CHAPTER 2

LITERATURE REVIEW
2.1 ZA Alloys
ZA alloys were initially developed for gravity casting. Their mechanical
properties compete directly with bronze; cast iron and aluminium using
sand, permanent mold and plaster mold-casting methods. Distinguishing
features of the ZA alloys are their high aluminium content and excellent
bearing properties.
During the 1980’s, ZA alloys evolved as valuable die casting materials.
It is important to note that when considering ZA alloy for die -casting.
Only ZA-8 can be hot chamber die cast. Hot chamber casting (which the
ZAMAK alloys employ) is highly automated and the most efficient die
casting process. ZA-12 and ZA-27 require special melting procedures
and must be die cast like aluminium using the less efficient cold
chamber die casting process. A brief description of each alloy is
provided. The ZAMAK alloy family is identified by its numbers 3, 5, 7
& 2. ZA alloys consist of ZA-8, ZA-12 and ZA-27.
2.2 Zinc Metal
Zinc is a bluish white metal and does not occur freely in nature. Its
principal ores are Zincite (ZnO), Franklinite (ZnO, Fe203), Calamine
(ZnCO3) and Zinc Blende.
Zinc has a melting point of 419.5oC. It has a hexagonal close -packed
crystal structure and a density of 7.14 g/cc and a specific gravity of 6.86.
Because of low melting temperature and low solidification temperature
range, it permits a faster rate of die casting and can be used in the form
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of an alloy die castings, and the excellent corrosion resistance of zinc
has led to its use for galvanizing of steel.
It is one of the less expensive non-ferrous metals produced from
sulphide, silicate or carbonate ores by a process which involves
concentration and roasting followed by either reduction of the zinc ore
by carbon and simultaneously distilling zinc in batch or continuous
retorts or by leaching out the oxides with sulphuric acid and
electrolysing the solution after purification. Zinc that is distilled contains
impurities (mainly Pb, Cd and Fe) that may be removed by fractional
redistillation to produce 99.99% pure zinc. It can also be produced by
heating zincite or zinc oxide in an electric furnace, which results in the
liberation of zinc in the form of vapour. This vapour is condensed to get
metallic zinc.
Zinc as an alloying element is characterised by its very limited solubility
in other metals. Only few metals have an appreciable solid solubility in
zinc. Its solid solubility in aluminium can reach 80% by weight, in
copper 39% by weight and in iron 20% by weight, although it does not
form a continuous series of solid solutions with any other metals. Its
solubility in most other metals is less than 3%. The dissolution of gold
and silver in solid zinc is to the extent of about 10%, while copper and
cadmium have a maximum solubility of 3%.
Its low creep resistance restricts the use of unalloyed zinc. Zinc
recrystallises readily which leads to the elimination of structural
hardening effects during deformation, the extent of the recovery is
dependent on time and thus on the rate at which the stress is applied.
This recovery mechanism and the accompanying reduction in the
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amount, of strain hardening causes decrease in creep resistance. This is
one of the most crucial disadvantages, which restricts the application of
zinc as an engineering material. However in the recent years, alloying of
zinc with small amounts of titanium and copper offers resistance to
creep. Alloying of zinc with 0.65 to 1.25% copper produces significantly
stronger metal than the unalloyed zinc, which possesses good ductility
and working properties. They can be work-hardened and may be
employed for parts that should withstand loads higher than the unalloyed
zinc. The addition of about 0.01% magnesium to this alloy increases the
creep resistance considerably.
2.2.1 Development of the family of Zinc based alloys
In the 70s and 80s, the zinc industry has promoted zinc as to be
effectively competent for many applications against the well-established
copper, aluminium and even iron-based foundry alloys. A family of zinc
alloys was introduced with a wide range of foundry characteristics and
mechanical properties capable of meeting a large spectrum of
performance criteria. Gervais et al(42) have considered the metallurgical
considerations that lead to the development of a new high aluminium,
zinc based alloy (Al-27%, Cu-2%, Mg-0.01 %, Zn-balance) and of a
permanent molding alloy (Al-8%, Cu-1%, Mg-0.015%, Zn-balance) and
the effects of casting variables and of casting practices. Zn-11% Al alloy
was first developed by ILZRO, but it was required to develop a family
of alloys, each with specific characteristics to effectively compete
against well-developed alloy systems such as the brass. The market
development efforts indicated that there was an immediate need for a
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sand casting alloy, which is stronger a nd more ductile than the Zn-11 %
Al alloy. But review of literature and the experience has clearly shown
that the binary zinc- aluminium system would form the basis of the new
alloys.
The intervals of solidification are quite large for a significant range of
zinc contents, which is an important factor in gravity cast alloys. The
system features a eutectic reaction at about 5% Al (380oC) and a
eutectoid reaction at 22% Al (275o C). Zinc die casting alloys have near
eutectic compositions, whereas the well-known super plastic zincaluminium
alloys take advantage of the eutectoid reaction to produce the
required fine grain structure. The phase diagram also implies that it is
possible to develop heat treatments for some alloys and that a variety of
hardening mechanisms would be operative, depending on the cooling
rate upon casting or after heat treatment. The most important solid-state
reactions, which take place are:
(a) Solution hardening: The primary alpha aluminium rich phase may
contain as high as 30% super saturation of zinc in substitutional sites.
(b) Precipitation and ageing of the alpha and of the beta phases.
(c) Development of a relatively fine microstructure at high
concentrations of aluminium. Addition of copper and magnesium
normally strengthens and hardens ZA-alloys.
Magnesium is effective in small concentrations and also assures that
intragranular corrosion will not take place in atmospheres of high
humidity when impurities such as lead, tin, and cadmium are high.
Copper additions are also made to increase creep strength and to
improve corrosion resistance. But addition of too much copper to zinc35
aluminium alloys influences the ageing characteristics. The mechanical
properties will decrease by a greater extent and undesirable dimensional
growth will occur with time. Zinc alloys are susceptible to ageing
because all phases are not in equilibrium in the as-cast condition.
ZA alloys are prepared using special high-grade zinc (99.99%),
commercial purity Al (99.5%), electrolytic tough pitch copper (99.9%),
and commercial purity Mg (99.8%). Melting is carried out in an
induction-melting furnace. Since aluminium does not readily dissolve in
molten zinc, it must be melted first, along with any copper addition. The
zinc added to the Al and Mg melt must be preferably introduced just
before casting. The alloy bath must be stirred vigorously to ensure batch
homogeneity and must be allowed to rest prior to skimming.
2.3 Optimization of Aluminium and Copper Content
Plotting tensile properties for various copper levels as a function of the
Al content carried out a study of the preferred aluminium composition
range. The tensile strength increased with Al content up to about 26 or
27% Al, regardless of the copper content. In the absence of copper, the
tensile strength rises with Al over the full range of compositions
investigated, whereas on the copper bearing alloys, the tensile strength
levels off or decreases with Al content higher than about 26 or 27%.
With regard to ductility, it was observed that for low and intermediate
copper levels, maximum ductility is attained at Al contents of 25 to
27%, while at higher copper levels Al content has no effect on ductility.
Based on these results it was concluded that the optimum Al and Cu
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contents were in the range of 26 to 27% Al and 1 to 2.5% Cu
respectively.
2.4 Zinc Aluminium alloys
ZA-alloys are used because of their high castability, easy finishing, good
mechanical properties, and freedom from intragranular corrosion.
Addition of aluminium improves strength, reduces grain size, minimizes
attack of molten zinc alloy on the iron and steel parts and in casting
equipment increases fluidity and castability.
2.5 Effect of Addition of Different Elements in the preparation of
ZA alloys
Copper: Copper addition minimizes effect of impurities and in small
quantities increases the tensile strength and hardness of zinc casting
alloys. Copper addition up to 2% weight increases alloy tensile strength
and lowers tensile elongation. The addition of copper also improves the
alloys creep and corrosion resistance. Copper moderately retards the
kinetics of the eutectoid reaction, which occurs at 275oC. Though
beneficial in small amounts, a high copper content is detrimental since it
causes a decrease in mechanical properties and loss of dimensional
stability with time due to changes in ageing response.
Magnesium: It is used to strengthen and harden the Zn-Al alloys.
Magnesium in small amounts is added to zinc alloys since it prevents
intergranular corrosion. Excessive amounts of magnesium lower the
fluidity of the metal, promote hot cracking and decreases elongation.
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Even though it is a minor alloying element it is rather important since it
tends to retard intergranular corrosion. Similar to copper, magnesium
addition also retards the eutectoid reaction. High concentration of
magnesium can promote hot shortness. Formation of magnesium oxide
can adversely affect the castability of the alloy.
Silicon: Additions of up to 8% silicon, followed by prolonged heat
treatment is reported to have improved the wear resistance of the alloys.
2.6 Effect of Trace Elements or Impurities
Lead, tin and cadmium content should be less than 0.005% and Fe less
than 0.01%. These elements have the following characteristics:
I. They are high-density metals with low melting points and low
hardness.
II. They have solubility in zinc.
They may form very low melting eutectic, which freeze lasts during
solidification, at the grain boundaries.
Lead: Solubility of lead in zinc is very low. A monotectic is formed at
417°C and liquid exists in equilibrium down to 318°C.
Tin: Tin forms a low melting eutectic with Zn at 198°C even at as low
level of 0.001 %. Tin causes hot shortness of the alloy.
Cadmium: At low levels, cadmium exists in solid solution and causes
coring in microstructure.
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Iron: In excess of 0.01 %, Fe particles appear as an inter-metallic
compound containing Fe. This Fe-Zn compound precipitates at the grain
boundaries and affects the machinability of the castings.
Researchers recognized that the presence of impurities as the cause for
intergranular corrosion and that careful control of their content were
needed. The governing mechanism and the role played by the various
alloying elements in promoting or retarding intergranular corrosion are
not clearly understood. However, magnesium and copper are known to
retard intergranular corrosion. Beside lead, cadmium and tin, other
impurities that are controlled are iron and silicon, which form hard and
brittle compounds, thus making machining and finishing operations
difficult.
2.7 Properties of ZA alloys
Typical properties of three ZA alloys namely ZA-27, ZA-11 and ZA-8
are discussed below. The density of the three alloys reflects the
Aluminium content. ZA-27 alloy is about 17% lighter than ZA-11 alloy
and about 21% lighter than the ZA-8 alloy. The electrical conductivity
of the alloys is relatively high and increases with the Aluminium level.
The meeting range corresponds to the highest liquidus and lowest
solidus at practical cooling rates. The solidification interval increases
with Aluminium content it is 29o C for ZA-8 alloy, 55°C for ZA-11 and
112°C for ZA-27 alloy. Such a variation of the freezing range has an
effect on the casting performance. The three alloys have a good
combination of mechanical properties. The ZA-27 alloy is superior to
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the other alloys, tensile strength is close to 50% higher than the other
two alloys. The ductility of ZA-27 is slightly higher and creep resistance
is significantly more than the other two alloys. The zinc-based alloys are
stronger and harder than the conventional brass and aluminium alloys
and they are stronger than common grade cast iron and annealed
malleable iron. The composition of ZA-8, ZA-12 and ZA-27 is shown in
Table 1.