CO2 Decomposition by Oxide Ceramics Intercalated in Layered Compound

Iron oxide polymers intercalated and/or loaded within täniolite have been studied as a CO₂ decomposition medium. Fe²⁺ was exchanged for Li⁺ in täniolite, oxidized by air-bubbling at 60°–70°C. The basic d -spacing (13.75 Å in the Li⁺ form) was expanded to give 14.86 Å in the Fe²⁺ form. Oxidation by air in the form of suspension gave a 15.3-Å phase, which was ascribed to formation of magnetite within the interlayer. The interlayer distance of the intercalated phase remained the same upon heating at 300°C. The magnetite–intercalated täniolite was heated to activate in a H₂ and/or H₂O steam. CO₂ decomposition reactivity at 300°C has been evidenced by evolution of CO gas. The high reactivity for CO₂ decomposition is ascribed to the highly dispersed iron oxide ceramics within the interlayer of täniolite Li[(Mg₂Li)(Si₄O₁₀)]F₂ n H₂O.     

Mixed Oxide Capacitor of CuO—BaTiO3 as a New Type CO2 Gas Sensor

An oxide capacitor consisting of BaTiO₃ and an oxide is studied as a new type CO₂ sensor based on capacitance change. Sensitivity to CO₂, as well as the optimum operating temperature, was strongly dependent on the particular oxide mixed with BaTiO₃. Among the elements investigated in this study, CuO–BaTiO₃ exhibited the highest sensitivity to CO₂. In particular, the CuO–BaTiO₃ mixed oxide at the equimolar composition is highly sensitive to CO₂. The optimum operating temperature and frequency for CuO–BaTiO₃ are 729 K and 100 Hz, respectively, and the 80% response time to 2% CO₂ is within 25 s. The equimolar mixture of CuO and BaTiO₃ can measure the CO₂ concentration from 100 to 60 000 ppm. Carbonation of oxide seems to play a key role for the detection of CO₂ on these mixed oxide capacitors. The optimum operating temperature of these mixed oxide capacitors for CO₂ detection, therefore, correlates with the decomposition temperature of the carbonate corresponding to the oxide mixed with BaTiO₃. The capacitance increase of CuO–BaTiO₃ upon exposure to CO₂ seems to result from the elevated height of the potential barrier at the grain boundary between CuO and BaTiO₃. Carbonation of CuO in the element seems to bring about the elevation in the height of the potential barrier.     

Formation of BaTiO3 from BaCO3 and TiO2 in Air and in CO2

The formation of BaTiO₃ from equimolar BaCO₃ and TiO₂ (rutile) mixtures was studied in air and in CO₂. A small amount of BaTiO₃ is formed first directly from BaCO₃ and TiO₂ at the surface of contact. From then on it is a diffusion-controlled reaction, and both BaTiO₃ and Ba₂TiO₄ are produced, with Ba₂TiO₄ being formed in much larger amounts. In 1 atmosphere of CO₂, the intermediate Ba₂TiO₄ was suppressed up to a temperature of about 1100°C. in agreement with thermodynamic calculations. Ba₂TiO₄ reacts fast with 1 atmosphere of CO₂ below about 1100°C. to produce BaTiO₃and BaCO₃     

Effect of Li2CO3 on Reaction Between CaO and CO2

Reaction between CaO powders and CO₂( g ) is often limited by slow diffusion of CO₂ through the CaCO₃ product. Additions of Li₂CO₃ are shown to increase the reaction rate. At temperatures around 940 K, near to the Li₂CO₃-CaCO₃ eutectic temperature, 935 K, complete reaction of the CaO with CO₂ can be achieved when the heating rate and Li₂CO₃ content are optimized. At lower temperatures Li₂CO₃ causes lesser but measurable increases in reaction rates. SEM and surface area observations suggest different reaction paths when Li₂CO₃ is present, when Li₂CO₃ and eutectic are present, and when eutectic alone is present.     

CO2 Retention in High-Alkali Borate Glasses

A study of the high-alkali region of glass formation in the system Na₂O +B₂O₃ reveals that retention of CO₂ from carbonate starting materials can become a serious preparative problem at the high-alkali extreme. Results presented for glasses prepared using both Na₂O and Na₂CO₃ show that residual CO₂ can lead to major differences in physical properties which in this work are represented by the viscosity-related glass transition temperature .     

Oxide Ion Disorder in Nd2Hf2O7

The compound Nd₂Hf₂O₇ was synthesized via a solid-state route and the crystal structure determined by electron diffraction and Rietveld refinement of both X-ray and neutron diffraction data. A small amount of disorder was found on the anion sublattice, while no evidence of disorder in the cation sublattice could be verified. The compound is cubic with space group Fd 3 m , structurally lying between the ideal pyrochlore and fluorite forms, with 0.26% of the oxide ions residing on the 8 a sites usually vacant in pyrochlores. The lattice constant is 10.6469(2) Å, and the overall fit parameter was R _wp=0.0398.     

Free Volume of Network-Forming Oxide Glasses in the Systems P2O5-(GeO2,TeO2,Sb2O3,V2O5)

The free-volume fraction (V_f) defined by Simha and Boyer was measured for network-forming oxide glasses in the systems P₂O₅-(GeO₂, TeO₂,Sb₂O₃.V₂O₅). The V_f values varied from 0.06 to 0.25. The systems P₂O₅-TeO₂: and P₂O₅-Sb₂O₃ have V_f∼0.1, which is near the magnitude of the free-volume fraction for normal metaphosphate glasses and many organic high polymers.     

Studies in Lithium Oxide Systems: V, Li2O-Li20 B2O3

Nine compositions containing 40 to 68% B₂O₃ were used to study the high-lithia portion of the system Li₂O-B₂O₃ by quenching and differential thermal analysis methods. The compounds 3Li₂O 2B₂O₃ and 3Li₂O B₂O₃ melted incongruently at 700°± 6°C, and 715°± 15°C., respectively. The compound 2Li₂O B₂O₃ is assumed to dissociate slightly below 650°± 15° C., although the data could also be interpreted as in-congruent melting. Below 600°± 6°C. it does dissociate to the 3:2 and 3:1 compounds. In this narrow temperature interval the 2:1 compound had an inversion at 618°± 6°C. Both forms of the 2:1 compound could be quenched to room temperature. X-ray diffraction data for the compounds are tabulated, and the complete phase diagram for the system Li₂O-B₂O₃ is presented.     

Internal Friction of Network-Forming Oxide Glasses in the System P2O5-(GeO2, TeO2, Sb2O3, V2O5)

The internal friction of only network-forming oxide glasses containing a P₂O₅ component, i.e., in the systems P₂O₅-GeO₂, P₂O₅-TeO₂, P₂O₅-Sb₂O₃, and P₂O₅-V₂O₅, was measured as a function of temperature by a free torsional vibration method. P₂O₅-TeO₂ and P₂O₅-Sb₂O₃ glasses exhibited clearly high-temperature peaks in a plot of internal friction vs temperature in spite of the absence of nonbridging oxygens and network modifiers. Therefore, we conclude that the high-temperature peaks appeared when strong and weak parts coexisted in the network structure.     

Oxygen Fugacity Control in Nonflowing Atmospheres: I, Experimental Observations in CO/CO2 and O2/N2 Mixtures

The performance of a stabilized zirconia sensor and electrochemical oxygen pump combination in the isothermal control of oxygen fugacity in a nonflowing atmosphere was studied in a closed furnace system in the temperature range of 800° to 1100°C. Under certain conditions, large differences in oxygen pressure were found between sensors at the same constant temperature in close proximity to each other. This result reflected the existence of a stable steplike oxygen fugacity "front" in the furnace, separating regions which differed by several orders of magnitude in oxygen fugacity. This oxygen pressure profile in the furnace resulted from the steady-state transport of oxygen from oxygen leakage sources to the pump. The existence, magnitude, and position of the oxygen fugacity front were found to depend on the gas-phase composition, the relative locations of the leakage sources and the pump, the oxygen fugacity of the reference electrode, and the magnitude of the oxygen flux in the gas phase.     

Synthesis of Al2O3–CeO2 Mixed Oxide Nano-Powders

Ceria (CeO₂)-doped alumina (Al₂O₃) composite nano-particles were synthesized using sucrose as a chelating agent and template material. As-synthesized powders were characterized using X-ray diffraction technique for their phase analysis, BET surface area analyzer for specific average surface area, and transmission electron microscope for particle size and morphology. Both CeO₂ and Al₂O₃ delayed the amorphous to crystalline phase transformation for each other. These composite nano-powders had particle size in the range of 20–50 nm with an aspect ratio of 1.5 with platelet morphology and surface area between 100 and 300 m²/g. Synthesis parameters were optimized varying the sucrose to metal ion ratio, calcinations time and temperature. This method can be applied to synthesize various monolithic and mixed metal oxide based ceramic nano-particles.     

Prediction of Immiscibility Boundaries of the Systems K2O-SiO2, K2O-Li20-SiO2, K20-Na2O-Si02, and K2O-BaO-SiO2

In earlier work, a prediction method of the immiscibility boundary of a ternary silicate glass system was developed involving two known binary immiscibility boundaries and a measured immiscibility temperature of one ternary glass composition. In the present work, the method is extended to the case where one of the two binary immiscibility boundaries is not known and is applied as an example to ternary silicate systems containing K₂O. First, the immiscibility boundary of the system K₂O-SiO₂ is estimated by measuring the immiscibility temperatures of three glasses in the system K₂O-Li₂O (or Na₂O)-SiO₂. Using this result the immiscibility boundaries of the systems K₂O-Li₂O-SiO₂, K₂O-Na₂O-SiO₂, and K₂O-BaO-SiO₂ are estimated. The results agree reasonably well with the experimentally determined immiscibility temperatures at selected compositions.     

Studies in Lithium Oxide Systems: IX, Li2o-Al2O3-TiO2

Compatible phases in the system Li₂O-Al₂O₃-TiO₂ at various temperature levels were determined mainly by solid-state reactions for the portion of the ternary system bounded by Li₂O Al₂O₂, Li₂O.TiO₂, Al₂O, and TiO₂. The existence of a ternary compound, Li₂O.Al₂O₃.4TiO₂, and nine joins was established. The ternary compound has a lower limit of stability at 1090°± 15°C. and dissociates and recombines rapidly at 1380°± 15°C.     

Synthesis of ZrO2 and Y2O3-Doped ZrO2 Thin Films Using Self-Assembled Monolayers

Undoped or Y₂O₃-doped ZrO₂ thin films were deposited on self-assembled monolayers (SAMs) with either sulfonate or methyl terminal functionalities on single-crystal silicon substrates. The undoped films were formed by enhanced hydrolysis of zirconium sulfate (Zr(SO₄)·4H₄O) solutions in the presence of HCl at 70°C. Typically, these films were a mixture of two phases: nanocrystalline tetragonal- ( t -) ZrO₂ and an amorphous basic zirconium sulfate. However, films with little or no amorphous material could be produced. The mechanism of film formation and the growth kinetics have been explained through a coagulation model involving homogeneous nucleation, particle adhesion, and aggregation onto the substrate. Annealing of these films at 500°C led to complete crystallization to t -ZrO₂. Amorphous Y₂O₃-containing ZrO₂ films were prepared from a precursor solution containing zirconium sulfate, yttrium sulfate (Y₂(SO₄)₃8·H₂O), and urea (NH₂CONH₂) at pH 2.2–3.0 at 80°C. These films also were fully crystalline after annealing at 500°C.     

Studies in Lithium Oxide Systems: II, Li2O Al2O3–Al2 O 3

Solid-state reactions between Li₂O and Al₂ O₃ were studied in the region between Li₂O.Al₂ O ₃ and Al₂ O ₃. The compound Li₂ O Al₂ O ₃ melts at 1610°± 15°C. and undergoes a rapid reversible inversion between 1200° and 1300°C. Vaporization of Li₂ O from compositions in the system proceeds at an appreciable rate at 1400°C, as shown by fluorescence. Lithium spinel, Li₂ O -5Al₂O₃, was the only other compound observed. The effect of Li₂ O on the sintering of alumina was investigated.     

The Crystallization of Ba-Substituted CsTiSi2O6.5 Pollucite Using CsTiSi2O6.5 Seed Crystals

Barium (Ba)-substituted CsTiSi₂O_6.5 materials of two types, Cs _x Ba_{1− x} TiSi₂O_{(7− x /2)} and Cs _x Ba_{(1− x )/2}TiSi₂O_6.5 were synthesized with the pollucite structure with 1≥ x ≥0.6. When the Ba-substituted precursor materials were heat treated to 850°C for 4 h, a mixture of amorphous and unidentifiable phases formed. However, with the addition of 10 wt% of crystalline CsTiSi₂O_6.5 to the Ba-containing precursors, nearly single-phase pollucite was obtained after 20 h at 750°C for x ≥0.6. The added crystalline CsTiSi₂O_6.5 particles act as nuclei that allow the Ba-containing materials to crystallize into the pollucite phase and to avoid the formation of unwanted phases that would otherwise nucleate and grow. These new materials can be used to study the stability of CsTiSi₂O_6.5 as a durable ceramic waste form, which could accommodate with time both Cs and its decay product, Ba.     

Studies in Lithium Oxide Systems: XII, Li2O-B2O3-Al2O3

Tentative phase relations in the binary system BnOa-A1₂O₃ are presented as a prerequisite to the understanding of the system Li₂O-B₂O₃-Al₂O₃. Two binary compounds, 2A1₂O₃.B₂O₃ and 9A1₂O₃.-2B₂O₃, melted incongruently at 1030° f 7°C and about 144°C, respectively. Two ternary compounds were isolated, 2Li₂O.A1₂O₃.B₂O₃ and 2Li₂O. 2AI₂O₃. 3B₂0₃. The 2:1:1 compound gave a melting reaction by differential thermal analysis at 870°± 20° C, but the exact nature of the melting behavior was not determined. The 2:2:-3 compound melted at 790°± 20° C to Li_zO.-5Al₂O₃ and liquid. X-ray diffraction data for the compounds are presented and compatibility triangles are shown.