INDUSTRIAL METALLURGY ASSIGNMENT PRESENTATION

ON

HEAT TREATMENT OF MAGNESIUM ALLOYS WITH RESPECT

TO GRAIN REFINEMENTS

19M632 - NISHANTH I
19M633 - NITHEESH KUMAAR M V
19M634 - NITHIS K K
19M635 - PAVAN KUMAR P R
19M636 - PRABAAHAR A
19M637 - PRADEEP P
20M907 - NARESH KRISHNA G
 INTRODUCTION
● Magnesium, has a hexagonal close-packed (HCP) crystal structure,it is an excellent example of a true metallic-bond it
has a homogeneous non-localized free electron cloud, at least when in the pure state ,
● A recent study revealed that has abnormal intrinsic stacking fault energy (SFE). Such directionality in bond structure
indicates localization in free electron density.
● The superior strengthening response of aluminium to alloying, even as a dilute solute solution, may thus be due to an
additional effect to the already existing directionality in the bond structure.

● HCP crystal lattice and major planes of magnesium are shown in FWith lattice parameters a = 3.18 Å and c = 5.19 Å,
slightly less than the ideal c/a ratio of 1.62354 (at 25°C) of Mg crystal, appears important in explaining some
fundamental characteristics of the metal.
● A comparison of c/a ratios as well as critical resolved shear stress (CRSS)for basal planes of different HCP metals is given
in below Table
● Mg, in turn, results in a somewhat larger primitive cell volume compared to other HCP metals, leading to smaller SFE
levels
METAL CRSS(PSI) c/a

Mg 63 1.624

Cd 82 1.886

Zn 26 1.856

Ti 16000 1.588

Be 5700 1.586

● For example, 36 ergs/ cm2 for basal plane of magnesium.

● Let us remember that aluminium is considered to have an unusually high SFE as an example of FCC metal. While copper has a lowly
SFE of 40 ergs/cm2 that creates a faulted region of only about 35 Å, aluminium, with its ~7 Å wide fault, has 200 ergs/cm2 SFE.3
● For the sake of further comparison, it may be pointed out that the SFEs based on the first-principles calculations for Mg and Zr on
the high SFE {11–22} pyramidal plane associated with the two <11–2–3>/6 partials are 173 and 388 ergs/cm2, respectively.4
● These values have very important consequences in terms of dislocation core width, mobility and configurations, and repercussions on
 ASTM Designation for Mg Alloys

F as fabricated
O as annealed
H10,H11 slightly strain hardened
H23,F24,H26 strain harden and partially annealed
T4 solution treated
T5 artificially aged
T6 heat treated and artificially aged
 A - Aluminium
C- Copper
E- Rare earth metals
H- Thorium
K- Zirconium
L- Lithium
M- Manganese
Q- Silver
S- Silicon
W- Yttrium
Z- Zinc

For example AZ63

Constituents : Mg,Al,Zn ( where Al 6%, Zn 3 % rest Mg)
Wrought Mg - alloys
● AZ80A and ZK60A are effectively solution treated after forging - because
of the hot working temperature is close to 400°C - so precipitation
hardening during subsequent aging at room temperature occurs

● AZ80A and ZK60A are used for “high” temperature ~ 150°C -

applications

● ZK60A - T5 contains no Al - so is more expensive - but had greater

strength and ductility than AZ80A
Sand Cast Mg - Alloys
● Mg reacts with SiO2 - causing the skin of the casting to be blackened
(oxidized) to an appreciable depth below the surface

● To obtain a bright surface - “inhibitors” - such as sulphur, boric acid

or KBF4 - are mixed with the molding sand

● The reactive nature of Mg also means that sand cast alloys are
subject to microporosity - caused by evolution of hydrogen - with a
consequent deterioration of its mechanical properties

● Insoluble gases - such as He and Cl - are bubbled through the melt

before casting to remove reactive gases such as H (hydrogen)
Sand cast Mg - Alloys
● It is also evident from the phase diagrams that sand cast alloys will contain brittle
networks of eutectic constituents

● To improve the ductility of these castings they can be solution treated to dissolve
the eutectic constituents - and this treatment also increases the tensile strength

● Aging a solution-treated alloy strongly increases the yield point - and slightly
lowers the ductility - but has relatively little effect on the ultimate strength

● Increasing the amount of Al increases the strength - compared AZ63 with AZ92 -
but lowers the casting quality and increases the amount of microporosity

● The stronger Mg-Zn-Zr alloys are also more difficult to cast

Die Cast Mg- Alloys
● Die cast alloys have excellent dimensional tolerances- and can be formed in
complicated shapes as the liquid is forced into a steel mold under pressure

● Alloy AM60A is used for auto wheels

● Alloy AS14A is used for crankcases for air cooled engines like VWs

● AZ91B is a general purpose alloy- recently used for dashboards in GM

tracks

● Die cast alloys are significantly stronger than sand cast alloys- as they not
susceptible to microporosity
Annealing of Wrought Mg alloys:

Generally all wrought Mg alloys behave the same on annealing.

For example let’s discuss about the case of AZ31 :

● Specimen taken for process is thin sheet of thickness 1.6 mm and temper 1

● Polishing by water-based diamond suspension

● Further polishing with Alumina and finally etched for microstructure observation
under SEM.

● Heated around 300 degree celsius for few minutes and then cooled
This figure shows the microstructure of AZ31 right
after polishing and etching placed under the
scanning electron microscope.

As there are many twin and grain boundaries which

are caused due to result of rolling the material.

At 300 degree Celsius annealing begins within 30 to

60 seconds the grain and twin boundaries started
moving.

Further the process results in mutual crossing of

twin boundaries which often facilitates the
nucleation of new grains
Source : A. Jageer/ Journal on annealing of commercial magnesium alloys
 Grain Refining of Wrought AZ31 by Rolling

● In preparing raw material for rolling 8 inch

dia ingot is rolled to a plate of 100 mm width
and 2 mm thickness by indirect extrusion
method

● Heating upto 400 degree celsius for 5 minutes

and rolling by keeping at 100 degree celsius
further reduces thickness upto 0.5 mm 2 mm extruded

● For high reduction ratios more heating and

rolling phases are done
Resulting Microstructure after Grain Refining of AZ31

Heating and rolling

leads to superplasticity
leads to reduction in
grain size

Source : T.C.Chang/Journal of material processing technology

1.3 mm microstructure

1 mm microstructure

0.5 mm microstructure
Heat treatment of cast AZ61 alloy
● A cubic sample of 50 mm ingot is cast and then heated to 400 degree
celsius for 30 minutes in kept in electric resistance furnace.

● Followed by MDIF by industrial air pneumatic hammer machine (Multi-

directional Isothermal Forging)

● After a while forging direction is changed by 90⁰ after each passes

leading to different microstructures.
Resulting Microstructures
Major takeaways:

● Presence of lenticular
(mechanical) twins in
figure a)
● Intersection of twins
and nucleation in fig b)
● Activation of secondary
twins in fig d)
● Grains starting to be
relatively coarse in fig
e)
● Activation of high
density twins leading to
SEM images of MDIF is shown clearly in even coarser grains in
this diagram fig g) and h)
Precipitation hardening of Mg-Ca-Zn alloy:
As we know Mg-Ca alloy has good strength and creep resistance there is the process of adding
Zn precipitate the experiment following is conducted

Experiment :

● Alloys of nominal composition Mg-1Ca and Mg-Ca 1% - Zn 1% were prepared from high
purity Mg, Ca, and Zn by induction heating in an argon atmosphere and casting into a
mould coated with graphite.

● These castings were then encapsulated in a glass tube under argon atmosphere, solution
treated for 24h at 510°C (Mg-1Ca) and 470°C (Mg-lCa-lZn), and quenched by breaking
the glass tube in water. Sections were subsequently aged in an oil bath of 200°C.

● Then microstructure is analyzed in TEM prior to which specimen is nicely polished and
etched
 ● Addition of ternary element Zn permits the alloy to undergo certain microstructural and
property changes

Resulting Microstructure:
● Comprising a relatively uniform distribution of spherical eutectic colonies throughout the
matrix phase.

● The ternary alloy addition is found very similar to binary alloy ( here Ca)

● 2 types of solid precipitates :

● A thin hexagonal or triangular plate shape ( were commonly distributed in local clusters, and
appeared to be the product of heterogeneous nucleation on dislocations)

● uniformly distributed in the matrix phase

 Microstructure involving thin hexagonal or triangular
plate

Microstructure involving thin plate uniformly distributed

Age Hardening response :

● The Mg-1Ca alloy had an average hardness of approximately 39 HV in the solution treated and
quenched condition.

● With isothermal ageing at 2OO degree C, the average hardness increased gradually with increasing
ageing time to a peak of approximately 50 HV after 8 hour , and then decreased to a value of about 44
HV after 240 hour .

First figure shows hardening by aging about 8 hours

Second figure shows hardening by aging about 240

hours
 Stress Relieving

● Stress Relieving is the treatment of a metal or alloy by heating to a predetermined temperature

below its lower transformation temperature followed by cooling in air.
● The primary purpose is to relieve stresses that have been absorbed by the metal from
processes such as forming, straightening, machining or rolling.
Stress relieving of cast Mg alloy:

● Residual stresses are stresses impacted on material by various reasons even when
absence of external load or thermal gradient

● Castings may have residual stresses as a result of solidification due to mould

restraints, due to non-uniform cooling after heat treatment, or from quenching.
Machining operations may also induce some residual stresses. Weld-repair may
also cause residual stresses.

● Although magnesium castings do not normally contain large residual stresses, but
as these alloys have low modulus of elasticity, even low residual stresses could
cause large elastic strains.
 ● For example stress relieving in ZK 61 cast alloy is done by heating it to 330
degree celsius for 2 hours and then cooled upto 140 degree celsius

● Followed by further heating on 140 degree celsius for 48 hours and then cooled
back to room temperature.

Stress relieving of Mg wrought alloys :

● Stress relieving is used to remove or reduce residual stresses induced in

wrought magnesium products by cold and hot working, shaping and forming,
straightening, and welding.

● For example for relieving of stress in AZ 31 alloy , the specimen is annealed at

a temperature of 260 degree celsius for 15 minutes followed by hard rolling at
150 degree celsius for 60 minutes does the job.
SOLUTION HEAT TREATMENT

The influence of T4 and T6 heat treatments on selected properties of aluminium and

magnesium alloys
 Conventional Heat Treatment

Since the component integrity allows heat treatments to be conducted,

mainly by preventing blistering, the focus during selection of process
parameters should be on the unique features of the thixotropic
microstructure. Exposures at temperatures higher than approximately 300°C
lead to disappearance of semisolid features (Fig. 5). It is of interest that the
alloy properties after heat treatment still depend on the initial microstructure
defined by the semisolid processing temperature.
 Novel Heat Treatment
It is anticipated that the heat treatment designed specifically for alloys generated by semisolid processing
should take advantage of the unique thixotropic microstructure. Therefore, steps which lead to the formation of
homogeneous equiaxed grains, such as solution annealing, should be avoided. Heat treatment of semisolid
structures has the following objectives:

(i) It should break up the network of Mg17Al12 phase to raise ductility

(ii) The temperature should be high enough to allow for phase transformations but with limited grain
growth
(iii) It should avoid precipitation of fresh Mg17Al12 phase to not reduce ductility
(iv) Cost should be reduced.

Such a thermal exposure causes transformation of regions with high Al content, corresponding mainly to the
liquid fraction during semi-solid processing. The new heat treatment, proposed for rheo-diecast structures,
represents a single step process, conducted at temperatures around solvus line for shorter periods of time as
compared to the conventional technique. Microscopically it causes a partial dissolution of non-equilibrium
Mg17Al12 phase, breaking the network it forms around the primary solid phase. The treatment offers an
improved combination of strength and ductility. As compared to the T4 condition, it generates much higher
strength with slightly reduced elongation
 Role of Alloying elements during ageing

Aluminium:
Under equilibrium conditions the maximum solid solubility of aluminium in Mg is rather high at
12.7 wt% (11.5 at%) at 437°C and reduces to about 3 wt% at 90°C. In cast structures, however,
the solid solution is enriched below 437°C to only 3-4 at%. During aging of Mg-Al alloys, two
types of precipitation take place

Zinc:
The additions of zinc to Mg-Al alloys are expressed by reduced solid solubility of Al in Mg which
increases the volume fraction of the precipitated phases, thus increasing the material strength. The
intermetallic compound Mg17Al12 is replaced by Mg17(Al,Zn)12, frequently quoted as
Mg17Al11.5Zn0.5. Small additions of Zn to Mg-Ca alloys enhance age hardening. If the amount of
Zn is excessive, the effect is detrimental since it leads to formation of MgZn 2 phase, known to be
less effective in age hardening. A unique role of Zn is achieved when combined with rare-earth
elements. A modification of Mg-2.1Gd-0.6Y-0.2Zr leads to improvement of mechanical properties
with good combination of strength and elongation, e.g. 430 MPa and 12%, respectively.
Calcium:

Calcium improves oxidation resistance, hardness and creep resistance. Moreover,

small amounts of Ca are effective in improving strength due to precipitation of the
Mg2Ca phase. Additions of Ca to the Mg-Zn system enhance the age hardening
response by refining the precipitates.

Rare-Earth Elements (RE):

The RE elements used commercially with Mg include La, Ce, Nd, Gd and Y.
Although RE exhibit substantial differences, Mg alloys with individual RE possess
similar features. A rapid hardening response has been noted in alloys containing
Gd which is attributed to a greater volume fraction of more effective precipitates.
During sheet manufacturing, RE can weaken the strong basal textures thereby
improving the rolling process. The weakening tendency of basal texture with
increasing content of Ce, Nd and Y is related to their solid solubility in
magnesium.