的Cr(NO3)2、0.75%的CaCrO4、余量为H2O的溶液；
（5）热处理：采用明火炉进行回火热处理，控制空气流量与燃气流量比例为9.5~10.5,炉膛内压力为-5~0Pa；控制回火温度为450℃、保温时间为50min。

Claims (4)

1.一种耐海洋大气腐蚀钢板的生产方法，其特征在于：钢的重量百分组成为C=0.03%~0.08%、Si=0.15%~0.30%、Mn=0.60%~1.50%、P≤0.025%、S≤0.010%、Al=0.020%~0.050%、Ti=0.007%~0.030%、Nb=0.010%~0.060%、Cu=0.20%~0.50%、Ni=0.50%~3.50%、Cr≤0.50%、Mo≤0.30%，余量为Fe和不可避免的杂质元素；关键工艺步骤包括：
（1）加热：加热前对铸坯表面进行机械修磨，修磨深度以去除连铸过程形成的表面氧化铁皮为基准，然后喷涂含SiO2、Al2O3、MgO的高温抗氧化涂料，涂层厚度为0.1~0.3mm；加热过程不使用焦炉煤气作燃料并控制炉内残氧量≤2.5%，控制均热温度为1250±20℃、加热时间≤300min；
（2）轧制：铸坯出加热炉后进行初除鳞，然后进行粗轧和精轧的两阶段控制轧制，粗轧轧制的板坯表面温度≥1000℃，精轧轧制的板坯表面温度在900~760℃间且精轧压缩比≥3，每个阶段轧制时间≤180s并至少除鳞3道次；同时控制两个阶段间隔间板坯表面温度在1000~900℃范围内的时间≥60s并确保精轧轧制前除鳞；所有除鳞均使高压水压力不低于22MPa且除鳞喷嘴距钢板表面不大于500mm；
（3）冷却：轧后以≥5℃/s的冷却速度加速冷却至600~400℃，之后继续冷却至钢板表面温度一直到250℃，控制该段区间的冷却时间≥600s；
（4）表面处理：钢板在室温下进行抛丸处理，抛丸除锈等级不低于Sa2.5且钢板表面粗糙度为40~80um；然后在钢板表面上喷洒质量分数为2%～10%的含Ni离子或Cu离子或Cr离子或Ca离子或几种离子混合的水溶液；
（5）热处理：采用明火炉进行回火热处理，控制空气流量与燃气流量的比为9~11，炉膛内压力为-5~0Pa；控制回火温度为400~600℃、保温时间≥45min。
2.根据权利要求1所述的一种耐海洋大气腐蚀钢板的生产方法，其特征在于：步骤（4）中，所述含Ni离子的溶液为Ni(NO3)2溶液、所述含Cu离子的溶液为Cu(NO3)2溶液、所述含Cr离子的溶液为Cr(NO3)2溶液、所述含Ca离子的溶液为Ca(H2PO2)2或CaCrO4溶液。
3.根据权利要求1所述的一种耐海洋大气腐蚀钢板的生产方法，其特征在于，步骤（4）中，钢板抛丸后在表面上喷洒质量分数为2%～3%的Ni(NO3)2、0.5%～1.0%的Ca(H2PO2)2，余量为H2O的溶液。
4.根据权利要求1所述的一种耐海洋大气腐蚀钢板的生产方法，其特征在于：步骤（4）中，钢板抛丸后在表面上喷洒质量分数为1%～2%的Ni(NO3)2、1%～2%的Cu(NO3)2、1%～2%的Cr(NO3)2、0.5%～1.0%的CaCrO4、余量为H2O的溶液。
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