Mg-Alloys

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 General properties of Mg-Alloys
Mg density is 1.74 g/cm3 –compared to 2.7 g/cm3 for Al and
7.8 g/cm3 for steel- on a mass basis, Mg has the greatest
stiffness/weight- and steel the least.
Mg is relatively difficult to weld – as it must be protected
from the atmosphere by an inert gas – using tungsten arc or
consumable Mg.

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 CRSS values for different slip and
twinning modes and their variation
with temperature.

(A) Basal slip, (B) prismatic slip,

(C) pyramidal slip, and (D) twinning in Mg.

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Factors affecting slip and twinning in magnesium alloys:
• Temperature,
• Grain size,
• Grain orientation (texture),
• Solute atoms, and
• Second-phase particles.

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Effect of alloying elements

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Effect of alloying elements

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Effect of alloying elements

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Directions in the development of magnesium alloys

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• Introduction of several rare earth (RE) elements, notably cerium,
neodymium, and yttrium into a number of commercial magnesium
alloys.
• Most RE elements have high solid solubilities in magnesium
because their atomic sizes are favorable, and they have electron
negativities (e.g., Ce 1.21, Nd 1.19, and Y 1.20) similar to
magnesium (1.20).
• These elements increase the strength of magnesium and its alloys,
particularly at elevated temperatures.

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• β phase Mg17Al12 appears in alloys containing more than 2%
aluminium.
• A network of β forms around grain boundaries as the aluminium
content is increased and the ductility decreases rapidly.
• In slowly cooled castings, discontinuous precipitation of the β phase
may occur at grain boundaries with the formation of a cellular or
pearlitic structure.
• Discontinuous precipitation of lamellae of the β phase is considered
to be undesirable in Mg-Al alloys subject to creep conditions.
• Adding trace of gold (~0.1 at.%) which segregates in grain
boundaries and suppresses the growth of discontinuous precipitates.
• change in microstructure, creep resistance is improved. 19
Figure. Cast structures in alloy AZ80: (A) chill cast alloy
with the β phase (Mg17Al12) present in the grain
boundaries. and (B) discontinuous precipitation in more
slowly cooled alloys 20
Cast Mg-Al and Mg-Al–Zn alloys –
• susceptibility to microporosity
• good casting qualities and resistance to corrosion is satisfactory.
• suitable for use at temperatures up to 110–120°C above which
creep rates become unacceptable-- undergo creep mainly by
grain boundary sliding and the phase Mg17Al12, which has a
melting point of approximately 460°C.
Creep properties improved by
• Reducing the Al content- difficult to cast- reduce fluidity
• Introducing Si- (Mg2Si, adding Ca suppress coarse, Chinese script)
• High solidification rate
• Rare Earth(RE) and alkaline earth elements- stable intermetallic
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• Addition of zinc to Mg-Al alloys causes some strengthening.
• Amount of zinc is limited because of an increase in susceptibility to
hot cracking during solidification.
• Examples are AZ63 (Mg–6Al–3Zn–0.3Mn) and AZ91 (Mg–9Al–0.7Zn–
0.2Mn).
• AZ91 is the most widely used of all magnesium alloys.
• Mg–8Zn–4Al alloy contains a high volume fraction of primary
intermetallic compounds, most of which are a quasi-crystalline
phase with the approximate composition Mg9Zn4Al3.

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 Mg-Al–RE alloys
• Mg–Al–RE alloys are only suitable for die casting because fast cooling is needed
to form a relatively fine dispersion of the compound Al11RE3, rather than coarser
particles of Al2RE
• AE42 (Mg–4Al–2RE–0.3Mn), has a good combination of mechanical properties
including creep strength that is superior to the Mg–Al–Si alloys.
• Improvement in the creep resistance of AE42 was achieved by adding more RE
elements, which led to the development of alloy AE44 (Mg–4Al–4RE).
• The better creep resistance exhibited by AE44 is attributed to an increased
volume fraction of intermetallic phases and reduced level of aluminum in α-Mg
matrix.
• Both Al11RE3 and Al2RE phases have good thermal stability, with no significant
decomposition or coarsening occurring at temperatures up to 200°C.
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• Alkaline earth additions of calcium and strontium to Mg–Al alloys is another
way to improve creep resistance.
• calcium and strontium have low solubilities in magnesium and form stable
particles of Al2Ca or Al4Sr, mainly at grain boundaries.

• When RE elements are also present,

the Al11RE3 phase forms within the
grains that reduces dislocation slip.
Ex. AX81 (Mg–8Al–1Ca),
AXE522 (Mg–5Al–2Ca–2RE), and
AJ62 (Mg–6Al–2.3Sr).

Figure General effects of (A) aluminium and (B)

alkaline and RE elements on the properties
and cost of die cast magnesium alloys. 24
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Magnesium–zinc based alloys
• Zinc causes more solid solution
strengthening than an equal atomic
percent of aluminum but its solubility is
much less.
• Mg–Zn alloys also respond to age
hardening.
• GP zones solvus for the alloy Mg–5.5Zn Figure 6.7 Solid solution strengthening
of binary Mg–Al and Mg–Zn alloys.
lies between 70°C and 80°C.
• Pre-ageing below this solvus before ageing at a higher temperature (e.g., 150°C)
refines the size and dispersion of rods of the coherent phase MgZn2 that may
form from the GP zones.
• Maximum hardening is associated with the presence of this coherent phase.

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Probable precipitation processes in magnesium alloys

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• Addition of calcium and strontium, accelerate the rate of ageing but delay
over-ageing, refine the sizes, and increases the densities of precipitation.
• Addition of copper to binary Mg–Zn alloys causes a marked improvement in
ductility and induces a relatively large response to age hardening.

• Advantage- properties are more

reproducible. Elevated temperature
stability is also improved.
• ZC63 or ZCM630 (Mg–6Zn–3Cu–
0.5Mn).
• Addition of copper or cobalt to Mg–Zn
alloys raises the eutectic temperature. Figure. Schematic representations of the
precipitate sizes, morphologies, and habit
• It permits higher solution treatment planes with respect to the α-Mg matrix for
(A) Mg–4Zn and (B) Mg–4Zn–0.35Ca aged for
temperatures, thereby ensuring 2.7 h at 177°C.
maximum solution of zinc and copper.
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• The structure of the eutectic is also changed from the Mg–Zn compound
distributed around grain boundaries and between dendrite arms, to truly
lamellar in the ternary copper-containing alloys
• Heat treatment cycle involves solution treatment for 8 h at 440°C, hot
water quench, followed by ageing for 16–24 h at 180–200°C.
• Two main precipitates, β′1 (rods) and β′2 (plates), which appear to be
similar in structure to the phases observed in binary Mg–Zn alloys.
• Density of precipitates
is much greater and
more uniform when
copper or cobalt is
present.

Figure Comparison of precipitate densities in (A) Mg–8Zn

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and
(B) Mg–8Zn–0.6Co alloys peak-aged at 150°C.
Mg–RE–Zn alloys
• Developed for elevated temperature applications.
• MEZ (Mg–2.5RE–0.5Zn–0.35Mn) was developed by Magnesium Elektron for
high-pressure die castings.
• This alloy has better creep resistance than AE42 at temperatures above 150°C,
but has low tensile yield strength and ductility at room temperature.
• EZ41 (Mg–1.63La–0.97Ce–0.96Nd–0.11Y–0.5Zn) and also known as AM–
HP2, exhibits excellent creep resistance at temperatures 150–200°C.

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MlA (Mg–1.5Mn),
ME20 (Mg–2Mn–0.5Ce), and
ME21(Mg–2Mn–0.7Ce).

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• Raising the manganese content increases strength as well as
improving corrosion resistance and weldability.
• Addition of RE elements also improves the formability by
weakening the basal texture.
• These alloys have so far found only limited applications.

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 ZIRCONIUM-CONTAINING CASTING ALLOYS

• The maximum solubility of zirconium in molten magnesium is 0.6%.

• Binary Mg–Zr alloys are not sufficiently strong for commercial
application.
• The addition of other alloying elements has been necessary.
The selection of these elements has been governed by three main
factors:
1. Compatibility with zirconium
2. Foundry characteristics
3. Properties desired of the alloy

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Mg–Zr phase diagram

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Mg–RE–Zr alloys
Further improvements in the creep resistance of magnesium alloys
• high solid solubility of yttrium.(12.5 wt%).
• Yttrium is particularly effective in solid solution strengthening.
• Mg–Y alloys also respond to age hardening at relatively high
ageing temperatures.
• The precipitates formed in binary Mg–Y alloys appear to be β′ that
have a body-centered orthorhombic structure and an Mg7(NdY)
composition
• Addition of neodymium to Mg–Y alloys significantly enhances the
age hardening response.
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• Mg–Y–Nd–Zr alloys have been developed which combine high
strength at ambient temperatures with good creep resistance at
temperatures up to 300°C.
• Precipitation in Mg–Y–Nd alloys is again complex. Extremely fine
GP zones are formed on ageing below 200°C.
Precipitation of three other metastable phases-
• Precipitation of fine plates of a phase on the {1120} planes, and
globular particles of the body-centered orthorhombic phase β′
that has an Mg7(NdY) composition.
• With continued aging, the first precipitate is replaced by relatively
coarse plates of a face-centered cubic (fcc) phase β1 that forms on
the prismatic {1100} planes at the β′ particles. 53
• This phase, is the major hardening precipitate in Mg–Y–Nd alloys aged to peak
strength at 250°C.
• It has the composition Mg3(Nd,Y) and is similar to other Mg3X phases (X = Nd,
La, Ce, Pr, and Sm).
• Energetically difficult for β1 to nucleate, and it has been found that cold work
prior to ageing (T8 temper) promotes the formation of β1 at the expense of β′.
• Continued ageing at 250°C leads to gradual precipitation of the equilibrium β
phase (Mg14Nd2Y) on the {1100} planes.
• Maximum strengthening combined with an adequate level of ductility was
found to occur in an alloy containing approximately 6% yttrium and 2%
neodymium.
• WE54 (Mg–5.25Y–3.5RE(1.5–2Nd)–0.45Zr).
• In the T6 condition tensile properties at room temperature are 0.2% PS 200
MPa, TS 275 MPa, elongation 4%. 54
• WE43 (Mg–4Y–2.25Nd–1Heavy RE–0.4 min Zr) was developed.
• Because of its high strength at elevated temperatures, WE43 is being used for
some cast components in racing car engines and for aeronautical
applications such as helicopter transmission casings.
• Mg–Gd–Y–Zr alloy
• Mg–Nd–Gd–Zn–Zr alloy
Magnesium–RE–zinc–zirconium (Mg-RE-Zn-Zr) alloys
• Good casting characteristics because the presence of the RE elements
promotes the formation of relatively low melting point eutectics that improve
fluidity and tend to prevent microporosity.
• Good creep resistance is attributed both to the strengthening effect of
precipitate form within the grain during ageing and the grain boundary
phases.
• Adding zirconium to refine grain size and further increase in strength of Mg-
RE alloy. ZE41 (Mg–4.2Zn–1.3Ce–0.6Zr) 55
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 Mg–Li based alloys
• Development of lightweight metals with high specific strength and
improved plasticity remains of high priority to the automotive,
aerospace, and defense industries.
• Reducing mass is requisite to increasing fuel efficiency and
reducing emissions.
• Magnesium–lithium (Mg–Li) base alloys present tremendous
potential for ultralight structural metals.
• Low density of Li (ρ = 0.53 g/cm3) can reduce the density of Mg
alloys from 1.77–1.83 g/cm3 to 1.3–1.65 g/cm3.

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• Mg–Li phase diagram shows this element to have extensive solid
solubility in magnesium.
• only about 11% lithium is needed to form a new β phase, which
has a body-centered cubic (bcc) structure, thereby offering the
prospect of extensive cold formability.

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Mg–Li phase diagram
• Mg-Li alloys have three different crystal structure configurations
depending on the Li concentration.
• First structure is based on the α-Mg hexagonally close packed
(HCP) unit cell which is stable to approximately 5.7 wt.% Li.
• α-Mg alloys possess the highest strength and greatest work
hardenability.
• Second, a duplex α + β phase field exists between 5.7 wt% Li to
~10.3 wt.% Li. α + β alloys possess moderate strengths, increased
ductility, and good work hardenability.
• Finally, the β-body centered cubic (BCC) solid solution is stable
beyond 10.3 wt.% or a Mg/Li ratio of less than 8.7 by mass.
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• β-Li alloys possess the lowest strength, greatest ductility, and least
work hardenability.
• β-BCC structure is of high interest as it has a greater number of slip
planes available in comparison to the α-HCP structure, which
enables improved formability and decreases in texture anisotropy.
• These properties make Li-rich α + β and β alloys attractive materials
for development in highly formable, lightweight applications.

• LA141A-T7 (Mg-14Li-1.5Al) featuring a stabilized Al-Li phase- found

use in military and aerospace applications.
• higher strength alloys such as LA136 (Mg-13Li-6Al) suffered from
cast ingot segregation and poor weldability.
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Development of Mg–Li alloys declined as
• Microstructural instability could not be controlled at temperatures
below 100 °C leading to rapid over-aging of alloys.
• Inherent safety challenges of handling Li.
• cast ingot segregation and poor weldability.
• Traces of sodium caused grain boundary embrittlement.
➢ Greater stability has since been achieved by adding other
elements and one composition LA141 (Mg–14Li–1Al), which is
weldable, has been used for armor plates and for aerospace
components.
➢ Elevated temperature stability can also be improved by the
addition of 0.5% Si. 61
• MA18 (Mg–10.8Li–2.25Zn–0.75Al–0.25Ce) has a bcc lattice, whereas
• MA21 (Mg–8.75Li–4.8Al–4.5Cd–1.5Zn–0.08Ce) has a mixed hcp/bcc
structure. These alloys are also weldable.

Fig: The Property Space of Mg-Li based Alloys.

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CORROSION BEHAVIOUR OF Mg ALLOYS
• Corrosion of Mg alloys depends greatly on their composition and
microstructure (grain size, the size, shape and distribution of
second phases), post-processing and media.
• Corrosion modes of Mg alloys can be divided into uniform or
general corrosion and localized corrosion based on the
phenomenon from electrochemical, composition, and
microstructural perspectives on macroscale.
• The localized corrosion includes galvanic corrosion, pitting
corrosion, filiform corrosion, intergranular corrosion (IGC),
exfoliation corrosion (EFC), crevice corrosion, stress corrosion
cracking (SCC), corrosion fatigue (CF) and erosion corrosion. 63
 Pitting morphology of extruded
Figure : Galvanic corrosion resulting AM60 in 3.5%NaC1 aqueous solution
from inter-metallic elements

Intergranular corrosion morphology of

AZ80-T5 in 3.5%NaCI aqueous solution 64
• Pitting and filiform corrosion generally occur due to micro-
galvanic corrosion between the intermetallic compounds and
their neighboring α-Mg matrix.
• Corrosion rate of magnesium lies between aluminium and mild
steel.
• Magnesium has electrode potential of –2.30 V at 25°C, w.r.t. the
hydrogen taken as zero.
• Solution potential is lower, e.g., –1.7 V in dilute chloride solution
due to polarization of the surface with a film of Mg(OH)2.
• High susceptibility to impurities and lack of passive film stability
in solutions below pH 10.5.
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• Magnesium is readily attacked by all mineral acids except chromic
and hydrofluoric acids, due to formation of a protective film of
MgF2 which prevents attack.
• Mg alloys suffered rapid attack in moist conditions due mainly to
the presence of impurities, notably iron, nickel, and copper.
• These elements, or compounds they form, act as minute cathodes
in the presence of a corroding medium, creating micro-galvanic
cells with the relatively anodic magnesium matrix.
• The detrimental effect of iron in zirconium-free alloys is reduced by
adding manganese (as MnCl2) to the melt.

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• AZ91C has largely been superseded by higher-purity versions
known as AZ91D for pressure die casting and AZ91E for gravity die
casting which have stricter limits for the nickel, iron, and copper
contents.
• Some magnesium alloys may be susceptible to SCC which is
especially severe in chromate–chloride solutions.
• Zirconium-containing alloys are less susceptible and SCC only
occurs at stresses approaching the yield stress of the alloy
concerned.
• Wrought products are more likely to undergo SCC than castings

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 COMMON PRACTICE TO PROTECT THE Mg ALLOYS
• Fluoride anodizing—this involves alternating current anodizing at up
to 120 V in a bath of 25% ammonium bifluoride which removes
surface impurities and produces a thin, pearly white film of MgF2.
• Chemical treatments involving pickling and conversion of the oxide
coating— components are dipped in chromate solutions which
clean and passivate the surface to some extent through formation
of a film of Mg(OH)2 and a chromium compound.
• Electrolytic anodizing, including proprietary treatments that deposit
a hard ceramic-like coating that offers some abrasion resistance in
addition to corrosion protection.
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• Sealing with epoxy resins— component is heated to 200–220°C to
remove moisture, cooled to approximately 60°C, and dipped in the
resin solution. Draining and air-drying to evaporate solvents, the
component is baked at 200–220°C to polymerize the resin.
• Standard paint finishes—apply a chromate-inhibited primer
followed by good quality top coat.
• Electroplating—several stages of surface cleaning and the
application of pretreatments, such as a zinc conversion coating, are
required before depositing chromium, nickel, or some other metal.

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Cathodic protection
• Mg and its alloys can be used to protect many other structural
materials from corrosion when connected to them in a closed
electrical circuit due to their active electrode potential.
• Magnesium acts as an anode and is consumed sacrificially,
thereby offering protection to metals such as steel.
• Magnesium alloys AZ63 and M1A (Mg–1.5Mn) offer higher relative
voltages and are used for this purpose.
• Examples of cathodic protection used are ships’ hulls, pipelines,
and steel piles.

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Sheet alloys
• Magnesium alloy sheets are produced by stages including casting,
homogenization, machining, and repeated hot rolling.
• Depending on alloy composition, they are homogenized for up to
24 h in the temperature range 300–500°C.
• Purpose of the homogenization treatment is to dissolve
intermetallic particles resulting from the casting process and to
achieve a uniform distribution of alloying elements.
• Rollability and formability of magnesium alloy sheet is
significantly influenced by hot rolling parameters, such as
temperature, thickness reduction per pass, rolling speed, and
alloy composition. 73
• At higher temperatures, additional deformation modes, combined
with an accelerated dynamic recrystallization process and grain
growth, give rise to better rollability of magnesium sheet.
• Larger thickness reduction per pass leads to a higher degree of
plastic deformation, resulting in finer sizes of recrystallized grains
and more homogeneous microstructure.
• Improved rollability at high rolling speeds is attributed to the
activation of more deformation modes at higher strain rates
together with the occurrence of dynamic recrystallization.
Ex. AZ 31, ZK31 (Mg–3Zn–0.7Zr) , ZM21 (Mg–2Zn–1Mn),
ZE10 (Mg 1.2Zn–0.2RE), and
ZEK100 (Mg–1.4Zn–0.1RE–0.1Zr)
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