A complete phase diagram would also show the conditions where SiO 2 forms a gas, above 2477degC at normal pressures, but since I don't have data on pressure dependence for that area, this temperature range is omitted. Phase diagram does not contain all silica polymorphs. It only shows those polymorphs that form from pure SiO 2 at certain temperatures and pressures.
A complete phase diagram would also show the conditions where SiO 2 forms a gas, above 2477degC at normal pressures, but since I don't have data on pressure dependence for that area, this temperature range is omitted. Phase diagram does not contain all silica polymorphs. It only shows those polymorphs that form from pure SiO 2 at certain temperatures and pressures.
A complete phase diagram would also show the conditions where SiO 2 forms a gas, above 2477degC at normal pressures, but since I don't have data on pressure dependence for that area, this temperature range is omitted. Phase diagram does not contain all silica polymorphs. It only shows those polymorphs that form from pure SiO 2 at certain temperatures and pressures.
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.