Formation of the ζ phase at an interface between an Fe substrate and a molten 0.2 mass% Al–Zn during galvannealing

An interstitial free (IF) steel was dipped in a bath of molten Zn containing 0.2 mass% Al. The as-dipped (galvanized) steel was then annealed above the melting point of Zn (galvannealed), say at 773 K, for a period ranging from 1 to 30 s. Evolution of the microstructure of the Zn-containing coating was examined by transmission electron microscopy (TEM) and the chemical composition around the Zn(Al)/Fe interface was analyzed by energy dispersion spectroscopy (EDS) in a dedicated scanning transmission electron microscope (STEM). In the as-dipped (galvanized) steel a continuous layer of Fe₂Al₅ existed at the Zn(Al)/Fe interface, but no Fe–Zn intermetallic compounds were observed. Galvannealing at 773 K for 1 s resulted in the formation of the ζ phase at the Zn(Al)/Fe₂Al₅ interface, which grew at the expense of the Zn(Al) coating during the subsequent galvannealing. Possible mechanisms of nucleation of Fe–Zn intermetallic compounds are discussed.     

Synergistic effect of Cu and Si on hot-dipping galvalume coating

The coating microstructures and thicknesses of the iron panels galvanized in galvalume baths containing 0.0, 0.1, 0.5 and 1.0 wt.%Cu for 10 s, 30 s, 60 s, 180 s, 300 s and 600 s have been studied detailedly. The results indicate that Cu can effectively control the Fe–Al reactivity by the synergistic effect with Si. The addition of Cu makes Si be enriched in the reaction region during the hot-dipping. It promotes the formation of the τ₅ phase and hinders the growth of the Fe₂Al₅ phase. The diffusion path model was introduced to studying the effects of Cu and Si in the present study. The addition of 0.5–1.0 wt.%Cu in galvalume bath forms a stable diffusion path, iron substrate/Fe₂Al₅/FeAl₃/τ₅/overlay. The violent reaction between the iron substrate and the Al–Zn liquid is under control by the compact intermetallic layer, and it decreases the thickness of the intermetallic layer.     

Effect of Fe-Zn alloy layer on the corrosion resistance of galvanized steel in chloride containing environments

In this study, the effect of Fe-Zn alloy layer that is formed during galvanizing process on the corrosion behavior of galvanized steel has been investigated. The galvanostatic dissolution of galvanized steel was carried out in 0.5 M NaCl solution to obtain the Fe-Zn alloy layer on the base steel. The alloy layer was characterized to be composed of FeZn₁₃, FeZn₇ and Fe₃Zn₁₀ intermetallic phases, which constitute the zeta, delta1 and gamma layers of galvanized steel, respectively. It was observed that the alloy layer has similar cathodic polarization behavior but different anodic polarization behavior compared to galvanized steel. The anodic current plateau of alloy layer was up to 100 times lower than that of galvanized coating. Corrosion test performed in wet-dry cyclic condition has shown that the alloy layer has lower corrosion rate as compared to galvanized steel. From the results of corrosion test of alloy layer and base steel, it was concluded that Zn²⁺ has positive effect on the protectiveness of the zinc corrosion products. The measurement of surface potential over the alloy/steel galvanic couple has confirmed the galvanic ability of alloy layer to protect both the alloy layer itself and the base iron during initial stage of atmospheric corrosion.     

The corrosion behavior of plasma sprayed Fe2Al5 coating in molten Zn

Aluminum coating was plasma sprayed on Fe-0.14-0.22 wt.% C steel substrate, and heat diffusion treatment at 923 °C for 4 h was preformed to the aluminum coating to form Fe₂Al₅ inter-metallic compound coating. The corrosion mechanism of the Fe₂Al₅ coating in molten zinc was investigated. SEM and EDS analysis results show that the corrosion process of the Fe₂Al₅ layer in molten zinc is as follows: Fe₂Al₅ → Fe₂Al₅Zn_x (η) → η + L(liquid phase) → L + η + δ(FeZn₇) → L + δ → L. The η phase and the eutectic structure (η + δ) prevent the diffusion of zinc atoms efficiently. Therefore the Fe₂Al₅ coating delays the reaction between the substrate and molten zinc, promoting the corrosion resistance of the substrate.     

Reactive wetting during hot-dip galvanizing of high manganese alloyed steel

The present study discusses reactive wetting during hot-dip galvanizing of high Mn alloyed steel (X-IP1000, 23 wt.% Mn) and is focused on investigating the influence of the metallic Mn concentration in the steel bulk composition on phase formation at the interface steel/coating. Samples were in-line bright annealed (1100 °C/ 60 s in N2-5%H2 at DP −50 °C) prior hot-dipping to avoid external MnO on the steel surface. This approach was applied to avoid influencing the wetting reaction by an aluminothermic MnO reduction, because this is considered to lead to an unwanted zeta-phase (FeZn13) formation in the coating by hot-dipping of Mn alloyed steels (< 5.0 wt.% Mn). The influence of hot-dipping parameters, which are contributing to the kinetics of the wetting reaction, was examined in terms of varying bath-Al content (0.17 and 0.22 wt.%), bath temperature (440-500 °C) and strip entry temperature (420-520 °C). The structure and chemical composition of both galvanized coating and interface steel/coating were characterized. While external MnO was verifiably avoided, brittle zeta-phase distinctively appeared at the interface steel coating together with the typical Fe₂Al₅ phase. This shows that the model of aluminothermic MnO reduction failed in the present case. This study suggests an alternative model explaining the appearance of zeta-phase with the removal of bath-Al by metallic Mn, which is dissolved out of the steel bulk into the Zn bath. The present investigation shows that alloying elements in the steel bulk may influence coating quality not only “indirectly” by external formation of nonwettable oxides, but also “directly” by influencing phase equilibria and kinetics of the wetting reaction. Understanding these phenomena will improve processing of (high) alloyed steel concepts as well as industrial Zn bath management.     

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.     

AZ31B镁合金/镀锌钢板电阻点焊接头形成机理

针对2.0 mm厚的AZ31B镁合金以及1.0 mm厚的SPHC镀锌钢板,采用KDWJ-17型三相次级整流电阻焊机进行焊接试验,通过光学金相、扫描电镜等方法分析接头各区域的组织结构和成分分布.提出了镁锌低熔点化合物挤压机制,分析了Zn元素在镁合金和镀锌钢板电阻点焊中的作用.结果表明,Zn与Mg元素形成的低熔点化合物MgZn₂在电极压力的作用下能填满由于焊接变形引起的间隙,使反应界面密封,促进Fe,Al元素在界面发生处扩散,Fe与Al元素在界面处发生反应生成Fe₂Al₅化合物,从而形成高强度的镁合金与镀锌钢板的电阻点焊接头.     

Enhanced reactive diffusion of Zn in a nanostructured Fe produced by means of surface mechanical attrition treatment

Nanostructured pure Fe was produced on a coarse-grained (CG) sample using surface mechanical attrition treatment (SMAT). The formation behaviors of Fe-Zn compound layer were studied in nanostructured Fe electroplated with a Zn layer. In comparison with the CG sample, the Fe-Zn reaction in the nanostructured Fe showed an onset temperature decrease of ∼21 °C and an increased enthalpy change of ∼70%. The activation energy for the growth of Fe-Zn compound layer decreased from ∼167.1 kJ mol⁻¹ in the CG sample to ∼108.0 kJ mol⁻¹ in the SMAT sample. The grain size of the formed FeZn₁₃ phase in the Zn/SMAT-Fe sample was much smaller than that in the Zn/CG-Fe sample after the same diffusion treatment. The enhanced reactive diffusion behaviors in the SMAT sample are attributed to the existence of a large number of grain boundaries in the nanostructured Fe.     

Solid-state reactions upon mechanical alloying of an Fe32Al68 binary mixture

The sequence of solid-state reactions that occur upon mechanical alloying of powder mixtures of Al and Fe taken in an atomic ratio of 68: 32 has been studied by the methods of X-ray diffraction analysis, M?ssbauer spectrometry, and Auger spectrometry. Upon the formation of a nanocrystalline state (<10 nm), there takes place a mutual penetration of Al atoms into Fe and Fe atoms into Al particles. The rate of consumption of the fcc Al is substantially higher than that of the bcc Fe. The process of the mechanical alloying (MA) was found to be two-stage. At the first stage, up to 2 at % Fe is dissolved in the fcc Al, and an amorphous Fe₂₅Al₇₅ phase is formed in the interfaces, whose amount reaches 70 at % at the finish of the initial stage. In the interfaces of the ??-Fe phase, a disordered bcc phase of composition Fe₆₆Al₃₄ is formed, which contains up to 12 at % Al segregates. At the second stage, the amorphous phase crystallizes into an orthorhombic intermetallic compound Fe₂Al₅. The residual ??-Fe, bcc Fe₆₆Al₃₄, and segregated Al form a bcc phase of composition Fe₃₅Al₆₅.     

Mechanical properties, deformation behaviors and interface adhesion of (AlCrTaTiZr)Nx multi-component coatings

In this study, (AlCrTaTiZr)N_x multi-component coatings with quinary metallic elements were developed as protective hard coatings for tribological application. The mechanical properties, creep behaviors, deformation mechanisms and interface adhesion of the (AlCrTaTiZr)N_x coatings with different N contents were characterized. With increasing the N₂-to-total (N₂ + Ar) flow ratio, R_N, during sputtering deposition, the (AlCrTaTiZr)N_x coatings transformed from an amorphous metallic phase to a nanocomposite and finally a crystalline nitride structure. The hardness of the coatings accordingly increased from 13 GPa to a high value of about 30 GPa, but the creep strain rate also increased from 1.3 × 10^− 4 to 7.3 × 10^− 4 1/s. The plastic deformation of the amorphous metallic coating deposited with R_N = 0% proceeded through the formation and extension of shear bands, whereas dislocation activities dominated the deformation behavior of the crystalline nitride coatings deposited with R_N = 10% and 30%. With increasing R_N, the interface adhesion energy between the coatings and the substrates was also enhanced from 6.1 to 22.9 J/m².     

Relation between microstructure and adhesion of hot dip galvanized zinc coatings on dual phase steel

The microstructure of hot dip galvanized zinc coatings on dual phase steel was investigated by electron microscopy and the coating adhesion characterized by tensile testing. The zinc coating consists of a zinc layer and columnar ζ-FeZn₁₃ particles on top of a thin inhibition layer adjacent to the steel substrate. The inhibition layer is a thin compact and continuous layer that consists of η-Fe₂Al_5–xZn_x fine and coarse particles. The coarse faceted particles are on top and fine faceted particles are at the bottom. The steel surface is covered with small fraction manganese oxides, which may impair adhesion of the zinc coating. The adhesion at various interfaces that exist in zinc-coated steel was quantitatively estimated using a so-called “macroscopic atom” model. In addition, the adhesion at the interfaces in zinc-coated steel was qualitatively assessed by examining the fracture and delamination behavior upon tensile testing. In accordance with this model, fracture along zinc grain boundaries preceded fracture along the zinc layer/inhibition layer and ζ-FeZn₁₃ particle/inhibition layer interfaces.     

The effect of hot-dipped aluminum coatings on Fe-8Al-30Mn-0.8C alloy

The morphology and microstructure of an intermetallic layer formed on the surface of Fe-8Al-30Mn-0.8C alloy by hot-dip aluminization treatment have been examined in detail. The phases present in the coating are unambiguously identified by means of transmission electron microscopy. After aluminization, a two layer coating was formed consisting of an external Al layer and a (Fe, Mn)₂Al₅ intermetallic on top of the substrate. The (Fe,Mn)₂Al₅ compound has an orthorhombic structure with lattice parameters a = 0.752 nm, b = 0.667 nm and c = 0.417 nm. The activation energy (E_FeMnAl) for the growth of such an intermetallic layer is calculated to be 52.7 kJ/mol. These results are different from those observed in aluminized low-carbon steel (E_Fe). The difference between E_FeMnAl and E_Fe is attributed to the alloying elements (Mn) in the present alloy. Environmental salt fog corrosion and high temperature oxidation tests were carried out to examine the corrosion and oxidation resistance. The results indicated that both the corrosion and oxidation resistance of the Fe-8Al-30Mn-0.8C alloy treated by hot-dip aluminization can be significantly increased.     

Adhesion, hardness and structure of thermal sprayed Al/SiC composite coat on graphite

Combustion powder spraying has been used in the coating of graphite by a layer of Al and SiC composite utilizing the Box-Wilson design that fixes the optimum spraying parameters of Al/SiC wt.% composition, substrate temperature and spraying distance. Graphite substrate surface was conditioned by subjecting to sand blast roughing and nitrogen flushed furnace treating. Under the spraying conditions considered, a single spraying pass attains a coating layer 65 ± 15 µm of average thickness. Two optimum spraying conditions that concern adhesion of coating to graphite and its hardness are obtained. Upon spraying for adhesion purpose, the coat/graphite adhesion strength is found to depend mainly on graphite surface conditioning, but for hardness purpose, it is found to depend mainly on SiC wt.% composition.Microstructure of transversal coating section indicates that adhesion efficiency is due to physical interlocking of molten sprayed materials on the roughened and treated graphite surface. Phases identified from fractured coatings by XRD analysis show individual phase of Al, SiC and graphite in addition to small amount of new extra phases that combine the three constituents such as Al₄C₃ and Al₄Si₂C₅. These phases play a role with the good physical interlocking in achieving adhesion strength that exceeds that of graphite.     

Experimental Determination and Atomistic Simulation on the Structure of FeZn<Subscript>13</Subscript>

By X-ray diffraction combined with Rietveld structure refinement, the crystal structure of FeZn₁₃ was determined experimentally in this study. The results indicated that the structure of FeZn₁₃ is monoclinic and the lattice parameters are a = 1.3408 nm, b = 0.7605 nm, c = 0.5074 nm, and β = 127.206°. It was confirmed that Fe atoms occupy the 2c position (0, 0, 0.5) in space group C2/m, and the coordinates of Zn atoms at the Zn(1) position are (0.114, 0.5, 0.293), which supports the results from Belin et al. (Acta Cryst. C 56:267, 2000). In addition, an atomistic calculation was carried out to determine the crystal structure based on the interatomic potentials obtained using the lattice inversion method, and Fe atoms are substituted by Zn atoms in the narrow solubility range of FeZn₁₃, which is the fundamental for studying the solubility and site preference of alloying elements of FeZn₁₃. Good agreement between the experimental results and the theoretical calculations was achieved.     

Determination of liquid-phase boundaries in Zn-Fe-Mx systems

Iron solubilities in molten Zn-Al alloys were experimentally determined at temperatures from 450 to 480 °C, a range relevant to continuous galvanizing operation. The Fe solubility was found to decrease slowly with increasing Al content in regions where ζ (FeZn₁₃) or δ (FeZn₇) is the equilibrium compound and rapidly in the region where the η (Fe₂Al₅Zn _x ) phase is the equilibrium compound. Analyses of the experimental data indicated that Fe solubility is governed by the thermodynamic properties of the intermetallic compound in equilibrium with the molten Zn-Al alloy. A model was developed to describe the liquid surface in the Zn-rich corner of the Zn-Fe-Al system. The methodology developed in the exercise has proven applicable for the determination of the liquid surface in the Zn-Fe-Ni system.     

Determination of liquid-phase boundaries in Zn-Fe-Mx systems

Iron solubilities in molten Zn-Al alloys were experimentally determined at temperatures from 450 to 480 °C, a range relevant to continuous galvanizing operation. The Fe solubility was found to decrease slowly with increasing Al content in regions where ζ (FeZn₁₃) or δ (FeZn₇) is the equilibrium compound and rapidly in the region where the η (Fe₂Al₅Zn _x ) phase is the equilibrium compound. Analyses of the experimental data indicated that Fe solubility is governed by the thermodynamic properties of the intermetallic compound in equilibrium with the molten Zn-Al alloy. A model was developed to describe the liquid surface in the Zn-rich corner of the Zn-Fe-Al system. The methodology developed in the exercise has proven applicable for the determination of the liquid surface in the Zn-Fe-Ni system.     

Development of anodic coatings on aluminium under sparking conditions in silicate electrolyte

Spark anodizing of aluminium at 5 A dm⁻² in sodium metasilicate/potassium hydroxide electrolytes is studied, with particular emphasis on the mechanism of coating growth, using transmission electron microscopy and surface analytical techniques, with coatings typically 10 μm, or more, thick. Two-layered coatings develop by deposition of an outer layer based on amorphous silica, associated with low levels of alkali-metal species, at the coating surface and growth of an inner, mainly alumina-based, layer, with an amorphous region next to the metal/coating interface. Formation of crystalline phases in the inner layer, mainly γ-Al₂O₃, with some α-Al₂O₃ and occasional δ-Al₂O, is assisted by local heating, and possibly also by ionic migration processes, arising from the rapid coating growth at sites of breakdown. Due to local access of electrolyte species in channels created by breakdown events, the silicon content in the inner coating regions varies widely, ranging from negligible levels to about 10 at.%. Silica deposition at the coating surface and formation of Al₂SiO₅ and Al₆Si₂O₁₃ phases is promoted by increased time of anodizing and concentration of metasilicate in the electrolyte. However, at sufficiently high concentration of metasilicate and pH, when more extreme voltage fluctuations accompany breakdown, the two-layered nature of coatings is replaced by a mixture of aluminium-rich and silicon-rich regions throughout the coating thickness.     

Phase evolution and dendrite growth in laser cladding of aluminium on zirconium

Aluminium was laser clad on a pure zirconium substrate using the blown powder method. The microstructure across the laser-clad coating was studied. Starting from the bottom to the top surface of the coating, a series of phase evolutions had occurred: (Zr) → (Zr) + AlZr₂ + AlZr₃ → Al₄Zr₅ + Al₃Zr₂ → Al₃Zr₂ + AlZr₂ → Al₂Zr → Al₂Zr + Al₃Zr. This resulted in an epitaxial columnar crystal growth at the re-melt substrate boundary, a band of backward growth Al₃Zr₂ dendrites towards the lower half of the coating, and a two-phase eutectic dendritic growth of Al₂Zr + Al₃Zr towards the top of the coating. The evolution of the various phases and microstructures is discussed in conjunction with the Al-Zr phase diagram, the criteria for planar interface instability, and the theory of eutectic growth under rapid solidification conditions (the TMK model).     

Phase constituents and microstructure of laser cladding Al2O3/Ti3Al reinforced ceramic layer on titanium alloy

Laser cladding of the Fe₃Al + TiB₂/Al₂O₃ pre-placed alloy powder on Ti-6Al-4V alloy can form the Ti₃Al/Fe₃Al + TiB₂/Al₂O₃ ceramic layer, which can greatly increase wear resistance of titanium alloy. In this study, the Ti₃Al/Fe₃Al + TiB₂/Al₂O₃ ceramic layer has been researched by means of electron probe, X-ray diffraction, scanning electron microscope and micro-analyzer. In cladding process, Al₂O₃ can react with TiB₂ leading to formation of amount of Ti₃Al and B. This principle can be used to improve the Fe₃Al + TiB₂ laser cladded coating, it was found that with addition of Al₂O₃, the microstructure performance and micro-hardness of the coating was obviously improved due to the action of the Al-Ti-B system and hard phases.     

Zr-based glass-forming film for fatigue-property improvements of 316L stainless steel: Annealing effects

With a 200-nm-thick Zr₅₃Cu₂₉Al₁₂Ni₆ glass-forming film, the four-point-bending fatigue life of a 316L stainless-steel substrate is improved from 4.4 × 10⁵ cycles for the uncoated sample by ~ 10 times to 4.5 × 10⁶ cycles at a stress level of 750 MPa. The fatigue life is further improved by more than 22 times to > 10⁷ cycles when the film is annealed in the supercooled liquid region. The excellent mechanical properties of the thin film, specifically high strength and improved ductility, coupled with the good film adhesion to the substrate as well as the improved surface roughness, are the key factors that improve the fatigue resistance of the coated materials.