Dielectric constants of apatite,epidote, vesuvianite,and zoisite,and the oxide additivity rule

The dielectric constants and dielectric loss values of 4 Ca-containing minerals were determined at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: vesuvianitel κ′ _a=9.93 tan δ=0.006 κ′ _c=9.79 tan δ=0.005 vesuvianitel κ′ _a=10.02 tan δ=0.002 κ′ _c=9.85 tan δ=0.003 zoisite1 κ′ _a =10.49 tan δ=0.0006 κ′ _b =15.31 tan δ=0.0008 κ′ _c=9.51 tan δ=0.0008 zoisite2 κ′ _a =10.55 tan δ=0.0011 κ′ _b =15.45 tan δ=0.0013 κ′ _c=9.39 tan δ=0.0008 epidote κ′ ₁₁= 9.52 tan δ=0.0008 κ′ ₂₂=17.1 tan δ=0.0009 κ′ ₃₃= 9.37 tan δ=0.0006 fluorapatite1 κ′ _a =10.48 tan δ=0.0008 κ′ _c = 8.72 tan δ=0.0114 fluorapatite2 κ′ _a =10.40 tan δ=0.0010 κ′ _c=8.26 tan δ=0.0178 The deviation (δ) between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α _D (mineral)=∑ α _D (oxides) for vesuvianite is ～ 0.5%. The large deviations of epidote and zoisite from the additivity rule with Δ=+ 10.1 and + 11.7%, respectively, are attributed to “rattling” Ca ions. The combined effects of both a large F thermal parameter and possible F-ion conductivity in fluorapatite are believed to be responsible for Δ=+2–3%. Although variation of oxygen polarizability with oxygen molar volume (V_o) is believed to affect the total polarizabilities, the variation of V_o in these Ca minerals is too small to observe the effect.     

Dielectric constants of crystalline and amorphous spodumene,anorthite and diopside and the oxide additivity rule

The dielectric constants and dissipation factors of LiAlSi₂O₆, CaAl₂Si₂O₈ and CaMgSi₂O₆ in both the crystalline (α-spodumene, anorthite, and diopside) and amorphous forms were determined at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: spodumene κ′ ₁₁=7.30 tan δ= 0.0007 κ′₂₂=8.463 tan δ= 0.0002 κ′₃₃ =11.12 tan δ= 0.0007 anorthite κ′ _a ^*=5.47 tan δ= 0.0009 κ′_b ^*=8.76 tan δ= 0.0010 κ′_c ^*=7.19 tan δ= 0.0013 diopside κ′₁₁=9.69 tan δ= 0.0016 κ′₂₂ = 7.31 tan δ= 0.0007 κ′₃₃=7.29 tan δ= 0.00019 LiAlSi₂O₆ κ′=8.07 tan δ= 0.047 amorphous CaAl₂Si₂O₈ κ′=7.50 tan δ= 0.0024 amorphous CaMgSi₂O₆ κ′=8.89 tan δ= 0.0021 amorphous The dielectric properties of a spodumene glass, progressively crystallized at different conditions, were also determined. As the crystallization temperature was increased from 720 to 920° C, κ′ increased from 6.22 to 6.44. The dissipation factor, tan δ, remained constant at 0.020. Similarly, as the crystallization time at 750° C increased from 0.5 hr to 6.0 hr, κ′ increased from 6.28 to 6.35. The deviations of the measured dielectric polarizabilities as determined from the Clausius-Mosotti equation from those calculated from the sum of oxide polarizabilities according to α _D(mineral, glass) = σ α _D(oxides) are +7.4% for α-spodumene, +1.2% for diopside, and +28.0, +19.6 and +15.9% for amorphous spodumene, anorthitie and diopside compositions, respectively. Positive deviations in α-spodumene and anorthite are consistent with lower than normal apparent cation bond valence sums and are believed to be evidence for loosely bonded “rattling” Li and Ca ions. Diopside, with Ca and Mg ions having normal bond valence sums, exhibits no abnormal deviation from additivity. Larger positive deviations in amorphous SiO₂, LiAlSi₂O₆, CaAl₂Si₂O₈ and CaMgSi₂O₆ are postulated to arise from a combination of loosely bonded cations and disordered O⁼ ions where the oxygen dielectric polarizability increased from its normal value of 2.0 ų in well-behaved oxides to 2.2–3.0 Å₃ in the amorphous phases.     

Dielectric constants of tephroite,fayalite and olivine and the oxide additivity rule

The dielectric constants and dissipation factors of synthetic tephroite (Mn₂SiO₄), fayalite (Fe₃SiO₄) and a forsteritic olivine (Mg_1.80Fe_0.22SiO₄) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: tephroite, κ′_a= 8.79 tan δ_a = 0.0006 κ′_b = 10.20 tan δ_b = 0.0006 κ′_c= 8.94 tan δ_c= 0.0008 fayalite, gk′_a = 8.80 tan δ_a = 0.0004 gk′_b= 8.92 tan δ_b = 0.0018 gk′_c = 8.58 tan δ_c = 0.0010 olivine, gk′_a = 7.16 tan δ_a = 0.0006 gk′_b = 7.61 tan δ_b = 0.0008 gk′_c = 7.03 tan δ_c = 0.0006 The low dielectric constant and loss of the fayalite indicate an exceptionally low Fe³⁺ content. An FeO polarizability of 4.18 ų, determined from α_D(FeO) = [α_D (Fe₂SiO₄)-α_D(SiO₂)]/2, is probably a more reliable value for stoichiometric FeO than could be obtained from Fe_xO where x = 0.90–0.95. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α_D(M₂M′X₂) = 2α_D(MX) + α_D(M′X₂) is ～+2.8% for tephroite and +0.2% for olivine. The deviation from additivity in tephroite is discussed.     

Elastic behavior and pressure-induced structure evolution of topaz up to 45 GPa

The behavior of a natural topaz, Al_2.00Si_1.05O_4.00(OH_0.26F_1.75), has been investigated by means of in situ single-crystal synchrotron X-ray diffraction up to 45 GPa. No phase transition or change in the compressional regime has been observed within the pressure-range investigated. The compressional behavior was described with a third-order Birch–Murnaghan equation of state (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are as follows: K _V = 158(4) GPa and K _V ′ = 3.3(3). The confidence ellipse at 68.3 % (Δχ² = 2.30, 1σ) was calculated starting from the variance–covariance matrix of K _V and K′ obtained from the III-BM-EoS least-square procedure. The ellipse is elongated with a negative slope, indicating a negative correlation of the parameters K _V and K _V ′, with K _V = 158 ± 6 GPa and K _V ′ = 3.3 ± 4. A linearized III-BM-EoS was used to obtain the axial-EoS parameters (at room-P), yielding: K(a) = 146(5) GPa [β _a = 1/(3K(a)) = 0.00228(6) GPa^?1] and K′(a) = 4.6(3) for the a-axis; K(b) = 220(4) GPa [β _b = 0.00152(4) GPa^?1] and K′(b) = 2.6(3) for the b-axis; K(c) = 132(4) GPa [β _c = 0.00252(7) GPa^?1] and K′(c) = 3.3(3) for the c-axis. The elastic anisotropy of topaz at room-P can be expressed as: K(a):K(b):K(c) = 1.10:1.67:1.00 (β _a:β _b:β _c = 1.50:1.00:1.66). A series of structure refinements have been performed based on the intensity data collected at high pressure, showing that the P-induced structure evolution at the atomic scale is mainly represented by polyhedral compression along with inter-polyhedral tilting. A comparative analysis of the elastic behavior and P/T-stability of topaz polymorphs and “phase egg” (i.e., AlSiO₃OH) is carried out.     

Dielectric constants of BeO,MgO, and CaO using the two-terminal method

Using fused SiO₂, CaF₂, and SrF₂ samples with accurately known dielectric constants, we have evaluated the accuracy and precision of two-terminal dielectric constant measurements on small single crystals using empirically determined edge corrections. Values of κ′ at 1 MHz of 3.836±0.05 for silica, 6.814±0.07 for CaF₂ and 6.463±0.09 for SrF₂ indicate an accuracy and precision of 1.0–1.5% for samples having areas of 0.05–1.0 cm². Dielectric constants of BeO, MgO, and CaO measured by this technique are: BeO, κ′_a=6.87 and κ′_c=7.74; MgO, κ′= 9.90; and CaO, κ′=11.95 where κ′_a and κ′_c are the dielectric constants parallel to the a and c axes, respectively. Dielectric loss measurements on CaO in vacuum between 5–400 K at 10–10⁵ Hz indicate significant dispersion at temperatures higher than 300 K, but the effect of the losses on the dielectric constant is less than 1% at 1 MHz and 300 K.     

Dielectric constants of chrysoberyl,spinel, phenacite,and forsterite and the oxide additivity rule

The dielectric constants and dielectric loss values of BeAl₂O₄ (chrysoberyl), MgAl₂O₄ (spinel), Be₂SiO₄ (phenacite), and Mg₂SiO₄ (forsterite) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: chrysoberyl, κ′ _a =9.436, κ′ _b =9.071, κ′ _c =8.269; spinel, κ′ _a =8.18; phenacite, κ′ _a =6.28, κ′ _c =6.06; and forsterite, κ′ _a =6.867, κ′ _b =7.392, κ′ _c =6.739. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α_D(M₂M′X₄) = 2α_D(MX)+α_D(M′X₂) is ~ 1.0%.     

Ertixiite—a new mineral from the Altay Pegmatite Mine,Xinjiang, China

Ertixiite (Na₂Si₄O₉), a new mineral found in a miarolitic cavity of the Altay Pegmatite Mine, Xinjiang, China, is associated with topaz, apatite, quartz, cleavelandite, etc. The mineral is white, granular, and transparent. HNV=570.08?850.96 kg/mm² (Moh’s 5.8?6.5), D=2.35, N=1.502. Cubic system,a=5.975 Å, V=213.311 Å, Z=1,D _x =2.34g/cm³. The chemical composition of ertixiite (the average of six samples) is: Na₂O 17.97, CaO 2.82, SiO₂ 77.86, Al₂O₃ 1.45, FeO 0.05, total 100.15. The strongest lines in the X-ray powder pattern are 3.443(2, 111), 2.647(2. 210), 2.674(2,210), 1.996(8,221), 1.798(10,311), and 1.492(2,400).     

The crystal structure of sudburyite

Sudburyite is known to occur in many copper and nickel sulfide deposits in China. Its ideal formula is PdSb. The three-dimensional parameters as determined by an automatic single crystal X-ray diffractometer PW 1100 are:a ₀=4.083,c ₀=5.602 Å,Z=2. Space groupD _6h ⁴ -P6³/mmc. It is isostructural with niccolite, with parametes Pd 000,00 1/2; Sb 2/3 1/3 ¼, 1/3 2/3 ¾ andR=0.11.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Paleoclimatic interpretation of the past 30 ka from isotopic studies of the deep confined aquifer of the North China plain

The δ¹⁸O and δD values in the deep confined aquifer beneath the North China Plain which is located at 112°30′E–119°30′E and 34°46′N–40°25′N, reflect differences in paleoclimatic conditions between the Holocene and the late Pleistocene. Groundwater samples whose ¹⁴C ages are between 12 and 25 ka B.P have ranges of −9.4 to −11.7‰ for δ¹⁸O and −76‰ to −85‰ for δD values. These very negative δ¹⁸O and δD values reflect the cold and arid climate in the last glacial period. The temperature estimated in this period is 6–9 °C cooler than that of the present. The entire ranges of δ¹⁸O and δD values for samples with ¹⁴C dating from 7 ka B.P to present are −7.7‰ to −10.2‰ and −63‰ to −73‰, respectively. The greater δ¹⁸O and δD enrichments of these samples indicate a period of relatively humid and warm climate in the Holocene. However, the wide ranges of δ¹⁸O (−9.0‰ to −11.1‰) and δD (−66‰ to −80‰) values for samples with ¹⁴C age ranging from 12 to 7 ka B.P. imply an unstable climatic condition of rapidly increasing temperature, which marks the transition from the Pleistocene to the Holocene.     

Biomarkers record environmental changes along an altitudinal transect in the wettest place on Earth

The combined application of plant wax δD (δD_wax) and branched glycerol dialkyl glycerol tetraethers (brGDGTs) has been suggested as proxy for paleo-elevation. In some of the altitudinal transects studied so far, nonlinear precipitation gradients, large variations in seasonality, soil and vegetation types introduced substantial amounts of scatter in the relationship between these proxies and altitude. To further evaluate the principal functioning of the proxies, δD_wax and brGDGTs were analysed in surface soils along an altitude gradient (from 28 m up to 1865 m a.s.l.) in Meghalaya, India. The transect experiences limited seasonal temperature variation and receives very high monsoonal precipitation along the whole elevation gradient. The δD_wax show a significant relation with altitude (r² = 0.72). The additional fits with stream water δD (r² = 0.72) and modelled precipitation δD (r² = 0.72) indicate that δD_wax tracks the altitude effect on precipitation. Also the brGDGT distribution shows a correlation with altitude, reflecting the decrease in temperature with higher elevation (r² = 0.65, or r² = 0.66 using the original and recalibrated methylation of branched tetraethers-cyclisation of branched tetraethers (MBT–CBT) proxy). Application of the original MBT–CBT calibration generates calculated air temperatures that overestimate measured air temperature by ∼6 °C, whereas temperatures similar to measured are obtained with the revised calibration. These results indicate that δD_wax and brGDGTs may faithfully and accurately track environmental changes with altitude for transects where seasonal and diurnal temperature variability is relatively limited. Furthermore, proxy application to locations that experience high rainfall increases the suitability as climatic indicators, as it excludes soil moisture availability as a limiting factor.     

Strontium and samarium diffusion in diopside

The volume chemical diffusion of trace amounts of Sr in diopside has been measured as a function of temperature (1100–1300°C), pressure (1 bar–20 kbar), crystallographic direction, and composition. Three experimental/analytical techniques were employed: radiotracer and sectioning; stable tracer and ion microprobe; and Rutherford back-scattering spectroscopy. Comparison of the three yielded excellent agreement. Both natural and synthetic single crystal samples were used with results in the natural diopside giving diffusivities approximately two orders of magnitude greater than those in the man-made crystals. Samarium diffusion in the synthetic crystals was also examined with the ion probe technique with results similar to Sr.Arrhenius relations for diffusion (D = D₀exp[?ΔH_a/RT]) were calculated for different pressures and analytical techniques, and activation volumes (gDV_a) were derived from the equation D = D' exp[?PΔV_a/ RT]. Values of ΔV_a were negative for Sr diffusion. An empirical relation describing the temperature and pressure dependence of D for Sr in the c direction of the synthetic samples is: D(P, T) = 1200 (cm²/sec) exp[?122 (Kcal/mol)/RT (°K)]exp[?P (bar)/(2.94T ? 4640)R]. The expression for D_Sr in the natural samples (c direction) at one atmosphere is: D(0, T) = 54 (cm²/sec) exp[?97 (Kcal/mol)/RT (°K)]. A single compensation trend for all the data was evident for all values of D₀ and ΔH_a in the synthetic crystals.A number of models of geologic processes were investigated in light of the present data. Closure temperatures (T_c) were calculated for examples of mineral-mineral age-dating and trace element geothermometry. High values of T_c indicate that pyroxenes record emplacement events and are generally not disturbed unless a fluid enters the system. Isotopic equilibration times were examined for lower crustal xenoliths and the mantle source region for MORB using the formula of Hofmann and Hart (1978). Equilibration was shown to be too fast for production of isotopic anomalies in MORB via disequilibrium melting. Also. reasonable residence times at lower crustal temperatures were shown to produce the mineralogical-scale isotopic homogeneity observed in a crustal xenolith from Kilbourne Hole, New Mexico.     

Structural and vibrational behaviour of fluorapatite with pressure. Part I: in situ single-crystal X-ray diffraction investigation

Using single-crystal X-ray diffraction from a diamond anvil cell, the compressibility of a synthetic fluorapatite was determined up to about 7?GPa. The compression pattern was anisotropic, with greater change along a than c. Unit cell parameters varied linearly with β _a =3.32(8)?10^?3 and β _c =2.40(5)?10^?3 GPa^?1, giving a ratio β _a :β _c =1.38:1. Data fitted with a third-order Birch-Murnaghan EOS yielded a bulk modulus of K ₀=93(4)?GPa with K′=5.8(1.8). The evolution of the crystal structure of fluorapatite was analysed using data collected at room pressure, at 3.04 and 4.72?GPa. The bulk modulus of phosphate tetrahedron is about three times greater than the bulk modulus of calcium polyhedra. The values were 270(10), 100(4) and 86(3) GPa for P, Ca1 (nine-coordinated) and Ca2 (seven-coordinated) respectively. While the calcium polyhedra became more regular with pressure, the distortion of the phosphate tetrahedron remained unchanged. The size of the channel extending along the [001] direction represented the most compressible direction. The Ca2–Ca2 distance decreased from 3.982 to 3.897?Å on compression from 0.0001 to 4.72?GPa. The anisotropic compressional pattern may be understood in terms of the greater compressibility of the channel size over the polyhedral units. The reduction of the channel volume was measured by the evolution of the trigonal prism, having the Ca2–Ca2–Ca2 triangle as its base and the c lattice parameter as its height. This prism volume changed from 47.3?ų at room pressure to 44.78?ų at 4.72?GPa. Its relatively high bulk moduli, 86(3) GPa, indicated that the channel did not collapse with pressure and the apatite structure could remain stable at very high pressure.     

Crystal data for some sodium rare earth silicates

Single crystal synthesis, X-ray powder diffraction data, and electron microprobe data are given for some Na rare earth silicates of the types NaMSiO₄, Na₃MSi₂O₇, Na₃MSi₃O₉, and Na₅MSi₄O₁₂. NaYSiO₄ is orthorhombic with SG Pbn2₁, a=5.132, b=11.156, anc c=6.405 Å. NaGdSiO₄ is tetragonal with SG I4 or I \(\bar 4\) with a=11.743 and c=5.444 Å. A second form of NaGdSiO₄ is orthorhombic with SG P2₁ nb or Pmmb, a=9.179, b=27.29, and c=5.472 Å. Na₃YSi₂O₇ is hexagonal with a=9.416 and c=13.776 Å. Na₃YSi₃O₉ is orthorhombic with a=15.215, b=15.126, and c=15.036 Å. Na ion conductivities of Na₃YSi₂O₇ and Na₃YSi₃O₉ at 300° C of 5×10^?6 (Θ-cm)^?1 and 6×10^?6 (Θ-cm)^?1, respectively, are substantially less than that for Na₆YSi₄O₁₂, 1×10^?1 (Θ-cm)^?1.     

Transformation of curite into metaautunite paragenesis and electrokinetic properties

Genesis of metaautinute [Ca(UO₂/PO₄)₂ · 7H₂O] starting from curite hints at the existence of an intermediate hydrogen autunite stage [HUO₂PO₄ · 4H₂O]. The substitution of protons in hydrogen autunite by Ca²⁺ ions is proved by electrokinetic measurements. As a consequence of the similarity between X-ray powder patterns of hydrogen autunite and meta-autunite a glycolation method has been applied in order to distinguish the two species. The cell dimensions have been determined from Guinier X-ray diffraction patterns. Both minerals are tetragonal with a=6.981±0.005 Å and c=8.448±0.005 Å for metaautunite and a=7.084±0.005 Å and c=8.777±0.005 Å for hydrogen autunite. For both minerals, the zeta-potential is mostly negative and is strongly influenced by temperature, pH and concentration of cations in the suspension. The surface conductivity has been calculated from the value of the zetapotential. The electrokinetic properties of metaautunite are very similar to those of metatorbernite.     

Elastic behaviour and structural evolution of topaz at high pressure

The elastic behaviour and the high-pressure structural evolution of a natural topaz, Al_2.00Si_1.05O_4.00(OH_0.26F_1.75), have been investigated by means of in situ single-crystal X-ray diffraction up to 10.55(5) GPa. No phase transition has been observed within the pressure range investigated. Unit-cell volume data were fitted with a third-order Birch-Murnaghan Equation of State (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are: V ₀=345.57(7) ų, K _T0=164(2) GPa and K′=2.9(4). The axial-EoS parameters are: a ₀=4.6634(3) Å, K _T0(a)=152(2) GPa, K′(a)=2.8(4) for the a-axis; b ₀=8.8349(5) Å, K _T0(b)=224(3) GPa, K′(b)=2.6(6) for the b-axis; c ₀=8.3875(7) Å, K _T0(c)=137(2) GPa, K′(c)=2.9(4) for the c-axis. The magnitude and the orientation of the principal Lagrangian unit-strain ellipsoid were determined. At P−P ₀=10.55 GPa, the ratios ε₁:ε₂:ε₃ are 1.00:1.42:1.56 (with ε₁||b, ε₂||a, ε₃||c and |ε₃| > |ε₂| > |ε₁|). Four structural refinements, performed at 0.0001, 3.14(5), 5.79(5) and 8.39(5) GPa describe the structural evolution in terms of polyhedral distortions.     

Domain twinning of Laihunite and refinement of its crystal structure

Domain twinning of laihunite has been investigated based on diffracton phenomena, and its crystal structure has then been refined. Space group with respect to the domain isP2₁/c, and cell parametersa=5.813,b=4,812,c=10.211(A), β=90.87°. Atomic coordinate and bond length have been recalculated. Discussions are made of the Fe²⁺ distribution, lattice distortion, degree of order of laihunite and the relationship of this mineral with fayalite and ferrifayalite. The authors still hold that laih unite should be considered as a new silicate mineral with dominant Fe³⁺ and less amount of Fe²⁺.     

Synthesis,crystallographic data,solubility and electrokinetic properties of meta-zeunerite,meta-kirchheimerite and nickel-uranylarsenate

{M[UO₂¦AsO₄]₂ · nH₂O} with M=Cu²⁺, Co²⁺, Ni²⁺ has been synthesized from reagent grade chemicals and by ion exchange of trögerite {HUO₂AsO₄ · 4 H₂O}. Synthetic meta-zeunerite (M=Cu²⁺), meta-kirchheimerite (M=Co²⁺) and nickel-uranylarsenate are all tetragonal. The cell parameters determined from Guinier-Hägg diffraction data for {Cu[UO₂¦AsO₄]₂ · 8 H₂O} are a=b=7.10 Å and c=17.42 Å, with Z=2 and the measured density 3.70 g cm^?3. The cell parameters for {Co[UO₂¦AsO₄]₂ · 7 H₂O} and {Ni[UO²¦AsO⁴]² · 7 H₂O} are a=b=20.25 Å and c=17.20 Å, with Z=16 and the measured density 3.82 and 3.74 g cm^?3, respectively. The solubility products for synthetic Cu-, Co- and Ni-uranylarsenate at 25° C are 10^?49.20, 10^?45.34 and 10^?45.10, respectively. The zeta-potential remains negative between pH=2 and pH=9 and is strongly affected by the presence of different cations.     

The crystal structure and thermal expansion tensor of MgSO<Subscript>4</Subscript>–11D<Subscript>2</Subscript>O(meridianiite) determined by neutron powder diffraction

We have collected high-resolution neutron powder diffraction patterns from MgSO₄·11D₂O over the temperature range 4.2–250 K. The crystal is triclinic, space-group \( \text{P} \bar{1} \) (Z = 2) with a = 6.72746(6) Å, b = 6.78141(6) Å, c = 17.31803(13) Å, α = 88.2062(6)°, β = 89.4473(8)°, γ = 62.6075(5)°, and V = 701.140(6) ų at 4.2 K, and a = 6.75081(3) Å, b = 6.81463(3) Å, c = 17.29241(6) Å, α = 88.1183(3)°, β = 89.4808(3)°, γ = 62.6891(3)°, and V = 706.450(3) ų at 250 K. Structures were refined to wRp = 3.99 and 2.84% at 4.2 and 250 K, respectively. The temperature dependence of the lattice parameters over the intervening range have been fitted with a modified Einstein oscillator model which was used to obtain the coefficients of the thermal expansion tensor. The volume thermal expansion, α_V, is considerably smaller than ice Ih at all temperatures, and smaller even than MgSO₄·7D₂O (although ?α_V/?T is very similar for both sulfates); MgSO₄·11D₂O exhibits negative α_V below 55 K (compared to 70 K in D₂O ice Ih and 20 K in MgSO₄·7D₂O) The relationship between the magnitude and orientation of the principal axes of the expansion tensor and the main structural elements are discussed.     

Elasticity of diopside

The thirteen single-crystal elastic moduli for diopside as determined by the acoustic technique based on Brillouin scattering are: c₁₁=2.23, c₂₂=1.71, c₃₃=2.35, c₄₄=0.74, c₅₅=0.67, c₆₆=0.66, c₁₂=0.77, c₁₃=0.81, c₁₅=0.17, c₂₃=0.57, c₂₅=0.07, c₃₅=0.43, c₄₆=0.073. The Reuss bound of the adiabatic bulk and shear moduli calculated from these data are K _s=1.08 Mbar and G=0.651 Mbar. The room-pressure isothermal bulk modulus, K _T , and the pressure derivative of the bulk modulus, K′ _T have also been determined on a four-circle diffractometer, from a single crystal mounted in a gasketed opposed-anvil diamond cell, giving values of K _T =1.13 Mbar and K′ _T =4.8. The principal axes of the strain ellipsoid, calculated from the elastic moduli and observed in the static compression data, are identical, and the linear compressibilities are in reasonable agreement. The single-crystal elastic moduli can be correlated with the structural features of diopside.