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Titanium was discovered in 1791 by the English clergyman William Gregor (1761-
1817). Gregor was not a professional scientist, but studies minerals as a hobby. On
one occasion, he attempted a chemical analysis of the mineral ilmenite and found
a portion that he was unable to classify as one of the existing elements. He wrote
a report on his work, suggesting that the unidentified material was a new
element. But he went no further with his own research. It was not until four years
later that German chemist Martin Heinrich Klaproth returned to an investigation of
ilmenite and isolated the new element. He suggested the name of titanium for the
element in honor of the Titans, mythical giants who ruled the Earth until they
were overthrown by the Greek gods. Titanium is corrosion resistant, very strong
and has a high melting point. It has a relatively low density (about 60% that of
iron). It is also the tenth most commonly occurring element in the Earth's crust.
That all means that titanium should be a really important metal for all sorts of
engineering applications. In fact, it is very expensive and only used for rather
specialized purposes.
Titanium-Occurrence
Titanium is in the earth's crust with an abundance estimated at about 0.63%. The
most common sources of titanium are ilmenite, rutile, and titanite. The metal is
often obtained commercially as a byproduct of the refining of iron ore. It can be
produced from its ores by electrolyzing molten titanium chloride (TiCl4): TiCl4 —
electric current → Ti + 2Cl2, or by treating hot titanium chloride with magnesium
metal: 2Mg + TiCl4 → Ti + 2MgCl2.
Titanium-Properties
Titanium exists in two allotropic forms, one of which is a dark gray, shiny metal.
The other allotrope is a dark gray amorphous powder. The metal has a melting
point of 3,051°F (1,677°C), a boiling point of 5,931°F (3,277°C), and a density of
4.6 g/cm3. At room temperature, titanium tends to be brittle, although it becomes
malleable and ductile at higher temperatures. Chemically, titanium is relatively
inactive. At moderate temperatures, it resists attack by oxygen, most acids,
chlorine, and other corrosive agents. Titanium is known as a transition metal on
the periodic table of elements denoted by the symbol Ti. It is a lightweight, silver-
gray material with an atomic number of 22 and an atomic weight of 47.90. It has a
density of 4510 kg/m3, which is somewhere between the densities of aluminum
and stainless steel. It has a melting point of roughly 3,032°F (1,667°C) and a
boiling point of 5,948°F (3,287 C). It behaves chemically similar to zirconium and
silicon. It has excellent corrosion resistance and a high strength to weight ratio.
While titanium is relatively abundant, it continues to be expensive because it is
difficult to isolate. The leading producers of titanium concentrates include
Australia, Canada, China, India, Norway, South Africa, and Ukraine.
The problem is that titanium forms carbide, TiC, if it is heated with carbon,
so you don't get the pure metal that you need. The presence of carbide
makes the metal brittle.
• Other problems
The titanium is produced by reacting titanium (IV) chloride, TiCl4 - NOT the
oxide - with either sodium or magnesium. That means that you first have to
convert the oxide into the chloride. That in turn means that you have the
expense of the chlorine as well as the energy costs of the conversion.
Traces of oxygen or nitrogen in the titanium tend to make the metal brittle.
The reduction has to be carried out in an inert argon atmosphere rather than
in air. That also adds to costs.
RUTILE:
Rutile is a mineral composed primarily of Titanium dioxide,TiO2.
Rutile is the most common natural form of TiO2 .Three rarer polymorphs of
TiO2 are known:
anatase (sometimes known by the obsolete name 'octahedrite'), a tetragonal
mineral of pseudo-octahedral habit;
brookite, an orthorhombic mineral and;
eclogites.
Rutile has among the highest refractive indices of any known mineral and
also exhibits high dispersion.
Natural rutile may contain up to 10% iron and significant
amounts of niobium and tantalum. Rutile derives its name from the Latin rutilus,
red, in reference to the deep red color observed in some specimens when viewed
by transmitted light. This picture is acicular crystals of rutile protruding from a
quartz crystal.
, Rutile in quartz
Crystal structure: The unit cell of rutile. Ti atoms are grey;
Rutile has a body centered tetragonal unit cell, with unit cell parameters
a=4.584Å, and c=2.953Å. It therefore has a density of 4240 kg/m3. The titanium
cations have a co- ordination number of 6 meaning they are surrounded by an
octahedron of 6 oxygen atoms.
Synthetic rutile: Synthetic rutile was first produced in 1948 and was sold under a
variety of names. Very pure synthetic rutile is transparent and almost colorless
(slightly yellow) in large pieces. Synthetic rutile can be made in a variety of colors
by doping, although the purest material is almost colorless. The high refractive
index gives an adamantine lusture and strong refraction that leads to a diamond-
like appearance. The near-colorless diamond substitute is sold under the name
Titania, which is the old-fashioned chemical name for this oxide. However, rutile
is seldom used in Jewellery because it is not very hard (scratch-resistant),
measuring only about 6 on the mohs hardness scale. It has a high refractive index
(2.62-2.90)and a dispersion 6.5 times that of diamond which gives it an
exceptional display of fire, and far too much to be diamond. Unlike diamond,
Synthetic Rutile exhibits doubling of the back facets. Even with a bluish film
added to the stone, some yellow body colour always remains.
The ore rutile (impure titanium (IV) oxide) is heated with chlorine and coke at a
temperature of about 900°C.
Reaction:TiO2+2Cl2+2C→TiCl4+2CO
Other metal chlorides are formed as well because of other metal compounds in
the ore. Very pure liquid titanium(IV) chloride can be separated from the other
chlorides by fractional distillation under an argon or nitrogen atmosphere, and is
stored in totally dry tanks. Titanium(IV) chloride is a typical covalent chloride. It is
a colorless liquid which fumes in moist air due to reaction with water to give
titanium (IV) oxide and fumes of hydrogen chloride. Everything has to be kept very
dry to prevent this happening.
1. Reduction by sodium
The titanium(IV) chloride is added to a reactor in which very pure sodium has been
heated to about 550°C - everything being under an inert argon atmosphere. During
the reaction, the temperature increases to about 1000°C.The product formed is
called titanium sponge.
Reaction: TiCl4+4Na→Ti+4NaCl
After the reaction is complete, and everything has cooled (several days in total -
an obvious inefficiency of the batch process), the mixture is crushed and washed
with dilute hydrochloric acid to remove the sodium chloride.
2. Reduction by magnesium
The method is similar to using sodium, but this time the reaction is:
TiCl4+ 2Mg→Ti+2MgCl2
The magnesium chloride is removed from the titanium by distillation under very
low pressure at a high temperature
Melting:
Titanium sponge is melted under argon to produce ingots.
C Fractionation
TiO2 +Cl2 TiCl4 + CO2
(with FeCl3 impurity) TiCl4
Red Heat molten Mg or Na 800
Under Ar
Fused Ti sponge heat Spongy metallic Ti
Ti ingots (free of Mg) (impurity of Mg and
MgCl2
Under Ar 1000⁰C
Kroll Process
Company Technology Route Grade Installed Cap.,TPA
Travancore NL/Trioxide(Sulpha Anatase 24,500
Titanium Products te)
Ltd.
Kolmak Chemicals Indigenous(Sulphat Anatase 2,400
Ltd. e)
Kerala Minerals & KMML(Chloride) Rutile 22,000
Metals Ltd.
Kilburn Chemicals (Sulphate) Anatase 3,960
Ltd.
Total Capacity 52,800
Al2O3 2.9
quantities of magnesium and manganese and the full chemical formula can be
expressed as (Fe, Mg, Mn, Ti) O3. Ilmenite forms a solid solution with geikilite
(MgTiO3) and pyrophanite (MnTiO3) which are magnesium and manganiferous end-
members of the solid solution series.
The upgrading reaction can be carried out both under atmospheric or pressure
leaching conditions. However, all of these methods mentioned above have the
disadvantages of high energy consumption and corrosive effect due to the use of
high temperature and high concentrated acid in the upgrading process. Therefore,
it is imperative to develop a new and cleaner production process for upgrading of
ilmenite.
In the present study, a new process for the decomposition of ilmenite has been
proposed. In this process, ilmenite is decomposed in fluid medium of concentrated
KOH solution under atmospheric pressure and an intermediate with high in
titanium and low in iron is obtained by separation, which can be converted into
pigment grade titanium dioxide after further treatment. In comparison with the
conventional process of upgrading of ilmenite, this process requires relatively mild
reaction conditions and high decomposition rate of ilmenite can be fulfilled at
relatively low temperature under atmospheric pressure. Therefore, the energy
consumption of the new technology is lower than the existing those and may have
strong potential applications.
Experimental
Materials
The solid KOH was reagent grade and the deionized water was used in the
experiment. The ilmenite used as raw material to produce pigment grade titanium
dioxide through the sulfate method was supplied by the Yuxing Chemical and
Industrial Company (Shan Dong province, China). The ilmenite was dried, and
screened into four particle size fractions to examine the effect of particle size on
titanium extraction. The mineralogical analysis of the sample was carried out by
XRD and the result indicated that no other phases were identified except the
ilmenite phase.
Equipment
The batch reactor used in this study was a 300 ml SUS316 stainless steel container,
whose inner diameter is 60 mm, and equipped with a thermometer, a mechanical
stirrer and a reflux condenser. The reactor was heated by a heating furnace to
reach and maintain the desired temperature within ± 1 °C.
Procedure
All the experiments were conducted in batch. For each run, 160 g solid KOH and
the required amount of deionized water were first charged into the reactor. After
that, the reactor was heated under continuous stirring. When the temperature
reached the preset value and kept stable, a certain amount of ilmenite was added
to the reactor. Then, the mixture of the reactants was stirred at specific stirring
speed under atmospheric pressure.
The reaction of ilmenite with concentrated KOH solution led to the formation of
potassium titanate (K4Ti3O8) and iron oxide, and this could be described as follows:
The titanium extraction was calculated by dissolving the sample in HCl, and the
dissolution took place according to the following reaction:
After the complete dissolution of the sample, the chloride solution was filtered off
and analyzed for its titanium content, and then the extent of titanium extraction
was calculated
• Titanium dioxide is the most widely used white pigment because of its
brightness and very high refractive index (n = 2.7).
• Titanium dioxide is used to mark the white lines on the tennis courts of the
All England Lawn Tennis and Croquet Club, best known as the venue for the
annual grand slam tennis tournament The Championships, Wimbledon.
As a photocatalyst:
• Titanium dioxide, particularly in the anatase form, is a photocatalyst under
ultraviolet light. Recently it has been found that titanium dioxide, when
spiked with nitrogen ions, or doped with metal oxide like tungsten trioxide,
is also a photocatalyst under visible and UV light.
• The process occurs under ambient conditions very slowly, direct UV light
exposure increases the rate of reaction.
• The formation of photocyclized intermediate products, unlike direct
photolysis techniques, is avoided.
• Oxidation of the substrates to CO2 is complete.
• The photocatalyst is inexpensive and has a high turnover.
Other application:
It is also used by film and television companies as a substitute for snow when
filming scenes which require a winter setting.
Aerospace and marine:
• Due to their high tensile strength to density ratio high corrosion resistance
and ability to withstand moderately high temperatures without creeping,
titanium alloys are used in aircraft, armor plating, naval ships, spacecraft,
and missiles. For these applications titanium alloyed with aluminium,
vanadium, and other elements is used for a variety of components including
critical structural parts, fire walls, landing gear, exhaust ducts (helicopters),
and hydraulic systems.
• The SR-71 "Blackbird" was one of the first aircraft to make extensive use of
titanium within its structure, paving the way for its use in modern military
and commercial aircraft.To name a few the Boeing 777, the Boeing 747, the
Boeing 737, the Airbus A340, Airbus A330, and Airbus A320.
Industrial:
• Welded titanium pipe and process equipment (heat exchangers, tanks,
process vessels, valves) are used in the chemical and petrochemical
industries primarily for corrosion resistance.
Architectural:
• The Guggenheim Museum Bilbao and the Cerritos Millennium Library were
the first buildings in Europe and North America, respectively, to be sheathed
in titanium panels.
• Other construction uses of titanium sheathing include the Frederic C.
TITANIUM:
• Air frames
In the aerospace industry, titanium is mainly used in the form of the following
alloy compositions:
Pure titanium is used in the form of sheets, tubes, rods, and bars.
Precautions:
• Titanium can catch fire when a fresh, non-oxidized surface comes in contact
with liquid oxygen. Such surfaces can appear when the oxidized surface is
struck with a hard object, or when a mechanical strain causes the
emergence of a crack. This poses the possible limitation for its use in liquid
oxygen systems, such as those found in the aerospace industry.
.
What are "ores"?
Concentrating the ore: This simply means getting rid of as much of the unwanted
rocky material as possible before the ore is converted into the metal. A common
example of this involves froth flotation.
Titanium Ore: Any mineral from which titanium is extracted, principally ilmenite
(FeTiO3) and rutile (TiO2). Brazil, India, and Canada are major producers. Both
these ore minerals are found either in rock formations or concentrated in heavy
mineral sands.