Attachment of individual particles to a stationary air bubble in model systems

A particle–bubble attachment apparatus, similar to that used by Whelan and Brown [Bull. Inst. Min. Met. Trans. 65 (1956) 181] is developed to study free falling glass beads (d_p=131 μm) with different surface treatment attaching to a stationary air bubble (d_b=3 mm). The entire process of the particle–bubble attachment is photographically recorded using a high framing-rate camera and analyzed frame by frame. It is found that the hydrophilic particle slides on the top half of the bubble, and then the particle leaves the bubble, as anticipated. The particle sliding velocity increases with increasing angular position on the bubble surface. For the hydrophobic particle, it was found that the particle slides over the entire bubble surface without detaching from the bubble. The sliding velocity, however, reaches a maximum at an angular position of 90–100°, and then slows down to zero. A smaller sliding velocity is obtained for the hydrophobic particle than that of the hydrophilic particle at a given angular position. The attachment efficiency for the hydrophobic particle reduces with increasing initial angular positions, suggesting that the hydrophobicity alone does not directly guarantee the attachment to a bubble. Adding surfactant (sodium dodecyl sulfate [SDS]) to the test solution makes the hydrophobic particle become less hydrophobic or even hydrophilic, thereby decreasing the attachment efficiency. A much longer induction time is obtained in our present work than that reported in the literature. A simplified particle sliding velocity and attachment model is developed, and a good agreement between the theoretical prediction and experimental measurement is obtained.     

Hydrocarbon generation from coal,extracted coal and bitumen rich coal in confined pyrolysis experiments

Three sets of pyrolysis experiments were performed on extracted coal (R_o% 0.39), coal (initial bitumen 13.5 mg/g coal) and bitumen enriched coal (total bitumen 80.9 mg/g coal) at two heating rates of 2 °C/h and 20 °C/h in confined systems (gold capsules). For all three experiments, the yields of bitumen, Σn-C₈₊, aromatic components and ΣC_2–5 at first increase and then decrease with increasing EASY%R_o and reach the highest values within the EASY%R_o ranges of 0.67–1.08, 1.07–1.19, 1.46–1.79 and 1.46–1.68, respectively. In contrast, C₁/ΣC_1–5 ratio at first decreases and then increases with EASY%R_o and reaches a minimum value in EASY%R_o range of 0.86–1.08, closely corresponding to the maximum values of the yields of bitumen and Σn-C₈₊. Methane yields increase consistently with EASY%R_o. Nearly half of the maximum yield of methane from kerogen was generated at EASY%R_o > 2.2. The differences in methane yields among the three experiments at the same thermal stress are relatively minor at EASY%R_o < 2.2, but are greater with thermal stress at EASY%R_o > 2.2. This demonstrates that the kerogen always retained relatively more hydrogen and hydrocarbon generative potential at the postmature stage of bitumen rich coal than the extracted coal or coal.The maximum yield of ethane is 20–25% higher in the bitumen rich coal experiment than the extracted coal or coal, while the maximum yields of C₃, C₄ and C₅ in the former are double to triple those in the latter. This result demonstrates that the added bitumen in bitumen rich coal substantially increased the generation of these wet gases. However, the averaged values of activation energies (with the same frequency factors) for both the generation and cracking of individual wet gases are similar and do not show consistent trends among the three experiments. For all three experiments, activation energies for the generation and cracking of wet gases are significantly lower than those in previously published oil pyrolysis experiments with same frequency factors (Pan et al., 2012; Organic Geochemistry 45, 29–47). Methane δ¹³C values at the maximum temperature or EASY%R_o are close to those of initial wet gases, especially C₃, implying that the major part of methane shared a common initial precursor with wet gases, i.e., free and bound liquid alkanes.     

The aqueous solubility of trichloroethene (TCE) and tetrachloroethene (PCE) as a function of temperature

Using a flexible Au bag autoclave and a precision high-pressure liquid chromatography pump to control pressure, the liquid–liquid aqueous solubilities of TCE and PCE were measured as a function of temperature from 294 to 434 K (at constant pressure). The results were used to calculate the partial molal thermodynamic quantities of the organic liquid aqueous dissolution reactions: ΔḠ_soln, ΔH̄_soln, ΔS̄_soln and ΔC̄_{p soln}. Calculated values for these quantities at 298 K for TCE are: ΔḠ_soln=11.282 (±0.003) kJ/mol, ΔH̄_soln=−3.35 (±0.07) kJ/mol, ΔS̄_soln=−49.07 (±0.24) J/mol K, and ΔC̄_{p soln}=385.2 (±3.4) J/mol K. Calculated values for these quantities at 298 K for PCE are: ΔḠ_soln=15.80 (±0.04) kJ/mol, ΔH̄_soln=−1.79 (±0.58) kJ/mol, ΔS̄_soln=−59.00 (±1.96) J/mol K and ΔC̄_{p soln}=354.6 (±8.6) J/mol K. These thermodynamic quantities may be used to calculate the solubility of TCE and PCE at any temperature of interest. In the absence of direct measurements over this temperature range, the Henry's Law constants for TCE and PCE have been estimated using the measured aqueous solubilities and calculated vapor pressures.     

Determination of Hydrocarbon Charging History by Diagenetic Sequence and Fluid Inclusions: A Case Study of the Kongquehe Area in the Tarim Basin

Petrographic analysis of hydrocarbon inclusions in reservoirs is the basis and prerequisite for study of hydrocarbon charge history using fluid inclusion analysis.Samples from Silurian reservoirs in the Kongquehe area were studied with microscopy,cathode luminescence and scanning electron microscopy,and the paragenetic sequence of diagenetic events was established.Aqueous and oil inclusions were found in four different occurrences,i.e.,① in healed cracks in detrital quartz grains,② in quartz overgrowths that were formed relatively early in diagenesis,③ in healed cracks crosscutting quartz overgrowths and detrital quartz,and ④ in paragenetically late calcite cements.Solid bitumens were found in intergranular pores and in late fractures,whereas gas inclusions occur in healed cracks crosscutting quartz overgrowths and detrital quartz.The homogenization temperatures of aqueous(Th_(aq)) and oil incluisons(Th_0) within individual fluid inclusion assemblages are very consistent,suggesting that the microthermometric data are reliable.The Th_(aq) values are generally larger than Th_0,indicating the oil charging events took place at significant depths.The results suggest that there were at least two episodes of hydrocarbon charging in the Kongquehe area:the early hydrocarbon charging occurred in late Caledonian,dominated by oil,and the late hydrocarbon charging occurred in the Yanshan-Himalayan,first by oil and then gases.In addition,two episodes of hydrocarbon reservoir adjustment and destruction occurred in the Hercynian and Himalayan,respectively,forming solid bitumen.     

Calculation of amorphous silica solubilities at 25° to 300°C and apparent cation hydration numbers in aqueous salt solutions using the concept of effective density of water

The solubility of amorphous silica in aqueous salt solutions at 25° to 300°C can be calculated using information on its solubility in pure water and a model in which the activity of water in the salt solution is defined to equal the effective density. p_e, of “free” water in that solution. At temperatures of 100°C and above, p_e closely equals the product of the density of the solution times the weight fraction of water in the solution. At 25°C, a correction parameter must be applied to p_e that incorporates a term called the apparent cation hydration number, h. Because of the many assumptions and other uncertainties involved in determining values of h, by the model used here, the reported numbers are not necessarily real hydration numbers even though they do agree with some published values determined by activity and diffusion methods. Whether or not h is a real hydration number, it would appear to be useful in its inclusion within a more extensive activity coefficient term that describes the departure of silica solubilities in concentrated salt solutions from expected behavior according to the model presented here. Values of h can be calculated from measured amorphous silica solubilities in salt solutions at 25°C provided there is no complexing of dissolved silica with the dissolved salt, or if the degree of complexing is known. The previously postulated aqueous silica-sulfate complexing in aqueous Na₂SO₄ solutions is supported by results of the present effective density of water model.     

Atmospheric pressure changes due to volcanic eruptions and possible water level fluctuations

The data of Reed (1983) are analysed to produce the following empirical equations for the amplitude p ₀ (overall fluctuation) in Pascals of the air pressure wave associated with a volcanic eruption of volume V km³ or a nuclear explosion of strength M Mt: Here s is the distance from the source in km. $$\begin{gathered} \log _{10} p_0 = 4.44 + \log _{10} V - 0.84\log _{10} s \hfill \\ {\text{ }} = 3.44 + \log _{10} M - 0.84\log _{10} s. \hfill \\ \end{gathered} $$ Garrett's (1970) theory is examined on the generation of water level fluctuations by an air pressure wave crossing a water depth discontinuity such as a continental shelf. The total amplitude of the ocean wave is determined to be where c ₂ ¹ = gh ₁, c ₂ ² = gh ₂, g is acceleration of gravity, h ₁ and h ₂ are the water depths on the ocean and shore side of the depth discontinuity, c is the speed of propagation of the air pressure wave, and ? is the water density. $$B = \left[ {\frac{{c_2^2 }}{{c^2 - c_2^2 }} + \frac{{c^2 (c_1 - c_2 )}}{{(c - c_1 )(c^2 - c_2^2 )}}} \right]\frac{{p_0 }}{{g\varrho }}$$ It is calculated that a 10 km³ eruption at Mount St. Augustine would cause a 460 Pa air pressure wave and a discernible water level fluctuation at Vancouver Island of several cm amplitude.     

Stability of an unsupported vertical circular excavation in clays under undrained condition

By using the axisymmetric finite elements static limit analysis formulation, proposed recently by the authors, the stability numbers (γH/c_o) for an unsupported vertical circular excavation in clays, whose cohesion increases with depth, have been determined under undrained condition; γ = unit weight, H = height of the excavation and c_o = cohesion along ground surface. The results are obtained for various values of H/b and m; where b = the radius of the excavation and m = a non-dimensional parameter which accounts for the rate of the increase of cohesion with depth. The values of the stability numbers increase continuously both with increases in H/b and m. The results obtained in this study compare well with those available in literature.     

New type of possible high-pressure polymorphism in NiAs minerals in planetary cores

The nickel arsenide (B8₁) and related crystal structures are among the most important crystallographic arrangements assumed by Fe and Ni compounds with light elements such as Si, O, S, and P, expected to be present in planetary cores. Despite the simple structure, some of these materials like troilite (FeS) exhibit complex phase diagrams and rich polymorphism, involving significant changes in interatomic bonding and physical properties. NiP (oP16) represents one of the two principal structure distortions found in the nickel arsenide family and is characterized by P–P bonding interactions that lead to the formation of P₂ dimers. In the current study, the single-crystal synchrotron X-ray diffraction technique, aided by first principles density functional theory (DFT) calculations, has been applied to examine the compression behavior of NiP up to 30 GPa. Two new reversible displacive phase transitions leading to orthorhombic high-pressure phases with Pearson symbols oP40 and oC24 were found to occur at approximately 8.5 and 25.0 GPa, respectively. The oP40 phase has the primitive Pnma space group with unit cell a = 4.7729(5) Å, b = 16.6619(12) Å, and c = 5.8071(8) Å at 16.3(1) GPa and is a superstructure of the ambient oP16 phase with multiplicity of 2.5. The oC24 phase has the acentric Cmc2₁ space group with unit cell a = 9.695(6) Å, b = 5.7101(9) Å, and c = 4.7438(6) Å at 28.5(1) GPa and is a superstructure of the oP16 phase with multiplicity of 1.5. DFT calculations fully support the observed sequence of phase transitions. The two new phases constitute logical next stages of P sublattice polymerization, in which the dilution of the P₃ units, introduced in the first high-pressure phase, decreases, leading to compositions of Ni₂₀(P₃)₄(P₂)₄ and Ni₁₂(P₃)₄, and provide important clues to understanding of phase relations and transformation pathways in the NiAs family.     

Ilmenite-type solid solutions between MgSiO3 and Al2O3 and some structural systematics among ilmenite compounds

Complete solid solutions with the ilmenite structure from pure MgSiO₃ to 75% MgSiO₃·25% Al₂O₃ have been synthesized in the pressure region between 240 and 300 kbar at 1000–1400°C in a diamond-anvil cell coupled with laser heating. The results suggest that complete solid solutions with the ilmenite structure might be formed between MgSiO₃ and Al₂O₃ under high pressure-high temperature conditions. The lattice parameters for the ilmenite solid solutions between MgSiO₃ and Al₂O₃ deviate from ideality in the same manner as those found by Berry and Combs along the FeVO₃–Fe₂O₃ join. For the ordered A²⁺ B⁴⁺O₃ ilmenite-type compounds, c_o is determined primarily by the size of the relatively large A²⁺ cation, whereas a_o depends strongly on the radii of both A²⁺ and B⁴⁺ cations. Such systematics might account for the fact that c_o and a_o for the ilmenite-type MgSiO₃ are respectively smaller and larger than those for Al₂O₃. The lattice parameters _ao and molar volumes for the A₂³⁺O₃ corundum-type compounds and the disordered A²⁺B⁴⁺O₃ ilmenites follow a different trend and are, therefore, readily distinguished from the ordered A²⁺B⁴⁺O₃ ilmenites.     

Variations of the geomagnetic field during the Cretaceous

This study provides a compilation of the paleointensity records for the Cretaceous period derived from sediments of the Russian Plate and adjacent areas. The paleoinetensity values were calibrated using the laboratory redeposition experiments. Remarkable differences in the relative paleointensity variations were detected at the Berriasian–Early Barremian, Late Barremian–Santonian and Early–Late Maastrichtian boundaries. In the Berriasian–Early Barremian interval, the paleointensity varied stochastically, with the amplitude of about 1H_o and the mean value of 0.63H_o (H_o is the present-day geomagnetic field intensity assumed to be 40 μT). The records for the Barremian–Santonian give a picture of the geomagnetic field with alternating high- and low-amplitude features. The mean paleointensities remain constantly high (being on average 0.87H_o), and intervals of low-amplitude variation alternate with the pronounced bursts (3.5H_o). The Late Maastrichtian interval is characterized by high-amplitude paleointensity variations (4H_o) and a sharp drop towards the end of the interval. All records show remarkable similarities near the boundaries between geological time intervals, which are an increase in the amplitude and mean values of intensity at the end of intervals followed by a decrease towards the beginning of the subsequent interval.     

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.     

Synthetic fluid inclusions XVIII: Experimental determination of the PVTX properties of H2O-CH4 to 500 °C, 3 kbar and XCH4 ?4 mol.%

The pressure-volume-temperature-composition (PVTX) properties of H₂O-CH₄ were determined from the bubble point curve to 500 °C and 3 kbar for compositions ?4 mol.% CH₄ using the synthetic fluid inclusion technique. H₂O-CH₄ inclusions were produced by loading known amounts of Al₃C₄ and H₂O into platinum capsules along with pre-fractured and inclusion-free quartz cores. During heating the Al₃C₄ and H₂O react to produce CH₄, and the H₂O-CH₄ homogeneous mixture was trapped as inclusions during fracture healing at elevated temperature and pressure. The composition of the fluid in the inclusion was confirmed using the weight loss technique after the experiment and by Raman spectroscopic analysis of the inclusions.Homogenization temperatures of the inclusions were determined and the results were used to construct iso-T_h lines, defined as a line connecting the formation temperature and pressure with the homogenization temperature and pressure. The pressure in the inclusion at the homogenization temperature was calculated from the Duan equation of state (EOS). The slope (ΔP/ΔT) of each iso-T_h line was calculated and the results fitted to a polynomial equation using step-wise multiple regression analysis to estimate the slope of the iso-T_h line as a function of the homogenization temperature and composition according to:

(ΔP/ΔT)=a+b·m+c·m⁴+d·(T_h)²+e·m·T_h+f·m·(T_h)⁴,     

Interaction between dissolved silica and calcium carbonate: 1. Spontaneous precipitation of calcium carbonate in the presence of dissolved silica

The kinetics of spontaneous precipitation of CaCO₃ from aqueous solution in the presence of dissolved silica was investigated by recording pH as a function of time. The presence of dissolved silica, at concentrations below saturation with respect to the amorphous phase, decreases induction time for CaCO₃ nucleation, but does not affect CaCO₃ polymorphism. For a “pure” system without silica, the surface free energy, σ, determined from classical nucleation theory is 42 mJ m⁻². This agrees well with values reported in the literature for vaterite and indicates some degree of heterogeneous nucleation, which can occur because of the relatively low degree of supersaturation used for the experiments. In the presence of 1 and 2 mM silica, σ is 37 and 34 mJ m⁻², indicating an increasing degree of heterogeneous nucleation as the amount of polymeric silica increases. The ratio of Ca²⁺ to CO₃²⁻ activity was a governing parameter for determining which CaCO₃ polymorph precipitated. At high Ca²⁺ to CO₃²⁻ activity ratios, almost all initial solid was vaterite, whereas at low ratios, a mixture of vaterite and calcite was observed. In solutions with low Ca²⁺ to CO₃²⁻ activity ratios, the presence of silica at concentrations above saturation with respect to amorphous silica led to formation of only calcite and strongly influenced the crystalline structure and morphology of the precipitates. At high Ca²⁺ to CO₃²⁻ ratios, system behaviour did not differ from that without silica.     

Petalit,LiAlSi4O10: Verfeinerung der Kristallstruktur,Diskussion der Raumgruppe und Infrarot-Messung

Zusammenfassung Die Kristallstruktur von Petalit, LiAlSi₄O₁₀ (a _o =11,7540(11) Å,b _o =5,1395(5) Å,c _o =7,6296(7) Å, =113,04(1)°;Z=2; RaumgruppeC _2h ⁴ -P2/a wurde an natürlichem Material für 1926 Reflexe aufR=0,031 verfeinert. Li hat tetraedrische Koordination. [Si₄ ^[4]O₁₀]-Schichten sind über [Al^[4]O₄]-Tetraeder zu einem dreidimensionalen Gerüst verknüpft. Signifikante Anhaltspunkte für eine Symmetrieerniedrigung nachC _s ² -Pa wurden nicht gefunden. Messungen des Infrarot-Pleochroismus an orientiert geschliffenen Platten von Petalit zeigen das Vorhandensein von wenigen Zehntel Gewichtsprozent OH und deren Orientierung.

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Petalite, LiAlSi₄O₁₀: Refinement of the crystal structure and discussion of the space group and infrared measurements

Summary The crystal structure of natural petalite, LiAlSi₄O₁₀ (a _o =11.7540(11) Å,b _o =5.1395(5) Å,c _o =7.6296(7) Å, =113.04(1)°;Z=2; space groupC _2h ⁴ -P2/a), was refined using 1926 reflexions toR=0.031. Li has tetrahedral coordination. [Si₄ ^[4]O₁₀] sheets are connected by [Al^[4]O₄] tetrahedra to form a three-dimensional network. Significant evidence for the lower symmetryC _s ² -Pa was not found. The measurements of the infrared pleochroism in oriented petalite crystal plates show evidence of OH groups, in the range of a few tenths of weight percent, as well as their orientation.

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Mit 3 Abbildungen     

Calcite dissolution kinetics in the system CaCO3-H2O-CO2 at high undersaturation

Dissolution rates of limestone covered by a water film open to a CO₂-containing atmosphere are controlled by the chemical composition of the CaCO₃-H₂O-CO₂ solution at the water-mineral interface. This composition is determined by the Ca²⁺-concentration at this boundary, conversion of CO₂ into H⁺ and in the solution, and by diffusional mass transport of the dissolved species from and towards the water-limestone interface. A system of coupled diffusion-reaction equations for Ca²⁺, , and CO₂ is derived. The Ca²⁺ flux rates at the surface of the mineral are defined by the PWP-empirical rate law. These flux rates by the rules of stoichiometry must be equal to the flux rates of CO₂ across the air-water interface. In the solution, CO₂ is converted into H⁺ and . At low water-film thickness this reaction becomes rate limiting. The time dependent diffusion-reaction equations are solved for free drift dissolution by a finite-difference scheme, to obtain the dissolution rate of calcite as a function of the average calcium concentration in the water film. Dissolution rates are obtained for high undersaturation. The results reveal two regimes of linear dissolution kinetics, which can be described by a rate law F = α_i(m_ic_eq − c), where c is the calcium concentration in the water film, c_eq the equilibrium concentration with respect to calcite. For index i = 0, a fast rate law, which here is reported for the first time, is found with α₀ = 3 × 10⁻⁶ m s⁻¹ and m₀ = 0.3. For c > m₀c_eq, a slow rate law is valid with α₁ = 3 × 10⁻⁷ m  s⁻¹ and m₁ = 1, which confirms earlier work. The numbers given above are valid for film thickness of several tenths of a millimetre and at 20 °C. These rates are proven experimentally, using a flat inclined limestone plate covered by a laminar flowing water film injected at an input point with known flow rate Q and calcium concentration. From the concentration measured after flow distance x the dissolution rates are determined. These experiments have been performed at a carbon-dioxide pressure of 0.00035 atm and also of 0.01 atm. The results are in good agreement to the theoretical predictions.     

Contribution of bacteria to redox potential (E h) measurements in sediments

Increasing evidence suggests that bacteria are capable of creating specific redox conditions which are visible as species-specific continuous redox potential (E _h) measurements. It has been demonstrated that continuous measurements of E _h are valuable for tracking bacterial metabolic activities of bacterial species in liquid cultures. However, it remains uncertain whether this phenomenon is widespread among bacterial species and whether E _h measurements reflect similar mechanisms in more complex systems such as soils and sediments. The purpose of this study is therefore to evaluate whether bacteria that naturally occur in sediments have the capacity to control E _h and assess the relative partitioning of biological processes involved in E _h in natural sediments. To this end, continuous E _h measurements are linked to growth of bacteria in liquid cultures and bacterial metabolic activity in aquatic sediment microcosms containing the bioturbator Tubifex spp., in which we evaluate bacterial partitioning in microcosms treated with the bacteriocide formalin. The tested bacterial species (Micrococcus luteus, Paracoccus pantotrophus and Aminobacter aminovarans) appeared to have specific stable E _h signals during linear-exponential growth phase, suggesting that these species are capable of exerting an extracellular control on E _h measurements, thereby supporting the notion that species-specific E _h signals may be widespread among bacterial species. Formalin treatment reduced temporal variability of E _h in sediment microcosms. This outcome suggests that bacterial metabolism and inherent relative contributions of members of bacterial community principally determine development of E _h in sediment systems and that quantitation of sediment electrochemical properties may offer a potential indicator that characterizes bacterial processes.     

Synthetic Mn3+-kyanite and viridine, (Al2-xMn x 3+ ) SiO5, in the system Al2O3-MnO-MnO2-SiO2

Experiments on the join Al₂SiO₅-“Mn₂SiO₅” of the system Al₂O₃-SiO₂-MnO-MnO₂ in the pressure/temperature range 10–20 kb/900–1050° C with gem quality andalusite, Mn₂O₃, and high purity SiO₂ as starting materials and using /_O2-buffer techniques to preserve the Mn³⁺ oxidation state had following results: At 20 kb/1000°C orange-yellow kyanite mixed crystals are formed. The kyanite solid solubility is limited at about (Al_1.88Mn _0.12 ³⁺ )SiO₅ and, thus, equals approximately that on the join Al₂SiO₅-“Fe₂SiO₅” (Langer and Frentrup, 1973) indicating that there is no Jahn-Teller stabilisation of Mn³⁺ in the kyanite matrix. 5 mole % substitution causes the kyanite lattice constants a _o, b _o, c _o, and V _o to increase by 0.015, 0.009, 0.014 Å, and 1.6 ų, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn³⁺-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusite_ss (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al_1.86Mn _0.14 ³⁺ )SiO₅-(Al_1.56Mn _0,44 ³⁺ )SiO₅. Thus, Al→Mn³⁺ substitutional degrees are appreciably higher in andalusite than in kyanite, proving a strong Jahn-Teller effect of Mn³⁺ in the andalusite structure, which stabilises this structure type at the expense of kyanite and sillimanite and, thus, enlarges its PT-stability range extremely. 17 mole % substitution cause the andalusite constants a _o, b _o, c _o, and V _o to increase by 0.118, 0.029, 0.047 Å and 9.4 ų, resp. At “Mn₂SiO₅”-contents smaller than about 7 mole %, viridine coexists with Mn-poor kyanite. At “Mn₂SiO₅”-concentrations higher than the maximum kyanite or viridine miscibility, braunite (tetragonal, ideal formula Mn²⁺Mn³⁺[O₈/Si0₄]), pyrolusite and SiO₂ were found to coexist with the Mn³⁺-saturated ky _ss or and _ss, respectively. In both cases, braunites were Al-substituted (about 1 Al for 1 Mn³⁺). Pure synthetic braunites had the lattice constants a _o 9.425, c _o, 18.700 Å, V _o 1661.1 ų (ideal compn.) and a _o 9.374, c _o 18.593 ų, V _o 1633.6 ų (1 Al for 1 Mn³⁺). Stable coexistence of the Mn²⁺-bearing phase braunite with the Mn⁴⁺-bearing phase pyrolusite was proved by runs in the limiting system MnO-MnO₂-SiO₂.     

Bearing capacity computation for a ring foundation using the stress characteristics method

The stress characteristics method (SCM) has been used to compute the bearing capacity of smooth and rough ring foundations. Two different failure mechanisms for a smooth footing, and four different mechanisms for a rough footing have been considered. For a rough base, a curvilinear non-plastic wedge has been employed below the footing. The analysis incorporates the stress singularities at the inner as well as outer edges of the ring footing. Bearing capacity factors, N_c, N_q and N_γ are presented as a function of soil internal friction angle (ϕ) and the ratio (r_i/r_o) of inner to outer radii of the footing.     

A study on microwave dielectric properties of solid bitumen

Microwave complex dielectric constants were measured with the cavity perturbation method for natural bitumens of various degrees of metamorphism as well as for bitumen samples subjected to thermal metamorphism under lab conditions. The results show a positive correlation between microwave complex dielectric constant and metamorphic degree and that the magnitude of variation in this parameter is greater than that of H/C,R _max, free radical concentration,d ₀₀₂ value, back-peak temperature in organic DTA and density. Microwave complex dielectric constant can be used as an indicator of oil-gas-generating threshold. For bitumen from oil- generating areas,ε′<5 andε″<0.070; and for that from oil-pyrolyzed gas areas,ε′=5?15 andε″=0.07?0.03.