Rutile

Rutile is a mineral composed primarily of

titanium dioxide (TiO2), and is the most
common natural form of TiO2. Other rarer
polymorphs of TiO2 are known including
anatase, akaogiite, and brookite.
 Rutile

General

Category Oxide minerals

Formula TiO2
(repeating unit)

Strunz classification 4.DB.05

Crystal system Tetragonal

Crystal class Ditetragonal

dipyramidal (4/mmm)
H-M symbol: (4/m 2/m
2/m)

Space group P42/mnm

Unit cell a = 4 5937 Å c =

Unit cell a 4.5937 Å, c
2.9587 Å; Z = 2

Identification

Color Reddish brown, red,

pale yellow, pale blue,
violet, rarely grass-
green; black if high in
Nb–Ta

Crystal habit Acicular to Prismatic

crystals, elongated and
striated parallel to
[001]

Twinning Common on {011}, or

{031}; as contact twins
with two, six, or eight
individuals, cyclic,
polysynthetic

Cleavage {110} good, {100}

moderate, parting on
{092} and {011}
 {092} and {011}

Fracture Uneven to sub-

conchoidal

Mohs scale hardness 6.0–6.5

Luster Adamantine to
submetallic

Streak Bright red to dark red

Diaphaneity Opaque, transparent in

thin fragments

Specific gravity 4.23 increasing with

Nb–Ta content

Optical properties Uniaxial (+)

Refractive index nω = 2.613, nε = 2.909

(589 nm)

Birefringence 0.296 (589 nm)

Pleochroism Weak to distinct

brownish red-green-
yellow
Dispersion Strong

Fusibility Fusible in alkali

carbonates

Solubility Insoluble in acids

Common impurities Fe, Nb, Ta

Other characteristics Strongly anisotropic

References [1][2][3][4]

Rutile has one of the highest refractive

indices at visible wavelengths of any
known crystal and also exhibits a
particularly large birefringence and high
dispersion. Owing to these properties, it
is useful for the manufacture of certain
optical elements, especially polarization
optics, for longer visible and infrared
wavelengths up to about 4.5 μm.

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. Rutile was first described in 1803
by Abraham Gottlob Werner.

Occurrence

Rutile output in 2005

Rutile is a common accessory mineral in
high-temperature and high-pressure
metamorphic rocks and in igneous rocks.

Thermodynamically, rutile is the most

stable polymorph of TiO2 at all
temperatures, exhibiting lower total free
energy than metastable phases of
anatase or brookite.[5] Consequently, the
transformation of the metastable TiO2
polymorphs to rutile is irreversible. As it
has the lowest molecular volume of the
three main polymorphs, it is generally the
primary titanium bearing phase in most
high-pressure metamorphic rocks, chiefly
eclogites.
Rutile in quartz

Within the igneous environment, rutile is

a common accessory mineral in plutonic
igneous rocks, though it is also found
occasionally in extrusive igneous rocks,
particularly those such as kimberlites
and lamproites that have deep mantle
sources. Anatase and brookite are found
in the igneous environment particularly
as products of autogenic alteration
during the cooling of plutonic rocks;
anatase is also found in placer deposits
sourced from primary rutile.

The occurrence of large specimen

crystals is most common in pegmatites,
skarns, and granite greisens. Rutile is
found as an accessory mineral in some
altered igneous rocks, and in certain
gneisses and schists. In groups of
acicular crystals it is frequently seen
penetrating quartz as in the fléches
d'amour from Graubünden, Switzerland.
In 2005 the Republic of Sierra Leone in
West Africa had a production capacity of
23% of the world's annual rutile supply,
which rose to approximately 30% in
2008.
Crystal structure

The unit cell of rutile. Ti atoms are gray; O atoms are

red.

Extended crystal structure of rutile

Rutile has a tetragonal unit cell, with unit
cell parameters a = b = 4.584 Å, and c =
2.953 Å.[6] The titanium cations have a
coordination number of 6, meaning they
are surrounded by an octahedron of 6
oxygen atoms. The oxygen anions have a
coordination number of 3, resulting in a
trigonal planar coordination. Rutile also
shows a screw axis when its octahedra
are viewed sequentially.[7]

Rutile crystals are most commonly

observed to exhibit a prismatic or
acicular growth habit with preferential
orientation along their c axis, the [001]
direction. This growth habit is favored as
the {110} facets of rutile exhibit the
lowest surface free energy and are
therefore thermodynamically most
stable.[8] The c-axis oriented growth of
rutile appears clearly in nanorods,
nanowires and abnormal grain growth
phenomena of this phase.

Uses and economic

importance

Acicular crystals of rutile protruding from a quartz

crystal
In large enough quantities in beach
sands, rutile forms an important
constituent of heavy minerals and ore
deposits. Miners extract and separate
the valuable minerals – e.g., rutile, zircon,
and ilmenite. The main uses for rutile are
the manufacture of refractory ceramic, as
a pigment, and for the production of
titanium metal.

Finely powdered rutile is a brilliant white

pigment and is used in paints, plastics,
paper, foods, and other applications that
call for a bright white color. Titanium
dioxide pigment is the single greatest
use of titanium worldwide. Nanoscale
particles of rutile are transparent to
visible light but are highly effective in the
absorption of ultraviolet radiation. The
UV absorption of nano-sized rutile
particles is blue-shifted compared to bulk
rutile, so that higher-energy UV light is
absorbed by the nanoparticles. Hence,
they are used in sunscreens to protect
against UV-induced skin damage.

Small rutile needles present in gems are

responsible for an optical phenomenon
known as asterism. Asteriated gems are
known as "star" gems. Star sapphires,
star rubies, and other "star" gems are
highly sought after and are generally
more valuable than their normal
counterparts.
Rutile is widely used as a welding
electrode covering. It is also used as a
part of the ZTR index, which classifies
highly weathered sediments.

Rutile, as a large band-gap

semiconductor, has in recent decades
been the subject of significant research
towards applications as a functional
oxide for applications in photocatalysis
and dilute magnetism [9]. Research
efforts typically utilize small quantities of
synthetic rutile rather than mineral-
deposit derived materials.

Synthetic rutile
Synthetic rutile was first produced in
1948 and is sold under a variety of
names. It can be produced from the
titanium ore ilmenite through the Becher
process. Very pure synthetic rutile is
transparent and almost colorless, being
slightly yellow, in large pieces. Synthetic
rutile can be made in a variety of colors
by doping. The high refractive index gives
an adamantine luster and strong
refraction that leads to a diamond-like
appearance. The near-colorless diamond
substitute is sold as "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.

As the result of growing research interest

in the photocatalytic activity of titanium
dioxide, in both anatase and rutile phases
(as well as biphasic mixtures of the two
phases), rutile TiO2 in powder and thin
film form is frequently fabricated in
laboratory conditions through solution
based routes using inorganic precursors
(typically TiCl4) or organometallic
precursors (typically alkoxides such as
titanium isopropoxide, also known as
TTIP). Depending on synthesis
conditions, the first phase to crystallize
may be the metastable anatase phase,
which can then be converted to the
equilibrium rutile phase through thermal
treatment. The physical properties of
rutile are often modified using dopants to
impart improved photocatalytic activity
through improved photo-generated
charge carrier separation, altered
electronic band structures and improved
surface reactivity.

See also
List of minerals

References
1. Handbook of Mineralogy .
2. Webmineral data .
3. Mindat.org .
4. Klein, Cornelis and Cornelius S.
Hurlbut, 1985, Manual of Mineralogy,
20th ed., John Wiley and Sons, New
York, pp. 304–05, ISBN 0-471-80580-
7.
5. Hanaor, D. A. H.; Assadi, M. H. N.; Li,
S.; Yu, A.; Sorrell, C. C. (2012). "Ab
initio study of phase stability in
doped TiO2" . Computational
Mechanics. 50 (2): 185–94.
arXiv:1210.7555 .
Bibcode:2012CompM..50..185H .
doi:10.1007/s00466-012-0728-4 .
6. Diebold, Ulrike (2003). "The surface
science of titanium dioxide" (PDF).
 Surface Science Reports. 48 (5–8):
53–229.
Bibcode:2003SurSR..48...53D .
doi:10.1016/S0167-5729(02)00100-
0 . Archived from the original (PDF)
on 2010-06-12.
7. "Rutile Structure" , Steven Dutch,
Natural and Applied Sciences,
University of Wisconsin – Green Bay.
8. Hanaor, Dorian A.H.; Xu, Wanqiang;
Ferry, Michael; Sorrell, Charles C.;
Sorrell, Charles C. (2012). "Abnormal
grain growth of rutile TiO2 induced
by ZrSiO4". Journal of Crystal
Growth. 359: 83–91.
arXiv:1303.2761 .
 Bibcode:2012JCrGr.359...83H .
doi:10.1016/j.jcrysgro.2012.08.015 .
9. Magnetism in titanium dioxide
polymorphs J. Applied Physics

External links

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