Zinc and its alloys

Dr. S. Jerome
Department of MME
NIT Trichy
MTPC -27 Non Ferrous Physical Metallurgy
Introduction
• Zn is one of the world’s major metals. Although it is not especially abundant (76
ppm of Earth’s crust).
• Its annual production of 8.5 million tons ranks fourth behind Fe, Al, and Cu.
• Zn’s largest use is for protective coatings on steel to retard corrosion and to
harden the surface, but it is also used to make brass
• Zn-based pressure die-casting alloys.
Physical properties of Zinc
Corrosion of Zinc
• Zn has little reaction with dry air at room temperature, but humid air
containing CO2 forms an adherent gray, hydrated Zn carbonate that inhibits
further corrosion.
• Above 200◦C, however, Zn oxidizes rapidly.
• Zn is attacked by most mineral acids (dilute H2SO4 being the exception) and
alkalis.
• Zn has a low seawater electrode potential (−1.10 V). Since Fe’s electrode
potential is higher at −0.68 V, Zn acts as the sacrificial anode in Zn–Fe galvanic
couples, making Fe the protected cathode.
• The largest use of Zn is as a protective coating for steel. The adherent corrosion
barrier on Zn’s surface coupled with its action as a sacrificial anode when that
barrier is scratched or damaged makes it a more effective anticorrosion coating
for steel than simple barrier coatings such as paint or nobler metals
Mechanical Properties
• Zn has an HCP crystal structure with a c/a ratio (1.856) much higher than the ideal
value (1.633).
• At room temperature, high-purity Zn is ductile, but lower-purity Zn is somewhat
brittle and difficult to deform without cracking.
• Commercial-purity Zn (about 99%) has an ultimate tensile strength of about 110 MPa.
• Room-temperature slip occurs almost entirely on the (0001) 1120 slip system,
although {1122} 1123 slip has also been observed.
• Above room temperature, slip also occurs on the (1010) prism planes. Deformation is
aided by twinning on the (1012) pyramidal planes.
• High-purity Zn’s low critical resolved shear stress (0.08 MPa) results from its weak
bonding between (0001) planes and the fact that room temperature is 43% of the
homologous melting temperature.
• Diffusion is an active process at room temperature, and pure Zn creeps appreciably at
ambient temperatures.
• Work hardening begins to anneal away in high-purity Zn in just a few seconds at room
temperature, and the metal will recover and recrystallize completely within several
hours.
Zn Alloying behaviour
• Au and Ag dissolve up to about 10 wt% in Zn.
• Cd, Cu, Mn, and Al have maximum solubilities of a few percent.
• Zn’s solubility in other metals is somewhat greater, but only a few metals
will dissolve large amounts of Zn.
• Zn has great solubility in Al (over 80 wt%), Cu and Fe can dissolve 40% Zn,
and Mg and Cd can dissolve several percent Zn.
• The short list of elements with extensive solubility in and for Zn constrains
alloying options; however, several useful alloys have been developed to
improve mechanical properties and enhance coating performance
Applications of Zinc

• The engineering applications of Zn are defined largely by its corrosion

resistance, low melting point, and low cost.
• Zn’s ability to protect ferrous metals from rusting at minimal cost is
extraordinarily important.
• Zn’s low melting point makes it easy to apply to steel and cast iron surfaces.
• Zn coatings on ferrous metals consume half of the world’s Zn production.
• Zn die-casting alloys have strength and cost intermediate between polymers
and Al die castings, and this makes them the preferred material for many
applications.
• Over 50 billion Zn die-cast components are produced each year.
• Zn also sees substantial use as an alloying addition in brass and 7000 series Al
alloys.
Zn coatings on Steel

• The Fe–Zn phase diagram shows near-zero

solubility of Fe in Zn and several intermetallic c
• When steel with a well-cleaned surface is
submerged in molten Zn at about 450◦C (hot-dip
galvanizing), the two metals react at the
interface.
• The molten Zn quickly reaches its saturation
concentration of Fe (<0.02%).
• Zn atoms diffuse rapidly into the steel, and Fe
atoms diffuse more slowly outward into the
surface layers, forming thin layers of
intermetallic compounds.
• These layers not only provide good adherence
for the outermost layer of nearly pure Zn, they
also increase surface hardness and wear
resistance.
• The Si content of the steel strongly affects galvanizing behavior. Steel
containing intermediate levels of Si (0.06 to 0.5%) reacts more rapidly with
Zn, and thicker coatings result, but at high Si contents, reactivity between
the steel and the molten Zn drops to low levels, producing thin coatings.
• Zn purity also affects galvanizing behavior. Most hot-dip galvanizing is
performed with Zn of 98.5 to 99.5% purity, with the major impurity being
Pb. The presence of about 1% Pb in molten Zn lowers the surface tension of
the molten Zn against steel by about 40%, which improves Zn’s wettability
on the steel surface.
• Small amounts of Al (<0.005%) in the Zn improve the luster of the final
product, but larger amounts of Al inhibit formation of the Fe–Zn
intermetallic layers and alter the thickness and structure of the coating.
• Some steel sheet and wire is galvanized by a continuous process in which
the steel moves at high speed (up to 3 m/s) through a Zn bath.
Electroplating of Zn
• Electroplating can be used in place of hot dipping to apply Zn to steel.
• Galvanizing steel body panels for automobiles poses special challenges because the Zn
surface must be very smooth to be “paintable.”
• Ordinary hot-dip galvanizing does not meet this requirement, so electroplating with alloy
of Zn–Ni, Zn–Fe, or other Zn alloys is used.
• By adjusting solution pH and current density, electroplated layers of Zn containing 9 to
13% Ni or Zn containing about 18% Fe are deposited.
• Zn coatings can also be applied by oxyfuel spray of liquid Zn onto the steel surface.
• Electrolytic and thermal spray coatings usually are less effective than hot-dip processes at
protecting steel, so additional protection can be imparted by treating the surface with
phosphoric acid to form a crystalline layer of insoluble Zn2Fe(PO4)2 phosphate ranging
from 3 to 50 μm thick.
• This improves corrosion performance and paint adherence.
• Chromate coatings were once heavily used to enhance the corrosion protection provided
by the Zn layer; however, chromate coatings use has declined due to safety concerns
about Cr solutions.
• During the first weeks after galvanized metal is placed into service, a protective Zn carbonate
surface layer forms.
• The hard intermetallic layers make the metal more resistant than bare steel to mechanical
damage, but even if the coating is cut or scratched, the Zn surrounding the damaged site acts
as a sacrificial anode, preferentially oxidizing while protecting the exposed steel from rust.
• Only when the Zn near the damaged site has been consumed completely does the steel begin
to rust.
• Galvanizing can prevent rust on steel exposed to the weather for periods of 20 years or more
on sites with low air pollution. However, in humid atmospheres containing SO2, sulfurous acid
(H2SO3) forms on the surface, attacking the Zn carbonate layer and shortening the protective
life of the galvanizing layer.
• Steel can also be protected from corrosion by attaching massive pieces of Zn metal to
surfaces such as ships’ hulls and undersea pipelines.
• The Zn acts as a sacrificial anode, corroding slowly while protecting the surrounding steel.
• Still another corrosion protection strategy is the use of paint containing high volume fractions
(92 to 95 vol% in the dried paint) of Zn metal dust.
• These paints offer much of the galvanic protection of hot-dip galvanizing and are less
expensive to apply to large parts, but their adherence and service lifetimes are inferior to
those of hot-dip treatment, and they do not increase surface hardness because no Zn–Fe
intermetallics form.
Zn as an alloying element
• Brasses are Cu–Zn alloys with Zn content ranging from a few percent up to nearly
50%.
• Brass was among the first alloys used by humankind, and brass remains widely
popular today for its strength, easy formability, corrosion resistance, attractive
color, and moderate cost.
• About 10% of the world’s Zn production is consumed by the brass industry. Al has
great solubility for Zn , and Zn acts as a precipitation hardener in the 7000 series
Al alloys based on the Al–Zn–Mg ternary system.
• These alloys contain up to 6 wt% Zn and have the highest strengths of all the
commercial Al alloys. They are widely used in the aircraft and automotive
industries.
• Zn is also a useful strengthener in Mg-based alloys and in Sn, Ag, Au, and solder
alloys.
Die casting alloys
• The most widely used pressure die-casting alloys
are based on the eutectic at 381◦C in the Al–Zn
system.
• Al reduces the rate of attack of molten Zn on
steel dies and plungers.
• Al contents greater than 4.3 wt% are usually
avoided since fracture toughness drops with Al
contents near the eutectic.
• Cu is sometimes added (0.25 to 3.5%) to Zn–Al
die-casting alloys to increase strength on aging,
but Cu lowers fracture strength and causes
greater dimensional change during post casting
aging.
• Mg (0.08% maximum) is often added to reduce
the intergranular corrosion effect from tramp
impurities such as Pb, Sn, In, As, Sb, Bi, and Hg.
• Rapid solidification occurs when the liquid alloy is injected
under pressure into the watercooled steel mold.
• Since the commercial alloys are slightly hypoeutectic, the
first solid to form is pro-eutectic β phase (Zn with a small
amount of Al in solid solution).
• The remaining liquid segregates during freezing into Zn-rich
β phase and Al-rich α phase.
• After casting, the alloy gradually ages at room temperature,
precipitating Al-rich α phase within the β regions to
accommodate the 0.07 wt% maximum solubility of Al in Zn
at room temperature.
• Pressure die casting with Zn–Al alloys is well suited to
produce intricate shapes and large production runs.
• Zn die castings are often used for frames for electronic
devices, complete with holes cast with internal threads.
• Designs that formerly contained several parts can sometimes
be replaced with a single Zn die casting, simplifying assembly
operations and lowering costs.
• Shrinkage factors are considerably smaller than in Al die
castings, and the lower temperatures needed for Zn alloys
reduce energy costs and prolong die life.
Wrought products of Zn
• About 10% of all Zn is fabricated by rolling into plate, sheet, rod, wire, and foil.
• Zn with 1% Pb and 0.05% Cd is rolled into thick sheet and formed into battery cans for C–
Zn dry-cell batteries.
• A Zn–0.8% Cu alloy plated with 6 μm of Cu is rolled and stamped to produce the U.S.
one-cent coin.
• Zn foil is applied by adhesive to ferrous structures too large to galvanize by hot dipping.
• Wire is used for Zn thermal spray.
• The most popular Zn alloy for roofing, gutters, and flashings (0.7 to 0.9% Cu, 0.08 to
0.14% Ti) is stronger and much more creep resistant than commercial-purity Zn.
• Zinc plate and sheet are formed in a continuous casting/hot rolling operation. The metal
is strengthened by Cu in solid solution and by Zn–Cu ε phase and TiZn15 intermetallics.
• The intermetallics form at grain boundaries during solidification (Fig a)
• but break up during rolling to produce long strings of fine particles (Fig. b).
• The hot rolling induces dynamic recrystallization, distributing TiZn15 particles on
recrystallized grain boundaries; these particles are sufficiently fine and discontinuous to
avoid intergranular corrosion.
• Zn–Cu–Ti alloy given suitable rolling and annealing treatment can sustain a load of 115
MPa at room temperature with creep strain of only 1 to 2% per year, a creep
performance about two orders of magnitude better than that of pure Zn and nearly as
good as commercial-purity Al.