The Nature of Solute Clusters and GP-Zones in the Al-Mg-Si System

"This work investigates the early stages of precipitation in Al-Mg-Si alloys using a combination of high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), selected area electron diffraction (SAED) and density functional theory (DFT) calculations. Quenching from a high temperature (solution) treatment leaves an alloy in a high-energy unstable state, with solute and vacancies in supersaturation. Thus, already at room temperature (RT) a large driving force exists for solute atoms to cluster and order on the Al matrix positions. DFT calculations indicate that strain alleviation is important at this stage. We observe larger regions of Mg-dominated L10 ordering together with a Si-dominated ordering of smaller clusters in a particular geometry connected to the Si-network found in all the precipitates. In addition, building blocks of the main hardening phase ?'', stabilized by vacancies, are observed at higher, typical pre-aging temperatures.INTRODUCTION Al-Mg-Si (6xxx) alloys are widely used in industry due to a combination of favorable properties such as strength, ductility, corrosion resistance and lightweight. They undergo a complex production route, usually consisting of the following thermo-mechanical steps: casting, homogenization, extrusion or rolling, solution heat treatment (SHT) and artificial aging (AA). The SHT takes place at temperatures above the solvus line in the phase diagram, usually between 500°C and 570°C, followed by a rapid cooling to RT. This ensures that high amounts of solute atoms, uniformly distributed on the cubic face-centered (FCC) Al lattice, together with a large amount of vacancies, are quenched-in. The material is therefore in a super-saturated and unstable state. During the subsequent AA, at temperatures usually between 150°C and 220°C, the solute atoms diffuse and cluster, forming metastable precipitates with needle/ lath/ rod morphologies having the main growth direction along <100>Al. With a maximum alloy solute level (Mg + Si) of only 2%, these precipitates increase material strength up to three times that of pure Al, and are essential for the final material properties. To understand and make better use of this phenomenon, it is imperative to research the nature of the precipitates (such as their atomic structure), measure their key parameters (number density, size, volume fraction) and connect it to material properties (Marioara, Andersen, Zandbergen & Holmestad, 2005; Marioara et al., 2014). The following precipitation sequence is given for the Al-Mg-Si system:"