PVD技术沉积锌镁合金镀层的研究进展

 在下游应用领域,传统镀锌板所暴露出的焊接、成型等缺陷,以及世界范围内对钢板防腐镀层节锌、环保要求的日益强烈,促使钢铁公司和汽车制造厂采用新颖的PVD技术研发在钢板上高效沉积的锌镁合金镀层。作为升级换代的智能镀层材料,锌镁合金镀层吸引了世界范围的广泛关注。回顾了锌镁合金镀层的PVD制备工艺,分析了锌镁合金镀层的耐蚀机制,说明了锌镁合金镀层作为下一代镀层材料的优势,展望了中国采用PVD技术研发锌镁合金镀层的发展潜力和方向。     

Influence of Surface Roughness of Galvanized Steel Sheet on Self-lubricated Coating

Three different thicknesses of self-lubricated coatings were prepared on galvanized steel sheets with different surface roughness(Ra).Performances of the coatings were evaluated by various laboratory tests.Scanning electron microscopy(SEM),atomic force microscope(AFM),neutral salt spraying test(NSST),reciprocating friction and wear test were taken in order to characterize the coatings.Results show that the self-lubricated coating has good corrosion resistance and lubricating property.In 0.857-1.629μm of Ravalue,the relationship between friction coefficients of the self-lubricated steel sheets and the surface roughness of the galvanized steel sheets likes a parabolic curve,and has a peak value of friction coefficient in certain range of Ra.Affected by the hereditary surface topography of the galvanized steel sheet,dents on the surface of self-lubricated steel become deeper and larger with the increase of the surface roughness of the galvanized steel sheets.The influence of the surface roughness of the galvanized steel sheet on the corrosion resistance of the self-lubricated coating steel is similar to that on friction coefficient of self-lubricated coatings,like a parabolic curve.     

New developments for vacuum coating of steel strips

Vapor deposited coatings onto strip steel are a promising alternative as functional layers for corrosion protection or high abrasion resistance.Conventional coating systems have some limits regarding environmental compatibility,the range of coating materials and application properties. Physical vapor deposition(PVD) is an environment-friendly technology and enables nearly unlimited material and process variety.Electron beam high-rate evaporation with deposition rates up to some micrometers per second is ...     

Surface and Coating Analysis of Press‐Hardened Hot‐Dip Galvanized Steel Sheet

The use of continuous galvanized steel sheet as feedstock material for press hardening leads to components of very high strength levels with classical cathodic corrosion protection. The present work provides an insight into this technology with special focus on surface oxidation and intermetallic phase formation during the austenisation process. For that reason hot dipped galvanized 22MnB5 steel sheets, with a blank thickness of 1.5 mm and an average coating weight of 70 g m^?2, were annealed in a temperature range of 400–900°C in steps of 50°C without soaking before quenching in water. Surface and cross‐cuts were analyzed by SEM, EDX, and XRD to illustrate the phase formation and the surface changes during thermal treatment. Corrosion behavior was also studied based on electrochemical investigations and an accelerated, cyclic, automotive corrosion tests called VDA, which is a mixture of salt spray test and alternating climate test. It was found that austenisation of galvanized steel sheet causes a significant change of the coating. The generated coating still offers cathodic protection for the steel substrate and has higher corrosion resistance than standard galvanized steel sheet. Surface oxidation also occurs during the press hardening process leading to a surface covered with successively arranged layers of Al₂O₃ and ZnO, containing also further oxidized alloying elements.     

宝钢热镀锌无铬耐指纹产品

比较了热镀锌含铬耐指纹钢板和无铬耐指纹钢板的涂层结构,研究了宝钢热镀锌无铬耐指纹钢板的各项表面特性,包括耐蚀性、耐指纹性、导电性等,并根据家电用户的使用特点,针对性地设计了耐湿热性、耐高温性、耐溶剂性、涂装性等性能的实验室评价方法。详细阐述了耐指纹膜厚度与该产品表面电阻值以及通过率之间的关系。结果表明,宝钢热镀锌无铬耐指纹钢板性能优良,基本能够满足用户的需求。     

Development of Zn‐Mg alloy coatings by JVD

To promote continuous dry coatings for steel strip by PVD, CRM develops its own JVD (jet vapour deposition) simulator and applies an economical integration strategy combining continuous annealing of steel and vapour deposition by JVD. The JVD system is a very compact system, characterised by a high productivity, a very high metal yield, possibility of working at high partial pressure (up to 1 mbar), homogeneous metal distribution and alloy composition and good coating adherence. It was verified that continuous annealing is a very efficient surface pre‐treatment for steel strip in a wide range of industrial dew points. No additional thermal energy is needed for strip heating since this PVD system is introduced in the end section just after continuous annealing. Application to the Zn‐Mg system is described. Influence of annealing parameters, residual gas pressure, coating speed, steel strip temperature and chemistry are discussed.     

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.     

热镀锌无铬耐指纹钢板涂装前处理工艺探讨

在一定生产工艺条件下,通过试验揭示了热镀锌无铬耐指纹产品涂装前处理工艺的变化对耐指纹皮膜的影响规律,进一步研究膜重对产品应用性能（包括导电性、耐摩擦性、耐指纹性、耐热性、涂装性及耐蚀性等）的影响规律,并提供相关的技术参考。结果表明,经前处理后,耐指纹皮膜质量有一定的损失,而膜重是影响产品最终应用性能决定性的因素,将钢板出厂膜重控制在1.0～1.3g/m2范围内,可生产出综合性能优良的热镀锌耐指纹产品。     

重量法测定电镀锌板和热镀锌板镀锌质量的比较

根据GB/T1839-2008采用的重量法分别测定了电镀锌板单面镀锌质量和热镀锌板单面镀锌质量;利用辉光放电发射光谱法测定电镀锌板和热镀锌板的镀锌质量,并表征了溶解前后电镀锌板和热镀锌板的镀层结构。结果发现:热镀锌板和电镀锌板镀层结构略有不同,但重量法能有效溶解镀锌板的镀层,使纯镀锌层、锌铁交界层及渗入钢基中的锌全都溶解下来。此外,试验还发现重量法和辉光放电发射光谱法测定电镀锌板和热镀锌板镀锌质量的分析结果有较好的一致性,这也进一步证明重量法是测定不同类型镀锌板的镀锌质量的较准确方法。另外,根据辉光放电发射光谱法测定不同镀锌板镀层结构的分析结果及电感耦合等离子体原子发射光谱法(ICP-AES)测定镀层中铁和铝含量的分析结果,讨论了重量法测定电镀锌板及热镀锌板镀锌质量误差的来源和大小。发现引起重量法测定不同镀锌板的误差主要由镀层中除锌元素以外的铁和铝元素的溶解引起的。而重量法测定电镀锌板镀锌质量的误差要远远小于重量法测定热镀锌板镀锌质量误差,这说明重量法更适合电镀锌板镀锌质量的测定。     

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.     

Up‐scaling of a Low Temperature PACVD Process for the Deposition of α/γ‐Nanocrystalline Alumina Coated Tools for Thixocasting of 1.2208 steel

An industrial‐scale pulsed plasma‐assisted chemical vapor deposition (PACVD) process for crystalline alumina growth was developed. To obtain a homogeneous coating thickness distribution over complex geometries and large dimensions, a suitable gas injection system was designed. A phase formation diagram for alumina coatings as a function of pulse length and cathode voltage has been compiled, allowing for the deposition of dense α/γ‐Al₂O₃ coatings at a substrate temperature of 590 °C. Moulds coated with an α/γ‐Al₂O₃ coating were utilized in steel thixocasting at temperatures of ～1400 °C. The coatings were intact after thixocasting and showed significantly improved chemical wear resistance compared to plain steel moulds.     

汽车用镀锌钢板的最新发展

近２０年来，由于汽车工业的发展对镀层板的耐腐蚀性提出了越来越高的要求，并且对镀锌板的需求量也持续增长，锌及锌合金镀层板的产量，质量，品种和规格有很大的提高和扩大，相应的生产技术也得到了迅速发展。文章概要介绍了国外最新的镀锌板生产技术的发展，以及对未来技术需求和发展前景的展望。     

真空镀锌镁合金镀层微观结构表征

采用真空蒸发镀膜方法,在电镀锌板表面沉积一定厚度Mg,然后对其进行合金化退火处理获得了新型锌镁合金镀层。并结合扫描电镜(SEM)、透射电子显微镜(TEM)及X射线光电子能谱(XPS)等方法对锌镁合金相形成类别及微观结构进行了表征。结果表明,经300℃左右热处理获得的锌镁合金相主要为MgZn2,TEM观察到的MgZn2多为长方形齿状,合金层中存在Zn和Mg两元素含量比例基本恒定且无梯度变化的区域。镀层表面还存在微量MgCO3、MgO及Mg(OH)2;MgO不仅存在于表面,也存在于镀层之中。     

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。     

Characterization of Steel Thixoforming Tool Materials by High Temperature Compression Tests

The experimental set‐up and the results of high temperature compression tests for the characterization of tool materials for steel thixoforming are presented. The scope of this test is to reproduce the load profile of steel thixoforming processes consisting of mechanical, thermal, tribological, and chemical components on the forming mould. Tool materials were chosen following a concept within the Collaborative Research Center ‐ SFB 289 ‐ “Forming of metals in the semi‐solid state and their properties”. Three materials groups are distinguished: thin film deposited by physical vapor deposition (PVD) and plasma assisted chemical vapour deposition (PACVD), thick coatings (thermal spraying), and bulk ceramic materials. Samples were characterized using scanning electron microscopy (SEM), electron‐dispersive spectroscopy (EDS) and X‐Ray diffraction analysis (XRD). The results show varying resistance of the tool materials concerning the load profile. In order to provide an appropriate tool solution for the thixoforming of steels, different load profiles within the forming moulds are identified and the corresponding tool part is made from that material with the best performance.     

Protective Coatings on Heat-Resistant Nickel Alloys (Review)

The literature on materials for protective coatings on heat-resistant nickel alloys and methods for their production is reviewed in order to generalize the results and determine the principal directions for solution of the problem under consideration. It is shown that a promising approach is the development of layered composite ceramic coatings which, thanks to a graded variation of properties, are able to provide an optimal combination of adherence, mechanical strength, and corrosion and heat resistance. The methods of physical vapor deposition, plasma spraying, and electron-beam deposition remain the principal industrial processes for coating deposition.     

Corrosion Resistance of Different Metallic Coatings on Press‐Hardened Steels for Automotive

The corrosion resistance of laboratory press‐hardened components in aluminized, galvanized or galvannealed boron steels was evaluated through VDA 621‐415 cyclic test for the automotive industry. 22MnB5 uncoated steel for hot stamping and standard galvanized steel for cold forming were also included as references. Corrosion resistance after painting (cosmetic corrosion) was quantified by measuring the delamination of electro‐deposited paint from scribed panels. The rusting on their edges was used for determining the cut‐edge corrosion resistance. The corrosion resistance on unpainted deformed panels (perforating corrosion) was quantified by mass losses and pit depth measurements. Zinc‐coated boron steels were found to be more resistant to cosmetic corrosion than the other materials, and slightly more resistant to cut‐edge corrosion than the aluminized one. Red rust apparition could not be avoided due to the high iron content in all these hot‐stamped coatings. The three coated boron steels showed similar performances in terms of resistance to perforation. Aluminized boron steel presents the advantage of being less sensitive to hot‐stamping process deviation. Its robustness has been proved for many years on cars.     

锌和镀锌钢的稀土表面改性

通过在Ce(NO_3)_3水溶液中对锌和电镀锌钢进行化学转化(钝化)处理,在试样表面形成了铈转化膜。利用电子探针显微分析(EPMA)、X射线光电子能谱(XPS)和X射线衍射(XRD)等研究了转化膜的形貌、成分和结构,探讨了锌表面铈转化膜的形成机理。在氯化钠溶液中测定了试样的腐蚀率、极化曲线和电化学交流阻抗谱(EIS)等腐蚀性能参量,并与未钝化和普通铬酸盐钝化试样的情况作了对比。结果表明,本实验得到的锌表面稀土转化膜主要是由CeO_2、Ce_2O_3和ZnO组成的复合氧化物膜,铈转化膜的存在阻碍了锌在电化学腐蚀过程中的阴极反应和阳极反应,导致电荷传递电阻增大,腐蚀率降低。在一定条件下,铈转化膜对锌和镀锌钢的肪蚀效果优于铬酸盐转化膜。     

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。     

Hot-dip Galvanizing of Carbon Steel after Cold Rolling with Oxide Scale and Hydrogen Descaling简

A new processing method for producing hot dip galvanized steel is designed and tested, in which pickling is skipped. Hot-rolled low carbon steel sheets are roiled with oxide scale in an experimental mill at room temperature, prior to annealing under a 20% hydrogen reducing atmosphere and galvanizing on a hot-dip galvanizing simulator. Micro-cracks formed in the oxide scale during cold rolling roughen the steel surface and enlarge the specific surface. Through-thickness cracks provide transport channels for hydrogen, and hence the reduction of oxide scale is en- hanced. When the sheet is dipped in the zinc bath, cracks are submerged by liquated zinc and the defects are not dis- tinct after hot-dip galvanizing. The overlay coating occludes with rough surface of the sheet, whereby a superior coat- ing adherence is realized.