Subject Geology

Paper No and Title Crystallography and Mineralogy

Module No and Title Alumino-silicate Group

Module Tag Min X

Principal Investigator Co-Principal Investigator Co-Principal Investigator

Prof. Talat Ahmad Prof. Devesh K Sinha Prof. P. P. Chakraborty

Vice-Chancellor Department of Geology Department of Geology
Jamia Millia Islamia University of Delhi University of Delhi
University Delhi Delhi
Paper Coordinator Content Writer Reviewer
Prof. Naresh C. Pant Dr. Ashima Saikia Prof. Santosh Kumar
Department of Geology Department of Geology Department of Geology
University of Delhi University of Delhi Kumaun University
Delhi Delhi Nainital

Anchor Institute: Jamia Millia Islamia, Delhi

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 TABLE OF CONTENTS
1. Learning outcomes
2. The classification of alumino-silicates based on SiO4 tetrahedron
3. Structure and chemistry
3.1 Kyanite
3.2 Andalusite
3.3 Sillimanite
4 Crystallographic properties.
5 Physical properties
6 Optical properties
7. Occurrence
8. Use

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 1. Learning outcomes

After studying this module you shall be able to:

 To develop a basic understanding of chemical co-ordination leading to formation of

minerals with various structures.
 To develop the ability to identify minerals in hand-specimen and thin section
 To develop appreciation for the application of mineral science to everyday life.

2. The classification of alumino-silicates based on SiO4 tetrahedron

Silicon is known to be the second most abundant element after oxygen forming the Earth’s crust
and mantle. Silicate minerals predominate vast majority of rocks of the Earth’s crust as the Si-O
bond is considered to be stronger than any other bond prevalent amongst oxygen and any other
element. As the [SiO4] tetrahedral dominate silicate structures, the way it arranges itself within a
particular structure has long been the way of silicate classification. [SiO4] tetrahedral are either
isolated from each other or connected by corner sharing to other [SiO4] tetrahedra. The different
frameworks provided by variable corner sharing tetrahedra with other cations fitting into suitable
interstices provided by this frame work defines the various types of silicate structures This
framework of cations and [SiO4] tetrahedra is of prime importance in understanding the way in
which a mineral would adapt to changes in its physical and chemical environment. Many silicate
minerals also show substitution of Al for Si in the tetrahedron which is accompanied by
compensating replacement in cation content to maintain charge neutrality.
Based on [SiO4] tetrahedra linkage the alumonisilicate minerals (kyanite, andalusite and
sillimanite) with a composition AlAl (SiO4)O are clubbed under the nesosilicates. In all the three
minerals; chains of Al-O octahedral occurs parallel to the crystallographic axis, each octahedra
shares two oxygens with the above and below octahedron thus giving rise to Al-O chains of AlO4
composition. The chains are cross linked by the remaining Al and Si ions. In all cases Si is
tetrahedrally coordinated by oxygen ions, resulting in discrete (SiO4)4- structural units. The
remaining Al ion is in 6 fold coordination in kyanite, 5 fold coordination in andalusite and 4 –fold
coordination in sillimanite.
These three minerals are of same composition but exist as different structures owing to different
cross linking and chain positioning depending on the temperature and pressure conditions, hence

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 are considered polymorphs. They have been widely studied in petrology as they are useful as
pressure temperature markers of metamorphism in crustal rocks.

3. Structure and chemistry

3.1 Kyanite - Greek word kyanos, dark blue substance

The structure of kyanite consists of chains of edge sharing Al-O octahedra that are linked
together by the remaining Si, Al and O ions, Si being coordinated by four oxygen ions and Al by
six oxygen ions. (Fig.1) Kyanite has a relatively dense structure in which oxygen atoms are
arranged in slightly distorted cubic close packing.

Fig. 1 Articulation of AlO6 octahdera and SiO4 terahedra in a-b plane of Kyanite.

Kyanite has a relatively pure AlAlOSiO4 composition. Minor substitution of Fe3+ and Cr3+ can
be accommodated by the kyanite structure. The small amount of Ti4+ substitution is due to
frequent inclusion of rutile in kyanite.
Synthetic kyanite can be produced in lab at a 900 ºC and 10-40 kbar. The phase diagram of
Al2SiO5 composition shows the triple point between kyanite, andalusite and sillmanite to lie at
about 4.5 kilobars and 550ºC. It may invert to andalusite or sillimanite by a change in the
pressure or temperature conditions. Kyanite also gets converted to mullite and glass on heating
to ca. 1300 ºC.

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 Kyanite may alter to sericite, margarite or pyrophyllite. The kyanite of regional metamorphism
may be involved in number of metamorphic reactions and may show reaction textures with
minerals like andalusite, sillimanite, staurolite, garnet and cordierite.

3.2 Andalusite –discovered in Andalusia, Spain.

It has chains of edge sharing Al-O octahedral groups parallel to c- axis. Lateral linkage between
the octahedra is provided by Si between four tetrahedrally arranged oxygen atoms alternating
with Al between five oxygen atoms (Fig.2).

Fig. 2 Arrangement of SiO4 tetrahdra and AlO6 octahedra in Andalusite a-b plane.

The mineral is relatively pure AlAlOSiO4 and shows substitution of Mn3+ and Fe3+ for octahedral
aluminium. Extensive solid solution to Kanonaite is reported for andalusite with 32.2 percent
Mn2O3 leading to a composition (Mn3+,Al)AlSiO5. The term Viridine has been used for
andalusite containing 4-8 percent Fe2O3 and 19.6 percent Mn2O3.
Andalusite can be synthesized from kaolinite or from a mixture of Al2O3 + SiO2 at temperatures
450-650ºC and water vapour pressure between 0.6-2 Kbar.
Alteration to sericite, chlorite and other sheet silicates is commonly exhibited by andalusite. It
also shows metamorphic reaction relations with minerals such as cordierite, staurolite, garnet,
sillimanite and kyanite.

3.3 Sillimanite-after Benjamin Silliman (1779-1864) American chemist and mineralogist.

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 The structure of sillimanite consists of edge sharing octahedra of Al-O parallel to c –axis.
Double chain of terahedra containing Si and Al alternately in 4 fold coordination provides the
lateral linkage between octahedral chains (Fig. 3).
The composition of sillimanite is relatively pure Al2SiO5. Fe3+ and Cr 3+
may replace the Al in
the structure. Minor amount of absorbed and entrapped water is found to be present in the
fibrous fibrolite variety of sillimanite.

Fig. 3 Structure of Sillimanite in a-b plane

It can be synthesized from its component oxides at high pressure and temperature condition. The
triple point between kyanite, sillimanite, andalusite lies at about 500 + 50ºC and 4 + 0.5kbar. At
temperatures higher than 1000ºC it is known to convert to mullite + quartz.
It is known to be involved in many metamorphic reactions hence reaction textures with
associated minerals are commonly exhibited by it. Alteration product mostly includes muscovite,
sericite, pyrophyllite, kaolinite and montmorillonite.

4. Crystallographic properties
Sillimanite Andalusite Kyanite

Formula weight 162.05 162.05 162.05

α 1.710-1.718 1.633-1.642 1.653-1.661
β 1.719-1.724 1.639-1.644 1.657-1.662
γ 1.724-1.734 1.644-1.650 1.672-1.683
Z 4 4 4
Crystal system Orthorhombic Orthorhombic Triclinic
Point Group mmm mmm -1

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 Space Group Pbnm Pnnm P -1
Unit Cell
a(Å) 7.4883 7.7980 7.1262
b(Å) 7.6808 7.9031 7.8520
c(Å) 5.7774 5.5566 5.5747
Vol(Å3) 332.29 342.44 293.72
Molar Vol 50.035 51.564 44.227
Density 3.2386 3.1426 3.6640

5. Physical properties
5.1 Kyanite in hand specimen
It commonly forms columnar or bladed elongated crystals. It has a patchy blue, grey or white and
rarely light green colour (Fig. 4). Vitreous to pearly in lusture and gives a white streak. It has a
hardness of 4-5 parallel to c direction and ~71/2 at right angles to c crystallographic direction.
Specific gravity ranges from 3.53-3.67. Cleavage is perfect on {100}. Cleavage fragments are
usually splintery. Splintery fractures are common and crystals are of brittle nature. A basal
parting is conspicuous on {001} cutting at about
85º to the length of crystals. Twinning is not
obvious in hand sample though single and
multiple twins with {100} composition planes are
common.

Fig. 4. Kyanite bearing schist of regional metamorphic

terrain.

5.2 Andalusite in hand specimen

Andalusite crystals are commonly elongate prisms with a nearly square cross section. A variety
called Chiastolite known to display carbonaceous inclusions along the diagonals of the prism. It
can also occur as anhedral grains and irregular masses. Mostly are pink, white or pinkish brown
in colour. Usually gives a hardness of 6 – 8 and specific gravity of 3.13-3.16. Vitreous in lusture
and gives a white streak. {110} prismatic cleavages are observed parallel to prism faces in cross
sections though may not be evident in hand samples. Subconchoidal and uneven fractures are
common and crystals are of brittle nature. Twinning on {101} composition plane is rare.

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 5.3 Sillimanite in hand specimen
Sillimanite usually forms fibrous or slender prismatic grains. Color wise the crystals are either
colourless or white. Vitreous in luster and gives white streak. It has hardness in the range of 6-8.
Specific gravity ranges from 3.23-3.27. Sillimanite exhibits a good cleavage {010} parallel to
length of crystals. Crystals are brittle in nature and may show uneven fracture. No twinning is
reported for sillimanite.

6. Optical properties

Under plane polarized light

Kyanite It shows high relief, are commonly bladed in habit, radiating aggregates of blades are
also common (Fig. 5 left). Usually colourless in thin sections but may sometimes show pale blue
colour. Display weak pleochroism X˂Y˂Z: X = colourless, Y = light violet blue, Z = light cobalt
blue. Cleavage {110} perfect

Fibrolite
Kyanite

Fig. 5 (Left) Kyanite in eclogite mantle xenoliths of Wajrakarur Kimberlite field, Andhra Pradesh , India (PPL
image, 5X); (Right). Fibrolite grain (golden brown) as seen in a Sillimanite bearing Schist from Arunachal
Himalyas. (CPL image, 5X)

Andlusite It shows moderately high positive relief and is commonly euhedral elongate prism.
Usually colourless in thin section. Exhibits weak pleochroism X= reddish pink, Y=Z= greenish
yellow, Cleavage {110} good.
Sillimanite It shows moderately high relief and is usually colourless in thin section though
fibrolite masses can exhibit a pale brown colour (Fig. 5 Right). Most sillimanite in thin section is
not visibly pleochroic. Cleavage {010} is perfect on basal section of sillimanite

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 Under cross polarized light
Kyanite It is anisotropic in nature, shows low birefringence, shows first order grey
polarization colours, shows oblique extinction on cleavage and prism edge, are biaxial negative.
Optic orientation Z ˄ c and Y ˄ b are both about 27-30 º and X ˄ a is only few degrees, optic
axial plane is nearly normal to {100}, 2Vα = 73-86º, sign of elongation is length slow positive
elongation (Fig. 6).
OA
c
Z

OA 001
010
100 Y

a
X

Fig. 6 Optic orientation of kyanite

Andalusite It is anisotropic in nature with a low birefringence, shows first order grey
polarization colours, straight extinction on prism edge or on cleavage trace, basal section shows
symmetrical extinction, are biaxial negative. Optic orientation X = c, Y = b, Z = a, optic plane is
(010) for all composition ranges, 2Vα = 73-82º, sign of elongation negative length fast (Fig. 7).
OA
X c
OA

110

Y
b
a
Z

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 Fig.7 Optic orientation of Andalusite
Sillimanite It is anistropic in nature, shows moderate birefringence, high first order to low
second order polarization colours, straight extinction on single cleavage trace and are biaxial
positive. Optic orientation α = x, β = y, γ = z, optic axial plane is (010), 2Vγ = 21-30º, Sign of
elongation is length slow positive elongation (Fig. 8).
Z c OA
OA

110
b
Y
a
X

Fig. 8 Optic orientation of Sillimanite

7. Occurence
Each polymorph is known to have a specific pressure- temperature range over which it is stable
with andalusite being the low pressure polymorph, kyanite stable at high pressures and sillimanite
is stable at high temperatures. So, these minerals have found extensive application in establishing
the pressure –temperature conditions of rocks bearing them. The stability fields of these minerals
are related by phase diagram (Fig. 9) Being a very important mineral in metamorphic petrology
the P-T stability of the aluminium silicates has been extensively studied. However problems with
establishing the P-T field for these polymorphs include Al-Si order- disorder in sillimanite and
small compositional variations of the minerals. It has been shown that small amounts of Fe and
/or Mn entering the structure of andalusite may significantly effect its stability conditions.

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 Fig. 9 Phase diagram for the Al2SiO5 polymorphs. The arrows show that kyanite will react to form sillimanite
with increasing temperature or with decreasing pressure. Although not labeled, the pink triangular field at the
bottom is the stability field for andalusite. (Source: http://serc.carleton.edu)

The alumino-silicate polymorphs kyanite, sillimanite and andalusite are characteristic minerals of
medium to high grade pelitic metamorphic rocks like mica schist, biotite gneiss and hornfels.
Andalusite is commonly found in contact metamorphic aureoles of shallow and intermediate
depth intrusive and also in rocks subjected to medium grade metamorphism at relatively low
pressures. Sillimanite is restricted to rocks that are subjected to higher temperatures and kyanite is
characteristic of rocks subjected to relatively high pressures. Based on the bulk composition of
the rock and grade of metamorphism underwent by a rock; these polymorphs may be found
associated with cordierite, staurolite, garnet, chlorite, muscovite, biotite, plagioclase, k-feldspar
and chloritoid. Eclogites an ultra high-pressure metamorphic rock are also known to contain
kyanite in association with pyrope rich garnet and omphacite pyroxene.
These polymorphs are not stable in a weathering environment even tough may occur as important
detrital minerals.
These polymorphs are less commonly also being reported from granites and granitic pegmatites.
It’s debatable whether they are primary magmatic minerals or product of post magmatic
crystallization or are xenocrysts. Xenocrysts may originate from partially assimilated
metamorphic wall rock or could be relicts of the rocks from which the magma was derived by
partial melting. There exists no compelling evidence as to why these minerals cannot crystallize

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group
 from magma of appropriate composition under appropriate pressure –temperature conditions.
However one should be evaluate each case based on field textural and related chemical evidences
thoroughly.

8. Use
On heating the aluminium silicates to high temperatures it gets converted to Mullite [Al (Al1-2xSi1-
2x) O5-x] plus quartz. Mulite is used as a refractory mineral. Mutilised aluminium silicates find use
in manufacture of refractory materials such as high alumina bricks and related products used to
line blast furnaces and kilns and in applications requiring resistance to temperature. Andalusite
also finds use in manufacture of ceramic products, abrasives and filler materials.

Reference Books:

1. Klien, Cornelis and Hurlbut, Cornelius S., (1985). Manual of

Mineralogy (after James D. Dana), 20th Edn. John Wiley & Sons,
New York. ISBN: 0471805807, 978-0471805809.

2. Putnis Andrew (1992), An Introduction to Mineral Sciences, 1st

Edn., Cambridge University Press, UK. ISBN: 0521429471, 978-

0521429474.

3. Deer, W. A., Howie, R. A., & Zussman, J. (2013). An Introduction

to the Rock-forming Minerals, 3rd Edn., Mineralogical Society of

Great Britain & Ireland. ISBN: 0903056275, 978-0903056274.

PAPER: Crystallography and Mineralogy

GEOLOGY
MODULE : Alumino-silicate Group