State‐of‐the‐Knowledge on Coating Systems for Hot Stamped Parts

In the present contribution, recent developments of coatings for hot stamped steels are reviewed. The use of bare steel in the initial hot stamping technology is discussed, including the application of lubricant oils which are used as oxidation inhibitors on bare steel surfaces. The aluminized coatings are introduced, focusing on the microstructure evolution of aluminized coatings during the hot stamping process. An analysis of the cracking of the coating, caused by the formation of brittle Fe–Al intermetallic phases and their high temperature deformation, is presented. The development of a ductile aluminide coating formed during the diffusion treatment of an aluminized coating is discussed. This aluminide coating can endure both high temperature oxidation and severe plastic deformation. The recently developed galvanized and galvannealed coatings are also reviewed and the influence of the gas atmosphere during the heating cycle on the coating stability is emphasized. The solutions which have been proposed to avoid liquid Zn‐induced embrittlement are analyzed. The use of Zn–Ni alloy coating, which is characterized by a higher melting temperature, is reviewed. The behavior of sol–gel hybrid coatings on hot stamped steels is discussed. The possible use of the recently developed Al–Zn alloy coatings, dual layer Zn–Al and Zn–Al–Mg coatings is also introduced. The application of Zn–Al–Mg post‐process galvanizing is also discussed. In each case, all available information related to the weldability, paintability, and corrosion resistance of the coating systems is also reported. Finally, the advantages and technical challenges associated with each type of coating are reviewed.     

Analysis of Microstructure and Mechanical Properties of Different Hot Stamped B‐bearing Steels

Hot stamping is a technique to produce ultra high strength automobile components. The common material used in hot stamping process is coated and/or uncoated 22MnB5 boron alloyed steel. Ferritic‐pearlitic microstructure in as‐delivered sheets is transformed to fully lath martensitic after hot stamping. In the present research, hot stamping under water or nitrogen cooling media was investigated using different boron alloyed steel grades. Microstructural analyses, linear and surface hardness profiling as well as tensile tests of hot stamped samples were performed. Various microstructures of fully bainitic and/or fully martensitic were produced. The resulting microstructures provided yield strengths of 650–1370 MPa and tensile strengths of 850–2000 MPa. There is an optimum carbon equivalent content for which the highest formability index value, UTS × A₂₅, is achieved. Using a nitrogen cooled punch resulted in higher yield strength without significant changes in ultimate tensile strength. It is concluded that a wide range of B‐bearing steels having an extended carbon equivalent range with an acceptable formability index value can be used by increasing the cooling rate in the die assembly.     

Some Highlights on New Steel Products for Automotive Use

This paper is a short review on some recent developments regarding steels for automotive use. A new precoated steel suitable for to hot stamping processing has been developed, which is most appropriate for producing anti‐intrusion parts. Another evolution of precoated steels is a new inorganic treatment (NIT), which has proved to be efficient in increasing the stamping productivity of precoated steels. In the field of corrosion protection, a new generation of thin organic coatings has been implemented and in the future Zn‐Mg metallic coatings will help to save auxiliary anticorrosion measures such as wax and mastics. To offer steels with high stiffness but low weight, Arcelor has developed a new multimaterial sandwich which shows a good potential for large panels due to its high stiffness. Finally, some breakthrough steel products are discussed as possible candidates for mid/long term applications.     

Effect of NiCl_2-Based Fluxes on Interfacial Layer Formation of Hot Dip Galvanized Steels

While the thick growth of intermediate phase layers generally benefits the corrosion resistance of galvanized steels,it is unfavorable from the standpoints of mechanical integrity and economics.Thus,the influence of nickel chloride-based fluxes and the typical zinc-ammonium chloride flux on galvanized coating thickness as well as coating morphology and composition is examined.The investigation of pretreated hot dip galvanized steel specimens for various durations has verified that nickel chloride fluxes inf...     

Zn-Al-Mg 镀层的微观组织及相组成分析

Zn-Al-Mg镀层钢板具有优异的切口保护性能和耐大气腐蚀性能,但Zn-Al-Mg镀层的相组成至今尚存在争议。为了更好地控制Zn-Al-Mg镀层结构、镀层钢板的成形性和耐蚀性,利用SEM、XRD、GDS和TEM等设备分析了Zn-Al-Mg镀层钢板的微观组织,确定了Zn-Al-Mg镀层是由Zn、Al和MgZn₂三相组成。通过TEM分析发现,Zn-Al-Mg镀层与钢板的界面存在厚度为0.01 μm的Al-Fe合金层和厚度为0.1 μm的Zn-Mg合金层。     

The development of surface treatment products and technologies of steel sheets in Baosteel

The surface treatment technology can improve the corrosion resistance of steel sheets and increase the value of steel application.The surface treated steel sheets in Baosteel include zinc galvanized steel sheets,sin galvanized steel sheets,chromium galvanized steel sheets,and colour coating steel sheets with the application in the area from construction to automobiles,appliance,package,etc.The development,application and manufacturing technique of these products have become the core competition power of Baosteel. The article reviews the developments of surface treated steel sheets and surface treatment technologies in Baosteel in 10 years,especially hot dip galvanized high strength steel products used in vehicles.The article also looks forward into further developments of surface treatment steel products and technologies in Baosteel,which will focus on:①the new products of hot dip galvanized advanced high strength steels;②more environmental friendly products or functional coating products;③the development of surface treatment technologies to meet the requirement of higher surface quality in the marcket;④new type of surface treatment and coating technologies.     

含硼结构级镀锌钢带热轧工艺优化

为开发高质量含硼结构级热镀锌产品,以含硼与无硼的美标SS340热轧镀锌钢带为研究对象,由原料热轧钢带生产入手,运用力学拉伸试验、金相组织观察、TEM手段,对比分析了硼元素对其性能的影响。结果表明,微合金元素硼加入后,形成BN强化相,明显使热轧钢带基体晶粒粗大,引起屈服强度值降低。优化热轧工艺参数和化学成分后,提升了含硼热轧钢带的屈服强度,可以保证最终镀锌产品的性能。     

Corrosion Resistance of Reactive Element Aluminide Diffusion Coatings on a Nickel‐based Superalloy and an Austenitic Stainless Steel

Continuously cast aluminium alloy wires containing active elements such as yttrium, cerium, lanthanum or silicon were used as evaporation sources for ion vapour deposition on nickel‐based Inconel IN738 and stainless steel 310S substrate materials. The samples were subsequently diffusion heat‐treated to form protective corrosion resistant nickel aluminide and iron aluminide coatings. The coated alloy materials were exposed for prolonged periods to high temperature cyclic oxidation, molten sulphate, and molten carbonate environments to evaluate their resistance to hot oxidation. For IN738, the lanthanum‐modified aluminide coating provided good thermal cyclic oxidation performance while the cerium‐modified coating exhibited effective hot corrosion resistance in a molten sulphate environment. For 310S stainless steel, all of the modified aluminide coatings provided equally good corrosion protection when exposed to molten carbonate attack under an oxidizing atmosphere.     

热浸镀工艺对热成形钢铝硅镀层的影响

随着汽车轻量化的不断发展,热成形钢得到越来越快的发展,普通镀层已满足不了热成形工艺的要求。热浸镀铝硅钢板具有优良的耐热耐腐蚀性能、抗高温氧化性能和外观装饰性能等,得到普遍的应用。目前国内对铝硅镀层研究甚少,国内汽车制造厂使用的镀铝硅热冲压成形钢主要依靠进口。利用CAG-III热浸镀锌模拟试验机,针对不同热浸镀工艺对热成形钢板进行热浸镀铝硅试验,通过扫描电镜等手段进行表面和截面形貌观察及能谱分析。试验结果表明,铝硅镀层截面组织主要由铝基固溶体、Al-Fe-Si三元合金和Fe-Al二元合金组成,当浸镀温度为690 ℃、浸镀时间为5 s时为最优浸镀工艺。     

pH值对货油舱用耐蚀钢腐蚀特性的影响

针对油轮货油舱底部的高氯离子强酸性腐蚀环境,参照了IMO《货油舱用耐蚀钢实验程序》的要求,深入研究了腐蚀溶液的pH值对其腐蚀特性的影响,对比分析了普通E36级船板钢以及等强度级别的耐蚀船板钢腐蚀行为的差异.研究结果表明,pH值对钢的腐蚀速率有显著影响.pH＜3.0时,耐蚀钢的耐腐蚀性能,尤其是耐点蚀性能明显优于传统钢;pH≥3.0时,耐蚀钢和传统钢的腐蚀速率未表现出明显差异.强酸性氯离子环境下,实验钢的纯净度、微量耐蚀合金设计、显微组织共同决定了其耐腐蚀性能.钢中的非金属夹杂物是诱发局部腐蚀的主要原因;Cu、Ni、Sn元素的复合添加能显著提高耐蚀钢的腐蚀电位,同时耐蚀合金元素在锈层内部富集,提高了耐蚀钢表面锈层的致密性与稳定性;单一均匀的贝氏体显微组织有利于提高实验钢在酸性氯离子环境下的耐蚀性能,这主要是由于贝氏体组织中富碳相较少且分布均匀.     

先进镀锌高强钢中液态金属脆化的研究进展及挑战

先进高强钢广泛用于汽车车身结构,能够在保证车辆安全性的同时使整体车身减重,满足节能减排的要求,在汽车轻量化方面已凸显出巨大的应用潜力.通常汽车用高强钢板需要进行表面镀锌处理以提高车身结构的抗腐蚀能力.但镀锌高强钢板在点焊过程中容易产生液态金属脆化,降低焊接接头的承载性能.镀锌热成形高强钢在热成形过程中也会产生液态金属脆...     

汽车用热基镀锌高强钢的研发进展

 日益复杂的服役环境,对汽车底盘及结构内件耐蚀性提出了更高要求,常规酸洗板已无法满足。以低合金高强钢(HSLA)、铁素体贝氏体钢(FB)和复相钢(CP)为代表的热基镀锌高强钢兼具热轧钢板的高成形性及镀层钢板的高耐蚀性,取代酸洗板用于汽车底盘和结构内件制造,不仅可以提高整车防腐性能,还可以降低零件修复、更换和再生产带来的能源消耗与碳排放,为汽车企业选材用材升级、降本增效提供了重要解决方案。汽车用热基镀锌高强钢对组织性能及表面质量的要求极其严格,国内外具备产品开发及稳定供货能力的企业很少。从化学成分、热轧、冷却、卷取和退火等工艺参数对微观组织及析出相的影响方面阐述了热基镀锌高强钢组织性能调控机理,以色差、漏镀和锌流纹等缺陷为例概述了热基镀锌高强钢表面问题产生的原因及相应的攻关方向。重点介绍了锌铝镁镀层在耐腐蚀方面的优势以及热基锌铝镁产品的主要应用途径。综述了国内外汽车用热基镀锌高强钢的生产及应用现状,指出进一步提升综合性能、改善表面质量和拓展极限规格是其发展方向。同时指出,需要持续关注热基镀锌高强钢生产和应用方面的问题,如色差、漏镀和锌流纹等表面问题,焊接飞溅、气孔和LME裂纹问题以及针对底盘特定腐蚀环境的耐蚀性数据积累及评价。     

热镀锌液中Al含量及工艺对TRIP钢表面质量的影响

通过对TRIP590钢进行不同Al含量锌液热镀锌对比试验,研究了锌液中不同Al含量及热镀锌工艺对TRIP钢镀层性能的影响。试验结果表明,镀锌液中加入5%Al,均热退火温度800℃,可明显提高TRIP钢的镀层质量,改善热镀TRIP钢的抗腐蚀性能。     

Influence of Oxide Morphologies on Galvanizability of Third Generation Automotive Steel

Focusing on improving the galvanizability of the third generation automotive steel, the effect of surface ox ide morphologies on the galvanizability was studied. The results show that the surface oxide types of sample steels by X ray photoelectron spectroscopy （XPS） analysis after annealing in different conditions are the same. Only MnO, MnO2 and Cr2O3 were detected and no complex oxide exists on the surface. Morphologies of surface oxides can greatly influence the galvanizability of the third generation automotive steel. Nodule-like oxide surface can contribute to better wettability and inhibition layer than vitreous film like oxide surface. Galvanized panels of nodule-like oxide surface steels only show pinhole sized bare spots, while panels galvanized from vitreous film-like oxide surface steels reveal larger areas of bare spots and uncoated areas. Inhibition layer observed in galvanized panels of nodule-like oxide surface steels is compact but not homogeneous; some inhibition layer grains are fine, and others are coarse, while the inhibition layer grains of panels galvanized from vitreous film-like oxide surface steels have a non-compact morphology with some particularly fine equiaxed crystals which developed deficiently.     

硼含量对低碳钢耐蚀性的影响

 为考察不同硼含量低碳钢的腐蚀规律,利用盐雾腐蚀试验研究了不同硼含量低碳钢的腐蚀行为,结合X射线衍射（XRD）和傅里叶红外光谱（FTIR）对腐蚀产物进行了分析。试验结果表明：含硼低碳钢腐蚀速率与硼质量分数有关,硼质量分数0.002%试验钢腐蚀速率低于无硼钢,硼质量分数高于0.002%的试验钢腐蚀速率超过无硼钢,并且随硼含量增加,试验钢的腐蚀速率逐渐增加;阐述了硼的腐蚀机制。     

热成型钢及热成型技术

对热成型钢的成分设计、热成型工艺过程以及表面氧化的处理进行了论述。热成型工艺可以通过直接热成型或者间接热成型实现;热成型钢都是含硼钢,硼能抑制成型过程中铁素体形核;通过锰、铬和钼等提高淬透性防止珠光体形成;一般热成型钢中含有0.2%左右的碳。热成型钢可通过喷丸的方法消除表面氧化层或者镀层技术保护其表面不受氧化。     

A Numerical and Experimental Investigation into Hot Stamping of Boron Alloyed Heat Treated Steels

Hot stamping of steel sheets using water or nitrogen cooling media was studied on a laboratory scale. Sheets of grade 22MnB5 boron steels in three different thicknesses were investigated and the results of experimental hot stamping tests were considered. Microstructural analysis, linear and surface hardness profiling as well as tensile tests of formed samples were carried out. After hot stamping, mostly fully martensitic microstructures, which yield ultra high strength levels, were produced. It is concluded that die cooling media, i.e., water or nitrogen, have a significant effect on material properties after hot stamping. Using liquid nitrogen as coolant in the punch instead of water increases yield strength by 50 to 65MPa. Moreover, the evolution of the temperature and force during the hot stamping process was simulated by using a coupled thermomechanical FEM program. The results of numerical simulation and experimental results are in good agreement.     

New types of coating systems for steel sheets by high‐rate evaporation in combination with plasma processes

High‐rate evaporation in combination with plasma processes is a promising approach to obtain new types of steel sheet coating with improved corrosion resistance and application properties. To estimate the potential for the application of PVD‐coatings (physical vapour deposition) different coating systems for steel sheet as well as for hot‐dip or electro‐galvanized steel sheet were designed. The samples were produced on a laboratory scale using PVD processes with very high deposition rates (in the order of 1 μm s^‐1) as well as high‐power plasma processes for the pre‐treatment. The relationship between the composition, microstructure and properties of the coating systems, in particular concerning corrosion protection, abrasion during forming, phosphating and paint adhesion, were studied. It was found that the corrosion resistance of galvanized steel sheets can be considerably improved by vapour deposition of metal or inorganic films with a thickness of several hundred nanometers. Investigations on vapour deposition of titanium and stainless steel coatings on steel sheets, for applications in a severely corrosive environment, showed that the corrosion resistance in relation to the coating thickness can be significantly enhanced by means of plasma activation during the vapour deposition process. Finally, an outlook on possible industrial applications including an estimation of the process costs will be presented. For certain coating systems the results look promising. Consequently, these particular coating systems will be investigated in more detail by means of using a large‐scale in‐line deposition plant for metallic strips and sheets.     

热镀锌钢板钼酸盐钝化膜的改性及耐蚀性

 为了探寻一种热镀锌钢板用环保型无铬钝化剂,采用在钼酸盐钝化液中加入适量H3PO4、SiO2、Ti(Ⅳ)盐等添加剂对钼酸盐钝化膜改性,并利用SEM、EDS、XRD和中性盐雾试验等测试手段研究了所得钝化膜的表面形态、成分、组成和抗盐雾性能,同时讨论了钝化膜的成膜机理与防蚀机理。结果表明,改性钼酸盐钝化膜是一种复合钝化膜,其表面呈现出良好的抗白锈能力。它可以有效地提高镀锌板的耐蚀性能,其中Mo P Si Ti体系钝化膜的防护性能比热镀锌板提高5倍,这是由于膜中各组分协同作用所致。     

Development of an Aluminized Multi‐Phase Steel with Dual Phase Properties for High Temperature Corrosion Resistance Applications

A high strength, high Mn, Cr‐Mo containing multi‐phase steel grade was aluminized with a 90 wt% Al – 10 wt% Si alloy coating, using a laboratory hot‐dip simulator. The adhesion of the coating to the steel strip was evaluated and the microstructure of the as deposited material was assessed. The coated sheet steel was tested at high temperatures by monitoring the weight gain of the samples and their mechanical properties as a function of time. It was found that the thermal properties of the aluminized sheet were excellent. The analysis of the coating/substrate interface revealed the dissolution of brittle intermetallic phases, explaining the excellent high temperature resistance performance of the Al‐Si coating up to temperatures as high as 900°C. In addition, the use of a continuous annealing cycle common in current aluminizing lines, resulted in a dual phase microstructure.