Phase Diagram of Silica Polymorphs

Figure 1 shows the temperature and pressure conditions at which SiO

2
polymorphs are stable in a so-calledphase diagram of
SiO
2
. A complete phase diagram would also show the conditions where SiO
2
forms a gas, above 2477C at normal pressures,
but since I don't have data on pressure dependence for that area, this temperature range is omitted.


Fig.1: Phase diagram of silica
Data from:
Hollemann and Wyberg, 1985
Wenk and Bulakh, 2003
Rykart, 1995
The phase diagram in Fig.1 does not contain all SiO
2
polymorphs.
It only shows those polymorphs that form from pure SiO
2
at certain temperatures and pressures.
It does not show metastable polymorphs.
It does not show the polymorph seifertite (I don't have any data on its pressure/temperature behavior and its stability field lies
well outside the shown temperature/pressure range).

Most of the phase boundaries (the borders between the areas) are inclined to the right. For example, quartz will transform into
-quartz at 573 at normal pressures, but the transition temperature quickly increases with pressure. At a pressure of 2 GPa
(Giga pascal, 10
9
pascal) -quartz forms at about 1000C. The rising temperature increases the vibrations of the atoms so they
need more space, but the external pressure compresses the crystal lattice and counteracts the effect of temperature
[4]
.
-quartz, -quartz, -tridymite, and -cristobalite have already been introduced as low pressure polymorphs, while coesite and
stishovite are called high pressure polymorphs and are not stable at normal pressures. Coesite andstishovite have a higher
density than the low pressure polymorphs, in particular stishovite, which has a specific density of 4.29 g/cm
3
. While Coesite is
still made of interconnected SiO
4
tetrahedra, stishovite assumes a completely different arrangement of atoms in its crystal
lattice. In all low pressure polymorphs as well as in coesite, the silicon atoms are surrounded by 4 oxygen atoms. The silicon in
them is said to have a coordination number of 4. This is also the case in all silicate minerals. The coordination number of
stishovite is 6, so the silicon atoms are all surrounded by 6 oxygen atoms. The crystal structure of stishovite does not fit in the
classification scheme of silicates, so stishovite could well be considered a non-silicate. Stishovite and coesite are both not stable
at normal pressures and normal temperatures, but since their transitions into a low pressure silica polymorphs arereconstructive
phase transitions that involve a complete rearrangement of the atoms in the crystal lattice, both aremetastable at normal
conditions.
-quartz is not stable above 3 GPa and not stable at temperatures above 1200C, so its stability field occupies only a small part
in the phase diagram. It looks as if it might be stable at normal pressures and temperatures and thus accumulate at the Earth's
surface, but it might not be that abundant in the varying geological environments inside the Earth's crust and mantle. Where can
we expect to find the various polymorphs inside the Earth? To answer that question, the left y-axis of the diagram in Fig.1 is a
scale of the pressure, and the right y-axis shows a scale of depth in the Earth's mantle and crust that corresponds to the pressures
(it is only a rough estimate, as the pressure does not increase perfectly linear with depth and also varies locally). That way one
can superimpose a diagram of the pressure and temperature conditions (p-T conditions) of the Earth's crust and upper mantle,
as shown in Fig.2.



Fig.2: Geotherms and natural P/T conditions superimposed on the phase diagram of silica
Data from:
Fowler, 2004
Okrusch and Matthes, 1995
Skinner and Porter, 1987
Markl, 2004

The change of temperature with depth is plotted as a so-called geotherm
[5]
, the rate at which the temperature changes is called
the geothermal gradient, usually given as degrees Kelvin per 100 m. The geothermal gradient is not the same everywhere, and
it normally decreases with depth, that is, the temperature raises first quickly at shallow depths and then more and more slowly at
greater depths.
The possible p-T conditions found on Earth are confined to a narrow corridor between 2 gray-shaded areas in Fig.2. Typical
geotherms for stable continental, young and old oceanic crust are shown as solid colored lines. The bottom line of the diagram
along the x-axis corresponds to conditions at the surface, and the temperature range for rocks at the surface is between
approximately -100C (in the arctic) and 1300C (in hot volcanic magma
[6]
). The conditions at the left border of the corridor are
found when crust is quickly subducted at plate boundaries, whereas the conditions at the right border are met in quickly rising
magma, for example, at volcanic eruptions.
Fig. 2 also shows the average thickness of oceanic (7km) and continental crust (35km). Continental crust shows large variations
in thickness: Where continental plates collide, it may be up to 90km thick, in rift zones it might be just 10km.
Judging from the geotherms, -quartz will be the stable form of silica in the entire continental and oceanic crust under normal
conditions. Only where hot magma is pushed up quickly one might expect to find -quartz. If a silica-rich crust gets subducted
to great depth, the -quartz in it will not be transformed to -quartz, even if the temperature exceeds 573. Silica glass will
never form from a silica-rich magma, and -cristobalite is also very unlikely to form. Of course it is still a different matter if -
or -quartz will actually form under certain p-T conditions inside the Earth, as the presence of free silica is mainly determined
by the chemical composition of the rock.

Crystallographic Data

Name
Crystal
System
Crystal Class
Hermann
-Mauguin
Symbols
Space Group
-Quartz trigonal
trigonal -
trapezohedral
3 2
P3
1
21 (left hand)
P3
2
21 (right hand)
-Quartz hexagonal
hexagonal -
trapezohedral
6 2
P6
4
22 (left hand)
P6
2
22 (right hand)
-Tridymite triclinic
triclinic -
pedial
1 F1
-Tridymite hexagonal dihexagonal - 6/m 2/m 2/m P6
3
/mmc
dipyramidal
-Cristobalite tetragonal
tetragonal -
trapezohedral
4 2 2 P 4
1
2
1
2
-Cristobalite cubic hexoctahedral 4/m 3 2/m Fd3m
Moganite monoclinic
monoclinic -
prismatic
2/m I2/a
Coesite monoclinic
monoclinic -
prismatic
2/m C 2/c
Stishovite tetragonal
ditetragonal -
dipyramidal
4/m 2/m 2/m P 4/mnm
Seifertite orthorhombic
orthorhombic -
dipyramidal
2/m 2/m 2/m Pbcn
Keatite tetragonal
tetragonal -
trapezohedral
4 2 2 P4
3
2
1
2
Opal
macroscopically
amorphous
- - -
Lechatelierite amorphous glass - - -
Melanophlogite tetragonal
ditetragonal -
dipyramidal
4/m 2/m 2/m P 4
1
/nbc
Chibaite cubic
isometric -
diploidal
m3 (2/m 3) Fd3
Silhydrite orthorhombic ? ? ?

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