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A
SEMINAR REPORT ON
EXTRACTION OF TITANIUM
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ACKNOWLEDGEMENT
I take this opportunity to express my sense of gratitude and indebtedness
to my guide METALLURGICAL ENGG for helping me
a lot to complete the seminar report without whose sincere and kind efforts
this seminar report would not have been a success.
I am also grateful to , HOD OF METALLURGICAL ENGG for his
instant permission and constant support in preparing the seminar report.
Yours Sincerely
ROLL NO: 27614
REGD.NO:0801105130
METALLURGICAL ENGINEERING
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This is to certify that , Regd.No-0801105130 Roll.No-27614 of 7th semester of
for academic year 2011-2012, a student of
Metallurgical Engineering of
has successfully completed his seminar.
.
DR. S.C. PATTNAIK MS. SWARNALATA BEHERA
H.O.D GUIDE
DEPARTMENT OF METALLURGICAL ENG
ABSTRACT
Discovered by Gregor in 1791; named by Klaproth in 1795. Impure titanium
was prepared by Nilson and Pettersson in 1887; however, the pure metal (99.9%)
was not made until 1910 by Hunter by heating TiCl4 with sodium in a steel bomb.
Titanium is present in meteorites and in the sun. Rocks obtained during the Apollo 17
lunar mission showed presence of 12.1% TiO2. The element is the ninth most
abundant in the crust of the earth. Titanium is almost always present in igneous
rocks and in the sediments derived from them. It occurs in the minerals rutile,
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ilmenite, and sphene, and is present in titanates and in many iron ores. Deposits of
ilmenite and rutile are found in Florida, California, Tennessee,New York, and
elsewhere. Titanium is present in the ash of coal, in plants, and in the human body.
The metal was a laboratory curiosity until Kroll, in 1946, showed that titanium could
be produced commercially by reducing titanium tetrachloride with magnesium. This
method is largely used for producing the metal today. The metal can be purified by
decomposing the iodide. Titanium, when pure, is a lustrous, white metal. It has a low
density, good strength, is easily fabricated, and has excellent corrosion resistance. It
is ductile only when it is free of oxygen. The metal burns in air and is the only
element that burns in nitrogen. Titanium is resistant to dilute sulfuric and
hydrochloric acid, most organic acids, moist chlorine gas, and chloride solutions.
Natural titanium consists of five isotopes with atomic masses from 46 to 50. All are
stable. Fifteen other unstable isotopes are known. The metal is dimorphic. The
hexagonal alpha form changes to the cubic beta form very slowly at about 880C.
The metal combines with oxygen at red heat, and with chlorine at 550C. Titanium is
important as an alloying agent with aluminum, molybdenum, manganese, iron, and
other metals. Alloys of titanium are principally used for aircraft and missiles where
lightweight strength and ability to withstand extremes of temperature are
important. Titanium is as strong as steel, but 45% lighter. It is 60% heavier than
aluminum, but twice as strong. Titanium has potential use in desalination plants for
converting sea water into fresh water. The metal has excellent resistance to seawater and is used for propeller shafts, rigging, and other parts of ships exposed
to salt water. A titanium anode coated with platinum has been used to provide
cathodic protection from corrosion by salt water.
CONTENTS
INTRODUCTION
PROPERTIES
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TITANIUM ALLOY
TITANIUM SPONGE
PRODUCTION OF TITANIUM TETRACHLORIDE
WHAT IS KROLL PROCESS
HEAT TREATMENT OF TITANIUM
APPLICATION OF TITANIUM
CONCLUSION
INTRODUCTION
Titanium as a useful metal alloy was not commonly used until the late 1940s. It is most
often alloyed with molybdenum, manganese, iron, and aluminum. By weight titanium is one
of the strongest readily available metals, making it ideal for wide range of practical
applications. It is 45% lighter than steel with comparable strength, and twice as strong as
aluminum while being only 60% heavier.
As an element, Titanium has an atomic number of 22. Its atomic mass is 47.867 amu, it has
a relatively high boiling point of 1660 Celsius (3020 Fahrenheit). Titanium-44, Titanium-45,
andTitanium-51 are all radioactive isotopes, created when it is bombarded with deuterons.
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In commercial use, titanium alloys are used anywhere strength and weight are an issue.
Bicycle frames, automobile and plane parts, and structural pieces are some common
examples. In medical use titanium pins are used because of their non-reactive nature when
contacting bone and flesh. Many surgical instruments, as well as body piercings are made
of titanium for this reason as well.
Titanium is suggested for use in desalinization plants because of its strong resistance to
corrosion from sea water (particularly when coated with platinum). Many ships
use titanium for moving components constantly exposed to sea water, such as propellers
and rigging.
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PROPERTIES OF TITANIUM
The primary physical properties oftitaniumas a metallic chemical element include its non-
magnetic property, low density, and tough strength-to-weight ratio. It was first discovered inEngland in 1791 by Reverend William Gregor, who was also a minerologist, who originally
named the metal manaccanite after the parish of Mannaccan in Cornwall, England, where
he discovered it. Titanium ore is common in the Earth's crust in minerals such as ilmenite or
iron titanate, FeTiO3, and rutile, more commonly known astitanium dioxide, TiO2.
Chemical properties of titanium include its corrosion-resistant nature that makes it suitable
for medical instruments, since it does not interact chemically with human tissues. Its
resistance to many forms of acid make it useful in industrial applications where caustic
chemicals are processed. Titanium is also one of the few elements that can burn in theabsence of oxygen. In a pure nitrogen atmosphere, it will react at a temperature of 1,470
Fahrenheit (800 Celsius) to form titanium nitride, TiN.
Titanium dioxide is a widely used compound of the metal, applied as a form of pigment in
paints, sunblock lotion, and food colorings. The overwhelming bulk of titanium ore that is
mined worldwide is converted into a pure form of TiO2, while the rest is alloyed with metals
such asvanadiumandaluminumfor use in structural surfaces, where it weighs 40% less
than carbon-strengthened steel.
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The oxide mineral properties of titanium compounds led to purification difficulties after its
discovery. Pure titanium at a level of 99.9% of the metal wasn't isolated until 119 years later
by Matthew Hunter in 1910, a metallurgist from New Zealand who named the purification
method the Hunter process. Additional methods of purification of the metal were discoveredin 1936, and, by 1948, worldwide production of it had climbed to three tons per year. This
number was soon to skyrocket due to unique properties of titanium, and 2011 global
production is estimated at 223,000 metric tons.
The strong mechanical properties of titanium make it essential in aircraft airframe structures
that make extensive use of the metal, and, as of 2006, aircraft manufacturing saw global
prices for titanium begin to rise rapidly. This is in part due to the fact that it is expensive to
purify the metal, and it costs five times more than aluminum to refine. The cost is 10 times
more to create titanium metal ingots and finished metal products than aluminum. The world
market demand for pure titanium is 10,000 times smaller than that of the steel market aswell, which contributes to price fluctuations. As of 2005, the nations gearing up to be the top
titanium refiners were Japan and China, followed closely by Russia and the United States.
TITANIUM ALLOY
Titanium alloy is a metallic material that consists of titanium mixed with other metals, usually
small quantities of palladium, vanadium, aluminum, and/or tin. These metals provide
improved properties over pure titanium, such as corrosion resistance, good weldability
(fabricability), stability, and strength at elevated temperatures. Pure titanium is very hard,
which can make it challenging to weld and shape.
The only typical application for pure titanium is orthopedic and dental implants, while the
myriad other applications of titanium, including aerospace engineering, high-temperature
engines, medical and marine processing, and athletic equipment use titanium alloy. Many
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alloys of other metals also contain small amounts of titanium, but these they are not
considered titanium alloys unless titanium makes up the majority of the substance.
Titanium is often considered a wonder metal for its high strength and lightness. About as
strong as steel and twice as strong as aluminum, titanium is 45% lighter than steel and only
60% heavier than aluminum. It also has the benefit of being non-reactive with the human
body, making it ideal for medical implants such as pins to hold together broken bones.
However, its high cost has limited its use.
Titanium is relatively common in the Earth's crust, making up about 0.57% (the 9th most
common element), but extracting it from its ores -- the minerals Rutile (TiO2), Ilmenite
(FeTiO3) and Sphene (CaTiSiO5) -- can be pricey, due to the high heat input required.
Elemental titanium was only first isolated in its pure form in 1910, when Matthew A. Hunter
heated TiCl4with sodium at 800 C (1472 F).There are 38 common types of titanium alloy, but the typical mix is 90% titanium, 6%
aluminum, and 4% vanadium. This mix is called Grade 5. There are titanium grades 1
through 38, with 38 being the most recently invented. The grades do not indicate strength or
anything, they are just used for easy reference, though the earlier grades were the first to
be commonly produced. Grade 5 titanium is also known as Titanium 6AL-4V, which is
considered suitable for military use. This grade of titanium alloy is stable in applications up
to 400 C (752 F), with the stereotypical application being in aircraft turbines, which rotate
very quickly and get very hot.
Besides seeing widespread use in military hardware, titanium alloy can be found in the
connecting rods in high-end automobiles like Porsche and Ferrari. The presence of thesemetals is part of what can make these cars so expensive, but also reliable and capable of
high speeds. A similar high-end material found in premium products is carbon fiber.
TITANIUM SPONGE
Titaniumsponge is a porous form of titanium that is created during the first stage of
processing. In its natural form, titanium is widely available within the earths crust. Afterbeing extracted, it is processed to remove excess materials and convert it into a usable,
although costly, product.
The conversion process used with raw titanium is called theKroll process. This is a
complex, multistage, batch process that requires very high heat and specialized equipment.
The Kroll process converts the metal oxide into chloride by passing the metal over
extremely hot rutile or ilmenite and carbon to create titanium tetrachloride. These chemicals
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are separated through a process calledfractional distillationin which the components of a
mixture are separated based on their different boiling points.
The material resulting from the Kroll process is titanium sponge. This sponge is then
subjected to leaching or heatedvacuum distillationto remove further impurities. The
remaining materials in the sponge are jack hammered, crushed, pressed and melted to
remove even more impurities.In the next stage of the process, the titanium sponge is melted. It is then put through a
process of fractional distillation to remove excess liquid and combined with molten
magnesium ironaluminum,vanadiumormolybdenumandargonin a very hot furnace.
At this point, the converted titanium sponge is ready for fabrication. Some firms sell titanium
sponge as a finished product, while others complete the conversion process internally. The
sponge can now be formed into mill shapes such as a bar, plate, sheet or tube. These
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products are then shipped to different mills and fabricators to created finished products for
commercial use.
Titanium is used to produce parts for jet engines, missiles, orthopedicimplants, jewelry and
mobile telephones. The most importantproperties of titaniumare its low density and high
level of corrosion resistance. Although six times as expensive as steel, titanium is very
resistant to corrosion in both sea water and chlorinated water, making it popular with a wide
range of manufacturers.
Titanium was first discovered and documented by William Gregor in 1791. Although purified
titanium is quite costly, it is available in its basic form, in almost all living creatures. It can
also be found in rocks, water and soil. The process of extracting it and combining it with
alloys is what makes the procedure complex and expensive.
Titanium is relatively common in the Earth's crust, making up about 0.57% (the 9th most
common element), but extracting it from its ores -- the minerals Rutile (TiO2), Ilmenite
(FeTiO3) and Sphene (CaTiSiO5) -- can be pricey, due to the high heat input required.
Elemental titanium was only first isolated in its pure form in 1910, when Matthew A. Hunter
heated TiCl4withsodiumat 800 C (1472 F).
There are 38 common types of titanium alloy, but the typical mix is 90% titanium, 6%
aluminum, and 4% vanadium. This mix is called Grade 5. There are titanium grades 1
through 38, with 38 being the most recently invented. The grades do not indicate strength or
anything, they are just used for easy reference, though the earlier grades were the first to
be commonly produced. Grade 5 titanium is also known as Titanium 6AL-4V, which isconsidered suitable for military use. This grade of titanium alloy is stable in applications up
to 400 C (752 F), with the stereotypical application being inaircraftturbines, which rotate
very quickly and get very hot.
Besides seeing widespread use in military hardware, titanium alloy can be found in the
connecting rods in high-end automobiles like Porsche and Ferrari. The presence of these
metals is part of what can make these cars so expensive, but also reliable and capable of
high speeds.
WHAT IS KROLL PROESS
The Kroll process is a method used to convert ore intotitaniummetal. Engineers,
manufacturing firms, and medical companies use titanium for a variety of different purposes
because it is as strong as steel but is more lightweight. Traces of titanium can be found in
minerals such as rutile and ilmenite, but the pyrometallurgical Kroll process removes
impurities and produces a metal that can be used in medical implants, construction, and
aircraft design.
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Titanium was discovered in Great Britain in 1791 by a man named William Gregor. A
Germanscientistnamed Martin Heinrich Klaproth named it after the Greek god Titan during
the same year. Scientists began developing ways to extract the newly discovered element
from rutile and ilmenite, and in 1910 a chemist named Matthew Hunter developed a method
for producing titanium metal by mixing rutile with coke and chlorine. The Hunter process
became the first industrial scale process for producing this metal.
During the 1930s, a scientist from Luxembourg called William Kroll began experimenting
with titanium. In 1938, he developed what later became known as the Kroll method. Kroll
moved to the United States after the outbreak of World War II, and his process for
producing titanium metal was patented in the United States in 1940. The patent was later
nullified by the federal government because Kroll was not a United States citizen.
.
The Kroll process begins by passing chlorine gas through rutile
in a chlorinator. During the first stage of the process, titanium tetrachloride and chlorides are
produced from the ore. Oxygen is removed from the titanium tetracholdire through a
distillation process, and this leaves the titanium tetrachloride in a liquid form. Scientists add
liquid magnesium or sodium to the titanium tetrachloride, and the end result is a metallic
sponge.
Thistitanium spongeis crushed and then put into a consumable electrode vacuum arc
furnace. The sponge melts inside the furnace but, unlike other metals, it is not poured
because it solidifies in the vacuum. A titanium ingot produced during the Kroll process can
weigh in excess of 5,000 kilograms (5.51 tons). The multiple steps of the Kroll process
mean that titanium is much more expensive to produce than similar types of metal, such as
steel.
After developing the Kroll process, William Kroll used a similar technique to create
zirconium metal. Both titanium and zirconium are now used to make parts for space
vessels. Titanium, unlike zirconium, is not a health hazard, and is therefore also used for
medical implants.
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WHAT IS KROLL PROESS
The Kroll process is a method used to convert ore intotitaniummetal. Engineers,
manufacturing firms, and medical companies use titanium for a variety of different purposes
because it is as strong as steel but is more lightweight. Traces of titanium can be found inminerals such as rutile and ilmenite, but the pyrometallurgical Kroll process removes
impurities and produces a metal that can be used in medical implants, construction, and
aircraft design.
Titanium was discovered in Great Britain in 1791 by a man named William Gregor. A
Germanscientistnamed Martin Heinrich Klaproth named it after the Greek god Titan during
the same year. Scientists began developing ways to extract the newly discovered element
from rutile and ilmenite, and in 1910 a chemist named Matthew Hunter developed a method
for producing titanium metal by mixing rutile with coke and chlorine. The Hunter process
became the first industrial scale process for producing this metal.
During the 1930s, a scientist from Luxembourg called William Kroll began experimentingwith titanium. In 1938, he developed what later became known as the Kroll method. Kroll
moved to the United States after the outbreak of World War II, and his process for
producing titanium metal was patented in the United States in 1940. The patent was later
nullified by the federal government because Kroll was not a United States citizen.
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The Kroll process begins by passing chlorine gas through rutile in a chlorinator. During the
first stage of the process, titanium tetrachloride and chlorides are produced from the ore.
Oxygen is removed from the titanium tetracholdire through a distillation process, and this
leaves the titanium tetrachloride in a liquid form. Scientists add liquid magnesium or sodium
to the titanium tetrachloride, and the end result is a metallic sponge.
Thistitanium spongeis crushed and then put into a consumable electrode vacuum arc
furnace. The sponge melts inside the furnace but, unlike other metals, it is not poured
because it solidifies in the vacuum. A titanium ingot produced during the Kroll process can
weigh in excess of 5,000 kilograms (5.51 tons). The multiple steps of the Kroll process
mean that titanium is much more expensive to produce than similar types of metal, such as
steel.
After developing the Kroll process, William Kroll used a similar technique to create
zirconium metal. Both titanium and zirconium are now used to make parts for space
vessels. Titanium, unlike zirconium, is not a health hazard, and is therefore also used formedical implants.
PRODUCTION OF TITANIUM TETRACHLORIDE
The production of titanium metal accounts for only 5 percent of annual titanium mineral consumption; the
rest goes to the titanium pigment industry. Pigments are produced using either asulfate processor a
more environmentally acceptable carbo-chlorination process (described below) that converts TiO2 into
TiCl4. The latter process also supplies the TiCl4 necessary for the production of titanium metal.
Environmental and economic constraints dictate that the ore feed stocks converted by carbo-chlorination
processes now in use contain greater than 90 percent TiO2. Only natural rutile meets this requirement, but
ilmenite can be upgraded through combinations of pyrometallurgical and hydrometallurgical techniques to
produce a synthetic rutile of 90 to 93 percent TiO2. In addition, titaniferous magnetite ores can be smelted
to producepig ironand titanium-rich slags. Rutile, leucoxene, synthetic rutile, and slag can then be
mixed to provide a feed stock of more than 90 percent TiO 2 for the chlorination process.
In the first step of this process, the oxide ores are reacted with chlorine in a fluidized bed of petroleum
coke. Oxygen combines with carbon (C) in the coke to produce carbon monoxide(CO) andcarbon
dioxide(CO2), while the titanium and chlorine react to form a gaseous TiCl4, as in the following reaction:
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(TheXand Yrepresent variable quantities whose ratio depends on the reaction temperature, which varies
between 850 and 1,000 C [1,550 and 1,800 F].) The raw TiCl 4 is cleaned of fine particles of entrained
coke and titanium ore, and then it is liquified and passed through a distillation column to remove volatile
impurities of both high and lowboiling points. Vanadium oxychloride, an impurity with a boiling pointsimilar to TiCl4, is stripped from the product stream by reaction withmineral oil. The TiCl4 is then
redistilled to remove other impurities in a reflux distillation column. This process produces TiCl4 of a purity
exceeding 99.9 percent. Since any contaminants in the TiCl4 would later be reduced along with the
titanium metal, high-quality TiCl4 must be produced to achieve high-quality metal.
HEAT TREATMENT OF TITANIUM
HEAT TREATMENT OF TITANIUM
Titaniumheat treating is the industrial process of applying extremely high temperatures to
titanium so that the metal becomes more workable for manufacturing
purposes.Annealingand stress relieving are the two most common types of titanium heat
treating used today.
Annealing is the titanium heat treating method that serves mainly to make the titanium resist
fracture while increasing its ductility, or ability to be stretched into thin wire. The stress
relieving method of titanium heat treating, on the other hand, is used mostly to reduce the
amount of stress the titanium undergoes while being welded or formed.
Titanium often requires either annealing or stress relieving. Titanium that is not stress
relieved may crack after being welded or formed, while titanium meant for extensive
machine processing usually will not hold up to such heavy processing without first being
annealed. Temperatures as high as 1100 degrees Fahrenheit (593 degrees Celsius) for
stress relieving and 1450 degrees Fahrenheit (788 degrees Celsius) for annealing are not
uncommon in titanium heat treating.
Contamination is a crucial issue in titanium heat treating. Fabrication shops often have
separate areas for titanium since titanium is especially prone to contamination from air,
moisture, dust, and grease. Other high-performance metals, such asstainless steeland
nickel-base alloys do not require as strict attention to cleanliness as they are not as
sensitive as titanium to contamination while being formed or welded.
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It is important to note that pure elemental titanium is rarely used in modern manufacturing
as it is a rather soft metal on its own. Titanium alloys, mixtures of titanium with other metals,
allow for maximum hardening properties. However, each particulartitanium alloywill
respond differently to the titanium heat treating process.
The National Aeronautics and Space Administration's (NASA) firstSpace Shuttlehelped the
public become more aware of the use of titanium alloys and titanium heat treating as the
Shuttle used titaniumheat shieldinsulation tiles for the ability to remain strong in high
temperatures. Since the firstSpace Shuttle, NASA continued to incorporate titanium alloys
in their designs because of their non-melting, strong properties. Manufacturers of quality
swords and knives also rely on the strength of titanium alloys. Titanium alloys are even
stronger for their weight than steel. Titanium alloys are also resistant to corrosives such as
acids, solvents and bases.
APPLICATION OFTITANIUM
Aerospace Applications
Since the advent of the jet engine, titanium has been used in new alloys and production
techniques to meet ever tighter standards for high-temperature performance, creep resistance,strength, and metallurgical structure.
Through triple melting, or in some cases, electron beam cold hearth melting, the highest qualitytitanium metal alloys are achieved. These alloys are used in aerospace applications such as
engines and airframes.
Jet Engines
Titanium is used for critical jet engine rotating applications. In the newest technology jet
engines, wide chord titanium fan blades increase efficiency while reducing noise.
Airframes
In the airframe structural market, innovative alloys replace steel and nickel alloys in landing gear
and nacelle applications. These substitutions enable airframe manufacturers to save weight and
improve aircraft efficiency.
Aircraft quality plate and sheet are hot-rolled from forged slab. To achieve critical plate flatnessvacuum creep flattening is used. Superplastic forming/diffusion bonding has led to increased use
of titanium alloy sheet in new airframe designs.
Aircraft quality strip, in commercially pure grades and beta alloys is produced in coil form with
continuous vacuum annealing assuring extremely low hydrogen content.
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With each new design, commercial aircraft manufacturers increase the use of titanium in
airframes.
Industrial Applications
The uses for titanium in industry are growing faster than ever before as more and more engineersare discovering it can reduce lifecycle costs across a broad range of equipment and processes.
Titanium has an exceptionally high strength to weight ratio. Titanium's favourable density
(approximately half that of ferrous and nickel based metals) means that when equipment costsare calculated on a per unit area of measure basis, rather than per pound, the differential cost of
material required narrows dramatically. In other words, about half as much titanium is required
to do the same job, based on strength, or the same weight of titanium will go twice as far. Further
closing the gap, when applied properly, titanium requires no corrosion allowance; pressure andstructural requirements for the system are the only criteria for specifying wall thickness. Any
remaining higher up front costs are almost always recouped in multiple due to increased
production time and reduced maintenance.
Titanium forms a very tenacious surface oxide layer, which is an outstanding corrosion inhibitor.
In many harsh environments it can outlast competing materials as much as 5:1. Lower failurerates translate to less downtime, reduced maintenance and total lower cost. As a result, titanium
has found a home in numerous industries ranging from power generation to chemical processing
to desalination plants.
Power Generation
In power generating plants, where saline, brackish or polluted waters are used as the coolingmedium, titanium thin wall condenser tubing will last for the life of the condenser (with a 40-
year warranty against failure under proper conditions) and eliminate the need for a corrosionallowance.
Chemical Processing
Many chemical processing operations specify titanium to increase equipment life. It offers
lifecycle cost advantages over copper, nickel and stainless steel grades, while providing initial
cost advantages over materials such as high nickel alloys, tantalum and zirconium.
Petroleum
In petroleum exploration and production, titanium pipe's light weight and flexibility make it anexcellent material for deep sea production risers. In addition, titanium's immunity to attack by
sea water makes it the preferred material for topside water management systems. It is used on
existing platforms in the North Sea and many more projects are in the planning stages. And sinceit shows virtually no corrosion in salt water, titanium is also the material of choice in
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desalination plants worldwide.
Other Industries
Titanium alloys are used in dozens of other industrial purposes, such as flue gas desulphurisation
for pollution control, PTA plants for polyester production, pressure vessels, heat exchangers, andhydrometallurgial autoclaves. Each grade is tailored to specific operating conditions,
emphasizing strength for different pressures, alloy content for different corrosive agents and
ductility for different fabrication requirements.
Emerging Applications
Pursuing, developing and supporting new uses for titanium is a priority for the titanium industry.This includes help for companies that are developing new uses for titanium, by providing
dependable metal supply, advanced metallurgical design and expertise, and in some cases capital
support.
Computer Industry
In the computer industry, titanium is a promising substrate for hard disk drives. Compared toaluminium, which is the primary material currently used, titanium provides significant
advantages. Its non-magnetic properties prevent interference with the data storage process; its
ability to withstand heat allows higher temperatures during the coating process, which improvesmanufacturing rates; and the purity of titanium permits closer read/write head tolerances,
increasing disk capacity.
Automotive Industry
In the automotive industry, uses are being developed for titanium in the automotive/motorcycleafter markets and racing market. Engine parts such as connecting rods, wrist pins, valves, valveretainers and springs, rocker arms and camshafts, to name a few, lend themselves to fabrication
from titanium, because it is durable, strong, lightweight and resists heat and corrosion. While
titanium initially may be more expensive for these applications, designs that exploit its uniquecharacteristics yield parts that more than pay for themselves with better performance and a
longer life.
An all-titanium exhaust system is also being developed to reduce weight and increase longevity.
Use of titanium on production vehicles is also being evaluated for engine parts to improveefficiencies and suspension springs to increase interior space.
Geothermal Power
There are new opportunities in geothermal power generation, where highly caustic steamreleased from the earth is captured to generate electricity. The low lifecycle cost of titanium in
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these applications provides significant savings compared to competing materials.
Composites
Titanium is being widely used in metal matrix composites. As the cost of fabricating these
exceptionally strong, lightweight components declines, their popularity and the utilization oftitanium will grow.
Specialised Applications
Promoting unique, non-traditional uses for titanium Titanium's unique combination of attributes -
light weight, high strength, biocompatibility, and durability in extreme environments - make it an
excellent material for a variety of non-traditional applications.
Human Implants
Titanium is completely inert to human body fluids, making it ideal for medical replacement
structures such as hip and knee implants. Titanium actually allows bone growth to adhere to the
implants, so they last longer than those made of other materials. Reconstructive titanium plates
and mesh that support broken bones are also commonly used today.
Armour Applications
High strength-to-weight ratio and superior ballistic properties make titanium well suited forarmour applications. Used as protective armour on personnel carriers and tanks, it makes the
vehicles much lighter, increasing mobility of the force. Personal armour vests and helmets for
police made from titanium are far lighter and more comfortable than those made from competingmaterials.
Other Applications
Titanium is also now found in a wide variety of consumer products such as jewellery, watch
cases, eyeglasses, bicycles and clocks. The golf industry has found that lightweight titanium club
heads can be bigger than those made of steel, enlarging the "sweet spot" of the club and thusincreasing distance and accuracy.
CONCLUSION
Titanium is the second most abundant transition metal on Earth (6320 ppm) and plays
a vital role as a material of construction because of its:
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Excellent Corrosion Resistance
High Heat Transfer Efficiency
Superior Strength-To-Weight Ratio
For example, when it's alloyed with 6% aluminum and 4% vanadium, titanium hashalf the weight of steel and up to four times the strength.
Whilst a biological function in man is not known, it has excellent biocompatibility--
that is the ability to be ignored by the human body's immune system--and an extreme
resistance to corrosion. Titanium is now the metal of choice for hip and knee
replacements.
REFERENCE
1. M. Hansen, K. Anderko: Constitution ofBinaryAlloys,McGraw-Hili, New York 1958.
2. U. Zwicker: Titanund TItanlegienmgen, SpringerVerlag,Berlin 1974.
3. The Economics ofTitanium, 3rd. ed., Roskill InformationService Ltd., London 1980.
4. K. Riidinger: "TItan", in C. Rohrbach (ed.): WerkstofJe,
erforscht, gepriift, verarbeitet, TechnischewissenschaftlicheVortrage auf der Industrieausstellung,
Colloquiurn-Vlg., Berlin 1971, pp. 129-172.
5. H. H. Weigand: "TItan und TItanlegierungen", StahlEisen 80 (1960) 174-182,301-309.6. K. Riidinger: "TItan und TItanlegierungen - Moderne
Werkstoffe - Auswahl - Prfifung - Anwendung- Obersichten iiber Sondergebiete der
Werkstoffiechnik fur Studium und Praxis", Z. Werkstofftech.
9 (1978) 181-189, 214-218.7. Atomic Energy Commission (ed.): The Reactor
Handbook, vol. 1, AECD 3645, 1955, p. 352.8.A D. Schelberg, M. B. Sampson,A C. G. Mitchell,
Phys. ReI( 74 (1948) 1239.9. 1. S. V. Allen, M.l. Pool, 1. D. Kurbatov, L. L. Quill,Phys. Rev. 60 (1941) 425-429.
10. G. T Seaborg, 1. Pearlman,Rev. Mod. Phys. 20(1948) 585-667.
11. 1. Seren, H. N. Friedlander, S. H. Turkel, Phys. Rev.72 (1947) 888-901.
12. H. Walke, E. 1. Williams, G. R. Evans, Proc. Soc.
London Ser. A 171 (1939) 360-382.13. T. H. Schofield, Proc. Phys. Soc. London Sect. B 67(1954) 845-847.
14. K. D. Deardorff, E. T. Hayes,J. Met. 8 (1956) 509511.
15.A D. McQuillan, M. K. McQuillan: Titanium, Butterworth,London 1956.
16. G. Hagg, Z. Phys. Chell/. Abt. B 11 (1931) 433-454.17. S. Koncz, S. Szanto, H. Waldhauser,Natunvissenschaften42 (1955) 368-369.
18.A. D. McQuillan, Proc. Soc. London Ser. A 204(1950) 309-323. .
19. 1. Backhurst,J. Iron Steel Inst. London 198 (1968)124-134.
20. B. W. Levinger, Trans. Am. Inst. Min. Metall. Pet.
Eng. 197 (1953) 195.
21. H. T. Clark, Trans. Alii. Inst. Min. Metall. Pet. Eng.
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185 (1949) 588-589.
22. 1. M. Blocher, 1. E. Campbell,J. Am. Chem. Soc. 71(1949) 4040-4042.
23. P. Schiiler,DEW-Tech.Ber. 7 (1967) 5-12.Titanium
24. K. Bungardt, K. Riidinger,Z. Metallkd. 52 (1961)120-135.
25. K. Bungardt, K.Riidinger,Metall (Berlin) 14 (1960)988-994.
26. K. Riidinger: "TItan", in E. Rabald, D. Behrens(eds.):DECHEMA-Werkstoff-Tabelle, PhysikalischeEigenschaften, Deutsche Gesellschaft fOr ApParatewesen,FrankfurtlM. 1966.
27. R.. G. Netzel, 1. R. Dillinger, Proc. Int. Con[. Low
Temp. Phys. 7th 1961, 389-391.
28. W. Spyra,DEW-Tech. Ber. 5 (1965) 20-24.
29. F. R. Brotzen, E. L. Harmon, 1r.,A R.. Troiano,Trans. Am. Inst. Min. Metall. Pet. Eng. 203 (1955)414.
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titanium processing,
preparation of the ore for use in various products.
Titanium (Ti) is a soft, ductile, silvery gray metal with amelting pointof 1,675 C (3,047 F). Owing to the
formation on its surface of an oxide film that is relatively inert chemically, it has excellent corrosion
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resistance in most natural environments. In addition, it is light in weight, with a density (4.51 grams per
cubic centimetre) midway between aluminum and iron. Its combination of low density and high strength
gives it the most efficient strength-to-weight ratio of common metals for temperatures up to 600 C
(1,100 F).Because its atomic diameter is similar to many common metals such as aluminum, iron, tin, and
vanadium, titanium can easily be alloyed to improve its properties. Like iron, the metal can exist in two
crystalline forms: hexagonal close-packed (hcp) below 883 C (1,621 F) and body-centred cubic (bcc) at
higher temperatures up to its melting point. This allotropic behaviour and the capacity to alloy with many
elements result in titanium alloys that have a wide range of mechanical and corrosion-resistant properties.
Although titanium ores are abundant, the high reactivity of the metal with oxygen, nitrogen, and hydrogen
in the air at elevated temperatures necessitates complicated and therefore costly production and
fabrication processes.
History
Titanium ore was first discovered in 1791 in Cornish beach sands by an English clergyman, William
Gregor. The actual identification of the oxide was made a few years later by a German chemist, M.H.
Klaproth. Klaproth gave the metal constituent of this oxide the name titanium, after the Titans, the giants
ofGreek mythology.
Pure metallic titanium was first produced in either 1906 or 1910 byM.A. HunteratRensselaer
Polytechnic Institute(Troy, N.Y., U.S.) in cooperation with the General Electric Company. These
researchers believed titanium had a melting point of 6,000 C (10,800 F) and was therefore a candidate
for incandescent-lamp filaments, but, when Hunter produced a metal with a melting point closer to 1,800
C (3,300 F), the effort was abandoned. Nevertheless, Hunter did indicate that the metal had some
ductility, and his method of producing it by reacting titanium tetrachloride (TiCl4) with sodium under
vacuum was later commercialized and is now known as the Hunter process. Metal of significant ductility
was produced in 1925 by the Dutch scientists A.E. van Arkel and J.H. de Boer, who dissociated titanium
tetraiodide on a hot filament in an evacuated glass bulb.
In 1932William J. Krollof Luxembourg produced significant quantities of ductile titanium by combining
TiCl4 with calcium. By 1938 Kroll had produced 20 kilograms (50 pounds) of titanium and was convinced
that it possessed excellent corrosion and strength properties. At the start ofWorld War IIhe fled Europe
and continued his work in theUnited Statesat the Union Carbide Company and later at the U.S. Bureau
of Mines. By this time, he had changed thereducing agentfrom calcium to magnesium metal. Kroll is
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now recognized as the father of the modern titanium industry, and theKroll processis the basis for most
current titanium production.
A U.S. Air Force study conducted in 1946 concluded that titanium-based alloys were engineering
materials of potentially great importance, since the emerging need for higher strength-to-weight ratios injetaircraftstructures and engines could not be satisfied efficiently by either steel or aluminum. As a
result, the Department of Defense provided production incentives to start the titanium industry in 1950.
Similar industrial capacity was founded in Japan, the U.S.S.R., and theUnited Kingdom. After this
impetus was provided by theaerospace industry, the ready availability of the metal gave rise to
opportunities for new applications in other markets, such as chemical processing, medicine, power
generation, and waste treatment.
Ores
Titanium is the fourth most abundant structural metal on Earth, exceeded only by aluminum, iron, and
magnesium. Workablemineral depositsare dispersed worldwide and include sites in Australia, the
United States, Canada,South Africa,Sierra Leone, Ukraine, Russia, Norway, Malaysia, and several
other countries.
The predominate minerals are rutile, which is about 95 percent titanium dioxide(TiO2), and ilmenite
(FeTiO3), which contains 50 to 65 percent TiO 2. A third mineral, leucoxene, is an alteration of ilmenite from
which a portion of the iron has been naturally leached. It has no specific titanium content. Titanium
minerals occur in alluvial and volcanic formations. Deposits usually contain between 3 and 12 percent
heavy minerals, consisting of ilmenite, rutile, leucoxene, zircon, and monazite.
Mining and concentrating
Although workable known reserves of rutile are diminishing, ilmenite deposits are abundant. Typical
mining is by open pit. A suction bucket wheel on a floating dredge supplies a mineral-rich sand to a set of
screens called trommels, which remove unwanted materials.
Typically, the minerals are separated from waste material bygravity separationin a wet spiral
concentrator. The resulting concentrates are separated by passing them through a complex series of
electrostatic, magnetic, and gravity equipment.
Extraction and refining
TiCl4
The production of titanium metal accounts for only 5 percent of annual titanium mineral consumption; the
rest goes to the titanium pigment industry. Pigments are produced using either asulfate processor a
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more environmentally acceptable carbo-chlorination process (described below) that converts TiO2 into
TiCl4. The latter process also supplies the TiCl4 necessary for the production of titanium metal.
Environmental and economic constraints dictate that the ore feed stocks converted by carbo-chlorination
processes now in use contain greater than 90 percent TiO2. Only natural rutile meets this requirement, butilmenite can be upgraded through combinations of pyrometallurgical and hydrometallurgical techniques to
produce a synthetic rutile of 90 to 93 percent TiO2. In addition, titaniferous magnetite ores can be smelted
to producepig ironand titanium-rich slags. Rutile, leucoxene, synthetic rutile, and slag can then be
mixed to provide a feed stock of more than 90 percent TiO 2 for the chlorination process.
In the first step of this process, the oxide ores are reacted with chlorine in a fluidized bed of petroleum
coke. Oxygen combines with carbon (C) in the coke to producecarbon monoxide(CO) andcarbon
dioxide(CO2), while the titanium and chlorine react to form a gaseous TiCl4, as in the following reaction:
(TheXand Yrepresent variable quantities whose ratio depends on the reaction temperature, which varies
between 850 and 1,000 C [1,550 and 1,800 F].) The raw TiCl 4 is cleaned of fine particles of entrained
coke and titanium ore, and then it is liquified and passed through a distillation column to remove volatile
impurities of both high and lowboiling points. Vanadium oxychloride, an impurity with a boiling point
similar to TiCl4, is stripped from the product stream by reaction withmineral oil. The TiCl4 is then
redistilled to remove other impurities in a reflux distillation column. This process produces TiCl 4 of a purity
exceeding 99.9 percent. Since any contaminants in the TiCl4 would later be reduced along with the
titanium metal, high-quality TiCl4 must be produced to achieve high-quality metal.
Titanium sponge
In the production of titaniumpigments, the TiCl4 would be reoxidized to TiO2, but, in the production of
titanium metal, it is reduced with either sodium (Na) in the Hunter process or with magnesium (Mg) in
theKroll process:
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These reactions take place in large, sealed steel vessels at approximately 800 to 1,000 C (1,450 to
1,800 F) in an inert argon atmosphere to avoid contamination of the final product by air or moisture. Both
processes produce titanium in the form of a highly porous material called sponge, with the salts NaCl or
MgCl2 entrapped in the pores. The sponge is crushed, and the metal and salts are separated by either a
dilute acid leach or by high-temperaturevacuum distillation. The salts are recycled throughelectrolytic
cellsto produce sodium or magnesium for reuse in metal reduction and chlorine for reuse in chlorination
of the ore.
A different process that offers hope for an improved and simplified method of producing titanium metal is
the direct electrowinning of titanium from TiCl4 in fused chloride salt baths. In this case, titanium sponge
collects on a steel cathode, and chlorine gas is given off at the carbon anode. The required use in this
process of high-melting-point salts, combined with the need for maintaining an inert environment, present
major technical and economical hurdles that have to be overcome in order to achieve commercial status.
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Titaniumingot
PRODUCTION OF TITANIUM SPONGE
The large heat of formation of titanium dioxide(945.4 kllmol) combined with the
highsolubilityofoxygen in titanium at high temperatureshas so far made it impossible to
developan economic process for the directreduction of titanium dioxide to low-oxygen titaniumetal. The standard industrial processesfor the production of titanium metal aretherefore based
on titanium halides.
Crude TiCl 4
Purification ofcrude titanium tetrachloride
TITANIUM SPONGE
Titaniumsponge is a porous form of titanium that is created during the first stage of
processing. In its natural form, titanium is widely available within the earths crust. Afterbeing extracted, it is processed to remove excess materials and convert it into a usable,
although costly, product.
The conversion process used with raw titanium is called theKroll process. This is a
complex, multistage, batch process that requires very high heat and specialized equipment.
The Kroll process converts the metal oxide into chloride by passing the metal over
extremely hot rutile or ilmenite and carbon to create titanium tetrachloride. These chemicals
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are separated through a process calledfractional distillationin which the components of a
mixture are separated based on their different boiling points.
The material resulting from the Kroll process is titanium sponge. This sponge is then
subjected to leaching or heatedvacuum distillationto remove further impurities. The
remaining materials in the sponge are jack hammered, crushed, pressed and melted to
remove even more impurities.
In the next stage of the process, the titanium sponge is melted. It is then put through a
process of fractional distillation to remove excess liquid and combined with molten
magnesium, ironaluminum,vanadiumormolybdenumandargonin a very hot furnace. The
purpose of combining these materials is to add strength and stability to the titanium sponge
and create a pliable metal alloy.
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At this point, the converted titanium sponge is ready for fabrication. Some firms sell titanium
sponge as a finished product, while others complete the conversion process internally. The
sponge can now be formed into mill shapes such as a bar, plate, sheet or tube. These
products are then shipped to different mills and fabricators to created finished products forcommercial use.
Titanium is used to produce parts for jet engines, missiles, orthopedicimplants, jewelry and
mobile telephones. The most importantproperties of titaniumare its low density and high
level of corrosion resistance. Although six times as expensive as steel, titanium is very
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resistant to corrosion in both sea water and chlorinated water, making it popular with a wide
range of manufacturers.
Titanium was first discovered and documented by William Gregor in 1791. Although purified
titanium is quite costly, it is available in its basic form, in almost all living creatures. It can
also be found in rocks, water and soil. The process of extracting it and combining it with
alloys is what makes the procedure complex and expensive.
Titanium is relatively common in the Earth's crust, making up about 0.57% (the 9th most
common element), but extracting it from its ores -- the minerals Rutile (TiO2), Ilmenite
(FeTiO3) and Sphene (CaTiSiO5) -- can be pricey, due to the high heat input required.
Elemental titanium was only first isolated in its pure form in 1910, when Matthew A. Hunter
heated TiCl4withsodiumat 800 C (1472 F).
There are 38 common types of titanium alloy, but the typical mix is 90% titanium, 6%aluminum, and 4% vanadium. This mix is called Grade 5. There are titanium grades 1
through 38, with 38 being the most recently invented. The grades do not indicate strength or
anything, they are just used for easy reference, though the earlier grades were the first to
be commonly produced. Grade 5 titanium is also known as Titanium 6AL-4V, which is
considered suitable for military use. This grade of titanium alloy is stable in applications up
to 400 C (752 F), with the stereotypical application being inaircraftturbines, which rotate
very quickly and get very hot.
Besides seeing widespread use in military hardware, titanium alloy can be found in the
connecting rods in high-end automobiles like Porsche and Ferrari. The presence of these
metals is part of what can make these cars so expensive, but also reliable and capable ofhigh speeds. A similar high-end material found in premium products iscarbonfiber.
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HEAT TREATMENT OF TITANIUM
Titaniumheat treating is the industrial process of applying extremely high temperatures to
titanium so that the metal becomes more workable for manufacturing
purposes.Annealingand stress relieving are the two most common types of titanium heat
treating used today.
Annealing is the titanium heat treating method that serves mainly to make the titanium resist
fracture while increasing its ductility, or ability to be stretched into thin wire. The stress
relieving method of titanium heat treating, on the other hand, is used mostly to reduce the
amount of stress the titanium undergoes while being welded or formed.
Titanium often requires either annealing or stress relieving. Titanium that is not stress
relieved may crack after being welded or formed, while titanium meant for extensive
machine processing usually will not hold up to such heavy processing without first being
annealed. Temperatures as high as 1100 degrees Fahrenheit (593 degrees Celsius) for
stress relieving and 1450 degrees Fahrenheit (788 degrees Celsius) for annealing are not
uncommon in titanium heat treating.
Contamination is a crucial issue in titanium heat treating. Fabrication shops often have
separate areas for titanium since titanium is especially prone to contamination from air,
moisture, dust, and grease. Other high-performance metals, such asstainless steeland
nickel-base alloys do not require as strict attention to cleanliness as they are not as
sensitive as titanium to contamination while being formed or welded.
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It is important to note that pure elemental titanium is rarely used in modern manufacturing
as it is a rather soft metal on its own. Titanium alloys, mixtures of titanium with other metals,
allow for maximum hardening properties. However, each particulartitanium alloywill
respond differently to the titanium heat treating process.
The National Aeronautics and Space Administration's (NASA) firstSpace Shuttlehelped the
public become more aware of the use of titanium alloys and titanium heat treating as the
Shuttle used titaniumheat shieldinsulation tiles for the ability to remain strong in high
temperatures. Since the firstSpace Shuttle, NASA continued to incorporate titanium alloysin their designs because of their non-melting, strong properties. Manufacturers of quality
swords and knives also rely on the strength of titanium alloys. Titanium alloys are even
stronger for their weight than s
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