One of the major goals of mineral science is attaining an understanding of the atomic-scale mechanisms and dynamics of minerals that control their structural transformations as a function of pressure, temperature or chemical composition in the natural environment. Examples of research programmes that sail under this heading include those devoted to observing and modelling the role of phase transformations on controlling mineral microstructures, ordering, elasticity, transport, premelting and exsolution. The geological relevance and intrinsic importance (as being representative of specific properties or thermodynamic/ kinetic behaviour) of mineral transformations has long been appreciated. It prompted the recent initiation of a network on Mineral Transformations (http://www.esc.cam.ac.uk/mintrans/) under the European Union TMR Programme. In response to this development, a special session on Mineral Transformations was held at the EUG congress in Strasbourg last year.

Recent experimental and theoretical studies provide new insight into the variety of high-pressure transformations in minerals that comprise the Earth’s deep mantle and core. Representative examples of reconstructive, displacive, electronic and magnetic transformations studied by new diamond-anvil cell techniques are examined. Despite reports for various transitions in (Mg,Fe)SiO3-perovskite, the stability field of the orthorhombic phase expands relative to magnesiowüstite + SiO2 with increasing pressure and temperature. The partitioning of Fe and Mg between Mg-rich silicate perovskite magnesiowüstite depends strongly on pressure, temperature, bulk Fe/Mg ratio, and ferric iron content. The soft-mode transition in SiO2 from the rutile- to CaCl2-type structure, originally documented by X-ray powder diffraction, Raman scattering, and first-principles theory has been explored in detail by single crystal diffraction, and transitions to higher-pressure forms have been examined. The effect of H on the transformations of various nominally anhydrous phases and transitions in dense hydrous Mg-silicates are also examined. New studies of the phase diagram of FeO include the transition to rhombohedral and higher-pressure NiAs polymorphs, and provide prototypical examples of coupled structural, electronic, and magnetic transitions. High-spin/low-spin transitions in FeO have been examined by high-resolution X-ray emission spectroscopy to 150 GPa, and the results are compared with similar studies of Fe2O3 and FeS. Finally, laser-heating studies to above 150 GPa and 2500K show that (hcp) ε-Fe has a large P-T stability field. Radial XRD measurements carried out at room temperature to 220 GPa have constrained the elasticity, rheology and sound velocities of ε-Fe at core pressures.

The effects of ion irradiation in the ABO4-type compounds were compared by performing experiments on four materials that include the most common crystal structures (monazite vs. zircon) and chemical compositions (phosphates vs. silicates) for these phases. Pure synthetic single crystals of ZrSiO4, monoclinic ThSiO4, LaPO4 and ScPO4 were irradiated using 800 keV Kr+ ions. Radiation damage accumulation was monitored as a function of temperature in situ in a transmission electron microscope. The activation energies for recrystallization during irradiation were calculated to be 3.1–3.3 eV for the orthosilicates but only 1.0–1.5 eV for the isostructural orthophosphates. For the ion-beam-irradiated samples, the critical temperature, above which the recrystallization processes are faster than damage accumulation and amorphization cannot be induced, is >700°C for ZrSiO4 but it is only 35°C for LaPO4. At temperatures above 600°C, zircon decomposed during irradiation into its component oxides (i.e. crystalline ZrO2 plus amorphous SiO2). The data are evaluated with respect to the proposed use of the orthophosphates and orthosilicates as host materials for the stabilization and disposal of high-level nuclear waste. The results show that zircon with 10 wt.% Pu would have to be maintained at temperatures in excess of 300°C in order to prevent it from becoming completely amorphous. In contrast, a similar analysis for the orthophosphates implies that monazite-based waste forms would not become amorphous or undergo a phase decomposition.

Many natural minerals and synthetic materials display twin microstructures resulting from displacive phase transitions. These microstructures may be removed temporarily from the sample by heating above the relevant transition temperature, though the twinning generally returns on subsequent cooling.

In anorthoclase, the spatial distributions of twins before and after brief annealing above TC are often identical. This property appears to be a common feature in many materials which undergo ferroelastic phase transitions, and is known as ‘twin memory’. The atomic mechanisms responsible for this twin memory may be investigated by studying the annealing regimes required to remove the memory effect; how long must a sample be annealed, and at what temperature, to induce ‘twin amnesia’.

High-resolution X-ray diffraction (XRD) has been used to investigate twin memory and twin amnesia in anorthoclase. In anorthoclase, the primary constraint on twin amnesia is thermodynamic, rather than kinetic. The critical temperature to induce amnesia correlates well with the top of the (Na, K) solvus in disordered alkali feldspar. For this reason, the proposed mechanism for twin memory involves the segregation of alkali cations in thin lamellae at the twin boundaries.

Networks of interacting twin walls form hierarchical, mesoscopic structures in minerals. The typical thickness of transformation twins at T ≪ TC is ˜3 nm and increases at T → TC as . The internal structure of twin walls is derived to be chiral in systems with coupled order parameters. The effect of wall bending is discussed.

Phase relations along the join bornite (Cu5FeS4)-digenite (Cu8.52Fe0.12S4.88) have been redefined using a combination of in situ high-resolution neutron diffraction and differential scanning calorimetry (DSC). Time-of-flight neutron diffraction patterns were collected on a synthetic sample of bn90 at 16 temperatures between 35 and 350°C. This data is compared with data from a natural end-member bornite sample obtained in an earlier study under identical conditions. Phase relations along the bornite-digenite join are inferred from the temperature evolution of the lattice parameters and the intensity of subcell and supercell reflections of coexisting phases.

The DSC scans over the temperature range 50–300°C were performed on a natural digenite sample and samples synthesized at 5 mol.% intervals along the join Cu5FeS4-Cu9S5. The thermal anomalies are correlated with structural phase transitions in componen phases and the solvus temperature for each bulk composition. A phase diagram topology is defined, which was consistent with both diffraction and calorimetric data, but in marked contrast to previous diagrams, shows a consolute point at X = Cu5FeS4 and T = 265°C. This temperature corresponds to that of the tricritical intermediate-high transition in bornite. Isothermal annealing experiments carried out on synthetic starting materials for up to 7 months showed coarsening behaviour consistent with the revised phase diagram topology.

The monoclinic structural distortion in lead phosphate and lead arsenate is correlated with the ferroelastic phase transition R3̄m → C2/c and R3̄m → P21/c respectively. The resulting domain patterns in the mixed compounds depend on their chemical composition. The intersection of ferroelastic W domain walls with the (100) surface of lead phosphate-arsenate mixed crystals has been imaged using tapping mode atomic force microscopy. Dilution of the strain leads to characteristic surface deformations which deviate from those in pure lead phosphate. In high twinned lead phosphate-arsenate, X-ray diffraction (XRD) was used to show renormalization effects and scattering phenomena stemming from the twin walls. The wall trajectory was found to be independent of chemical variations using transmission electron microscopy.

The clinopyroxenes kanoite and spodumene were studied by single-crystal X-ray diffraction in a diamond anvil cell (DAC) at room temperature. At the displacive phase transitions between the C2/c and P21/c polymorphs both phases coexist within the same crystal. In this two-phase region the pressure in the DAC remains constant. The experimental results demonstrate that pressure buffering at first-order phase transitions can occur in the DAC.

Four samples of Fe-bearing prismatic sillimanite, containing ∼1 wt.% Fe2O3, were annealed experimentally at temperatures of 1465 and 1675°C, and pressures between 1 atm and 30 kbar. Transmission electron microscopy (TEM) and analytical TEM (ATEM) investigation of the samples reveal that the starting material partly transformed into mullite during the annealing, and that this process was assisted by partial melting. The exsolved partial melt (now a glass), observed at triple junctions and in the form of small precipitates (∼10–1000 nm in size) within the sillimanite matrix, contains >80 wt.% SiO2. It also contains ∼11 wt.% Al2O3, some FeO and detectable amounts of K2O and CaO. Dissociated c dislocations in sillimanite are preferential nucleation sites for SiO2-rich precipitates. The equilibrium compositions of residual sillimanite-mullite were measured with a 2 nm wide probe at the interface with the SiO2-rich glass in each sample after heat treatment. We used these equilibrium compositions to constrain the parameters of a point defect model for sillimanite mullitization proposed by Raterron et al. (1999). With the revised parameterization, it is now possible to calculate the position of the boundary between fields of mullite + melt and mullite in the SiO2–Al2O3 phase diagram, and to predict the effect of pressure on this boundary. However, to be used as a standard, this model still needs to be calibrated in the pure SiO2–Al2O3 system (without impurities such as iron).

The crystal structure of a manganoan cummingtonite, composition [M4](Na0.13Ca0.41Mg0.46Mn1.00) [M1,2,3](Mg4.87Mn0.13)(Si8O22)(OH)2, (Z = 2), a = 9.5539(2) Å, b = 18.0293(3) Å, c = 5.2999(1) Å, β = 102.614(2)° from Talcville, New York, has been refined at high temperature using in situ neutron powder diffraction. The P21/m to C2/m phase transition, observed as spontaneous strains +ε1 = −ε2, occurs at ˜107°C. Long-range disordering between Mg2+ and Mn2+ on the M(4) and M(2) sites occurs above 550°C. Mn2+ occupies the M(4) and M(2) sites preferring M(4) with a site-preference energy of 24.6±1.5 kJ mol−1. Disordering induces an increase in XMnM2 and decrease in XMnM4 at elevated temperatures. Upon cooling, the ordered states of cation occupancy are ‘frozen in’ and strains in lattice parameters are maintained, suggesting that re-equilibration during cooling has not taken place.

The phase transitions in tridymite and the nature of the high-temperature phase are investigated using a combination of Rigid Unit Mode theory, neutron total scattering measurements analysed using the Reverse Monte Carlo method, and molecular dynamics simulations. The unusually large number of phase transitions in tridymite can be explained within the Rigid Unit Mode theory. The Rigid Unit Mode theory also gives an interpretation of the disordered high-temperature phase as revealed by the neutron scattering data and the molecular dynamics simulations. There is a close correspondence between the structure of the disordered high-temperature phase of tridymite and that of β-cristobalite.

Feldspar of composition Ca0.2Pb0.8Al2Si2O8 (PbF80An20) was synthesized from melt and subsequently isothermally annealed at T = 960°C for 4 days. In situ HT X-ray powder spectra of PbF80An20 feldspar, triclinic I1̄ at room temperature, were collected in the temperature range 20–800°C, and a displacive continuous ferroelastic transition to a I2/c monoclinic phase was observed. An analysis of the symmetry-required components of the spontaneous strain tensor reveals the second order character (β = 0.46 ± 0.02) of the transition with TC = 680 ± 15°C. A linear coupling was observed between the e4 and e6 components of the spontaneous strain. The transition is analogous to those observed, with increasing temperature, along the join An–SrF and in disordered Na-rich alkali feldspars. A comparison with Ca0.2Sr0.8Al2Si2O8 feldspar (TC = 680°C, McGuinn and Redfern, 1997) shows that PbF80An20 has a higher spontaneous strain (εs = 0.028 in PbF80An20vs 0.020 in Ca0.2Sr0.8Al2Si2O8) and a higher e4 component, possibly related to the higher distortion of the non-tetrahedral polyhedron in lead feldspar.

High-resolution, neutron time-of-flight, powder diffraction data have been collected on natural crocoite between 873 and 1073 K. Thermal analysis carried out in the 1920s had suggested that chemically pure PbCrO4 exhibited two structural phase transitions, at 964 K, to the β phase, and at 1056 K, to the γ phase. In this study, no evidence was found for the α-β structural phase transition, however a high-temperature phase transition was found at ∼1068 K from the ambient-temperature monazite structure type to the baryte structure type. The phase transition, close to the temperatures reported for the β to γ phase modifications, is first order and is accompanied by a change in volume of −1.6%. The crystal structure of this phase has been refined using the Rietveld method to agreement factors of Rp = 0.018, Rwp = 0.019, Rp = 0.011. No evidence for premonitory behaviour was found in the temperature dependence of the monoclinic lattice constants rom 873 K to 1063 K and these have been used to determine the thermal expansion tensor of crocoite just below the phase transition. At 1000 K the magnitudes of the tensor coefficients are α11, 2.66(1) × 10−5 K−1; α22, 2.04(1) × 10−5 K−1; α33, 4.67(4) × 10−5 K−1; and α13, −1.80(2) × 10−5 K−1 using the IRE convention for the orientation of the tensor basis. The orientation of the principal axes of the thermal expansion tensor are very close to those reported previously for the temperature range 50–300 K.

The high-pressure behaviour (up to 30 kbar) of dehydrated analcime, Na[AlSi2O6), has been studied in detail using polarized microscopy and Raman micro-spectroscopy. Samples were compressed using a diamond anvil cell in a quasi-hydrostatic medium (glycerol or water-ice). Two transitions at 3.7 and 11 kbar were observed.

At the first transition, phase II is observed under cross polarized light as a contrasting black zone, moving from the edge to the centre of the sample. At this transition the strong Raman doublet at ∼480 and 500 cm−1 transforms discontinuously to a singlet, which is similar to that of quasi-cubic natural analcime. This transition, with an increase of effective symmetry, seems unusual on increasing pressure.

The analcime framework may be thought of as an array of four-, six-, or eight-membered interconnected rings. Phase transitions in the analcime group are considered in the literature in terms of deformations of the six-membered rings. However, the present work shows that these phase transitions should be associated with deformations of the four-membered rings (as the minimum size secondary building units) by rotation of rigid TO4 units. The strongest Raman band frequency is correlated with the mean T-O-T angle inside the four-membered ring: a rate of 4.5 cm−1/degree was found for analcimes and leucites. Using this correlation, one can estimate from Raman data the possible deformation of four-membered rings at the phase transitions.

At high temperature, MgAl2O4 spinel is stabilized by disorder of Mg and Al between octahedral and tetrahedral sites. This behaviour has been measured up to 1700 K in recent neutron experiments, but the extrapolation of subsequently fitted thermodynamic models is not reliable. First principles simulation of the electronic structure of such minerals can in principle accurately predict disorder, but would require unfeasibly large computing resources. We have instead parameterized on-site and short-ranged cluster potentials using a small number of electronic structure simulations at zero temperature. These potentials were then used in large-scale statistical simulations at finite temperatures to predict disordering thermodynamics beyond the range of experimental measurements. Within the temperature range of the experiment, good agreement is obtained for the degree of order. The entropy and free energy are calculated and compared to those from macroscopic models.

An olivine grain from peridotite nodule 9206 (Udachnaya kimberlite) was heated in air at 700°C for 9 h. It was investigated by EMPA, by IR and UV spectroscopy and by TEM. The TEM examination reveals hexagon-like inclusions up to several hundred nm in size with a core and rim structure. The AEM data show that the inclusions contain only Mg, Fe and Si as cations. The rims have almost the same composition as the olivine matrix whereas the cores are enriched in iron and depleted in Mg. Electron diffraction data, SAED and CBED, indicate that the rims are composed of a ‘secondary’ olivine while the cores are composed of coexisting feroxyhite FeOOH, bernalite Fe(OH)3 and β-cristobalite SiO2. The presence of nm-sized inclusions in minerals is expected to influence the interpretation of spectroscopic results if spectroscopy is carried out without knowledge of the microstructure.

It is speculated that the complex microstructure of the inclusions is a result of a solid state transformation of a precursor phase, probably a hydrous magnesian silicate, during the experimental heating and oxidation.

The dehydroxylation of Ca-, K-, Mg- and Na-saturated Wyoming montmorillonite has been studied by thermogravimetry (TG), infrared (IR) spectroscopy and X-ray diffraction (XRD). Samples saturated with either Ca2+ or Mg2+ show a predominantly diffusion-controlled reaction step, whereas Wyoming montmorillonite with Na+ and K+ in the interlayer exhibit control closer to first order. The activation energy of dehydroxylation is not significantly correlated to the type of interlayer cation present, in turn demonstrating that the role of vacancy location in the octahedral sheet is more significant a control on dehydroxylation.

The tin-bearing muscovite granite from Ervedosa contains unzoned primary muscovite. This Hercynian S-type granite was hydrothermally altered at the stanniferous quartz vein walls and contains three types of muscovite: (1) very small unzoned muscovite replacing albite; (2) small unzoned hydrothermal muscovite replacing K-feldspar and quartz; and (3) zoned subhedral muscovite.

In the zoned muscovite, the core has a composition similar to that of magmatic muscovite from the unaltered granite, while the rim has a composition similar to that of hydrothermal muscovite replacing K-feldspar and quartz in the altered granite. The rim corresponds to a late overgrowth richer in the celadonitic component than the core. Infiltrated mineralizing fluids reacted with biotite and K-feldspar of the unaltered granite. We interpret the rim of muscovite to have precipitated from these solutions.