CN114807785B - 390 MPa-grade corrosion-resistant steel plate and production method thereof - Google Patents
390 MPa-grade corrosion-resistant steel plate and production method thereof Download PDFInfo
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C21D2211/00—Microstructure comprising significant phases
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Abstract
本发明提供一种390MPa级耐蚀钢板及其生产方法，涉及合金技术领域，钢板采用的低C、低Mn、低S配合Sb+Cr+Ni+Cu+P耐腐蚀性元素复合添加的低合金成分体系，相对于现有耐蚀钢高P、高N、高Ni、高Cu或者添加稀土元素的合金成分体系，合金量少，所采用的合金体系在保证钢板耐蚀性的同时，大幅降低了钢板的原料成本和生产难度。
The invention provides a 390MPa grade corrosion-resistant steel plate and a production method thereof, and relates to the field of alloy technology. The low-C, low-Mn, low-S used in the steel plate is combined with Sb+Cr+Ni+Cu+P to add corrosion-resistant elements. The composition system, compared with the existing corrosion-resistant steel alloy composition system with high P, high N, high Ni, high Cu or adding rare earth elements, the amount of alloy is less, and the alloy system adopted can greatly reduce the corrosion resistance of the steel plate while ensuring the corrosion resistance of the steel plate. It reduces the raw material cost and production difficulty of the steel plate.
Description
技术领域technical field
本发明涉及合金技术领域，具体地涉及一种390MPa级耐蚀钢板及其生产方法。The invention relates to the field of alloy technology, in particular to a 390MPa corrosion-resistant steel plate and a production method thereof.
背景技术Background technique
钢结构建筑是一种新型的建筑体系，用钢板等替代了钢筋混凝土，其具有以下优势：钢的容重与强度比一般木材、混凝土和砖石小，更加轻便；钢结构断面小，与钢筋混凝土结构相比可增加建筑有效面积8%左右；钢结构具有良好的延展性，抗震性更好；钢材可重复利用，减少建筑垃圾，更加绿色环保。因此，钢结构建筑是未来建筑的发展方向。钢结构建筑一般处于大城市工业大气腐蚀环境中，大气中的腐蚀性气体SO2在水中的溶解度比氧高1300倍，当其溶于金属表面的水膜后，生成H2SO3或H2SO4，金属表面PH值可达3~3.5，会大幅加速钢结构的腐蚀。目前钢结构建筑防腐蚀的主要手段是钢结构表面涂装防腐涂料或镀锌层，一般3~5年进行一次防腐涂装维护，10~15年进行一次重新防腐涂装，涂装过程造成健康危害和环境污染。如使用耐工业大气腐蚀钢板，可显著提高钢结构建筑建造效率，降低全寿命周期成本。Steel structure building is a new type of building system, which replaces reinforced concrete with steel plates, etc. It has the following advantages: the bulk density and strength of steel are smaller than ordinary wood, concrete and masonry, and it is lighter; Compared with the structure, the effective area of the building can be increased by about 8%; the steel structure has good ductility and better earthquake resistance; the steel can be reused, reducing construction waste and being more environmentally friendly. Therefore, steel structure buildings are the development direction of future buildings. Steel structure buildings are generally located in the industrial atmospheric corrosion environment of large cities. The solubility of corrosive gas SO 2 in the atmosphere in water is 1300 times higher than that of oxygen. When it dissolves in the water film on the metal surface, it generates H 2 SO 3 or H 2 SO 4 , the pH value of the metal surface can reach 3~3.5, which will greatly accelerate the corrosion of steel structures. At present, the main means of anti-corrosion of steel structure buildings is to apply anti-corrosion paint or galvanized layer on the surface of steel structures. Generally, anti-corrosion coating maintenance is carried out every 3 to 5 years, and anti-corrosion coating is carried out once every 10 to 15 years. The coating process causes health problems. hazards and environmental pollution. If the industrial atmospheric corrosion-resistant steel plate is used, the construction efficiency of steel structure buildings can be significantly improved and the life cycle cost can be reduced.
但现有的耐工业大气腐蚀钢其均存在部分缺点，主要有：However, the existing industrial atmospheric corrosion-resistant steels have some shortcomings, mainly including:
添加大量的P或N来提高耐蚀性，如专利CN102534381A、CN103233167A、CN112662947A、CN112795844B、CN113293334A、CN103540871B、CN103993229B、CN107502835B、CN108286026A、CN109402508B，但添加大量P或N均不利于钢材的低温韧性或焊接性。添加大量的P或N来提高耐蚀性，如专利CN102534381A、CN103233167A、CN112662947A、CN112795844B、CN113293334A、CN103540871B、CN103993229B、CN107502835B、CN108286026A、CN109402508B，但添加大量P或N均不利于钢材的低温韧性或焊接性.
添加大量的Cu或Ni或N来提高耐蚀性，如专利CN112813360B、CN108396231B、CN113584376A，但添加大量的Cu或Ni合金成本均较高，不利于产品的推广应用。Add a large amount of Cu or Ni or N to improve corrosion resistance, such as patents CN112813360B, CN108396231B, CN113584376A, but the cost of adding a large amount of Cu or Ni alloy is high, which is not conducive to the popularization and application of products.
添加稀土提高耐蚀性，如专利CN102268613B、CN105734406A、CN108070796B、CN108754303A、CN111850429B、CN111575449A、CN113061805A、CN114086074A，但稀土收得率波动大、炼钢过程繁杂，不适用于大批量生产。Adding rare earths improves corrosion resistance, such as patents CN102268613B, CN105734406A, CN108070796B, CN108754303A, CN111850429B, CN111575449A, CN113061805A, CN114086074A, but the rare earth yield fluctuates greatly and the steelmaking process is complicated, so it is not suitable for mass production.
因此，开发一种综合性能优良的耐工业大气腐蚀的钢结构建筑用钢板迫在眉睫。Therefore, it is imminent to develop a steel plate for steel structure construction with excellent comprehensive performance and resistance to industrial atmospheric corrosion.
发明内容Contents of the invention
本发明的目的在于提供一种390MPa级耐蚀钢板及其生产方法。The object of the present invention is to provide a 390MPa corrosion-resistant steel plate and its production method.
本发明提供一种390MPa级耐蚀钢板，所述钢板的化学成分以质量百分比计包括：Sb:0.05~0.10%、C:0.07~0.10%、Si:0.4~0.5%、Mn:1.15~1.25%、Cr:0.2~0.3%、Ni:0.5~0.6%、Cu:0.2~0.3%、Nb:0.02~0.04%、Al:0.02~0.04%、P:0.015~0.025%，其余为Fe和不可避免的杂质，其中杂质包括：S≤0.002%、O≤0.002%、N≤0.004%；The invention provides a 390MPa grade corrosion-resistant steel plate. The chemical composition of the steel plate includes: Sb: 0.05-0.10%, C: 0.07-0.10%, Si: 0.4-0.5%, Mn: 1.15-1.25%. , Cr:0.2~0.3%, Ni:0.5~0.6%, Cu:0.2~0.3%, Nb:0.02~0.04%, Al:0.02~0.04%, P:0.015~0.025%, the rest is Fe and unavoidable Impurities, including: S≤0.002%, O≤0.002%, N≤0.004%;
所述钢板的耐大气腐蚀性指数I≥6.3，其中，耐大气腐蚀性指数的计算公式为：The atmospheric corrosion resistance index I≥6.3 of the steel plate, wherein, the calculation formula of the atmospheric corrosion resistance index is:
I=26.01(%Cu)+3.88(%Ni)+1.20(%Cr)+1.49(%Si)+17.28(%P)-7.29(%Cu)(%Ni)-9.10(%Ni)(%P)-33.39(%Cu)2，I=26.01(%Cu)+3.88(%Ni)+1.20(%Cr)+1.49(%Si)+17.28(%P)-7.29(%Cu)(%Ni)-9.10(%Ni)(%P )-33.39(%Cu) 2 ,
其中，括号内元素符号为相应元素的质量百分数，%元素符号表示相应元素的质量百分数乘以100；Among them, the element symbol in brackets is the mass percentage of the corresponding element, and the % element symbol represents the mass percentage of the corresponding element multiplied by 100;
所述钢板的屈服强度≥390MPa。The yield strength of the steel plate is ≥390MPa.
作为本发明的进一步改进，所述钢板的化学成分以质量百分比计还包括：Sn:0.02~0.10%。As a further improvement of the present invention, the chemical composition of the steel plate further includes: Sn: 0.02-0.10% in mass percentage.
作为本发明的进一步改进，所述钢板的微观组织包括铁素体和珠光体，其中，珠光体含量≤8%，铁素体包括多边形铁素体、准多边形铁素体和针状铁素体。As a further improvement of the present invention, the microstructure of the steel plate includes ferrite and pearlite, wherein the pearlite content is ≤8%, and the ferrite includes polygonal ferrite, quasi-polygonal ferrite and acicular ferrite .
作为本发明的进一步改进，所述钢板的碳当量CE≤0.40，其中，碳当量CE的计算公式为：As a further improvement of the present invention, the carbon equivalent CE of the steel plate is ≤0.40, wherein the calculation formula of the carbon equivalent CE is:
CE=(%C)+(%Mn)/6+(%Cr+%Mo+%V)/5+(%Ni+%Cu)/15，CE=(%C)+(%Mn)/6+(%Cr+%Mo+%V)/5+(%Ni+%Cu)/15,
其中，括号内元素符号为相应元素的质量百分数，%元素符号表示相应元素的质量百分数乘以100。Wherein, the element symbol in brackets is the mass percentage of the corresponding element, and the % element symbol represents the mass percentage of the corresponding element multiplied by 100.
作为本发明的进一步改进，所述钢板在GB/T10561标准下的A、B、C、D类夹杂物评级均≤1.5级，且A、B、C、D类夹杂物评级之和≤3.0级，所述钢板横截面上尺寸大于15μm的夹杂物的面密度≤0.1个/mm2。As a further improvement of the present invention, the grades of A, B, C, and D inclusions of the steel plate under the GB/T10561 standard are all ≤1.5, and the sum of the ratings of A, B, C, and D inclusions is ≤3.0 , the areal density of inclusions with a size greater than 15 μm on the cross-section of the steel plate is ≤0.1/mm 2 .
作为本发明的进一步改进，所述钢板的抗拉强度为510~660MPa，屈强比≤0.80，断后伸长率≥25%，-40℃冲击吸收能量KV2≥150J。As a further improvement of the present invention, the tensile strength of the steel plate is 510-660MPa, the yield ratio is ≤0.80, the elongation after fracture is ≥25%, and the impact absorbed energy KV 2 at -40°C is ≥150J.
作为本发明的进一步改进，在周期浸润腐蚀试验中，所述钢板的平均腐蚀失重率≤1.2g/（m2·h），其中，周期浸润腐蚀试验的试验条件为：As a further improvement of the present invention, in the periodic infiltration corrosion test, the average corrosion weight loss rate of the steel plate is ≤1.2g/(m 2 ·h), wherein the test conditions of the periodic infiltration corrosion test are:
温度：45±2℃，湿度：70±5%RH，腐蚀介质：(1.0±0.05)×10-2mol/L亚硫酸氢钠水溶液，循环周期：60±3min，浸润时间：12±1.5min，试验延续时间：72小时。Temperature: 45±2℃, humidity: 70±5%RH, corrosion medium: (1.0±0.05)×10 -2 mol/L sodium bisulfite aqueous solution, cycle period: 60±3min, soaking time: 12±1.5min , Test duration: 72 hours.
作为本发明的进一步改进，所述钢板焊接热输入量≤100kJ/cm时，焊后热影响区-40℃冲击吸收能量KV2≥80J。As a further improvement of the present invention, when the welding heat input of the steel plate is ≤100kJ/cm, the impact absorbed energy KV 2 of the post-weld heat-affected zone at -40°C is ≥80J.
作为本发明的进一步改进，所述钢板厚度不大于100mm。As a further improvement of the present invention, the thickness of the steel plate is not greater than 100mm.
作为本发明的进一步改进，所述钢板的生产方法包括依序进行的如下工序：As a further improvement of the present invention, the production method of the steel plate includes the following steps carried out in sequence:
铁水预脱硫、转炉冶炼、LF精炼、RH精炼、连铸、加热、控制轧制、控制冷却。Hot metal pre-desulfurization, converter smelting, LF refining, RH refining, continuous casting, heating, controlled rolling, controlled cooling.
作为本发明的进一步改进，所述控制轧制工序中，采用两阶段控制轧制，其中，终轧温度控制在820±15℃。As a further improvement of the present invention, in the controlled rolling process, two-stage controlled rolling is adopted, wherein the final rolling temperature is controlled at 820±15°C.
作为本发明的进一步改进，所述控制轧制工序中，采用多功能间歇式冷却系统进行水冷冷却，钢板终冷温度控制在580±30℃。As a further improvement of the present invention, in the controlled rolling process, a multifunctional intermittent cooling system is used for water cooling, and the final cooling temperature of the steel plate is controlled at 580±30°C.
基于同一发明思路，本发明还提供一种390MPa级耐蚀钢板生产方法，所述钢板的化学成分以质量百分比计包括：Sb:0.05~0.10%、C:0.07~0.10%、Si:0.4~0.5%、Mn:1.15~1.25%、Cr:0.2~0.3%、Ni:0.5~0.6%、Cu:0.2~0.3%、Nb:0.02~0.04%、Al:0.02~0.04%、P:0.015~0.025%，其余为Fe和不可避免的杂质，其中杂质包括：S≤0.002%、O≤0.002%、N≤0.004%；Based on the same idea of the invention, the present invention also provides a method for producing a 390MPa-grade corrosion-resistant steel plate. The chemical composition of the steel plate includes: Sb: 0.05-0.10%, C: 0.07-0.10%, Si: 0.4-0.5 %, Mn:1.15~1.25%, Cr:0.2~0.3%, Ni:0.5~0.6%, Cu:0.2~0.3%, Nb:0.02~0.04%, Al:0.02~0.04%, P:0.015~0.025% , the rest are Fe and unavoidable impurities, including: S≤0.002%, O≤0.002%, N≤0.004%;
所述生产方法包括：铁水预脱硫、转炉冶炼、LF精炼、RH精炼、连铸、加热、控制轧制、控制冷却；The production method includes: pre-desulfurization of molten iron, converter smelting, LF refining, RH refining, continuous casting, heating, controlled rolling, controlled cooling;
其中，所述控制轧制工序具体包括：Wherein, the controlled rolling process specifically includes:
采用两阶段控制轧制，包括第一阶段奥氏体再结晶区轧制和第二阶段奥氏体未再结晶区轧制，在所述第二阶段奥氏体未再结晶区轧制中终轧温度控制在820±15℃。Two-stage controlled rolling is adopted, including the first-stage rolling in the austenite recrystallization zone and the second-stage rolling in the austenite non-recrystallization zone, and the final rolling in the second-stage austenite non-recrystallization zone rolling The rolling temperature is controlled at 820±15°C.
作为本发明的进一步改进，所述钢板的化学成分以质量百分比计还包括：Sn:0.02~0.10%。As a further improvement of the present invention, the chemical composition of the steel plate further includes: Sn: 0.02-0.10% in mass percentage.
作为本发明的进一步改进，所述控制冷却工序具体包括：As a further improvement of the present invention, the controlled cooling process specifically includes:
采用多功能间歇式冷却系统进行水冷冷却，钢板终冷温度控制在580±30℃。The multi-functional batch cooling system is used for water cooling, and the final cooling temperature of the steel plate is controlled at 580±30°C.
作为本发明的进一步改进，所述控制轧制工序还包括：As a further improvement of the present invention, the controlled rolling process also includes:
将通过所述连铸铸造获得连铸坯轧制为厚度不大于100mm的钢板。The continuous casting slab obtained by the continuous casting is rolled into a steel plate with a thickness not greater than 100 mm.
本发明的有益效果是：本发明采用的低C、低Mn、低S配合Sb+Cr+Ni+Cu+P或Sb+Cr+Ni+Cu+P+Sn耐腐蚀性元素复合添加的低合金成分体系，相对于现有技术中耐蚀钢高P、高N、高Ni、高Cu或者添加稀土元素的合金成分体系而言，合金元素添加量少，所采用的合金体系在保证了钢板耐蚀性的前提下，大幅降低了钢板的原料成本和生产难度。在生产流程中，通过控制终轧温度和终冷温度，对钢板的微观组织、夹杂物尺寸和数量实现了精准控制，提高了钢板的耐工业大气腐蚀性能、低温韧性和焊接性能，最终获得了综合性能良好的耐工业大气腐蚀的390MPa级建筑用钢板。The beneficial effect of the present invention is: low C, low Mn, low S used in the present invention cooperate with Sb+Cr+Ni+Cu+P or Sb+Cr+Ni+Cu+P+Sn corrosion-resistant low alloy Composition system, compared with the alloy composition system of high P, high N, high Ni, high Cu or adding rare earth elements in the prior art, the addition of alloy elements is small, and the alloy system adopted ensures the corrosion resistance of the steel plate. Under the premise of corrosion resistance, the raw material cost and production difficulty of the steel plate are greatly reduced. In the production process, by controlling the final rolling temperature and final cooling temperature, the microstructure, inclusion size and quantity of the steel plate are precisely controlled, and the industrial atmospheric corrosion resistance, low temperature toughness and welding performance of the steel plate are improved, and finally obtained 390MPa grade construction steel plate with good comprehensive performance and corrosion resistance to industrial atmosphere.
附图说明Description of drawings
图1是本发明实施例4提供的390MPa级耐蚀钢板1/4厚度处的金相组织图片。Fig. 1 is a photo of the metallographic structure at 1/4 thickness of the 390MPa corrosion-resistant steel plate provided by Example 4 of the present invention.
图2是本发明对比例4提供的390MPa级耐蚀钢板1/2厚度处的金相组织图片。Fig. 2 is a picture of the metallographic structure at 1/2 thickness of the 390MPa grade corrosion-resistant steel plate provided by Comparative Example 4 of the present invention.
图3是本发明对比例4提供的钢板1/4厚度处的金相组织图片。Fig. 3 is a picture of the metallographic structure at the 1/4 thickness of the steel plate provided in Comparative Example 4 of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明具体实施方式及相应的附图对本发明技术方案进行清楚、完整地描述。显然，所描述的实施方式仅是本申请一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本申请保护的范围。In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments of the present invention and corresponding drawings. Apparently, the described implementations are only some of the implementations of this application, not all of them. Based on the implementation manners in the present invention, all other implementation manners obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present application.
本实施方式提供一种390MPa级耐蚀钢板及其生产方法，其相比于现有的耐工业大气腐蚀钢，所采用的低C、低Mn、低S配合Sb+Cr+Ni+Cu+P或Sb+Cr+Ni+Cu+P+Sn耐腐蚀性元素复合添加的低合金成分体系，在保证了耐腐蚀性的前提下，显著降低了原料成本和生产工艺难度，并提升了钢板的低温韧性和焊接性能。进一步的，在化学成分综合设计的基础上，以TMCP（Thermo-mechanical Control Process，热机械控制工艺）技术进行钢板制备，通过控制终轧温度和终冷温度，对钢板的微观组织、夹杂物尺寸和数量实现了精准控制，获得了综合性能良好的390MPa级耐工业大气腐蚀建筑用钢板。This embodiment provides a 390MPa grade corrosion-resistant steel plate and its production method. Compared with the existing industrial atmospheric corrosion-resistant steel, the low C, low Mn, and low S used in conjunction with Sb+Cr+Ni+Cu+P Or Sb+Cr+Ni+Cu+P+Sn The low-alloy composition system of compound addition of corrosion-resistant elements, under the premise of ensuring corrosion resistance, significantly reduces the cost of raw materials and the difficulty of production technology, and improves the low temperature of the steel plate. toughness and weldability. Further, on the basis of the comprehensive design of chemical composition, the steel plate is prepared with TMCP (Thermo-mechanical Control Process) technology, and the microstructure and inclusion size of the steel plate are controlled by controlling the final rolling temperature and final cooling temperature. Precise control of the quantity and quantity has been achieved, and a 390MPa-grade steel plate for industrial atmospheric corrosion-resistant construction with good comprehensive performance has been obtained.
390MPa级耐蚀钢板的化学成分以质量百分比计包括：Sb:0.05~0.10%、C:0.07~0.10%、Si:0.4~0.5%、Mn:1.15~1.25%、Cr:0.2~0.3%、Ni:0.5~0.6%、Cu:0.2~0.3%、Nb:0.02~0.04%、Al:0.02~0.04%、P:0.015~0.025%，其余为Fe和不可避免的杂质，其中杂质包括：S≤0.002%、O≤0.002%、N≤0.004%。The chemical composition of 390MPa grade corrosion-resistant steel plate includes: Sb:0.05~0.10%, C:0.07~0.10%, Si:0.4~0.5%, Mn:1.15~1.25%, Cr:0.2~0.3%, Ni : 0.5~0.6%, Cu: 0.2~0.3%, Nb: 0.02~0.04%, Al: 0.02~0.04%, P: 0.015~0.025%, the rest is Fe and unavoidable impurities, and the impurities include: S≤0.002 %, O≤0.002%, N≤0.004%.
在本发明一些实施方式中，还可添加Sn：0.02~0.10%。In some embodiments of the present invention, Sn: 0.02-0.10% can also be added.
本发明中钢板的化学成分的设计，其核心思想是通过复合添加少量的耐腐蚀性元素，在提升钢板的耐腐蚀性的同时，综合提升其性能。The core idea of the design of the chemical composition of the steel plate in the present invention is to comprehensively improve the performance of the steel plate while improving the corrosion resistance of the steel plate by compounding and adding a small amount of corrosion-resistant elements.
具体地，钢板的化学成分的设计原理说明如下：Specifically, the design principle of the chemical composition of the steel plate is explained as follows:
Sb：在钢中添加Sb，当钢锈蚀一段时间后，由于钢表面Sb元素富集，可在钢的表面形成致密的、与钢基体牢固结合的Sb2O5保护性锈层，锈层能够有效阻止有害离子的侵入，大幅延缓钢基体进一步受到锈蚀。另外，当Sb与Cu联合使用时，均匀分布的Sb与Cu，能够降低钢中腐蚀微循环的电流，从而使整体腐蚀电流下降，抑制钢板表面阳极PH降低部位处的腐蚀。通过Sb的综合作用可显著提高钢板在工业大气腐蚀环境中的耐点蚀性，但当SB含量超过0.1%后，其易在晶界偏聚，影响钢板的低温韧性和焊接性能，因此，在本发明中，将Sb含量控制在0.05~0.10%，从而在确保钢板耐腐蚀性的前提下，保证钢板的低温韧性和焊接性能良好。Sb: Add Sb to the steel. After the steel has been corroded for a period of time, due to the enrichment of Sb on the surface of the steel, a dense Sb 2 O 5 protective rust layer that is firmly combined with the steel matrix can be formed on the surface of the steel. The rust layer can Effectively prevent the intrusion of harmful ions, and greatly delay the further corrosion of the steel substrate. In addition, when Sb and Cu are used in combination, the uniform distribution of Sb and Cu can reduce the corrosion microcirculation current in the steel, thereby reducing the overall corrosion current and inhibiting the corrosion at the lower pH of the anode on the steel plate surface. The comprehensive effect of Sb can significantly improve the pitting corrosion resistance of the steel plate in the industrial atmospheric corrosion environment, but when the SB content exceeds 0.1%, it is easy to segregate at the grain boundary, which affects the low-temperature toughness and welding performance of the steel plate. In the present invention, the Sb content is controlled at 0.05-0.10%, so as to ensure good low-temperature toughness and weldability of the steel plate on the premise of ensuring the corrosion resistance of the steel plate.
C：C为强化元素，C含量能显著影响钢材的组织结构从而直接影响钢板的强度，但C含量较高时，会使珠光体含量升高，进而使钢板的低温韧性和焊接性能变差。因此，在本发明中，将C含量控制在0.07~0.10%，结合其他元素的整体设计，不仅可以保证强化效果，还可以改善钢板低温韧性和焊接性能，且无需在连铸工序中采用专用保护渣以消除液面波动大的问题。C: C is a strengthening element. The content of C can significantly affect the structure of the steel and directly affect the strength of the steel plate. However, when the content of C is high, the content of pearlite will increase, and the low temperature toughness and welding performance of the steel plate will deteriorate. Therefore, in the present invention, the C content is controlled at 0.07-0.10%, combined with the overall design of other elements, not only can ensure the strengthening effect, but also can improve the low-temperature toughness and welding performance of the steel plate, and there is no need to use special protection in the continuous casting process. Slag to eliminate the problem of large fluctuations in the liquid level.
Si：Si为固溶强化、脱氧元素，当前学界与业界对于Si在钢中对于其耐蚀性所起到作用的机理存在不同观点，但通常认为添加Si所形成的三维网络结构SiO2可以促进α-FeOOH的形成与晶粒细化，并且，锈层的Fe3O4中的Fe可以被Si取代，形成更稳定的SiO2。另外，当Sb与Cu联合使用时，锈层中的SiO2也可提高Cu的富集度，从而提高耐工业大气腐蚀性能。但Si含量较大时，会提高P、S、Sb、Sn等元素的在晶界处的偏聚，降低钢板的低温韧性和焊接性，并且会对耐蚀性起到反作用。因此，在本发明中，将Si含量控制在0.4~0.5%，在不影响钢板低温韧性和焊接性的前提下，保证脱氧效果、提高强度和耐蚀性。Si: Si is a solid solution strengthening and deoxidizing element. At present, there are different views on the mechanism of Si in steel for its corrosion resistance in the academic circles and in the industry, but it is generally believed that the three-dimensional network structure SiO 2 formed by adding Si can promote corrosion resistance. The formation of α-FeOOH is associated with grain refinement, and Fe in Fe 3 O 4 in the rust layer can be replaced by Si to form more stable SiO 2 . In addition, when Sb is used in combination with Cu, SiO2 in the rust layer can also increase the enrichment of Cu, thereby improving the corrosion resistance of industrial atmosphere. However, when the Si content is large, it will increase the segregation of P, S, Sb, Sn and other elements at the grain boundaries, reduce the low-temperature toughness and weldability of the steel plate, and have a negative effect on the corrosion resistance. Therefore, in the present invention, the Si content is controlled at 0.4-0.5%, so as to ensure the deoxidation effect and improve the strength and corrosion resistance without affecting the low-temperature toughness and weldability of the steel plate.
Mn：Mn为固溶强化元素，可以提高钢板的淬透性，从而提高其强度，同时Mn还可以与有害元素S结合以降低钢板的热脆性。但过多的Mn会加剧P、Sb、Sn等元素的偏析，进而减弱钢板的耐腐蚀性，劣化钢板心部低温韧性和焊接性能。因此，在本发明中，将Mn含量控制在1.15~1.25%，一方面可以保证钢板的强度，另一方面可以减轻偏析对钢板耐腐蚀性、低温韧性和焊接性能的影响。Mn: Mn is a solid solution strengthening element, which can improve the hardenability of the steel plate, thereby increasing its strength. At the same time, Mn can also combine with harmful elements S to reduce the hot brittleness of the steel plate. However, too much Mn will aggravate the segregation of P, Sb, Sn and other elements, thereby weakening the corrosion resistance of the steel plate, and deteriorating the low-temperature toughness and welding performance of the steel plate core. Therefore, in the present invention, the Mn content is controlled at 1.15-1.25%, on the one hand, the strength of the steel plate can be ensured, and on the other hand, the influence of segregation on the corrosion resistance, low-temperature toughness and welding performance of the steel plate can be reduced.
Cr：Cr可以促进钢表面锈层中疏松的未完全氧化相转变为更致密稳定的相，减少锈层中孔隙、裂纹的出现，提高钢的耐蚀性。Cr在锈层靠近基体端会发生聚集，形成钝化膜，降低锈层的阴离子选择性，阻挡外来阴离子的渗入，保护钢板基体。当Cr与Cu协同作用时，可细化α-FeOOH，提高锈层稳定性。但当Cr含量较大时，易形成碳化物，使钢的耐蚀性降低。因此，在本发明中，将Cr含量控制在0.2~0.3%，能够使钢的耐腐蚀性不随时间延长而降低。Cr: Cr can promote the transformation of the loose incompletely oxidized phase in the rust layer on the steel surface into a denser and more stable phase, reduce the appearance of pores and cracks in the rust layer, and improve the corrosion resistance of the steel. Cr will gather at the end of the rust layer near the substrate to form a passivation film, reduce the anion selectivity of the rust layer, block the infiltration of external anions, and protect the steel plate substrate. When Cr and Cu act synergistically, α-FeOOH can be refined and the stability of the rust layer can be improved. However, when the Cr content is large, it is easy to form carbides, which reduces the corrosion resistance of the steel. Therefore, in the present invention, the Cr content is controlled at 0.2-0.3%, so that the corrosion resistance of the steel will not decrease with time.
Ni：加入Ni元素可以使钢的自腐蚀电位正移，增大阳极溶解反应发生的阻力，而促进锈层中α-FeOOH相形成，提高锈层稳定性，并且，Ni元素可能在锈层内部富集，使得锈层阴离子选择性降低，减缓钢板基体腐蚀。另外，添加Ni可提高钢板的低温韧性和焊接性能，但添加过多的Ni会造成合金成本较高。因此，在本发明中，将Ni含量控制在0.5~0.6%，保证钢板耐腐蚀性能、低温韧性和焊接性能的同时，能够合理控制合金成本。Ni: Adding Ni element can make the self-corrosion potential of steel positively shift, increase the resistance of anodic dissolution reaction, promote the formation of α-FeOOH phase in the rust layer, and improve the stability of the rust layer, and the Ni element may be inside the rust layer Enrichment reduces the anion selectivity of the rust layer and slows down the corrosion of the steel plate matrix. In addition, adding Ni can improve the low-temperature toughness and weldability of the steel plate, but adding too much Ni will result in higher alloy cost. Therefore, in the present invention, the Ni content is controlled at 0.5-0.6%, so as to ensure the corrosion resistance, low-temperature toughness and welding performance of the steel plate, and at the same time reasonably control the cost of the alloy.
Cu：在钢中加入Cu对其耐蚀性有较好提高作用，且其价格低廉，被广泛用于耐蚀钢中，其主要作用机制有多种：Cu可阻碍锈层的晶体化，促进α-FeOOH和非晶态Fe3O4的形成；并且，Cu可在锈层薄弱处富集，在腐蚀过程中形成氧化物，紧密连接锈层和钢基体，减少锈层中的裂纹、空隙等，提高耐点蚀性能；另外，Cu元素有活化阴极的作用，使得钢基体被钝化，腐蚀速率下降。但Cu含量较高时，不利于钢板的焊接性能。因此、在本发明中，将Cu含量控制在0.2~0.3%，既提高耐腐蚀性，又不影响焊接性能。Cu: Adding Cu to steel has a good effect on improving its corrosion resistance, and its price is low, so it is widely used in corrosion-resistant steel. There are many main mechanisms of action: Cu can hinder the crystallization of rust layer, promote The formation of α-FeOOH and amorphous Fe 3 O 4 ; and, Cu can be enriched in the weak part of the rust layer, forming oxides during the corrosion process, closely connecting the rust layer and the steel matrix, and reducing cracks and voids in the rust layer Etc., improve pitting corrosion resistance; in addition, Cu element has the effect of activating the cathode, which makes the steel matrix passivated and the corrosion rate decreases. However, when the Cu content is high, it is not conducive to the welding performance of the steel plate. Therefore, in the present invention, the Cu content is controlled at 0.2-0.3%, which not only improves the corrosion resistance, but also does not affect the welding performance.
Nb：Nb为细晶元素和强碳化物形成元素，其能够避免C与Cr结合影响钢板耐腐蚀性，并且Nb能够促进α-FeOOH的快速形成和含量的增加。当Nb含量较大时，其会劣化焊接接头热影响区低温韧性，并会对耐腐蚀性造成反作用，因此，在本发明中将Nb含量控制在0.02~0.04%，在保证晶粒细化效果和耐腐蚀性的同时，不会对焊接接头热影响区低温韧性产生不利影响。Nb: Nb is a fine-grained element and a strong carbide-forming element, which can prevent the combination of C and Cr from affecting the corrosion resistance of the steel plate, and Nb can promote the rapid formation and increase of the content of α-FeOOH. When the Nb content is large, it will deteriorate the low-temperature toughness of the heat-affected zone of the welded joint, and will have a negative effect on the corrosion resistance. Therefore, in the present invention, the Nb content is controlled at 0.02~0.04% to ensure the effect of grain refinement At the same time as corrosion resistance, it will not adversely affect the low-temperature toughness of the heat-affected zone of the welded joint.
Al：Al为重要的脱氧元素，本发明中将Al含量控制在0.02~0.04%，保证Al的有益效果的同时，降低冶炼难度，避免浇铸过程中堵塞水口。Al: Al is an important deoxidizing element. In the present invention, the Al content is controlled at 0.02-0.04%, which ensures the beneficial effect of Al, reduces the difficulty of smelting, and avoids blocking the nozzle during the casting process.
P：P为典型的提高钢耐腐蚀性能的元素，P可以起到阳极去极化剂的作用，加快Fe2+的氧化速率以及钢的均匀溶解，能有效帮助钢表面形成均匀的α-FeOOH锈层。并且，P能够形成PO4 3-，一方面，PO4 3-能够络合H+改善界面PH值，减缓阴极析氢还原反应并减缓对锈层的溶解，另一方面，PO4 3-能够在阳极溶解过程中与Fe2+和Mn2+结合，形成难溶的磷酸盐膜，阻挡阳极溶解反应，起到缓蚀剂作用。另外，P和Cu之间也有较好的协同耐蚀作用，从而综合起到提高钢耐腐蚀性能的作用。同时，P也为易偏析元素，其含量过高时，会显著降低钢板心部的低温韧性和焊接性能。因此，在本发明中将P含量控制在0.015-0.025%，保证耐腐蚀性能的同时，不会产生严重的偏析，劣化钢板的低温韧性和焊接性能。P: P is a typical element that improves the corrosion resistance of steel. P can act as an anode depolarizer to accelerate the oxidation rate of Fe 2+ and the uniform dissolution of steel, which can effectively help the steel surface to form a uniform α-FeOOH rust layer. Moreover, P can form PO 4 3- . On the one hand, PO 4 3- can complex H + to improve the interface pH value, slow down the cathodic hydrogen evolution reduction reaction and slow down the dissolution of the rust layer. On the other hand, PO 4 3- can be in During the anode dissolution process, it combines with Fe 2+ and Mn 2+ to form an insoluble phosphate film, which blocks the anode dissolution reaction and acts as a corrosion inhibitor. In addition, there is also a good synergistic corrosion resistance between P and Cu, which can comprehensively improve the corrosion resistance of steel. At the same time, P is also an element that is easy to segregate, and when its content is too high, the low temperature toughness and weldability of the steel plate core will be significantly reduced. Therefore, in the present invention, the P content is controlled at 0.015-0.025%, to ensure corrosion resistance, and at the same time, serious segregation will not occur, which will deteriorate the low-temperature toughness and welding performance of the steel plate.
Sn：Sn在钢中对耐蚀性所起到的作用机理还有待研究，当前有观点认为Sn可在钢的表面形成致密的SnO2保护性锈层，从而起到提高耐蚀性的作用。当Sn含量过高时，易在晶界偏聚，影响低温韧性和焊接性能，因此，在本发明中，将Sn含量控制在0.02~0.10%，在不降低耐腐蚀性的前提下，保证钢板的低温韧性和焊接性能良好。Sn: The mechanism of Sn on corrosion resistance in steel remains to be studied. At present, there is a view that Sn can form a dense SnO 2 protective rust layer on the surface of steel, thereby improving corrosion resistance. When the Sn content is too high, it is easy to segregate at the grain boundary, which affects the low-temperature toughness and welding performance. Therefore, in the present invention, the Sn content is controlled at 0.02~0.10%, and the corrosion resistance of the steel plate is guaranteed without reducing the corrosion resistance. Good low temperature toughness and welding performance.
S、O和N：为杂质元素，在本发明中分别控制其含量为：S≤0.002%、O≤0.002%、N≤0.004%，结合整体化学成分的设计，既保证了钢板的综合性能，又避免含量控制要求过严导致的生产难度大、生产成本高。S, O and N: are impurity elements. In the present invention, their contents are respectively controlled as follows: S≤0.002%, O≤0.002%, N≤0.004%. Combined with the design of the overall chemical composition, it not only ensures the comprehensive performance of the steel plate, It also avoids production difficulties and high production costs caused by too strict content control requirements.
进一步的，钢板的碳当量CE控制在≤0.40，以确保钢板具有良好的焊接性，其中，根据B/T1591-2018标准，碳当量CE的计算公式为：Further, the carbon equivalent CE of the steel plate is controlled at ≤0.40 to ensure that the steel plate has good weldability. According to the B/T1591-2018 standard, the calculation formula of the carbon equivalent CE is:
CE=(%C)+(%Mn)/6+(%Cr+%Mo+%V)/5+(%Ni+%Cu)/15。CE=(%C)+(%Mn)/6+(%Cr+%Mo+%V)/5+(%Ni+%Cu)/15.
钢板的耐大气腐蚀性指数I≥6.3，其中，耐大气腐蚀性指数的计算公式为：The atmospheric corrosion resistance index of the steel plate I≥6.3, where the calculation formula of the atmospheric corrosion resistance index is:
I=26.01(%Cu)+3.88(%Ni)+1.20(%Cr)+1.49(%Si)+17.28(%P)-7.29(%Cu)(%Ni)-9.10(%Ni)(%P)-33.39(%Cu)2，I=26.01(%Cu)+3.88(%Ni)+1.20(%Cr)+1.49(%Si)+17.28(%P)-7.29(%Cu)(%Ni)-9.10(%Ni)(%P )-33.39(%Cu) 2 ,
其中，括号内元素符号为相应元素的质量百分数，%元素符号表示相应元素的质量百分数乘以100。Wherein, the element symbol in brackets is the mass percentage of the corresponding element, and the % element symbol represents the mass percentage of the corresponding element multiplied by 100.
综上所述，本发明采用的低C、低Mn、低S配合Sb+Cr+Ni+Cu+P或Sb+Cr+Ni+Cu+P+Sn耐腐蚀性元素复合添加的低合金成分体系，相对于现有技术中耐蚀钢高P、高N、高Ni、高Cu或者添加稀土元素的合金成分体系而言，合金元素添加量少，所采用的合金体系在保证了钢板耐蚀性的前提下，大幅降低了钢板的原料成本和生产难度，并且还能够有效提升钢板的低温韧性和焊接性能，从而获得综合性能优良的耐工业大气腐蚀的390MPa级建筑用钢板。In summary, the present invention adopts low-C, low-Mn, low-S low-alloy composition system with Sb+Cr+Ni+Cu+P or Sb+Cr+Ni+Cu+P+Sn compound addition of corrosion-resistant elements Compared with the alloy composition system of high P, high N, high Ni, high Cu or the addition of rare earth elements in the corrosion-resistant steel in the prior art, the addition of alloy elements is small, and the alloy system adopted can ensure the corrosion resistance of the steel plate Under the premise of the steel plate, the raw material cost and production difficulty of the steel plate are greatly reduced, and the low-temperature toughness and welding performance of the steel plate can be effectively improved, so as to obtain a 390MPa grade steel plate for construction with excellent comprehensive performance and resistance to industrial atmospheric corrosion.
本发明还提供了前述钢板的生产方法，在本实施方式中，生产方法包括工序：铁水预脱硫、转炉冶炼、LF精炼、RH精炼、连铸、加热、控制轧制、控制冷却。The present invention also provides a production method of the aforementioned steel plate. In this embodiment, the production method includes steps: molten iron pre-desulfurization, converter smelting, LF refining, RH refining, continuous casting, heating, controlled rolling, and controlled cooling.
其中，控制轧制工序具体包括：Among them, the controlled rolling process specifically includes:
采用两阶段控制轧制，包括第一阶段奥氏体再结晶区轧制和第二阶段奥氏体未再结晶区轧制，在第一阶段轧制通过反复交错进行形变、再结晶使原奥氏体晶粒充分再结晶，第二阶段轧制在再结晶温度以下进行大压下量轧制，促进微合金元素的应变诱导析出并实现奥氏体晶粒的细化和加工硬化，奥氏体晶粒被拉长的同时产生了变形带和大量位错，使奥氏体晶粒内积累足够的形变能，为相变提供更多的形核位置，从而细化晶粒。Two-stage controlled rolling is adopted, including rolling in the austenite recrystallization zone in the first stage and rolling in the austenite non-recrystallization zone in the second stage. In the first stage rolling, deformation and recrystallization of the original austenite The tenite grains are fully recrystallized, and the second stage rolling is carried out with a large reduction below the recrystallization temperature to promote the strain-induced precipitation of microalloying elements and realize the refinement of austenite grains and work hardening. When the bulk grains are elongated, deformation bands and a large number of dislocations are generated, so that sufficient deformation energy is accumulated in the austenite grains, and more nucleation sites are provided for the phase transformation, thereby refining the grains.
具体的，在第二阶段轧制中，终轧温度控制在820±15℃，结合前述的微合金元素成分及添加量，可以有效细化晶粒，并提高钢板的低温韧性。Specifically, in the second-stage rolling, the final rolling temperature is controlled at 820±15°C, combined with the above-mentioned microalloy element composition and addition amount, it can effectively refine the grains and improve the low-temperature toughness of the steel plate.
控制冷却工序具体包括：The controlled cooling process specifically includes:
采用多功能间歇式冷却系统进行水冷冷却，钢板终冷温度控制在580±30℃。The multi-functional batch cooling system is used for water cooling, and the final cooling temperature of the steel plate is controlled at 580±30°C.
多功能间歇式冷却系统(Multi-purpose interrupt cooling，MULPIC)是位于精轧机后的快速冷却装置，其根据冷却模型进行钢板的快速冷却，其主要作用是控制冷却速度和终冷温度，冷却钢板到规定的质量和密度，并确保整个钢板机械性能的均衡性。在本实施方式中，将终冷温度控制在580±30℃，使形变奥氏体最终相变为铁素体+珠光体，其中，铁素体包括多边形铁素体、准多边形铁素体和针状铁素体，珠光体含量≤8%。Multi-purpose interrupt cooling (MULPIC) is a rapid cooling device located behind the finishing mill. It performs rapid cooling of the steel plate according to the cooling model. Its main function is to control the cooling speed and final cooling temperature. Cool the steel plate to Specified quality and density, and ensure the uniformity of the mechanical properties of the entire steel plate. In this embodiment, the final cooling temperature is controlled at 580±30°C, so that the deformed austenite finally transforms into ferrite+pearlite, wherein the ferrite includes polygonal ferrite, quasi-polygonal ferrite and Acicular ferrite, pearlite content ≤ 8%.
珠光体是铁素体和渗碳体的共析体，铁素体和渗碳体间的电位差大，易形成腐蚀微电池，因此，珠光体耐腐蚀性较差。通过对控制轧制的终轧温度和控制冷却工序的终冷温度进行把控，以使得钢板中的珠光体含量≤8%，从而可避免珠光体含量过多而对钢板耐腐蚀性能造成不良影响，确保钢板整体的耐腐蚀性能优异。Pearlite is a eutectoid of ferrite and cementite. The potential difference between ferrite and cementite is large, and it is easy to form a corrosion micro-battery. Therefore, pearlite has poor corrosion resistance. By controlling the final rolling temperature of the controlled rolling and the final cooling temperature of the controlled cooling process, the pearlite content in the steel plate is ≤8%, so as to avoid excessive pearlite content and cause adverse effects on the corrosion resistance of the steel plate , to ensure the overall excellent corrosion resistance of the steel plate.
进一步的，将所述钢板在GB/T10561标准下的A、B、C、D类夹杂物评级控制在均≤1.5级，且A、B、C、D类夹杂物评级之和控制在≤3.0级，所述钢板横截面上尺寸≥15μm夹杂物的面密度控制在≤0.1个/mm2。Further, the ratings of inclusions of types A, B, C, and D of the steel plate under the GB/T10561 standard are all controlled to be ≤1.5, and the sum of ratings of inclusions of types A, B, C, and D is controlled to be ≤3.0 Level, the areal density of inclusions with a size ≥ 15 μm on the cross-section of the steel plate is controlled at ≤ 0.1 inclusions/mm 2 .
夹杂物是萌生点蚀最敏感的位置，夹杂物的尺寸影响诱发阶段点蚀孔初始形成尺寸，其中，圆当量直径超过20μm的非金属夹杂物对耐腐蚀性影响最大，因此，为保证所述钢板的耐腐蚀性，需严格控制夹杂物的尺寸和数量。Inclusions are the most sensitive locations for pitting initiation, and the size of inclusions affects the initial size of pitting pits during the induction stage. Among them, non-metallic inclusions with a circle equivalent diameter exceeding 20 μm have the greatest impact on corrosion resistance. Therefore, in order to ensure the The corrosion resistance of the steel plate requires strict control of the size and quantity of inclusions.
本发明其他工序步骤所涉及的具体工艺参数可以参考现有技术中的类似规格钢板的生产工艺参数，本发明对此不做具体限定。For the specific process parameters involved in other process steps of the present invention, reference may be made to the production process parameters of steel plates of similar specifications in the prior art, which is not specifically limited in the present invention.
具体的，对于最终所获得的钢板，其性能表征如下：Specifically, for the finally obtained steel plate, its properties are characterized as follows:
力学性能方面，钢板屈服强度≥390MPa，抗拉强度为510~660MPa，屈强比≤0.80，断后伸长率≥25%，-40℃冲击吸收能量KV2≥150J。In terms of mechanical properties, the yield strength of the steel plate is ≥390MPa, the tensile strength is 510~660MPa, the yield strength ratio is ≤0.80, the elongation after fracture is ≥25%, and the impact absorbed energy KV 2 at -40°C is ≥150J.
耐腐蚀性能方面，在周期浸润腐蚀试验中，钢板的平均腐蚀失重率≤1.2g/(m2·h)，其中，周期浸润腐蚀试验参考TB/T 2375-93《铁路用耐候钢周期浸润腐蚀试验方法》，其试验条件为：In terms of corrosion resistance, in the periodic infiltration corrosion test, the average corrosion weight loss rate of the steel plate is ≤1.2g/(m 2 h), among which, the periodic infiltration corrosion test refers to TB/T 2375-93 "Periodic Infiltration Corrosion of Weathering Steel for Railways". Test method", the test conditions are:
温度：45±2℃，湿度：70±5%RH，腐蚀介质：(1.0±0.05)×10-2mol/L亚硫酸氢钠水溶液，循环周期：60±3min，浸润时间：12±1.5min，试验延续时间：72小时。Temperature: 45±2℃, humidity: 70±5%RH, corrosion medium: (1.0±0.05)×10 -2 mol/L sodium bisulfite aqueous solution, cycle period: 60±3min, soaking time: 12±1.5min , Test duration: 72 hours.
焊接性能方面，钢板焊接热输入量≤100kJ/cm时，焊后热影响区-40℃冲击吸收能量KV2≥80J。In terms of welding performance, when the heat input of steel plate welding is ≤100kJ/cm, the impact absorbed energy KV 2 of the post-weld heat-affected zone at -40°C is ≥80J.
综上所述，本发明采用的低C、低Mn、低S配合Sb+Cr+Ni+Cu+P或Sb+Cr+Ni+Cu+P+Sn耐腐蚀性元素复合添加的低合金成分体系，相对于现有技术中耐蚀钢高P、高N、高Ni、高Cu或者添加稀土元素的合金成分体系而言，合金元素添加量少，所采用的合金体系在保证了钢板耐蚀性的前提下，大幅降低了钢板的原料成本和生产难度，在生产流程中，通过控制终轧温度和终冷温度，对钢板的微观组织、夹杂物尺寸和数量实现了精准控制，提高了钢板的耐工业大气腐蚀性能、低温韧性和焊接性能，最终获得了综合性能良好的耐工业大气腐蚀的390MPa级建筑用钢板。In summary, the present invention adopts low-C, low-Mn, low-S low-alloy composition system with Sb+Cr+Ni+Cu+P or Sb+Cr+Ni+Cu+P+Sn compound addition of corrosion-resistant elements Compared with the alloy composition system of high P, high N, high Ni, high Cu or the addition of rare earth elements in the corrosion-resistant steel in the prior art, the addition of alloy elements is small, and the alloy system adopted can ensure the corrosion resistance of the steel plate Under the premise, the raw material cost and production difficulty of the steel plate are greatly reduced. In the production process, by controlling the final rolling temperature and final cooling temperature, the microstructure, inclusion size and quantity of the steel plate are precisely controlled, and the steel plate is improved. Industrial atmosphere corrosion resistance, low temperature toughness and welding performance, finally obtained a 390MPa grade construction steel plate with good comprehensive performance and industrial atmosphere corrosion resistance.
以下通过4个实施例和4个对比例，进一步对本发明的具体实施方式予以介绍。Below through 4 examples and 4 comparative examples, the specific embodiment of the present invention is further introduced.
实施例1～4以及对比例1～4均提供了一种钢板，钢板的化学成分、碳当量CE和耐大气腐蚀性指数I如表1所示。Examples 1-4 and Comparative Examples 1-4 all provide a steel plate, and the chemical composition, carbon equivalent CE and atmospheric corrosion resistance index I of the steel plate are shown in Table 1.
其中，对比例1的Sb含量低于本发明要求的0.05~0.10%，Ni含量低于本发明要求的0.5~0.6%，Cu含量低于本发明要求的0.2~0.3%，耐大气腐蚀性指数I低于本发明要求的6.3。Wherein, the Sb content of comparative example 1 is lower than 0.05～0.10% required by the present invention, the Ni content is lower than 0.5～0.6% required by the present invention, the Cu content is lower than 0.2～0.3% required by the present invention, and the atmospheric corrosion resistance index I is lower than 6.3 required by the present invention.
对比例2的P含量低于本发明权利要求的0.015~0.025%，Cu含量低于本发明权利要求的0.2~0.3%，耐大气腐蚀性指数I低于本发明要求的6.3。The P content of comparative example 2 is lower than 0.015 ~ 0.025% of the claims of the present invention, the Cu content is lower than 0.2 ~ 0.3% of the claims of the present invention, and the atmospheric corrosion resistance index I is lower than 6.3 of the requirements of the present invention.
对比例3的Si含量低于本发明权利要求的0.4~0.5%，Cu含量低于本发明权利要求的0.2~0.3%，耐大气腐蚀性指数I低于本发明要求的6.3。The Si content of comparative example 3 is lower than 0.4 ~ 0.5% of the claims of the present invention, the Cu content is lower than 0.2 ~ 0.3% of the claims of the present invention, and the atmospheric corrosion resistance index I is lower than 6.3 of the claims of the present invention.
对比例4是普通的390MPa级建筑用钢，不含Sb、Cr、Ni、Cu、Sn耐腐蚀性元素。Comparative example 4 is a common 390MPa grade construction steel, which does not contain Sb, Cr, Ni, Cu, Sn corrosion-resistant elements.
实施例1~4和对比例1~4中钢板生产方法均为：依序采用铁水预脱硫、转炉冶炼、LF精炼、RH精炼、连铸、加热、控制轧制、控制冷却，控制冷却工序结束后即制备出成品钢板。The production methods of the steel plates in Examples 1-4 and Comparative Examples 1-4 are as follows: pre-desulfurization of molten iron, converter smelting, LF refining, RH refining, continuous casting, heating, controlled rolling, controlled cooling, and the controlled cooling process ends. After that, the finished steel plate is prepared.
其中，在所述控制轧制工序中，采用两阶段控制轧制制备成厚度如表2所示的钢板，终轧温度为820±15℃。Wherein, in the controlled rolling process, two-stage controlled rolling is adopted to prepare steel plates with the thicknesses shown in Table 2, and the final rolling temperature is 820±15°C.
在所述控制冷却工序中，采用多功能间歇式冷却系统进行水冷冷却，终冷温度为580±30℃。In the controlled cooling process, a multifunctional intermittent cooling system is used for water cooling, and the final cooling temperature is 580±30°C.
实施例1~4和对比例1~4的终轧温度和终冷温度具体如表2所示。The final rolling temperature and final cooling temperature of Examples 1-4 and Comparative Examples 1-4 are specifically shown in Table 2.
在实施例1~4和对比例1~4的各个钢板冷却后，进行取样检测，检测结果描述如下。After the steel plates of Examples 1-4 and Comparative Examples 1-4 were cooled, samples were taken for testing, and the testing results are described as follows.
实施例1~4和对比例1~4的夹杂物检测结果如表3所示。由表3可知，实施例1~4和对比例1~3的横截面上尺寸≥15μm夹杂物的面密度均≤0.1个/mm2，且A、B、C、D类夹杂物评级之和控制在≤3.0级。对比例4中Mn、S、O含量高于本发明要求，因此夹杂物含量＞1.5级，且四类夹杂物评级之和＞3.0级。The inclusion detection results of Examples 1-4 and Comparative Examples 1-4 are shown in Table 3. It can be seen from Table 3 that the areal densities of inclusions with a size ≥15 μm on the cross-sections of Examples 1-4 and Comparative Examples 1-3 are all ≤0.1 pieces/mm 2 , and the sum of ratings of Type A, B, C, and D inclusions Controlled at ≤3.0 level. In Comparative Example 4, the contents of Mn, S, and O are higher than the requirements of the present invention, so the content of inclusions is greater than grade 1.5, and the sum of ratings of the four types of inclusions is greater than grade 3.0.
实施例1~4和对比例1~4中钢板的屈服强度、抗拉强度、屈强比、断后伸长率、-40℃冲击吸收能量KV2如表4所示。由表4可知，实施例1~4和对比例1~4中钢板力学性能均满足本发明的要求。对比例4中C含量高于本发明要求，组织为铁素体+珠光体，珠光体含量高于8%，因此-40℃冲击吸收能量KV2低于150J。Table 4 shows the yield strength, tensile strength, yield ratio, elongation after fracture, and -40°C impact absorbed energy KV 2 of the steel plates in Examples 1-4 and Comparative Examples 1-4. It can be seen from Table 4 that the mechanical properties of the steel plates in Examples 1-4 and Comparative Examples 1-4 all meet the requirements of the present invention. In Comparative Example 4, the C content is higher than the requirements of the present invention, the structure is ferrite + pearlite, and the pearlite content is higher than 8%, so the impact absorbed energy KV 2 at -40°C is lower than 150J.
参考TB/T 2375-93《铁路用耐候钢周期浸润腐蚀试验方法》，采用周期浸润腐蚀试验机检测实施例1~4和对比例1~4钢板的耐工业大气腐蚀性能，试验温度为45±2℃，湿度为70±5%RH，腐蚀介质为(1.0±0.05)×10-2mol/L亚硫酸氢钠水溶液，试验时间为72小时，每一循环周期为60±3min，其中浸润时间为12±1.5min。实施例1~4和对比例1~4的平均腐蚀失重率如表5所示。Referring to TB/T 2375-93 "Periodical Infiltration Corrosion Test Method of Weathering Steel for Railways", the periodic infiltration corrosion tester is used to test the industrial atmospheric corrosion resistance of the steel plates of Examples 1~4 and Comparative Examples 1~4, and the test temperature is 45 ± 2°C, humidity 70±5%RH, corrosion medium (1.0±0.05)×10 -2 mol/L sodium bisulfite aqueous solution, test time is 72 hours, each cycle is 60±3min, in which the soaking time It is 12±1.5min. The average corrosion weight loss rates of Examples 1-4 and Comparative Examples 1-4 are shown in Table 5.
由表5可知，实施例1~4钢板的平均腐蚀失重率均≤1.2g/(m2·h)。对比例1~4的平均腐蚀失重率均高于本发明要求，其中，对比例4的耐工业大气腐蚀性能最差。It can be seen from Table 5 that the average corrosion weight loss rate of the steel plates in Examples 1-4 are all ≤1.2g/(m 2 ·h). The average corrosion weight loss rates of Comparative Examples 1 to 4 are all higher than the requirements of the present invention, and wherein Comparative Example 4 has the worst industrial atmospheric corrosion resistance.
对实施例4进行双丝埋弧焊，环境温度2℃，焊前不预热，焊后不保温或热处理，焊接热输入量97±3kJ/cm，焊接接头热影响区熔合线FL、FL+2mm、FL+5mm和FL+20mm处的-40℃低温冲击功检测结果如表4所示。由表6可知，实施例4的焊接性能优异。Double-wire submerged arc welding was performed on Example 4, the ambient temperature was 2°C, no preheating before welding, no heat preservation or heat treatment after welding, the welding heat input was 97±3kJ/cm, the fusion line FL, FL+ in the heat-affected zone of the welded joint Table 4 shows the test results of -40°C low temperature impact energy at 2mm, FL+5mm and FL+20mm. It can be seen from Table 6 that the welding performance of Example 4 is excellent.
如图1所示，为本发明实施例4提供的钢板的1/4厚度处的金相组织图片，如图2所示，为本发明实施例4提供的钢板的1/2厚度处的金相组织图片，如图3所示，为本发明对比例4提供的钢板的1/4厚度处的金相组织图。对比图1和图3可知，添加合金元素后的钢板晶粒明显更加细小，在图3中可以观察到呈现为黑色的珠光体数量更多，分布更加密集。As shown in Figure 1, the metallographic structure picture at the 1/4 thickness place of the steel plate provided for the embodiment 4 of the present invention, as shown in Figure 2, the metallographic structure picture at the 1/2 thickness place of the steel plate provided for the embodiment 4 of the present invention The phase structure picture, as shown in FIG. 3 , is the metallographic structure picture at the 1/4 thickness of the steel plate provided in Comparative Example 4 of the present invention. Comparing Figure 1 and Figure 3, it can be seen that the grains of the steel plate after adding alloy elements are obviously finer, and it can be observed in Figure 3 that the number of black pearlite is more and the distribution is more dense.
结合上述检测结果，可知本发明所提供的390MPa级耐蚀钢板不仅成本可控、工艺流程简单高效，而且所得钢板的耐工业大气腐蚀性、低温韧性、焊接性能优异，利于在钢结构建筑领域推广应用。Combining the above test results, it can be seen that the 390MPa corrosion-resistant steel plate provided by the present invention not only has controllable cost, simple and efficient process flow, but also has excellent corrosion resistance to industrial atmosphere, low temperature toughness, and excellent welding performance, which is beneficial to the promotion in the field of steel structure construction application.
应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施方式中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。It should be understood that although this description is described according to implementation modes, not each implementation mode only contains an independent technical solution, and this description in the description is only for clarity, and those skilled in the art should take the description as a whole, and each The technical solutions in the embodiments can also be properly combined to form other embodiments that can be understood by those skilled in the art.
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施方式的具体说明，并非用以限制本发明的保护范围，凡未脱离本发明技艺精神所作的等效实施方式或变更均应包含在本发明的保护范围之内。The series of detailed descriptions listed above are only specific descriptions of feasible implementations of the present invention, and are not intended to limit the scope of protection of the present invention. Any equivalent implementation or change that does not depart from the technical spirit of the present invention All should be included within the protection scope of the present invention.
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