Defect and Diffusion Forum Submitted: 2019-03-30

ISSN: 1662-9507, Vol. 397, pp 101-110 Revised: 2019-05-22

doi:10.4028/www.scientific.net/DDF.397.101 Accepted: 2019-05-23
© 2019 Trans Tech Publications Ltd, Switzerland Online: 2019-09-24

Study of Precipitation Hardening in Two Al-Mg-Si Alloys with and

without Copper and Excess Silicon Using Kissinger and Boswell
Methods
Fares SERRADJ1,a*, Hichem FARH2,3,b and Brahim BELFARHI1,c
1
Physics Laboratory of Guelma (LPG), May, 8th 1945 Guelma University, Algeria.
2
Department of Material Sciences, Faculty of Exact Sciences, Larbi Tebessi University 12002,
Tebessa, Algeria
3
Laboratoire des Composants actif et Matériaux, Oum el Bouaghi, Algeria
a
serradj.fares@univ-guelma.dz, bfarhichem@gmail.com,
c
belfarhi.brahim@univ-guelma.dz

Keywords: Al-Mg-Si alloys, DSC, TEM, XRD, precipitation, activation energy, excess Si,
Kissinger-Akahira-Sunose & Boswell isoconversional methods.

Abstract. The precipitation of two Al-Mg-Si (6xxx series) alloys with and without copper (Cu) and
excess silicon (Si) has been investigated by using the Differential Scanning Calorimetry (DSC),
Transmission Electron Microscopic (TEM) and X Ray Diffraction (XRD) analysis.
The analysis of the DSC curves showed that the excess Si accelerates the precipitation. The values
of activation energies for each peak of DSC curves were determined by using Kissinger–Akahira–
Sunose (KAS) and Boswell isoconversional methods. The alloy which has an excess Si and copper
requires larger activation energy for precipitation despite the acceleration of the precipitation by the
excess Si. TEM observation result shows there is smaller size and higher density of precipitate in
excess Si alloy than those of excess-free.

1. Introduction
High formability, good corrosion resistance, considerable specific strength, low density and low
cost are the best qualities and properties of Al-Mg-Si alloys [1]. These alloys have a great
importance because of their use in various industrial sectors, such as the automotive, aeronautical
and electrical industries [1–3].
The mechanical and the structural properties of Al-Mg-Si alloys can be improved by adding other
elements such as copper, iron, and chrome… and/or by using different heat treatment [4]. About
these metal elements, there are many reports about the small addition of copper (Cu) into Al-Mg-Si
alloys to enhance their mechanical properties, especially their ductility [4–8].
After homogenization treatment, these alloys are usually artificially aged to reach their highest
mechanical strength [4, 9]. However, the double aging heat leads to a very high improvement of
mechanical properties [9]. Most of the previous researches on Al-Mg-Si alloys have focused
primarily on two parameters; artificial aging and time [4]. The effect of natural aging, pre-aging on
the paint-bake response and precipitation hardening of Al-Mg-Si alloys was investigated by several
researchers [3, 4, 8, 10–13].
For these alloys, precipitation hardening effect depends on the shape, size and morphology of the
precipitates formed during aging treatment. During artificial aging treatment, the alloys go through
several transformation phases from supersaturated solid solution (SSSS) to stable phase.
The precipitation sequence of the Al-Mg-Si alloys is frequently written [4–15]:
SSSS o atomic clusters of Si and Mg or Mg/Si co–clusters
o Guinier–Preston: G.P (AlMg4Si6) needle zones
o metastble E ’’ (Mg5Si6) needle-shaped phase
o metastble E ’ (Mg18Si10) rod-shaped phase, U1(type A), U2(type B), B ’(type C)

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102 Study and Characterization of Alloys and Materials

o stable E (Mg2Si) platelets phase

Where: U1(type A), U2(type B) and B ’(type C) phases are (MgAl2Si2) needle-shapes, (AlMgSi)
needle shapes and (Al3Mg9Si7) lath-shapes, respectively [16,18].
In Al-Mg-Si alloys, copper is an alloying element increasing volume fraction of precipitates.
Addition of copper alters the precipitation sequence of Al-Mg-Si system as follows [16–20]:
SSSS o atomic clusters o G.P zones o metastble E ’’, type L, type C, QP, QC phases o
metastble E ’+ lath-shaped Q ’ phases o stable Q phase.
The purpose of this research is to investigate the effect of 0.45 % excess silicon (Si) and the
small addition of copper (0.1 % Cu) on the kinetics transformation and the precipitation in two
alloys: Al-Mg-Si free and Al-Mg-excess-Si-Cu .
To acquire a better understanding of precipitation hardening kinetics, during non-isothermal
annealing of two Al-Mg-Si alloys at different constant heating rates, the Kissinger–Akahira–Sunose
(KAS) and Boswell have been used as basic isoconversional methods. These isoconversional
methods are extensively used for analyzing non-isothermal decomposition, crystallization and
degradation kinetics for large variety of materials and compounds [21–24].
The main experimental techniques used in this investigation were Differential Scanning
Calorimetry (DSC), Transmission Electron Microscopy (TEM) and X–Ray Diffraction (XRD).

2. Experimental Procedures
The two alloys were provided by Canadian Aluminum (Alcan) International Limited as extruded
sections 40 mm wide 3 mm thick. The chemical compositions of these alloys are given in Table 1.
The excess Si was calculated according to the following formula [25]:
wt.Mg wt.Fe  wt.Mn
Excess Si = wt.%Si – – (Eq.1)
. 
Tab 1. Chemical compositions of the investigated alloys.
Alloy 01 Alloy 02
Alloying element wt%
Al bal bal
Mg 0.20 0.21
Si 0.20 0.62
Cu 0.001 0.10
Fe 0.18 0.17
Mn 0.032 0.03
Excess Si 0.031 0.45
The sheet samples were solution treated for 15 mn at 803 K and quenched in cold water.
Artificial aging was carried out at a temperature of 458 K to imitate the paint bake temperature used
in automotive applications and 573 K. All specimens were quenched to room temperature at the
completion of aging.
Differential Scanning Calorimetry (DSC) analysis was carried out in a SETARAM DSC 131 at
various heating rates (2, 5, 7 and 10 K/mn). The samples undergo the thermal cycle that starts with
heating the samples from room temperature to 823 K with different heating rates (2, 5, 7 and
10 K/mn) and ends with cooling them to the room temperature.
The microstructural characterizations were made by a Transmission Electron Microscopic (TEM)
Philips EM400 (120kV) equipped with EDX system. Thin slides were prepared from samples
treated by the double jet method. Thinning was carried out at 243 K (liquid nitrogen cooling) at a
voltage of –12 V.
The X ray diffraction (XRD) patterns were collected using a BRUKER D8 ADVANCE
diffractometer using CuKD radiation with X ray generator power set at 1.6 kW (40 kV and 40 mA).