Mineralogy, Mössbauer spectroscopy and electrical conductivity of heterosite (Fe3+, Mn3+)PO4

Mineralogical analysis, electrical conductivity and thermopower are reported for monocrystalline heterosite (Fe³⁺, Mn³⁺)PO₄ with the orthorhombic olivine-type structure. The ⁵⁷Fe Mössbauer spectrum could be adequately described using two Fe³⁺ doublets. By impedance spectroscopy (20 Hz–1 MHz) the electrical DC conductivity σ_DC and AC conductivity σ_AC were determined parallel (∥) and perpendicular to the [001] direction (space group Pnma) in the range ～160–440 K. The graph log σ_DC?1/T shows a slightly bent curve in both directions with activation energies of E _A ～0.30 and ～0.15 eV in the high and low temperature ranges, respectively. The reduced E _A is associated with electronic conduction; σ_DC ∥ [001] follows Mott’s T ^1/4 variable range hopping law at lower temperatures with hopping between localized levels. The values of σ_AC are increased relative to σ_DC at high frequencies and low temperatures, obeying Jonscher’s universal dynamic response law; for σ_AC ∥ [001], the variation with temperature of the frequency exponent is in fair agreement with the model of small polaron hopping. The absolute thermopower Θ is negative and low between ～295 and ～440 K, Θ does hardly vary with temperatures in both directions; the temperature independency of Θ ∥ [001] is consistent with the small polaron hopping model.     

Mineralogy,Mössbauer spectra and electrical conductivity of triphylite Li(Fe<Superscript>2+</Superscript>,Mn<Superscript>2+</Superscript>) PO<Subscript>4</Subscript>

The electrical conductivity of monocrystalline triphylite, Li(Fe²⁺,Mn²⁺)PO₄, with the orthorhombic olivine-type structure was measured parallel (∥) to the [010] direction and ∥ [001] (space group Pnma), between ～400 and ～700 K. Electrical measurements on triphylite are of technological interest because LiFePO₄ is a promising electrode material for rechargeable Li batteries. Triphylite was examined by electron microprobe, ICP atomic emission spectroscopy, X-ray diffraction, Mössbauer spectroscopy and microscopic analysis. The DC conductivity σ_DC was determined from AC impedance data (20 Hz–1 MHz) extrapolating to zero frequency. Triphylite shows σ_DC with activated behavior measured ∥ [010] between ～500 and ～700 K during the first heating up, with activation energy of E _A = 1.52 eV; on cooling E _A = 0.61 eV was found down to ～400 K and extrapolated σ_DC (295 K) ～10^?9 Ω^?1cm^?1; ∥ [001] E _A = 0.65 eV and extrapolated σ_DC(295 K) ～10^?9 to 10^?10 Ω^?1cm^?1, measured during the second heating cycle. The enhanced AC conductivity relative to σ_DC at lower temperatures indicates a hopping-type charge transport between localized levels. Conduction during the first heating up is ascribed to ionic Li⁺ hopping. DC polarization experiments showed conduction after the first heating up to be electronic related to lowered activation energy. Electronic conduction appears to be coupled with the presence of Li⁺ vacancies and Fe³⁺, formed by triphylite alteration. For comparison, σ_DC was measured on the synthetic compound LiMgPO₄ with olivine-type structure, where also an activated behavior of σ_DC with E _A ～1.45 eV was observed during heating and cooling due to ionic Li⁺ conduction; here no oxidation can occur associated with formation of trivalent cations.     

Electrical conductivity,thermopower and <Superscript>57</Superscript>Fe Mössbauer spectroscopy of aegirine (NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)

DC and AC electrical conductivities were measured on samples of two different crystals of the mineral aegirine (NaFeSi₂O₆) parallel () and perpendicular () to the [001] direction of the clinopyroxene structure between 200 and 600 K. Impedance spectroscopy was applied (20 Hz–1 MHz) and the bulk DC conductivity _DC was determined by extrapolating AC data to zero frequency. In both directions, the log _DC – 1/T curves bend slightly. In the high- and low-temperature limits, differential activation energies were derived for measurements [001] of E_A 0.45 and 0.35 eV, respectively, and the numbers [001] are very similar. The value of _DC [001] with _DC(300 K) 2.0 × 10^{–6 –1}cm^–1 is by a factor of 2–10 above that measured [001], depending on temperature, which means anisotropic charge transport. Below 350 K, the AC conductivity () (/2=frequency) is enhanced relative to _DC for both directions with an increasing difference for rising frequencies on lowering the temperature. An approximate power law for () is noted at higher frequencies and low temperatures with () ^s, which is frequently observed on amorphous and disordered semiconductors. Scaling of () data is possible with reference to _DC, which results in a quasi-universal curve for different temperatures. An attempt was made to discuss DC and AC results in the light of theoretical models of hopping charge transport and of a possible Fe²⁺ Fe³⁺ electron hopping mechanism. The thermopower (Seebeck effect) in the temperature range 360 K < T <770 K is negative in both directions. There is a linear – 1/T relationship above 400 K with activation energy E 0.030 eV [001] and 0.070 eV [001]. ⁵⁷Fe Mössbauer spectroscopy was applied to detect Fe²⁺ in addition to the dominating concentration of Fe³⁺.     

Electrical conductivity, thermopower and 57Fe Mössbauer spectroscopy of an Fe-rich amphibole, arfvedsonite

The electrical charge transport was examined in an Fe-rich amphibole, arfvedsonite, using frequency dependent AC resistivity (impedance spectroscopy) and thermopower Θ measurements in the temperature range 30–800°C. Two different semiconducting charge transfer mechanisms were observed which are due to volume conduction for measurements parallel and perpendicular to the [001] direction; they arise probably from a conduction mechanism related to lattice defects, both with activation energies E_A ≈ 0.4 eV. The extrapolated DC conductivity, for a fixed temperature, along [001] is about 5–6 times higher than that perpendicular to [001]. From the temperature independent positive Θ values it follows that hole conduction occurs, and a hopping-type charge transport is acting, probably effected by electron hopping Fe²⁺ → Fe³⁺. Possible charge transfer paths are discussed. ⁵⁷Fe Mössbauer spectra enabled to determine the relative concentrations of Fe²⁺ and Fe³⁺. From a comparison of these data and from Θ results it is concluded that the main fraction of Fe²⁺ and Fe³⁺ take part in long range charge transport.     

Electric conductivity of Fe2SiO4–Fe3O4 spinel solid solutions

 The spinel solid solution was found to exist in the whole range between Fe₃O₄ and γ-Fe₂SiO₄ at over 10 GPa. The resistivity of Fe_{3− x} Si _x O₄ (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe³⁺ and Fe²⁺ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy of the electron hopping becomes larger with increasing γ-Fe₂SiO₄ component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe³⁺–Fe²⁺ electron hopping with increasing the total Si content. This is probably because a large number of Si⁴⁺ ions occupies the octahedral site and the adjacent Fe²⁺ keeping the local electric neutrality around Si⁴⁺ makes a cluster, which generates a local deformation by Si substitution. The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases from 124(±2) K at x=0 (Fe₃O₄) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si⁴⁺ substitution. Received: 15 March 2000 / Accepted: 4 September 2000     

Thermophysical properties of ilvaite CaFe 2 2+ Fe3+Si2O7O (OH); heat capacity from 7 to 920 K and thermal expansion between 298 and 856 K

The heat capacity of ilvaite from Seriphos, Greece was measured by adiabatic shield calorimetry (6.4 to 380.7 K) and by differential scanning calorimetry (340 to 950 K). The thermal expansion of ilvaite was also investigated, by X-ray methods, between 308 and 853 K. At 298.15 K the standard molar heat capacity and entropy for ilvaite are 298.9±0.6 and 292.3±0.6 J/(mol. K) respectively. Between 333 and 343 K ilvaite changes from monoclinic to orthorhombic. The antiferromagnetic transition is shown by a hump in C _p ⁰ with a Néel temperature of 121.9±0.5 K. A rounded hump in C _p ⁰ between 330 and 400 K may possibily arise from the thermally activated electron delocalization (hopping) known to take place in this temperature region.     

Formation of the disk structure and jets in the symbiotic system Z and during periods of activity in 2006–2010

We present an analysis of spectrophotometric observations of the latest cycle of activity of the symbiotic binary Z And from 2006 to 2010. We estimate the temperature of the hot component of Z And to be ≈150 000−170 000 K at minimum brightness, decreasing to ≈90 000 K at the brightness maximum. Our estimate of the electron density in the gaseous nebula is N _e = 10¹⁰−10¹² cm⁻³ in the region of formation of lines of neutral helium and N _e = 10⁶−10⁷ cm⁻³ in the region of formation of the [OIII] and [NeIII] nebular lines. A trend for the gas density derived from helium lines to increase and the gas density derived from [OIII] and [NeIII] lines to simultaneously decrease with increasing brightness of the system was observed. Our estimates show that the ratios of the theoretical and observed fluxes in the [OIII] and [NeIII] lines agree best when the O/Ne ratio is similar to its value for planetary nebulae. The model spectral energy distribution showed that, in addition to a cool component and gaseous nebula, a relatively cool pseudophotosphere (5250–11 500 K) is present in the system. The simultaneous presence of a relatively cool pseudophotosphere and high-ionization spectral lines is probably related to a disk-like structure of the pseudophotosphere. The pseudophotosphere formed very rapidly—over several weeks—during a period of increasing brightness of Z And. We infer that in 2009, as in 2006, the activity of the system was accompanied by a collimated bipolar ejection of matter (jets). In contrast to the situation in 2006, the jets were detected even before the system reached its maximum brightness. Moreover, components with velocities close to 1200 km/s disappeared at the maximum, while those with velocities close to 1800 km/s appeared.     

Evidence of native radiation-induced paramagnetic defects in natural illites from unconformity-type uranium deposits

This study presents the first unequivocal identification of natural radiation-induced defects in illites. Middle Proterozoic illites related to unconformity-type uranium deposits of Canada and Australia were studied using electron paramagnetic resonance (EPR) spectroscopy at X- and Q-band frequencies. The saturation behaviour of EPR spectra as a function of power demonstrates that native defects of illites are different from those known in other clays as kaolinite, dickite or smectite. Q-band spectra indicate the presence of several––at least two––native defects. The EPR signal is dominated by an axially distorted spectrum with apparent principal components as follows: g _∥ = 2.032 and g _⊥ = 1.993. The corresponding defect is named as A_i center. The study of oriented specimen confirms the strong anisotropy, and shows that the main defect has its g _∥ component perpendicular to the (ab) plane of illite. These defects in illite correspond to electron holes located on oxygen atoms of the structure and likely associated to Si, according to the lack of hyperfine structure. The A_i center in illite has similar EPR parameters to the A center in kaolinite and dickite. The isochronal annealing data suggest that illite can be used as a dosimeter in the geosphere. However, the determination of half-life and activation energy of the A_i center requires additional work.     

Copper valence,structural separation and lattice dynamics in tennantite (fahlore): NMR,NQR and SQUID studies

Electronic and magnetic properties of tennantite subfamily of tetrahedrite-group minerals have been studied by copper nuclear quadrupole resonance (NQR), nuclear magnetic resonance (NMR) and SQUID magnetometry methods. The temperature dependences of copper NQR frequencies and line-width, nuclear spin-lattice relaxation rate T ₁⁻¹ and nuclear spin-echo decay rate T ₂⁻¹ in tennantite samples in the temperature range 4.2–210 K is evidence of the presence of field fluctuations caused by electronic spins hopping between copper CuS₃ positions via S₂ bridging atom. The analysis of copper NQR data at low temperatures points to the magnetic phase transition near 65 K. The magnetic susceptibility in the range 2–300 K shows a Curie–Weiss behavior, which is mainly determined by Fe²⁺ paramagnetic substituting ions.     

Thermal expansion and dehydroxylation of phengite micas

Phengite samples (2M ₁ and 3T politypes) and a synthetic end-member muscovite specimen were studied by in situ high-temperature synchrotron radiation X-ray diffraction. The measured volume thermal expansion of 2M ₁ phengite (<α _V> ≈ 36.6 × 10⁻⁶ K⁻¹) was systematically greater than <α _V> of the 3T polytype (≈33.3 × 10⁻⁶ K⁻¹). A positive linear correlation between the average thermal expansion on (001) plane and the mean tetrahedral rotation angle at ambient condition is proposed on the ground of new measurements and literature data. Dehydroxylation processes were observed in 2M ₁, starting at 1,000 K in 3T at 800 and 945 K in synthetic muscovite. Rietveld refinements allowed a determination of structural variations upon heating of phengite samples and their dehydroxylate phases. The phengite structure expands by regularizing the tetrahedral sheet and by reducing the bond length differences between the outer and inner coordination shell of the interlayer site. The dehydroxylate phase derived from 2M ₁ is characterized by fivefold polyhedra in the low temperature form as a consequence of two OH groups reacting to form H₂O + O (residual). The dehydroxylate exhibits an increase of the cation–cation distances along the M–Or–M bonds with respect to low-temperature phengite structures. For the 3T phase, we were unable to achieve completion of dehydroxylation. The refined structural model of the dehydroxylate phase shows two hydroxyl sites, but at a short distance from one another. This result suggests that the dehydroxylation reaction did not proceed to completion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The effect of chemical composition and oxygen fugacity on the electrical conductivity of dry and hydrous garnet at high temperatures and pressures

The in situ electrical conductivity of hydrous garnet samples (Py₂₀Alm₇₆Grs₄–Py₇₃Alm₁₄Grs₁₃) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe₂O₃ + Fe₃O₄, Ni + NiO, Fe + Fe₃O₄, Fe + FeO, and Mo + MoO₂). Experimental results indicate that within a frequency range from 10⁻² to 10⁶ Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py₂₀Alm₇₆Grs₄, Py₃₀Alm₆₇Grs₃, Py₅₆Alm₄₃Grs₁, and Py₇₃Alm₁₄Grs₁₃) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py₇₃Alm₁₄Grs₁₃ garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm³/mol, respectively. The results show that small hopping polarons ( \textFe_\textMg ^· ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH ^· {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.     

Electronic absorption by Ti3+ ions and electron delocalization in synthetic blue rutile

Polarized absorption spectra, σ and π, in the spectral range 30000–400 cm⁻¹ (3.71–0.05 eV) were obtained on crystal slabs // [001] of deep blue rutile at various temperatures from 88 to 773 K. The rutile crystals were grown in Pt-capsules from carefully dried 99.999% TiO₂ rutile powder at 50 kbar/1500 °C using graphite heating cells in a belt-type apparatus. Impurities were below the detection limits of the electron microprobe (about 0.005 wt% for elements with Z≥13). The spectra are characterized by an unpolarized absorption edge at 24300 cm⁻¹, two weak and relatively narrow (Δν_1/2≈3500–4000 cm⁻¹), slightly σ-polarized bands ν₁ at 23500 cm⁻¹ and ν₂ at 18500 cm⁻¹, and a complex, strong band system in the NIR (near infra red) with sharp weak peaks in the region of the OH stretching fundamentals superimposed on the NIR system in the σ-spectra. The NIR band system and the UV edge produce an absorption minimum in both spectra, σ and π, at 21000 cm⁻¹, i.e. in the blue, which explains the colour of the crystals. Bands ν₁ and ν₂ are assigned to dd transitions to the Jahn-Teller split upper E_g state of octahedral Ti³⁺. The NIR band system can be fitted as a sum of three components. Two of them are partly π-polarized, nearly Gaussian bands, both with large half widths 6000–7000 cm⁻¹, ν₃ at 12000 cm^–1 and the most intense ν₄ at 6500 cm⁻¹. The third NIR band ν₅ of a mixed Lorentz-Gaussian shape with a maximum at 3000 cm⁻¹ forms a shoulder on the low-energy wing of ν₄. Energy positions, half band widths and temperature behaviour of these bands are consistent with a small polaron type of Ti³⁺Ti⁴⁺ charge transfer (CT). Polarization dependence of CT bands can be explained on the basis of the structural model of defect rutile by Bursill and Blanchin (1983) involving interstitial titanium. Two OH bands at 3322 and 3279 cm⁻¹ in σ-spectra show different stability during annealing, indicating two different positions of proton in the rutile structure, one of them probably connected with Ti³⁺ impurity. Total water concentration in blue rutile determined by IR spectroscopy is 0.10 wt-% OH. The EPR spectra measured in the temperature interval 20–295 K show the presence of an electron centre at temperatures above 100 K and Ti³⁺ ions in more than one structural position, but predominantly in compressed interstitial octahedral sites, at lower temperatures. These results are in good agreement with the conclusions based on the electronic absorption data. Received: 24 March 1997 / Revised, accepted: 14 October 1997     

Solid solutions of (Mg,Fe<Superscript>2+</Superscript>)-cordierite: Synthesis,water content,and magnetic properties

The dependence of water concentration in synthetic (Mg, Fe²⁺)-cordierite on the composition of the solid solution was examined in experiments that lasted for 10 days at = 200–230 MPa, t = 600–700°C, and oxygen fugacity corresponding to the Fe-FeO buffer. Mass spectrometric data indicate that the dependence of water concentration in cordierite on its Fe mole fraction Fe²⁺/(Fe²⁺ + Mg) has maxima at compositions with F = 0.2–0.3. IR diffuse reflectance spectroscopic data and data on the structural setting of H₂O molecules in the structural channels of alkali-free (Mg, Fe²⁺)-cordierite indicate that the H-H vector of some H₂O molecules (H₂O-II) is perpendicular to [001] of the crystal. The dependence of the magnetic properties of synthetic (Mg, Fe²⁺)-cordierite was studied by static magnetization technique at 5–300 K in an external magnetic field up to 20 kOe in strength.     

Structure and compressibility of synthetic ZnAl2O4 (gahnite) under high-pressure conditions, from synchrotron X-ray powder diffraction

 The structural behavior of synthetic gahnite (ZnAl₂O₄) has been investigated by X-ray powder diffraction at high pressure (0–43 GPa) and room temperature, on the ID9 beamline at ESRF. The equation of state of gahnite has been derived using the models of Birch–Murnaghan, Vinet and Poirier–Tarantola, and the results have been mutually compared (the elastic bulk modulus and its derivatives versus P determined by the third-order Birch–Murnaghan equation of state are K ₀=201.7(±0.9) GPa, K ^′ ₀=7.62(±0.09) and K ^″ ₀=−0.1022 GPa⁻¹ (implied value). The compressibilities of the tetrahedral and octahedral bond lengths [0.00188(8) and 0.00142(5) GPa⁻¹ at P=0, respectively], and the␣polyhedral volume compressibilities of the four-␣and␣sixfold coordination sites [0.0057(2) and 0.0041(2) GPa⁻¹ at P=0, respectively] are discussed. Received: 15 January 2001 / Accepted: 23 April 2001     

Manganese olivine II: point defect relaxation

To investigate the point defect chemistry and the kinetic properties of manganese olivine Mn₂SiO₄, the point defect relaxation time (τ) characterizing the rate of re-equilibration of electrical conductivity following a change in oxygen fugacity was measured for single crystals oriented for electrical conduction along the [010] direction. The experiments were carried out at temperatures T = 1173–1473 K and oxygen fugacities with the MnSiO₃ activity controlled at unity. The value of τ, which ranges from 130 to 1463 s, increases with decreasing temperature. At 1273 K, the value of τ in the regime is a factor of ∼1.8 smaller than that in the regime. The point defect relaxation time was used to calculate the chemical diffusivity (). Values of lie in the range 2.2× 10^{− 10} − 2.5×10^{− 9} m²/s. For the regime, a semi-log plot of vs 1/T yields a concave downward curve. Based on these results combined with those from Part I of this work for the point defect structure and electrical conductivity in Mn-olivine, it is proposed that the relaxation rate of electrical conduction is determined by the coupled diffusion of manganese vacancies and electron holes which rate-control the relaxation process at low and high temperatures, respectively. Deconvolution of the curve into two straight-line segments yields values for the mobilities and the diffusivities for Mn vacancies and electron holes. These results, combined with the measured electrical conductivity data, were used to calculate the concentrations of Mn vacancies and electron holes. These results in conjunction with those published for other transition-metal silicate olivines reveal the following: The mobility of electron holes in Mn-olivine is about two orders of magnitude smaller than that in Fe-olivine and is somewhat larger than that in (Mg_0.9Fe_0.1)-olivine. The mobilities of metal vacancies in these three olivines are similar both in magnitude and in temperature dependence. The concentrations of the majority point defects are the highest in Fe-olivine crystals and the lowest in Co-olivine crystals, while those in Mn-olivine and (Mg_0.9Fe_0.1)-olivine crystals lie in between. The deviation from stoichiometry in the cation sublattice for a transition-metal silicate olivine is about two orders of magnitude lower than that for the corresponding transition-metal oxide. Received: 10 January 1996 / Revised, accepted: 29 May 1997     

Electrical conductivity of dry and hydrous NaAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript> glasses and liquids at high pressures

We report the first study of electrical conductivities of silicate melts at very high pressures (up to 10 GPa) and temperatures (up to 2,173 K). Impedance spectroscopy was applied to dry and hydrous albite (NaAlSi₃O₈) glasses and liquids (with 0.02–5.7 wt% H₂O) at 473–1,773 K and 0.9–1.8 GPa in a piston-cylinder apparatus, using a coaxial cylindrical setup. Measurements were also taken at 473–2,173 K and 6–10 GPa in two multianvil presses, using simple plate geometry. The electrical conductivity of albite melts is found to increase with temperature and water content but to decrease with pressure. However, at 6 GPa, conductivity increases rapidly with temperature above 1,773 K, so that at temperatures beyond 2,200 K, conductivity may actually increase with pressure. Moreover, the effect of water in enhancing conductivity appears to be more pronounced at 6 GPa than at 1.8 GPa. These observations suggest that smaller fractions of partial melt than previously assumed may be sufficient to explain anomalously high conductivities, such as in the asthenosphere. For dry melt at 1.8 GPa, the activation energy at T > 1,073 K is higher than that at T < 1,073 K, and the inflection point coincides with the rheological glass transition. Upon heating at 6–10 GPa, dry albite glass often shows a conductivity depression starting from ~1,173 K (due to crystallization), followed by rapid conductivity enhancement when temperature approaches the albite liquidus. For hydrous melts at 0.9–1.8 GPa, the activation energies for conductivity at ≥1,373 K are lower than those at <973 K, with a complex transition pattern in between. Electrical conductivity and previously reported Na diffusivity in albite melt are consistent with the Nernst–Einstein relation, suggesting the dominance of Na transport for electrical conduction in albite melts.     

Fast ion conduction character and ionic phase-transitions in disordered crystals: the complex case of the minerals of the pearceite–polybasite group

The minerals of the pearceite–polybasite group, general formula (Ag,Cu)₁₆ M ₂S₁₁ with M = Sb, As, have been recently structurally characterized. On the whole, all the structures can be described as a regular succession of two module layers stacked along the c axis: a first module layer (labeled A), with general composition [(Ag,Cu)₆(As,Sb)₂S₇]²⁻, and a second module layer (labeled B), with general composition [Ag₉CuS₄]²⁺. In detail, in the B layer of the pearceite structure silver cations are found in various sites corresponding to the most pronounced probability density function locations of diffusion-like paths. We have shown for the first time that the observed structural disorder in the B layer is strongly related to the fast ion conduction character exhibited by these minerals. This paper reports an integrated XREF, DSC, CIS and EPMA study on all the members of the pearceite–polybasite group. DSC and conductivity measurements pointed out that the 222 members show ionic-transitions at 340 K (arsenpolybasite-222) and 350 K (polybasite-222), whereas the 221 members have transitions at lower temperature, that is, 310–330 K (arsenpolybasite-221) and 335 K (polybasite-221). For the 111 members (pearceite and antimonpearceite), the transition occurs below room temperature at 273 K. In situ single-crystal X-ray diffraction experiments showed that these minerals present the same high temperature structure and are observed at room temperature either in their high temperature (HT) fast ion conductivity form or in one of the low temperature (LT) fully ordered (222), partially ordered (221) or still disordered (111) forms, with transition temperatures slightly above or below room temperature. The pearceite–polybasite group of minerals can be considered as a homogeneous series with the same aristotype, fast ion conducting form at high temperature. Depending upon the Cu content, an ordering occurs with transition temperatures related to that content: the lower the Cu content, the higher the transition temperature from the fast ion conducting HT form to the non-ion conducting form.Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Shlykovite KCa[Si4O9(OH)] · 3H2O and cryptophyllite K2Ca[Si4O10] · 5H2O, new mineral species from the Khibiny alkaline pluton, Kola Peninsula, Russia

New minerals, shlykovite and cryptophyllite, hydrous Ca and K phyllosilicates, have been identified in hyperalkaline pegmatite at Mount Rasvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. They are the products of low-temperature hydrothermal activity and are associated with aegirine, potassium feldspar, nepheline, lamprophyllite, eudialyte, lomonosovite, lovozerite, tisinalite, shcherbakovite, shafranovskite, ershovite, and megacyclite. Shlykovite occurs as lamellae up to 0.02 × 0.02 × 0.5 mm in size or fibers up to 0.5 mm in length usually combined in aggregates up to 3 mm in size, crusts, and parallel-columnar veinlets. Cryptophyllite occurs as lamellae up to 0.02 × 0.1 × 0.2 mm in size intergrown with shlykovite being oriented parallel to {001} or chaotically arranged. Separate crystals of the new minerals are transparent and colorless; the aggregates are beige, brownish, light cream, and pale yellowish-grayish. The cleavage is parallel to (001) perfect. The Mohs hardness of shlykovite is 2.5–3. The calculated densities of shlykovite and cryptophyllite are 2.444 and 2.185 g/cm³, respectively. Both minerals are biaxial; shlykovite: 2V _meas = −60(20)°; cryptophyllite: 2V _meas > 70°. The refractive indices are: shlykovite: α = 1.500(3), β = 1.509(2), γ = 1.515(2); cryptophyllite: α = 1.520(2), β = 1.523(2), γ = 1.527(2). The chemical composition of shlykovite determined by an electron microprobe (H₂O determined from total deficiency) is as follows, wt %: 0.68 Na₂O, 11.03 K₂O, 13.70 CaO, 59.86 SiO₂, 14.73 H₂O; the total is 100.00. The empirical formula calculated on the basis of 13 O atoms (OH/H₂O calculated from the charge balance) is (K_0.96Na_0.09)_Σ1.05Ca_1.00Si_4.07O_9.32(OH)_0.68 · 3H₂O. The idealized formula is KCa[Si₄O₉(OH)] · 3H₂O. The chemical composition of cryptophyllite determined by an electron microprobe (H₂O determined from the total deficiency) is as follows, wt %: 1.12 Na₂O, 17.73 K₂O, 11.59 CaO, 0.08 Al₂O₃, 50.24 SiO₂, 19.24 H₂O, the total is 100.00. The empirical formula calculated on the basis of (Si,Al)₄(O,OH)₁₀ (OH/H₂O calculated from the charge balance) is (K_1.80Na_0.17)_Σ1.97Ca_0.99Al_0.01Si_3.99O_9.94(OH)_0.06 · 5.07H₂O. The idealized formula is K₂Ca[Si₄O₁₀] · 5H₂O. The crystal structures of both minerals were solved on single crystals using synchrotron radiation. Shlykovite is monoclinic; the space group is P2₁/n; a = 6.4897(4), b = 6.9969(5), c = 26.714(2)?, β = 94.597(8)°, V = 1209.12(15)?³, Z = 4. Cryptophyllite is monoclinic; the space group is P2₁/n; a = 6.4934(14), b = 6.9919(5), c = 32.087(3)?, β = 94.680(12)°, V= 1451.9(4)?, Z = 4. The strongest lines of the X-ray powder patterns (d, ?-I, [hkl] are: shlykovite 13.33–100[002], 6.67–76[004], 6.47–55[100], 3.469–45[021], 3.068–57[$ \bar 1 $ \bar 1 21], 3.042–45[121], 2.945–62[ 23], 2.912–90[025, 12, 211]; cryptophyllite 16.01–100[002], 7.98–24[004], 6.24–48[101], 3.228–22[$ \bar 1 $ \bar 1 09], 3.197–27[0.0.10], 2.995–47[122], 2.903–84[123, 204, $ \bar 1 $ \bar 1 24, 211], 2.623–20[028, 08, 126]. Shlykovite and cryptophyllite are members of new related structural types. Their structures are based on a two-layer packet consisting of tetrahedral Si layers linked with octahedral Ca chains. Mountainite, shlykovite and cryptophyllite could be combined into the mountainite structural family. Shlykovite is named in memory of Russian geologist V. G. Shlykov (1941–2007); the name cryptophyllite is from the Greek words meaning concealed and leaf that allude to its layered structure (phyllosilicate) in combination with a lamellar habit and intimate intergrowths with visually indistinguishable shlykovite. Type specimens of the minerals are deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.     

Thermal expansion and decomposition of jarosite: a high-temperature neutron diffraction study

The structure of deuterated jarosite, KFe₃(SO₄)₂(OD)₆, was investigated using time-of-flight neutron diffraction up to its dehydroxylation temperature. Rietveld analysis reveals that with increasing temperature, its c dimension expands at a rate ~10 times greater than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) sheet of [Fe(O,OH)₆] octahedra and [SO₄] tetrahedra with increasing temperature. Fitting of the measured cell volumes yields a coefficient of thermal expansion, α = α₀ + α₁ T, where α₀ = 1.01 × 10⁻⁴ K⁻¹ and α₁ = −1.15 × 10⁻⁷ K⁻². On heating, the hydrogen bonds, O1···D–O3, through which the (001) octahedral–tetrahedral sheets are held together, become weakened, as reflected by an increase in the D···O1 distance and a concomitant decrease in the O3–D distance with increasing temperature. On further heating to 575 K, jarosite starts to decompose into nanocrystalline yavapaiite and hematite (as well as water vapor), a direct result of the breaking of the hydrogen bonds that hold the jarosite structure together.