Evidence for pressure induced polarization rotation, octahedral tilting and reentrant ferroelectric phase in tetragonal (Pb0.5Bi0.5)(Ti0.5Fe0.5)O3

Despite the technological significance of the tetragonal PbTiO3 for the piezoelectric transducer industry, its high pressure behaviour is quite controversial as two entirely different scenarios, involving pressure induced (1) morphotropic phase boundary (MPB) like structural transition with concomitant rotation of the ferroelectric polarization vector and (2) antiferrodistortive (AFD) phase transition followed by emergence of a reentrant ferroelectric phase, have been proposed in recent theoretical and experimental studies. We have attempted to address these controversies through a high resolution synchrotron x-ray diffraction study of pressure induced phase transitions in the tetragonal phase of a modified PbTiO3 composition containing 50% BiFeO3, where BiFeO3 was added to enhance the AFD instability of PbTiO3. We present here the first experimental evidence for the presence of the characteristic superlattice reflections due to an AFD transition at a moderate pressure pc1 ~2.15 GPa in broad agreement with scenario (2), but the high pressure ferroelectric phase belongs to the monoclinic space group Cc, and not the tetragonal space group I4cm predicted under scenario (2), which permits the rotation of the ferroelectric polarization vector as per scenario (1). We show that the monoclinic distortion angle and ferroelectric polarization of the Cc phase initially decrease with increasing pressure for p < 7 GPa, but start increasing above pc2 ~ 7 GPa due to an isostructural Cc-I to Cc-II transition reminiscent of MA(apc > bpc ~ cpc) to MB(apc< bpc ~ cpc) transition predicted for MPB systems. We also show that octahedral tilting provides an efficient mechanism for accommodating pressure induced volume reduction for the stabilisation of the reentrant ferroelectric phase Cc-II.Comment: 34 pages, 8 figure

An unexpected cubic symmetry in group IV alloys prepared using pressure and temperature

The cubic diamond (Fd-3m) group IVA element Si has been the material driver of the electronics industry since its inception. We report synthesis of a new cubic (Im-3m) group IVA material, a GeSn solid solution, upon heating Ge and Sn at pressures from 13 to 28 GPa using double-sided diamond anvil laser-heating and large volume press methods. Both methods were coupled with in-situ angle dispersive X-ray diffraction characterization. The new material substantially enriches the seminal group IVA alloy materials landscape by introducing an eightfold coordinated cubic symmetry, which markedly expands on the conventional tetrahedrally coordinated cubic one. This cubic solid solution is formed, despite Ge never adopting the Im-3m symmetry, melting inhibiting subsequent Im-3m formation and reactant Ge and Sn having unlike crystal structures and atomic radii at all these pressures. This is hence achieved without adherence to conventional formation criteria and routes to synthesis. This advance creates fertile avenues for new materials development

Opacity and conductivity measurements in noble gases at conditions of planetary and stellar interiors

The noble gases are elements of broad importance across science and technology and are primary constituents of planetary and stellar atmospheres, where they segregate into droplets or layers that affect the thermal, chemical, and structural evolution of their host body. We have measured the optical properties of noble gases at relevant high pressures and temperatures in the laser-heated diamond anvil cell, observing insulator-to-conductor transformations in dense helium, neon, argon, and xenon at 4,000–15,000 K and pressures of 15–52 GPa. The thermal activation and frequency dependence of conduction reveal an optical character dominated by electrons of low mobility, as in an amorphous semiconductor or poor metal, rather than free electrons as is often assumed for such wide band gap insulators at high temperatures. White dwarf stars having helium outer atmospheres cool slower and may have different color than if atmospheric opacity were controlled by free electrons. Helium rain in Jupiter and Saturn becomes conducting at conditions well correlated with its increased solubility in metallic hydrogen, whereas a deep layer of insulating neon may inhibit core erosion in Saturn

Phase relations in the system Fe-Ni-Si to 200 GPa and 3900 K and implications for Earth’s core

Phase relations in Fe–5 wt%Ni–4 wt%Si alloy was examined in an internally resistive heated diamond anvil cell under high pressure (P) and temperature (T) conditions to about 200 GPa and 3900 K by in-situ synchrotron X-ray diffraction. The hexagonal close-packed (hcp) structure was observed to the highest P–T condition, supporting the idea that the stable iron alloy structure in Earth's inner core is hcp. The P–T locations of the phase transition between the face-centred cubic (fcc) and hcp structures were also constrained to 106 GPa. The transition occurs at 15 GPa and 1000 K similar to for pure Fe. The Clausius–Clapeyron slope is however, 0.0480 GPa/K which is larger than reported slopes for Fe (0.0394 GPa/K), Fe–9.7 wt%Ni (0.0426 GPa/K), and Fe–4 wt%Si (0.0394 GPa/K), stabilising the fcc structure towards high pressure. Thus the simultaneous addition of Ni and Si to Fe increases the dP/dT slope of the fcc–hcp transition. This is associated with a small volume change upon transition in Fe–Ni–Si. The triple point, where the fcc, hcp, and liquid phases coexist in Fe–5 wt%Ni–4 wt%Si is placed at 145 GPa and 3750 K. The resulting melting temperature of the hcp phase at the inner core-outer core boundary lies at 550 K lower than in pure Fe

A MHz X-ray diffraction set-up for dynamic compression experiments in the diamond anvil cell

An experimental platform for dynamic diamond anvil cell (dDAC) research has been developed at the High Energy Density (HED) Instrument at the European X-ray Free Electron Laser (European XFEL). Advantage was taken of the high repetition rate of the European XFEL (up to 4.5 MHz) to collect pulse-resolved MHz X-ray diffraction data from samples as they are dynamically compressed at intermediate strain rates (≤103 s−1), where up to 352 diffraction images can be collected from a single pulse train. The set-up employs piezo-driven dDACs capable of compressing samples in ≥340 µs, compatible with the maximum length of the pulse train (550 µs). Results from rapid compression experiments on a wide range of sample systems with different X-ray scattering powers are presented. A maximum compression rate of 87 TPa s−1 was observed during the fast compression of Au, while a strain rate of ∼1100 s−1 was achieved during the rapid compression of N2 at 23 TPa s−1

Direct measurement of thermal conductivity in solid iron at planetary core conditions

The conduction of heat through minerals and melts at extreme pressures and temperatures is of central importance to the evolution and dynamics of planets. In the cooling Earth’s core, the thermal conductivity of iron alloys defines the adiabatic heat flux and therefore the thermal and compositional energy available to support the production of Earth’s magnetic field via dynamo action1, 2, 3. Attempts to describe thermal transport in Earth’s core have been problematic, with predictions of high thermal conductivity4, 5, 6, 7 at odds with traditional geophysical models and direct evidence for a primordial magnetic field in the rock record8, 9, 10. Measurements of core heat transport are needed to resolve this difference. Here we present direct measurements of the thermal conductivity of solid iron at pressure and temperature conditions relevant to the cores of Mercury-sized to Earth-sized planets, using a dynamically laser-heated diamond-anvil cell11, 12. Our measurements place the thermal conductivity of Earth’s core near the low end of previous estimates, at 18–44 watts per metre per kelvin. The result is in agreement with palaeomagnetic measurements10 indicating that Earth’s geodynamo has persisted since the beginning of Earth’s history, and allows for a solid inner core as old as the dynamo

Thermal Conductivity of Materials under Conditions of Planetary Interiors

The presented thesis focuses on study of transport and thermoelastic properties of materials under conditions of planetary interiors by means of high-pressure experimental tools and finite element modeling, and their role in the dynamics and states of cores of terrestrial planets. Experiments in laser-heated diamond anvil cell (LHDAC) in combination with numerical simulations of heat transfer in DAC are shown to yield information on thermal conductivity of a pressurized sample. The novel technique consists of one-sided laser heating and double-sided temperature measurements and utilizes a precise determination of several parameters in course of the experiment, including the sample geometry, laser beam power distribution, and optical properties of employed materials. The pressure-temperature conditions at the probed portion of the sample are, however, not uniform. To address this problem, thermal pressure in the laser-heated diamond anvil cell and anisotropic thermal conductivity originating from the texture development upon uniaxial compression have been studied by means of numerical simulations. The method for determination of thermal conductivity is applied to iron at pressures up to 70 GPa and temperatures of 2000 K, meeting the Earth’s lower mantle conditions and covering Mercury’s entire core. The obtained results are extrapolated to the conditions of the Earth’s core-mantle boundary using a theoretical model of the density dependence of thermal conductivity of metals and published values on Grüneisen parameter and bulk modulus. After considering the effect of minor core elements, the obtained value at these conditions supports case for the downward revision of the thermal conductivity in the core. From the point of view of core dynamics and energy budget, the lower thermal conductivity implies more favorable conditions to drive the dynamo. Similar scenario applies for Mercury where, for high values of thermal conductivity, heat flux conducted along the iron-core adiabat exceeds the actual heat flux through the core-mantle boundary. This leads to a negative rate of entropy production in the core that makes it impossible to sustain the dynamo process presumably responsible for the observed magnetic field of Mercury

High-pressure structural study of MnF2\mathrm{MnF_{2}}

Manganese fluoride (MnF$_{2}$) with the tetragonal rutile-type structure has been studied using a synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy in a diamond anvil cell up to 60 GPa at room temperature combined with first-principles density functional calculations. The experimental data reveal two pressure-induced structural phase transitions with the following sequence: rutile → SrI$_{2}$ type (3 GPa)→ α−PbCl$_{2}$ type (13 GPa). Complete structural information, including interatomic distances, has been determined in the case of MnF$_{2}$ including the exact structure of the debated first high-pressure phase. First-principles density functional calculations confirm this phase transition sequence, and the two calculated transition pressures are in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phases. The results are discussed in line with the possible practical use of rutile-type fluorides in general and specifically MnF$_{2}$ as a model compound to reveal the HP structural behavior of rutile-type SiO$_{2}$ (Stishovite)