Crystallization of BeO, Be2SiO4, and SiO2 from Li2MoO4-MoO3

Single crystals of phenacite (Be₂SiO₄), bromellite (BeO), and tridymite (SiO₂) were grown from an Li₂MoO₄-MoO₃ flux. Phenacite, with rhombohedral symmetry, grew in three distinct shapes with aspect ratios (length/width) as follows: needles (>3), rods (>1.1 to 1.5), and rhombohedral-faced crystals (=1). The latter grew as single crystals; the others were twinned on the     . For most experiments the temperature was held constant at 1165°C and the Li₂MoO₄/MoO₃ ratio at 1/16. The growth mechanism for crystallization was the evaporation of MoO₃. The system produced one to three phases, depending on the BeO/SiO₂ ratio. Bromellite grew until a BeO/SiO₂ ratio of 0.8 was attained. It grew as a hemipyramidal crystal having a short prism with a curved     top or as a hexagonal plate. The pyramid- and prism-shaped crystals were twinned, although a few hexagonal plates were single. Tridymite grew in small hexagonal plates when the BeO/SiO₂ ratio was less than 1.5. The effect of temperature, nucleation, and flux composition on crystal shape, twinning, and occurrence is discussed.     

Phase Diagram for the SiF4 Join in the System SiO2-Al2O3-SiF4

Alumina reacts with 1 atm of SiF₄ below 660°± 7°C to form A1F₃ and SiO₂. At higher temperatures the product is a mixture of fluorotopaz and AIF₃. Mixtures of fluorotopaz and AIF3 decompose in 1 atm of SiF₄ at 973°± 8°C and form tabular α-alumina. The equilibrium vapor pressure of SiF₄ above mixtures of fluorotopaz and AlF₃ is log p (atm) = 9.198 – 11460/ T (K). Fluorotopaz itself decomposes at 1056°± 5°C in 1 atm of SiF₄ to give acicular mullite, 2Al₂O₃^.1.07SiO₂. Alumina and mullite are stable in the presence of 1 atm of SiF₄ above 973° and 1056°C, respectively. The phase diagram of the system SiO₂-Al₂O₃-SiF₄ shows only gas-solid equilibria.     

Phase Equilibria in the System Si3N4-SiO2-BeO-Be3N2

The 1780°C isothermal section of the reciprocal quasiternary system Si₃N₄-SiO₂-BeO-Be₃N₂ was investigated by the X-ray analysis of hot-pressed samples. The equilibrium relations shown involve previously known compounds and 8 newly found compounds: Be₆Si³N₈, Be₁₁Si₅N₁₄, Be₅Si²N₆, Be₉Si₃N₁₀, Be₈SiO₄N₄, Be₆O₃N₂, Be₈O₅N₂, and Be₉O₆N₂. Large solid solubility occurs in β-Si₃N₄, BeSiN₂, Be₉Si₃N₁₀, Be₄SiN₄, and β-Be₃N₂. Solid solubility in β-Si₃N₄ extends toward Be₂SiO₄ and decreases with increasing temperature from 19 mol% at 1770°C to 11.5 mol% Be₂SiO₄ at 1880°C. A 4-phase isotherm, liquid +β-Si₃N₄ ( ss )Si₂ON₂+ BeO, exists at 1770°C.     

Phase Diagram for Mullite-SiF4

At 1 atm of SiF₄, mullite and SiF₄ react below 660° 7°C to form A1F₃ and SiO₂. From 660° to 1056°± 5°C, the product is fluorotopaz. Mullite is stable in the presence of 1 atm of SiF₄ above 1056°C. The transition temperatures at other pressures of SiF₄ can be calculated from log p (atm) = 11.587 – 10811/ T (K) and log p (atm) = 9.9609 – 13238/ T (K). The phase diagram shows only gas–solid equilibria, but there is evidence for a metastable melt from which acicular mullite and fluorotopaz grow.     

Phase Equilibria in the System Li2O-BeO-SiO2

The equilibrium phase diagram for the system Li₂O-BeO-SiO₂ contains only one ternary compound, Li₂BeSi0₄. Liquidus relations for compositions containing 33 mol% SiO₂ were determined; 10 liquidus invariant points were located and 7 subsolidus compatibility triangles. The most refractory compositions lie on the join BeO-Li₂BeSiO₄, with a solidus temperature of 1320°C. Metastable phases observed were a high-quartz phase, Li_2x(Si₁-_xBe_x)O₂, x 0.33; phase X which is probably a metastable orthosilicate between Li₂BeSiO₄ and Be₂SiO₄; and phase Y which lies on the join Li₂BeSiO₄-SiO₂. The crystal chemistry and glass network-forming properties of BeO are discussed.     

Vapor Pressure, Enthalpy, Evaporation Coefficient, and Enthalpy of Activation of the Beryllium Nitride (Be3N2) Decomposition Reaction

Beryllium nitride (Be₃N₂) vaporizes congruently in the range 1640° to 1960°K by the reaction Be, N₂( c ) = 3Be( g ) + N₂( g ). The equilibrium nitrogen partial pressure, in atmospheres, at the composition for congruent sublimation is given by the expression log P _N2= [(–1.952 ± 0.038) × 10⁴] T ⁻¹+ (6.509 ± 0.207). The measured enthalpy of decomposition (370 ± 5 kcal at 298° K) yields an enthalpy of formation for Be₃N₂( c ) of –136 ± 6 kcal/mole. The upper limit to the evaporation coefficient at 1600° to 2000°K can be set as 10^–4 by comparison of equilibrium data to Langmuir data obtained with a sample of 18% porosity. The apparent enthalpy of activation for the reaction is 409 ± 7 kcal/mole at 1800°K for the porous Langmuir specimen. An expression is developed to predict the temperature dependence of the reduced apparent pressures in Knudsen studies of substances with low evaporation coefficients in terms of the enthalpy of activation. The variation in temperature dependence of the Langmuir measurements and Knudsen measurements with three different-sized orifices is consistent with predictions from this expression.     

The Join Ca2SiO4-CaMgSiO4

New data obtained on the join Ca₂SiO₄-CaMgSiO₄ established a limit of crystalline solubility of Mg in α-Ca₂SiO₄ corresponding to the composition Ca_1.90Mg_0.10SiO₄ at 1575°C. The α-α'Ca₂SiO₄ inversion temperature is lowered from 1447° to 1400°C by Mg substitution in the lattice. α'-Ca₂SiO₄ takes Mg into its lattice up to the composition Ca_1.94Mg_0.06SiO₄ at 1400°C and to Ca_1.96Mg_0.04SiO₄ at 900°C. A new phase (T) reported previously by Gutt, with the approximate composition Ca_1.70Mg_0.30SiO₄, was stable between 979° and 1381°C, and should be stable at liquidus temperatures in multicomponent systems involving CaO–MgO–SiO₂.     

Fluoride Model Systems: IV, The Systems LiF-BeF2 and PbF2-BeF2

Additional information on phase equilibria in the subsolidus region of the system LiF-BeF₂ was obtained and a study was made of the system PbF₂–BeF₂. In the system LiF-BeF₂ the compound LiBeF₃ occurs; it decomposes below the solidus at 300° C. to yield Li₂BeF₄ and the quartz form of BeF₂. An additional subsolidus compound having the probable composition LiBe₂F₅ forms below 275°C. No evidence was found for the existence of the alleged compound LiBe₂F₅. In the system PbF₂-BeF₂ two compounds occur: 3PbF₂.BeF₂ and PbF₂-BeF₂; the former melts congruently at 482°± 5°C. and the latter at 585°± 5°C. Extensive solid solution exists between PbF₂.BeF₂ and BeF₂. The cristobalite form of BeF₂ crystallizes from glasses of high BeF₂ content at temperatures of 450°C. or lower but is converted to the quartz form by heating at higher temperatures or in the presence of liquid.     

Compound Formation and Phase Equilibria in the System PbO-SiO2

Compound formation in the system PbO-SiO₂ was studied; the results are contrasted with those previously reported. Fifteen binary phases, 4 of which had not been reported, were prepared in the present study. The new phases include Pb₅Si₈O₂₁, an orthorhombic polymorph of PbSiO₃, Pb₃SiO₅, and a high-SiO₂ phase containing ∼ 60 mol% SiO₂. It was shown that Pb₃SiO₅ is thermodynamically stable relative to Pb₂SiO₄ and 4PbO.SiO₂ below 640±5°C. A revised phase equilibrium diagram is presented.     

Fluoride Model Systems: II, The Binary Systems CaF2–BeF2, MgF2–BeF2, and LiF–MgF2

Data obtained by quenching, thermal, and high-temperature X-ray techniques are presented for the three binary systems CaF₂–BeF₂, MgF₂–BeF₂, and LiF–MgF₂. The systems CaF₂–BeF₂ and MgF₂–BeF₂ are presented as weakened models of the systems ZrO₂–SiO₂ and TiO₂–SiO₂, respectively. The compound CaBeF₄ is a model of ZrSiO₄ (zircon). New data obtained for the system LiF–MgF₂ explain many discrepancies among the results of previous authors. Solid solution is almost complete between LiF and MgF₂ at elevated temperatures, but a small gap occurs at the eutectic (735°C.) with extensive exsolution at lower temperatures.     

Thermal Diffusivity of Be4B, Be2B, and BeB6

The thermal diffusivities of polycrystalline Be₄B, Be₂B, and BeB₆ were measured by the flash method. Generally, the thermal diffusivities at a given temperature decrease with increasing boron content. The thermal diffusivities of Be₄B, Be₂B, and BeB₆ varied from 0.13 to 0.072 to 0.031 cm²/s, respectively, at 200°C and from 0.068 to 0.038 to 0.007 cm²/s at 1000°C. Heat transport in BeB₆ is expected to occur almost entirely by phonon conduction, whereas electronic conduction probably plays a major role in Be₄B and Be₂B. Analytical expressions for the thermal diffusivities (α) of Be₄B and Be₂B at 200° to 1000°C and of BeB₆ at 25° to 1500°C are: α(Be₄B)=1/(5.83+9.05×10 3 T ), α(Be₂B)=1/(10.92+1.40×10 2 T ), and α(BeB₆)=5.60×10 4+5.72/ T +77.3/T²-4.09×10⁴/T³ cm²/s.     

Phase Equilibrium Diagram CaO—CaF2—2CaO.SiO2

Differential thermal analysis and quenching experiments were used to establish the ternary phase diagram CaO-CaF₂-2CaO.SiO₂. Hermetically-closed platinum capsules were used to prevent fluorine loss in the form of HF, SiF₄, and CaF₂ by reaction of the CaF₂ with water vapor or SiO₂, or by evaporation. The melting point of pure CaF₂ was 1419°± 1°C. There is one binary eutectic in the system CaO-CaF₂ and there are two ternary eutectics in the system CaO-CaF₂-2CaO.SiO₂. The results of the present study were combined with literature data to construct the phase diagram CaO-CaF₂-SiO₂.     

Crystallization of Beta NaFeO2 from a Glass Along the Na2SiO3-Fe2O3 Join

Fine-particle beta sodium ferrite (β-NaFeO₂), rather than α-Fe₂O₃, may be responsible for superparamagnetic behavior in a glass of composition (in mole fractions) 0.37Na₂O-0.26Fe₂O₃-0.37SiO₂. The 700°C isothermal section of the phase diagram of the Na₂O-Fe₂O₃-SiO₂ system is given, showing a three-phase field bounded by Na₂SiO₃-NaFeO₂-Fe₂O₃; there is no evidence for the existence (at 700°C) of compounds of molar composition 6Na₂O-4Fe₂O₃-5SiO₂ or 2Na₂O-Fe₂O₃-SiO₂. The Moessbauer spectrum of β-NaFeO₂ has an internal magnetic field of 487 kOe at room temperature.     

Subsolidus Studies in the System PbO-SiO2

The subsolidus region of the PbO-SiO₂ system was studied by DTA and X-ray diffraction. X-ray diffraction analysis showed the presence of five compounds: 4PbO.SiO₂, 3PbO·SiO₂, 2PbO·SiO₂, 3PbO·2SiO₂, and PbO·SiO₂. The compound 4PbO·SiO₂ has previously been reported to have three polymorphic forms; there are two polymorphs of 2PbO·SiO₂ with the inversion at 460°±15°C. The compounds 3PbO·SiO₂ and 3PbO·2SiO₂ were unstable above 430°±10° and 585°±15°C, respectively; PbO·SiO₂ was unstable below 525°±15°C. DTA patterns were determined for glasses of the composition of each of these compounds.     

Phases in the System Ba2SiO4-Ca2SiO4

The system Ba₂SiO₄-Ca₂SiO₄ was studied by heating mixtures of Ba₂SiO₄ and Ca₂SiO₄ at 1723 K. Six distinct phases resulted; they were examined by both X-ray diffraction and differential thermal analysis. The phases β -(Ba_0.05Ca_1.95)SiO₄ and α-(Ba_0.15Ca_1.85)SiO₄ are isostructural with corresponding high-temperature modifications of Ca₂SiO₄. The X phase (Ba_0.48Ca_1.52SiO₄) is orthorhombic, is a pure phase rather than a solid solution, and is defined for the first time in the present work. The T phase (Ba_1.31Ca_0.69SiO₄) is hexagonal and interpreted in terms of a unit cell with a doubled c parameter, in contrast with literature data.     

Phase Equilibria for the Ternary Fused-Salt System NaF–BeF2–UF4

The phase equilibrium diagram for the ternary fused-salt system NaF–BeF₂–UF₄ was based on evidence from differential thermal analysis, polarized light microscopy, and X-ray examination of samples obtained from thermal-gradient quenching studies and from high-temperature filtration experiments. All the stable compounds in the binary systems NaF–BeF₂ and NaF–UF₄ displayed primary-phase fields in the ternary system, including a new subsolidus compound which was observed and tentatively assigned the formula NaF · 4UF₄. No ternary compounds or solid solutions were observed. The following three eutectics were found in the ternary system: (1) 72.5 NaF, 17.0 BeF₂, and 0.5 mole % UF₄ at 486°C, (2) 56.0 NaF, 43.5 BeF₂, and 10.5 mole % UF₄ at 339°C, and (3) 43.5 NaF, 56.0 BeF₂, and 0.5 mole % UF₄ at 345°C.     

Effect of Bi2O3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Zn2SiO4 Ceramics

Bi₂O₃ was added to a nominal composition of Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature. When the Bi₂O₃ content was <8.0 mol%, a porous microstructure with Bi₄(SiO₄)₃ and SiO₂ second phases was developed in the specimen sintered at 885°C. However, when the Bi₂O₃ content exceeded 8.0 mol%, a liquid phase, which formed during sintering at temperatures below 900°C, assisted the densification of the ZS ceramics. Good microwave dielectric properties of Q × f =12,600 GHz, ɛ_r=7.6, and τ_f=−22 ppm/°C were obtained from the specimen with 8.0 mol% Bi₂O₃ sintered at 885°C for 2 h.     

Crystalline Solution in the System MgO-Mg,SiO4,-MgAl2,O4,

Crystalline solubility relations in the system MgO-Mg₂SiO₄MgAl₂O₄ (periclase-forsterite-spinel) were studied using coprecipitated gels as starting materials. The substitution 2Al = Mg + Si was investigated along the join Mg₂SiO₄-Mg-Al₂O₄,. At 1720°C the maximum crystalline solution in forsterite is about 0.5 mole % MgAI₂O₄, and in spinel it is slightly more than 5.0 mole % Mg₂SiO₄. The solubility of MgO in forsterite was 0.5 mole % at 1860°C, whereas more than 11 mole % Mg₂SiO₄ can be dissolved in the periclase structure at this temperature. Ternary crystalline solution exists in the periclase structure to a composition of Mg_0.853Al_0.063Si_0.026O at 1710°C.     

Studies of Silica-Structure Phases: I, GaPO4, GaAsO4, and GaSbO4

In the course of work on all compositions which would probably yield silica-structure phases, a detailed study was made of the A³⁺B⁵⁺O₄-type compounds with gallium as the trivalent element. Two forms of GaPO₄ exist corresponding to quartz and cristobalite; the quartz form has a thermal expansion of the low-quartz type and no stable α-β transition is found in this phase. It inverts stably to the cristobalite form at 933°± 4°C. The cristobalite form melts at 1670°C. and the liquid cannot be made to form a glass. The cristobalite form also has a metastable displacive transition at 616°± 2°C. GaAsO₄ exists only in a form corresponding to the lowquartz structure. It disproportionates into Ga₂O₃ and As₂O₅ at about 1000°C. GaSbO₄ could only be prepared in one form corresponding to the rutile structure. The influence of such phases on SiO₂ was determined by studying a few mixtures in the system SiO₂-GaPO₄. The SiO₂ end member appears to admit about 25% GaPO₄ into solid solution in the cristobalite phase at the highest temperature. Even under hydrothennal conditions, however, equilibrium cannot be easily attained at the lower temperatures in a few hundred hours. The results are presented in a not-impossible diagram for the system GaPO₄-SiO₂.     

Melting Phenomena in the System CaO–SiO2– H2O: I, The Join Ca2SiO,-Ca(OH)2

The liquidus-solidus relations along the join Ca₂SiO₄-Ca(OH), in the system CaO-SiO₂-H₂O have been determined at 1000 atm up to 1110°C. This join is binary and contains the calcium silicate hydrate, calciochondrodite, Ca5-(SiO₄(OH)₂. Calciochondrodite melts incongruently to Ca₂SiO₂+ liquid (composition 23 wt% Ca₂Si0₄) at 955°C. The eutectic between calcium hydroxide and calciochondrodite lies at 13% Ca₂Si0₄ and 822°C. Preliminary experiments, also at 1000 atm, in the ternary system CaO-Ca₂Si0₄-Ca(OH), indicate that the eutectic at which the fields of primary Ca(OH)₂, CaO, and Ca₂(Si0₄)₂(OH)₂ meet is close to the CaO-Ca. (OH), side of the triangle at approximately 805° C. The ternary reaction point Ca₂SiO_l+ liquid ⇌Ca₅(SiO₄)₂(OH)₂+ CaO + liquid is believed to lie in the low-CaO (<5%) high-Ca(OH)₂ (>70%) part of the system.