Hot dip fine Zn and Zn-Al alloy double coating for corrosion resistance at coastal area

A new hot dip Zn-7Al alloy coating was performed on a structural steel by double coating of fine Zn and Zn-7 wt.% Al alloy, to prevent severe corrosion in coastal area. The alloy-coated steels were exposed to seaside, quasi-industrial, and rural districts to compare with conventional Zn coating. Double coating was significantly effective in preventing corrosion, particularly in a seaside. It was estimated from the exposure test for 10 years that the life of the Zn-7Al alloy-coated steel would be almost four times that of the Zn-coated steel in the seaside. A bending test showed that no exfoliation occurred at the interface between the coated alloy and substrate steel. TEM observation revealed that the excellent adhesiveness of the doubly coated fine Zn and Zn-7Al alloy to the steel substrate was due to formation of the interface region consisting of heterogeneous fine phase mixture of zinc, aluminium and iron.     

Modelling the relationship between microstructure of Galfan-type coated steel and cut-edge corrosion resistance incorporating diffusion of multiple species

This paper describes a considerable extension to a previously documented [S.G.R. Brown, N.C. Barnard, 3D computer simulation of the influence of microstructure on the cut edge corrosion behaviour of a zinc aluminium alloy galvanized steel, Corrosion Science 48 (2006) 2291-2303], first-order model used to simulate the localized degradation experienced in Zn-4.5 wt% Al steel coatings exposed to 5% NaCl aqueous solution. The temporal localization and intensity of discrete corrosion effects are predicted using established relationships and, in contrast to earlier models, the evolution of multiple concentration fields is included and calculated using straight-forward finite difference techniques. Changes in composition are included in the quantification of both anodic and cathodic processes involved in the corrosion of steel coatings in contact with aerated saline solutions. Reported [J. Elvins, J.A. Spittle, D.A. Worsley, Microstructural changes in zinc aluminium alloy galvanising as a function of processing parameters and their influence on corrosion, Corrosion Science 47 (2005) 2740-2759] and modelled performances of typical Galfan composition coated steels are evaluated for different coating microstructures undergoing so-called cut-edge corrosion. In summary, this latest model successfully matches measured rates of metal loss during localized corrosion. Additionally, the inclusion of multiple species diffusion functionality has greatly improved the simulation of the cathodic reaction in particular and the overall form of the current density distribution near the corroding surface.     

Improving wear resistance and corrosion resistance of AZ31 magnesium alloy by DLC/AlN/Al coating

A novel protective coating, consisting of three layers (top: diamond-like carbon, middle: aluminum nitride, bottom: aluminum), was deposited on the surface of AZ31 magnesium alloy layer by layer. Nano-indenter, electrochemical system and tribological tester were performed to investigate the hardness, wear resistance and corrosion resistance of the coated AZ31 magnesium alloy, respectively. The DLC/AlN/Al coating improved the magnesium alloy's surface hardness and reduced its friction coefficient, which consequently induced a great improvement of the magnesium alloy's wear resistance. Furthermore, the corrosion resistance of the AZ31 magnesium alloy with the DLC/AlN/Al coating was also enhanced with the corrosion current density decreasing from 2.25 × 10⁻⁵ A/cm² to 1.28 × 10⁻⁶ A/cm² in a 3.5 wt.% NaCl solution.     

Fluxless laser beam joining of aluminium with zinc coated steel

Abstract

A laser welding–brazing (LWB) process to join zinc coated steel and aluminium sheets in two different flange geometries is reported. The deep drawing steel sheets are covered by a zinc layer of maximum thickness 10 μm, and a zinc based filler wire was used in the welding experiments with a Nd–YAG laser. Because of the differences in melting temperatures between iron (1808 K), aluminium (933 K), and zinc (693 K), it is possible to weld the aluminium alloy only. Owing to the zinc coating on the steel side, a Zn–Al alloy can be brazed onto the steel without any flux agent. The inevitable formation of a Fe–Al intermetallic phase at the bondline of the weld seam and the steel can be limited to a thickness of less than 5 μm and to a proportion of the contact area only. Mechanical as well as dynamic tests show results comparable to those obtained via other joining techniques. Salt chamber corrosion tests of varnished specimens display minor damage and no decline in tensile strength.     

Corrosion evaluation of microarc oxidation coatings formed on 2024 aluminium alloy

Dense alumina ceramic coatings of 7 μm thickness were fabricated on 2024 aluminium alloy by microarc oxidation (MAO). The corrosion behaviour of the MAO coated alloys was evaluated using potentiodynamic polarisation and EIS measurements. The results show that the corrosion process of the coated alloy can be divided into three stages: (1) the initial stage (the first 2-6 h of immersion): penetration of corrosion medium into the aluminium alloy was inhibited by coating; (2) the second stage (after 24 h of immersion), corrosion medium penetrated to attack the interface between the substrate and the coating; (3) the final stage (after about 96 h): corrosion process was controlled by the diffusion of corrosion products.     

Characterisation of coating on rebar surface using Hot-dip Zn and Zn-4.9Al-0.1 misch metal bath

The corrosion of rebar is one of the primary causes of premature deterioration of the concrete structure. The ideal option to overcome this situation would be to provide corrosion protection right at the time of manufacturing of the rebar before it is encased in the concrete and hence, warrants the use of corrosion resistance rebar.The present paper outlines characterisation of coating obtained on rebar surface from pure Zn and Zn-4.9Al-0.1 misch metal bath. The coating was characterised by SEM, EDS, Galvanostatic and XRD techniques. In case of pure Zn bath, distinct phases such as eta, zeta, delta and gamma 1 and gamma were identified in coating where as in case of Zn-4.9Al-0.1 misch metal bath no such distinctive phases were found. The coating obtained from Zn-4.9Al-0.1 misch metal bath was thinner and consisted of outer Al₂O₃ phase followed Zn-Al phase resulting in better ductility compare to the coating obtained from pure Zn bath. Comparative corrosion resistance performances of both types of coating respect to uncoated rebar were evaluated by salt spray and tafel test. were conducted in simulated aggressive chloride and concrete pore solution of coated and The coating obtained form Zn-4.9Al-0.1 misch metal bath was found to be more anodic and showed 1.5-3 times better corrosion resistance in concrete pore solution and 2.5 times better resistance against aggressive chloride attack compare to the coating obtained from pure Zn bath. Both the coatings dissolved in faster rate in highly alkaline environment (pH = 13.6) where as dissolution rate decreased with decrease of pH in pore solution. The sacrificial as well as barrier protection of Zn-Al alloy coating was found to be more effective than pure Zn coating. Both types of coated bars showed reduction in bond strength in concrete structure. It is attributed by the faster dissolution of the coating, leading to hydrogen gas evolution thereby creating a gap between the rebar surface and concrete structure.     

Microstructure of the coating and mechanical properties of galvanized chromium-rich martensitic steel

Protecting the modern high-strength steels against corrosion is a challenge because the coating technology must be compatible with forming and must preserve the mechanical performances. Batch galvanizing after hot stamping could provide a simple solution to this complex problem. A commercial high-strength martensitic steel containing 13 wt.% Cr, 0.35 wt.% Si, 0.3 wt.% Mn and 0.15 wt.% carbon has been galvanized with a commercial zinc alloy. Galvanizing produces a ~ 15 μm thick coating that is bright, continuous and metallurgically bonded. The intermetallic layer is made of ? crystals, which forms an open 3-dimensional structure. Tin, nickel and aluminium are found able to moderate the Sandelin effect. Comparison with other steels galvanized the same way indicates that chromium slows down the kinetics of the metallurgical reaction. Chromium distributes both in the ? and η phases, and follows a diffusion-like profile in the coating. The nickel from the alloy concentrates in the Fe-Zn intermetallic compound. Aluminium segregates at the surface and interface. It also provides a gettering effect that fixes silicon in sub-micron particles dispersed in the ? and η phases. Tensile experiments and fatigue tests demonstrate that the mechanical performances of the martensitic steel are preserved after coating. Comparison with similar experiments performed on a TRIP800 steel indicates that using galvanized martensitic steel is best worth in static applications.     

热浸Zn-Ti合金镀层的耐腐蚀性能

为了抑制热镀锌过程中因含硅活性钢引起的镀层超厚生长,采用在纯锌浴中加Ti的方法,研究了热浸Zn-Ti合金镀层的耐蚀性能.采用浸泡腐蚀、电化学极化、交流阻抗以及X射线光电子能谱等方法,研究了热浸Zn-Ti合金镀层的耐蚀性能.结果表明:Zn-Ti舍金镀层在5%NaCl溶液中的自发腐蚀倾向小于Zn镀层,其极化电阻和交流阻抗增大,腐蚀电流密度减小,耐蚀性能提高.Zn-Ti镀层表面形成的氧化膜由ZnO和TiO2组成.Zn-Ti合金镀层的耐腐蚀性能优于纯锌镀层是由于在镀层表面形成了更加稳定的TiO2膜.     

Formation of an aluminum-alloyed coating on AZ91D magnesium alloy in molten salts at lower temperature

An aluminum-alloyed coating was formed on an AZ91D magnesium alloy in molten salts containing AlCl₃ at a lower temperature of 380 °C. The microstructure and phase constitution of the alloyed layer were investigated by optical microscopy, scanning electron microscopy, energy dispersive spectrum and X-ray diffraction. The nano-hardness of the coating was studied by nanoindentation associated with scanning probe microscopy. The corrosion resistance of the coated specimen was evaluated in a 3.5 wt.% NaCl solution by electrochemical impedance spectroscopy and cyclic potentiodynamic polarization. The results show that the aluminum-alloyed coating consists of Mg₂Al₃ and Mg₁₇Al₁₂ intermetallic layers. The formation of the coating is dictated by the negative standard free energy of the reaction: 2AlCl₃ + 3 Mg = 3MgCl₂ + 2Al. This process is associated with a displacement reaction mechanism and diffusion process that takes place during the molten salt treatment. High activity of Al elements in molten salts contributes to the lower temperature formation of the Al-alloyed coating. The alloyed coating markedly improves the hardness as well as the corrosion resistance of the alloy in comparison with the untreated AZ91D magnesium alloy, which is attributed to the formation of the intermetallic compounds.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.     

电弧喷涂Zn-22Al-Mg-RE合金涂层的耐蚀性能

采用电弧喷涂技术和自主研发的合金丝材在Q345基体上制备出Zn-22Al-Mg-RE合金涂层。通过SEM、铜加速乙酸盐雾试验、XRD和极化曲线来比较纯锌涂层和Zn-22Al-Mg-RE合金涂层的微观结构及耐蚀性能。结果表明,Zn-22Al-Mg-RE合金涂层相比于纯锌涂层结合强度提高了40%,在铜加速乙酸盐雾试验中出现第一锈点的时间延长1倍以上。电化学实验结果也表明合金涂层具备更优异的耐蚀性能。研究认为,Zn-22Al-Mg-RE合金涂层腐蚀产物中出现大量稳定致密的Zn6Al2(OH)16CO3·4H2O物相,是耐蚀性能提高的主要原因之一。     

Influence of the β phase on the corrosion performance of anodised coatings on magnesium-aluminium alloys

The effect of the β phase in Mg-Al alloys on the corrosion performance of an anodised coating was studied. It was found that the corrosion resistance of the anodised coating was closely associated with the corrosion performance of the substrate alloy. In particular, Mg alloys with a dual phase microstructure of α + β with intermediate aluminium contents (namely 5%, 10% and 22% Al) after anodisation had the highest corrosion rate and the worst corrosion resistance provide by the anodised coating. The poor performance of an anodised coating was attributed partly to lower corrosion resistance of the substrate alloy and partly to the higher porosity of the anodised coating.     

Investigation into the effects of metallic coating thickness on the corrosion properties of Zn-Al alloy galvanising coatings

Galvalloy (4.5% Al 95.5% Zn) coatings were produced on a continuous coil coating line at Corus Colors’ Shotton works with varying metallic coating thickness from 7.8 μm (120 g m⁻²) to 48 μm (325 g m⁻²) controlled using air knives. An overall decrease in aluminium content from 5.1% to 4.5 wt% and a primary zinc volume fraction increase from 16.2% to 32.8% occurred as the coating thickness is decreased. This reflects greater nucleation in thinner coatings and some removal of Al enriched molten phases. The scanning vibrating electrode technique (SVET) was used to show that increasing the coating thickness from 7.8 to 48 μm resulted in a decrease in the level of zinc removed during corrosion from a 20 mm exposed cut edge from 530 to 220 μg in the 24 h exposure to 5% NaCl solution. The same trend was also observed when external zinc runoff measurements were made at the Port Talbot weathering site. The increasing corrosion observed at lower coating weights results from greater undercutting of these coatings that are further away from a eutectic composition and an increasing tendency for crevice driven corrosion brought about through primary zinc dendrite interconnectivity.     

Microstructure and corrosion performance of a cold sprayed aluminium coating on AZ91D magnesium alloy

A pure Al coating was deposited on AZ91D magnesium alloy through cold spray (CS) technique. The microstructure of the coating was characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that the grain interfaces and subgrains formed close to the particle/particle boundaries. Electrochemical tests revealed that the cold sprayed pure Al coating had better pitting corrosion resistance than bulk pure Al with similar purity in neutral 3.5 wt.% NaCl solution. In addition, a mass-transfer step was found to be involved in the corrosion during 10 days immersion.     

Studies on the development of TZM alloy by aluminothermic coreduction process and formation of protective coating over the alloy by plasma spray technique

TZM alloy is a potential candidate for high temperature structural applications. However, in the preparation of this alloy by conventional melt-casting route, difficulties are encountered in achieving homogenized alloy composition in view of high melting temperature of the alloy and presence of minor alloying components. Therefore, an alternative technique of aluminothermic co-reduction was adopted to prepare TZM alloy of composition, Mo-0.5Ti-0.1Zr-0.02 °C, wt.% by simultaneous reduction of uniformly premixed oxides of MoO₂, TiO₂ and ZrO2 by aluminium in presence of requisite amount of carbon. The as-reduced alloy was further arc melted for consolidation. Since, TZM alloy is by nature highly susceptible to oxidation at elevated temperature in air or oxygen, therefore feasibility of development of silicide type of coating over the synthesized alloy by plasma coating technique was also examined. Silicon powder coated on TZM alloy surface by plasma spray technique was finally converted into MoSi₂ coating by sintering at 1350 ^°C for 2-4 h duration under argon. A double layer coating structure was formed with two distinct phases. The inner thin layer was consisted of Mo₂Si₅ phase (~ 10 μm) followed by thick outer layer of MoSi₂ (~ 150 μm). The coating showed good adhesion strength and stable oxidation with negligible mass gain (10 g/m²) at 1000 ^°C in air.     

Chemistry of corrosion products on Zn-Al-Mg alloy coated steel

Zn-Al-Mg alloy (ZM) coating provides a decisively enhanced corrosion resistance in a salt spray test according to DIN EN ISO 9227 (NSS) compared to conventional hot-dip galvanised zinc (Z) coating because of its ability to form a very stable, well adherent protecting layer of zinc aluminium carbonate hydroxide, Zn₆Al₂(CO₃)(OH)₁₆·4H₂O on the steel substrate. This protecting layer is the main reason for the enhanced corrosion resistance of the ZM coating. Surface corrosion products on ZM coated steel consist mainly of Zn₅(OH)₆(CO₃)₂, ZnCO₃ and Zn(OH)₂ with additions of Zn₅(OH)₈Cl₂ · H₂O and a carbonate-containing magnesium species.     

Laboratory-scale performance of a binary Cu-Al alloy as an anode for aluminium electrowinning

A binary Cu-Al alloy (9.4 wt.% Al) has been investigated as a potential inert anode for aluminium electrowinning. Anodes have been tested in a laboratory electrolysis cell both with and without preformed oxides. Electrolysis was conducted in cryolitic electrolytes with anode current densities of 0.5 A cm⁻². The anodes operated satisfactorily as measured by electrical parameters. However, substantial corrosion of the Cu-metal substrate was observed. The external oxide generated on pre-treated anodes was porous and allowed the electrolyte to penetrate through to the Cu-metal whereby corrosion was initiated. An untreated anode formed an in situ surface alumina film, but this did not prevent corrosion of the substrate.     

In situ investigation of sacrificial behaviour of hot dipped AlSi coating in sulphate and chloride solutions

The electrochemical behaviour of the cut-edge of hot-dipped aluminium–silicon-based alloy coated steel is studied in immersed conditions in sulphate and in chloride media. Preliminary studies performed on steel-pure Al bi-electrode demonstrate that a significant galvanic current can develop at short times (t < 1000 s) only in chloride solutions. In situ measurements of current density and pH distributions over cut-edge coated steels immersed in chloride solutions revealed a quasi-steady state current between the coating and the steel substrate, resulting from local (pitting like) dissolution of the aluminium–silicon-based alloy coating. In sulphate solutions, the coating is not at all sacrificial and remains passive.     

Microstructural changes in zinc aluminium alloy galvanising as a function of processing parameters and their influence on corrosion

The effect of cooling rate and substrate gauge upon the microstructure and corrosion resistance of Galfan (Zn-4.5 wt.%Al) coated steels is presented. The coatings, applied to steel of gauges 0.47 mm (light gauge) and 0.67 mm (heavy gauge) on a coil coating line, were subjected to three different cooling rates by increasing output from 55% to 100% of the total power from a high powered cooling rig. The increase in cooling rate did not significantly alter the volume fraction of the primary zinc, this remaining at ∼20%. However, the size and number of the primary zinc dendrites were altered. The fast cooled samples contained small but numerous (∼3000 mm⁻² in the heavy gauge and ∼2850 mm⁻² in the light gauge) dendrites as opposed to the slow cooled samples where there were fewer (∼1850 mm⁻² for the heavy gauge and ∼1500 mm⁻² in the light gauge) dendrites of greater size. Characterisation of the surface revealed a reduction in eutectic cell size (∼1.8 mm to ∼0.8 mm on the heavy gauge and ∼2.1 mm to ∼1.2 mm on the light gauge) with increasing cooling rate. This leads to an increased unit length of depressed boundary between the eutectic cells. The eutectic microstructure is also finer (with reduced inter-lamella spacing) in the fast cooled samples again reflecting the more rapid nucleation of the coating.The scanning vibrating electrode technique (SVET) has been used to quantify the effects of these microstructural changes upon the surface and cut edge corrosion performance. There is an increase in corrosion activity on the surface of the fast cooled samples (metal loss 150 μg to 260 μg on the heavy gauge and 50 μg to 80 μg on the light gauge) primarily due to the increased length of depressed boundaries. Applying the same analysis to the cut edge, a decrease in corrosion occurs upon the faster cooled specimens. Metal loss calculations show a decrease (140 μg to 75 μg on the heavy gauge and 190 μg to 115 μg on the light gauge) as the cooling rate is increased. The higher intensity long lived anodes at the cut edge in the slower cooling rate samples are directly related to the increase in zinc dendrite size within the coating as nucleation rates are reduced.     

(Zr,Ti)CN coatings as potential candidates for biomedical applications

(Zr,Ti)CN hard coatings, deposited by DC magnetron sputtering on Ti6Al4V alloy and Si substrates, were investigated as possible candidates to be used as protective layers for medical implants. Two coating types, with different non-metal/metal ratios, were prepared. The films were analyzed for elemental and phase composition, crystallographic structure, mechanical properties, corrosion behavior, surface wettability and cell viability. The coatings were found to have composite structures, in which a (Zr,Ti)CN crystalline phase coexists with an amorphous a-C(N) one. Film thickness and hardness in the ranges 1.8-2.1 μm and 25-29 GPa, respectively, were measured. The coated samples exhibited an improved corrosion resistance as compared with the Ti6Al4V alloy. Both coating types were found to be hydrophobic, the contact angles being higher than 100°. Cell viability measurements proved that the osteosarcoma cells are adherent to the coating surface, the highest viability (90.5%) after one week incubation being found for the film with high non-metal content.