Hydrogen bonding interactions in phase A [Mg7Si2O8(OH)6] at ambient and high pressure

Neutron powder diffraction data of phase A (Mg₇Si₂O₈(OH)₆) were collected at ambient pressure and 3.2?GPa (calculated from the compressibility of phase A) from the deuterated compound, and the structure was refined using the Rietveld method. The derived crystal structure implies that hydrogen atoms occupy two distinct sites in phase A, both forming hydrogen bonds of different lengths with the same oxygen atom. This picture is supported by IR spectra, which exhibit two absorption bands at 3400 and 3513?cm^?1 corresponding to OH stretching vibrations, and proton NMR spectra, which display two peaks with equal intensities and isotropic chemical shifts of 3.7 and 5?ppm. The D-D distance [D(1)-D(2) distance] at ambient pressure was found to be 2.09?±?0.02?Å from the neutron diffraction data and 2.09?±?0.05?Å from the NMR spectra. At 3.2?GPa, there is no statistically significant increase in the O-D interatomic distance while the hydrogen bonding interaction D···O appears to increase for one of the hydrogen sites, D(1), which has the stronger hydrogen bonding interaction compared with the other hydrogen, D(2), at ambient pressure. The O-D bond valences, determined indirectly from the D···O distances were 0.86 and 0.91 at ambient pressure, and 0.83 and 0.90?at 3.2?GPa, for D(1) and D(2), respectively.     

On the system Ba [Al2Si2O8]-Ca[Al2Si2O8]

First results obtained in the study of the Ca-Ba diadochic substitution in the several polymorphic modifications of BaAl₂Si₂O₈ are reported:

1. in the hexagonal modifications synthesized at 1200° C by a solid state reaction, Ca replaces Ba up to 37% (atomic fraction);
2. in the hexagonal modifications obtained by crystallization of a melt, the replacement is limited to 25%;
3. in the monoclinic modifications obtained by heating the above mentioned modifications to 1450° C, the replacement is limited to 25% again.

A remarkable feature of the low and high hexagonal modifications is that their unit-cell parameters show no variation with composition. These hexagonal phases, furthermore, seem identical irrespective of the method of synthesis. The unit-cell parameters of the monoclinic phases vary very little with composition.     

Sodium trisilicate: A new high-pressure silicate structure (Na2Si[Si2O7])

Crystals of sodium trisilicate (Na₂Si₃O₇) have been grown in the presence of melt at 9 GPa, 1200 °C using the MA6/8 superpress at Edmonton, and the X-ray structure determined at room pressure (R=2.0%). Na₂Si₃O₇ is monoclinic with a=8.922(2) Å, b= 4.8490(5) Å, c=11.567(1) Å, β=102.64(1)° (C2/c), D _x = 3.295 g·cm^-3. Silicon occurs in both tetrahedral and octahedral coordination (^[6]Si∶^[4]Si = l∶2). The SiO₄ tetrahedra form a diorthosilicate [Si₂O₇] group and are linked by the isolated SiO₆ octahedra via shared corners into a framework of 6-membered (^[4]Si-^[4]Si-^[6]Si^[4]Si-^[4] Si-^[6]Si) and 4-membered (^[4]Si-^[6]Si-^[4]Sr-^[6]Si) rings: 〈^[6]Si-O〉=1.789 Å, 〈^[4]Si-O〉= 1.625 Å, ^[4]Si-O-^[4]Si=132.9° and the bridging oxygen is overbonded (s = 2.22). Channels parallel to b-axis and [110] accommodate Na in irregular 6-fold coordination: 〈Na-O〉 = 2.511 Å.     

Structural characterisation of the high-pressure phase CaAl4Si2O11

Single crystals of CaAl₄Si₂O₁₁ were synthesised at 1,500?°C and 14 GPa in a multi-anvil press, and the structure of the phase determined by single-crystal X-ray diffraction at room conditions. The structure-type is that of the “hexagonal barium ferrites”. The space group of the average structure is P6 ₃ /mmc and the cell parameters are a?=?5.4223(4) Å, c?=?12.7041(6) Å, V?=?323.28(5) ų, with Z?=?2, and its density is 3.905?g?cm^?3, which is reasonable for a high-pressure alumino-silicate phase. The 22 oxygen and two calcium atoms within the unit-cell form an approximate hexagonal-close-packed array. Ten of the twelve octahedral interstices within this array that have only oxygen atoms for apices are filled with Si and/or Al. M1 octahedra share edges to form a spinel-like sheet of octahedra. The average bond length ?=?1.833 Å suggests mixed occupancy by Si and Al. The M1 octahedral sheets are linked by shared corners to pairs of face-sharing M2 octahedra containing Al, with ?= 1.918 Å. The remaining two cations of the unit-cell contents statistically occupy four tetrahedrally-coordinated interstices, which occur as face-sharing pairs. The average bond length for these sites (1.742 Å) suggests that they are occupied by Al, although Si occupancy cannot be excluded by the data. It is proposed that only one interstice of each pair is locally occupied, with the possibility of some short-range ordering of such occupancies. Complete long-range order leading to the acentric space group P6 ₃ mc is excluded by the data, as is the possibility of the average structure being comprised of merohedral (0?0?0?1) twins of P6 ₃ mc symmetry.     

Synthesis and thermal stability of 2 \frac{1}{2}-octahedral sodium mica,NaMg2.5 (OH)2∫i4O10]

A new 2 \(\frac{1}{2}\) -octahedral sheet silicate, NaMg_2.5 Si₄O₁₀ (OH)₂, has been synthesized from oxide mixtures in the temperature range 500–600°C at pressures between 1 and 5 kb. The lattice parameters are a ₀ = 5.298 Å, b ₀ = 9.047 Å, c ₀ = 9.479 Å and ß=99.55°. X-ray data are given in the text. At temperatures above 605° C/1 kb and 630° C/5 kb, it decomposes to magnesiorichterite plus quartz.     

The thermal expansion of synthetic aluminosilicate-sodalites,M 8(Al6Si6O24)X 2

Thermal expansion data, determined by powder X-ray diffraction methods are presented for 11 members of the (Li,Na,K,Rb)₈(Al₆Si₆O₂₄)Cl₂ solid solution series, 3 members of the (Na,K)₈(Al₆Si₆O₂₄)Br₂ solid solution series and Na₈(Al₆Si₆O₂₄)I₂. Only the latter showed a discontinuity in its expansion curve at 810° C wigh a mean linear expansion coefficient of 22.0×10^?6 °C^?1 below and 7.7×10^?6 °C^?1 above the discontinuity. The mean expansion coefficients from 0° to 500° C decrease gradually over the range of room temperature cell edges from 8.4 to 8.89 Å, then increase up to a cell edge of 9.01 Å above which they decrease sharply and extrapolate to a zero coefficient at 9.4 Å. These variations may be related to the expansion characteristics of the bonds between the cavity cations and cavity anions in different sodalites. The aluminosilicate-sodalites which show a discontinuity in their thermal expansion curves are those with large cavity anions, I^? or SO ₄ ^2? ; the discontinuity is believed to occur at the point when the x-coordinate of the cavity cation becomes 0.25.     

High-pressure crystal chemistry of phenakite (Be2SiO4) and bertrandite (Be4Si2O7(OH)2)

Compressibilities and high-pressure crystal structures have been determined by X-ray methods at several pressures for phenakite and bertrandite. Phenakite (hexagonal, space group R \(\bar 3\) ) has nearly isotropic compressibility with β=1.60±0.03×10^?4 kbar^?1 and β=1.45±0.07×10^?4 kbar^?1. The bulk modulus and its pressure derivative, based on a second-order Birch-Murnaghan equation of state, are 2.01±0.08 Mbar and 2±4, respectively. Bertrandite (orthorhombic, space group Cmc2₁) has anisotropic compression, with β _a =3.61±0.08, β _b =5.78±0.13 and β _c =3.19±0.01 (all ×10^?4 kbar^?1). The bulk modulus and its pressure derivative are calculated to be 0.70±0.03 Mbar and 5.3±1.5, respectively. Both minerals are composed of frameworks of beryllium and silicon tetrahedra, all of which have tetrahedral bulk moduli of approximately 2 Mbar. The significant differences in linear compressibilities of the two structures are a consequence of different degrees of T-O-T bending.     

The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.     

Hydroxyl stretching in phyllosilicates at high pressures and temperatures: an infrared spectroscopic study

The hydroxyl stretching frequencies of four phyllosilicates have been measured at high pressures and temperatures using an externally heated diamond-anvil cell and synchrotron infrared spectroscopy. Spectra were measured up to 26, 31, 21 and 8 GPa at room temperature for samples of talc, pyrophyllite, muscovite and 10-Å phase, respectively. Spectra were also measured in the range 273–500 K at ambient pressure for all samples and at 8–9 GPa for talc and pyrophyllite. The frequency of the Mg₃OH band in talc increases with pressure due to the absence of hydrogen bonding. The different orientation of the hydroxyl group in pyrophyllite and muscovite leads to hydrogen bonding and a decrease in the frequency of the Al₂OH band with pressure. 10-Å phase is approximately equivalent to talc with the addition of interlayer H₂O. In a spectrum of a sample synthesised for 143 h, two hydroxyl stretching bands are clearly resolved on compression. One is the same as the Mg₃OH band in talc, indicating the presence of intra-layer hydroxyl in a talc-like environment with no hydrogen bonding. The other, which separates from the talc-like band at 1 GPa, is associated with intra-layer hydroxyl that is hydrogen bonded to interlayer H₂O. There are equivalent bands in high-pressure spectra of a sample of deuterated 10-Å phase, synthesised for 400 h. This sample shows a greater extent of hydrogen bonding at ambient pressure than the 143 h sample. For all of the phases studied, increasing temperature leads to a decrease in frequency for every hydroxyl stretching vibration, both at low and high pressures. The shifts in frequency with temperature are an order of magnitude greater than the shifts with pressure when normalised to previously measured structural parameters.     

On local structural changes in lizardite-1T: {Si4+/Al3+}, {Si4+/Fe3+}, [Mg2+/Al3+], [Mg2+/Fe3+] substitutions

Geometrical changes induced by cation substitutions {Si⁴⁺/Al³⁺}[Mg²⁺/Al³⁺], {2Si⁴⁺/2Al³⁺} [2Mg²⁺/2Al³⁺], {Si⁴⁺/Fe³⁺} [Mg²⁺/Al³⁺] or [Mg²⁺/Fe³⁺], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8% in the 1T and 2H ₁, up to ~30% in the 2H ₂ polytype. Si⁴⁺ by Fe³⁺ substitution in the tetrahedral sheet with an Al³⁺ (Fe³⁺) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets depends on the substituting cation and the degree of substitution.     

Characterization of NH4-phlogopite (NH4) (Mg3) [AlSi3O10] (OH)2 and ND4-phlogopite (ND4) (Mg3) [AlSi3O10] (OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

 A synthesis technique is described which results in >99% pure NH₄-phlogopite (NH₄) (Mg₃) [AlSi₃O₁₀] (OH)₂ and its deuterium analogue ND₄-phlogopite (ND₄) (Mg₃) [AlSi₃O₁₀] (OD)₂. Both phases are characterised using both IR spectroscopy at 298 and 77 K as well as Rietveld refinement of their X-ray powder diffraction pattern. Both NH₄ ⁺ and ND₄ ⁺ are found to occupy the interlayer site in the phlogopite structure. Absorption bands in the IR caused by either NH₄ ⁺ or ND₄ ⁺ can be explained to a good approximation using T_d symmetry as a basis. Rietveld refinement indicates that either phlogopite synthesis contains several mica polytypes. The principle polytype is the one-layer monoclinic polytype (1M), which possesses the space group symmetry C2/m. The next most common polytype is the two-layer polytype (2M ₁ ) with space group symmetry C2/c. Minor amounts of the trigonal polytype 3T with the space group symmetry P3₁12 were found only in the synthesis run for the ND₄-phlogopite. Electron microprobe analyses indicate that NH₄-phlogopite deviates from the ideal phlogopite composition with respect to variable Si/Al and Mg/Al on both the tetrahedral and octahedral sites, respectively, due to the Tschermaks substitution ^VIMg²⁺+^IVSi⁴⁺↔^VIAl³⁺+^IVAl³⁺ and with respect to vacancies on the interlayer site due to the exchange vector ^XII(NH₄)⁺+^IVAl³⁺↔^XII□+^IVSi⁴⁺. Received: 30 August 1999 / Accepted: 2 October 2000     

Transmission electron microscope study of dislocations in orthopyroxene (Mg,Fe)2Si2O6

The orthopyroxene crystal structure can be viewed as the stacking of alternating tetrahedral and octahedral layers parallel to the (100) plane. Easy glide occurs in the (100) plane at the level of the octahedral layer to prevent breakage of the strong Si-O bonds. Dislocations with c and b Burgers vectors have been activated in (100) by room temperature indentation in an orthoenstatite gem quality single crystal. Investigations in transmission electron microscopy show that the b dislocations (b?9 Å) are not dissociated while the c's (c=5.24 Å) are dissociated into four partials. This result is interpreted by considering the oxygen sublattice as a distorted FCC one. The four c partials are thus Shockley partials bounding three stacking faults. For the two outer ones, synchroshear of the cations is necessary to keep unchanged their sixfold coordination; the oxygen sublattice is locally transformed into a HCP lattice. This accounts for the observed low splitting (?100 Å) of these faults as compared to the median one (?500 Å) which does not affect the oxygen sublattice and does not require cation synchroshear. In a Fe rich orthopyroxene (eulite), semi coherent exsolution lamellae have been studied. Either only c edge dislocations or both b and c edge dislocations occur in the phase boundaries depending upon the thickness of the lamellae. Only the c dislocations are dissociated. From the observed spacing between these mismatch dislocations a crude estimate of the exsolution temperature is proposed T _ex ? 700° C.     

Five-coordinate Cd in the crystal structure of triploidite-type Cd2(AsO4)(OH)

This paper reports on hydrothermal synthesis and crystal structure refinement of dicadmium arsenate hydroxide, Cd₂(AsO₄)(OH), obtained at 220 °C and autogenous pressure. Its crystal structure is monoclinic, space group P2₁/a, with a = 13.097(3), b = 14.089(3), c = 10.566(2) Å, β = 108.38(3)°, V = 1850.2(6) ų (Z = 16). It is isotypic with the members of the triploidite group of minerals and synthetic compounds, and thus shows a close topological relationship with the triplite group. The complex framework contains edge- and corner-sharing CdO₄(OH) and CdO₄(OH)₂ polyhedra, linked via corner-sharing to AsO₄ tetrahedra (average As—O distances range between 1.682 and 1.688 Å). Four five-coordinated Cd sites are at the centers of distorted trigonal bipyramids (average Cd—O distances are between 2.225 and 2.251 Å), whereas the remaining four Cd sites have a distorted octahedral coordination environment (average Cd—O distances are between 2.297 and 2.320 Å). The positions of all the hydrogen atoms were located in a difference-Fourier map and refined with an isotropic displacement parameter. The hydrogen-bonds are weak to very weak. The unusual five-coordination of Cd is briefly discussed in relation to comparable minerals and compounds. Among triploidite-type compounds, Cd₂(AsO₄)(OH) is the member with the largest unit cell reported so far, and the second known arsenate member.     

Single-crystal elastic properties of alunite, KAl3(SO4)2(OH)6

The single-crystal elastic constants of natural alunite (ideally KAl₃(SO₄)₂(OH)₆) were determined by Brillouin spectroscopy. Chemical analysis by electron microprobe gave a formula KAl₃(SO₄)₂(OH)₆. Single crystal X-ray diffraction refinement with R ₁ = 0.0299 for the unique observed reflections (|F _o| > 4σ _F) and wR ₂ = 0.0698 for all data gave a = 6.9741(3) Å, c = 17.190(2) Å, fractional positions and thermal factors for all atoms. The elastic constants (in GPa), obtained by fitting the spectroscopic data, are C ₁₁ = 181.9 ± 0.3, C ₃₃ = 66.8 ± 0.8, C ₄₄ = 42.8 ± 0.2, C ₁₂ = 48.2 ± 0.5, C ₁₃ = 27.1 ± 1.0, C ₁₄ = 5.4 ± 0.5, and C ₆₆ = ½(C ₁₁–C ₁₂) = 66.9 ± 0.3 GPa. The VRH averages of bulk and shear modulus are 63 and 49 GPa, respectively. The aggregate Poisson ratio is 0.19. The high value of the ratio C ₁₁/C ₃₃ = 2.7 and of the ratio C ₆₆/C ₄₄ = 1.6 are characteristic of an anisotropic structure with very weak interlayer interactions along the c-axis. The basal plane (001) is characterized by 0.1% longitudinal acoustic anisotropy and 0.9–1.1% shear acoustic anisotropy, which gives alunite a characteristic pseudo-hexagonal elastic behavior, and is related to the pseudo-hexagonal arrangement of the Al(O,OH)₆ octahedra in the basal layer. The elastic Debye temperature of alunite is 654 K. The large discrepancy between the elastic and heat capacity Debye temperature is also a consequence of the layered structure.     

Ephesite,Na(LiAl2) [Al2Si2O10] (OH)2: I. thermal stability and standard state thermodynamic properties

Ephesite, Na(LiAl₂) [Al₂Si₂O₁₀] (OH)₂, has been synthesized for the first time by hydrothermal treatment of a gel of requisite composition at 300≦T(° C)≦700 and \(P_{H_2 O}\) upto 35 kbar. At \(P_{H_2 O}\) between 7 and 35 kbar and above 500° C, only the 2M₁ polytype is obtained. At lower temperatures and pressures, the 1M polytype crystallizes first, which then inverts to the 2M₁ polytype with increasing run duration. The X-ray diffraction patterns of the 1M and 2M₁ poly types can be indexed unambiguously on the basis of the space groups C2 and Cc, respectively. At its upper thermal stability limit, 2M₁ ephesite decomposes according to the reaction (1) $$\begin{gathered} {\text{Na(LiAl}}_{\text{2}} {\text{) [Al}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{{\text{10}}} {\text{] (OH)}}_{\text{2}} \hfill \\ {\text{ephesite}} \hfill \\ {\text{ = Na[AlSiO}}_{\text{4}} {\text{] + LiAl[SiO}}_{\text{4}} {\text{] + }}\alpha {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}} {\text{ + H}}_{\text{2}} {\text{O}} \hfill \\ {\text{nepheline }}\alpha {\text{ - eucryptite corundum}} \hfill \\ \end{gathered}$$ Five reversal brackets for (1) have been established experimentally in the temperature range 590–750° C, at \(P_{H_2 O}\) between 400 and 2500 bars. The equilibrium constant, K, for this reaction may be expressed as (2) $$log K{\text{ = }}log f_{{\text{H}}_{\text{2}} O}^* = 7.5217 - 4388/T + 0.0234 (P - 1)T$$ where \(f_{H_2 O}^* = f_{H_2 O} (P,T)/f_{H_2 O}^0\) (1,T), with T given in degrees K, and P in bars. Combining these experimental data with known thermodynamic properties of the decomposition products in (1), the following standard state (1 bar, 298.15 K) thermodynamic data for ephesite were calculated: H _f,298.15 ⁰ =-6237372 J/mol, S _298.15 ⁰ =300.455 J/K·mol, G _298.15 ⁰ =-5851994 J/mol, and V _298.15 ⁰ =13.1468 J/bar·mol.     

Characterisation of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

Tobelite (NH₄) Al₂ [AlSi₃O₁₀] (OH)₂, the ammonium analogue of muscovite, and its deuterated form ND₄-tobelite (ND₄) Al₂ [AlSi₃O₁₀] (OD)₂ have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO₂-Al₂O₃ oxide mix with Al₂O₃ in excess of 5 mol% and a 25% NH₃ solution whose relative abundance was such that the amount of NH₄ ⁺ stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND₄-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K⁺ in muscovite, the NH₄ ⁺ or ND₄ ⁺ molecule occupies the interlayer site. IR absorption bands caused by NH₄ ⁺ and ND₄ ⁺ can be explained, to a very good approximation, on the basis of T_d symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal T_d symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K⁺ by NH₄ ⁺ has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND₄-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M ₁ (C2/c) and 2M ₂ (C2/c). Tobelite and ND₄-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND₄-tobelite synthesised at 200 Mpa, is 2M ₂. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH₄ ⁺ or ND₄ ⁺ compared to K⁺ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND₄-tobelite.     

Thermodynamic and magnetic properties of knorringite garnet (Mg3Cr2Si3O12) based on low-temperature calorimetry and magnetic susceptibility measurements

The low-temperature heat capacity of knorringite garnet (Mg₃Cr₂Si₃O₁₂) was measured between 2 and 300 K, and thermochemical functions were derived from the results. The measured heat capacity curves show a sharp lambda-shaped anomaly peaking at around 5.1 K. Magnetic susceptibility data show that the transition is caused by antiferromagnetic ordering. From the C _p data, we suggest a standard entropy (298.15 K) of 301 ± 2.5 J mol^?1 K^?1 for Mg₃Cr₂Si₃O₁₂. The new data are also used in conjunction with previous experimental results to constrain ?H _f ° for knorringite.     

High temperature solvent growth of anorthite on the join CaAl2Si2O8-SiO2

Stoichiometric anorthite, CaAl₂Si₂O₈, Pˉ1, with sharp a, b, c, and d diffractions was grown, using a CaV₂O₆ solvent, by cooling at 2 ° C per hour from 1450 to 750 ° C in air. Euhedral crystals up to 5 × 3× 0.5 mm, with prominent {010} and well-developed {110} and {001}, were obtained by spontaneous nucleation. Nonstoichiometric anorthite with excess SiO₂ (CaAl₂Si₂O₈+Si₂Si₂O₈) was grown on the join CaAl₂Si₂O₈-SiO₂. Chemical analysis of the synthetic anorthite, having the highest SiO₂ content, with maximum vacancies on M-site gave □_0.110 Na_0.006Ca_0.884Al_1.80Si_2.20O₈, and X-ray diffraction showed a trend from stoichiometric Pˉ1 through diffuse Pˉ1 to body-centered Iˉ1 probably reflecting increasing disorder caused by a higher Si/Al ratio in the T-sites and the positional disorder accompanied by M-site vancancies. Annealing of the nonstoichiometric diffuse Iˉ1 anorthite in air at 1050 ° C for 14 days resulted in exsolution of minute SiO₂ inclusions due to probable ordering in the T-sites and filling of M-sites by Ca. Stoichiometric Pˉ1 anorthite was not obtained by annealing at 1050 ° due to appreciable solubility of SiO₂ in CaAl₂Si₂O₈. Metastable hexagonal CaAl₂Si₂O₈ was found to be a twinned monoclinic crystal with cell dimensions: a = 10.24 (2), b = 17.74 (3), c= 14.99 (5) ?, β = 92.05 (5) °, space group C2.