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Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO2. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P2O5 is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P2O5 on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P2O5 results in a relatively small change in viscosity, while further addition of P2O5 results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm3/mol for P2O5 in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm3/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P2O5 on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully.
The intensity analysis along the crystal truncation rods has been used to analyse in situ the adsorption behaviour and the structure of K and Cs on Cu(0 0 1) at submonolayer coverages and room temperature. Up to about 0.25 ML K atoms adsorb in hollow sites followed by formation of a quasihexagonal superstructure. In contrast, for Cs adsorption the data can be interpreted by the formation of quasihexagonal Cs islands that grow with increasing coverage. For K an effective radius of 1.6(1) Å independent of coverage is determined. For Cs we fnd d = 2.1 (1) Å after formation of the quasihexagonal superstructure.
An ion-microprobe U-Pb age of 2552+ or -11 Ma has been obtained on zircon separated from a regional banded-tuff horizon in the Nauga Formation (Beukes, 1980b) (upper Campbell Group, Griqualand West Sequence, South Africa). This age permits time constraints to be placed on lithologically correlated units within the adjacent Transvaal Sequence and correlations to be made with the further removed Hamersley Group in Australia. Calculated rock accumulation rates of 2 to 4 m/m.y. for these strata of mainly shale and banded iron formation suggest that sedimentation rates were significantly slower in the late Archean-Early Proterozoic than is generally assumed.
Surface X-ray diffraction has been used to analyze in situ the room-temperature adsorption behaviour and the structure of K and Cs on Cu(100) at submonolayer coverages. Adsorption of K takes place in fourfold hollow sites up to coverages of about 0.25 monolayers (ML), where 1 ML corresponds to 1.53 × 1015 atoms/cm2. At higher coverages the formation of a quasi-hexagonal incommensurate adlayer is observed. In contrast, for Cs adsorption we observe from the very beginning the formation of the quasi-hexagonal structure up to the completion of the adlayer at about 0.30 ML. For K adsorption in the hollow sites we determine an adsorption height, d = 2.25(15) Å, corresponding to an effective K radius of reff = 1.6(1) Å close to the ionic radius of 1.33 Å. We do not observe a change in the effective radius as a function of coverage. For the quasi-hexagonal Cs structure we find an (average) adsorption height d = 2.94 Å corresponding to an effective radius of reff = 2.18 and 1.93 Å, for the limiting ca hollow- and bridge-site adsorption, respectively. The analysis of the superlattice reflections corresponding to the quasi-hexagonal incommensurate structures indicated that the K adlayer is strongly modulated. The first Fourier component of the substrate-induced modulation was determined to u01 = 1.29(3) Å. In contrast, for Cs/Cu(001) static modulation is much less important (u01 0.2 Å). Variation of the Cs adlayer density by changing the substrate temperature allows continuous expansion and contraction of the adsorbate unit cell. No commensurate-incommensurate transition has been observed.
The effect of pressure on titanium coordination in glasses, with composition K2TiSi4O11, quenched isobarically from liquids equilibrated at high pressure (5, 10, 15, 20, 25, 30 kbar respectively) and T=1600° C has been investigated by X-ray absorption spectroscopy (XAS). The XANES spectra collected at the Ti K-edge clearly show a variation with pressure that is related to changes in the geometrical environment around the Ti atoms. By comparison with spectra of standard materials, the XANES spectra of the glasses suggest a relatively low average coordination number (near 5) in samples quenched at low pressure and a higher coordination number (near 6) in samples quenched from the highest pressure. The combination of XANES data with density and compressibility measurements supports the idea that a mixture of 6- and lower coordinated (4- and/ or 5-coordinated) Ti geometries are present in the 1 bar glass, and an increasing proportion of 6-coordinated Ti occurs in the glasses synthesized at progressively higher pressures.
The (3 × 3) reconstruction of the InSb( ) surface has been analysed using grazing incidence X-ray diffraction. The reconstruction is characterized by hexamers above a complete InSb double-layer centred around an Sb atom. No vacancies are found in the structure as predicted theoretically. The results agree with scanning tunnelling microscopy measurements.
We describe the application of a novel image processing method, which allows quantitative analysis of cell and tissue movement in a series of digitized video images. The result is a vector velocity field showing average direction and velocity of movement for every pixel in the frame. We apply this method to the analysis of cell movement during different stages of the Dictyostelium developmental cycle. We analysed time-lapse video recordings of cell movement in single cells, mounds and slugs. The program can correctly assess the speed and direction of movement of either unlabelled or labelled cells in a time series of video images depending on the illumination conditions. Our analysis of cell movement during multicellular development shows that the entire morphogenesis of Dictyostelium is characterized by rotational cell movement. The analysis of cell and tissue movement by the velocity field method should be applicable to the analysis of morphogenetic processes in other systems such as gastrulation and neurulation in vertebrate embryos.
The solubility of Ni in a silicate melt has been measured using a new, mechanically assisted equilibration technique over a wide range of controlled ƒO2 values. The melt composition corresponds to the 1 atm eutectic in the system CaAl2Si2O8-CaMgSi2O6 + 10 wt% CaO. The experiments were performed at 1300°C and over an ƒO2 range of 10−8.5 to 10−13.75, and over a temperature range of 1270 to 1390°C at a constant gas mixing ratio ( ). The experiment consists of a sample of melt contained within a crucible of Ni metal and held in a 1 atm gas mixing furnace. A Ni spindle is entered into the sample from above and continuously rotated at a constant angular velocity using a viscometer head. The stirring of the sample serves to accelerate the approach to equilibrium between the liquid sample and the metal crucible (and spindle). This arrangement allows relatively rapid equilibration of Ni content following changes to higher or lower ƒO2 values. Samples of the melt may be taken at any time for analysis and thus the equilibrium solubility of Ni in the silicate melt may be determined from unambiguous experimental reversals. The Ni contents of samples, analysed both by INAA and by ICP-AES, range from 25 to 5300 ppm. The data presented in this paper indicate that the oxidation state of Ni in the investigated melt is Ni2+ over the entire range of ƒO2 investigated. This conclusion contrasts with recent reports in the literature of an inflection in the ƒO2 dependence of Ni solubility, which has been interpreted as solution of neutral Ni at low ƒO2 (Morse et al., 1991; Colson, 1992; Ehlers et al., 1992). We also present data for the temperature dependence of Ni solubility in the investigated melt. The solubility decreases with increasing temperature at constant ƒO2. The present results are in good agreement with the metal-loop-equilibration experiments reported by Holzheid et al. (1994).
Ti K-edge XANES spectra have been collected on a series of Ti-bearing silicate glasses with metasilicate and tetrasilicate compositions. The intensity of the preedge feature in these spectra has been found to change with glass composition and varies from 29 to 58% (normalized intensity) suggesting a variation in structural environent around the absorbing atom. The pre-edge peak intensity increases for the alkali titanium tetrasilicate glasses from 35% to 58% in the order Li < Na < K < Rb, Cs whereas for the metasilicate compositions there is a maximum for the K-bearing glass. The pre-edge peak intensity remains constant for the alkaline earth titanium metasilicate glasses, Ca and Sr (34%) but increases slightly for Ba (41%). As the intensity of this feature is inversely correlated with coordination number, a comparison of the pre-edge intensity data for the investigated glasses with those of materials of known coordination number leads us to establish a regression equation and to infer that the average coordination number of Ti in these glasses ranges from 4.8 to 5.8. Large alkali cations appear to stabilize a relatively low average coordination number for Ti in silicate melts. The Ti structural environment results appear also to vary as a function of SiO2 content within the K2O-TiO2-SiO2 system. A number of physical properties of the melts from which these glasses were quenched and of other Ti-bearing silicate melts, have been determined in recent years. Clear evidence of a variable coordination number of Ti, consistent with the interpretation of the present XANES data is available from density measurements. These and other property determinations are compared with the present spectroscopic observations in an attempt to relate structure and properties in these melts which contain a major component with variable coordination number.
The (3×3) reconstruction of the InSb( ) surface has been investigated by grazing incidence X-ray diffraction and scanning tunneling microscopy. The structure is characterized by 6-atom rings on top of a slightly buckled InSb top double layer. Two types of rings have been found, an elliptic ring consisting of 4 In and 2 Sb atoms and a trigonal ring with 3 In and 3 Sb atoms. The bond angles and lengths are consistent with the concept of rehybridization and depolarization which explains the reconstructions of the (111) and (110) surfaces.
There are cells acattered in the rear, prespore region of the Dictyostelium slug that share many of the properties of the prestalk cells and that are therefore called anterior-like cells (ALCs). By placing the gene encoding a cell surface protein under the control of an ALC-specific promoter and immunologically labeling the living cells, we analyze the movement of ALCs within the slug. There is a posterior to anterior cellular flow, and the ALCs change their movement pattern as they enter the prestalk zone. Prestalk cells are periodically shed from the migrating slug. They must be replaced if the correct ratio of prestalk to prespore cells is to be maintained, and we present evidence for the trans-differentiation of prespore into prestalk cells, with ALCs functioning as intermediates in the transition. The slug has, therefore, a surprisingly dynamic structure, both with respect to cellular differentiation and cell movement.
“Delta” crystals are solid solutions of miscible materials with large lattice parameter differences which contain high concentration gradients in one direction (parallel to a lattice plane strongly diffracting X-rays). The system GaSb-InSb has been chosen as suitable for study. By means of a “gradient projection method”, the growth of nearly linear composition profiles with relatively steep slopes of the lattice parameter (up to (Δa/ ) / Δz = 8.3% cm-1), adjustable by the temperature gradient, have been performed. However, the grown ingots were not monocrystalline due to the use of too high a growth rate.
The effect of non-deformable inclusions on the frequency-dependent rheology of a rhyolite melt plus crystals has been investigated using a sinusoidal torsion deformation device for measurements of shear viscosity and modulus in the frequency range of 5 mHz to 20 Hz at temperatures of 750–1050°C. The relaxed shear viscosity and unrelaxed shear modulus of rhyolite magma (rhyolite melt plus crystals plus bubbles) decreases with increasing bubble content and increases with the addition of crystals. At a crystal concentration of about 45% a relaxed value of the shear viscosity is not attainable. The presence of rigid inclusions results in an imaginary component of the shear modulus that becomes more symmetrical and shifted to the low-frequency—high-temperature range with respect to that for a crystal-free melt. The slope of log(Q−1) (internal friction) as a function of the dimensionless variable log(ωτ), is unaffected in the low-temperature—high-frequency range of crystals, with Q−1 ≈ 1/(ωτ)0.5 (the same as for bubble- and crystal-free rhyolite). For the present type of suspension, the internal friction is practically constant and independent of log(ωτ) in the high-temperature—low-frequency limit (ωτ 1). The shape of the Cole-Cole diagram becomes symmetrical and can be described as a Caputo body with parameter γ ≈ 0.45, whereas for bubble-bearing and inclusion-free rhyolite melts the shape of diagram relates to the β-relaxation exponent with β ≈ 0.5. The present work demonstrates that magma may or may not follow a power-law rheology depending on the relative volume proportion between crystals and bubbles.
Hg1 - xCdxTe and Cd1 - xZnxTe single crystals were grown by the tracwelling heater method (THM), applying two different techniques of artificially stirring the solution zone. Accelerated crucible rotation (ACRT) was used in a vertical growth arrangement and compared a technique with constant rotation around the horizontal axis of the ampoule. The dominant hydrodynamic mechanisms of noth methods are discribed by the rotating disc model and are suggested to be almost identical with respect to the growth conditions at the interface. Convective flow is effectively enhanced adhacent to the growing crystal, where the matter transport is regarded as the rate-limiting step of solution growth. Inclusion density analysis by IR microscopy was used to characterise the crystals of Cd1 - xZnxTe grown at different rates. It was shown that forced convection allows an increase in the crystal growth rate from a few mm day-1 with ACRT or horizontally rotating THM.
The effect of composition on the relaxed adiabatic bulk modulus (K0) of a range of alkali- and alkaline earth-titanosilicate [X 2 n/n+ TiSiO5 (X=Li, Na, K, Rb, Cs, Ca, Sr, Ba)] melts has been investigated. The relaxed bulk moduli of these melts have been measured using ultrasonic interferometric methods at frequencies of 3, 5 and 7 MHz in the temperature range of 950 to 1600°C (0.02 Pa s < s < 5 Pa s). The bulk moduli of these melts decrease with increasing cation size from Li to Cs and Ca to Ba, and with increasing temperature. The bulk moduli of the Li-, Na-, Ca- and Ba-bearing metasilicate melts decrease with the addition of both TiO2 and SiO2 whereas those of the K-, Rb- and Cs-bearing melts increase. Linear fits to the bulk modulus versus volume fraction of TiO2 do not converge to a common compressibility of the TiO2 component, indicating that the structural role of TiO2 in these melts is dependent on the identity of the cation. This proposition is supported by a number of other property data for these and related melt compositions including heat capacity and density, as well as structural inferences from X-ray absorption spectroscopy (XANES). The compositional dependence of the compressibility of the TiO2 component in these melts explains the difficulty incurred in previous attempts to incorporate TiO2 in calculation schemes for melt compressibility. The empirical relationship KV-4/3 for isostructural materials has been used to evaluate the compressibility-related structural changes occurring in these melts. The alkali metasilicate and disilicate melts are isostructural, independent of the cation. The addition of Ti to the metasilicate composition (i.e. X2TiSiO5), however, results in a series of melts which are not isostructural. The alkaline-earth metasilicate and disilicate compositions are not isostructural, but the addition of Ti to the metasilicate compositions (i.e. XTiSiO5) would appear, on the basis of modulus-volume systematics, to result in the melts becoming isostructural with respect to compressibility.
The physical properties, viscosity, density, heat capacity and thermal expansivity, of relaxed supercooled liquids in the temperature range just above the glass transition have been determined for ten compositions along the compositional binary Na2O---SiO2, in the range of 2–45 mole% Na2O, by a combination of scanning calorimetry, dilatometry and micropenetration viscometry. The viscosity, density, heat capacity and thermal expansivity in the glassy state have also been determined. The heat capacities illustrate a linear composition dependence for the glassy state and a smooth but strongly non-linear composition dependence for the supercooled liquid state. The thermal expansivities were determined by dilatometry up to the glass transition and, by a normalized comparison of relaxation behavior in the glass transition interval, to temperatures 50°C above the glass transition. The expansivity is a linear function of the molar composition in the glass but a strongly non-linear function of molar composition in the supercooled liquid. The viscosity data just above the glass transition temperature, combined with data from high temperature using the concentric cylinder method, illustrate that the composition dependence of viscosity is strongly non-linear and exhibits an inflection as a function of composition. The glass transition temperature, taken as the peak temperature of the calorimetric measurements, is not in general an isokom in this system. The data for these property determinations in the Na2O---SiO2 system provide much improved constraints on the partial molar properties of SiO2 liquid and partial molar properties of the SiO2 component in silicate melts. The complex behavior of the transport properties, i.e. the glass transition temperature and the viscosity, point to complexities in viscous flow beyond that of simple binary mixing of the Na2O and SiO2 components.
Thermal diffusivity of rhyolite melt and rhyolite foam (70–80% porosity) has been measured using the radial heat transfer method. Cylindrical samples (length 50–55 mm, diameter 22 mm) of rhyolite melt and foam have been derived by heating samples of Little Glass Mountain obsidian. Using available data on heat capacity and density of rhyolite melt, the thermal conductivity of samples has been determined. The difference in thermal conductivity between rhyolite melt and foam at igneous temperatures ( 1000°C) is about one order of magnitude. The effect of thermal insulation of magmas due to vesiculation and foaming of the top layer is discussed in terms of the data obtained using a simple illustrative model of magma chamber convection.
The style of magma eruption depends strongly on the character of melt degassing and foaming. Depending on the kinetics of these processes the result can be either explosive or effusive volcanism. In this study the kinetics of foaming due to the internal stresses of gas expansion of two types of obsidian have been investigated in time series experiments (2 min-24 h) followed by quenching the samples. The volumetric gas-melt ratio has been estimated through the density measurements of foamed samples. The variation of gas volume (per unit or rhyolite melt volume) with time may be described by superposition of two exponentials responsible for gas generation and gas release processes respectively. An observed difference in foaming style in this study is interpreted as the result of variations in initial contents of microlites that serve as bubble nucleation centers during devolatilization of the melts. Quantitatively the values of the gas generation rate constants (k g) are more than an order of magnitude higher in microlite-rich obsidian than in microlite-free obsidian. Possible origins of differences in the degassing style of natural magmas are discussed in the light of bubble nucleation kinetics in melts during foaming. In a complementary set of experiments the mechanical response of vesicular melt to external shear stress has been determined in a concentric cylinder viscometer. The response of vesicular melt to the pulse of shear deformation depends on the volume fraction of bubbles. The obtained response function can be qualitatively described by a Burgers body model. The experimental shear stress response function for bubble-bearing melt has an overshoot due to the strain-dependent rheology of a twophase liquid with viscously deformable inclusions.
Chemical diffusivities of B in synthetic melts of haplogranitic composition have been measured by the diffusion couple technique at 1 atm between 1200–1600°C. The compositional profiles were measured by ion microprobe and modelled using the Boltzmann-Matano formalism to retrieve compositionally dependent interdiffusion coefficients. At the experimental conditions, B2O3 is found to exchange primarily with SiO2 and the interdiffusion coefficient increases with increasing replacement of Si by B in the melt. No isotopic fractionation of boron was observed in the diffusion zone at the experimental conditions. The compositional dependence of diffusivity increases with decreasing temperature. The activation energy of diffusion (~70 kcal) is similar to that for viscous flow in melts of the same composition and is relatively insensitive to B content between 1–10 wt% B2O3 in the melt. However, the addition of the initial 1 wt% B2O3 to a haplogranitic melt appears to dramatically lower the activation energy for these processes from ~ 100 kCal to ~70 kCal. Thus, common geochemical concentrations of B may affect petrogenesis of granitic rocks by their influence on these transport properties. Some implications of these results for crystal growth and dissolution in B-bearing melts and boron isotopic variation of granitic melts have been discussed. If diffusion is the rate-limiting process, boron isotopic heterogeneity may be maintained in granitic melts at magmatic temperatures on time scales of millions of years on a millimeter scale. The influence of small amounts of B on transport properties may also contribute toward resolution of an enigma regarding emplacement mechanisms of peraluminous granites.
The thermal expansivity of liquid GeO2 at temperatures just above the glass transition has been obtained using a combination of scanning calorimetry and dilatometry. The calorimetric and dilatometric curves of c p and dV/dT are normalized to the temperature derivative of fictive temperature versus temperature using the method of Webb et al. (1992). This normalization, based on the equivalence of relaxation parameters for volume and enthalpy, allows the completion of the dilatometric trace across the glass transition to yield liquid expansivity and volume. The values of liquid volume and expansivity obtained in this study are combined with high temperature densitometry determinations of the liquid volume of GeO2 by Sekiya et al. (1980) to yield a temperature-volume relation for GeO2 melt from 660 to 1400 °C. Liquid GeO2 shows a strongly temperature-dependent liquid molar expansivity, decreasing from 20.27 × 10–4 cm3 mol–1°C–1 to 1.97 × 10–4cm3 mol–1 °C–1 with increasing temperature. The coefficient of volume thermal expansion ( v ) decreases from 76.33 × 10–6 °C–1 to 2.46 × 10–6 °C–1 with increasing temperature. A qualitatively similar volume-temperature relationship, with v decreasing from 335 × 10–6 °C–1 to 33 × 10–6 °C–1 with increasing temperature, has been observed previously in liquid B2O3. The determination of the glass transition temperature, liquid volume, liquid and glassy expansivities and heat capacities in this study, combined with compressibility data for glassy and liquid GeO2 from the literature (Soga 1969; Kurkjian et al. 1972; Scarfe et al. 1987) allows the calculation of the Prigogine-Defay ratio (), c p -c v and the thermal Grüneisen parameter ( th) for GeO2. From available data on liquid SiO2 it is concluded that liquid GeO2 is not a good analog for the low pressure properties of liquid SiO2.
The effect of P2O5 on the viscosity of a haplogranitic (K2O-Na2O-Al2O3-SiO2) liquid has been determined at 1 atm pressure in the temperature interval of 700 - 1650°C. Viscosity measurements of a haplogranite, haplogranite + 5.1 wt.% P2O5 and haplogranite + 9.5 wt.% P2O5 have been performed using the concentric cylinder and micropenetration methods. The viscosity of haplogranite liquid decreases with the addition of P2O5 at all temperatures investigated. The viscosity decrease is nonlinear, with the strongest decrease exhibited at low P2O5 concentration. The temperature-dependence of the viscosity of all the investigated liquids is Arrhenian, as is the case for P2O5 liquid. The Arrhenian activation energy is slightly lower in the P2O5-bearing liquids than in the P2O5-free haplogranite with the result that the effect of P2O5 on viscosity is a (weak) function of temperature. At temperatures corresponding to the crystallization of phosphorus-rich granitic and pegmatitic systems the addition of 1 wt.% of P2O5 decreases the viscosity 0.2 log10 units. The effect of P2O5 on haplogranitic melt viscosity is much less than that for B2O3, F2O−1 on the same melt composition (Dingwell et al., 1992 and this study). This implies that P2O5 concentration gradients in high-silica melts during, for example, phosphate mineral growth or dissolution in granitic magmas, will not significantly influence melt viscosity.
Owing to the two-dimensional periodicity of a superstructure on the crystal surface, the intensity in reciprocal space is continuously distributed along rods normal to the sample surface. The analysis of rod scans in surface X-ray diffraction provides information about the structure parameters normal to the sample surface. For high resolution to be achieved, the measurements must extend to momentum transfers q that are as large as possible. At large exit angles, the conventional Lorentz factor must be modified to take account of the finite aperture of the detector and the continuous intensity along the lattice rod. For two types of Z-axis diffractometer used in surface X-ray crystallography, an analytical expression for the resolution correction of rod-scan intensity data has been developed. It takes into account an anisotropic detector resolution T(, ), the finite width of the diffracted beam and the primary-beam divergence parallel to the sample surface, . The calculation of the convolution functions is simplified by a projection onto the q = 0 plane. The effects of different detector settings and the influences of the primary-beam divergence and the sample quality on the measured intensity are demonstrated for several examples.
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.
The heat capacities of a rhyolite and an andesite glass and liquid have been investigated from relative-enthalpy measurements made between 400 and 1800 K. For the glass phases, the experimental data agree with empirical models of calculation of the heat capacity. For the liquid phases, the agreement is less good owing to strong interactions between alkali metals and aluminum, which are not currently accounted for by empirical heat capacity models. The viscosity of both liquids has been measured from the glass transition to 1800 K. The temperature dependence of the viscosity is quantitatively related to the configurational heat capacity (determined calorimetrically) through the configurational entropy theory of relaxation processes. For both rhyolite and andesite melts, the heat capacity and viscosity do not differ markedly from those obtained by additive modeling from components with mineral compositions.
It is found that the adsorption of potassium on Al(111) at 90 K and at 300 K both result in a (√3 × √3)R0° structure. Through a detailed LEED analysis it is revealed that at 300 K the adatoms occupy substitutional sites and at 90 K the adatoms occupy on-top sites; both geometries have hitherto been considered as very unusual. The relationship between bond length and coordination is discussed with respect to the present results, and with respect to other quantitative studies of alkali-metal/metal adsorption systems.
The structure of the √3 × √3 R30° overlayer formed by CO molecules adsorbed on a Ru(0001) was analyzed by low energy electron diffraction. Anisotropic atomic motions under the influence of thermal excitation were taken into account by adopting the concept of split positions. Apart from considerable improvement in the structural refinement this technique provides information about dynamic processes. In particular, the molecular axis of the CO molecules was found to be tilted on the average by (12±3° at 150 K, which is attributed to excitation of the bending mode vibration (i.e., frustrated translation).
