Experimental and numerical study of microstructure formation and the origin of crystallographic misorientation in Al-Zn-Si alloy coatings

Al-Zn-Si alloy coatings are widely used for the corrosion protection of steel sheets. In addition to the favorable corrosion properties, the Al-43wt%Zn-1.6wt%Si coatings present several features which are of metallurgical interest. The first one is their surface appearance dominated by the typical spangle morphology exhibiting dull and shiny areas on the coating surface. Further on, the dendrite tips do apparently not grow along the 〈100〉 crystallographic directions that are typical for fcc-metals, but rather along directions in between 〈100〉 and 〈110〉. In addition, continuous variations of the crystallographic orientation, up to 35°, are observed within individual grains of Al-Zn-Si coatings [Sémoroz1 01]. The objective of the present study is to establish a better understanding of the microstructure development which is responsible for the formation of both the characteristic spangle pattern and the important variations of crystallographic orientation within the grains. In order to elucidate these questions, the present study includes three main axes, (i) a detailed microstructure characterization of industrially solidified samples, (ii) modeling work which encompasses microstructure modeling by the phase field method and a geometrical model, as well as the determination of the solid-liquid interfacial energy anisotropy by an inverse method, and (iii) re-solidification experiments aimed at studying the behavior of Al-Zn-Si layers under modified solidification conditions. The results show that the dendrite network spreads quickly in the coating layer at a temperature between 530 to 535°C. During growth, the dendrite tips are separated from the confining boundaries by a thin, solute-rich liquid film. It was found that the preferred dendrite growth directions are in between 〈100〉 and 〈110〉, 28.5° from 〈100〉. Further on, a mathematical expression for the interfacial energy anisotropy of the considered alloy has been determined. The combination of the geometrical model and surface topography measurements allowed concluding that the spangle pattern is due to preferential dendrite growth along one of the two boundaries confining the melt layer. In addition, the new experimental evidence forced to discard the mechanisms previously proposed for the formation of intragranular crystallographic misorientations. The experimental findings acquired during this study indicate that the solidification shrinkage occurring in the area of the grain envelope is the driving force for the formation of the observed intragranular misorientations. The solidification shrinkage leads to the development of tensile stresses in the oxide film covering the coating while it solidifies. These stresses apply on the dendrite network and lead to plastic deformation in the tip area of the growing dendrite arms.

Texture Formation in Hot-Dip Galvanized Coatings

Aurèle Mariaux

Continuous hot-dip galvanization is a process during which steel sheets are coated with a layer of Zn-Al alloy to protect them against corrosion. As the name indicates, this is achieved by dipping the preheated sheet into a bath of molten alloy. The sheet is then withdrawn and cooled down in air. The solidification microstructure of such coatings is made of large zinc grains (spangles), which preferentially have their hexagonal ‹0001› axis perpendicular to the sheet plane (basal texture). The mechanisms leading to this preferred orientation were investigated in this study, with a particular focus on nucleation and dendritic growth. An experiment was designed to reproduce the solidification stage of hot-dip galvanization on a laboratory scale. Industrial coatings were remelted in an infrared image furnace and solidified under controlled cooling conditions. Thanks to the wide range of possible cooling rates, the influence of this parameter on the size and orientation of the zinc grains could be investigated. The thermal plateau induced by the solidification of the thin coating could be detected, even for fairly thick steel sheets. However, the signal was better for larger coating/steel thickness ratio. A minimum coating thickness and Al content are needed if Fe-Zn intermetallic outbursts are to be avoided during remelting. Additionally, skin-pass, as well as any deformation of the coated sheets, must be avoided prior to these laboratory experiments. A coupled cellular automaton — finite volume model was concurrently developed to simulate solidification. It was then used to obtain the nucleation parameters of the spangles by inverse modeling based on the remelting experiments. The model accounts for the effects of zinc crystal symmetry and of the confined coating geometry on nucleation and growth phenomena. In particular, the preferred orientation of the grains is included in the nucleation site distribution. Its basal part is still an estimate, but it could be refined from new experimental measurements with the infrared remelting device. On a more fundamental side, a mathematical formulation of the anisotropic solid-liquid interfacial energy of Zn-Al alloys was derived from the equilibrium shape of liquid droplets in a solid matrix. This property changes by more than 40% between the c axis and the basal plane. This very large variation has important effects on the solidification mechanisms. The interfacial energy, as well as the wetting conditions for an anisotropic grain, were then implemented in a phase field model, which was used to simulate the growth of zinc dendrites in coatings. It revealed that the growth directions and velocities are strongly influenced by the film thickness and by anisotropic wetting effects. The possibility that the preferred zinc orientation could be induced by the textured steel substrate was investigated by comparing the orientation of zinc grains with that of the ferrite grains underneath. It was observed that spangles with a random orientation distribution are independent of the substrate. Unfortunately, the observed specimen did not exhibit a basal coating texture and thus, the existence of a relation between basal grains and ferrite texture could not be investigated. The anisotropy formulation was also used to extend the classical theory of heterogeneous nucleation to anisotropic metals. These computations showed that a basal orientation of the nuclei is strongly favored from an energy point of view. Such developments can explain the occurrence of basal grains around holes that form during infrared remelting, so-called rose structures. Preferential basal nucleation and the wetting influence on dendrite growth are also responsible for the morphology transition observed in Galfan, a Zn-Al coating of eutectic composition: when appropriate cooling conditions are applied, a shiny layer of basal grains forms at the top surface before the onset of eutectic solidification. Finally, these mechanisms could also explain the preferential basal orientation of regular hot-dip galvanized coatings. However, the conditions on a galvanizing line do not meet the criteria that are requested to activate them in Galfan. Additionally, the texture of hot-dip coatings is reported to depend on the surface preparation of the sheet, although the anisotropic nucleation theory does not consider the steel substrate. Further investigations on these contradictions are needed before these mechanisms can be used to explain the preferred orientation in regular galvanized coatings.

EPFL2010

Characterization and modeling of twinned dendrite growth

Mario Alberto Salgado Ordorica

The formation of feathery grains during semi-continuous casting of Al-alloys [1, 2] is an interesting problem from both practical and theoretical points of view. These structures are formed by a lamellar sequence of twinned and untwinned regions separated by straight and wavy-like boundaries. Each pair of lamellae contains twinned dendrites split in their trunk center by a coherent {111} twin plane, while lateral arms meet at an incoherent {111} boundary. In practice, feathery grains are considered as defects which reduce the mechanical properties of a solidified ingot. In theory, an understanding of twinned dendrite growth includes different solidification phenomena, e.g., interfacial energy anisotropy, crystallographic growth directions, twinning, growth competition mechanisms, etc. Although several studies have been performed in order to understand the physics leading to the nucleation and growth of twinned dendrites, various questions remain unanswered. In this work, a comprehensive study of twinned dendrite growth has been undertaken, with the main objectives being: i) to study the effect of different alloying elements and solidification conditions on twin formation in binary Al-alloys; ii) to establish a better understanding on the stability of twinned dendrites and the growth kinetic advantage that they exhibit over regular ones; and iii) to elucidate the stable shape of the twinned dendrite tip. In order to study alloying-element effects, binary Al-X alloys (where X = Zn, Mg, Cu and Ni), were produced under Directional Solidification (DS) conditions in the presence of a slight natural convection in the melt. Analysis of these castings has shown that feathery grains can form for all solute elements of interest, but not for all compositions. The probability of forming feathery grains is relatively high when the alloying elements are hcp (Zn or Mg), but decreases for fcc solute elements (Cu or Ni). A study on the effect of forced convection in the melt, performed using different experimental set-ups, confirms previous observations suggesting that it is the shearing components of the liquid slow which induce twin nucleation [3, 4]. However, the poor reproducibility of these experiments and the variable rate of feathery grains formation indicate that twin nucleation is governed by a highly stochastic behavior. The probability of such an event decreases as the melt slow is less complex and the associated Stacking Fault Energy (SFE) of the alloying element is increased. In terms of growth kinetics advantage, a characterization using various metallography techniques and X-ray synchroton tomography has shown that this is in part due to the complex morphology of twinned dendrites. Indeed, it has been confirmed that these dendrites grow along ‹110› directions with ‹110›, and also sometimes ‹100› secondary arms, the primary trunk spacing of these dendrites being much less anisotropic than previously thought [5, 6]. It has been shown that twinned dendrites grow in a stable manner at a lower undercooling than regular ones. In addition, the distribution and orientation of their side arms favors their growth at the expense of less developed regular dendrites. A mechanism to explain the lateral multiplication of twin planes is also proposed in this work. In terms of stability, observations after partial remelting of twinned DS specimens, then re-solidification in a Bridgman furnace, have shown that even if twin planes remain stable during partial remelting, independent regular non-twinned dendrites issued from the twinned and untwinned parts of the seed grow during solidification. This implies that the formation of twinned dendrites is not only related to the ability to nucleate a stacking fault, but also to the imposed solidification conditions. The favorable growth kinetics of twinned dendrites is also explained by their tip morphology. Three hypotheses have been evaluated in this work: i) the grooved tip [7], stabilized by the Young-Laplace equilibrium condition; ii) the doublon [5], i.e., a double tip dendrite that grows with a narrow liquid channel in its center that solidifies at a composition close to C0; and iii) the pointed (or edgy) tip [8], equilibrated by torque terms of γsl when it is too anisotropic. Observations performed at the twinned dendrite tip have revealed the presence of a small groove, which eliminates definitively the hypothesis of the edgy tip. Further examination of the stable growth morphology of twinned dendrites has been done by using a phase field model that reproduces the presence of a twin plane through an appropriate boundary condition. The results of these simulations show that twinned dendrites are doublons that grow with a narrow liquid channel (0.2 to 3 µm width) whose depth depends strongly on the alloy composition and the solidification conditions. In order to validate these simulations, Focused Ion Beam (FIB)-microtomography and X-ray chemical analysis (EDS) in a Scanning Transmission Electron Microscope (STEM) were performed on small specimens extracted from twinned dendrite trunks. These have shown the existence of a positive solute gradient in a region localized within 2 µm around the twin plane, i.e., as expected for a doublon morphology. Additionally, the presence of small particles aligned within the twin plane is in agreement with the formation of small liquid pockets below the doublon root as predicted by the numerical model, but further work is required to explain this remarkable feature. Finally, composition measurements performed after quenching a partially remelted specimen also seem to confirm the existence of a doublon. This work contributes to the understanding on twinned dendrite growth kinetics in several aspects, principally the effect of alloying elements on twin formation, their growth kinetic advantage, their stability and their stable tip morphology. However, further work must be carried out to overcome the limited knowledge on the mechanisms leading to twinned dendrite nucleation. In the same manner, the growth mechanisms of the doublon morphology should also be further investigated in future works.

EPFL2009

Two-phase modelling of hot tearing in aluminium alloys using a semi-coupled method

Vincent Mathier

Hot tearing is one of the most severe defects observed in castings, e.g. in billets or sheet ingots of aluminum alloys produced by DC casting. It is due to both tensile strains and a lack of interdendritic feeding in the mushy zone. In order to predict this phenomenon at the scale of an entire casting, the two-phase averaged conservation equations for mass and momentum must be solved in the mushy (i.e. mixed solid and liquid) region of the material. In recent contributions, M'Hamdi et al [1] proposed a strongly coupled resolution scheme for this set of equations. The solution of the problem was obtained using a rheological model established by Ludwig et al [2] and that captures the partially cohesive nature of the mushy alloy. In the present contribution, the problem is addressed using a slightly different approach. The same rheological model (i.e. saturated porous media treatment) is used, but the influence of the liquid pressure is neglected at this stage. This assumption allows for a weakly coupled resolution scheme in which the mechanical problem is first solved alone using ABAQUS™ and user subroutines. Then the pressure in the liquid phase is calculated separately accounting for the viscoplastic deformation of the porous solid skeleton and solidification shrinkage. This is done with a code previously developed for porosity calculations, and that uses a refined mesh in the mushy zone [3]. This semi-coupled method was implemented and its numerical convergence studied from the point of view of both time step and mesh size. Guidelines for selecting these numerical parameters as well as the conditions under which the semi-coupled method may be applied are provided. The model was then applied to three cases, i.e. two tensile tests conducted on mushy alloys [4, 5] and the casting of an entire billet [6]. Experimental data was indeed available concerning these problems prior to the present work. This information was used for the validation of the thermal and mechanical models that were setup to describe these different cases. The results of the semi-coupled approach were also used to describe in more details these different castings. First of all, the numerical study of the mushy zone tearing test [5] proved helpful for distinguishing different fracture modes. The role of the high strain rate applied to the mushy alloy in this case was also outlined. Another tensile test, referred to as the rig test [4], was successfully modeled in the present framework. The numerical results could be used to quantify the redistribution of strain in the mushy sample. As a consequence, intrinsic properties of the material, such as its ductility, could be extracted from the results. This study also gave further insight about the conditions under which tearing occurs in the samples. Finally, the semi-coupled method was used to study the DC casting process. In this case, a real process performed under realistic conditions for the production of an industrial scale billet was modeled. As it is more complex and difficult to characterize experimentally, the conditions for hot tearing formation are less accessible. However, the isotherm velocity, the strain, the strain rate and the liquid pressure could be described reasonably accurately. It was thus possible to correlate experimental observations of the hot tear with various calculated indicators of hot tearing susceptibility. Even with this information, it remains difficult to formulate new hot tearing criteria because all the indicators follow a similar trend during the casting and their respective contributions can thus not be distinguished. The present work showed that the level of accuracy and detail that can be reached using two-phase models with appropriate materials properties and boundary conditions is satisfactory. It is indeed possible to model the relevant phenomena (heat flow, solid deformation and liquid feeding) at the scale of an entire casting. The variation of the different simulated fields can be described down to a scale of the order of a few millimeters. In that sense, this approach is one important aspect required to build a multiscale model for the problem of hot tearing. It is expected that coupling such a method with granular models (which cover length scales from a few microns to a few centimeters [7]) will allow for a more complete description of the phenomena at hand. In the future, the development of such a multiscale numerical tool may prove to be the most efficient way towards quantitative predictions of hot tearing formation in real solidification processes.

EPFL2007