Partition coefficients of Nb and Ta between rutile and anhydrous haplogranite melts

Partition coefficients (D) for Nb and Ta between rutile and haplogranite melts in the K₂O-Al₂O₃-SiO₂ system have been measured as functions of the K₂O/Al₂O₃ ratio, the concentrations of Nb₂O₅ and Ta₂O₅, the temperature, in air and at 1 atmosphere pressure. The Ds increase in value as the K^* [K₂O/(K₂O + Al₂O₃)] molar ratio continuously decreases from highly peralkaline [K^* ∼ 0.9] to highly peraluminous [K^* ∼ 0.35] melts. The D values increase more dramatically with a unit decrease in K^* in peraluminous melts than in peralkaline melts. This compositional dependence of Ds can be explained by the high activity of NbAlO₄ species in peraluminous melts and the high activity of KONb species (or low activity of NbAlO₄ species) in peralkaline melts. A coupled substitution, Al⁺³ + Nb⁺⁵ (or Ta⁺⁵) = 2Ti⁺⁴, accounts for the Ds of Nb (Ta) being much greater in peraluminous melts than in peralkaline melts because this substitution allows Nb (Ta) to enter into the rutile structure more easily. The Ds of Ta between rutile and melt are greater than those of Nb at comparable concentrations because the molecular electronic polarizability of Ta is weaker than that of Nb. The Nb⁺⁵ with a large polarizing power forms a stronger covalent bond with oxygen than Ta⁺⁵ with a small polarizing power. The formation of the strong bond, Nb-O, distorts the rutile structure more severely than the weak bond, Ta-O; therefore, it is easier for Ta to partition into rutile than for Nb. These results imply that the utilization of the Nb/Ta ratio in liquid as a petrogenetic indicator in granitic melts must be done with caution if rutile (or other TiO₂-rich phases) is a liquidus phase. The crystallization of rutile will increase the Nb/Ta ratio of the residual liquid because the Ds of Ta between rutile and melts are greater than those of Nb. Received: 28 December 1998 / Accepted 27 September 1999     

Effects of F,B2O3 and P2O5 on the solubility of water in haplogranite melts compared to natural silicate melts

The effects of F, B₂O₃ and P₂O₅ on the H₂O solubility in a haplogranite liquid (36 wt. % SiO₂, 39 wt. % NaAlSi₃O₈, 25 wt. % KAlSi₃O₈) have been determined at 0.5, 1, 2, and 3 kb and 800, 850, and 900°C. The H₂O solubility increases with increasing F and B content of the melt. The H₂O solubility increase in more important at high pressure (2 and 3 kb) than at low pressure (0.5 kb). At 2 kb and 800°C, the H₂O solubility increases from 5.94 to 8.22 wt. % H₂O with increasing F content in the melt from 0 to 4.55 wt. %, corresponding to a linear H₂O solubility increase of 0.53 mol H₂O/mol F. With addition of 4.35 wt. % B₂O₃, the H₂O solubility increases up to 6.86 wt. % H₂O at 2 kb and 800°C, corresponding to a linear increase of 1.05 mol H₂O/mol B₂O₃. The results allow to define the individual effects of fluorine and boron on H₂O solubility in haplogranitic melts with compositions close to that of H₂O-saturated thermal minima (at 0.5–3 kb). Although P has a dramatic effect on the phase relations in the haplogranite system, its effect on the H₂O solubility was found to be negligible in natural melt compositions. The concominant increase in H₂O solubility and F can not be interpreted on the basis of the available spectroscopic data (existence of hydrated aluminofluoride complexes or not). In contrast, hydrated borates or more probably boroxol complexes have been demonstrated in B-bearing hydrous melts.     

Solubility of Au in Cl- and S-bearing hydrous silicate melts

The solubility of Au in Cl- and S-bearing hydrous rhyodacitic and andesitic melts has been experimentally investigated at 1050 °C, 200 MPa and log fO₂ close to the Ni/NiO solid oxygen buffer (NNO). The concentrations of Au in the experimental glasses have been determined using Laser Ablation ICP-MS (LA) with special efforts to avoid incorporation of Au micronuggets in the analysis. It is concluded that metal micronuggets are an experimental artefact and produced by Au partitioning into the fluids during heating with consequent precipitation on fluid dissolution in the melting glass powder. Hence, the micronuggets do not represent quench phases and must be excluded from the analysis. The micro-analytical data obtained by LA show that Au concentrations vary from ∼0.2 to ∼2.5 ppm by weight, generally consistent with the literature data for other melt compositions. The measured Au concentrations increase with increasing amounts of Cl and S dissolved in the silicate melt and show a correlation with the apparent activities of Cl and S in the system. The apparent activities of Cl and S are defined by the simplified linear relationship between volatile concentrations in the melt and activity of volatiles. The maximum activity (a^∗ = 1) is assumed to be reached at the saturation of the systems in respect of Cl-rich brine or FeS liquid for Cl and S, respectively. The dependence of Au solubility on the concentrations/activities of Cl and S at the fixed redox conditions shows that Au may form not only oxide- but also Cl- and S-bearing complexes in silicate melts. Furthermore, it indicates that exsolution of S and Cl from the melt by degassing/segregation/crystallization processes may lead to mobilization and extraction of Au into the fluid, liquid and/or mineral phase(s).     

Transport properties of high albite crystals,near-endmember feldspar and pyroxene glasses,and their melts to high temperature

Thermal diffusivity (D) was measured using laser-flash analysis (LFA) from oriented single-crystal albite and glasses near LiAlSi₃O₈, NaAlSi₃O₈, CaAl₂Si₂O₈, LiAlSi₂O₆ and CaMgSi₂O₆ compositions. Viscosity measurements of the supercooled liquids, over 2.6 × 10⁸ to 8.9 × 10¹² Pa s, confirm strongly non-Arrhenian behavior for CaAl₂Si₂O₈, and CaMgSi₂O₆, and near-Arrhenian behavior for the others. As T increases, D _glass decreases, approaching a constant near 1,000 K. Upon crossing the glass transition, D decreases rapidly. For feldspars, D for the melt is ~15% below D of the bulk crystal, whereas for pyroxenes, this difference is ~40%. Thermal conductivity (k _lat = ρC _P D) of crystals decreases with increasing T, but k _lat of glasses increases with T because heat capacity (C _P ) increases with T more strongly than density (ρ) and D decrease. For feldspars, k _lat for the melt is ~10% below that of the bulk crystal or glass, whereas this decrease for pyroxene is ~50%. Therefore, melting substantially impedes heat transport, providing positive thermal feedback that could promote further melting.     

Comparison of low-temperature with high-temperature diffusion of sodium in albite

Diffusion of sodium in albite from Amelia County, Virginia, was examined at high and intermediate temperatures by means of the sectioning technique and at low temperatures by means of an exchange technique. These studies indicate that diffusion is heterogeneous at low and intermediate temperatures, but goes to volume diffusion at high temperatures. Apparent diffusion coefficients of the order of magnitude of 10⁻¹⁸ cm²/sec and an activation energy of approximately 3000 cal/mole sodium are determined for the low-temperature movement. An activation energy of approximately 35 kcal/mole sodium is determined for the high-temperature movement.     

Solubility of manganotantalite, zircon and hafnon in highly fluxed peralkaline to peraluminous pegmatitic melts

The behavior of tantalum and zirconium in pegmatitic systems has been investigated through the determination of Ta and Zr solubilities at manganotantalite and zircon saturation from dissolution and crystallization experiments in hydrous, Li-, F-, P- and B-bearing pegmatitic melts. The pegmatitic melts are synthetic and enriched in flux elements: 0.7–1.3 wt% Li₂O, 2–5.5 wt% F, 2.8–4 wt% P₂O₅ and 0–2.8 wt% B₂O₃, and their aluminum saturation index ranges from peralkaline to peraluminous (ASI_Li = Al/[Na + K + Li] = 0.8 to 1.3) with various K/Na ratios. Dissolution and crystallization experiments were conducted at temperatures varying between 700 and 1,150°C, at 200 MPa and nearly water-saturated conditions. For dissolution experiments, pure synthetic, end member manganotantalite and zircon were used in order to avoid problems with slow solid-state kinetics, but additional experiments using natural manganotantalite and zircon of relatively pure composition (i.e., close to end member composition) displayed similar solubility results. Zircon and manganotantalite solubilities considerably increase from peraluminous to peralkaline compositions, and are more sensitive to changes in temperature or ASI of the melt than to flux content. A model relating the enthalpy of dissolution of manganotantalite to the ASI_Li of the melt is proposed: ∆H _diss (kJ/mol) = 304 × ASI_Li − 176 in the peralkaline field, and ∆H _diss (kJ/mol) = −111 × ASI_Li + 245 in the peraluminous field. The solubility data reveal a small but detectable competitivity between Zr and Ta in the melt, i.e., lower amounts of Zr are incorporated in a Ta-bearing melt compared to a Ta-free melt under the same conditions. A similar behavior is observed for Hf and Ta. The competitivity between Zr (or Hf) and Ta increases from peraluminous to peralkaline compositions, and suggests that Ta is preferentially bonded to non-bridging oxygens (NBOs) with Al as first-neighbors, whereas Zr is preferentially bonded to NBOs formed by excess alkalies. As a consequence Zr/Ta ratios, when buffered by zircon and manganotantalite simultaneously, are higher in peralkaline melts than in peraluminous melts.     

Solubility of carbon dioxide in melts of andesite,tholeiite, and olivine nephelinite composition to 30 kbar pressure

Carbon dioxide solubilities in H₂O-free hydrous silicate melts of natural andesite (CA), tholeiite (K 1921), and olivine nephelinite (OM1) compositions have been determined employing carbon-14 beta-track mapping techniques. The CO₂ solubility increases with increasing pressure, temperature, and degree of silica-undersaturation of the silicate melt. At 1650° C, CO₂ solubility in CA increases from 1.48±0.05 wt % at 15 kbar to 1.95±0.03 wt % at 30 kbar. The respective solubilities in OM1 are 3.41±0.08 wt % and 7.11±0.10 wt %. The CO₂ solubility in K1921 is intermediate between those of CA and OM1 compositions. At lower temperatures, the CO₂ contents of these silicate melts are lower, and the pressure dependence of the solubility is less pronounced. The presence of H₂O also affects the CO₂ solubility (20–30% more CO₂ dissolves in hydrous than in H₂O-free silicate melts); the solubility curves pass through an isothermal, isobaric maximum at an intermediate CO₂/(CO₂+H₂O) composition of the volatile phase. Under conditions within the upper mantle where carbonate minerals are not stable and CO₂ and H₂O are present a vapor phase must exist. Because the solubility of CO₂ in silicate melts is lower than that of H₂O, volatiles must fractionate between the melt and vapor during partial melting of peridotite. Initial low-temperature melts will be more H₂O-rich than later high-temperature melts, provided vapor is present during the melting. Published phase equilibrium data indicate that the compositional sequence of melts from peridotite +H₂O+CO₂ parent will be andesite-tholeiite-nephelinite with increasing temperature at a pressure of about 20 kbar. Examples of this sequence may be found in the Lesser Antilles and in the Indonesian Island Arcs.     

Transition metal ions in silicate melts—I. Manganese in sodium silicate melts

Optical absorption spectra obtained on glasses quenched from sodium silicate melts show Mn³⁺ to be the dominant species for melts heated in air and Mn²⁺ to be the dominant species for melts heated at Po₂ = 10^?17 bar. The absorption spectrum of Mn³⁺ consists of an intense band at 20,000cm^?1 with a 15,000cm^?1 satellite possibly arising from the Jahn-Teller effect. The independence of the spectrum from melt composition and the high band intensity is offered as evidence for a distinct Mn³⁺ complex in the melt. The spectrum of Mn²⁺ is weak and many expected bands are not observed. A two-band luminescence spectrum from Mn²⁺ has been tentatively interpreted as due to Mn²⁺ in interstitial sites in the network and Mn²⁺ coordinated by non-bridging oxygens.     

Solubility of palladium in picritic melts: 1. The effect of iron

In order to improve our understanding of HSE geochemistry, we evaluate the effect of Fe on the solubility of Pd in silicate melts. To date, experimentally determined Pd solubilities in silicate melt are only available for Fe-free anorthite-diopside eutectic compositions. Here we report experiments to study the solubility of Pd in a natural picritic melt as a function of pO₂ at 1300 °C in a one atm furnace. Palladium concentrations in the run products were determined by laser-ablation-ICP-MS. Palladium increases from 1.07 ± 0.26 ppm at FMQ-2, to 306 ± 19 ppm at FMQ+6.6. At a relative pO₂ of FMQ the slope in log Pd concentration vs. log pO₂ space increases considerably, and Pd concentrations are elevated over those established for AnDi melt compositions. In the same pO₂ range, ferric iron significantly increases relative to ferrous iron. Furthermore, at constant pO₂ (FMQ+0.5) Pd concentrations significantly increase with increasing X_FeO-total in the melt. Therefore, we consider ferric Fe to promote the formation of Pd²⁺ enhancing the solubility of Pd in the picrite melt significantly.The presence of FeO in the silicate melt has proven to be an important melt compositional parameter, and should be included and systematically investigated in future experimental studies, since most natural compositions have substantial FeO contents.     

Solubility and speciation of sulfur in silicate melts: The Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model

A Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model is developed by combining the framework of the Toop-Samis polymeric approach with the Flood-Grjotheim theoretical treatment of silicate melts and slags. Electrically equivalent ion fractions are computed over the appropriate matrixes (anionic and cationic) in a Temkin notation for fused salts, and are used to weigh the contribution of the various disproportionation reactions of type:

     

Recrystallization and peristerite formation in albite

Plagioclase in the range An₂-An₁₀ in a relatively undeformed Quartz—feldspar pegmatite is compared with similar material in a strongly deformed and recrystallized shear zone. Optical and transmission electron microscope observations and chemical data are discussed in terms of established mechanisms of strain induced recrystallization.Recrystallization occurs by the formation of subgrains from recovery, and their subsequent growth by boundary migration or coalescence by rotation. It is suggested that the recrystallization and grain growth are enhanced by a small increase in the anorthite content. Peristerite formation in the recrystallized grains is associated with the migration of high angle boundaries under upper greenschist facies conditions.     

Solubility behavior of alkali aluminosilicate components in aqueous fluids and silicate melts at high pressure and temperature

The solubility behavior of K₂O, Na₂O, Al₂O₃, and SiO₂ in silicate-saturated aqueous fluid and coexisting H₂O-saturated silicate melts in the systems K₂O-Al₂O₃-SiO₂-H₂O and Na₂O-Al₂O₃-SiO₂-H₂O has been examined in the 1- to 2-GPa pressure range at 1100°C. Glasses of Na- and K-tetrasilicate compositions with 0, 3, and 6 mol% Al₂O₃ were used as starting materials. In both systems, the oxides dissolve incongruently in aqueous fluid and silicate melt. When recalculated to an anhydrous basis, the aqueous fluids are enriched in alkalis and depleted in silica and alumina relative to their proportions in the starting materials. The extent of incongruency is more pronounced in the Na₂O-Al₂O₃-SiO₂-H₂O system than in the K₂O-Al₂O₃-SiO₂-H₂O system.The partition coefficients of the oxides, D_oxide^fluid/melt, are linear and positive functions of the oxide concentration in the fluid for each composition. There is a slight dependence of the partition coefficients on bulk composition. No effect of pressure could be discerned. For alkali metals, the fluid/melt partition coefficients range from 0.06 to 0.8. For Al₂O₃ this range is 0.01 to 0.2, and for SiO₂, it is 0.01 to 0.32. For all compositions, D_K2O^fluid/melt∼D_Na2O^fluid/melt>D_SiO2^fluid/melt>D_Al2O3^fluid/melt for the same oxide concentration in the fluid. D_K2O^fluid/melt, D_Na2O^fluid/melt, and D_SiO2^fluid/melt correlate negatively with the Al₂O₃ content of the systems. This correlation is consistent with a solubility model of alkalis that involve associated KOH°, NaOH°, silicate, and aluminate complexes.     

The effect of fluorine, boron and excess sodium on the critical curve in the albite–H2O system

Experiments to define the critical curve for a series of silicate melts in equilibrium with a hydrous fluid were carried out in a hydrothermal diamond anvil cell. Silicate compositions studied were albite with several wt% excess Na₂O, B₂O₃ and F₂O_-1. Complete miscibility between melt and water was observed at lower pressure and temperature conditions compared to pure albite for all compositions. For albite + excess Na₂O, the critical curve had been lowered by 143 and 247 °C at 10 kbar for 5 and 10 wt% excess Na. For albite +5 and 10 wt% F, the difference at 10 kbar was 147 and 246 °C respectively, and for albite +5 and 10 wt% B differences of 168 and 262 °C were found. These results are likely to be additive, with the presence of more than one of the components depressing the critical curve to even lower temperatures and pressures. The results suggest that in complex pegmatitic systems, complete miscibility between melt and fluid may be important in the final stages of crystallisation. The unusual properties of fluid phases under conditions close to the critical curve in a silicate melt-water system may be essential for the enrichment of trace elements in pegmatites as well as for the formation of typical pegmatite textures.     

Alkali ion migration in albite and K-feldspar

As part of a study of ion migration mechanisms in feldspars, the dynamical behaviour of the alkali metal cations ions in albite and K-feldspar has been investigated using a combination of dielectric spectroscopy and atomistic computer simulation techniques. The low-frequency dielectric properties of these minerals have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectra was observed for both albite and K-feldspar; the activation energy for these processes was determined to be 1.33 eV in both albite and K–feldspar. Atomistic simulation techniques were used to elucidate the mechanism and energetics of the cation migration processes. Mechanisms involving the conventional hopping of Na⁺ and K⁺ ions between cation sites in the (010) plane were found to give calculated energy barriers in good agreement with the experimentally determined activation energies. These results assist in understanding the nature of the processes responsible for the observed dielectric behaviour.     

On the theory of Al,Si ordering in albite

Calculations of the equilibrium distribution of Al, Si in the albite framework based on quasi-chemical theories of order, disorder transformations (Yang 1945; Yang and Li 1947; Li 1949) were made for a two-dimensional framework model. The ordering is caused by the energy of Al, Si interchange between sites of different crystal-chemical types and the energy of nearest neighbour interaction. By taking into account the decrease in the energy of interchange between sites with increasing disordering and with increasing temperature, and by examining different relationships for site-to-site interchange energy and the nearest neighbour interaction, it is possible to understand the basic characteristics of the transformation from low (essentially ordered) to high (essentially disordered) albite as revealed by experiment. These characteristics are: (1) abrupt variation of the equilibrium degree of order within a narrow temperature range and possible first order phase transformation for the transition from low-albite to high-albite, (2) hysteresis of the synthetic high albite transformation path and of the low albite hydrothermal “annealing” path, (3) presence of a temperature range where high albite is stable and has a continually changing equilibrium degree of order.     

Dislocation-assisted diffusion of oxygen in albite

Oxygen diffusion in albite has been determined by the integrating (bulk ¹⁸O) method between 750° and 450° C, for a P _H2O of 2 kb. The original material has a low dislocation density (<10⁶ cm^?2), and its lattice diffusion coefficient (D ₁), given below, agrees well with previous determinations. A sample was deformed at high temperature and pressure to produce a uniform dislocation density of 5 × 10⁹ cm^?2. The diffusion coefficient (D _a) for this deformed material, given below, is about 0.5 and 0.7 orders of magnitude larger than D ₁ at 700° and 450° C, respectively. This enhancement is believed due to faster diffusion along the cores of dislocations. Assuming a dislocation core radius of 4 Å, the calculated pipe diffusion coefficient (D _p), given below, is about 5 orders of magnitude larger than D ₁. These results suggest that volume diffusion at metamorphic conditions may be only slightly enhanced by the presence of dislocations. $$\begin{gathered} D_1 = 9.8 \pm 6.9 \times 10^{ - 6} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 33.4 \pm 0.6(kcal/mole)/RT] \hfill \\ \end{gathered} $$ $$\begin{gathered} D_a = 7.6 \pm 4.0 \times 10^{ - 6} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 30.9 \pm 1.1(kcal/mole)/RT] \hfill \\ \end{gathered} $$ $$\begin{gathered} D_p \approx 1.2 \times 10^{ - 1} (cm^2 /\sec ) \hfill \\ {\text{ }} \cdot \exp [ - 29.8(kcal/mole)/RT]. \hfill \\ \end{gathered} $$      

Solubility of platinum and palladium in silicate melts under high water pressure as a function of redox conditions

The solubility of platinum and palladium in a silicate melt of the composition Di ₅₅ An ₃₅ Ab ₁₀ was determined at 1200°C and 2 kbar pressure in the presence of H₂O-H₂ fluid at an oxygen fugacity ranging from the HM to WI buffer equilibria. The influence of sulfur on the solubility of platinum in fluid-bearing silicate melt was investigated at a sulfur fugacity controlled by the Pt-PtS equilibrium at 1200°C and a pressure defined in such a way that the \(f_{H_2 O} \) and \(f_{O_2 } \) values were identical to those of the experiments without sulfur. The experiments were conducted in a high pressure gas vessel with controlled hydrogen content in the fluid. Oxygen fugacity values above the NNO buffer were controlled by solid-phase buffer mixtures using the two-capsule technique. Under more reducing conditions, the contents of H₂O and H₂ were directly controlled by the argon to hydrogen ratio in a special chamber. The hydrogen fugacity varied from 5.2 × 10^?2 bar (HM buffer) to 1230 bar (\(X_{H_2 } \) = 0.5). Pt and Pd contents were measured in quenched glass samples by neutron activation analysis. The results of these investigations showed that the solubility of Pt and Pd increases significantly in the presence of water compared with experiments in dry systems. The content of Pd within the whole range of redox conditions and that of Pt at an oxygen fugacity between the HM to MW buffer reactions are weakly dependent on \(f_{O_2 } \) and controlled mainly by water fugacity. This suggests that, in addition to oxide Pt and Pd species soluble at the ppb level in haplobasaltic melts, much more soluble (ppm level) hydroxide complexes of these metals are formed under fluid-excess conditions. Despite a decrease in water fugacity under reducing conditions, Pt solubility increases sharply near the MW buffer. It was shown by electron paramagnetic resonance spectrometry that, in contrast to dry melts, fluid-saturated silicate melts do not contain a pure metal phase (micronuggets). Therefore, the increase in Pt solubility under reducing conditions can be explained by the formation of Pt hydride complexes or Pt-fluid-silicate clusters. At a sulfur fugacity controlled by the Pt-PtS equilibrium, the solubility of Pt in iron-free silicate melts as a function of redox conditions is almost identical to that obtained in the experiments without sulfur at the same water and oxygen fugacity values. These observations also support Pt dissolution in iron-free silicate melts as hydroxide species.     

Solubility of cassiterite in evolved granitic melts: effect of T, fO2, and additional volatiles

The aim of this experimental study was to determine the solubility of cassiterite in natural topaz- and cassiterite-bearing granite melts at temperatures close to the solidus. Profiles of Sn concentrations at glass–crystal (SnO₂) interface were determined following the method of (Harrison, T.M., Watson, E.B., 1983. Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content. Contributions to Mineralogy and Petrology 84, 66–72). The cassiterite concentration calculated at the SnO₂–glass interface is the SnO₂ solubility. Experiments were performed at 700–850 °C and 2 kbar using a natural F-bearing peraluminous granitic melt with 2.8 wt.% normative corundum. Slightly H₂O-undersaturated to H₂O-saturated melt compositions were chosen in order to minimize the loss of Sn to the noble element capsule walls. At the nickel–nickel oxide assemblage (Ni–NiO) oxygen fugacity buffer, the solubility of cassiterite in melts containing 1.12 wt.% F increases from 0.32 to 1.20 wt.% SnO₂ with an increasing temperature from 700 to 850 °C. At the Ni–NiO buffer and a given corundum content, SnO₂ solubility increases by 10% to 20% relative to an increase of F from 0 to 1.12 wt.%. SnO₂ solubility increases by 20% relative to increasing Cl content from 0 to 0.37 wt.% in synthetic granitic melts at 850 °C. We show that Cl is at least as important as F in controlling SnO₂ solubility in evolved peraluminous melts at oxygen fugacities close to the Ni–NiO buffer. In addition to the strong effects of temperature and fO₂ on SnO₂ solubility, an additional controlling parameter is the amount of excess Al (corundum content). At Ni–NiO and 850 °C, SnO₂ solubility increases from 0.47 to 1.10 wt.% SnO₂ as the normative corundum content increases from 0.1 to 2.8 wt.%. At oxidizing conditions (Ni–NiO +2 to +3), Sn is mainly incorporated as Sn⁴⁺ and the effect of excess Al seems to be significantly weaker than at reducing conditions.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—V. The polymeric structure of silica in albite and anorthite composition glass and the devitrification of amorphous anorthite

²⁹Si MAS NMR experiments have been carried out to determine the silica species distribution (Q distribution) in albite, NaAlSi₃O₈, and anorthite, CaAl₂Si₂O₈, composition glasses (designated albite and anorthite glass). Our results indicate that the Q distribution of albite glass contains all five possible silica species and shows a tendency towards high Q₃ and Q₄ concentrations, whereas anorthite glass does not contain Q₄ and has a high Q₀ concentration. Rationalizations are made in terms of the observed Q distributions to explain differences in devitrification behavior of these two glasses. ²⁷Al MAS NMR data for these glasses suggest that differences in devitrification behavior between these two glasses should be ascribed to small growth rates rather than small nucleation rates of crystalline albite from albite glass.     

Diffusion of Na,K, Rb and Cs in glasses of albite and orthoclase composition

The measurement of diffusion coefficients for Na, K, Rb and Cs has been realized by the technique of active salt deposits on glasses of albite and orthoclase composition, at normal pressure and in the temperature range 300–1000°C. The values of D are between 10^?6 and 10^?12 cm² s^?1 and, for every type of run, they vary with temperature according to Arrhenius laws, with activation energies ranging from 13 to 68 kcal mole^?1. These important variations are related to the size of the diffusing element (at 700°C in albite glass D_Na/D_K/D_RbD_Cs ～- 10⁷/10⁵/10³/1) and to the size of the major alkali element (for rubidium at 800°C D_or·gl/D_ab·gl ～- 20). By comparison with available data on diffusion in feldspars, we emphasize the influence of the defect density on the diffusion process.