12 Ti, Zr and Hf

Overview
The elements of group 4, titanium (Ti), zirconium (Zr), hafnium (Hf) y rutherfordium (Rf) are reactive,
electropositive elements. These can be used al adherents, diffusion-resistant oxide layers that
protects them from both aqueous corrosion and high temperature oxidation. The electronic
structure of these metals provides four bonding electrons per atom, giving them high melting
temperatures, with good ductility and abundance.

All three metals are HCP at room temperature, transforming to a BCC phase at high temperature.
They all are poor electrical and thermal conductors but Ti and Zr are often selected for use in
seawater, hot acids, sour gas petroleum wells (pozos petroleros), and high temperature exposure
air.

Ti ranks among 10 most abundant terrestrial elements, comprising 0.63% of Earth’s crust, Zr is about
162 ppm, and Hf 2.8ppm. Due to their extractive processors, these metals are more expensive than
their abundances would suggest.

Titanium (Ti)
History
1825 – First produced in low purity form but available pure Ti metal iuntil 1910.

1950s – Large scale production began for military aircraft.

Today – It remains difficult to refine, and some uses are for marine components, surgical implants,
and petroleum drill pipe.
Physical Properties

Reactivity
Ti is so reactive that its production and fabrication pose several daunting challenges. It was first
produced by Koll process, where Ti ore was converted to TiCl4 and reduced with Mg metal. The
Cambridge process is a promising method for reducing Ti by molten CaCl2 electrolytic process which
would lower Ti production costs.
These electrolytic processes form a mixed Ti metal plus alkali salt product called sponge Ti. Crushing
sponge Ti allows the salt to be removed. Then, it is pressed into large briquettes and melted into
billets. Due to its reactivity, it is melted into chilled molds by arc melting in vacuum or protective
atmospheres. Ti usually receives two vacuum melting operations for purification.

After Ti ingots are produced. The metal´s reactivity causes additional problems in hot working,
grinding, joining, machining and casting. Ti can be hot-forged and hot rolled in air, but above 500°C,
a significant thickness of oxide accumulates that hardens and embrittles the surface leading to
cracking. This can be removed by applying silicate-based coating, by mixing with HF-HNO3 (Fluoric
acid-nitric acid) for a 10 um thin and up to 600°C, or by inmersion in oxidizing molten salt baths at
200°C to 480°C. In addition, surface contaminants must be removed prior to joining to avoid
interstitial impurities. For machining it must be used carbide or high -speed steel cutting tools at
lower cutting speeds and higher feed rates due to its low thermal conductivity that retards heat
dissipation. Ti alloys would be casted to achieve near shape-products. However, forging, stamping
and machining operations dominate Ti fabrication.

Corrosion
When exposed to air, Ti immediately forms an oxide layer a few nanometers thick that protects the
metal from further oxidation. If this oxide layer is damaged it reforms in the presence of O or H 2O.
At elevated temperature Ti and O diffuse through the oxide layer, gradually thickening and
embrittled it. Due to the high solubility of O in Ti, it is one of the easiest metal to join by diffusion
bonding. This is by clamping two cleaned surfaces of Ti together, heating them in a protective
atmosphere and holding them about 900°C under stress for 1 to 6 hours.

Elasticity and Plasticity

Ti´s Young´s modulus is 116 GPa, makes it have a high modulus of resilience in high strength Ti alloys.

Pure Ti is one of the most ductile HCP metal with a principal slip system in the (1010)[1120] with a
secondary slip system in the (0001)[1120] and (1011)[1120]. Shear stresses change for these slip
systems with interstitial impurity. Strength rises and ductility decreases as interstitial impurity
content increases. Ti´s plasticity improves at higher temperatures.

HCP Ti (α-Ti) transforms to a BCC phase (β-Ti) at 882°C, and at high pressure a third phase forms
hexagonal (hP3) -Ti.

Alloys of Ti
Applications for Ti are based on two characteristics: excellent corrosion resistance and a high
strength/weight ratio, at elevated temperature. Ti is only selected when needed higher
performance, longer life or reduced maintenance (operating costs as in marine and aerospace
structures, chemical processing equipment, surgical implants, and sports implements.

 Pure Ti. Commercial-purity (CP) Ti has a better aqueous corrosion resistance, lower ductility
and fracture toughness as in heat exchangers, tanks and reactors vessels.
 α-Ti Alloys. Additions of α-stabilizing elements such as Al, Sn, or O raise α->β transus
temperature and increase strength by solid-solution hardening. An example is Ti-5% Al-2.5%
Sn that provides excellent weldability and good fracture toughness at cryogenic
temperatures.
  β-Ti Alloys. Additions of β-stabilizing elements such as V, Mo, Cr, and Cu, that lower the β-
>α transformation temperature. With sufficient β-stabilizer additions, the BCC crystal
structure can be retained to room temperature by air-cooling thin sections. It has excellent
formability at room temperature but a low strength. Heating moderately above room
temperature will form some phase α in the β use for hardening the alloy after forming.
 Alpha-Beta alloys. It contain both α- and β- stabilizing elements to allow formation of mixed
structures with excellent strength, toughness, and corrosion resistance. The alloy Ti-6% Al-
4% V, has dominated Ti metallurg, This alloys are formed in a high temperature β-matrix
and then is cooled until equilibrium is reached, a Windmanstätten structure results.

Applications of Ti
 Aerospace industry, especially in military aircraft where rigorous performance is required
(Boeing 757 and B1-B supersonic bomber).
 Chemical processing and petroleum industries for pipe, reaction vessels, heat exchangers,
filters and valves.
  Biomedical devices for artificial joint prostheses, dental implants, eyeglass frames,
endovascular stents (endoprotesis), heart valves, and wheelchairs.
 Marine include surface ships and submarines, propellers, and service water systems.
 Sporting goods manufacturers have developed golf clubs, bicycle frames, skis, and even
pool cues.
 Ti additions minimize intergranular corrosion in stainless steel by reacting with C.

Sources of Ti
Geological formations with high concentrations of the most useful Ti ores, rutile (TiO2) and
ilmenite (FeTiO3), are found in Australia, Brazil, Canada, Finland, India, Malaysia, Norway,
Portugal, Russia, Sierra Leone, South Africa, Sweden, and the United States. Ilmenite is most
common than rutile but it is more demanded rutile.

Structure-Property Relations in Ti.

 Nitinol Shape Memory Alloy. The NiTi intermetallic compound (usually called nitinol) has
numerous applications that exploit its shape memory effect. By analogy to the Fe-C
system, the high temperature phase is referred to as austenite and the low-temperature
phase is called martensite. If the metal is cycled repeatedly through several temperature
and deformation cycles, it establishes a shape pattern that will consistently return during
future transformations. It is used in nitinol eyeglass frames, in occluded arteries as
endovascular stents, orthodontic devices.
 Bauschinger Effect. Annealed metals have approximately equal tensile and compressive
yield strengths, if that tensile deformation increases the tensile yield strength actually
reduces compressive yield strength. This effect “works both ways”; that is, an initial
compressive strain also causes a drop in the metal’s tensile yield strength. This
directionality of strain hardening, called the Bauschinger effect, occurs in all
polycrystalline metals. This effect is caused by the tendency of dislocations to pile up in
dislocation tangles.
203

Zirconium (Zr)
History
1789 – Discovered by Martin Heinrich Klaproth while analyzing the mineral jargon (ZrSiO4).

1824 – Isolated by Jöns Jacob Berzelius.

1914 – Prepared in a pure form.

Physical Properties

Kroll process has been adapted to produce sponge Zr metal due to its reactivity.

Zr has the same HCP and BCC crystal structures with a hexagonal ω phase tha is stable at high
pressure. Formation of this last phase embrittles the metal. Metastable ω is formed by aging or
rapidly quenching pure Zr. At room temperature and low pressure, the ω phase eventually
transforms to α. The dominant slip system in Zr is the (1010)[1120] depending ductility on
twinning (maclas) at low temperatures.
Zr is a better thermal conductor than Ti, and has low coefficient of thermal expansion (COTE). Zr´s
absorption cross section for thermal neutrons is low, making it useful in nuclear reactor cores.

Alloys of Zr
 Pure Zr. It´s corrosion resistance is exploited in varios chemical processing operations
making with better corrosion resistance against attack by hot acids and corrosive aqueous
fluids.
 Zr Alloys for Nuclear Reactor Core Components. Are used in reactor cores for pipes;
calandria tubes, and fuel cladding.with Fe, Cr and Ni that improve the adherence of the
oxide layer.

Sources of Zr and Refining Methods

Australia and South Africa are the largest zircon producers. Zircon can be used directly or
processed to produce ZrO2. The primary Zr ore is zircon sand (ZrSiO4), which often occurs mixed
with Ti-bearing sands.

Structure-Property Relations in Zr
 Role of Twinning in Zr Plasticity. Twinning reorient portions of a grain facilitate dislocation
motion and ductile a metal.
 Radiation Damage in Zr Alloys. Intense radiation alter mechanical properties htat´s why
used in reactor cores.

Hafnium (Hf)
Physical Properties
Hf is metallurgically and chemically similar to Ti and Zr but has a higher melting temperature
(2222°C), a higher HCP->BCC transformation temperature (1760°C) and much greater density
(13.28 g/cm3). Hf´s coefficient of thermal expansion is low at 5.9x10-6°C-1. Its electrical and thermal
conductivities are 35.1 μΩ*cm and 22.3 W/m*K, respectively. Young´s modulus of 137 GPa. The
quoted price of $180 per kilogram for HF sponge.

It has been used as a control rod material in naval shipboard nuclear reactors. Pure Hf is strong
and has good ductility. It is proclivity for interstitial embrittlement impose special constraints. The
only alloying addition used in reactor applications is O, which increases strength while reducing
ductility.