Laboratory #2

AGE HARDENING

INTRODUCTION

The strength of a material can be significantly improved by the precipitation of a finely

dispersed second phase in the matrix. This is accomplished by a solution treatment of the
material at a high temperature followed by quenching. The second phase is then precipitated
at room or elevated temperatures. For aluminum alloys this procedure is usually referred to
as age hardening and is also known as precipitation hardening.

In the lab the effect of aging time on the strength of an Al alloy (6061) will be
studied. The first digit of the aluminum alloy designation, “6”, means that the Al alloy
contains magnesium and silicon. The relative weight percentages (wt.%) are given by the
third and the fourth digits, where “6” means that there is 0.6 wt.% Si and “1” means that
there is 1.0 wt.% Mg, respectively. The second digit “0” means that no other alloying
elements were used. Together the three elements, Al, Mg and Si, constitute a two-phase Al
alloy since Mg and Si form the single phase or compound Mg2Si (magnesium silicide) that
constitutes 1.6 wt.% of the alloy. Hence, Figure 1 depicts the pseudo-binary phase diagram
for the 6061 Al system: binary means that two phases may simultaneously coexist, and
pseudo means that there are more than two elements that constitute the two phases. An
example of a nonpseudo-binary phase diagram (called a binary phase diagram) would be
brass, which is composed of Cu and Zn. The two phases that could coexist are α + liquid,
where α-brass is a face centered cubic (FCC) solid solution of Cu and Zn.

Solid Solutions and Supersaturated Solid Solutions

The pseudo-binary phase diagram for 6061 Al depicted in Figure 1 also shows a vertical line
traced along the 1.6 wt.% Mg2Si component. Three points are labelled on this line each
corresponding to different temperatures. At close to 600°C, the phase diagram shows that a
single phase exists. This phase is called the α-Al phase which is an FCC structure. Since a
single phase exists in this temperature and compositional region, this means that Al and Mg

23
and Si all coexist with the atoms of each element being at random positions within solid
material. This is called a solid solution.

At room temperature, however, two phases exist: Al and Mg2Si. Increasing the
temperature starting from room temperature, depending upon the composition of the alloying
element(s) (1.6 wt.% Mg2Si, in this case), a certain temperature exists at which point the
Mg2Si phase or precipitate dissolves into the Al, forming the α-phase. Why is this? As the
temperature is increased the thermal energy increases the diffusion of the Mg and Si through
the Al. Eventually, enough thermal energy is provided such that the bonds in the Mg2Si
precipitates completely break down and a random distribution of Al and Mg and Si forms,
which is the equilibrium state at higher temperature. Note that the material is still a solid: no
melting has occurred. Hence, the α-phase is called a solid solution. This is analogous to
dissolving salt in water. Mixing H2O with NaCl provides a medium that makes it
energetically favorable for some of the NaCl bonds to break down. In this case a liquid (not
solid) solution of Na+ and Cl- forms with the H2O being the solvent and NaCl being the
solute.

So, at room temperature the equilibrium state for the 6061 Al system is α + Mg2Si,
while at higher temperature (≈ 550°C for 1.6 wt.% Mg2Si) the equilibrium state is the α-Al
state. If we slowly raise the temperature from room temperature, the thermal energy will
allow for the enhanced diffusion of Mg and Si from Mg2Si into the Al, and eventually the
solid solution α-phase will be reached. Similarly, if from high temperature we slowly cool
the α-phase, the the solid solution α-phase is less stable at lower temperatures, so the Mg and
the Si diffuse through the matrix and start to precipitate the Mg2Si phase. In other words, the
Mg and Si which was randomly distributed in the Al matrix at high temperature, diffuse
together to form the magnesium silicide compound at lower temperature. When the room
temperature equilibrium is achieved, most of the Mg and Si is in the form of Mg2Si, with
very little remaining in the α-Al state.

But what if the α-Al state is quenched from high temperature? (Quenching is when a
specimen is removed from a furnace and immersed in H2O, for example. Thus causing the
temperature to rapidly drop to the boiling temperature (100°C) or lower.) Diffusion is, in
part, a time and temperature dependent process: the longer the time and the higher the
temperature the more diffusion (or mass transport) of an atomic species that may take place.
The key to the discussion in the previous paragraph was that the temperature was slowly
raised or slowly lowered. Therefore, enough time is allowed for diffusion to take place at a

24
given temperature in order to maintain equilibrium of the relative amount of the phases that
are present at a given temperature.

Obviously, quenching does not allow for adequate diffusion to take place. In essence,
the microstructure at high temperature is effectively “frozen” in place by the quenching. In
this case the microstructure at high temperature is the solid solution of Al + Mg + Si (the α-
phase in Figure 1 existing above 550°C for the 1.6 wt.% composition). Therefore, the post-
quenched room temperature microstructure is the same, even though it should be the α +
Mg2Si phase. This is now called a supersaturated solid solution. To explain why it is
supersaturated, the NaCl analogy from above will be used. In dissolving NaCl in H2O, a
certain point is reached where no more NaCl can dissolve into the solution. The undissolved
NaCl crystals are visible at the bottom of the container. This is known as a saturated
solution. If now the salt water mixture is boiled, the thermal energy that has been supplied
will allow for more NaCl to dissolve. Eventually, a new (high temperature) saturation point
will be reached. If the saturated salt water solution is cooled rapidly, the salt that could not
be dissolved prior to heating will remain in solution. This is because not enough time was
allowed for some of the Na+ and the Cl- to recombine into NaCl via diffusional processes,
even though it is energetically unfavorable for much of this dissolved state to exist at room
temperature. The salt water solution is now call a supersaturated solution. (Recall that for
the Al-alloy, even at high temperature we always have a solid.) If this high temperature,
saturated salt water solution was slowly cooled instead of rapidly cooled, therefore allowing
enough time for equilibrium to be achieved, recrystallizing NaCl would become visible and
its amount would increase as the temperature decreased. Eventually, the only NaCl
remaining in solution would be that allowed for a saturated solution at room temperature.

Age Hardening

The supersaturated solid solution is not in equilibrium. By allowing for diffusion to occur,
the Mg and the Si will eventually form magnesium silicide precipitates. There are two ways
to aid in the diffusion of the Mg and Si (which is paramount to forming the Mg2Si
precipitates): by heating the alloy and/or by allowing enough time to elapse. This process is
called aging or age hardening or precipitation hardening. It may be done naturally (that is, at
room temperature) by providing enough time for the Mg and Si to diffuse. But, since
diffusion is hampered the lower the temperature, it may take years for enough diffusion to
form the Mg2Si precipitates and adequately enhance the physical properties of the alloy.

25
 Because of this, the supersaturated solid solution may be taken to some intermediate
temperature which is still in the α + Mg2Si part of the phase diagram, in order to speed up the
diffusion of the atomic species necessary to form the precipitate (in this case, Mg and Si to
precipitate Mg2Si). This is called artificial aging and is the most common method of aging.
Figure 1 shows a possible cooling path for the 6061 Al-alloy. The “X” at 550°C is the solid
solution α-phase. Quenching to the “X” at 20°C forms the supersaturated solid solution. In
this figure, the intermediate aging temperature is about 250°C: by holding several specimens
for different times at this aging temperature, we can determine the effect of aging time on the
mechanical properties of the material.

The electrical conductivity is one of the most sensitive properties of aluminum, being
particularly responsive to changes in composition and thermal condition. Conductivity is
readily measured with high precision. All known metallic additions to aluminum reduce its
electrical conductivity . Metals in solid solution depress the conductivity to a greater extent
than when out of solution. That is, as the amount of a metal in a solid solution with
aluminum increases, the resulting rapid decrease in conductivity is in marked contrast to the
much slower decrease in conductivity as the metal concentration exceeds its solid-solubility
limit.

The average decrease in conductivity per wt% metallic addition when in solid
solution and when out of solid solution can be quantified. The combined effect of two or
more additions on the resistivity (reciprocal of conductivity) depends on the relationship
between the elements.

Quenching an alloy after a solution heat treatment generally results in the lowest
electrical conductivity since a large part of the constituents present are retained in the
solution. By removing constituents from the solid solution by aging (particularly at elevated
temperatures) and, to a greater degree, annealing increases the electrical conductivity. (In
systems the age at room temperature there may be an initial decrease in conductivity,
attributed to Guinier-Preston zone formation.)

In this lab, conductivity is measured with an eddy-current inspection instrument

which is a non-destructive testing application of electromagnetic induction. Conductivity
values are based on the IACS (International Annealed Copper Standard). In this system, the
conductivity of annealed, unalloyed copper is arbitrarily set at 100 %, and conductivities of

26
other materials are expressed as a percentage of this standard. Unalloyed aluminum has a
conductivity of 61% IACS.

The conductivity tester used in this lab is equipped with four built-in conductivity
standards on the front panel. Using these, the conductivity tester should be calibrated before
the first measurement. The conductivity tester features two ranges (8-110 % and 25-65 %).
The expanded range is conveniently used for measuring aluminum alloys. Measurements is
made by placing the probe on the sample and reading the conductivity directly on the meter in
% IACS. To obtain an accurate reading look perpendicularly onto the needle so that the
shadow of the needle on the mirror vanishes. Accuracy is within 1 % IACS. In this lab the
properties to be examined are hardness and electrical conductivity. In this lab the mechanical
property that will be examined is the hardness. The hardness is a measure of the resistance of
a material to plastic deformation, is a simple and quick measurement, and is semi-
quantitatively related to the yield stress, an important material property. The conductivity is a
measure of the state of the aging sequence. Note that in general, the conductivity uniformly
increases with continued aging, while the hardness passes through a maximum, which defines
the overaged condition.

EXPERIMENTAL PROCEDURES

(1) Prior to your arrival at the lab, two furnaces have been set by the TA. Nine Al
specimens have been inserted into a furnace set at 550°C approximately 2 hr before the lab
for a solution treatment.

(2) At the beginning of the lab (after a 2 hr solution treatment) remove eight of the
specimens from the furnace using tongs and heat resisting gloves and quench them in water.
Allow the ninth specimen to air cool.

(3) Take one of the specimens out of the water, dry it off and measure its hardness and
conductivity. Use the Rockwell F scale to measure hardness and take an average of three
measurements. Use the Zetec conductivity tester to measure the conducitvity, use emery
paper to get a smooth surface to measure the conductivity on. Calibrate the conductivity
tester by using the standards on the front panel.

(4) Insert 7 of the specimens into the other furnace. It will be set at a temperature between
210 and 280°C.

27
(5) Remove a specimen from the furnace at 1, 2, 4, 8, 16, 32 and 64 min. Quench these in
water and measure their hardness and conductivity.

(6) While you are waiting for the specimen at 64 min., quench the air cooled specimen.
Dry it off and measure its hardness and conductivity.

ANALYSIS

(1) Plot the hardness versus the logarithm of the aging time. The y-axis is the hardness and
he x-axis should explicitly show the time in minutes.

(2) Additional data at other temperatures is given in Table I. Plot this data on another
graph

(3) What is the hardness of the air cooled sample?

(4) Plot the measured conductivity in a graph showing % IACS vs. aging time.

QUESTIONS

(1) Indicate the times for underaging, peak hardening and overaging for all the data.

(2) Why does overaging occur?

(3) What happens to the Mg2Si during the solution treatment?

(4) (a) Describe the differences between the age hardening behavior at the various
temperatures.
(b) Why do these differences occur?

(5) (a) How does the hardness of the air cooled specimen compare to that of the other
specimens?
(b) Why does this occur?
(c) Why do we quench the specimen before age hardening it?

(6) What would you expect to happen to the hardness if the specimens were aged for 24 hr
at the same temperature that you used? Why?

28
(7) If after quenching we allowed the specimen to sit in the lab at room temperature, what
would you expect to happen to the hardness with time? Why?

(8) Why does the Mg2Si strengthen the Al?

(9) Show the heat treatment steps that you used in the lab on the pseudo-binary phase
diagram in Figure 1. A mimeographed copy of this figure may be included in your report.

(10) Explain the observed trend in the conductivity vs. aging time graph.

29
 Table I

25°C
Time (min) 1 3 8 55 1020
Hardness (RF) 20 30 40 60 80

160°C
Time (min) 1 3 8 16 30 67
Hardness (RF) 20 40 60 80 90 70

230°C
Time (min) 1 2 3 7 33
Hardness (RF) 20 40 60 80 65

260°C
Time (min) 1 1.5 3.33 7 20
Hardness (RF) 20 50 75 60 40

300°C
Time (min) 1 7
Hardness (RF) 20 10

30
 600 α + Liquid
X 595°C
1.85%

Temperature (°C)
α

400

X
α + Mg2Si
200

X
0
Al 1 1.6 2 3
wt.% Mg 2Si

Figure 1. Pseudo-binary phase diagram for Al-Mg 2Si.

REFERENCES

Askeland, D.R. The Science and Engineering of Materials, Alt. Eds., PWS Engineering,
1984, pp.275-85, 313-9.

Guy, A.G. Physical Metallurgy for Engineers, Addison-Wesley, 1962, pp.124-6, 273-82.

Van Vlack, L.H. Elements of Materials Science and Engineering, 5th Ed., 1985, pp.435-9,
450-3.

Wulff, J., et al. Structure and Properties of Materials, Vol. 1, pp.183-4; Vol. 2, pp.121-3;
Vol. 3, pp.88-9, 173-9.

Van Vlack, L.H. & Osborn, C.J. Study Aids for Introductory Materials Courses, pp.145-7.

31